Emerging Contaminants in Fish & Water Samples from Both Sides of the Border

Beth Murphy, US EPA GLNPO

Sean Backus, Environment Canada

Chemical Screening• Environmental Protection Agency

– Muir / Howard List– Investigator Interest– State / Tribal Interest

• Environment Canada– CMP chemicals– Special Studies

Interlab Study• EPA and EC have recently shared a set of

fish tissue samples to be used in an inter laboratory comparison study.– Results are very positive– Plan to continue to share samples– Will allow division of labor between two labs

with a great degree of confidence.

EPA Data Source• All data is provided by the Clarkson

University Research Team– Clarkson University: Dr. Tom Holsen, Dr. Phillip Hopke, & Dr.

Bernard CrimminsSUNY Oswego: Dr. James PaganoSUNY Fredonia: Dr. Michael Milligan

EPA Screening Approaches

A. Perform detailed “Full Scan” analysis of Great Lakes Fish

– Large composite sample ~30g extracted– Separate the extract prior to analysis using

modified column chromatography based– Analyze extracts for previously unidentified

peaks (non-legacy contaminants)

B. Utilize EPA Sponsored Potential Emerging Contaminant List (Muir and Howard, 2009) –

http://www.epa.gov/grtlakes/p2/PBT_progress.pdf

Limitations

• Spectra are complex

• Literature not available for most compounds

Br

Br

Br

Cl

Br

Br

1. Halocyclohexanes

2. Pentachlorothiophenol

3. Chlorocyclopentane/ene

4. Hexabromocyclododecane

5. Polychlorinated diphenyl ethers

Br

BrBr

C l

C l Br

SH

Cl

ClCl

Cl

Cl

1

2 ClCl

Cl Cl

ClCl

3

Br

BrBr Br

Br

Br

4

Full Scan Tentative Identifications by EPA

Utilize EPA Sponsored Potential Emerging Contaminant List (Muir and Howard, 2009)

• Compile standards from “List” compounds and those tentatively identified during broad screen.

PentaBromoChlorocycloHexane1,2-Dibromo-4-(1,2-dibromoethyl)-cyclohexaneHexachlorocyclopentadieneCyanuric chloridePentachlorothiophenol3,5-Dichloro-2,4,6-trifluoropyridinePentachloropyridine2,4,6-Tribromophenol solution

Compounds AcquiredDibutyl chlorendate solutionSAYTEX® BT-93WHexabromocyclododecaneChlorocyclopentanePerbromophthalate/benzoateDecabromodiphenyl EthaneTetradecabromo-1,4-diphenoxybenzeneTetrabromophthalic anhydrideDecabromodiphenyl ethane

Emerging contaminants confirmed in Lakes Michigan and Superior Trout as

part of GLFMP

Pentachlorothiophenol2,4,6-TribromophenolHexabromocyclododecaneTetrabromoethylcyclohexane (TBECH)PFC Analysis

•Also found in Lake Michigan Eggs (2006)•BDE-209 Not found in trout but found in eggs!!!•Musk / Fragarances currently being analyzed

Great Lakes Restoration Initiative

• The Great Lakes Fish Monitoring and Surveillance Program is included in the recently released RFP for the GLRI.

Contaminants of Concern

Contaminants of Concern• Contaminants of Concern continue to be found with

increasing frequency in the Great Lake’s ecosystem. • Persistent organic pollutants (POPs) are of particular concern

because of their toxicity, their tendency to accumulate in human and animal tissue, and their persistence in the environment.

• Legacy contaminants such as PCBs and PAHs continue to be a source of concern as restoration of historic sites is undertaken.

• There is a growing body of science on the environmental occurrence, distribution, and mobility of emerged classes of contaminants such as polybrominated diphenyl ethers (PBDEs), and perfluorinated compounds, (PFCs).

Contaminants of Concern• Recent awareness that many of the products and

chemicals designed to offer improvements in industry, agriculture, medical treatment, and day-to-day life are causing contamination of air, water, and land resources and continues to lead to studies on emergingcontaminants of concern.

• Chemicals such as organosiloxanes, pharmaceuticals and personal care products, current use pesticides, replacement flame retardants, and nanoparticlescontinue to stimulate new science in the Great Lakes Basin.

