Developing Baseline Information on PBDEs in Lake Ontario Surface WaterDeveloping Baseline Information on PBDEs in Lake Ontario Surface Water

Frederick Luckey, New York State DEC

Simon Litten, New York State DEC

Brian Fowler, AXYS Analytical Services

Problem StatementProblem Statement

• Levels of PBDE, a widely used flame retardant are increasing in wildlife and human tissue around the world.

• In the Great Lakes, Lake Ontario lake trout appear to have some of the highest PBDE levels.

• Although a considerable amount of data is now available on PBDE levels in biota, there were no measurements of PBDE in surface waters in North America.

O

Br

Br

Br

Br

ObjectiveObjective

• Develop baseline measurements of PBDE in Lake Ontario surface water.

• Identify dominant PBDE congeners.

PolybrominatedDiphenyl EthersPolybrominatedDiphenyl Ethers (PBDEs)(PBDEs)

• Flame retardant widely used in plastics, polymers, foams, electrical equipment, and building materials

• Global production > 150,000 tons /year

• 209 congeners / 8 homolog groups like PCBs

• Highly bioaccumulative (Kows 5 to 6);

• No US Federal environmental criteria /standards

• No EPA approved analytical methods

• Levels increasing in wildlife and human tissue.

CC1212HH10-n10-nBrBrnnOO

2,2’,4,4’- tetrabromodiphenyl ether2,2’,4,4’- tetrabromodiphenyl etherIUPAC BDE- 47IUPAC BDE- 47

O

Br

Br

Br

Br

2’2’3’3’

5’5’

22

44

33

666’6’4’4’

55

Polybrominated Diphenyl Ethers (PBDEs)Polybrominated Diphenyl Ethers (PBDEs)

Polybrominated Diphenyl Ethers Polybrominated Diphenyl Ethers (PBDEs)(PBDEs)

Congener – One of 209 possible configurations of the number and position of bromines on the two phenyl rings.

Homolog – Set of congeners having the same number of bromines.

Mono-bromodiphenyl etherbromodiphenyl ether 1 Bromine

Di -bromodiphenyl etherbromodiphenyl ether 2 Bromines

Tri-bromodiphenyl etherbromodiphenyl ether 3 Bromines

Tetra -bromodiphenyl ether bromodiphenyl ether 4 Bromines

Penta -bromodiphenyl ether bromodiphenyl ether 5 Bromines

Hexa-bromodiphenyl ether 6 Brominesbromodiphenyl ether 6 Bromines

Hepta-bromodiphenyl ether 7 Brominesbromodiphenyl ether 7 Bromines

Octa-bromodiphenyl ether 8 Brominesbromodiphenyl ether 8 Bromines

Nona- bromodiphenyl etherNona- bromodiphenyl ether 9 Bromines

Deca -bromodiphenyl etherbromodiphenyl ether 10 Bromines

O

Br

Br

Br

Br

Adapted from: Luross et al. 1999. Determining a spatial distribution Adapted from: Luross et al. 1999. Determining a spatial distribution of BDPE in Lake Trout from the Great Lakes. Poster Session, SETACof BDPE in Lake Trout from the Great Lakes. Poster Session, SETAC 20th Annual Meeting. Nov. 1999 Philadelphia.20th Annual Meeting. Nov. 1999 Philadelphia.

PBDE in Great Lakes Lake TroutPBDE in Great Lakes Lake TroutDept. of Fisheries & Oceans, Canadian Centre for Inland WatersDept. of Fisheries & Oceans, Canadian Centre for Inland Waters

0

20

40

60

80

Superior Erie Ontario

Ng/g Wet WeightNg/g Wet Weight

0

1

2

3

4

1970 1975 1980 1985 1990 1995 2000 2005

PBDE trends in Human Breast Milk (Sweden)PBDE trends in Human Breast Milk (Sweden)

Adapted from D. Meironyte Guvenius and K.Noren. 2001.Adapted from D. Meironyte Guvenius and K.Noren. 2001.Proceedings of The 2Proceedings of The 2ndnd Intl Workshop on BFRs, pp 303-5 Intl Workshop on BFRs, pp 303-5..

