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Transcript of The quality of extravirgin olive oil obtained by an innovative extraction technology Zinnai A.,...
The quality of extravirgin olive oil obtained by an innovative extraction technology
Zinnai A Venturi F Sanmartin C DrsquoAgata M Taglieri I Andrich GDAFE University of Pisa
44th International Conference on Food Processing amp Technology10-12 August London UK
The product what is the The product what is the extravirgin olive oil extravirgin olive oil
The extravirgin olive oil (EVOO) is obtained only by physical processes without using any treatment different from washing settling centrifugation and filtration
This product has to reach a score ge 65 during official sensorial tasting session (in a range between 0 and 9) and be lacking in defects at the same time its free acidity (expressed like oleic acid grams vs 100 g of oil) has to be lower than 08
(Reg CE 15132001 23th July 2001)
Extraction Extraction technologytechnology
Quality of Quality of extracted extracted
oiloil
Why EVOO represents one of the main elements in the Mediterranean diet
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Its daily intake produces several health benefits
Its daily intake produces several health benefits
Only some references (among many papers)Huang CL Sumpio BE ldquoOlive oil the mediterranean diet and
cardiovascular healthrdquo J Am Coll Surg 207 407ndash416 (2008)V Llorente ndash Cortes R Estruch MP Mena E Ros MA Gonzales M Fitograve RM
Lamuela-Raventograves L Badimon ldquoEffect of Mediterranean diet on the expression of pro-atherogenic genes in a population at high cardiovascular
riskrdquo Atherosclerosis August 2009Reduction in the incidence of the type Diabetes 2
With the Mediterranean diet Salas-Salvado et al Diabetes Care 34 14-19 2011
What was the idea What was the idea Knowing that the addition of Knowing that the addition of carbonic snow to grapes let to produce high quality carbonic snow to grapes let to produce high quality
wines hellipwines hellip
Our research group decided to apply Our research group decided to apply this technology to extravirgin olive oil this technology to extravirgin olive oil
extraction extraction
The method The method An innovative EVOO extraction technology (Patent ndeg IT1405173-B) involving the addition of a cryogen (ex solid CO2) to the olives was developed in order to increase the extraction yield and obtain an oil characterized by an higher concentration of its health compounds (ex phenols tocopherols) and a stronger link with its production area
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
The product what is the The product what is the extravirgin olive oil extravirgin olive oil
The extravirgin olive oil (EVOO) is obtained only by physical processes without using any treatment different from washing settling centrifugation and filtration
This product has to reach a score ge 65 during official sensorial tasting session (in a range between 0 and 9) and be lacking in defects at the same time its free acidity (expressed like oleic acid grams vs 100 g of oil) has to be lower than 08
(Reg CE 15132001 23th July 2001)
Extraction Extraction technologytechnology
Quality of Quality of extracted extracted
oiloil
Why EVOO represents one of the main elements in the Mediterranean diet
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Its daily intake produces several health benefits
Its daily intake produces several health benefits
Only some references (among many papers)Huang CL Sumpio BE ldquoOlive oil the mediterranean diet and
cardiovascular healthrdquo J Am Coll Surg 207 407ndash416 (2008)V Llorente ndash Cortes R Estruch MP Mena E Ros MA Gonzales M Fitograve RM
Lamuela-Raventograves L Badimon ldquoEffect of Mediterranean diet on the expression of pro-atherogenic genes in a population at high cardiovascular
riskrdquo Atherosclerosis August 2009Reduction in the incidence of the type Diabetes 2
With the Mediterranean diet Salas-Salvado et al Diabetes Care 34 14-19 2011
What was the idea What was the idea Knowing that the addition of Knowing that the addition of carbonic snow to grapes let to produce high quality carbonic snow to grapes let to produce high quality
wines hellipwines hellip
Our research group decided to apply Our research group decided to apply this technology to extravirgin olive oil this technology to extravirgin olive oil