Contaminants of Concern

LegacyEmergedEmerging

Re-emerging

LEGACY- PCBsLake Ontario - PCBs age 4-6 lake trout

1975 1980 1985 1990 1995 2000 2005 2010

Con

cent

ratio

n (μ

g/g

wet

)

0

5

10

15

20

25

Figure 1. Trends of Total PCBs in Lake Trout (whole fish) collected from Lake Ontario

The mean concentration of total PCBs in whole body homogenates of lake trout in the latest year of monitoring (2008) in Lake Ontario was 1.10 ug/g wet (range = 0.54 – 4.5) which exceeds the target of 0.1 ug/g set in the GLWQA. Based on the mean annual decline calculated, the target concentration of 0.1 ug/g would be reached in the year 2037

LEGACY-Hg

-3.0

-2.0

-1.0

0.0

-3.0

-2.0

-1.0

0.0

-4.0

-3.0

-2.0

-1.0

0.0

Lake

Sup

erio

r

Thunder Bay-Pie Island Marathon Whitefish Bay

-4.0

-3.0

-2.0

-1.0

-4.0

-3.0

-2.0

-1.0

Ln M

ercu

ry (μ

g/g

wet

wt)

Lake

Hur

on

North Channel Owen Sound

-4.0

-3.0

-2.0

-1.0

Lake

Erie

Pelee Island

-3.0

-2.0

-1.0

0.0

1975 1980 1985 1990 1995 2000 2005 2010-3.0

-2.0

-1.0

1975 1980 1985 1990 1995 2000 2005 2010-3.0

-2.0

-1.0

1975 1980 1985 1990 1995 2000 2005 2010-3.0

-2.0

-1.0

1975 1980 1985 1990 1995 2000 2005 2010

Year

Lake

Ont

ario

Niagara-On-The-Lake Port Credit Port Hope - Cobourg Eastern Basin

P>0.05 P>0.05 P<0.001

P<0.001 P>0.05

P<0.001

P<0.001 P<0.001 P<0.001 P<0.001

Temporal trends of mercury (natural log-transformed, μg/g ww) in EC whole-body of 55-65cm lake trout (45-55cm walleye for Erie) collected between 1977 and 2007 from various locations in the Canadian Great Lakes. P-value is for statistical significance.

EMERGED

Drainage Basin

Pacific seaboard

Yukon

Columbia

Mackenzie

Hudson Bay

Nelson

St. Lawrence

St. Lawrence

Atlantic Seaboard

Spatial DistributionsSum46 BDE (-209)

Dominant species include:47,99,100,153,154Ontario > Superior > Huron > Erie agrees with Luross et al. 2002 – 1997 samples

0

10

20

30

40

50

60

70

80

Concen

tration  ng/g ww

Site

ΣnonaBDEΣoctaBDEΣheptaBDEΣhexaBDEΣpentaBDEΣtetraBDE

Concentrations of BDE homologues in fish collected from sites in 2007/2008.

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Con

cent

ratio

n ng

/g w

et w

gt. BDE-209

Zhu and Hites, 2004: Blanks 0.14 - 0.34 ng/g wet wgt.

n=27

Spatial DistributionsBDE-209

Temporal Trends

• Luross et al. 2002• HRGC/HRMS• Individual fish (n = 10)• 1997 only

• Ismail et al. 2009• GC/MS• Individual fish (n = 4-5)• 1979–2004 ~every 4 years

• Environment Canada• AXYS Analytical Services Ltd• HRGC/HRMS• Individual fish (n = 4-24)• 1997–2008 annually

• Zhu & Hites 2004• Environ. Sci. Technol. 38(10):

2779-2784.• GC/MS• Composites of 5 fish (n = 1-3)• 1980–2000 ~every 4 years

Datasets – Lake Ontario

Temporal Trends: BDE-47

BDE-47

1975 1980 1985 1990 1995 2000 2005 2010

Con

cent

ratio

n (n

g/g

wet

)

0

20

40

60

80

100

120

140

160

180

Ismail et al. 2009Environment CanadaZhu & Hites 2004

Luross et al. 2002: 58 ± 15 ng/g wet (1997)

2008 (n = 24)

