l\ly children, Thomas, Céline and Natalie, motivated me with their expectation that 1would finally he smart, and ...... Koppers Site, NC. EPA RREL. Dechlorination.
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LABORATORYSTUDYOFSOLVENT EXTRACTION OF POLYCHLORINATED BIPHENYLS IN SOIL
by ~(elissa ~IcShea
Valentin
A thesis submittcd to the Faculty of Graduatc Studies and Research in partial fulfillment of the requirements for the degree of
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~(aster of Science
Agricuitural and Biosystems Engineering ~lcGill
University, rvlonttéal
December 2000
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1+1
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McGill University Absttact LABORATORY STUDY OF SOLVENT EXTRACTION OF POLYCHLORINATED BIPHENYLS IN SOIL
By Metissa McShea Valentin
Polychlorinated hiphenyls (PCBs) are
toxic~
stable organic contarninants that are
present in air, water, soil, plants and animais all around the wodd. The market for PCB treatment technologies is estimated to be $300 to $600 million (Canadian
•
dollars) for the year 2000, and will expand in future yeats. Existing treatment technologies to remove peBs &om soil are undemtilized because they are more expensive than Iandfilling and incineration. 1bis thesis presents a laboratory study of an innovative PCB remediation process that will exttact PCBs &om soil in-ntll
for subsequent destruction above ground. 1bis remedy will remove peBs
from surficial soil without the neecl for excavation. Two laboratory studies were conducted on field-contaminated soil. The first experiment evaluated the effeetiveness of hexane, methyl isobutyl ketone, and ethyl acetate in removing peBs from soil. Ethyl acetate and ~fiBK were equally effective, removing 99% and 98% ofPCBs from dry sail in 4 days, respectively. In the second experiment, soil was exposed to ethyl acetate for varying amounts of rime, and some of the samples were treated a second rime with &esh solvent. PCB removal increased as treatment rime was increased from 10 minutes to 50, 250, and 1250 minutes, but the rate of PCB removal decreased as treatment rime încreased. The second 10minute extraction removed an additional 1-10% of the remaining PCBs.
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Université de McGill Résumé ETUDE DE L\BORATOIRE DE L'EXTRACTION DE PCBS À L'AIDE DE SOLVENTS Par Melissa ~fcShea Valentin
Les PCBs sont des produits chimiques. toxiques et stables qui sont présents dans l'air, l'eau, les plantes et les animau.'C à travers le monde. Le marché pour les technologies de traitements des PCBs est estimé entre 300 millions et 600 millions de dollars Canadiens pour l'an 2000, et s'étendra dans les années à venir. Les technologies existentes pour retirer les PCBs de la tene sont sous-utilisées parce qu'eUes sont plus chères que l'incinération et la mise cn dépotoirs. Cette
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thèse cst une étude de laboratoire d'une technologie innovatrice pour la remédiation des PCBs in-silll, qui pennetra de retirer les PCBS de la terre pour ensuite les détruire hors-terre. Cette solution retire les peBs des terres contaminées sans avoir à les transporter ou à creuser. Deme érodes de laboratoire furent conduites sur des specimens de sol contaminé. La première expérience évalua l'efficacité de l'hexane, du methyl isobutyl ketone de l'ethyl acetate pour retirer les PCBs du soL L'ethyl acetate et le
~flBK), et
~nBK
furent
aussi efficaces l'un que l'autre et retirèrent 99 % et 98% des PCBs en quatre jours respectivement. Dans la deuxième expérience, le sol fut exposé à l'ethyl acetate pendant diverses périodes de temps, et certains échantillons furent traités une deu.~ème fois
avec du solvent propre. Plus la dureé de l'expérience fut rallongée
de 10 minutes à 50, 250 et 1250 minutes, plus la quantité de peBs retirée du sol augmenta, mais le taux de PCBs retirés diminua. Le deuxième nettoyage de dix minutes retira un surplus de t % al 0% de plus de PCBs.
