U.S. and Canadian Lakewide Contaminant Monitoring

Beth Murphy U.S. EPA, Great Lakes National Program Office

Clarkson University Research Consortium

Environment Canada

U.S. EPA Great Lakes National Program Office

Ontario Ministry of the Environment

U.S. Geological Survey

NOAA

Overview of Presentation

1. Connection between CSMI and Monitoring Programs

2. Status of contaminants monitoring in the Great Lakes• Legacy contaminants• Emerging contaminants

3. Overview of U.S.EPA and Environment Canada Great Lakes monitoring and surveillance programs

4. Future Directions in Emerging Contaminant Research

Chemical Monitoring Programs & CSMI

• In general, chemical monitoring is not specific to any one lake. Programs collect and analyze data on a basin wide level.

• Programs are typically unable to incorporate annual changes into sampling regime.

• Results are compared and summarized through peer reviewed journal articles, governmental reporting (indicators), presentations, and collaborations between programs.

• Programs incorporating Legacy and “Emerging” chemicals into routine analysis.

• Funding dependant.

Chemical Prioritization

• CSMI• Great Lakes Water Quality Agreement

– Annex 3 Chemicals of Mutual Concern – “New” list of chemicals is in development – In previous agreement – included legacy contaminants

• PCBs, organochlorine pesticides, mercury

• Chemical Management Plan– Monitoring and Surveillance Working Group– Priorities integrated with Risk Assessment and Management– Includes new, emerged and emerging contaminants

• PBDEs and other flame retardants, PFCs, Siloxanes, other metals

• Historical Program trends• Surveillance• Collaboration potential

Legacy Contaminants in the Great Lakes

• Routine monitoring of: organochlorine pesticides, polycyclic aromatic hydrocarbons, PCBs, etc.

• Concentrations of legacy contaminants have generally declined in Great Lakes media

• PCBs & mercury are still driving fish consumption advisories

Current Use Chemicals

• Routine monitoring of: Flame Retardants, Hg, PCDD/Fs, Musks, PFOS/A, etc.

• Many of these chemicals concentrations are at steady state or are declining .

• Method development and benchmark criteria continue to make the analysis and interpretation of some of these chemicals difficult.

Emerging Contaminants in the Great Lakes

• Polychlorinated napthalenes• Fluorotelomer alcohols• Non-PBDE flame retardants• Perfluorinated compounds• Br / Cl compounds• Non-halogenated

compounds• Organometallic compounds

• Halogenated Compounds

• Siloxanes• Pharmaceuticals &

Personal care products (PPCPs)

• Degradation Products

Evolving list of chemicals for surveillance and monitoring:

Great Lakes Monitoring & Surveillance Programs

• Air• Fish• Sediment + +• Biota • Water • Tributary

Whole Fish Monitoring

National Fish Contaminants Monitoring and Surveillance Program – Environment Canada– Daryl McGoldrick– http://www.ec.gc.ca/scitech/default.asp?lang=en&n=8

28EB4D2-1

Great Lakes Fish Monitoring and Surveillance Program – US EPA– Elizabeth Murphy

• Clarkson University - tholsen@clarkson.edu

– http://www.epa.gov/grtlakes/monitoring/fish/index.html

Mercury in Lake Superior Lake Trout

Source: SOLEC 2011 Draft Technical report

• Declines observed until the early ~1990

• Appears as though concentrations have been increasing.

• Consistent with observations in other studies in the Great Lakes Region - see Ecotoxicology 20(7)

GLFMSP New Chemicals in Lake Trout

P. H. Howard and D. C. G. Muir, Environmental Science and Technology 2010, 44, 2277

Tetraphenyl tin

Triphenyl tin hydroxide

Confirmed - Catalyst – non-toxic?- Observed in Blubber by E. Hoh, ES&T 2012, 46, 8001.

