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Measuring PCBs in Lake Ontario Surface Water Using Full-Scan Congener MethodsMeasuring PCBs in Lake Ontario Surface Water Using Full-Scan Congener Methods
Frederick LuckeyU.S. Environmental Protection Agency, Region 2
Simon LittenNew York State Dept. of Environmental Conservation
Brian Fowler AXYS Analytical Services (Currently with Waters)
Implications for designing environmental assessment programs Implications for designing environmental assessment programs
ObjectivesObjectives
• Support the information needs of the Lake Ontario Support the information needs of the Lake Ontario Lakewide Management Plan by measuring surface water Lakewide Management Plan by measuring surface water concentrations of:concentrations of:
PCBsPesticidesDioxins / FuransMercury PBDEs
• Identify contaminants exceeding water quality criteria.
Mono- chlorinated biphenyl 1 Chlorine
Di - chlorinated biphenyl 2 Chlorines
Tri- chlorinated biphenyl 3 Chlorines
Tetra - chlorinated biphenyl 4 Chlorines
Penta - chlorinated biphenyl 5 Chlorines
Hexa- chlorinated biphenyl 6 Chlorines 6 Chlorines
Hepta- chlorinated biphenyl 7 Chlorines 7 Chlorines
Octa- chlorinated biphenyl 8 Chlorines 8 Chlorines
Nona- Nona- chlorinated biphenyl 9 Chlorines
Deca - chlorinated biphenyl 10 Chlorines
Polychlorinated Biphenyl (PCB) TerminologyPolychlorinated Biphenyl (PCB) Terminology
Congener – One of 209 possible configurations of the number and position of chlorines on the two phenyl rings.
Homolog – Set of congeners having the same number of chlorines / molecular weight.
10 PCB
Homolog
Groups
PCB Homolog Group
01020304050
Commercial PCB Formulation: Aroclor 1248
Us=Polychlorinated Biphenyl (PCB) TerminologyPolychlorinated Biphenyl (PCB) TerminologyUsing Homologs to Simplify Data AnalysisUsing Homologs to Simplify Data Analysis
%
Total PCB
2’2’3’3’
5’5’
22
44
33
666’6’
4’4’
55
2,2’,4,4’- tetrachlorobiphenyl2,2’,4,4’- tetrachlorobiphenyl
IUPAC # PCB- 47IUPAC # PCB- 47
Polychlorinated Biphenyl (PCB) TerminologyPolychlorinated Biphenyl (PCB) Terminology
Great Lakes BasinGreat Lakes Basin
• Spatially, temporally integratedSpatially, temporally integrated large volume water sampleslarge volume water samples
• 24 hour continuous sampling24 hour continuous sampling
• Sampled from ~1 m depthSampled from ~1 m depth
Lake Ontario Open Water SamplingLake Ontario Open Water Sampling
• Sampling in water depths >75 mSampling in water depths >75 m
Fall Fall 19991999
Research Vessel Research Vessel Lake Guardian Lake Guardian EPA Great Lakes National EPA Great Lakes National Program Office Program Office
Lake Ontario Surface Water Large Volume Lake Ontario Surface Water Large Volume SamplingSamplingWestern / Central / Eastern Basin Sampling Western / Central / Eastern Basin Sampling GridsGrids
Province of OntarioProvince of Ontario
New York StateNew York State
Nytex Netting
XAD Resin #1
Glass Fiber Cartridge Filter
Surface Water IntakeSurface Water Intake
1 um1 um
Total Organics Platform Sampler (TOPS)Total Organics Platform Sampler (TOPS)
XAD Resin #2
~I m deep~I m deep
filter out largefilter out largezooplanktonzooplankton
& debris& debris
capture solidscapture solids
capture capture dissolved dissolved
LakeLake
Large Volume Large Volume SamplerSampler
capture any break thrucapture any break thru
Lake Ontario Surface Water Large Volume SamplingLake Ontario Surface Water Large Volume Sampling
• XAD Resin Columns 35 grams each
flow rate 300 – 600 ml / min
sample volumes ~800 L
• Glass Fiber Cartridge Filters 2.5” diameter x 4”
flow rate 3 L / min
1 micron nominal pore size
sample volumes ~5000 L
Dissolved Phase
Solids Phase
Calculating PCB Water ConcentrationsCalculating PCB Water Concentrations
PCB mass (picograms)
TOPS Sample Volume (L)
= Water Conc. (pg/L)
is inversely proportional to Sample Specific
Detection Limit
Sample Volum
e
PCB Analytical MethodPCB Analytical Method
EPA Method 1668AEPA Method 1668A
• High resolution gas chromatography & mass spectrometry High resolution gas chromatography & mass spectrometry
• Solvent extracted & cleaned with liquid chromatography Solvent extracted & cleaned with liquid chromatography
• Samples spiked with Samples spiked with 1313CC1212-labelled PCB congeners-labelled PCB congeners
• Selected ion method Selected ion method
• EI mode at 10,000 resolutionEI mode at 10,000 resolution
• Identifies 160 congeners / coeluting congener groupsIdentifies 160 congeners / coeluting congener groups
Data HandlingData Handling
• Lab results corrected based on 19 Lab results corrected based on 19 1313CC1212-labelled PCB -labelled PCB
congener surrogate congener surrogate
recoveriesrecoveries
• Values <3X Lab or Field Blank Reject.Values <3X Lab or Field Blank Reject.
