Derek MuirNational Water Research Institute

Environment CanadaBurlington ON

Biomonitoring of perfluoroalkyl acids: An overview of the global and temporal trend data

Contributions from:Jon Martin, Dept Public Health, University of AlbertaMagali Houde, Environmental Biology, University of Guelph.Craig Butt and Scott Mabury, Chemistry, University of Toronto

Outline • Biomonitoring of PFAs – pros and cons• Overview of measurements of PFAs in biota and humans

• Geographical trends within Species or similar species• New temporal trends results

• Comparison of lab and field biomagnification/bioaccumulation• Are calculate BMFs using plasma or liver appropriate?• Bioaccumulation pathways?

• Conclusions• What is the biomonitoring data telling us?

Biomonitoring of perfluoroalkyl acids: An overview of the global and temporal trend data

Biomonitoring of PFAs – pros and cons

• Biota integrate exposures via water, sediment, soil and food webs • address the “so what” question re contaminants especially in remote environments

• Use of biota provides information on wildlife and human exposure, bioaccumulation potential, global distribution, temporal trends

• Great stability of PFAs (at least PFOS, PFCAs) allows for simple sample handling and storage and use of archived samples

Challenges• Precursors generally have not been determined – are they important?

Are they stable during sample storage?• Contamination especially for PFCAs due to storage or handling with

PTFE products could yield false positives• Are liver or plasma data appropriate for assessing biomagnification?• Effects of age, sex, feeding and migratory habits need to be

considered

New era of biomonitoring of PFAs begins (Giesy & Kannan ES&T, 35:139, 2001 )

Global distribution of PFC measurements in fish and wildlife (to mid-2005)

Arctic: polar bears, seals, seabirds, marine fish and invertebrates. Temporal trends

Baltic: seals, seabird temporal trends

Japan & South Korea: birds, seals

SE US coast: dolphins

Great Lakes fish and invertebrates

North Sea: fish, seals, dolphins

Geisy & Kannan; Kannan et al Others

ng/g

wet

wt

PFOS

Polar bears Pinnipeds Cetaceans Terrestrial mammals

0

500

1000

1500

2000

2500

3000

3500

PFOSA

PFOS and PFOSA in marine and terrestrial mammals (liver, kidney, plasma) – 17 studies, 16 with PFOSA+PFOS

Bottlenose dolphins,Charleston SC

Mink, US mid-west

Common dolphinMediterranean Sea

River otter, Oregon

Beluga, E. Hudson Bay

Baltic/North SeaSeals

Polar bears Hudson Bay, E. Greenland

Ringed seals, Arctic

ng/g

wet

wt

Polar bears Pinnipeds Cetaceans Terrestrial mammals

PFNA and PFOA in marine and terrestrial mammals (liver, kidney, plasma) – 10 studies with PFNA+PFOA and 13 with PFOA only

PFNA

0

100

200

300

400PFOS/10

PFOA

Gray and ringed sealBaltic Sea

Polar bears W. Canadian Arctic Bottlenose dolphins

Delaware Bay

DolphinsMediterranean Sea

0

100

200

300

400

5002000

2500

3000

Polar bear - Sanikiluaq

C7

C8

C9

C10

C11

C12

C13

C14

C15

PFB

SPF

HxS

PFO

SPF

DS

PFO

SAFT

8:2

a,b

FT8:

2 ac

id

FT10

:2 a

,b

0

20

40

60100

120

140

Ringed seal-Inukjuaq

Pattern of perfluoro acids in polar bear and ringed seal livers (E. Hudson Bay)

ng/g

wet

wt

Carboxylates Sulfonates Telomer acids

PFA Seal to Bear

C7 1C8 8C9 14C10 4C11 3C12 1C13 22C14 0.4C15 1PFBS 1PFHxS 310PFOS 23PFDS 1PFOSA 5

C. Butt, U of Toronto and M. Smithwick, U of GuelphUnpublished results 2004

NWT

High Arctic

South Hudson BaySouth Baffin Island

Arctic Circle

55°N

Svalbard

Trends of Perfluorinated carboxylic acidsin polar bear liver (ng/g wet wt) (Smithwick et al. 2005)