- Biocide- Identified on the Howard/Muir

610 list as a potential PBT chemical

Triphenyl phosphateConfirmed

Easily Oxidized

Triphenyl phosphiteM/H List top 50

Joint CSMI GLFMSPLake of the Year (LOY) ProgramDetailed Bioaccumulation

Study• Water (dissolved and

particulate) • Phytoplankton• Zooplankton• Mussels • Benthic macro

invertebrates• Forage fish• Lake trout

Top to bottom lake snapshot

Hg Bioaccumulation Lake Superior

Sport Fish Monitoring

Fillet Monitoring Programs– U.S. States

Minnesota http://www.health.state.mn.us/divs/eh/fish/

Wisconsin http://dnr.wi.gov/topic/fishing/consumption/

Michigan http://www.michigan.gov/eatsafefish– OMOE www.ontario.ca/fishguide– Tribes / First Nations

GLIFWC http://www.glifwc.org/

Mn Chippewa http://www.mnchippewatribe.org/wqd.htm

Lake State/Province PCB Dioxin Mercury Chlordane Mirex Toxaphene

Superior

Michigan1 x x x x    

Wisconsin x x      Minnesota x   x      

Ontario x x x     x

HuronMichigan1 x x x      Ontario x x x      

Erie

New York x          Ohio x   x      

Pennsylvania x          Michigan1 x x x      Ontario x x x      

OntarioNew York x x     x  Ontario x x x      

Michigan

Illinois x     x    Michigan1 x  x x x    Indiana x   x      

Wisconsin x   x      

Chemicals Driving Fish Consumption Advice

Air Monitoring

Integrated Atmospheric Deposition Network

Environment Canada– Hayley Hung Hayley.Hung@ec.gc.ca– http://www.ec.gc.ca/natchem//default.asp?lang=En&n=1590DD07-1

U.S. EPA– Todd Nettesheim Nettesheim.Todd@epa.gov

• Indiana University hitesr@indiana.edu– http://www.epa.gov/grtlakes/monitoring/air2/index.html

Great Lakes Atmospheric Research– Liisa Jantunen Liisa.Jantunen@ec.gc.ca– Mahiba Shoeib Mahiba.Shoeib@ec.gc.ca

Mercury Deposition Network

Illinois State Water Survey– David Gay, Program Coordinator dgay@illinois.edu– http://mercnet.briloon.org/projects/NADP_-

_Mercury_Deposition_Network_National_Atmospheric_Deposition_Program/141/

ln c

onc.

(pg/m3 )

-4

-2

0

2

4

6Urban Remote/Rural

r = 0.54 p < 0.0001 t2 = 1.1 ± 0.1 yr

r = 0.38, p < 0.0001, t2 = 1.6 ± 0.3 yr

Levels of tetrabromo esters are rapidly increasing in the air

Source: Ma et al., ES&T 2012, 46(1), 204-208

Organo-Phosphate Esters in Great Lakes Air

TCPP: tris(2-chloro propyl) phosphate

• Used mostly as flame retardants and plasticizers but have many other uses• Canadian Chemical Management Plan Priority compounds• High volume production compounds • Levels are very high for indoor air (100s ng/m3) and dust (1000s ng/g). • TCEP is being phased out in North America and has been banned in EU

• OPEs were analysed in air samples from Lake Superior 2011 and in archived air samples from 2005.

• Levels of S-OPEs averaged ~500pg/m3 which is 20-30 times higher than S-PBDEs.

• Levels were about the same in 2005 and 2011

TCEP: tris(2-chloro ethyl) phosphate TPP: tri-phenyl phosphate

Atmospheric Research

Sediment Monitoring

Great Lakes Sediment Surviellance Program (GLSSP)•U.S. EPA (Cooperative Agreement)

Todd Nettesheim: Nettesheim.Todd@epa.gov• University of Illinois at Chicago An Li anli@uic.edu

Environment CanadaChris Marvin- Chris.Marvin@ec.gc.caDebbie Burniston, WQMSD -  Debbie.Burniston@ec.gc.ca

Preliminary GLSSP summary for Superior

• Spatial distribution based on surface sediment samples: – Sites S022 (near Duluth) and S106 (east of Keweenaw

Peninsula) stand out to have much higher concentrations than other sites for target legacy pollutants (PCDD/Fs, PCBs, PCNs, DDE).

– PBDEs are also higher at S022. – PFCs may exhibit a different trend – lower concentrations at S022– Other emerging pollutants have low concentrations in general.

