John P. Giesy, Ph.D., FRSC ECO-TOXICOLOGICAL EVALUATION OF ENVIRONMENT

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ECO-TOXICOLOGICAL EVALUATION OF
PERFLUOROOCTANE SULFONATE (PFOS) IN THE
ENVIRONMENT
John P. Giesy, Ph.D., FRSC
Dept. Biomedical Veterinary Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon,
Saskatchewan, Canada
Department of Zoology, Michigan State university, East Lansing, Michigan, USA
Department of Biology and Chemistry, and State Key Laboratory in Marine Pollution, City University
of Hong Kong, Kowloon, Hong Kong, SAR, PR China
School of Biological Sciences, University of Hong Kong, Hong Kong, SAR, PR China
F F FF FF F
F
F C C C C O
C C C C S
F F F FF FF FO O
International Conference on Environmental Safety and
Ecological Criteria, Nanjing, China
June 30-July 2, 2013
City University
of Hong Kong
Affiliations- Thanks for the support!!!!!
Professor & Canada Research Chair
University of Saskatchewan
Emeritus Distinguished Professor of Zoology
Michigan State University
Honorary Professor, School of Biological Sciences
University of Hong Kong
Chair Professor at Large, Dept. Biology and Chemistry
City University of Hong Kong
Concurrent Professor, School of the Environment
Nanjing University
Guest Professor
Xiamen University
Einstein Professor
Chinese Academy of Sciences
Support
 Marine Pollution Conference
 Canada Research Chair program
 Program of 2012 "High Level Foreign Experts"
(#GDW20123200120) funded by the State Administration of
Foreign Experts Affairs, the P.R. China to Nanjing University
 Einstein Professor Program of the Chinese Academy of
Sciences
 Visiting Distinguished Professorship in the Department of
Biology and Chemistry and State Key Laboratory in Marine
Pollution, City University of Hong Kong
 International Conference on Environmental Safety and
Ecological Criteria
Presentation
There is a lot more detail in the presentation than
I can show today
I will go over many things quickly
More important to get overview than details
Copy of the presentation can be obtained by the
conference organizers
Key references are listed at the end of the
presentation—they can be obtained by number
from my web site
Properties of Fluorinated Organic Compounds
F is the most electronegative element. This confers a strong
polarity to the C-F bond. C-F bond is the strongest of known
covalent bonds (~110kcal/mol).
Even in the high-energy environment of the stratosphere, the
C-F bonds in CFCs are exceptionally stable.
Three non-binding electrons in F atom can form a protective
sheath that yields PFCs very stable. C-F bond can withstand
boiling with 100% sulfuric acid without any defluorination.
Structures of Sulfonated Fluorochemicals
POSF: Perfluorooctanesulfonylfluoride
POSF is the starting material for polymer
production
O
C8F17 S - F
O
PFOS: Perfluorooctanesulfonate
PFOS is the ultimate degradation product of
POSF-based compounds and the compound
found in the environment
F
F F
C
F
C
F F
F
C
F F
F F
C
FF
C
C
FF
F O
C
C
S
O
F O
O
C8F17 S - O
O
Biologically produced fluorochemicals
contain only one fluorine atom e.g., MFA
Most fluorochemicals in the environment
are anthropogenic
PFOS and POSF-based chemicals are on
Annex B of Stockholm Convention
Still produced in China
Uses of Fluorinated Surfactants
Adhesives : Wetting agents.
Antifogging : Glass surfaces exposed to humid
atmospheres - mirrors in bathrooms, automobile
windshields, eyeglass lenses, plastic (or
polyethylene) cover sheets in agriculture.
Antistatic agents : Antistatics prevent the buildup
of static electricity and dissipate the electric charge
formed on the substrate—Important for
microchips.
Cement additives : Reduce shrinkage of cement.
Uses of Fluorinated Surfactants
Cleaners for hard surfaces: Automotive waxes,
cleaning outside of airplanes, degreasing of metals.
Coatings: Paint additives - to improve dust repellency,
floor waxes.
