Establishing Baseline Levels on PBDEs in Lake Ontario Surface Water Frederick Luckey, New York State...
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Transcript of Establishing Baseline Levels on PBDEs in Lake Ontario Surface Water Frederick Luckey, New York State...
Establishing Baseline Levels on PBDEs in Lake Ontario Surface WaterEstablishing 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 StatementProblem 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.
O
Br
Br
Br
Br
ObjectiveObjective
• Develop baseline measurements of PBDE in Lake Ontario surface water.
• Identify composition and 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
• Highly bioaccumulative (pKows 5 to 6);
• No Canadian or US environmental criteria or standards
• No EPA approved analytical methods
• Levels increasing in the environment.
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)
Adapted from: Alaee, Luross, Sergeant, Muir and Solomon. Adapted from: Alaee, Luross, Sergeant, Muir and Solomon. Organohalogen Compounds, 1999, Organohalogen Compounds, 1999, 4040, pp 347-350., pp 347-350.
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
200
400
600
Superior Erie Ontario
ng/g, Lipid Weightng/g, Lipid 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/g,ng/g,LipidLipid
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) – generally 2nd highest2,2’,4,4’,5-penta BDE (BDE-99) – generally 2nd highest
Dominant PBDE Congeners Dominant PBDE Congeners Reported in BiotaReported in Biota
• BDE -47 & BDE-99 together comprise ~70% BDE -47 & BDE-99 together comprise ~70% of the flame retardant Bromkal 70-5DE.of the flame retardant Bromkal 70-5DE.
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, water intake 1 m depth, water intake
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 µm1 µm
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
60g resin60g resin
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 Methods;PBDE Analytical Methods;extraction and cleanupextraction and cleanup
• Extraction & clean-up for Filters and XAD resin as Extraction & clean-up for Filters and XAD resin as
for full congener PCB analysis (EPA Method 1668A); for full congener PCB analysis (EPA Method 1668A);
• Samples spiked with 2 Samples spiked with 2 1313CC1212-labeled BDE-77 & -126 -labeled BDE-77 & -126
and 18 and 18 1313CC12 12 labelled PCBs as surrogates and labelled PCBs as surrogates and
quantitation standards;quantitation standards;
• Soxhlet extraction of XAD resin and filters 16 h in Soxhlet extraction of XAD resin and filters 16 h in
DCM.DCM.
• Extract treated with concentrated sulphuric acid Extract treated with concentrated sulphuric acid
• Silica gel Acid-base Layered and florisil cleanup Silica gel Acid-base Layered and florisil cleanup
columns;columns;
GC program for PBDEsGC program for PBDEs
DB5-HT, 30m, 0.25 mm, 0.1 µm filmDB5-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 program100°C for 3 mins, 5 C°/min to 320°C, hold for 5 minsHP 6890 split/splitless Injector held at 300°C. Double gooseneck pyrex injector liner
Pressure programInject 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 PBDE Analytical Methods Methods (continued)(continued)
• Final volume 20µL, 1 µL injection Final volume 20µL, 1 µL injection
• Analysed by high resolution MS (Micromass Ultima) six Analysed by high resolution MS (Micromass Ultima) six
function V-SIR experiment 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 Selected ion method, molecular cluster, two most
intense ions intense ions
• Native and labeled PBDE Standards supplied by Native and labeled PBDE Standards supplied by Cambridge Isotope Labs (CIL). Cambridge Isotope Labs (CIL).
PBDE Analytical StandardsPBDE Analytical Standards
• Calibration standard (EO 4980) of 40 PBDE Calibration standard (EO 4980) of 40 PBDE congeners (mono to hepta) plus PBDE-209 for congeners (mono to hepta) plus PBDE-209 for identification & quantification of 41 congeners.identification & quantification of 41 congeners.
• Homologue group method would detect presence of Homologue group method would detect presence of congeners outside this congeners suite. No significant congeners outside this congeners suite. No significant levels of other PBDE congeners outside this list were levels of other PBDE congeners outside this list were detected.detected.
• 13CC1212 PBDE (BE77 and BE126) and selected PBDE (BE77 and BE126) and selected 13CC1212 PCBs used as surrogates and quantification standards. PCBs used as surrogates and quantification standards.
Data treatmentData treatment
• Levels of PBDEs found in method blank for each Levels of PBDEs found in method blank for each sample batch subtracted from field sample results on sample batch subtracted from field sample results on sample batch basissample batch basis
• Non-detects treated as zeroNon-detects treated as zero
• Deca-BDE and nona-BDEs high and variable, Deca-BDE and nona-BDEs high and variable, attributed to lab artifacts and not includedattributed to lab artifacts and not included
0
2000
4000
6000
8000
10000
Lab #1 Lab #2 -A Lab #2 -C
pg / Lab Blank
Original Lab
New LabNew Lab
Percent levels PBDE found in new lab ventilation system ducts!
PBDE Method Blank Contamination: PBDE Method Blank Contamination: Difference between Labs Difference between Labs
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
Total PBDE in Method Blanks in Old lab, New Lab Total PBDE in Method Blanks in Old lab, New Lab and After Removal of BFR Treated Materialsand After Removal of BFR Treated Materials
After After removal of removal of
BFR treated BFR treated insulationinsulation
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
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 Homologue 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 Suggestions for determination of determination of PBDE PBDE in Surface Watersin Surface Waters
• Routinely monitor blanks for potential sources of Routinely monitor blanks for potential sources of PBDEs. New construction materials should be given PBDEs. New construction materials should be given special attention.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.
• 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 Consider metered injection of labeled PBDE surrogates into filtered sample line to quantify surrogates into filtered sample line to quantify XAD efficiency.XAD efficiency.
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
R/V Lake Guardian Cruise R/V Lake Guardian Cruise Lake Lake Ontario 1999Ontario 1999