extraction extraction
The method The method An innovative EVOO extraction technology (Patent ndeg IT1405173-B) involving the addition of a cryogen (ex solid CO2) to the olives was developed in order to increase the extraction yield and obtain an oil characterized by an higher concentration of its health compounds (ex phenols tocopherols) and a stronger link with its production area
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Why EVOO represents one of the main elements in the Mediterranean diet
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Anti-inflammatory effect
Cardiovascular protection
Digestive health benefits
Anti-cancer activity
Its daily intake produces several health benefits
Its daily intake produces several health benefits
Only some references (among many papers)Huang CL Sumpio BE ldquoOlive oil the mediterranean diet and
cardiovascular healthrdquo J Am Coll Surg 207 407ndash416 (2008)V Llorente ndash Cortes R Estruch MP Mena E Ros MA Gonzales M Fitograve RM
Lamuela-Raventograves L Badimon ldquoEffect of Mediterranean diet on the expression of pro-atherogenic genes in a population at high cardiovascular
riskrdquo Atherosclerosis August 2009Reduction in the incidence of the type Diabetes 2
With the Mediterranean diet Salas-Salvado et al Diabetes Care 34 14-19 2011
What was the idea What was the idea Knowing that the addition of Knowing that the addition of carbonic snow to grapes let to produce high quality carbonic snow to grapes let to produce high quality
wines hellipwines hellip
Our research group decided to apply Our research group decided to apply this technology to extravirgin olive oil this technology to extravirgin olive oil
extraction extraction
The method The method An innovative EVOO extraction technology (Patent ndeg IT1405173-B) involving the addition of a cryogen (ex solid CO2) to the olives was developed in order to increase the extraction yield and obtain an oil characterized by an higher concentration of its health compounds (ex phenols tocopherols) and a stronger link with its production area
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
What was the idea What was the idea Knowing that the addition of Knowing that the addition of carbonic snow to grapes let to produce high quality carbonic snow to grapes let to produce high quality
wines hellipwines hellip
Our research group decided to apply Our research group decided to apply this technology to extravirgin olive oil this technology to extravirgin olive oil
extraction extraction
The method The method An innovative EVOO extraction technology (Patent ndeg IT1405173-B) involving the addition of a cryogen (ex solid CO2) to the olives was developed in order to increase the extraction yield and obtain an oil characterized by an higher concentration of its health compounds (ex phenols tocopherols) and a stronger link with its production area
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
The method The method An innovative EVOO extraction technology (Patent ndeg IT1405173-B) involving the addition of a cryogen (ex solid CO2) to the olives was developed in order to increase the extraction yield and obtain an oil characterized by an higher concentration of its health compounds (ex phenols tocopherols) and a stronger link with its production area
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
bull Nontoxic and donrsquot leave residuesNontoxic and donrsquot leave residues
bull Not inflammable Not inflammable
bull Good solvent (non-polar)Good solvent (non-polar)
bull Inert by an organoleptic point of Inert by an organoleptic point of viewview
bull Triple point easy to reach (-Triple point easy to reach (-575degC 51atm)575degC 51atm)
bull Easy to find and useEasy to find and use
bull low costs low costs
bull Anti-microbial and anti-oxidant Anti-microbial and anti-oxidant actionaction
bull Enzymes inhibitor (ex lypoxidase)Enzymes inhibitor (ex lypoxidase)
Among all the Among all the possible possible cryogens cryogens
suitable for food suitable for food technology technology
(N(N2L2L He HeLL Ar ArLL etc) etc)
COCO2s2s (or carbonic snow) (or carbonic snow)shows a lot of advantagesshows a lot of advantages
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
CO2s (-78degC 1
atm)
Olives (T= 12-16degC)
-Q-Q
+Q+Q
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Diffusion of cellular components in the Diffusion of cellular components in the extracellular liquid phase extracellular liquid phase