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lU
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TABLE OF CONTENTS
1
2
INTRODUcrION
1-1
1.1
PROBLEM STATEMENT
1-1
1.2
OBJECTIVES
1-2
1.3
THESIS ORGANlZATI ON
1-3
1.4
SCOPE OF WORK
1-3
UTERATURE REVlEW
2-1
IN11tODUcrION 2. t.l PCB Structure and Nomenclature 2.1.2 Toxicity 2. t.3 PCB Sources 2.1.4 Overview ofPCBs in the Environment 2.2 PCB FATE AND TRANSPORT IN THE ABIOTIC ENVIRONMENT 2.2.1 Solubility 2.2.1. t Aqueous Solubility Solubility in non-polar organic solvents 2.2. t .2 2.2.1.3 Cosolvents and Surfactants 2.2.1.4 Solubility in Supercritical Fluids 2.2.2 PCBs in Non-Aqueous Phase üquids 2.2.2.1 PrJtition Coefficient 2.2.2.2 Wettahility 2.2.2.3 Interfacial Tension 2.2.2.4 Capillary Pressure 2.2.2.5 Extraction 2.2.3 Evaporation Evaporation &om Pure Compound 2.2.3.1 2.2.3.2 Evaporation &om Soil.. 2.2.3.3 Evaporation &om water 2.2.4 Sorption 2.2.4.1 Adsorption Surnmary of Abiotic Processes 2.2.5 2.3 FATE AND TRANSPORT IN LIVING ORGANISl\:IS
2.1
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1V
2-1 2-1
2-3 2-4 2-5 2-7 2-7
2-8 2-8 2-8 2-10 2- t t 2.. t t 2- t 3 2- t 3 2-14
2- t 4 2-16 2-17 2- t 9 2- t 9 2-20
2-20 2-22 2-22
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2.4 REGULATIONS AND SITE REMEDIATIaN PCB Regtllations 2.4.1 The Remediation Marketplace 2.4.2 2.4.3 Site Remediation Overview 2.5 PCB 1"REAThlENT 2.5.1 Treatment of PCB-Contaminated Soil 2.5.1.1 Separation Processes 2.5.1.1.1 Solvent Extraction 2.5.1.1.2 Thennal Desorption 2.5.1.1.3 Soil Washing Destructive Processes 2.5. t.2 2.5.1.3 Immobilization Processes 2.5.1.3.1 I..andfill 2.5.1.3.2 Solidification 2.5.1.3.3 Capping 2.5.1.4 Treatrnent Trains SAtvlPLING AND ANALySIS 2.6 2.6.1 Sample Collection and Storage 2.6.2 Preparation of Soü and Sediment Samples 2.6.2.1 Surrogates 2.6.2.2 Extraction methods 2.6.2.3 Cleanup 2.6.3 PCB Detennination 2.6.3.1 Gas Chromatography 2.6.3.2 Detectors GCjEThIS and MS/MS (ion trap) 2.6.3.3 STATISTICALrvIETHODS 2.7 2.7.1 Transfonnations Sdecting an appropriate transfonnation 2.7. t.l Converring back to the original scale 2.7.1.2 2.7.2 Analysis of variance 2.7.3 Estimating standard deviation from replicate measurements 2.7.4 Confidence limits on a mean 2.7.5 Instrument and method limits of detection 2.7.5.1 Censored data 2.7.6 Confidence intervals on the calibration curve 2.7.7 Discrimination Intervals : 2.7.8 Summary ofStatisticai Tools StTh~I.ARY OF LlTERATIJRE REVIEW 2.8
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3
METHOD DE'VELOPMENT
, v
2-24 2-24 2-25 2-26 2-27 2-30 2-31 2-32 2-34 2-35 2-36 2-37 2-37 2-37 2-38 2-38 2-38 2-39 2-39 2-41 2~-t2
2-43 2-44 2-44 2-46 2-47 2-48 2-50 2-50 2-51 2-53 2-54 2-54 2-55 2-56 2-57 2-60 2-63 2-64
3-1
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3.1
INl"RODUCTION
3-1
3.2 E.,."XPERThfENTAL SEruP 3.2.1 Soil 3.2.2 Treatlllent Overview 3.2.3 Experiment 1 3.2.4 Experiment 2 3.3 PCB DETE~NATION 3.3. t 3.3.2 3.3.3 3.3.4
3-1 3- t 3..3 3-3 3-7 3-9