Cosmetics: Hair-conditioning formulations to improve
lubricity, and render hair oleophobic. e.g., POAA.
Electronics: Insulators for wires and cables.
Electroplating: Chromium, copper and nickel plating.
Uses of Fluorinated Surfactants
Etching: Glass articles are polished and etched with
solutions containing H2SO4, HF and a fluorinated
surfactant.
Fire-Fighting Foams: Formulated to float on
flammable liquids and extinguish flames. FS in
Aqueous Film-Forming Foams (AFFF) reduce the
surface tension of water and form a film on the fuel
surface.
Herbicides and Insecticides: Wetting agents, ant baits.
Leather: Provide water and oil repellency
Uses of Fluorinated Surfactants
Paper: Oil and water repellency. Used in folding
cartons for snack foods, carry-out fast food, cake
mixes, margarine, candy, bakery products and pet
foods.
Polishes and waxes: In floor waxes.
Textiles: Polyester etc. to impart soil, oil and water
repellency. Major use is in carpeting.
SUMMARY - Environmental Fate
PFOS is ubiquitous in the global environment in both
urban and remote locations
PFOS accumulates into human and wildlife tissues
PFOS can be toxic to invertebrates and vertebrates
under laboratory conditions
Issue: Are current concentrations of PFOS in the
environment expected to cause any adverse effects on
wildlife
Ecotoxicological Evaluation
•Determine target tissues & key effects of PFOS
•Elucidate modes of action of PFOS
•Determine critical effect concentrations of PFOS
•Determine concentrations of PFOS in the
environment
•Calculate Hazard Quotients (HQs) and Margins
of Safety (MOSs)
Perfluorooctane sulfonate
PFOS is a fatty acid analogue
Not metabolized
Amphiphilic
Preferentially retained in plasma
and liver

binds to protein
Affects membranes
Ecotoxicological Assessment For PFOS
Rationale for Testing
Discovery of PFOS in environmental Samples
Reliable, sensitive analytical methods now available
Generate hazard data for environmental risk
evaluation
Approach
Determine Toxicity Reference Values (TRVs) based
on standard practices
Calculate threshold water concentrations for
protection of aquatic life based on the US EPA-GLI
methods and OECD, PNEC
Determine tissue concentrations to protect
predatory birds and mammals
Compare measured concentrations in water or
tissues to TRVs
HQ = Concentration/TRV;
MOS = 1/HQ
Threshold Screening Concentrations for
the Protection of Aquatic Life









Great Lakes Initiative (GLI) US EPA
GLI used to calculate acute & chronic concentrations
Semi-probabilistic approach
Requires acute and chronic toxicity results for
aquatic species of various orders and families
Uses species and genus geometric means
Uses Acute to Chronic Ratios
Can calculate Tier I and Tier II GLI values
Similar to method of Stephan et al (1985)
Conservative (Protective)
Derivation of Water Values
Aquatic Ecotoxicology Data
Beach, SA., Newsted, JL., Coady, K., and Giesy, JP.
(2006). Ecotoxicological evaluation of perfluorooctane
sulfonate (PFOS). Rev. Environ. Contam. Toxicol. 186:
133-174.
Assessment Approach
 Great Lakes Water Quality Initiative or GLI (USEPA 1995)
 Comprehensive approach used by regulatory agencies
Utilizes environmental properties of chemical
Utilizes Environmental Fate Properties
Toxicological data for both humans and ecological
receptors
 Approach assumes primary exposure pathways to receptors
of concern is from water through species specific food chains
Great Lakes Water Quality Initiative
 Derivation of Water Quality Criteria (WQC) is a
two tier process depending on the availability of
toxicity data.
 If all data requirements set out in the GLI are
met, a Tier I value can derived

Final Chronic Value (FCV)
 If all data requirements are not met, a Tier II
values is calculated

Secondary (Screening) Chronic Value (SCV)
Great Lakes Initiative (GLI) data requirements
GLI Requirements
Species Tested
Acute
Result?
