pcb 101 spokane river forum may 25, 2011 dave hope, pacific rim laboratories inc
TRANSCRIPT
PCB 101PCB 101Spokane River ForumSpokane River Forum
May 25, 2011May 25, 2011
Dave Hope, Dave Hope,
Pacific Rim Laboratories IncPacific Rim Laboratories Inc
OutlineOutline
• Pacific Rim Laboratories Inc.Pacific Rim Laboratories Inc.
• PCB – what is it and why are we still PCB – what is it and why are we still interested in itinterested in it
• ToxicityToxicity
• How do we analyze it – Analytical MethodsHow do we analyze it – Analytical Methods
• What does Not Detected mean?What does Not Detected mean?
• Limitations to PCB analysisLimitations to PCB analysis
• Closing thoughtsClosing thoughts
Who Am I?Who Am I?
• Analytical ChemistAnalytical Chemist– PChem – ACPBCPChem – ACPBC– President, Canadian Council of Independent President, Canadian Council of Independent
LaboratoriesLaboratories– Owner, Lab Director Pacific Rim LaboratoriesOwner, Lab Director Pacific Rim Laboratories
• I am notI am not– ToxicologistToxicologist– ConsultantConsultant
Pacific Rim Laboratories Inc.Pacific Rim Laboratories Inc.
• Small ultra-trace organic laboratory Small ultra-trace organic laboratory specializing in the analysis of Persistent specializing in the analysis of Persistent Organic Pollutants by High Resolution Organic Pollutants by High Resolution Mass SpectrometryMass Spectrometry
• Located in Surrey, BC (suburb of Located in Surrey, BC (suburb of Vancouver)Vancouver)
• Accredited by WDOE, NELAC and SCC for Accredited by WDOE, NELAC and SCC for the analysis of PCB, PCDD/F and PBDE.the analysis of PCB, PCDD/F and PBDE.
• Work in the ppt, ppq and sub-ppq rangeWork in the ppt, ppq and sub-ppq range
How small is small?How small is small?
• $1 bill is approx. 100 cm$1 bill is approx. 100 cm22
• Area of Canada is 10M kmArea of Canada is 10M km22
• Finding a given dollar bill anywhere Finding a given dollar bill anywhere in Canada is 1 ppq (10in Canada is 1 ppq (10-15-15))
Polychlorinated Biphenyls Polychlorinated Biphenyls (PCB)(PCB)• Manufactured until early 1970’s (1980’s in
Eastern Europe)– Total production 1.3-1.5M Tonnes– Aroclor 1016, 1242, 1254, 1260– Kanaclor
• Byproduct in the manufacture of other chemicals– Copper sulphate from China contaminated with
PCB126, 169 and 77.
Chemical StructureChemical Structure
• 209 possible 209 possible congeners – mono congeners – mono thru thru decachlorobiphenyldecachlorobiphenyl
• Twelve are considered Twelve are considered dioxin like and have dioxin like and have been assigned Toxic been assigned Toxic Equivalency Factors Equivalency Factors (TEF) (TEF)
• MonoCBMonoCB 3 congeners3 congeners• DiCBDiCB 12 congeners12 congeners• TriCBTriCB 24 congeners24 congeners• TetraCBTetraCB 42 (2) 42 (2)
congenerscongeners• PentaCBPentaCB 46 (5) 46 (5)
congenerscongeners• HexaCBHexaCB 42 (4) 42 (4)
congenerscongeners• HeptaCBHeptaCB 24 (1) 24 (1)
congenerscongeners• OctaCBOctaCB 12 congeners12 congeners• NonaCBNonaCB 3 congeners3 congeners• DecaCBDecaCB 1 congeners1 congeners
PCBs on ECD – Mix of Aroclor PCBs on ECD – Mix of Aroclor 1242, 1254, 12601242, 1254, 1260
Global ProductionGlobal Production
• 48% produced 48% produced in USAin USA
• 50% of 50% of remaining remaining prduction prduction imported to imported to USAUSA
• 97% in 97% in Northern HemiNorthern Hemi
Applications of PCBApplications of PCB
• Closed systemsClosed systems
• Insulation and/or cooling fluid in Insulation and/or cooling fluid in transformers (48%)transformers (48%)
• Dielectric fluid in capacitors (21%)Dielectric fluid in capacitors (21%)
• SwitchesSwitches
• Partially open systemsPartially open systems
• Heat transfer fluidsHeat transfer fluids
• Hydraulic fluid in lifting Hydraulic fluid in lifting equipment, trucks and high equipment, trucks and high pressure pumpspressure pumps
• Vacuum PumpsVacuum Pumps
• Voltage RegulatorsVoltage Regulators
• Liquid Filled Electrical CablesLiquid Filled Electrical Cables
