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SBSE & “in liner” derivatization, for the analysis of...
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)20/02/2013 Veolia Environnement Recherche & Innovation
SBSE & “in liner” derivatization, for the analysis of polar substances in petroleum matrices
Christophe Tondelier
Introduction : SBSE at Veolia
Analytical support for Veolia R&D :
• Method developments
Disinfection By-Products / Taste & Odor in drinking water
French regulation (RSDE, DCE…) - COFRAC
• Treatment processes evaluation
Waste water treatments (municipal, industrial, Oil & Gas…)
Drinking water production
• Passive sampling tools
ARISTOT / PLATON
POCIS
• Characterizations (technical assistances)
Targeted (contaminants database) & untargeted screening
Rivers / Waste / Sea waters / Soil
LC-HRMS / GC-MS / GCxGC-MS
2/20/2013 Veolia Environnement Recherche & Innovation 2GCxGC-TOF(MS) chromatogram
LECO – Pegasus IV
Water taste & Odor
Refinery waste water
ARISTOT sampler
)20/02/2013 Veolia Environnement Recherche & Innovation
SBSE & “in liner” derivatization, for the analysis of polar substances in petroleum matrices
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Outline
1. Context1. Spent caustics in refinery plants
2. Naphthenic acids
2. Analytical development1. Naphthenic acids characterization
2. SBSE & spent caustics
3. Analytical configuration
4. In liner derivatization - theory
3. Applications1. Spent caustics analysis
2. A Naphthenic Acids Index
4. Conclusion / perspectives
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Outline
1. Context1. Spent caustics in refinery plants
2. Naphthenic acids
2. Analytical development1. Naphthenic acids characterization
2. SBSE & spent caustics
3. Analytical configuration
4. In liner derivatization - theory
3. Applications1. Spent caustics analysis
2. A Naphthenic Acids Index
4. Conclusion / perspectives
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Context – Spent caustics in refinery plants
Spent caustics = Petrochemical wastewaters
• Sulfidic SC � hydrocarbon wash for H2S removal
Loaded in sulfurous compounds
• Phenolic SC � cracked gasoline treatment
Recycled � small volume
Highly loaded in phenols and naphthenic acids (>80% TOC)
pH # 14 - TOC ~ 100 g/L
���� High toxicity
Removal pathways
• Biological treatment non available (toxicity)
• Incineration in treatment plants for hazardous waste
High costs & environmental impact
• Veolia R&D studies for alternative treatments
Analytical methods for rapid treatments evaluation
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Naphthenic acids
NA structures where R is an alkyl chain, Z describes the hydrogen deficiency, and m is the
number of CH2 units.
Major contributors to the toxicity of refinery wastewaters [1]
Complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids [2]
[1] Fedorak et al. Chemosphere 50 (2003) 1265–1274
[2] Fedorak et al. Chemosphere 60 (2005) 585–600
plenty of molecules
/ formula
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Outline
1. Context1. Spent caustics in refinery plants
2. Naphthenic acids
2. Analytical development1. Naphthenic acids characterization
2. SBSE & spent caustics
3. Analytical configuration
4. In liner derivatization - theory
3. Applications1. Spent caustics analysis
2. A Naphthenic Acids Index
4. Conclusion / perspectives
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Naphthenic acids characterization
Literature :
GC (or LC) separation – FID, MS… (Fedorak et al.)
Extraction with CH2Cl2 at pH 2
Silylation derivatization
Commercial standard mixture
• Mixture of Napht. Acids (NA) containing pentacarbonated cycles (1, 2 & 3)
Preparation of standard solution in dichloromethane (100 ppm)
Derivatization : 1mL solution + 50 µL BSTFA � 30 min @ 80°C
• GC/MS - 1/50 split injection
Groups of unknown NA
MS : Intense ions, Ø Mol. ions
Low sensitivity (injector degradation ?)
• COC injection + Negative CI (CH4)
Identification of NA groups
Cx H2x+1
Cy H2y
COOSi(CH3)3
Cx H2x+1
Cy H2y
COOSi(CH3)3
6.00 8.00 10.00 12.00 14.00 16.00 18.00
2000
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10000
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Time (min)
Abundance
6.00 8.00 10.00 12.00 14.00 16.00 18.006.00 8.00 10.00 12.00 14.00 16.00 18.00
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Naphthenic acids characterization
+ 14
CH2
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Naphthenic acids characterization
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Abundance
m/z = 215 � C12H22O2
m/z = 229 � C13H24O2
m/z = 243 � C14H26O2
m/z = 257 � C15H28O2
m/z = 271 � C16H30O2
m/z = 285 � C17H32O2
6 main mono-cyclic NA – Reconstituted Ion Chromatogram
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Naphthenic acids characterization
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Time (min)
Abundance
m/z = 241 � C14H24O2
m/z = 255 � C15H26O2
m/z = 269 � C16H28O2
m/z = 283 � C17H30O2
m/z = 297 � C18H32O2
m/z = 311 � C19H34O2
6 main di-cyclic NA – Reconstituted Ion Chromatogram
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SBSE & spent caustics ?
Spent caustics high TOC : Dilution required � low ppm level
SBSE suitability for NA ?
