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