• Liquid Filled Circuit BreakersLiquid Filled Circuit Breakers
• Open systems (21%)Open systems (21%)
• PaintsPaints
• Lubricating fluid in oils and greaseLubricating fluid in oils and grease
• Water-repellent impregnating agent Water-repellent impregnating agent and fire retardant for wood, paper, and fire retardant for wood, paper, fabric and leatherfabric and leather
• Laminating agent in paper Laminating agent in paper productionproduction
• Additive in glues, sealants and Additive in glues, sealants and corrosion protection coatingscorrosion protection coatings
• Carrier for insecticidesCarrier for insecticides
• Polymerisation catalyst support for Polymerisation catalyst support for petrochemicalspetrochemicals
• Immersion oils for microscopyImmersion oils for microscopy
• Pesticide FormulationPesticide Formulation
• Cable coatings/casingsCable coatings/casings
Stockholm ConventionStockholm Convention
• In 2001 the Stockholm convention was adopted, restricting the manufacturing and use of twelve Persistent Organic Pollutants – POPs– PCDD/F, PCB– Pesticides – Aldrin, Dieldrin, Endrin, DDT, Heptachlor,
Hexachlorobenzene, Mirex, Chlordane, Toxaphene
• Ratified in May 2004
• Currently 127 countries have ratified, excluding USA
• August 2010 – 9 additional chemicals included– Hexachlorocyclohexane (α, β, γ (Lindane)), PBDE (commercial
Penta and Octa), hexabromobiphenyl, chlordecone, pentachlorobenzene, PFOS/PFOA
– Endosulphan added last month
PCB ToxicityPCB Toxicity
• World Health Organization (WHO) defines twelve World Health Organization (WHO) defines twelve toxic congenerstoxic congeners– Due to positioning of chlorines, the molecule is unable to Due to positioning of chlorines, the molecule is unable to
rotate and forms structure similar to dioxinrotate and forms structure similar to dioxin
• 2,3,7,8-TCDD considered to have a toxicity of 1, 2,3,7,8-TCDD considered to have a toxicity of 1, all others are relative to TCDDall others are relative to TCDD
• Toxic Equivalency Factors (TEF)Toxic Equivalency Factors (TEF)– PCB126 (0.1), PCB169 (0.03), PCB077 (0.0001), PCB081 PCB126 (0.1), PCB169 (0.03), PCB077 (0.0001), PCB081
(0.0003)(0.0003)– PCB105, 114, 118, 123, 156, 157, 167, 189 (0.00003)PCB105, 114, 118, 123, 156, 157, 167, 189 (0.00003)
• PCB TEQ = PCB TEQ = ∑C∑Cxx x TEF x TEFx x for all PCB congenersfor all PCB congeners
Congener Chlorine Aroclor Composition (Wt %)
Number Substitution Frame et al. (1996) Data
Pattern (IUPAC) A1016 A1242 A1254a A1254g A1260
77 3,3',4,4' 0.31 0.2 0.03
81 3,4,4',5 0.01 0.01
105 2,3,3',4,4' trace 0.47 7.37 2.99 0.22
114 2,3,4,4',5 0.04 0.5 0.18
118 2,3',4,4',5 0.66 13.59 7.35 0.48
123 2,3',4,4',5' 0.03 0.32 0.15
126 3,3',4,4',5 0.02 0.01
156 2,3,3',4,4',5 0.01 1.13 0.82 0.52
157 2,3,3',4,4',5' 0.3 0.19 0.02
167 2,3',4,4',5,5' 0.35 0.27 0.19
169 3,3',4,4',5,5'
189 2,3,3',4,4',5,5' 0.01 0.01 0.1
ppm ppm ppm ppmToxicity
0.70 27 14 0.46
Toxicity of AroclorsToxicity of Aroclors
Regulatory Levels – FoodRegulatory Levels – FoodMax intake – 2 pg TEQ/kg bw/dayMax intake – 2 pg TEQ/kg bw/day
• European Food Regulations European Food Regulations (pg WHO-TEQ/g fat)(pg WHO-TEQ/g fat)
• PCDD/FPCDD/F (&PCB)(&PCB)• Fish (fresh wt):Fish (fresh wt): 4 4 (8) (8) • Pork: Pork: 1 1 (1.5)(1.5)• PoultryPoultry 2 2 (4)(4)• Beef / mutton: Beef / mutton: 33 (4.5)(4.5)• LiverLiver 66 (12) (12) • Milk: Milk: 3 3 (6)(6)• Eggs: Eggs: 3 3 (6)(6)• Vegetable oil: Vegetable oil: 0.75 0.75 (1.5)(1.5)• Mix Animal fat:Mix Animal fat: 22 (3)(3)• Fish oil: Fish oil: 2 2 (10)(10)
• European Feed RegulationsEuropean Feed Regulations• Feed*: Feed*: 0.75 pg WHO-TEQ/g0.75 pg WHO-TEQ/g• Pet foods:Pet foods: 2.25 pg WHO-2.25 pg WHO-
TEQ/gTEQ/g• Animal fat:Animal fat: 2 pg WHO-2 pg WHO-
TEQ/gTEQ/g• Minerals:Minerals: 1 pg WHO-1 pg WHO-
TEQ/gTEQ/g• Fish oil:Fish oil: 6 pg WHO-TEQ/g6 pg WHO-TEQ/g• Fish meal:Fish meal: 1.25 pg WHO-1.25 pg WHO-
TEQ/gTEQ/g• * - based on 12% moisture * - based on 12% moisture
contentcontent
Food levelsFood levels