CELLULAR
CRASH
WATER FREEZING
ICE VOLUME gt water volume
ADDITION CO2s
Mechanical action
Mechanical action
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
COCO2s2s + Olivesolive paste + Olivesolive paste
Able to prevent Able to prevent the possible the possible oxidation of oxidation of extracted oilextracted oil
Increase of the Increase of the extraction yieldextraction yield
Wished Wished aromatic aromatic profile profile
Higher Higher antioxidant antioxidant
contentcontent
COCO2g2g
Modulation of Modulation of the working the working
variables related variables related toto thethe
MALAXATION MALAXATION
Inert gaseous layer Inert gaseous layer
((COCO22gg airair = 15 = 15))
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
- they were determined the values for the main parameters (no reference are available) to use for the extraction of oil
What was doneWhat was done
- It was verified the influence of cryogen addition - It was verified the influence of cryogen addition (CO(CO2s2s) to the olives during pre-milling phase on ) to the olives during pre-milling phase on the the yield of the oil yield of the oil obtained and on obtained and on oil quality oil quality in in order to evaluate the suitability of the new method order to evaluate the suitability of the new method for EVOO productionfor EVOO production
Our research group
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
OIL
1
2
3
4
7
20-30 kg of olives
5
The micro oil mill used Oliomio Baby reg (TEM)The micro oil mill used Oliomio Baby reg (TEM)
6
Water
CO2(s)
Receiving hopper(1)
Wet olive residues
Knives crusher (2)
Horizontal continuous
malaxer (3)2-phases decanter
(7)
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
Where did the olives come fromWhere did the olives come from They are They are monovarietal and polyvarietal (monovarietal and polyvarietal (mix of some mix of some
varietiesvarieties) olives collected from Tuscany olive-) olives collected from Tuscany olive-yards in two different years yards in two different years
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
The olives utilized in each experimental runs The olives utilized in each experimental runs (( 60 kg) were preliminary mixed to ensure 60 kg) were preliminary mixed to ensure homogeneous feeds Each sample was split homogeneous feeds Each sample was split
in two fractions (30 kg)in two fractions (30 kg)
Traditional extraction
process
Traditional extraction
process
Addiction of CO2s
Addiction of CO2s
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Origin and cultivar of the raw matter Origin and cultivar of the raw matter utilizedutilized
Sample ID Geographical Cultivar
Traditional
Cryo origin
A 1 Tuscany (GR 2010)
Frantoio
B 2 Tuscany (SI 2010)
mix
C 3 Tuscany (SI 2010)
mix
D 4 Tuscany (SI 2010)
mix
E 5 Tuscany (GR 2014)
Leccino
F 6 Tuscany (GR 2014)
Frantoio
G 7 Tuscany (GR 2014)
Moraiolo
Frantoio Leccino Correggiolo Frantoio Leccino Correggiolo
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
CryoCryo TraditionalTraditional
Cryogenolives (ww)Cryogenolives (ww) 01 divide 02 01 divide 02 00
Temperature of olivesTemperature of olives (degC)(degC) ~-2~-2 115115
Temperature of pasteTemperature of paste (degC)(degC) ~240~240 ~240~240
Time of MalaxationTime of Malaxation (s)(s) 24002400 24002400
Time of ExtractionTime of Extraction (s)(s) 49004900 43004300
Water addedolivesWater addedolives ()() 8585 9393
Main operating variables adopted Main operating variables adopted during the experimental runs during the experimental runs
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method
In order to evaluate the effect induced by the addition of the cryogen on the oil extraction yield it was determined the Extractability
Index Variation (EIV) as the ratio between the difference of the oil extracted using CO2s and
that obtained by a traditional extraction process and the amount of product obtained by
traditional method EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100EIV = (EC-ET)ET EIV = (EC-ET)ET 100 100
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Oil extraction yieldOil extraction yieldOil extraction yieldOil extraction yield
Run EC ET
1A 858 825
2B 855 772
3C 912 827
4D 841 748
5E 808 793
6F 736 689
7G 844 774
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
