I risultati del progetto Green Site

Action 4 – Technology assessment

CONSORZIO VENEZIA RICERCHE – dott. Petra Scanferla

GREEN SITE


Sub – Action 4.1: Technical preparation (CVR)Sub – Action 4.2: Evaluation (ALLES)

• EXPECTED RESULTS:

� clean-up (extraction) efficiency should be higher than 90% (SFE) and

over 90 % of efficiency in oxidation (SCWO) of target organic compounds;

� improvement (by 30’-60’) of kinetic rates of extraction/oxidation of target

organic compounds;

� end-products generated should be easily managed and discharged

without further expensive or complex treatment;

� possibility to realize compact equipment, easy to transport and to install in

the intervention sites;

� practical guidelines on optimal use of prototype.

• AIM: assessing the prototype developed in order to investigate its

treatment efficacy of SFE and SCWO processes under real conditions with

selected contaminated soil and sediment samples.


1. Definition of the target organic pollutants

Starting points for the assessment

“ISAP - Indagine sui sedimenti e sulle acque dei canali di Porto Marghera e delle aree lagunari antistanti”MAV/CVN - ICRAM

A) characterizing the sediment contamination

of the forthcoming industrial channel that need to be dredged…

Primarily: PAHs


1. Definition of the target organic pollutants

B) characterizing the contaminated soil and

groundwater of the industrial area

Primarily PAHs than

amines and

organochlorine

PAHs

A) characterizing the sediment contamination

of the forthcoming industrial channel that need to be dredged…



2. Definition of the concentration

levels of the selected

contaminants in the samples

that will be used for the

evaluation of process

performance.

Chemical Class A Class B Class C Class C+

mg/Kg d.w. mg/Kg d.w. mg/Kg d.w. mg/Kg d.w.

As 15 25 50 >50

Cd 1 5 20 >20

Cr 20 100 500 >500

Cu 40 50 400 >400

Hg 0.5 2 10 >10

Ni 45 50 150 >150

Pb 45 100 500 >500

Zn 200 400 3000 >3000

Tot. Hydrocabons 30 500 4000 >4000

Total PAHs 1 10 20 >20

PCBs 0.01 0.2 2 >2

Chlor.Pesticides 0.001 0.02 0.5 >0.5

DISPOSAL SITES:

A,B,C: in lagoon

C+: no contact with lagoon

PAH:

50 and 100 mg/kg d.m.



A. Definition of procedures for the collection and preparation of ad

hoc sediment samples and extracts to be used for the evaluation

tests of the processes.

B. Identification of the matrices (solid, liquid and gaseous) that need

to be characterized during the tests.

C. Definition of protocols :

� Starting run and blank test Protocol

� Processes optimization Protocol

Protocols and Procedures


A. Collection and preparation of ad hoc sediment samples

IPA Naftalene mg/Kg s.s. 1194.7 Acenaftilene mg/Kg s.s. 39.4 Acenaftene mg/Kg s.s. 403.0 Fluorene mg/Kg s.s. 361.3 Fenantrene mg/Kg s.s. 1452.4 Antracene mg/Kg s.s. 230.6 Fluorantene mg/Kg s.s. 565.5 Pirene mg/Kg s.s. 335.8 Crisene mg/Kg s.s. 233.6 Benzo(a)antracene mg/Kg s.s. 212.6 Benzo(b+j)fluorantene mg/Kg s.s. 186.5 Benzo(k)fluorantene mg/Kg s.s. 116.2 Benzo(a)pirene mg/Kg s.s. 134.7 Benzo(e)pirene mg/Kg s.s. 117.6 Indeno(1,2,3-cd)pirene mg/Kg s.s. 52.4 Dibenzo(a,h)antracene mg/Kg s.s. 64.5 Benzo(g,h,i)perilene mg/Kg s.s. 78.9 IPA TOTALI mg/Kg s.s. 5779.6 Idrocarburi totali mg/Kg s.s. 13807


8 kg of sediment sample A 8 kg of sediment sample B

A. Collection and preparation of ad hoc sediment samples

SAMPLE A

PAH ≈ 50 ppm α β γ

Mean

conc. st.dev.