• Eggs – 2.1-38 ug/kg fatEggs – 2.1-38 ug/kg fat– 0.11 – 2.86 ng TEQ/kg fat0.11 – 2.86 ng TEQ/kg fat
• Meat – 50 – 1960 ng/kg fatMeat – 50 – 1960 ng/kg fat– 0.001 – 0.182 ng TEQ/kg fat0.001 – 0.182 ng TEQ/kg fat
• Fish 0.29 – 87 ug/kgFish 0.29 – 87 ug/kg– 0.1 – 2.4 ng TEQ/kg0.1 – 2.4 ng TEQ/kg
3557
7LP HP LQ
5HO
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QGDQ
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1/(P ]
0 6' ) $
1/(P ]
0 6' ) $
1/(P ]
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1/(P ]
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Fish sample – ClFish sample – Cl44-Cl-Cl77
105118
153138
52
110
74 66
70
60
156128
180 170182/187
3557
7LP HP LQ
5HO
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1/(P ]
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1/(P ]
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1/(P ]
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Fish sample – ClFish sample – Cl77-Cl-Cl1010
180 170
203199
194
206 209
PCB Analysis in BloodPCB Analysis in Blood
2020
tetra-PCBstetra-PCBs
penta-PCBspenta-PCBs hexa-PCBshexa-PCBs
• PCBs in bloodPCBs in blood– 200-800 ug /kg lipid200-800 ug /kg lipid– PCB153>138>180PCB153>138>180
>187>118>170>9>187>118>170>999
Analytical MethodsAnalytical MethodsGood – Better - BestGood – Better - Best
• GC/ECD MethodsGC/ECD Methods– EPA 8081, 8082, 608, 508EPA 8081, 8082, 608, 508
• GC/MS MethodsGC/MS Methods– EPA 8270EPA 8270
• GC/HRMS MethodsGC/HRMS Methods– EPA 1668EPA 1668
AnalytesAnalytesGood – Better - BestGood – Better - Best
• Total PCB – Aroclor equivalentsTotal PCB – Aroclor equivalents
• Homolog TotalsHomolog Totals– 10 levels of chlorination10 levels of chlorination
• Congener specific (209)Congener specific (209)
Sample Extraction & Clean-Sample Extraction & Clean-upup• ExtractionExtraction
– Water – liquid/liquid Water – liquid/liquid extractionextraction
– Soil – soxhletSoil – soxhlet– Tissue – acid digestion Tissue – acid digestion
followed by liquid/liquid followed by liquid/liquid extractionextraction
• Clean-upClean-up– Wash with conc. Sulfuric Wash with conc. Sulfuric
acidacid– Column on acidic silica gelColumn on acidic silica gel– Column on basic aluminaColumn on basic alumina
Quantitation MethodsQuantitation MethodsGood – Better - BestGood – Better - Best
• External standardExternal standard– compare with calibration curvecompare with calibration curve– Requires known final volume and amount injectedRequires known final volume and amount injected
• Internal StandardInternal Standard– Add standard just before analysisAdd standard just before analysis– Relative response factors determined from calibration curveRelative response factors determined from calibration curve– With area of IS peak and RRF, can calculate concentrationWith area of IS peak and RRF, can calculate concentration
• Isotope dilutionIsotope dilution– Stable isotopes added before extraction used to quantify resultsStable isotopes added before extraction used to quantify results– Corrects for loses during work-upCorrects for loses during work-up
EPA 8082EPA 8082
• Can be used to identify Aroclors or congenersCan be used to identify Aroclors or congeners
• 19 congeners – MonoCB – NonaCB19 congeners – MonoCB – NonaCB
• PCB1, 15, 18, 31, 44, 52, 66, 87, 101, 110, 138, PCB1, 15, 18, 31, 44, 52, 66, 87, 101, 110, 138, 141, 151, 153, 170, 180, 183, 187, 206141, 151, 153, 170, 180, 183, 187, 206
• IS Method: One internal standard and one IS Method: One internal standard and one surrogate standardsurrogate standard
Pattern RecognitionPattern Recognition
• Must match the Must match the pattern in the sample pattern in the sample with one of 7 Aroclor with one of 7 Aroclor standardsstandards
• Use 3-5 peaks in the Use 3-5 peaks in the standard to quantify standard to quantify sample (External Std)sample (External Std)
• Detection limits 0.05 Detection limits 0.05 ug/Lug/L
• Problems with pattern Problems with pattern recognition in recognition in weathered samplesweathered samples