The direct addition of cryogen to the olives during pre-milling phase could induce a
general increase in the oil extraction yield
[(EC-ET)ET]10040 108 103 124 19 68 94
[(EC-ET)ET]10040 108 103 124 19 68 94
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Whatrsquos about the oil extraction yield
Whatrsquos about the oil extraction yield
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
If itrsquos necessary this method allows to harvest olives early in order to reduce greatly the damages due to the third fly attack of Bactrocera oleae that can induce a significant loss in oil production (up to 60) as well as a decrease in oil quality
Water content
inside the fruit
Water content
inside the fruit
CELLULAR CRASH
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Percentage Increase () in tocopherols content (PITC)
60 06
Percentage Increase in Total phenols (PITPh)
51 106
Effects on oil Effects on oil quality of the new quality of the new extraction methodextraction method
p=005p=005
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Oil general chemical parameters
There arenrsquot reliable differences due to the new extraction method
This evidence is probably due to the high efficience of the
extraction plant (even in absence of cryogen addition)
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
RunFree acidity ( oleic acid)
Peroxide value (meq O2Kg)K232 K270 K
A 03 a 626 a 152 a 009 a 000
1 03 a 675 a 145 a 009 a 000
B 06 a 653 a 144 a 010 a 000
2 04 b 482 b 137 a 007 a 000
C 07 a 652 b 127 a 012 a 000
3 07 a 768 a 126 a 010 a 000
D 05 a 680 a 104 b 011 b 000
4 05 a 714 a 178 a 017 a 000
E 06 a 611 a 148 b 011 b 000
5 06 a 521 b 157 a 015 a 000
F 05 a 1067 b 166 a 013 b 000
6 05 a 1127 a 168 a 014 a 000
G 05 a 972 a 160 a 012 a 000
7 05 a 847 b 162 a 011 a 000
Limit value for EVOO le 08 le 20 le 25 le 022 000
Oil general chemical parameters Oil general chemical parameters
In relation to each couple of runs (A1divideG7) for each parameter values not sharing the same letter have significantly different mean concentration
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
CONCLUSIONSCONCLUSIONS
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
bull The general analytical parametersThe general analytical parameters (Reg 256891) donrsquot show reliable differences due to the new extraction process and prove the efficiency of micro oil mill used (Oliomio Babyreg)
bull The concentration of PHENOLS PHENOLS tends to increase but there is a great variability in experimental data (this variability doenrsquot seem to be related to the amount of water remaining in the oil)
bull The concentration of TOCOPHEROLS TOCOPHEROLS increases using the new extraction method
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
CONCLUSIONSCONCLUSIONS
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
bull The CO2s addition seems to increase the extraction yield (this effect is greater when the olives water content is greater)
bull The extraction yield is greater when itrsquos used an higher ration between CO2s added olives squeezed
bull The possibility of using olives early harvested could limit the losses due to Bactrocera oleae (this can be useful in ldquodifficul yearrdquo)
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
CONCLUSIONSCONCLUSIONS
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
bull The new extraction method could allow to obtain an EVOO with an higher concentration in bioactive compounds
EVOO can increases its nutritional properties and its antioxidant activity
and so its SHELFLIFE
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
- to control the changes in chemical and sensory qualities both for oil
extracted with the new system and the traditional one as a function of storage
time
What will be doneWhat will be done
- To set up a ldquomore complexrdquo innovative plant to - To set up a ldquomore complexrdquo innovative plant to verify the possibility to introduce other verify the possibility to introduce other modifications to the extraction process (ex verify if modifications to the extraction process (ex verify if the cryogen addition can be done even (or) during the cryogen addition can be done even (or) during the malaxation) the malaxation)
This project was selected for the
presentation at Expo Milan 24th August
2015 Italian Pavillon
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
ReferencesReferencesReferencesReferences