Chronic
Result?
O. mykiss
√
P. promelas
√
√
3. Phylum Cordata, 3rd family
Xenopus
√
√
4. Planktonic crustacean
D. magna
√
U. Complamatus
√
C. tentans
√
1. Class Osteichthyes,
Salmonidae
Family
2. Class Osteichthyes, 2nd family
5. Benthic crustacean
6. Insect
7. Family in a phylum other than
Arthropoda or chordata
8. Insect family not represented
√
Threshold Screening Concentrations for the Protection
of Aquatic Life
Aquatic Plants relatively tolerant
 NOAEC values from 5.3 to 150 mg PFOS/l
GLI Tier I value could not be calculated due to
insufficient number of families and especially
chronic data
Secondary Chronic Value (SCV) = 1.2 ug PFOS/l
(1,200 ng/l, ppTr)
See Review by Beach et al, 2005. Rev. Environ. Contam. Toxicol.
Acute and subchronic toxicity of PFOS to
freshwater phytoplankton
Species
96-EC50
96-NOEC
Selenastrum capricornutum
68 (63-70)
42
Selenastrum capricornutum
48 (45-51)
5.3
Chlorella vulgaris
82 (70-99)
8.2
Anabaena flos-aque
131 (106-142)
94
Navicula pelliculosa
263 (217-299)
150
* EC50 (mg/L) values with 95% confidence intervals in brackets.
* Effect levels bases on growth (cell density)
Toxicity of PFOS to macrophytes
Species
Lemna gibba
Lemna gibba
Myriophyllum
spicatum
Myropyllum
sibiricum
Test
Duration
EC50
(mg/L)
NOEC
(mg/L)
7d
108 a
15
7d
59 a
31 b
29
6.6
42 d
13 c
17 d
11.4
11.4
42 d
3.4 c
2.4 d
2.9
0.3
• Effect values based on frond number (b) or biomass (b)
• Effect values based on biomass (c) or root length (d)
Toxicity of PFOS to aquatic invertebrates
Species
Daphnia magna
Daphnia pulicaria
Test
Duration
48 hr
48 hr
48 hr
21 d
48 hr
Endpoint
Immobility
Survival
Survival
Adult survival
Immobility
NOAE
C
0.8
33
32
12
14
EC50/
LC50*
67
130
59
16
134
Crassostrea sp.
96 hr
Shell Growth
1.8
>2.9
Unio complamatus
96 hr
Survival
20
57
Artemia salina
48 hr
Survival
-
9.2
Mysidopsis bahia
96 hr
35 d
Survival
Growth/Repro.
1.1
0.24
3.5
-
* All concentrations in mg/L
Toxicity of PFOS to aquatic invertebrates (Continued)
Species
Chironomus tentans
Test
Duration
10 d
Chironomus tentans
20 d
Zooplankton
35 d
All concentrations given as mg/L
NC = not calculated
Endpoint
NOAEC
Survival
Growth
Survival
Growth
Emergence
Eggs/female
Community
Structure
0.05
0.05
0.094
0.022
< 0.002
NC
3.0
EC50/
LC50
> 0.15
0.087
0.092
0.094
0.095
No effect
-
Toxicity of PFOS to fish and amphibians
Species
Test a
NOEC
LOEC
LC50
Rainbow Trout
96 hr
NR
NR
7.8
Rainbow Trout
96 hr
6.3
13
22
Fathead Minnow
96 hr
3.2
5.4
9.1
Fathead Minnow
47 d
0.29
0.58
-
Fathead Minnow
28 d b
0.3
3.0
7.2
Leopard Frog
16 wk c
1.0
3.0
6.2
Xenopus
FETAX
4.8
8.0
16
A
Test were either static renewal or flow-through; Concentrations in mg/L.