GC/MS MethodsGC/MS Methods
• EPA 8270EPA 8270– Generic catch-all method Generic catch-all method – Uses GC/MS for ultimate identification, but causes a greatly Uses GC/MS for ultimate identification, but causes a greatly
reduced sensitivity (increased detection limit)reduced sensitivity (increased detection limit)– Detection limits 10 ug/L (Aroclor equivalents)Detection limits 10 ug/L (Aroclor equivalents)
• Homolog Total MethodsHomolog Total Methods– Uses GC/MS in SIM for greater sensitivity and selectivityUses GC/MS in SIM for greater sensitivity and selectivity– Internal Standard for each level of chlorinationInternal Standard for each level of chlorination– PCB defined as having peaks in QM and RM channels and PCB defined as having peaks in QM and RM channels and
being within 15% of theoretical mass ratiobeing within 15% of theoretical mass ratio– Quantifies on congener basis but not identifiedQuantifies on congener basis but not identified– Detection limits 0.001 ug/L on a congener basisDetection limits 0.001 ug/L on a congener basis
EPA Method 1668EPA Method 1668
• HRGC-HRMS congener specific method (first written HRGC-HRMS congener specific method (first written 1999, revised in November 2008, June 2010)1999, revised in November 2008, June 2010)
• Uses 27 internal standards (Uses 27 internal standards (1313CC1212-labeled congeners)-labeled congeners)– All twelve dioxin-like PCBsAll twelve dioxin-like PCBs– First and last eluters in each level of chlorination (LOC)First and last eluters in each level of chlorination (LOC)– Three Three 1313CC1212-clean-up standards and five -clean-up standards and five 1313CC1212-recovery -recovery
standardsstandards• Five (1-2000 ng/mL) or six point (0.2-2000 ng/mL) Five (1-2000 ng/mL) or six point (0.2-2000 ng/mL)
calibration for dlPCBs and LOC PCBscalibration for dlPCBs and LOC PCBs• Single point calibration for all remaining PCBsSingle point calibration for all remaining PCBs• Two methods of quantificationTwo methods of quantification
– Isotope dilution (for 27 congeners with labeled standards)Isotope dilution (for 27 congeners with labeled standards)– Internal standard – everything elseInternal standard – everything else
HRMS analysis - IssuesHRMS analysis - Issues
• Coelutions for TeCB, PeCB and HxCBCoelutions for TeCB, PeCB and HxCB– M-Cl gives significant peak, therefore cannot have M-Cl gives significant peak, therefore cannot have
coelutions with significant peaks of higher LOCcoelutions with significant peaks of higher LOC
• Each LOC requires four ionsEach LOC requires four ions– PeCB, HxCB, HpCB and OcCB overlapPeCB, HxCB, HpCB and OcCB overlap– Requires 16 ion channelsRequires 16 ion channels
• Need to maximize sensitivity, therefore Need to maximize sensitivity, therefore typical collection rates of 1 hz (no 10-100 hz typical collection rates of 1 hz (no 10-100 hz that can be found with ECDs or MSDs)that can be found with ECDs or MSDs)
GC ColumnsGC Columns
• 1668 is based on SPB-octyl column, or dual 1668 is based on SPB-octyl column, or dual column with DB-1. Has been met with mixed column with DB-1. Has been met with mixed reviews.reviews.
• Resolves 159 peaks (180 with DB-1)Resolves 159 peaks (180 with DB-1)– 30/42 TeCB30/42 TeCB– 29/46 PeCB29/46 PeCB– 31/42 HxCB31/42 HxCB– PCB156 and 157 coelutePCB156 and 157 coelute
• DB-5ms is another popular columnDB-5ms is another popular column• Performance specs similar to Octyl (165 peaks) Performance specs similar to Octyl (165 peaks)
however separates 156 & 157however separates 156 & 157
New column – SGE HT8 PCBNew column – SGE HT8 PCB
• 8% Phenyl (equiv.) Polycarborane-siloxane
• 60 m column, 0.25 mm i.d,60 m column, 0.25 mm i.d,– Initial Temp 90 C for 1 min.Initial Temp 90 C for 1 min.– RampRamp 20 C/min -> 190 C20 C/min -> 190 C– Ramp2Ramp2 1.5 C/min. -> 250 C1.5 C/min. -> 250 C– Ramp3Ramp3 4.0 C/min. -> 300 C4.0 C/min. -> 300 C– Final Temp 300 C for 4.2 min.Final Temp 300 C for 4.2 min.