35.6 ± 19.3 ng/g wet

Lake Ontario

1996 1998 2000 2002 2004 2006 2008

Con

cent

ratio

n (n

g/g

wet

)

0

20

40

60

80

100

120

1996 1998 2000 2002 2004 2006 2008

Con

cent

ratio

n (n

g/g

wet

)

0

20

40

60

80

1996 1998 2000 2002 2004 2006 2008

Con

cent

ratio

n (n

g/g

wet

)

0

5

10

15

20

25

30

Temporal Trends: Regulated BDEs

p = 0.001-3.7% / year

p = 0.008-2.5% / year

p = 0.034-1.8% / year

Σhexa-BDE

Σpenta-BDEΣtetra-BDE

All significant declining trends

Lake Ontario

EMERGING

EMERGING• Formal environmental

specimen banks (ESBs) exist in several countries– Sweden, Japan, USA,

Germany, Italy, others

• 2 within Environment Canada – NWRC: “Canadian Wildlife

Service Specimen Bank”– CCIW: “National Aquatic

Biological Specimen Bank (NABSB)”

Photo: Photo: FraunhoferFraunhofer IME IME

Photo: Photo: TjelvarTjelvar OdsjOdsjöö

Environmental Specimen Banking

Frozen HistoryEnvironmental specimen banks have:• Many important uses

– retrospective analyses• emerging contaminants• food webs changes

• Received increased interest– genetic studies– deferred analysis of emerging

contaminants until budgets improve

Photo: Photo: TjelvarTjelvar OdsjOdsjöö

O

Br

Br

Br

O

Br

Br

Br

1975 1980 1985 1990 1995 2000 2005 0.0

0.1

0.2

0.3

0.4

Brief History of the NABSB• Banking of Great Lakes fishes

began as a result of the Great Lakes Water Quality Agreement (GLWQA)– The Fish Contaminants

Surveillance Program (FCSP) –1977

– Fish tissues from the FCSP not analyzed are archived - a requirement of GLWQA (Annex 12 Section 5(e)).

• Great Lakes Fisheries Specimen Bank (GLFSB)

Source of SpecimensGreat Lakes Fish Contaminants Surveillance Program

Measuring trace metals and trace organics in top predator and forage fishes at approximately 10 locations annually since 1977

Primary target species:• lake trout and walleye• rainbow smelt, alewife

Also:• Mysis relicta, Diporeia hoyi, and plankton

Recent additions:• dreissenid mussels• round goby

Source of Specimens• Several focused, short term

projects targeted on specific threats have contributed samples from across Canada

Examples:– Toxic Substances Research

Initiative (TSRI)– Chemicals Management Plan

(CMP)– Clean Air Regulatory Agenda

(CARA-Hg)

Map of Canada showing locations where specimens archived in the NABSB were collected

EMERGING

Platinum Group Elements• The following slides present the preliminary

results of analyses for platinum group elements (PGEs) in fish tissues from the Great Lakes.

• The graphs present the results of fish and forage species from Lake Ontario (2006), Lake Superior (2006), and Hamilton Harbour (2004).

RutheniumM

ysis

Dip

orei

a

Alew

ife

Smel

t

Scu

lpin

Lake

trou

t

Lake

Tro

ut

Fres

hwat

er D

rum

Cha

nnel

Cat

fish

Rou

nd G

oby

[Ru]

(ng/

g w

et)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Lake OntarioLake SuperiorHamilton HarbourLOD

Rhodium

Mys

is

Dip

orei

a

Ale

wife

Sm

elt

Scul

pin

Lake

trou

t

Lake

Tro

ut

Fres

hwat

er D

rum

Cha

nnel

Cat

fish

Rou

nd G

oby

[Rh]

(ng/

g w

et w

eigh

t)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Lake OntarioLake SuperiorHamilton HarbourLOD

Palladium

Mys

is

Dip

orei

a

Ale

wife

Sm

elt

Scul

pin

Lake

trou

t

Lake

Tro

ut

Fres

hwat

er D

rum

Cha

nnel

Cat

fish

Rou

nd G

oby

[Pd]

(ng/

g w

et w

eigh

t)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Lake OntarioLake SuperiorHamilton HarbourLOD

Initial Discussion• PGE levels in fish are low and close to the detection limit

of the analysis – could be due to the analysis of high moisture content samples

• Ir were not detected in any samples• Pt detected only in lake trout from Lake Ontario and

Superior• Highest concentrations in lake trout from Lake Ontario –

Niagara-On-The-Lake• Lake trout from Lake Ontario are ~ 3-4 times higher than

in the forage species.