B Microcosm study
C Partial life cycle test
Derivation of a Screening Plant Value (SPV) for PFOS
Guidelines for deriving a SPV
• Based on least mean Genus Mean Chronic Value (GMCV)
for species tested
• Least GMCV was observed with Myriophyllum or water
milfoil
SPV = 2.4 mg PFOS/L
Secondary Acute Value For Aquatic Organisms
Secondary Acute Value (SAV) =
Lowest Acute Value
Secondary Acute Factor (SAF)
 Lowest species mean acute value (SMAV) is for Chironomus tentans
with an EC50 of 0.087 mg/L
 Secondary Acute Factor (SAF) is an adjustment factor that accounts
for various sources of uncertainty and depends on the number of data
requirements that have been met. For 6 requirements, SAF= 5.2
SAV =
0.087 mg/L PFOS
5.2
= 0.017 mg/L PFOS
Secondary Chronic Value for PFOS
Secondary Chronic Value (SCV) =
Secondary Acute Value
Acute to Chronic Ratio (ACR)
 Acute to chronic ratio (ACR) based on toxicity studies with D. magna,
fathead minnows and mysid shrimp.
 ACR derived as geometric mean of species specific ACR values.
 ACR = 13.9
17 ug/L PFOS
SCV =
13.9
= 1.2 ug/L PFOS
SCV = 1.2 µg PFOS/L
Species Sensitivity Distribution (SSD)
Water Values
Comparisons
1.2
SCV
SPV
SAV
1
Probability
0.8
0.6
0.4
LC50/EC50 Data
NOEC Data
0.2
0
0.001
0.01
0.1
1
PFOS Concentration (mg/L)
10
100
1000
Comparison of PFOS Concentrations in Laurentian Great
Lakes to its Chronic Value
Lake Erie
SCV = 1,200 ng/L
Lake Huron
Lake Ontario
Mich. Waters
Niagara River
0.10
1000
1.0
10
100
PFOS Concentrations (ng/L)
Comparison of PFOS Concentrations in Michigan
Waters Chronic Value
Detroit Region
SCV
1.0
10
100
PFOS Water Concentrations (ng/L)
10001000
Conclusions
 Currently there are sufficient data to derive a
Tier II water quality criterion for the Laurentian
Great Lakes
 Additional Studies are needed to address data
gaps such that a Tier I water quality criterion can
be estimated
 Based on Tier II methodology, current water
concentrations that have been measured in the
Great Lakes do not pose a significant risk to
aquatic organisms
Derivation of a Safe Water Concentration for PFOS
to Avian Species
Derivation of Toxicant Reference Values (TRVs)
Bird TRVs based on whole-life in vivo studies
with bobwhite and mallards
Mammalian TRVs (mink etc) based on pup
weight reduction in rats
Application of uncertainty factors
Northern Bobwhite Quail
Northern Bobwhite (Colinus virginianus)
• Order Galliformes, Family Odontophoridae
• Ground-dwelling upland game bird
• Feeds primarily on weeds, woody plants and
grasses. Adults and chicks also consume insects
and other invertebrates
Mallard
Mallard (Anas platyrhynchos)
 Order Anseriformes, Family Anatidae
 Surface feeding dabbling duck (waterfowl)
 Feed primarily on aquatic plants and
aquatic insects
Avian Ecotoxicological Studies
• Studies were designed according to OECD, FIFRA and
OPPTS guidelines for avian species
• All studies conducted with a well characterized PFOS stock
• Studies conducted under TSCA Good Laboratories
Procedures
• Exposure concentrations determined analytically
• Dose concentrations (liver and blood) determined analytically
• Analytical methods validated for each matrix
Northern Bobwhite Reproduction Test
Final LOAEL Values
Measures of PFOS Exposure
ADULT MALES
A