• Thermo DFS HRMS with dual Thermo DFS HRMS with dual Thermo Trace GCs, Thermo Trace GCs, split/splitless injectionsplit/splitless injection
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ResultsResults
• 209 resolvable by ECD @ 100 hz209 resolvable by ECD @ 100 hz
• 189 resolvable peak tops by HRMS189 resolvable peak tops by HRMS
• 37/42 TeCB37/42 TeCB
• 37/46 PeCB37/46 PeCB
• 40/42 HxCB40/42 HxCB
Congen 9 Pt CS209 Congen 9 Pt CS209 Congen 9 Pt CS209 Congen 9 Pt CS209 Congen 9 Pt CS209Number Std Number Std Number Std Number Std Number Std
PCB-001 10.44 10.29 PCB-054 25.37 25.37 PCB-104 33.92 33.90 PCB-155 43.35 43.37 PCB-188 55.30 55.31PCB-002 13.02 12.94 PCB-050 27.37 27.35 PCB-096 37.12 37.15 PCB-150 46.70 46.70 PCB-184 56.25 56.27PCB-003 13.30 13.23 PCB-053 28.95 28.98 PCB-103 38.48 38.50 PCB-152 47.77 47.77 PCB-179 57.48 57.50
PCB-051 29.71 29.73 PCB-100 39.55 39.55 PCB-145 50.01 48.99 PCB-176 58.31 58.31PCB-010 14.18 14.04 PCB-045 30.56 30.56 PCB-094 40.55 40.59 PCB-136 50.05 50.06 PCB-186 58.91 58.93PCB-004 14.29 14.22 PCB-046 32.09 32.09 PCB-093 41.75 PCB-148 50.58 50.58 PCB-178 59.98 60.00PCB-009 16.35 16.31 PCB-069 32.90 PCB-102 41.89 PCB-154 51.88 51.89 PCB-175 60.39 60.41PCB-007 16.60 16.49 PCB-052 33.01 PCB-098 41.96 PCB-151 52.99 52.99 PCB-182 60.54PCB-006 17.78 17.76 PCB-073 33.27 33.31 PCB-095 42.11 PCB-135 53.51 53.52 PCB-187 60.56PCB-008 18.31 PCB-043 33.45 PCB-088 42.55 42.59 PCB-144 53.73 53.87 PCB-183 60.94 60.95PCB-005 18.39 PCB-049 33.68 PCB-091 43.15 43.15 PCB-147 53.80 53.81 PCB-185 61.38 61.38PCB-014 19.95 19.88 PCB-065 33.95 PCB-121 43.69 43.73 PCB-149 54.56 PCB-174 61.66 61.66PCB-011 22.45 22.47 PCB-075 34.23 PCB-084 45.76 45.80 PCB-139 54.59 PCB-181 61.74 61.74PCB-013 23.17 PCB-062 34.39 34.27 PCB-092 45.98 45.99 PCB-140 55.08 55.10 PCB-177 61.90 61.89PCB-012 23.19 PCB-048 34.35 PCB-089 46.18 46.22 PCB-143 55.41 55.43 PCB-171 62.19 62.20PCB-015 46.47 23.96 PCB-047 34.40 PCB-090 46.84 46.88 PCB-134 55.61 55.63 PCB-173 62.40 62.40
PCB-044 36.33 36.35 PCB-101 47.17 47.19 PCB-142 56.03 56.02 PCB-172 62.99 62.99PCB-019 19.56 19.50 PCB-059 36.56 36.59 PCB-113 47.65 47.68 PCB-131 56.25 56.27 PCB-192 63.13 63.14PCB-030 20.41 20.38 PCB-042 36.98 36.99 PCB-099 48.10 48.12 PCB-133 56.70 56.70 PCB-180 63.32 63.35PCB-018 22.27 22.25 PCB-064 37.85 PCB-112 49.10 PCB-165 57.25 57.25 PCB-193 63.35 63.45PCB-017 22.67 22.61 PCB-072 38.27 PCB-119 49.34 PCB-132 57.45 57.50 PCB-191 63.55 63.57PCB-024 23.24 23.21 PCB-071 38.28 38.18 PCB-083 49.59 49.72 PCB-146 57.50 57.50 PCB-170 64.24 64.24PCB-027 23.75 23.73 PCB-041 38.37 38.33 PCB-109 49.73 49.72 PCB-161 57.78 57.78 PCB-190 64.35 64.38PCB-032 24.66 24.62 PCB-068 39.08 39.11 PCB-086 50.31 PCB-153 58.29 58.32 PCB-189 65.67 65.68PCB-016 24.90 24.88 PCB-040 39.81 39.83 PCB-125 50.43 PCB-168 58.39 58.39PCB-023 25.95 25.95 PCB-057 40.37 40.40 PCB-117 50.48 PCB-141 