Establishing Baseline Levels on PBDEs in Lake Ontario Surface Water Frederick Luckey, New York State DEC Brian Fowler, AXYS Analytical Services Simon Litten, New York State DEC

Problem Statement Levels of PBDE, generally increasing in wildlife and human tissue around the world. Survey data for lake trout from the Great Lakes indicates the highest PBDE levels have been found in Lake Ontario Although a considerable amount of data is now available on PBDEs in biota, there are no measurements of PBDE in surface waters in North America. Objective Develop baseline measurements of PBDE in Lake Ontario surface water. Identify composition and dominant PBDE congeners.

PolybrominatedDiphenyl Ethers (PBDEs) (PBDEs) Flame retardant widely used in plastics, polymers, foams, electrical equipment, and building materials Global production > 150,000 tons /year Highly bioaccumulative (pK ows 5 to 6); No Canadian or US environmental criteria or standards No EPA approved analytical methods Levels increasing in the environment.

C 12 H 10-n Br n O 2,2’,4,4’- tetrabromodiphenyl ether IUPAC BDE- 47 2’3’ 5’ ’ 4’ 5 Polybrominated Diphenyl Ethers (PBDEs)

Adapted from: Alaee, Luross, Sergeant, Muir and Solomon. Organohalogen Compounds, 1999, 40, pp PBDE in Great Lakes Lake Trout Dept. of Fisheries & Oceans, Canadian Centre for Inland Waters ng/g, Lipid Weight

PBDE trends in Human Breast Milk (Sweden) Adapted from D. Meironyte Guvenius and K.Noren Proceedings of The 2 nd Intl Workshop on BFRs, pp ng/g,Lipid 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 Trout Baltic Salmon Baltic Salmon Arctic Ringed Seals Faroe Island Pilot Whales Human Breast Milk Human Breast Milk 2,2’,4,4’,5-penta BDE (BDE-99) – generally 2nd highest 2,2’,4,4’,5-penta BDE (BDE-99) – generally 2nd highest Dominant PBDE Congeners Reported in Biota BDE -47 & BDE-99 together comprise ~70% of the flame retardant Bromkal 70-5DE. BDE -47 & BDE-99 together comprise ~70% of the flame retardant Bromkal 70-5DE.

Great Lakes Basin

Research Vessel Lake Guardian EPA Great Lakes National Program Office Lake Ontario Surface Water Large Volume Sampling Western sampling area Eastern Central Lake Ontario Province of Ontario Fall 1999

spatially, temporally integrated spatially, temporally integrated large volume water samples large volume water samples 24 hour continuous sampling 24 hour continuous sampling 1 m depth, water intake 1 m depth, water intake Lake Ontario Open Water Sampling duplicate samples duplicate samples water depths >75 m water depths >75 m Fall 1999

Nytex Netting XAD Resin #1 Glass Fiber Filter Surface Water Intake 1 µm Total Organics Platform Sampler (TOPS) XAD Resin #2 ~I m deep filter out large zooplankton & debris capture solids capture dissolved Lake Large Volume Sampler capture break thru 60g resin

Glass Fiber Filter Second XAD Column First XAD Column Large Volume Sampler Total Organics Platform Sampler (TOPS)

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) Fall 1999

PBDE Analytical Methods; extraction and cleanup Extraction & clean-up for Filters and XAD resin as for full congener PCB analysis (EPA Method 1668A); Extraction & clean-up for Filters and XAD resin as for full congener PCB analysis (EPA Method 1668A); Samples spiked with 2 13 C 12 -labeled BDE-77 & -126 and C 12 labelled PCBs as surrogates and quantitation standards; Samples spiked with 2 13 C 12 -labeled BDE-77 & -126 and C 12 labelled PCBs as surrogates and quantitation standards; Soxhlet extraction of XAD resin and filters 16 h in DCM. Soxhlet extraction of XAD resin and filters 16 h in DCM. Extract treated with concentrated sulphuric acid Extract treated with concentrated sulphuric acid Silica gel Acid-base Layered and florisil cleanup columns; Silica gel Acid-base Layered and florisil cleanup columns;

GC program for PBDEs DB5-HT, 30m, 0.25 mm, 0.1 µm film Analysis of mono- to deca-BDPE in a single injection with good GC resolution of lower PBDEs and minimal BE 209 degradation Temp program 100°C for 3 mins, 5 C°/min to 320°C, hold for 5 mins HP 6890 split/splitless Injector held at 300°C. Double gooseneck pyrex injector liner Pressure program Inject at 210 kPa and hold for 2 min, Program pressure down at 120 kPa/min to 90 pKa, then up at 4 kPa/min to 210 kPa and hold. Injector pressure reaches 210 kPa at 30 minutes after injection

PBDE Analytical Methods (continued) Final volume 20µL, 1 µL injection Final volume 20µL, 1 µL injection Analysed by high resolution MS (Micromass Ultima) six function V-SIR experiment Analysed by high resolution MS (Micromass Ultima) six function V-SIR experiment EI+ mode at 10,000 mass resolution. EI+ mode at 10,000 mass resolution. Selected ion method, molecular cluster, two most intense ions Selected ion method, molecular cluster, two most intense ions