PCB Congener Sdection GC/~IS Method and Data Handling Calibration ~Iodified Shéffe Discrimination Intervals
3.4 SMfPLE PREPARATION ~licrowave Assisted Extraction 3.4.1 3.4.2 Solvent Evaporation and Exchange 3.4.3 Florisil Cleanup 3.4.4 Surrogate Recovery 3.4.5 QA/QC and Safety
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3-28 3-28 3-28 3-29 3-29 3-30
3.5
STATISTICAL TREATMENTOF EXPERIMENTAL DATA
3..31
3.6
SU~RY
3-31
4 RESULTS AND DISCUSSION: EXPERIMENT 1, SOLVENT SELEcrION
4-1
4.1
O\'ERVIEW
4-1
4.2
EXJ>ERThIENTAL RESUL1"S
4-1
4.3
SURROGATE RECOVERY
4-2
4.4
DISCRThIINATION INTERVALS
4-3
4.5
ANALYSIS OF VARIANCE
4-4
4.6
CONGENER SPECIFIC TREATMENT RESULTS
4-7
4.7
S~fARY
4-12
5 RESULTS AND DISCUSSION: EXPERIMENT 2, ETHYL ACETATE TREATMENT
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3-9 3-14 3-16 3-21
5-1
5.1
OVERVIEW
5..1
5.2
TREATMENTRESULTS: TOTAL PCB
S-l
5.3
SU"RROGAm RECOVERY
5-9
5.4
ANALYSIS OF VARIANCE
5-12
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5.5
l\tlODIFIED SHÉFFE DISCRIMINATION INlERVALS
CONGENER SPECIFIC TREAThŒNT RESULTS 5.6 5.6.1 Summary of Congener-Specific Analysis of Contrast 5.7 SillvUwlARY OF E.XPERThIENT 2
6
SUltfMARY AND CONCLUSIONS
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RECOMMENDATIONS
6-1 6-1 6-1 6-2 6-3 6-3 6-4 6-5 6-5 6-6
7-5 DETE~(INATION
7.1
ERROR AND UNCERTAlNïY IN PCB
7.2
~TETIING
7-5
7.3
MINERi~
7.4
COLlJ1,fN STUDIES USING ETHYLACETATE
7-5
7.5
BENCH SCALE STIJDIES USING MmK
7-6
7.6
EX1McnON RATE
7-6
7.7
l\tfODEI..ING
7-6
7.8
VMY SOIL lYPE AND PCB CONCENTRATIONS
7-6
7.9
HEAL11-1 AND SAFElY
7-6
7-5 OIL
7-5
7-6
7.10 FLORISIL
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5-14 5-40 5-43
6..1
6.1 SUl\tIl\lARy 6.1.1 Overall Project Goals 6.1.2 rvlethod Development 6.1.2.1 Congener selection 6.1.2.2 Sample Preparation 6.1.2.3 GC/l\tIS and GC/~fS/~fS method development 6.1.2.4 Sratistical rvfethods 6.1.3 Experiment t: Bench Scale Solvent Sdection 6.1.4 Experimcnt 2: Extraction Optimi2ation 6.2 CONCLUSIONS
7
5-12
8
REFERENCES.................•.........................................•......................... 8-1
9
APPENDIXA
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LIST OF TABLES
lV1I11Iber Table 1: Relative Congener Toxicity Table 2: PCBs in the Global Environment Table 3: Aqueous Solubility of PCBs Table 4: Cosolvent Physical Properties Table 5: Octanol/Water Partition Coefficients (17.711 7.441 6.677 6.677 7.592
TEF (e)
1.E-04
5.E-04
1.E-04
1.E-04
1.E-01
MW (a,b)
326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 326.4 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9
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IUPAC
142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 1S8 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188