59.06 59.08 PCB-202 61.42 61.45PCB-034 26.41 26.39 PCB-067 41.32 41.35 PCB-097 50.63 PCB-137 59.51 59.52 PCB-200 61.85 61.87PCB-029 26.61 26.59 PCB-063 41.69 41.73 PCB-116 50.87 PCB-130 59.70 59.70 PCB-204 61.97 61.97PCB-026 27.56 27.54 PCB-058 41.92 41.93 PCB-115 51.11 PCB-163 60.06 PCB-197 62.26 62.27PCB-025 27.99 27.98 PCB-061 42.18 42.20 PCB-087 51.19 PCB-164 60.07 PCB-201 62.79 62.81PCB-031 28.50 28.49 PCB-074 42.73 42.78 PCB-111 51.78 51.89 PCB-138 60.19 60.21 PCB-198 64.05 64.08PCB-028 29.03 29.03 PCB-070 43.54 43.59 PCB-085 51.91 51.99 PCB-160 60.21 60.31 PCB-199 64.10 64.13PCB-021 29.98 29.99 PCB-055 43.78 43.78 PCB-110 52.60 52.65 PCB-158 60.37 60.39 PCB-196 64.37 64.39PCB-020 30.55 PCB-066 44.36 44.39 PCB-120 52.68 52.73 PCB-129 60.53 60.53 PCB-203 64.41 64.43PCB-033 30.59 PCB-080 44.37 44.49 PCB-082 54.02 54.05 PCB-166 60.79 60.79 PCB-195 65.37 65.36PCB-022 31.49 31.51 PCB-076 45.58 45.61 PCB-124 55.49 55.51 PCB-159 61.47 61.49 PCB-194 66.60 66.60PCB-036 32.70 32.73 PCB-060 46.94 47.00 PCB-108 55.81 PCB-128 61.59 61.61 PCB-205 66.96 66.95PCB-039 33.78 33.85 PCB-056 47.22 47.26 PCB-107 55.84 PCB-162 61.74 61.76PCB-038 35.41 35.43 PCB-079 49.75 49.84 PCB-123 56.14 56.15 PCB-167 62.09 62.09 PCB-208 64.69 64.72PCB-035 37.36 37.43 PCB-078 51.27 51.36 PCB-106 56.28 56.30 PCB-156 62.98 62.97 PCB-207 65.04 65.05PCB-037 38.64 38.72 PCB-081 52.51 52.59 PCB-118 56.59 56.61 PCB-157 63.17 63.17 PCB-206 67.59 67.59
PCB-077 54.16 54.20 PCB-114 57.27 57.29 PCB-169 64.43 64.46PCB-122 57.87 57.91 PCB-209 68.05 68.05PCB-105 59.08 59.09PCB-127 59.26 59.28PCB-126 61.33 61.36
55.86
54.59
60.0851.16
50.48
49.12
50.91
60.56
34.38
33.0141.81
33.68
33.94
37.86
18.30
23.16
30.56
What is the Detection Limit?What is the Detection Limit?
• Standard methods for MDL determinationStandard methods for MDL determination– 7-10 blank samples spiked at low level with analytes of 7-10 blank samples spiked at low level with analytes of
interestinterest– MDL = 3 * SD (approximately)MDL = 3 * SD (approximately)– Better precision leads to low MDLsBetter precision leads to low MDLs– Our MDLs are 1-13 pg/LOur MDLs are 1-13 pg/L
• Isotope dilution allows for lower theoretical MDLs Isotope dilution allows for lower theoretical MDLs due to lower SDdue to lower SD
• Many isotope dilution methods call for the reporting Many isotope dilution methods call for the reporting of Instrument Detection Limits based on 2.5 x SNof Instrument Detection Limits based on 2.5 x SN
• Can give IDLs <1 pg/LCan give IDLs <1 pg/L
Analyte PCB # Blank n t Average Stdev (s) RSD Recovery MDL (ts)
pg/L pg/L pg/L pg/L
2-MoCB 1 3.80 9 2.896 12.06 2.00 17% 165% 6.0
2,4'-DiCB 8 7.89 9 2.896 21.15 2.40 11% 265% 7.5
2,2',6-TriCB 19 9 2.896 8.10 0.62 8% 162% 1.8
2,2',5-TriCB 18 9 2.896 9.86 3.00 30% 197% 9
2,4,4'-TriCB 28 10.54 9 2.896 17.63 4.13 23% 142% 12
2,2',5,5'-TeCB 52 9 2.896 4.93 1.94 39% 99% 5.8