Dose (mg PFOS/kg in Feed)
ADI (mg PFOS/kg body weight/day) over 21-wk period
Serum (mg PFOS/mL) at study termination (21-wks)
Liver (mg PFOS/g) at study termination (21-wks)
NOAEL LOAEL
10
0.77
140
88
ADULT FEMALES
Dose (mg PFOS/kg in Feed)
ADI (mg PFOS/kg body weight/day) over 21-wk period
Serum ( m g PFOS/mL), pre-reproductive phase (5-wks)
Serum (m g PFOS/mL), reproductive phase, (21-wks)
Liver ( m g PFOS/g) at study termination (21-wks)
OFFSPRING
Yolk (mg PFOS/mL)
A
LOAEL was based on a decrease in the 14-d old survivability of offspring
All concentrations are reported on a wet weight basis
10
0.77
84
8.7
4.9
62
Mallard Definitive Reproduction Study
Final NOAEL and LOAEL Values
Measures of PFOS Exposure
A
NOAEL
ADULT MALES
Dose (mg PFOS/kg body weight)
ADI (mg/PFOS/kg body weight per day) over 21-wks
Serum (μg PFOS/ml) at study termination (21-wks)
Liver (μg PFOS/ml) at study termination (21-wks)
10
1.5
87
61
ADULT FEMALES
Dose (mg PFOS/kg body weight)
ADI (mg/PFOS/kg body weight per day) over 21-wks
Serum (μg PFOS/ml) pre-reproductive phase (5-wks)
Serum ( μg PFOS/ml) at study termination (21-wks)
Liver ( μg PFOS/g) at study termination (21-wks)
10
1.5
77
17
11
OFFSPRING
Yolk (μg PFOS/ml)
A All concentrations given on a wet weight basis
53
Derivation of Toxicant Reference Values (TRVs)
Based on whole-life in vivo studies with
bobwhite and mallards
Application of uncertainty factors
Uncertainty Factors for a Generic Trophic Level 4
Predator Exposed to PFOS
UNCERTAINTY FACTORS NOTES
Inter-taxon Extrapolation (A) Threshold dose derived from northern
bobwhite reproductive study. Assume
the TRV is derived for a species in the
same class but different order, A=5
Exposure Duration (B)
The bobwhite quail study used to
derive a test dose was a 20 week
dietary reproduction study, B=1
Toxicological Endpoint (C)
The LOAELvlaues were derived from
adult and juvenile bobwhite quail.
Significant effects were observed on
multiple endpoints including
reproduction, C=3
Uncertainty Factors for a Generic Trophic Level 4
Predator Exposed to PFOS (Cont.)
UNCERTAINTY FACTORS NOTES
Modifying Factors (D)
-Threatened Species
The bird is not listed or endangered, d1 = 0
- Relevance of Endpoint
Endpoints in study include chronic and
reproductive measurements d2 =0
- Lab to Field Extrapolation Dietary study was long term, low dose, and
simulated year-round exposure. However, the
study was not a two generation study, d3 =0.5
- Co-contaminants
-Endpoint Clarity
Co-contaminants were not present in the
study, d4 = 0
Weight gain, and reproductive effects in
bobwhite study are mechanistically and
ecologically clear, d5 =0
Uncertainty Factors for a Generic Trophic Level 4
Predator Exposed to PFOS (Cont.)
UNCERTAINTY FACTORS NOTES
Modifying Factors (D)
- Species Sensitivity
While bobwhite quail were shown to be
more sensitive than mallards, the
magnitude of the differences was
minimal. No other avian data are
available, d6 = 1
- Organ Ratios
Concentration in liver and serum were
directly measured, d7 = 0
- Intraspecies Variability Adult, egg and juvenile life stages were
evaluated in the study,
d8 = 0
Total Modifying Factors
D= (0+0+0.5+0+0+1+0+0) = 1.5
Uncertainty Factors for a Generic Trophic Level 4
Predator Exposed to PFOS (Cont.)