• Values >3X and <5X Lab or Field Blank FlagValues >3X and <5X Lab or Field Blank Flag
• Non-detects = ZeroNon-detects = Zero
Data HandlingData Handling
Lake Ontario Surface Water PCBs (pg/l)Lake Ontario Surface Water PCBs (pg/l)
Picograms/ Liter
(parts per quadrillion)
New York Water Quality Criteria
0 10 20 30 40 50
Central
Eastern
Western-1
Western-2
Solids
Dissolved
Can You Believe These Numbers?Can You Believe These Numbers? Importance of Quality ControlImportance of Quality Control
Field Sampling QA Checks
• XAD capture efficiency
• Suspended Solids capture efficiency
• Check on XAD “wash-out” effect - 1313CC1212 PCB surrogates
• Duplicate Samples & Field Blanks
• Manual Check on Flow Meter Accuracy
Lab QA Checks
• Samples spiked with internal 1313CC1212 PCB surrogates
• Lab Blanks
XAD Resin – Use of “Washout” Field SurrogatesXAD Resin – Use of “Washout” Field Surrogates 1313CC1212-Labelled PCB-31, PCB-95 PCB-153-Labelled PCB-31, PCB-95 PCB-153
Picogram / sample
1313CC1212-labelled PCB-153-labelled PCB-153
0
50000
100000
150000
LabBlank
FieldBlank
XAD #1 XAD #2 XAD #3 XAD #4 XAD #5
Spike Conc.
Measured Conc.
Lake Ontario Surface Water PCBs – Raw pg/sampleLake Ontario Surface Water PCBs – Raw pg/sample
Field & Lab Blank IssuesField & Lab Blank Issues
Picogram / sample
0 10000 20000 30000 40000
Blank
BlankBlank
Filter
XADFilter
Filter
FilterFilter
XAD
XADXAD
XAD
Field Sample
Lab Blank
Field Blanks
Lake Ontario Surface Water PCBsLake Ontario Surface Water PCBs
XAD Resin Field Blank IssuesXAD Resin Field Blank Issues
Picogram / sample
0 2000 4000 6000 8000 10000 12000
Sample - 1
Sample - 2
Sample - 3
Sample - 4
Sample - 5
Field Blank
BZ-44
BZ-45
BZ-68
XAD Column #1
Checking XAD Field Extraction EfficiencyChecking XAD Field Extraction Efficiency
XAD Column #2
( Divinylbenzene-styrene copolymer resin )
• Ideally all contaminants will be captured on 1Ideally all contaminants will be captured on 1stst XAD column XAD column
XAD Resin Capture EfficiencyXAD Resin Capture Efficiency Percent of Congeners Captured on First XAD Percent of Congeners Captured on First XAD ColumnColumn
• 100% of congener mass captured on the first column
Except for:
% Captured on 1st XAD Column
PCB Congener
IUPAC ID
0 20 40 60 80 100
31622
26 + 293742
486084
105135 + 151 + 154
187
Duplicate ResultsDuplicate ResultsComparison of PCB Homolog Total ConcentrationsComparison of PCB Homolog Total Concentrations
Pg / l
Pg / l
Dissolved Phase
XAD Resin
Solids Phase
Glass Fiber
Cartridge Filter
PCB Homolog Group
0
2
4
6
8
10
12
14
Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca
West #1
West #2
0
2
4
6
8
10
12
14
Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca
West #1
West #2
Lake Ontario Total PCBsLake Ontario Total PCBs Homolog Percent Relative AbundanceHomolog Percent Relative Abundance
%
Total PCB
PCB Homolog Group
0
10
20
30
Mono Di Tri Tetra Penta Hexa Hepta Octa Nona
Central
Eastern
Western #1
Western #2
PCB Homolog Patterns in Field PCB Homolog Patterns in Field BlanksBlanks
%
Total PCB
PCB Homolog Group
0
20
40
60
80
100
Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca
Filter
XAD
Lake Ontario Surface Water PCBs Lake Ontario Surface Water PCBs Suspended SolidsSuspended Solids
%
Total PCB
PCB Homolog Group
0
10
20
30
Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca
Central
Eastern
Western #1
Western #2
Average Lake Ontario Surface Water Total PCBsAverage Lake Ontario Surface Water Total PCBs Congeners > 1% of Total PCBsCongeners > 1% of Total PCBs
PCB Congener
IUPAC ID
0 2 4 6 8
147 + 149
3
56
129 + 138 + 160 + 163
153 + 168
83 + 99
118
37
86 + 87 + 97 + 119 + 125
64
26 + 29
49 + 69
40 + 41 + 71
66
22
1
110 + 115
90 + 101 + 113
15
21+ 33
16
93 + 95 + 98 + 100 + 102
17
4
61 + 70 + 74 + 76
8
18 + 30
52
31
20 + 28
11
% of Total PCB
Lake Ontario Surface Water Total PCBs Fall 1999Lake Ontario Surface Water Total PCBs Fall 1999 Relative Abundance of Dominant PCB Congeners Relative Abundance of Dominant PCB Congeners
% of Total PCBs
Di
Tetra
Tri
Penta
0 2 4 6
4
8
11
18 + 30