• Example : a monocyclic NA
C12H22O2 � 198 g/mol
Log ko/w = 4.74
SBSE recoveries for 100 mL water extraction
pKa ~ 5 � Extraction in acid condition (3 drops of 37% HCl)
• SBSE (at pH 2) is suitable for NA extraction
For GC analysis :
• Carboxylic acids function � DERIVATIZATION required
Idea : Post-extraction derivatization step named “in liner derivatization”
CH3
OH
O
Twister recovery calculator :
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Analytical configuration
MPS 2Gerstelized System :
• Agilent 6890 GC
• Agilent 5973 MS
• MultiPurpose Sampler
• TDU
Twister desorption
• Gripper
Automated Tube Exchange
TDU Liquid injections
• CIS 4 PTV inlet
Cryo-cooling
• Restek Rxi-5Sil MS Column
30m x 0.25mm x 0.25µm
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In Liner derivatization - theory
GerstelTDU
Cooled Zone(-70°C)
Helium
Split ventCIS liner
Liner option(PDMS foam)
AnalytesGerstel
TDU
Helium
Analytical column
Twister
TDU liner
Thermal Desorption
Cryo-focalisation
Constant cryo-cooling
GerstelCIS 4
STEP 1STEP 2
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In Liner derivatization - theory
GerstelTDU
Cooled Zone(-70°C)
Helium
Split vent
Liner option(PDMS foam)
GerstelTDU
Helium
Analytical column
Cryo-focalisation
Constant cryo-cooling
STEP 3
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In Liner derivatization - theory
GerstelTDU
Cooled Zone(-70°C)
Helium
Split vent
Liner option(PDMS foam)
GerstelTDU
Helium
Analytical column
1 µL BSTFA
ATEX
BSTFA injection
Cryo-focalisation
Constant cryo-cooling
STEP 3
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GerstelTDU
Cooled Zone(-70°C)
Helium
Split vent
Liner option(PDMS foam)
GerstelTDU
Helium
Analytical column
Cryo-focalisation
Constant cryo-cooling
In Liner derivatization - theory
TDU desorption
BSTFA volatilization
STEP 4
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GerstelTDU
Heated Zone(300°C)
Helium
Split vent
GerstelTDU
Helium
Analytical column
CIS desorption (slow)
� BSTFA vaporization
� Analytes derivatization
In Liner derivatization - theory
STEP 5
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In Liner derivatization - theory
GerstelTDU
Heated Zone(300°C)
Helium
Split vent
GerstelTDU
Helium
Analytical column
TMS derivatives
vaporization
& separation
STEP 6
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Outline
1. Context1. Spent caustics in refinery plants
2. Naphthenic acids
2. Analytical development1. Naphthenic acids characterization
2. SBSE & spent caustics
3. Analytical configuration
4. In liner derivatization - theory
3. Applications1. Spent caustics analysis
2. A Naphthenic Acids Index
4. Conclusion / perspectives
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Spent caustic analysis
GC/MS Total Ion chromatograms
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1.2e+07
1.6e+07
2e+07
2.4e+07
2.8e+07
3.2e+07
3.6e+07
4e+07
4.4e+07
4.8e+07
5.2e+07
Time (min)
Abundance
Spent caustic sample
NA mixture 500 ppb
D3
D4
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Time-->
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GC/MS Reconstituted Ion chromatogramsNaphthenic acids distribution
Sample 1
NA mixture 500 ppb
Spent caustic analysis
Ion 215.00 � C12H22O2
Ion 229.00 � C13H24O2
Ion 243.00 � C14H26O2
Ion 257.00 � C15H28O2
Ion 271.00 � C16H30O2
Ion 285.00 � C17H32O2
Hexacarbonated cycles
Pentacarbonated cycles
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Spent caustic analysis
GC/MS Reconstituted Ion chromatogramsPhenolic compounds distribution
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Abundance
Si
O m/z = 165 � C1 - Phenols
Si
O
m/z = 179 � C2 - Phenols
m/z = 193 � C3 - Phenols
m/z = 207 � C4 - Phenols
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A Naphthenic Acids « INDEX »
Calibration in SIM mode
• Target ion m/z = 117 : O
O CH3
CH3
CH3
Si
+
m/z = 117
TMS-carboxylic acids
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2e+07
2.4e+07
2.8e+07
3.2e+07
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5.2e+07
Time (min)
Abundance
Sample TIC
Sample RIC : m/z = 117
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A Naphthenic Acids « INDEX »
• RIC (m/z = 117) integration
Global quantification of all TMS naphthenic acids
Internal Standard : 2,3,5-trichlorophenol (TMS derivative)
• Calibration
ResultsTreatments evaluation
Total Area
y = 0,3296x + 2,9868R2 = 0,9817
0,0
20,0
40,0
60,0
80,0
100,0
0 50 100 150 200 250 300
NA conc. (ppb)
To
tal N
A /
IS a
rea
Treatment
time0 x hours y hours
NA conc. 43.6 g/L 21.9 g/L 7.0 g/L
Elimination - 50% 84%
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Conclusion & perspectives
SBSE - In liner derivatization - TD-GC/MS
• ☺ Simple, rapid & solventless extraction protocol
• ☺ Automated in line derivatization GC method
• � High amount BSTFA injection
BSTFA venting before analytes desorption
For spent caustic analysis
• A Naphthenic Acids index
• Treatments evaluation
Perspectives
• ☺ SBSE for polar compounds analysis
• Other applications :
Halogenated phenols in drinking water (medicinal taste)
Endocrine disruptors (hormones) in municipal waste waters
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