Ng/gNg/gLipidsLipids

Sweden Bans PBDE

• 2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in:2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in:

Great Lakes TroutGreat Lakes Trout Baltic SalmonBaltic Salmon

Arctic Ringed SealsArctic Ringed SealsFaroe Island Pilot WhalesFaroe Island Pilot Whales

Human Breast MilkHuman Breast Milk • 2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest

Dominant PBDE Congeners Dominant PBDE Congeners Reported in BiotaReported in Biota

• BDE -47 & BDE-99 together makeup ~70% of BDE -47 & BDE-99 together makeup ~70% of the flame retardant formulation - Bromkal 70-the flame retardant formulation - Bromkal 70-5DE.5DE.

Great Lakes BasinGreat Lakes Basin

Research Vessel Research Vessel Lake Guardian Lake Guardian EPA Great Lakes National Program EPA Great Lakes National Program Office Office

Lake Ontario Surface Water Large Volume Lake Ontario Surface Water Large Volume SamplingSampling

Western Western

sampling areasampling area

Eastern Eastern sampling areasampling areaCentralCentral

sampling areasampling area

LakeLake OntarioOntario

Province of OntarioProvince of Ontario

Fall Fall 19991999

• spatially, temporally integratedspatially, temporally integrated large volume water sampleslarge volume water samples

• 24 hour continuous sampling24 hour continuous sampling

• 1 m depth, isothermal1 m depth, isothermal

Lake Ontario Open Water Sampling Lake Ontario Open Water Sampling

• duplicate samplesduplicate samples

• water depths >75 mwater depths >75 m

Fall Fall 19991999

Nytex Netting

XAD Resin #1

Glass Fiber 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 break thrucapture break thru

Glass Fiber Filter

Second XAD Column

First XAD Column

Large Volume SamplerLarge Volume SamplerTotal Organics Platform Sampler (TOPS)Total Organics Platform Sampler (TOPS)

Calculating PBDE Water Concentrations Calculating PBDE Water Concentrations

PBDE mass per sample (picograms)

TOPS Sample Volume (L)

=Water Conc. (pg/L)

is inversely proportional to Sample Specific

Detection Limit

Sample

Volume

Lake Ontario Surface Water Sample Volumes (Liters)Lake Ontario Surface Water Sample Volumes (Liters)

Fall Fall 19991999

Dissolved Phase Solid PhaseXAD Resin Glass Fiber Filters

Liters Liters

Western Basin A 404 4271B 868 5037

Central Basin A 349 4337

Eastern Basin A 431 4563B 845 5522

PBDE Analytical MethodsPBDE Analytical Methods

• Extraction & clean-up for Filters and XAD resin same Extraction & clean-up for Filters and XAD resin same as EPA Method 1668A for PCB congeners; as EPA Method 1668A for PCB congeners;

• Samples spiked with Samples spiked with 1313CC1212-labelled BDE-77 & 126;-labelled BDE-77 & 126;

• Solvent extracted & cleaned with liquid Solvent extracted & cleaned with liquid

chromatography;chromatography;

• High resolution GC/HRMS (Micromass Ultima);High resolution GC/HRMS (Micromass Ultima);

• Selected ion method similar to EPA 1668A; Selected ion method similar to EPA 1668A;

• EI mode at 10000 resolution.EI mode at 10000 resolution.

• Standards prepared by Cambridge Isotope Labs (CIL)Standards prepared by Cambridge Isotope Labs (CIL)

PBDE Analytical StandardsPBDE Analytical Standards

• Calibration standard of 17 PBDE congeners (mono to Calibration standard of 17 PBDE congeners (mono to hepta); Allows for identification & quantification of 41 hepta); Allows for identification & quantification of 41 congeners.congeners.

• Same standards used by researchers in Same standards used by researchers in Canada & Europe. Canada & Europe.

• Method would recognize presence of non-target Method would recognize presence of non-target congeners. None were seen.congeners. None were seen.

Data HandlingData Handling

• Levels of PBDE congeners seen in method blanks Levels of PBDE congeners seen in method blanks subtracted from field sample resultssubtracted from field sample results

• Non-detects treated as zeroNon-detects treated as zero

0

2000

4000

6000

8000

10000

Lab #1 Lab #2 -A Lab #2 -C

pg / Lab Blank

Older Lab

Newly Newly Refurbished Refurbished

LabLab

Percent levels PBDE found in new ventilation system ducts!