Naphthalene 1,900 1,800 1,400 1,700 0,3

Acenaphthylene 0,540 0,430 0,400 0,457 0,1

Acenaphthene 4,700 3,800 3,500 4,000 0,6

Fluorene 8,900 5,600 4,700 6,400 2,2

Fenentrene 14,700 13,100 12,300 13,367 1,2

Anthracene 1,750 1,580 1,670 1,667 0,1

Fluorantrene 8,700 8,200 7,200 8,033 0,8

Pyrene 5,400 4,800 4,200 4,800 0,6

Benzo (a) anthracene 1,730 1,660 1,820 1,737 0,1

Chrysene 1,490 1,390 1,620 1,500 0,1

Benzo (b) fluoranthene 1,100 1,030 1,170 1,100 0,1

Benzo (k) fluoranthene 0,480 0,570 0,510 0,520 0,0

Benzo (j) fluoranthene 0,540 0,440 0,600 0,527 0,1

Benzo (e) pyrene 0,700 0,670 0,760 0,710 0,0

Benzo (a) pyrene 0,940 0,910 1,030 0,960 0,1

Perylene 0,272 0,263 0,300 0,278 0,0

Indeno (1,2,3-cd) Pyrene 0,490 0,460 0,550 0,500 0,0

Dibenzo (a, h) anthracene 0,161 0,152 0,181 0,165 0,0

Benzo (g, h, i) perylene 0,470 0,450 0,540 0,487 0,0

Dibenzo (a, i) pyrene 0,049 0,045 0,053 0,049 0,0

Dibenzo (a, e) pyrene 0,047 0,046 0,056 0,050 0,0

Dibenzo (a, l) pyrene 0,076 0,071 0,092 0,080 0,0

Dibenzo (a, h) pyrene 0,012 0,013 0,013 0,013 0,0

Total PAHs 55,0 48,0 45,0 49,3 5,1

Total hydrocarbons 53,0 48,2 62,0 54,4 7,0

mg/kg d.w . mg/kg d.w .

SAMPLE B

PAH ≈ 75 ppm α β γ

Mean

conc. st.dev.

Naphthalene 2,700 2,600 2,900 2,733 0,2

Acenaphthylene 0,710 0,650 0,570 0,643 0,1

Acenaphthene 6,500 5,400 5,700 5,867 0,6

Fluorene 8,700 7,200 7,000 7,633 0,9

Fenentrene 22,800 19,800 20,500 21,033 1,6

Anthracene 2,900 2,800 2,510 2,737 0,2

Fluorantrene 15,000 11,800 10,500 12,433 2,3

Pyrene 8,900 6,900 6,100 7,300 1,4

Benzo (a) anthracene 3,000 2,800 2,400 2,733 0,3

Chrysene 2,640 2,570 2,100 2,437 0,3

Benzo (b) fluoranthene 1,740 1,770 1,550 1,687 0,1

Benzo (k) fluoranthene 0,960 0,840 0,730 0,843 0,1

Benzo (j) fluoranthene 0,760 0,780 0,630 0,723 0,1

Benzo (e) pyrene 1,140 1,110 0,970 1,073 0,1

Benzo (a) pyrene 1,560 1,550 1,290 1,467 0,2

Perylene 0,460 0,460 0,380 0,433 0,0

Indeno (1,2,3-cd) Pyrene 0,820 0,810 0,690 0,773 0,1

Dibenzo (a, h) anthracene 0,280 0,264 0,225 0,256 0,0

Benzo (g, h, i) perylene 0,790 0,790 0,700 0,760 0,1

Dibenzo (a, i) pyrene 0,073 0,081 0,080 0,078 0,0

Dibenzo (a, e) pyrene 0,079 0,079 0,081 0,080 0,0

Dibenzo (a, l) pyrene 0,132 0,131 0,131 0,131 0,0

Dibenzo (a, h) pyrene 0,021 0,023 0,024 0,023 0,0

Total PAHs 83,0 71,0 68,0 74,0 7,9

Total hydrocarbons 122,0 130,0 141,0 131,0 9,5

mg/kg d.w. mg/kg d.w .