20 + 28
31
52
61 + 70 + 74 + 76
93 + 95 + 98 + 100 + 102Eastern
Central
West #1
West #2
1242 1016 1248
4 4 4.58 9 10
11 0 018 + 30 9 11 1020 + 28 3.6 4
31 4.5 4.7 9.352 4 4.3 8.3
61 + 70 + 74 + 76 5.6 3.75 6.6493 + 95 + 98 + 100 + 102 0.66 0.22
% of PCB Aroclor Mixture
Dominant Lake Ontario PCB Congeners Dominant Lake Ontario PCB Congeners and Commercial PCB Formulationsand Commercial PCB Formulations
PCB Congener
IUPAC ID
Important Great Lakes Monitoring ProgramsImportant Great Lakes Monitoring Programs Understanding Contaminant Sources & LoadingsUnderstanding Contaminant Sources & Loadings
Niagara River Upstream-Downstream Monitoring Program
International Atmospheric
Deposition Network
(IADN)
Sources of Lake Ontario PCB Loadings (Kg/Year)
-400 -300 -200 -100 0 100 200
St. Lawrence R. Outflows
Atmospheric Volatiliz.
Atmospheric Deposition
Point Sources
Lake Ontario Basin Tribs.
Niagara R. Basin
Other Great Lakes
Kilograms Per Year
Net Change -283 Kg/Year
0 2 4 6 8
147 + 149
3
56
129 + 138 + 160 + 163
153 + 168
83 + 99
118
37
86 + 87 + 97 + 119 + 125
64
26 + 29
49 + 69
40 + 41 + 71
66
22
1
110 + 115
90 + 101 + 113
15
21+ 33
16
93 + 95 + 98 + 100 + 102
17
4
61 + 70 + 74 + 76
8
18 + 30
52
31
20 + 28
11
PCB Congeners Not Included in IADN & US/DSPCB Congeners Not Included in IADN & US/DS
PCB Congener
IUPAC ID
PCB-11
IADN & US/DS
PCB-1
IADN
PCB-37
US/DS
% of Lake Ontario Surface Water PCBs
PCB-11 as % Total PCB
PCB-11 in Selected Surface WatersPCB-11 in Selected Surface Waters
0 2 4 6 8 10 12
Hudson RiverUpstrm
Hudson RiverDwnstrm
Newark Bay
Lake Ontario
Long IslandSound
Known Sources of PCB-11Known Sources of PCB-11Diarylide Yellow Pigment ManufacturingDiarylide Yellow Pigment Manufacturing
• Associated with 3,3’-dichlorobenzidine salts
• Intermediates in the manufacture of diarylide yellow
• Loss of distal ammonia groups produces PCB-11
Designing Environmental AssessmentsDesigning Environmental Assessments Selecting a PCB Analytical MethodSelecting a PCB Analytical Method
• Financial resources Financial resources
• Available Analytical equipment / labs / staffAvailable Analytical equipment / labs / staff
• Regulatory data requirements Regulatory data requirements
• Historical data sets Historical data sets
• Expected levels of contamination / interferencesExpected levels of contamination / interferences
• Detection limit requirementsDetection limit requirements
Factors to Consider:
• Use full-scan congener methods on some samples to ensure Use full-scan congener methods on some samples to ensure that all environmentally significant congeners are recognized.that all environmentally significant congeners are recognized.
• Ensure that detection limits are low enough to determine if Ensure that detection limits are low enough to determine if water quality criteria are being met.water quality criteria are being met.
• Evaluate full-scan results to determine if selected analytical Evaluate full-scan results to determine if selected analytical approach will adequately characterize target area.approach will adequately characterize target area.
Recommendations for Designing PCB Surface WaterRecommendations for Designing PCB Surface Water Environmental Assessment Monitoring StrategiesEnvironmental Assessment Monitoring Strategies
Lake Ontario Surface Water PCBs Lake Ontario Surface Water PCBs Fall 1999 Fall 1999
• Total PCBs are ~ 40 pg/L in open watersTotal PCBs are ~ 40 pg/L in open waters
• Tri- & Tetrachlorobiphenyls dominant homologs Tri- & Tetrachlorobiphenyls dominant homologs
• > 90% of PCBs in dissolved phase> 90% of PCBs in dissolved phase
• Similar congener & homolog patterns Similar congener & homolog patterns across lakeacross lake• Dominant congener, PCB-11, not included in Dominant congener, PCB-11, not included in routineroutine monitoring, unrelated to commercial PCB monitoring, unrelated to commercial PCB mixturesmixtures
AcknowledgeAcknowledgementsments
Thanks for the support provided by:
USEPA Great Lakes National Program OfficeCaptain & Crew of the R/V Lake Guardian