0

Chukchi/Beaufort Sea

East Greenland

50

100

150

200

250

300

350

400

ng/g

wet

wt

C8 C9 C10 C11

0

Smithwick et al. ES&T 2005

PFOS and major PFCAs increased in polar bear liver during the 1990s (Smithwick et al. submitted)

Con

cent

ratio

n (n

g/g

ww

) North Baffin Bay

35

3050

300500

2000

1

10

100

1000

1982 1984 1993 2001

PFOS PFOA PFNA PFDA

Doubling time (years)

PFOS 10PFNA 3.6PFDA 4.2

1972 1975

0

200

400

600

800

Seabirds Fish-eating terrestrial birds

Waterfow

PFOSPFOSA

PFCs in marine and terrestrial birds (liver, eggs, plasma)ng

/g w

et w

t

Tokyo Bay, Japan

Cormorant, California coast

Guillemot,Baltic Sea

White pelican, California coast

Glaucous gull, SvalbardMidway Atoll

Albatrosses

Fulmars and murres, Arctic

Kittiwake, Japan

Loon, N. Carolina

Osprey, Florida Herring Gull,

Great Lakes Loon, N. Quebec

Heron, Japan

0

10

20PFOA

Seabirds Fish-eating terrestrial birds

Waterfowl

PFNA

Great Blue Heron,

Louisiana

Ducks,Tokyo Bay

Con

cent

ratio

n (n

g/g

ww

)

Thick-Billed Murres

0123456789

200419931975

PFA profiles and temporal trends in Arctic seabird livers (Butt et al. Poster ENVR 027).

PFDSPFOSPFHxSPFOSA

C7 C8 C9C10 C11 C12 C13 C14 C15

10:2

FTCA8:2

FTCA10

:2 FTUCA

8:2 FTUCA

Northern Fulmars

0123456789

PFDSPFOSPFHxSPFOSA

C15C14C13C12C11C10C9C8C7

10:2

FTCA8:2

FTCA10

:2 FTUCA

8:2 FTUCA

200319931987

Trends of PFOS in guillemot eggs from the Baltic Sea (1968-2003) show overall doubling time of 7-10 yrs with possible

maximum in late 1990s (Holmström et al ES&T 2005)

Temporal Trends –Ringed Seals in the Canadian Arctic(Butt et al. poster ENV 027)

y = 0.1142x - 226.63R2 = 0.5382

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

1970 1980 1990 2000 2010

Ln (C

once

ntra

tion,

ng/

g)

* ND

PFNA (C9)

y = 0.1134x - 225.39R2 = 0.6384

0.0

0.5

1.0

1.5

2.0

2.5

1970 1980 1990 2000 2010

Ln (C

once

ntra

tion,

ng/

g)

*ND

PFDA (C10)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

1970 1980 1990 2000 2010

Ln (C

once

ntra

tion,

ng/

g)

PFOS

y = 0.1289x - 256.35R2 = 0.7314

0.0

0.5

1.0

1.5

2.0

2.5

1970 1980 1990 2000 2010

Ln (C

once

ntra

tion,

ng/

g) PFUnA (C11)

*ND

0

200

400

600

800

ng/g

wet

wt

Blue gill, Lake Biwa

Great Lakes fishes

Rainbow smelt, L. Ontario

Clams, shrimp, Arctic

Diporeia, L. Ontario

Oysters, US Gulf of Mexico

Yellow turtle, Mississippi

Yellow-fin tuna, Okinawa, & N. Pacific

Snapping turtle, Michigan

Ornate jobfish, Okinawa

PFCs in invertebrates and freshwater and marine fish and turtles

Invertebrates Freshwater fishes Marine fish & turtles

PFOSPFOSA

Invertebrates Freshwater fishes Marine fish & turtles0

40

80 PFOAPFNA

410

113

48

137

15.1

ErieN=6

HuronN=10

MichiganN=10

OntarioN=10

SuperiorN=10

PFOS (ng/g wet wt) in Great Lakes lake trout (whole fish; age = 4 yrs)Furdui et al. Poster ENV 024