Sampling points for SFE

Stocks/extracs sampling point

Sediment sampling pointafter SFE

B. Identification of the matrices : SFE


Sampling points for SFE

Stocks/extracs sampling point

Sediment sampling point after SFE

B. Identification of the matrices


C. Protocols realization

Sediment sampling

after SFE


Stocks/extracs sampling

after SFE



Emissions control after SCWO

Sampling points for SCWO

Liquid sample control after SCWO

B. Identification of the matrices : SCWO


SFE results

PAH ≈ 50 ppm Mean conc.

Sample

treated

Extraction

%

Sample

treated

Extraction

%

Sample

treated

Extraction

%

Sample

treated

Extraction

%

mg/kg d.w . mg/kg d.w . mg/kg d.w . mg/kg d.w . mg/kg d.w .

Naphthalene 1,700 0,013 99,2 0,006 99,6 0,051 97,0 0,041 97,6

Acenaphthylene 0,457 0,004 99,1 <0,001 99,9 <0,001 99,9 0,012 97,4

Acenaphthene 4,000 0,003 99,9 0,003 99,9 <0,001 100,0 0,011 99,7

Fluorene 6,400 0,006 99,9 0,012 99,8 <0,001 100,0 0,051 99,2

Fenentrene 13,367 0,018 99,9 0,076 99,4 0,071 99,5 0,253 98,1

Anthracene 1,667 0,005 99,7 0,008 99,5 0,004 99,8 0,027 98,4

Fluorantrene 8,033 0,006 99,9 0,094 98,8 0,156 98,1 0,245 97,0

Pyrene 4,800 0,006 99,9 0,062 98,7 0,092 98,1 0,144 97,0

Benzo (a) anthracene 1,737 <0,001 100,0 0,007 99,6 0,013 99,3 0,024 98,6

Chrysene 1,500 <0,001 100,0 0,012 99,2 0,021 98,6 0,033 97,8

Benzo (b) fluoranthene 1,100 <0,001 100,0 0,009 99,2 0,032 97,1 0,031 97,2

Benzo (k) fluoranthene 0,520 <0,001 99,9 0,004 99,2 0,011 97,9 0,013 97,5

Benzo (j) fluoranthene 0,527 <0,001 99,9 0,004 99,2 0,004 99,2 0,015 97,2

Benzo (e) pyrene 0,710 <0,001 99,9 0,007 99,0 0,019 97,3 0,021 97,0

Benzo (a) pyrene 0,960 <0,001 99,9 0,003 99,7 0,006 99,4 0,012 98,8

Perylene 0,278 <0,001 99,8 0,001 99,6 0,001 99,6 0,003 98,9

Indeno (1,2,3-cd) Pyrene 0,500 <0,001 99,9 0,004 99,2 0,005 99,0 0,008 98,4

Dibenzo (a, h) anthracene 0,165 <0,001 99,7 0,001 99,4 <0,001 99,7 0,003 98,2

Benzo (g, h, i) perylene 0,487 <0,001 99,9 0,005 99,0 0,010 97,9 0,010 97,9

Dibenzo (a, i) pyrene 0,049 <0,001 99,0 <0,001 99,0 <0,001 99,0 <0,001 99,0

Dibenzo (a, e) pyrene 0,050 <0,001 99,0 <0,001 99,0 <0,001 99,0 0,002 96,0

Dibenzo (a, l) pyrene 0,080 <0,001 99,4 <0,001 99,4 <0,001 99,4 0,002 97,5

Dibenzo (a, h) pyrene 0,013 <0,001 96,1 <0,001 96,1 <0,001 96,1 <0,001 96,1

Total PAHs 49,3 0,061 99,9 0,320 99,4 0,490 99,0 0,960 98,1

Total hydrocarbons 54,4 8,900 83,6 <5 95,4 5,000 90,8 <5 100,0

1^ Test 2^ Test 3^ Test 4^ Test

90 min. 90 min. 60 min. 60 min.


90 min. 90 min. 60 min. 60 min.

SFE results

PAH ≈ 75 ppm Mean conc.

Sample

treated

Extraction

%

Sample

treated

Extraction

%

Sample

treated

Extraction

%

Sample

treated

Extraction

%

mg/kg d.w. mg/kg d.w . mg/kg d.w. mg/kg d.w . mg/kg d.w.