Present in Aroclor Mixtures (a,e) Number and location of Chlonne on pce 1221 1242 1254 1260 other 2,2',3,4,5,62,2',3,4,5,6'X 2,2',3,4,5',62,2',3,4,6,6'X X 2,2" 3,4',5, S'2, 2', 3, 4', 5, 62,2',3,4',5,6'X X X 2, 2', 3,4',5',62, 2'. 3, 4',6, 6'2, 2', 3, 5, 5', 6X X X 2, 2', 3, 5,6, 6'· 2, 2', 4, 4', 5, 5'_ X X X 2.2',4,4',5',62, 2" 4, 4', 6, 6'X 2, 3, 3',4,4', SX 2, 3, 3',4,4', 5'X 2,3,3',4,4',6X X 2, 3, 3',4, 5, 5'· 2,3,3',4,5,6X 2, 3, 3', 4, 5', 62, 3, 3',4', 5, 5'_ 2, 3, 3'.4', 5,62,3,3',4', S', 62, 3, 3', 5, 5', 62,3,4,4',5,62, 3',4,4', S, 5'· X X X 2, 3', 4, 4', 5, 63, 3', 4,4', S, 5'· X 2, 2', 3, 3', 4, 4', 5X X X 2, 2', 3, 3',4,4',6X X 2,2',3,3',4,5,5"X X 2, 2', 3, 3', 4, 5, 6X X 2,2',3,3',4,5,6'X X X 2,2', 3, 3',4, 5', 6X X 2,2',3,3',4,6,6'X X 2,2',3,3',4',5,6X X 2,2',3,3',5,5',6X X 2, 2', 3, 3', 5,6, 6'2,2',3,4,4',5,5'X X X 2,2',3,4,4',5,6X 2, 2', 3, 4, 4', S, 6'2,2',3,4,4', S", 6X X X 2, 2', 3, 4, 4',6,6'2, 2', 3, 4, 5, 5',6X 2,2',3,4,5,6,6'2,2',3,4',5, S', 6X X X 2, 2', 3,4', 5,6,6"-
AppendixA
Page 4 of5
CAS 41411-61-4 68194-15-0 68194-14-9 74472-40·5 51908-16-8 68194-13-8 74472-42-7 38380-04-0 68194-08-1 52663-63-5 68194-09-2 35065-27-1 60145-22-4 33979-03-2 38380-08-4 69782-90-7 74472-42-7 39635-35-3 41411-62-5 74472-43-8 39635-34-2 74472-44-9 74472-45-0 74472-46-1 41411-63-6 52663-72-6 59291-65-S 32774-16-6 35065-30-6 52663-71-5 52663-74-8 68194-16-1 38411-25-5 40186-70-7 52663-65-7 52663-70-4 52663-67-9 52663-64-6 35065-29-3 74472-47-2 60145-23-5 52663-69-1 74472-48-3 52712-05-7 74472-49-4 52663-68-0 74487-85-7
log Kow TEF (e) (e) 6.517 6.607 6.677 6.257 6.897 6.647 6.737 7.281 6.327 6.647 6.227 7.751 6.767 7.123 7.187 5.E-Q4 7.187 S.E-04 7.027 7.247 6.937 7.087 7.247 6.997 7.027 7.057 6.937 7.277 1.E-05 7.117 7.427 1.E-02 7.277 1.E-04 6.704 7.337 7.027 7.117 7.177 6.767 7.087 7.147 6.737 7.367 1.E-oS 7.117 7.207 7.207 6.857 7.933 6.697 7.177 6.827
MW (a,b) 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 360.9 39S.3 39S.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3 395.3
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IUPAC
Present in Aroclor Mixtures (a,c) Number and Location 1242 1254 1260 other 1221 of Chlorine on PCB X 2,3,3',4,4', S, S'X X 2, 3, 3', 4, 4', S, 6X 2,3,3',4,4',5',62,3,3',4, S, S', 6X 2, 3, 3',4', S, S', 6X 2,2',3,3',4,4', S, S'X 2, 2', 3, 3', 4, 4', S, 6X 2,2',3,3',4,4', S, 6'X 2,2',3,3" 4,4',6,6'2, 2', 3, 3', 4, S, S', 6X X ~X,3,~,~~5,5X 2,Z,3,~,4,5,~6~ 2,X,3,~,4,S,6,6~ X X 2,2',3,3, S, S', 6,6'2,2',3,4,4', S, 5', 6X 2,2',3,4,4',5,6,6'X 2,3,3',4,4',5,5',6X 2,2',3,3',4,4', S, S', 62,Z,3,~.4,~.~6,6~ X 2.Z.3,~,4.5,S,~6~ X X 2,Z,3.~,4.~,~S,~6~
189 190 191 192 193 194 19S 196 197 198 199 200 201 202 203 204 205 206 207 208 209 NOTES Compiled by Erikson, 1997 a Reported by Schwartzenbach et.al. 1992 b c Compiled by Eisler and Be lisle, 1996
AppendixA
Page 50fS
CAS 39635-31-9 41411-64-7 74472-S0-7 74472-S1-8 69782-91-8 35694-08-7 S2663-78-2 42740-S0-1 33091-17-7 68194-17-2 S2663-7S-9 52663-73-7 40186-71-8 2136-994 S2663-76-0 74472-S2-9 74472-S3-0 40186-72-9 S2663-79-3 52663-77-1 20S1-24-3
log Kow TEF M"N (c) (c) (a,b) 7.717 1.E-04 395.3 7.467 395.3 7.SS7 395.3 7.527 395.3 7.S27 39S.3 8.683 429.8 7.567 429.8 7.6S7 429.8 7.307 429.8 7.627 429.8 7.207 429.8 7.277 429.8 76.27 429~8 8.432 429.8 7.657 429.8 7.307 429.8 8.007 429.8 9.143 464.2 7.747 464.2 8.164 464.2 9.603 498.7
