Sediment Contamination in Lake Erie: Sediment Contamination in Lake Erie:

Where weWhere we’’ve been and where weve been and where we’’re goingre going

Chris Marvin Environment CanadaBurlington, Ontario

Rob LetcherCanadian Wildlife Service

Ottawa, Ontario

lOntario Ministry of the Environment: Eric Reiner, Terry Kolic, Karen MacPherson, Patrick Crozier, Corinna Lucaciu

lEnvironment Canada: Mehran Alaee, Murray Charlton, Derek Muir, Scott Painter, Alice Dove, Ed Sverko, Paul Klawuun

lDepartment of Fisheries and Oceans: Gregg Tomy, Gary Stern

lUSGS: Donna Myers, Dan Button

lUSEPA: Ron Rossmann

lGLIER: U. of Windsor researchers: e.g., Jan Ciborowski, Doug Haffner, Ken Drouillard

lCollaborators via the Lake Erie Collaborative Comprehensive Survey (ECCS) 2004

0100200300400500600700

0100200300400500600700

1960 1970 1980 1990 20001960 1970 1980 1990 2000Canadian Federal TEL

US EPA TEC

Canadian Federal PEL

US EPA PEC

ng/gPEC = Probable effect concentration or the concentration at which effects are likely to occur PEL = Probable effect level or the concentration at which effects are likely to occur TEC = Threshold effect concentration or the concentration at which effects rarely occur. TEL = Threshold effect level or the concentration at which effects rarely occur.

Lake Erie PCBs 1972 - 2000

Legend 0 - 1010 - 2020 - 100

100 - 200200 +

Dioxins and Furans (pg/g TEQs)

Status of Legacy ToxicsStatus of Legacy ToxicsSignificant decreases in contamination over the period 1972 - 2004Some areas within the Detroit and St. Clair Rivers represent sources of contaminants to Lake Erie, including PCBs, mercury, dioxins and furans.Significance of loadings from contaminant sources in the Detroit River, compared to loadings from the upper lakes and connecting channels.

1980 20001990

Inte

nsity

2005

Dioxins/OCs/PCBs

New and Emerging (e.g., BFRs, fluoros)

Analysis Intensity

Academic/Government

Government

Commercial

LC/MS Analyses

GC/MS Analyses

ADDITIVE BFRs

Decabromodiphenyl ether (DecBDE)Octabromodiphenyl ether (OctaBDE)Pentabromodiphenyl ether (PentaBDE)Hexabromocyclododecanes (HBCDs; α, β, γ, δ, ε isomers)

Decabromodiphenyl ethane (DBDPE)1,2-Bis(2,4,6-tribromophenoxy) ethane (TBE or BTBPE)2,3,4,5,6-Pentabromoethylbenzene (PEB)Pentabromotoluene (5BT)Decabromobiphenyl (DeBB)1,4-Bis(pentabromophenoxy)tetrabromo benzeneTetradecabromodiphenoxy benzene 1,2-Dibromo-4(1,2 dibromomethyl) cyclohexaneBromo-chlorinated paraffinsDi-(2-ethylhexyl)tetrabromophthalic esterEthylene-bis-(tetrabromophthal imide)Ethylene-bis(5,6-dibromo-norbornane-2,3-dicarbox imide1,3,5-Tris(2,3-dibromo-propoxy)-2,4,6-triazine

REACTIVE BFRs

Tetrabromobisphenol A (TBBPA)

Tetrabromobisphenol A (TBBPA) derivatives:

bis-(2,3-dibromopropyl ether)bis-(2-hydroxyethyl ether)bis-(allyl ether)dimethyl ether

Tetrabromobispenol S2,4-Di-, 2,4,6-Tri- and pentabromophenolsTribromoneopentyl alcoholVinylbromideTribromophenyl allyl ether2,3-Dibromo-2-butene-1,4-diolTetrabromophthalic acid Na saltTetrabromophthalic anhydrideN,N´-Ethylene-bis-(tetrabromophthal imide)

Types of Brominated Flame Retardants (BFRs)Types of Brominated Flame Retardants (BFRs)

ng/g

(dw

)

0.00

1.00

2.00

3.00

4.00

<0.30 ng/g dw (MLOQ)

11.92

6.42 5.15

ng/g

(dw

)ΣΣ88PBDEPBDE

0.00

1.00

2.00

3.00

4.00

<0.05 ng/g dw (MLOQ)

11.73

BDEBDE--209209

PBDEs in Sediments From Lake EriePBDEs in Sediments From Lake Erie(Letcher et al. 2006. In prep.)

ng/g

ng/g

(( d.wd.w

.).)

BPABPA

0.000.00

1.001.00

2.002.00

3.003.00

4.004.00

<0.15 ng/g d.w. (MLOQ)

BPA and BPA and TBBPAsTBBPAs in Sediments From Lake in Sediments From Lake ErieErie

ng/g

ng/g

(( d.wd.w

.).)

TBBPATBBPA

0.000.00

1.001.00

2.002.00

3.003.00

4.004.00

<0.05 ng/g d.w. (MLOQ)

TriTri--BBPABBPA

(Chu et al. 2006. In prep.)

Other BFRs (western basin):Σ8PBDE 0.18 – 15.64 ng/g d.w.BDE209 < 0.32 – 6.10 ng/g d.w.

CCH3

CH3

HO OH

CCCHCH33

CHCH33BrBr

BrBr

HOHO

BrBr

OHOH

BrBr

Stepwise, Stepwise, reductive reductive

debrominationdebromination

t1/2 of TBBPA:water = 6 – 81 dayssediment = 48 – 84

daysfish = < 1 dayhumans = 2.2 days3

t1/2 of BPA:humans = 0.25 day4

Lake Erie most shallow and biologically active/productive of the five Great Lakes

Logical progression of research/monitoring programs in light of phasing out or banning of chemicals

Detroit River and L. Erie receive considerable amounts of discharge/input from urban, industrial and agricultural activities

Why assess new toxics in Lake Erie?

1160803

11561157

8041159

1161

1169

1168

0

500

1000

1500

2000

2500

3000

3500

0

500

1000

1500

2000

2500

HCBD (pg/g)Total PCBs (ng/g)

Marvin et al. 2006, Chemosphere, In PressMarvin et al. 2006, Chemosphere, In Press

The EndThe End