Naphthalene 2,733 0,013 99,524 0,068 97,5 0,036 98,7 0,041 98,5

Acenaphthylene 0,643 0,005 99,223 0,010 98,4 0,003 99,5 0,011 98,3

Acenaphthene 5,867 0,009 99,847 0,023 99,6 <0,001 100,0 0,022 99,6

Fluorene 7,633 0,054 99,293 0,087 98,9 <0,001 100,0 0,098 98,7

Fenentrene 21,033 0,211 98,997 0,170 99,2 0,028 99,9 0,380 98,2

Anthracene 2,737 0,025 99,086 0,016 99,4 0,003 99,9 0,039 98,6

Fluorantrene 12,433 0,174 98,601 0,320 97,4 0,074 99,4 0,300 97,6

Pyrene 7,300 0,107 98,534 0,207 97,2 0,052 99,3 0,186 97,5

Benzo (a) anthracene 2,733 0,025 99,085 0,034 98,8 0,020 99,3 0,032 98,8

Chrysene 2,437 0,032 98,687 0,046 98,1 0,027 98,9 0,045 98,2

Benzo (b) fluoranthene 1,687 0,023 98,636 0,056 96,7 0,046 97,3 0,030 98,2

Benzo (k) fluoranthene 0,843 0,009 98,933 0,024 97,2 0,015 98,2 0,012 98,6

Benzo (j) fluoranthene 0,723 0,010 98,618 0,021 97,1 0,025 96,5 0,017 97,6

Benzo (e) pyrene 1,073 0,017 98,416 0,039 96,4 0,038 96,5 0,023 97,9

Benzo (a) pyrene 1,467 0,009 99,386 0,019 98,7 0,021 98,6 0,014 99,0

Perylene 0,433 0,003 99,308 0,006 98,6 0,008 98,2 0,004 99,1

Indeno (1,2,3-cd) Pyrene 0,773 0,007 99,095 0,015 98,1 0,014 98,2 0,011 98,6

Dibenzo (a, h) anthracene 0,256 0,002 99,220 0,004 98,4 0,004 98,4 0,004 98,4

Benzo (g, h, i) perylene 0,760 0,008 98,947 0,019 97,5 0,021 97,2 0,014 98,2

Dibenzo (a, i) pyrene 0,078 <0,001 99,359 <0,001 99,4 <0,001 99,4 <0,001 99,4

Dibenzo (a, e) pyrene 0,080 <0,001 99,372 0,003 96,2 0,001 98,7 0,002 97,5

Dibenzo (a, l) pyrene 0,131 <0,001 99,619 0,002 98,5 0,001 99,2 0,003 97,7

Dibenzo (a, h) pyrene 0,023 <0,001 97,794 <0,001 97,8 <0,001 97,8 <0,001 97,8

Total PAHs 74,0 0,740 99,000 1,190 98,4 0,440 99,4 1,290 98,3

Total hydrocarbons 131,0 <5 100,000 6,700 94,9 8,700 93,4 16,100 87,7

1^ Test 2^ Test 3^ Test 4^ Test


SFE results

Σ PAH on the extracts from sample at 50 ppm

Σ PAH on the extracts from sample at 75 ppm


SFE results

90%

SFE results


C+

C

B

Class A22 KWh27 KWh

SFE results


B

Class A

22 KWh27 KWh

Capacity of SFE

pilot plant = 5 kg/h

pH 6,45 5,98 6,00 4,58 2,59

Mineral oil mg/L 68400 <0,1 <0,1 <0,1 5

Conductivity µS/cm 18,3 63,8 29,5 343

TDS mg/L <10 <10 <10 80

N nitrogen mg/L <0,1 <0,1 0,68 20

Chlorides mg/L 0,79 0,728 0,62 1200

Sulphates mg/L 11,1 0,75 21,6 1000

Cu mg/L <0,01 <0,01 <0,01 0,4