Year

1980 1985 1990 1995 2000

Who

le B

ody

PFO

S C

once

ntra

tion

(ug/

g)

0.01

0.1

1

log[PFOS] = 0.0567(Year) - 116

r2 = 0.49p<0.0001

PFOS Trend in Archived Lake Trout (whole fish) from Lake Ontario (1980-2001) (Martin et al ES&T 2004)

Doubling Time ~12 yrs

0

10

20

3040

50

60

70

80

BelgiumBrazil

Northern Canada

Gatineau/O

ttawa, C

anada

Northern Canada

ColombiaIndia

ItalyJa

panJa

panJa

panJa

panKorea

Malaysia

Poland

Rural Haldummulla, S

ri Lanka

Rural Talawak

ele,, Sri L

anka

Urban Colombo, Sri L

ankaUSAUSA

Seattle, W

ashington, U

SA

Portland, O

regon

Boston, M

assach

usetts

USA -commerci

al human se

rum

Maryland, U

SA

Seattle, W

ashington, U

SA

Michigan, U

SA

Minneapolis-St.P

aul, Minneso

ta

Maryland, U

SAUSA

Hagerstown, M

aryland

Los Angeles,

California

New York

City, USA

Charlotte

, North

Carolina

Kentucky, U

SA

ng/m

L

PFOSPFOA

World except USA USA

0

2

4

6

8

10PFOSAPFNA

ng/m

LPFCs in human whole blood, plasma or serum(see also ANA 019, 026, 033, 037, 043)

0

5

10

25

30

35

PFOS PFOA PCBs PBDEs

ng/g

wet

wei

ght

N. CanadaS. Canada

Northern Canadians have similar concentrations of PFOS and PFOA in maternal blood plasma as southern CanadiansSee also Posters ANA 036 and ANA 041

Tittlemeir and Ryan, Health Canada 2004

Trophic level3.0 3.5 4.0 4.5 5.0

-5

-4

-3

-2

-1

0

Charleston SC harbour food webHoude et al. in prep

Slimy SculpinDiporeia

Lake Trout

Rainbow SmeltAlewife

Mysis

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

BelugaNarwhal

zooplankton

Arctic cod

Redfish

ShrimpClams

-1.0

0

1.0

2.0

3.0

4.0

5.0

ln[P

FOS]

(ng/

gw

.w.)

Dolphin

Zooplankton

Striped mullet

PigfishPinfish

Sea trout

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

y = 0.938TL - 1.1142R = 0.409

y = 0.629TL - 2.02

R = 0.340

y = 1.78TL - 4.52R = 0.9

PFOS trophic magnification factors (TMFs)– using whole body concentrations in top predators (see also Poster ANA016)

Eastern Arctic food web (Tomy et al. 2004)

Lake Ontario food web (Martin et al. 2004)

Study Food web PFOS PFOA PFDA

Houde et al Whole body 2.6 1.0 1.4

Tomy et al With liver 3.1 1.2 -

Martin et al Pelagic - fish 5.9 0.6 3.7

Tomy et al Whole body 1.9 0.6 -

TMFs

No correlations between concentrations of PFAs in plasma and genderSignificant negative correlations between AGE - PFOA and AGE - PFHxS

PFAsPFAs vsvs age and gender in bottlenose dolphins age and gender in bottlenose dolphins ((HoudeHoude et al. 2005; Poster ANA 14)et al. 2005; Poster ANA 14)

0.1

1

10

0 10 20 30

PFHxS IRL

0.1

1

10

0 10 20 30 40

PFOA Charleston

AGE (Years)

Log

conc

entr

atio

n (n

g/g

w.w

.)