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Solid carbon dioxide to promote the extraction of extra virgin olive oil
AZinnai F Venturi C Sanmartin F Favati G AndrichGrasas y Aceitas (in press)
Extra-virgin olive oil production with the addition of solid CO2
AZinnai F Venturi C Sanmartin I Taglieri G Andrich
Agro FOOD Industry Hi Tech - vol 26(3) - MayJune 2015
Preliminary results on the influence of carbonic snow addition during the olive processing oil extraction yield and elemental
profile C Zoani G Zappa F Venturi C Sanmartin G Andrich and
A ZinnaiJournal of Nutrition and Food Sciences 4 277 (2014)
doi 1041722155-96001000277
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Thanks to hellipThanks to hellipbull Research groups of Prof Fabio Favati and
Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
bull Research groups of Prof Fabio Favati and Drssa Susanna Bartolini for their useful collaboration in the analytical phase of this research
bull ldquoSara Arrigonirdquo farm - La Spezia (Italy) that took part in the experimental activity
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Research supported by
SEE YOU IN MILAN TO EXPO 2015
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
Total OIL entrance(kg of crushed fruits x of oil inside the olives)
= Total OIL output
(kg of the olive residues x of oil inside the olive residues)
+EXTRACTED OIL
MASS BALANCE during extraction MASS BALANCE during extraction processprocess
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
0
10
20
30
40
50
60
000 005 010 015 020
CO2s olive (kg kg)
Fen
oli
To
tali
(pp
m a
cid
o g
alli
co)
0
003
006
009
012
015
018
Res
a e
stra
ttiv
a
(oli
o e
stra
tto
o
live
lav
ora
te)
(kg
k
g)
fenoli totali
resa estrattiva
a
ab
b
ab
Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno estratto kg olive lavorate) ottenute aggiungendo o meno
diverse quantitagrave di criogeno alle olive processate diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate) ( 0 010 015 020 kg criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive addizionando diverse quantitagrave di criogeno alle olive
(0 010 015 020 kg di criogeno kg olive lavorate) (0 010 015 020 kg di criogeno kg olive lavorate)
lettere diverse sottolineano lrsquoesistenza di differenze statisticamente significative (p = 005)
0
50
100
150
200
250
300
350
0 10 15 20
criogeno ( kg CO2s kg olive )
Vit
amin
a E
(pp
m a
-to
cofe
rolo
)
b a a a
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
We need 08 kg of CO2s to lower 100 kg of olives temperature by 1degC
Cost of 1 kg of CO2s= euro050
Cost to turn down the average temperature of 100
kg of olives by 10degC(15degC 5degC )
08kgdegC x 10degC x 050 eurokg=4euro
Considering an average oil yield of 15
The addition cost for a kg of extravirgin olive oil is
4 euro100 kg olives x 15100kg oilkg olives
lt 03eurokg oil
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Extraction yieldExtraction yield
01630152
01320146
000
005
010
015
020
A1 A2Extr
acti
on
yie
ld(k
g o
ilkg o
lives)
CCSC
The CO2s addition is more useful if the olives have a greater content in water (fruits less ripe )
EC
ET
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Run CRIO Yield TRAD Yield EIV
A11 122 110 109
A12 130 118 102
A2 163 132 235
A3 155 157 -13
A4 160 142 127
A5 152 146 41
B1 158 152 40
C1 120 128 -62
D1 148 145 22
D2 164 150 93
D3 173 162 68
Ea 88 85 35
Eb 92 85 82
Ec 126 85 482
Ripe index increasing
CO2g addedincreasing
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Determination of oil elemental profile sample pre-treatment
High PressureMicrowave Digestion
Milestone 1200 Mega
05 golive oil
Mineralized oil sample
(final V = 25 ml)
2 ml H2O2 + 6 ml HNO3
Different mixtures testedH2O2 30vv (1 divide 2 ml)+ HNO3 699vv (2 divide
6 ml)
Total dissoluti
on
high-purity water
(gt 18 MΩ)
time Power Pressure
1 min 250 WFree
pressure race
1 min 0 W
5 min 400 W
5 min 650 W
Vent = 5 min
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Circulation of the thermal fluid
Circulation of the thermal fluid
Addiction of cryogen
Addiction of cryogen
Thermal probes Thermal probes
Olives Olives
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
Preliminary results about oil extraction Preliminary results about oil extraction yield yield discussion discussion
The number of the experimental runs carried out until now is quite reduced