UNCERTAINTY FACTORS (UF)
Values
Inter-taxon Extrapolation (A)
Exposure Duration (B)
5
1
Toxicological Endpoint (C)
3
Modifying Factors (D)
Overall UF for TRV
1.5
UF= (5 x 1 x 3 x 1.5) = 22.5
Derivation of Uncertainty Factors
Calculate a Predicted No Effect
Concentration (PNEC) for Avian Species
Exposed to PFOS
OECD methods
• Uncertainty Factors based on “Technical guidance Document in Support
of Commission Directive 93/67/EEC on risk assessment for newly notified
substances and Commission regulation (EC) No. 1488/94
• Final uncertainty factor (UF) based on:
- Chronic reproduction studies conducted with two avian
species UF= 30
- NOAEL values were not determined for the most sensitive
toxicological endpoint in bobwhite quail. UF = 2
• UF = 30 x 2 = 60
Derivation of Safe Water Concentrations for the
Protection of Wildlife
Test Dose
x BW
Overall Uncertainty Factor
Wildlife Value =
WL
W + ∑ FTLi xBAFTLi
(
)
Derivation of Safe Water Concentrations for the
Protection of Wildlife
• WV = Wildlife Value in milligrams of PFOS per liter (mg/L)
• TD = Test dose or threshold dose in mg of PFOS per kg per day (mg/kg
body weight-day).
• UF = Overall Uncertainty factor interspecies, toxicological endpoint
and exposure duration extrapolations.
• BW = Average body weight in kilograms (kg) for the representative
species.
• FTLi = Species specific average daily amount of food consumed (kg/day)
for trophic level I
• W = Species specific average daily amount of water consumed (L/day)
• BAFWLTLi =Bioaccumulation factor for wildlife food in trophic level i.
For consumption of piscivorous birds by other birds, the BAF is
derived by multiplying the Trophic Level 3 BAF by the
biomagnification factor (BMF).
Avian Threshold Doses for PFOS
Liver
Egg Yolk
Threshold Average Daily Intake Serum
(mg PFOS/kg/d) ( μg PFOS/ml)( μg PFOS/g, wet wt)( μg PFOS/ml)
Dose
LOAEL
TRV
PNEC
a
b
0.77
35
21
62
0.034
1.6
0.93
2.8
0.038
1.7
1.0
3.1
Threshold dose for each end point is based on the geometric mean of female and male values.
The LOAEL based on the 10 ppm PFOS treatment in the bobwhite reproduction study.
Average daily intake in units of mg PFOS/kg body weight per day
TRV calculation based on an overall uncertainty factor (UF) of 22.5
PFOS Biomagnification Factor (BMF) for Avian Species
• Biomagnification Factor (BMF) needed to calculate a Wildlife Value (WV)
• BMF used to account for the accumulation of PFOS from piscivorous birds
consumed by upper trophic level predators (raptors)
• No Field Data are available to derive avian specific BMF for PFOS
• BMFs were estimated from chronic reproduction studies with mallards and
bobwhite quail and based on feed and tissues PFOS concentrations.
General BMF Equation:
Bird Tissue PFOS Concentration
BMF =
PFOS Concentration in Diet
Biomagnification Factor for PFOS in Avian Species
Avian BMF Calculation Assumptions and Criteria
• Assumed birds were at steady state
• Concentration data was not lipid normalized
• Male concentration data was used to estimate the BMF. Female data
was not used due to losses of PFOS during egg laying phase of study
• Liver concentrations were used to estimate BMF. Serum concentration
data was not used used due to the greater variability of this matrix
relative to that observed for liver in the same studies
• Assumed 100% assimilation of PFOS from diet
Biomagnification Factor for PFOS in Avian Species
Species
Feed
Liver
(ug PFOS/g) (ug PFOS/g)
BMF
Mallard
10
61
6.1
Quail
10
88
8.8
Geometric mean
7.3
Geometric mean of mallard and bobwhite quail BMFs used in the