Lab to Lab Differences in Levels ofLab to Lab Differences in Levels ofPBDE Method Blank ContaminationPBDE Method Blank Contamination

Lab to Lab Differences in Levels ofLab to Lab Differences in Levels ofMajor PBDE Congeners in Method BlanksMajor PBDE Congeners in Method Blanks

PBDE Congener PBDE Congener ID#ID#

“New”

“Old”

0

500

1000

1500

2000

2500

3000

47 99 100 154 209

pg/Blank Lab #1

Lab #2 - A

Lab #2 - B

0

500

1000

1500

2000

Blank 1 Field 1 Field 2 Field 3 Field 4

0

500

1000

1500

2000

Blank Field 1 Field 2 Field 3 Field 4

BDE-47 BDE-99

0

2000

4000

6000

Blank Field 1 Field 2 Field 3

0

2000

4000

6000

Blank Field 1 Field 2 Field 3

Comparison of Batch Specific Method Blanks withComparison of Batch Specific Method Blanks with Field Sample Results for BDE-47 & BDE-99.Field Sample Results for BDE-47 & BDE-99.

BDE-99BDE-47

“Old Lab”

“New Lab”

Picograms/sample

05

1015

20

West A West B Central East A East B

BDE-47

BDE-99

05

101520

West-B West-A Central East-A East-B

BDE-47

BDE-99

Calculated Water Concentrations for BDE-47 & BDE-99 Calculated Water Concentrations for BDE-47 & BDE-99 Before & After Correcting for Method BlanksBefore & After Correcting for Method Blanks

Before

After

pg/L

pg/L

Dissolved Phase

Dissolved Phase

Lake Ontario Western BasinLake Ontario Western BasinComparison of PBDE Captured on 1Comparison of PBDE Captured on 1stst & 2 & 2nd nd XAD Columns XAD Columns

PBDE Congener ID#PBDE Congener ID#

Fall Fall 19991999

XAD #1 XAD #2

0

0.5

1

17 25 28 47 99 100 153 154

XAD #1

XAD #2

pg/L

0

2000

4000

6000

8000

10000

Lab #1 Lab #2 -A Lab #2 -B Lab #2 -C Lab #2 - D Lab #2 - E Lab #2 - F

pg / Lab Blank

PBDE in Method Blanks in Old lab, Newly Built Lab PBDE in Method Blanks in Old lab, Newly Built Lab and After Removal of BFR Treated Materialsand After Removal of BFR Treated Materials

After After removal of removal of

BFR BFR insulationinsulation

R/V Lake Guardian Cruise R/V Lake Guardian Cruise Lake Lake Ontario 1999Ontario 1999

Lake Ontario Surface Water Total PBDE ConcentrationsLake Ontario Surface Water Total PBDE Concentrations

Fall Fall 19991999

Picograms / LiterPicograms / Liter

0 2 4 6 8

Western Basin - B

Western Basin - A

Central Basin

Eastern Basin - B

Eastern Basin - A

pg/L (parts per quadrillion)

SuspendedSolids

Dissolved

0 20 40 60 80 100 120

PBDE

PCB

SuspendedSolids

Dissolved

Lake Ontario Surface Water Lake Ontario Surface Water Average Total PCB & PBDE Concentrations Average Total PCB & PBDE Concentrations (pg/L)(pg/L)

pg/L

(1997)

(1999)

01020304050

Mono Di Tri Tetra Penta Hexa Hepta

Lake Ontario Surface Water PBDE Homolog PatternsLake Ontario Surface Water PBDE Homolog Patterns

Total (Dissolved + Suspended Solids)Total (Dissolved + Suspended Solids) Fall Fall 19991999

PBDE Homolog Group

Central

West

East%

01020304050

Mono Di Tri Tetra Penta Hexa Hepta

Lake Ontario Surface Water PBDE Homolog PatternsLake Ontario Surface Water PBDE Homolog Patterns

Dissolved Phase - Percent AbundanceDissolved Phase - Percent Abundance Fall Fall 19991999

PBDE Homolog Group

% Centra

l

West

East

01020304050

Mono Di Tri Tetra Penta Hexa Hepta

Lake Ontario Surface Water PBDE Homolog PatternsLake Ontario Surface Water PBDE Homolog Patterns

Suspended Solids - Percent Suspended Solids - Percent AbundanceAbundance

Fall Fall 19991999

PBDE Homolog Group

Central

West

East%

Lake Ontario Surface Water PBDE Congener Lake Ontario Surface Water PBDE Congener Conc.Conc.Eastern Basin - AEastern Basin - AComparison of Dissolved & Solids Conc.Comparison of Dissolved & Solids Conc.