3,4,4',5-TeCB 81 9 2.896 5.68 0.45 8% 114% 1.3
3,3',4,4'-TeCB 77 9 2.896 6.54 0.25 4% 131% 0.75
2,2',4,5,5'-PeCB 101 2.19 9 2.896 9.03 1.81 20% 137% 5.4
2,2',4,4',5-PeCB 99 1.38 9 2.896 6.22 1.22 20% 97% 3.7
2,3,3',4',6-PeCB 110 6.17 9 2.896 11.01 2.07 19% 97% 6.2
2,3',4,4',5'-PeCB 123 9 2.896 5.48 0.47 9% 110% 1.4
2,3',4,4',5-PeCB 118 3.33 9 2.896 9.36 0.99 11% 121% 3.0
2,3,4,4',5-PeCB 114 9 2.896 5.61 0.37 7% 112% 1.1
2,3,3',4,4'-PeCB 105 3.10 9 2.896 7.17 0.50 7% 81% 1.5
3,3',4,4',5-PeCB 126 9 2.896 4.99 0.47 9% 100% 1.4
2,2',3,4',5',6-HxCB 149 9.76 9 2.896 20.08 4.11 20% 206% 13
2,2',3,4,5,5'-HxCB 141 9 2.896 4.71 0.47 10% 94% 1.4
2,2',3,3',4,5-HxCB 138 1.02 9 2.896 10.00 1.38 14% 180% 4.1
2,3',4,4',5,5'-HxCB 167 9 2.896 5.28 0.56 11% 106% 1.7
2,3,3',4,4',5-HxCB 156 9 2.896 5.59 0.42 7% 112% 1.3
2,3,3',4,4',5'-HxCB 157 9 2.896 5.47 0.46 8% 109% 1.4
3,3',4,4',5,5'-HxCB 169 9 2.896 4.35 0.46 10% 87% 1.4
2,2',3,3',4,4',6-HpCB 171 9 2.896 9.60 1.30 13% 192% 3.9
2,3,3',4,4',5,5'-HpCB 189 9 2.896 5.54 0.41 7% 111% 1.2
2,2',3,3',5,5',6,6'-OcCB 202 9 2.896 5.54 0.60 11% 111% 1.8
2,2',3,3',4,5',6,6'-OcCB 201 9 2.896 3.66 0.34 9% 73% 1.0
2,2',3,3',4,4',5,5',6-NoCB 206 9 2.896 5.63 0.64 11% 113% 1.9
2,2',3,3',4,4',5,5',6,6'-DeCB 209 9 2.896 6.66 1.14 17% 133% 3.4
IUPAC Name PCB # CAS # Conc. IDL Flag
pg/L pg/L
2-MoCB PCB-001 2051-60-7 9.9 0.8 J
3-MoCB PCB-002 2051-61-8 5.6 0.8 J
4-MoCB PCB-003 2051-62-9 3.2 0.8 J
2,6-DiCB PCB-010 33146-45-1 3.7 3.7 UJ
2,2'-DiCB PCB-004 13029-08-8 30.2 3.7
2,5-DiCB PCB-009 34883-39-1 3.7 3.7 UJ
2,4-DiCB PCB-007 33284-50-3 3.7 3.7 UJ
2,3'-DiCB PCB-006 25569-80-6 3.7 3.7 UJ
2,3/2,4'-DiCB PCB-005/008 7.2 3.7 J
3,5-DiCB PCB-014 34883-41-5 3.7 3.7 UJ
3,3'-DiCB PCB-011 2050-67-1 44.4 3.7
3,4/3,4'-DiCB PCB-012/013 3.7 3.7 UJ
4,4'-DiCB PCB-015 2050-68-2 4.3 3.7 J
2,2',6-TrCB PCB-019 38444-73-4 0.9 0.9 UJ
2,4,6-TrCB PCB-030 35693-92-6 0.9 0.9 UJ
2,2',5-TrCB PCB-018 37680-65-2 12.6 0.9
2,2',4-TrCB PCB-017 37680-66-3 5.4 0.9 J
2,3,6-TrCB PCB-024 55702-45-9 0.9 0.9 UJ
2,3',6-TrCB PCB-027 38444-76-7 0.9 0.9 UJ
2,4',6-TrCB PCB-032 38444-77-8 0.9 0.9 UJ
2,2',3-TrCB PCB-016 38444-78-9 4.4 0.9 J
2,3,5-TrCB PCB-023 55720-44-0 0.9 0.9 UJ
2,3',5'-TrCB PCB-034 37680-68-5 0.9 0.9 UJ
2,4,5-TrCB PCB-029 15862-07-4 0.9 0.9 UJ
2,3',5-TrCB PCB-026 38444-81-4 0.9 0.9 UJ
2,3',4-TrCB PCB-025 55712-37-3 0.9 0.9 UJ
2,4',5-TrCB PCB-031 16606-02-3 8.6 0.9 J
2,4,4'-TrCB PCB-028 7012-37-5 6.8 0.9 J
2,3,4-TrCB PCB-021 55702-46-0 0.9 0.9 UJ
PCB-020/033 4.7 0.9 J
2,3,4'-TrCB PCB-022 38444-85-8 0.9 0.9 UJ
3,3',5-TrCB PCB-036 38444-87-0 0.9 0.9 UJ
3,4',5-TrCB PCB-039 38444-88-1 0.9 0.9 UJ
3,4,5-TrCB PCB-038 53555-66-1 0.9 0.9 UJ
3,3',4-TrCB PCB-035 37680-69-6 0.9 0.9 UJ
3,4,4'-TrCB PCB-037 38444-90-5 0.9 0.9 UJ
• Values >IDL Values >IDL are realare real
• Values Values between IDL between IDL and MDL???and MDL???