PFA Lake trout(Martin et al. 2004)

Various species(Taniyasuet al. 2003)

Various species of marine fish (Taniyasu et al. 2003)

Various species of marine fish (Kallenbornet al. 2004)

Lake Biwa, Japan

Iceland, Denmark, Swedish Baltic coast, Faroe Is

102,000

180

9,500

67,000

PFNA 4,900 -

PFDA >122,000 1100

PFUnA >166,000

Lab BCF (Martin et al. 2003)

Lake Ontario

4900

Tokyo Bay, Osaka Bay and other urban centers

8400

Based on Lake trout liver

PFOS 34,000 5,400

PFOA 208 8

Bioaccumulation factors for PFAs in freshwater and marine fishes based on coinciding fish and water measurements

Predator Prey PFOS N-EtFOSA

PFOA PFNA PFDA Reference

Predator Fish/forage fish/invertebrates Arctic Cod Zooplankton 0.4 238 0.04 Tomy et al 2004

Smallmouth bass, R. gobies

Algae, Cray fish 10 to 20

Kannan et al 2005

Chinook salmon Round Gobies 10 to 20

Kannan et al 2005

lake trout alewife 3.7 0.6 5.3 4.4 Martin et al

sculpin

prey

Pigfish

CodChinook salmon

0.4

2.9

27

8.4 0.004

5 to 10

lake trout 0.02 0.1 0.2 Martin et al

lake trout (diet weighted)

0.4 2.3 2.7 Martin et al

Mammals/birds - fishDolphin (whole) 2.3 21 25 Houde et al. in

prep

Beluga 2.7 Tomy et al. 2004

Mink Kannan et al 2005

PFA biomagnification factors in freshwater and marine food webs

Lab BMFs >>> 0.23-0.038-0.32

Smelt & alewife

Phytoplankton

Mysids Diporeia

Sculpin

Atmospheric inputs of PF acids

STP and tributary inputs (acids, precursors, monomers, polymers)

Continuous inputs and episodic events e.g. AFFFs

Zooplankton

Bioaccumulation pathways in Lake Ontario

Slow elimination by large fish compared to lab fish

Sediments appear to be major source

Bioavailability in sediments. Precursors, acids, polymers?

Direct uptake via gills or unidentified precursors?

Microbial food web –added trophic levels?

Dissolved phase

Long range transport in the atmosphere

PFA bioaccumulation pathways in the Arctic marine food webs?

Deposition in snow/rain

River inflow

Long range transport via ocean currents

Ringed seal Arctic cod

Plankton

Ice algae

pelagic amphipods

Melt water

Polar bear

Solely PF acids?Other precursors?

• Long food chains• Multiple trophic levels• Slow elimination in mammals –enterohepatic recirculation Sediment sources less

important

• PFOS is present at highest concentrations of all PFCs followed by PFOSA

• PFNA is generally the most prominent widely monitored PFCA • Top predators have highest PFC concentrations e.g. polar bears

– apex predator• Fish eating mammals generally higher than fish eating birds• Higher concentrations in fish, mammals and birds near urban

areas e.g. CA, Tokyo, Baltic, North Sea, US SE coastal waters• Filter/particle feeding invertebrates (Diporea, oysters) in near field

sites have elevated amounts• Humans have much different ratios of PFOS/PFOA than fish or

wildlife

Observations from the overview of biomonitoring results

Conclusions

• Despite large dataset, global coverage of PFAs in biota is poor• Plasma, liver and bird eggs all used effectively in biomonitoring

and temporal trend studies• Limited whole body measurements for top predators

• General lack of correlation with age/sex in wildlife implies elimination via urine and feces is important and half-lives are relatively short in some biota

• implies prevailing concentrations sustained by continuous inputs not legacy residues

• Lack of agreement between lab and field BAFs and BMFs for PFAs

• implies multiple sources – precursors not monitored• organism size is important and difficult to mimic in the lab• unmonitored trophic levels e.g. microbial food webs could

boost BMFs

Acknowledgements• New Substances Branch, Environment Canada• Existing Substances Branch, Environment Canada• Environment Canada Great Lakes 2020 Action Plan• Northern Contaminants Program, Indian and Northern

Affairs Canada