• Time trend based on core samples– Chronological resolution is limited by low sedimentation rates

• Research questions– Higher-than-expected concentrations of heavy (8-10 chlorines)

PCBs were found and are yet to be confirmed. – Site S008 may deserve further investigation

• Elevated levels of soot carbon were found

• Previous work suggested PCB contamination at site

PFCA in Tributaries and Open Water

Water Monitoring

Great Lakes Surveillance Program– Alice Dove www.ec.gc.ca/scitech– Indiana University

• Ron Hites hitesr@indiana.edu• Marta Venier mvenier@indiana.edu

Passive Sampling– Rainer Lohmann - University of Rhode Island

• rlohmann@mail.uri.edu• http://www.gso.uri.edu/users/lohmann

– Derek Muir - Environment Canada • Derek.Muir@ec.gc.ca

Mercury Cycling and Bioaccumulation in the Great Lakes – David P. Krabbenhoft – USGS – dkrabbe@usgs.gov – http://cida.usgs.gov/glri/projects/toxic_substances/mercury_cycling.html

Total mercury in Great Lakes Waters

Total Mercury

< 0.5 ng/L

0.5 - 0.75 ng/L

0.75 - 1.5 ng/L

1.5 - 3 ng/L

3 - 11 ng/L

Dissolved Lindane Trend

Air

pg/m3

7.6

0.0069

Water

pg/L

5.6

0.056

-5000.0-4000.0-3000.0-2000.0-1000.0

0.01000.0 ∑11PBDE

Deployment Site

Ave

rage

net

flux

rate

(n

g/m

2/da

y) DepositionVolatilization

Shipping Populated Rural Open Water

PBDE Passive Sampling Results (June-Oct ’11)

Ruge et al.

Air

OCP Passive Sampling Results (June-Oct ’11)

Water

SSM PAP

ASHTB

WIMAR

ONTDUL

MB SB FI EH

Easte

rn

Centra

l

West

ern-200000-100000

0100000200000300000400000500000 HCB

June-August

August-October

Site

Flux

rat

e (n

g/m

2/da

y)

SSM PAP

ASHTB

WI

MARONT

DULMB SB FI EH

Easte

rn

Centra

l

West

ern-30.00-25.00-20.00-15.00-10.00

-5.000.005.00

Endosulfan IJune-August

August-October

Site

Flux

rat

e (n

g/m

2/da

y)

Ruge et al.

α-HCH α-HCH

α-Endosulfan α-Endosulfan

OM

rain

methylation

Sed

imen

tation

methylation

Bottom waters

Epilimnion

Thermocline/Deep chlorophyll layer

Sediments (top 20 cm)

Runoff

MeHg Annual Fluxes and Standing Pools – Lake Michigan

Wet D

ep.

Sed

Ref

lux

Hypolimnion

12 kg1-15%

2 kg

1-2%

8 kg5-8%

3 kg2-4%

0.4 kg 4-8%

11,000 kg0.5%

Trib’s: Hg, nut’s, WavesSeiche

Estuary Open LakeRiver mouth

Quagga/Cladophora assemblages

Point-sources, AOCs

Hg D

ep.

Particle scavenging

MeHg release

Round goby

Lake Trout

methylation

Oxygen supression; HABs, pathogen, & methylmercury production

A collaboration between USGS and the UW-Madison

Linking Mercury Sources and Invasive Species in the Near-Shore Zone

Biota Monitoring

Chemicals Management Plan– Pam Martin Pamela.Martin@ec.gc.ca– Rob Letcher Robert.Letcher@ec.gc.ca

Great Lakes Herring Gull Monitoring Program (GLHGMP)– Shane de Solla Shane.deSolla@ec.gc.ca

NOAA Mussel Watch– Kimani Kimbrough Kimani.Kimbrough@noaa.gov– Ed Johnson Ed. Johnson @noaa.gov– http://ccma.nos.noaa.gov/about/coast/nsandt/downloa

d.aspx

Spatiotemporal (1990-2010) Trends of OPFRs in Herring

Gull Egg Pools

3

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 20100

10

20

30

40

50

OPFR

Con

cent

ratio

n (n

g/g

lw)

Year

TCEP TCPP TPP TBEP

Chantry Island

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 20100

20

40

60

80

100

120

OPFR

CO

ncen

trat

ion

(ng/

g lw

)

Year

Fighting Island

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 20100

10

20

30

40

50

60

70

80

90

OPFR

Con

cent

ratio

n (n

g/g

lw)

Year

Agawa Rocks

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 20100

20

40

60

80

100

OPFR

Con

cent

ratio

n (n

g/lw

)

