biomonitoring of perfluoroalkyl acids: an overview of the … … · · 2005-09-21biomonitoring...
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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