Zn mg/L 0,323 <0,05 0,448 0,5

Contaminated

Extract

Blank sample -

Liquid before

flame ignition

Emission

limit

D.Lgs

152/2006 (discharge

into

surface

water)

1st TEST Liquid output

during the

oxidation with

isopropyl

alcohol (7,5%)

Liquid output

during the

oxidation with

extractDM water


SCWO results

Extract treated in 50’:

14,35 Kg (~7% of organic contaminants)

99,99 %

pH 6,45 6,14 5,65 3,71 2,21

Mineral oil mg/L 66700 <0,1 <0,1 7,5 5

Conductivity µS/cm 18,3 52,4 50,3 878

TDS mg/L <10 <10 <10 80

N nitrogen mg/L 0,139 <0,1 0,87 20

Chlorides mg/L 1,36 0,371 0,666 1200

Sulphates mg/L 5,26 5,15 93 1000

Cu mg/L <0,01 <0,01 0,0136 0,4

Zn mg/L 2,74 0,43 0,394 0,5

DM water

Contaminated

Extract

Blank sample -

Liquid before

flame ignition

Emission

limit

D.Lgs

152/2006 (discharge

into

surface

water)

Liquid output

during the

oxidation with

isopropyl

alcohol (7,5%)

Liquid output

during the

oxidation with

extract

2nd TEST


SCWO results

99,99 %

Extract treated in 53’:

17,1 Kg (~7% of organic contaminants)

Capacity of SCWO

pilot plant = 20 kg/h

vapour water % <1 <1

TVOC mg/Nmc 8,4 9,3

O2 % v/v 9 4,7

CO2 % v/v 8,77 11,77

CO mg/Nmc 156 14,2 100

NOx mg/Nmc <0,1 <0,1 200

SO2 mg/Nmc 4,2 1,5 200

single PAH congeners ng/Nmc <2

Σ PAH - upper bound ng/Nmc 25 100.000 10.000

Σ PCDD+PCDF - upper bound ng/Nmc (I-TEQ) 0,003 10.000 0,1

Σ PCB - dioxin upper bound ng/Nmc 2,4 500.000

Air emission

during the

oxidation with

isopropyl

alcohol (7,5%)

Air emission

during the

oxidation with

contaminated

extract

2nd TEST

Emission

limit Dlgs

133/2005 (combustion

plant w ith

w aste

incinerator)

Emission

limit

D.Lgs

152/2006


SCWO results


Conclusions

• EXPECTED RESULTS:

� extraction efficiency should be higher than 90% (SFE) and

over 90 % of efficiency in oxidation (SCWO) of target

organic compounds;

� improvement (by 30’-60’) of kinetic rates of

extraction/oxidation of target organic compounds;

� end-products generated should be easily managed and

discharged without further expensive or complex treatment;

� possibility to realize compact equipment, easy to transport

and to install in the intervention sites;

� practical guidelines on optimal use of prototype

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