The number of the experimental runs carried out until now is quite reduced
BUTBUT
The results appear very encouraging and the new method seem very suitable for olive oil extraction
The results appear very encouraging and the new method seem very suitable for olive oil extraction
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
During the next crop season we will increase the number of experimental runs adopting several combinations of the working parameters (ie amount of cryogenamount of olives fruit ripening stage etc)
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
TQ mineralized
olive oil solution
Varian Vista MPX(axial configuration
simultaneous 112 Mpixel CCD detector)
study of spectral interferencesstudy of spectral interferences
preliminary qualitative analysis72 elements
preliminary qualitative analysis72 elements
quantitative analysisquantitative analysis
Gas flows optimization based on signal-to-background ratio (SB)
Auxiliary flow (lmin)
Nebulizer flow(lmin)
10 15 09 10 11 12
SBMg 3296 11720 13948 17998 19921 18412Mn 0128 0197 0245 0312 0303 0294Na 1827 1940 1827 3187 6121 4371
Zn - 213857 nm more sensitive but interfered by Fe
Zn - 206200 nm - less sensitive but without interferences
Analytical wavelengths (nm)
Al - 396152 nm K - 766491 nm Rb - 780026 nm
As - 188980 nm Li - 670783 nm S - 181972 nm
B - 249772 nm Mg - 279553 nm Sb - 206834 nm
Ba - 455403 nm Mn - 257610 nm Si - 251611 nm
Ca - 396847 nm Na - 589592 nm Sr - 407771 nm
Cr - 267716 nm Ni - 231604 nm Ti - 334941 nm
Cu - 327395 nm P - 213618 nm V - 311837 nm
Fe - 238204 nm Pb - 220353 nm Zn ndash 206200 nm
Instrumental conditions
RF Frequency 40 MHz (free running air-cooled)
RF Power 12 kW
Gas (plasma auxiliary nebulizer) Argon
Plasma flow 150 lmin
Auxiliary flow 15 lmin
Nebulizer flow 110 lmin
Replicates 5
Replicate read time 5 s
Operating parameters for ICP-AES quantitative analysis
ICP-AES Analysis
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-
Bruker Aurora M90 (90 degree ion mirror ion optics Collision Reaction Interface)110 diluted
mineralized olive oil solution
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Tuning with a 5 microgl Be Mg Co In Ba Ce Ti Pb and Th solution for
sensitivity and resolution optimization and mass calibration
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Check of the level of oxide ions by the CeO+Ce+ ratio lt 2
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
Monitoring of double charged ions by the signal 137Ba++137Ba+ lt 3
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
CheckCorrection of isobaric interferences examination of more isotopes of the same element(eg Rb85 Rb 87 Sr88Sr87 Nd142 Nd146 Nd144 Se77 Se78 Sn147 Sm148 Sm152 Gd157 Gd154 Er166 Er168 Yb170 Yb172) application of correction equations with respect to isotopes of other elements potentially interfering (eg Nd142 corrected by analyzing Ce140 Nd144 by Sm147 Sm152 by Gd157 Rb87 by Sr88 ) use of the Collision Reaction Interface ndash CRI (for As and Se)
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
Working rangesbull005 divide 5 microgl - As Cd Ce Er Eu Gd La Mn Nd Pb Pr Rb Sb Sc Se Sm Sr Th V Y Ybbull01 divide 10 microgl - Co Cr Cu Mg Ni
External calibration5 standard solutions + blankCurve Fit LinearWeighted Fit NoCorrelation coefficientsR gt 09999
Normal Sensitivity Mode (without CRI) High Sensitivity Mode As and Se ndash Normal mode with CRI
ICP-MS Analysis
- PowerPoint Presentation
- The product what is the extravirgin olive oil
- Why EVOO represents one of the main elements in the Mediterranean diet
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- What was done
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Effects on oil quality of the new extraction method
- Slide 19
- Slide 20
- CONCLUSIONS
- Slide 22
- Slide 23
- What will be done
- Slide 25
- Thanks to hellip
- Slide 27
- Slide 28
- Slide 29
- Fenoli totali ( ppm acido gallico) e rese estrattive (kg olio estratto kg olive lavorate) ottenute aggiungendo o meno diverse quantitagrave di criogeno alle olive processate ( 0 010 015 020 kg criogeno kg olive lavorate)
- Vitamina E (ppm di α-tocoferolo) presente negli oli estratti ottenuti addizionando diverse quantitagrave di criogeno alle olive (0 010 015 020 kg di criogeno kg olive lavorate)
- Slide 32
- Extraction yield
- Slide 34
- Determination of oil elemental profile sample pre-treatment
- Slide 36
- Slide 37
- Slide 38
- Slide 39
-