Fall Fall 19991999

PBDE Congener ID#

0

0.5

1

1.5

2

17 25 28 47 99 100 153 154

Dissolved

Solids

pg/L

01020304050

17 25 28 47 99 100 153 154

Lake Ontario Surface Water Major PBDE CongenersLake Ontario Surface Water Major PBDE Congeners

Total (Dissolved + Solids) – Relative PercentTotal (Dissolved + Solids) – Relative Percent

PBDE Congener ID#

Fall Fall 19991999

Central

West

East%

0

1

2

3

17 25 28 47 99 100 153 154

Lake Ontario Surface Water Lake Ontario Surface Water Concentration of Major PBDE Congeners Concentration of Major PBDE Congeners (pg/L)(pg/L)Total (Dissolved + Total (Dissolved + Solids)Solids)

PBDE Congener ID#PBDE Congener ID#

pg/L

Fall Fall 19991999

Central

West

East

PBDE’s in Lake Ontario Surface PBDE’s in Lake Ontario Surface WaterWaterPreliminary ConclusionsPreliminary Conclusions

• Total PBDEs are ~ 4 to 6 pg/L in open waters;Total PBDEs are ~ 4 to 6 pg/L in open waters;

• BDE-47 (tetra) & BDE-99 (penta) are the dominant BDE-47 (tetra) & BDE-99 (penta) are the dominant PBDE congeners, making up >70% total PBDEs;PBDE congeners, making up >70% total PBDEs;

• ~80% of PBDEs are dissolved;~80% of PBDEs are dissolved;

• Little difference between Eastern, Central and Little difference between Eastern, Central and Western Basin PBDE concentrations Western Basin PBDE concentrations or congener patterns.or congener patterns.

Suggestions for PBDE Suggestions for PBDE Surface Water ResearchersSurface Water Researchers

• Carefully check labs for potential sources of PBDEs. Carefully check labs for potential sources of PBDEs. New construction should be given special attention.New construction should be given special attention.

• Collect XAD resin samples in series and analyze Collect XAD resin samples in series and analyze separately as a check on significance of lab separately as a check on significance of lab contamination.contamination.

• Two or three lab method blanks per sample batch should allow better characterization of lab background PBDE conc.• Correct field sample results by subtracting levels of congeners measured in batch-specific method blanks.

• Consider slow injection of isotopically labelled Consider slow injection of isotopically labelled PBDE surrogates into sample intake line in order to PBDE surrogates into sample intake line in order to quantify how well XAD captures PBDE.quantify how well XAD captures PBDE.

AcknowledgementsAcknowledgements

Thanks for the support provided by:

USEPA Region 2

USEPA Great Lakes National Program Office

Captain & Crew of the R/V Lake Guardian

The Staff at AXYS Analytical Services

CC1212HH10-n10-nClClnn

2,2’,4,4’- tetrachlorobiphenyl2,2’,4,4’- tetrachlorobiphenylIUPAC # PCB- 47IUPAC # PCB- 47

Cl Cl

Cl

Cl

2’2’3’3’

5’5’

22

44

33

666’6’

4’4’

55

Polychlorinated Biphenyls (PCBs)Polychlorinated Biphenyls (PCBs)

Glass Fiber Filter

Surface Water IntakeSurface Water Intake

Flow MeterFlow Meter#1#1

Dissolved Phase Dissolved Phase Sample Volume = Meter #2 FlowSample Volume = Meter #2 Flow

Solids PhaseSolids PhaseSample Volume = Meter #1 + #2 Sample Volume = Meter #1 + #2 Flow Flow

LakeLake

LakeLake

Lake Ontario TOPS Sample Volumes Lake Ontario TOPS Sample Volumes Fall Fall 19991999

Flow MeterFlow Meter#2#2

XAD Resin #2

XAD Resin #1

Calculated Surface Water Concentrations for CongenersCalculated Surface Water Concentrations for CongenersBDE-47 & BDE-99 After Correcting for Method BlanksBDE-47 & BDE-99 After Correcting for Method Blanks

Dissolved Phase

0.0

1.0

2.0

3.0

West-B West-A Central East-A East-B

BDE-47

BDE-99

Solids Phase

0.0

0.2

0.4

0.6

West-B West-A Central East-A East-B

BDE-47

BDE-99

pg/L

pg/L

0

200

400

600

800

1000

1978 1982 1986 1990 1994 1998

Year

Adapted From: 2Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000.

PBDE in Trends in Lake Ontario Lake TroutPBDE in Trends in Lake Ontario Lake TroutDept. of Fisheries & Oceans, Canadian Centre for Inland WatersDept. of Fisheries & Oceans, Canadian Centre for Inland Waters

Ng/g Lipid