Year

Gull Island

Photo: R. Letcher

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 20100

10

20

30

40

50

60

OPFR

Con

cent

ratio

n (n

g/g

lw)

Year

Toronto Harbour

CMP

0

100

200

300

0

40

80

120Agawa Rocks

0

100

200

300

400

0

20

40

60

Gull Is

0

20

40

60

80

0

100

200

300

400

Channel-Shelter Is

0

100

200

300

0

20

40

60

Chantry Is

1990 1995 2000 2005 2010

PFO

S (n

g/g

ww

)

∑PFC

A (n

g/g

ww

)

PFOS ∑PFCA

PFOS

∑PFCA

PFOS

∑PFCA

PFOS

∑PFCA

PFOS

∑PFCA

0

20

40

60

80

0

100

200

300

400

Fighting Is

0

300

600

900

020

406080100

Niagara R

0

400

800

1200

1990 1995 2000 2005 20100

40

80

120Toronto Hbr

PFO

S (n

g/g

ww

)

∑PFC

A (n

g/g

ww

)

PFOS

∑PFCA

PFOS

∑PFCA

PFOS

∑PFCA

Twenty Years of Temporal Changes in PFOS and PFCAs in Herring Gull Eggs

L. Superior

L. Huron

L. M

ichi

gan

L. ErieL. Ontario

x

x

xx

xxx

Agawa Rocks

Toronto Hbr

Niagara River

Detroit River

Gull IsChantry Is

Channel-Shelter Is

CMP

Y ear

2,3

,7,8

TC

DD

(p

g/g

)

1980 1985 1990 1995 2000 2005 20100

50

100

150

200 Agaw aChannel Shelter (Huron)G ranite

Year

PC

Bs

(Aro

clor

125

4:12

60,

1:1)

ug/

g

1975 1980 1985 1990 1995 2000 2005 20100

10

20

30

40

50

60

70

80

90

Agawa (Superior)Channel Shelter (Huron)Granite (Superior)

Temporal of PCBs and 2,3,7,8 TCDD in Herring Gull Egg Pools

GLHGMP

NOAA Mussel Watch Program

lMussel Watch siteslMussel Watch AOC sitesAOC sites ( 2009/2010)

Tributary Monitoring

USGS– GLRI Toxic Contaminant Monitoring in Tributaries

• Steve Corsi srcorsi@usgs.gov• http://cida.usgs.gov/glri/projects/

toxic_substances/contaminant_loadings.html

Multi-tiered approach• 59 total tributaries• Passive samplers at all sites

– SPMD, POCIS– 30 day exposures

• PAHs• Organic Waste Contaminants• Organochlorine Pesticides• Total PCBs• PBDEs• Estrogenicity (yeast estrogen screen)

• Water samples at 54 sites– Organic Waste Contaminants, DOC, optical properties– Hydrologic and seasonal variability for 20 sites over two years– 1-6 samples for 34 sites

• Sediment samples at 15 sites– AOC focus– Sediment deposition: long-term exposure

• PCBs and Organochlorine pesticides

PAHs in Water Samples for Intensive Monitoring Sites

Conc

entr

ation

(µg/

L)

OWC Results

Coordination

• CSMI included in RFA requests – US• Binational Monitoring meetings• Joint publications / reporting• Peer Review• Regular communication

Future Direction

• Surveillance• Benchmark identification• Degradation products• Establishing links

– Environment and human– Food web changes and contaminant levels

Contributors

Tom Holsen – Clarkson U.

Bernard Crimmins – Clarkson U.

Philip Hopke – Clarkson U.

James Pagano – SUNY Oswego

Michael Milligan – SUNY Fredonia

Sean Backus - EC

Daryl McGoldrick – EC

Satyendra Bhavsar – OMOE

Todd Nettesheim – EPA

Liisa Jantunen – EC

Chris Marvin – EC

Kimani Kimbrough – NOAA

Ed Johnson - NOAA

Mahiba Shoeib – ECAlice Dove – ECVi Richardson – ECRainer Lohmann – URIDerek Muir – ECHayley Hung – ECRob Letcher - ECPam Martain - ECShane DeSolla – ECDavid Krabbenhoft – USGSSteve Corsi – USGSDavid Gay – ISWS

Questions?

Beth MurphyUS EPA Great Lakes National Program Office

Murphy.Elizabeth@epa.gov