What is Total PCB?What is Total PCB?
• Sounds simple, add up individual Sounds simple, add up individual results for all 209 congenersresults for all 209 congeners
• How do you handle different How do you handle different detection limits? Co-elutions? Low detection limits? Co-elutions? Low level concentrations?level concentrations?
• Should data be reported below EQL?Should data be reported below EQL?
PCB # A B C D E Blank
Homologs pg/L pg/L pg/L pg/L pg/L pg/L
Monochlorobiphenyls 10.8 10 12.3 10.7 11 0
Dichlorobiphenyls 19.6 74.6 50.5 52 14.4 0
Trichlorobiphenyls 63 12.6 0 11.3 0 0
Tetrachlorobiphenyls 101 0 10.4 0 0 0
Pentachlorobiphenyls 152 23.2 15.5 27.6 0 29.9
Hexachlorobiphenyls 69.2 0 0 0 0 0
Heptachlorobiphenyls 0 0 0 0 0 0
Octachlorobiphenyls 0 0 0 0 0 0
Nonachlorobiphenyls 0 0 0 0 0 0
Decachlorobiphenyl 0 0 0 0 0 0
Total PCB 415 110 88.7 102 25.4 29.9
PCB # A B C D E Blank
Homologs pg/L pg/L pg/L pg/L pg/L pg/L
Monochlorobiphenyls 14.5 18.7 18.5 20.1 17.6 9.3
Dichlorobiphenyls 19.6 86.1 50.5 52 14.4 0
Trichlorobiphenyls 88.2 42.5 31.5 36 34.7 0
Tetrachlorobiphenyls 132.8 29.5 33.6 37.7 24.4 0
Pentachlorobiphenyls 173.4 40.2 24 27.6 15.5 29.9
Hexachlorobiphenyls 119.3 9.2 14.5 4.6 5.6 1.8
Heptachlorobiphenyls 30.2 0 0 0 2.3 0
Octachlorobiphenyls 11.6 0 2.5 0 1.4 0
Nonachlorobiphenyls 0 0 0 0 0 0
Decachlorobiphenyl 4.4 0 0 0 0 0
Total PCB 594 226.2 175.1 178 115.9 41
PCB # A B C D E Blank
Homologs pg/L pg/L pg/L pg/L pg/L pg/L
Monochlorobiphenyls 10.8 10 12.3 10.7 11 0
Dichlorobiphenyls 19.6 74.6 50.5 52 14.4 0
Trichlorobiphenyls 63 12.6 0 11.3 0 0
Tetrachlorobiphenyls 101 0 10.4 0 0 0
Pentachlorobiphenyls 152 23.2 15.5 27.6 0 29.9
Hexachlorobiphenyls 69.2 0 0 0 0 0
Heptachlorobiphenyls 0 0 0 0 0 0
Octachlorobiphenyls 0 0 0 0 0 0
Nonachlorobiphenyls 0 0 0 0 0 0
Decachlorobiphenyl 0 0 0 0 0 0
Total PCB 415 110 88.7 102 25.4 29.9
What is Blank?What is Blank?
• PCB is omnipresentPCB is omnipresent
• Almost impossible to achieve a complete blank in Almost impossible to achieve a complete blank in the labthe lab
• Every sample we analyze has detectable PCB Every sample we analyze has detectable PCB levels.levels.
• In order to reduce blank levels in the labIn order to reduce blank levels in the lab– Use carbon filtered waterUse carbon filtered water– Disposable glassware (not always possible)Disposable glassware (not always possible)– Keep food samples away!Keep food samples away!
• <20 pg/L per congener is excellent<20 pg/L per congener is excellent
What is achievable?What is achievable?
• Less than 20 labs in North America Less than 20 labs in North America can run EPA 1668can run EPA 1668
• No analytical confidence at 3 pg/L for No analytical confidence at 3 pg/L for Total PCBTotal PCB
• Reductions will be hard to measureReductions will be hard to measure– Are they lab caused or real?Are they lab caused or real?
• Focus on Toxic PCBs rather than 209 Focus on Toxic PCBs rather than 209 congenerscongeners