EMERGING

Water

Emerging: BPA Sampling Sites Across Canada

35 sampling sites across Canada.

290 water samples collected monthly during 2008-2009.

BPA was detected above detection limit (0.005 µg/L) in 57% of the samples (164 samples).

The concentration levels were in the low µg/L range.

Frequency of Detection of BPA in Freshwater Samples Per SamplingSite During 2008-2009

0

20

40

60

80

100

Ups

tream

Hal

f-way

thro

ugh

Sou

th (O

liver

city

)

Stil

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ek(B

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by

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wa

Riv

er

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f Isl

and

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ver D

ams

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ek

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r &

Ups

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# 9

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stre

am

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th s

hore

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pan

Riv

er

Freq

uenc

y of

Det

ectio

n (%

)

Sampling Sites

BC ONQC

NB

NL

NS

Dow

nstre

amFa

r Dow

nstre

am

Fraser River

Ups

tream

Ups

tream

Hal

f-way

thro

ugh

Mill Creek D

owns

tream

(Pen

ticto

n S

TP)

Sou

th (O

liver

city

)

OkanagenRiver

Oso

yoos

Lake

Stil

l Cre

ek (B

urna

by c

ity)

Fish

trap

Cre

ek

Ser

pent

ine

Riv

err

Was

cana

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ek

SK

N.D

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iaga

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ver D

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loo

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ondo

n

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das

& W

ater

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# 9

01

Toronto

Hig

hlan

d C

reek

Grand River

Thames River

Hamilton Hb.

St. Lawrence River

N.D

.

Monthly Concentrations of BPA in Freshwater Samples Collected Across Canada

2.582

3.65

2.054

0.864

0

1

2

3

4

Sep.

08

Oct.08

Nov.0

8De

c.08

Jan.

09Fe

b.09

Mar

.09

Apr.0

9M

ay.0

9

Jun.

09

Jul.0

9Au

g.09

Sep.

09

Con

c. (µ

g/L)

Sampling Dates

Highland Creek(Toronto, On)

Wascana Creek(Saskatchewan)

Beavers Dams Creek(Toronto, On)

Hamilton’s Harbour #914(On)

Average Monthly Concentrations of BPA in Freshwater Samples Across Canada (2008-2009)

0.0

0.2

0.4

0.6

0.8

1.0

Mill

Cre

ek

Ser

pent

ine

river

Was

cana

Cre

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Otta

wa

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er

Hig

hlan

d C

reek

Tayl

or R

iver

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tream

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r & W

ater

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# 9

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owst

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th s

hore

Nap

pan

Riv

er

Sac

kvill

e R

iver

at B

edfo

rd

Con

c. (µ

g/L)

Sampling Sites

BC

ON

QC

SK

NB NLNS

Toronto

Grand River

ThamesRiver

Hamilton HB.St. Lawrence

River

Still

Cre

ek (B

urna

by c

ity)

Nia

gara

-on-

the-

lake

rive

r

Mim

ico

Cre

ek

Beav

er D

ams

Cre

ek

Dow

nstre

am K

itche

ner &

Wat

erlo

o

Ups

tream

Lon

don

HB#

909

. Dow

nstre

am D

unda

s&

Wat

erdo

wn’

sST

P

Nor

th S

hore

(dow

nstre

am M

ontre

al)

Wat

erfo

rd R

iver

RE-EMERGING

Long Term Trends of Chloride in the Great Lakes

Great Lakes Chloride: Long-Term Mass Balance and Loading Analysis. Steve Chapra, Alice Dove, and David Rockwell. Journal of Great Lakes Research. Volume 35, Issue 2, June 2009, Pages 272-284

Contaminants of Concern

LegacyEmergedEmerging

Re-emerging

Thank you!

Beth MurphyUS EPA GLNPO

773-835-0853murphy.elizabeth@epa.gov

Sean BackusEnvironment Canada

905-336-4646sean.backus@ec.gc.ca