Native and labeled PBDE Standards supplied by Cambridge Isotope Labs (CIL). Native and labeled PBDE Standards supplied by Cambridge Isotope Labs (CIL). PBDE Analytical Standards Calibration standard (EO 4980) of 40 PBDE congeners (mono to hepta) plus PBDE-209 for identification & quantification of 41 congeners. Calibration standard (EO 4980) of 40 PBDE congeners (mono to hepta) plus PBDE-209 for identification & quantification of 41 congeners. Homologue group method would detect presence of congeners outside this congeners suite. No significant levels of other PBDE congeners outside this list were detected. Homologue group method would detect presence of congeners outside this congeners suite. No significant levels of other PBDE congeners outside this list were detected. C 12 PBDE (BE77 and BE126) and selected C 12 PCBs used as surrogates and quantification standards. 13 C 12 PBDE (BE77 and BE126) and selected 13 C 12 PCBs used as surrogates and quantification standards.

Data treatment Levels of PBDEs found in method blank for each sample batch subtracted from field sample results on sample batch basis Levels of PBDEs found in method blank for each sample batch subtracted from field sample results on sample batch basis Non-detects treated as zero Non-detects treated as zero Deca-BDE and nona-BDEs high and variable, attributed to lab artifacts and not included Deca-BDE and nona-BDEs high and variable, attributed to lab artifacts and not included

Original Lab New Lab Percent levels PBDE found in new lab ventilation system ducts! PBDE Method Blank Contamination: Difference between Labs

Total PBDE in Method Blanks in Old lab, New Lab and After Removal of BFR Treated Materials After removal of BFR treated insulation

Lab to Lab Differences in Levels of Major PBDE Congeners in Method Blanks PBDE Congener ID# “New” “Old”

BDE-47BDE-99 Comparison 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

Calculated Water Concentrations for BDE-47 & BDE-99 Before & After Correcting for Method Blanks Before After pg/L Dissolved Phase

Lake Ontario Western Basin Comparison of PBDE Captured on 1 st & 2 nd XAD Columns PBDE Congener ID# Fall 1999 XAD #1XAD #2 pg/L

Lake Ontario Surface Water Total PBDE Concentrations Fall 1999 Picograms / Liter

Lake Ontario Surface Water Average Total PCB & PBDE Concentrations (pg/L) pg/L (1997) (1999)

Lake Ontario Surface Water PBDE Homolog Patterns Total (Dissolved + Suspended Solids) Total (Dissolved + Suspended Solids) Fall 1999 PBDE Homolog Group Central West East %

Lake Ontario Surface Water PBDE Homolog Patterns Dissolved Phase - Percent Abundance Dissolved Phase - Percent Abundance Fall 1999 PBDE Homologue Group % Central West East

Lake Ontario Surface Water PBDE Homolog Patterns Suspended Solids - Percent Abundance Suspended Solids - Percent Abundance Fall 1999 PBDE Homolog Group Central West East %

Lake Ontario Surface Water PBDE Congener Conc. Eastern Basin - A Comparison of Dissolved & Solids Conc. Fall 1999 PBDE Congener ID# pg/L

Lake Ontario Surface Water Major PBDE Congeners Total (Dissolved + Solids) – Relative Percent PBDE Congener ID# Fall 1999 Central West East %

Lake Ontario Surface Water Concentration of Major PBDE Congeners (pg/L) Total (Dissolved + Solids) PBDE Congener ID# pg/L Fall 1999 Central West East

PBDE’s in Lake Ontario Surface Water Preliminary 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; ~80% of PBDEs are dissolved; ~80% of PBDEs are dissolved; Little difference between Eastern, Central and Western Basin PBDE concentrations or congener patterns. Little difference between Eastern, Central and Western Basin PBDE concentrations or congener patterns.

Suggestions for determination of PBDE in Surface Waters Routinely monitor blanks for potential sources of PBDEs. New construction materials should be given special attention. Routinely monitor blanks for potential sources of PBDEs. New construction materials should be given special attention. Collect XAD resin samples in series and analyze separately as a check on significance of lab contamination. Collect XAD resin samples in series and analyze separately as a check on significance of lab contamination. Where blanks significant multiple (2 or 3) blanks per sample batch will allow better characterization of background conc. Blank correction on batch-specific basis may be required. Consider metered injection of labeled PBDE surrogates into filtered sample line to quantify XAD efficiency. Consider metered injection of labeled PBDE surrogates into filtered sample line to quantify XAD efficiency.

Acknowledgements 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

C 12 H 10-n Cl n 2,2’,4,4’- tetrachlorobiphenyl IUPAC # PCB- 47 2’3’5’24366’ 4’ 5 Polychlorinated Biphenyls (PCBs)

Glass Fiber Filter Surface Water Intake Flow Meter #1 Dissolved Phase Sample Volume = Meter #2 Flow Solids Phase Sample Volume = Meter #1 + #2 Flow Lake Lake Lake Ontario TOPS Sample Volumes Fall 1999 Flow Meter #2 XAD Resin #2 XAD Resin #1

Calculated Surface Water Concentrations for Congeners BDE-47 & BDE-99 After Correcting for Method Blanks pg/L

Adapted From: 2 Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2 ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June PBDE in Trends in Lake Ontario Lake Trout Dept. of Fisheries & Oceans, Canadian Centre for Inland Waters Ng/g Lipid

R/V Lake Guardian Cruise Lake Ontario 1999