calculation of wildlife values. BMF = 7.3
PFOS Bioaccumulation Factors
Bioaccumulation Factor (BAF) estimated from Bioconcentration
Factors (BCF) derived from laboratory studies
Laboratory Studies include:
- Bluegill (Lepomis macrochirus)
Whole body BCF = 3,614
(Drottar et al. 2001)
- Rainbow Trout (Oncorhynchus mykiss)
Carcass based BCF = 1,100
(Martin et al. 2003)
Assume that predominate route of PFOS accumulation by fish is
from water and not through food (BCF ~ BAF)
Geometric mean of both species is: BAF = 1,994
Derivation of Safe Water Concentrations
for the Protection of Wildlife
TD
WV =
UF
BAF
• WV = Wildlife Value in ng PFOS per liter
(ng/L)
• TD = Threshold dose (mg PFOS/kg bw/day)
• UF = Uncertainty Factor
• BAF = BCF x BMF x food consumption
Biomagnification Factor for PFOS in Avian Species
Species
Feed
Liver
(ug PFOS/g) (ug PFOS/g)
BMF
Mallard
10
61
6.1
Quail
10
88
8.8
Geometric mean
7.3
- BMF values calculated from the dietary chronic studies
- Geometric mean of mallard and bobwhite quail BMFs used in the
calculation of wildlife values. BMF = 7.3
- All measured values reported on a wet weight basis
Accumulation of PFOS by birds from water
BAF
BC
Water
F
BMF Threshold
Food
Dose
1,994 *
7.3
14,556
* BCF based on geometric mean of rainbow trout (BCF=1,100) and bluegill
(BCF=3,614)
Surrogate Avian Species Used in Wildlife Value
Estimates
Herring Gull (Larus argentatus)
• Order Charadriiformes, Family Laridae
• Feeds on a variety of foods including fish, crustacea, molluscs,
insects, small mammals and birds, and garbage
Bald Eagle (Haliaeetus leucocephalus)
• Order Falconiformes, Family Accipitridae
• Opportunistic feeder that consumes fish, birds, and small mammals
depending on availability
Belted Kingfisher (Ceryle alcyon)
• Order Coraciidormes, Family Alcedinidales
• Generally feeds only on fish but when available, will also consume
crayfish.
Exposure Parameters for Three Surrogate Avian
Species Identified for Deriving Wildlife Values
Species
Herring gull
Adult
Body
wt. (kg)
Water
ingestion rate
(L/day)
Food ingestion rate of
each prey in each
trophic level (kg/day)
Trophic level of prey
1.1
0.063
TL3: 0.192
Fish: 90 (TL3: 80; TL4: 20)
TL4: 0.0480
Other: 10
(% diet)
Other: 0.0267
Bald Eagle
4.6
0.160
TL3: 0.371
Fish: 92 (TL3: 80; TL4: 20)
TL4: 0.0929
Birds: 8: (PB: 70; other: 30)
PB: 0.0283
Other: 0.0121
Belted
Kingfisher
0.15
0.017
TL3: 0.0672
TL3: 100
Note: TL3 or TL4 = trophic level 3 or 4 fish; PB= piscivorous birds; Other = non-aquatic birds and
mammals
PFOS Wildlife Values
Concentration for Avian Species
Species
Herring Gull
Wildlife Value
(μg PFOS/L)
0.079
Bald Eagle
0.026
Kingfisher
0.038
Geometric Mean
0.043
Effects Ranges: Birds/Water
3,797 ng/L – Lethal to Adults
1,725 ng/L – Subtle effects on testes without any effects on survival,
growth or reproduction of quail (LOAEL)
TRV: 50 ng/L – No effects, includes safety factor of 36 (EPA GLI)
PNEC: 30 ng/L – No effects, includes safety factor of 60 (OECD)
Assessment of Current Concentrations of PFOS
Water concentrations compared to:


Protection of aquatic life
Protection of predatory birds and mammals
Tissue concentrations



Blood
Liver
Egg
Bird Egg
MOS
Minimum = NIL (0.51)
Geomean = 13.38
Exceedence
Cormorant MI
G.H. Owl MI
Caspian Tern MI
N = 60
TRV 1.7
Frequency
Minimum = 0.008
Maximum = 3.35
Geomean = 0.127
20
15
10
5
0
0.01
0.1
1.0
10.0
PFOS (mg/ml, ww)
Bird Liver
MOS
Minimum = NIL (0.34)
Geomean = 8.61
Exceedence
Bald Eagle MI
B. Pelican MS
C. Loon NC
R.T. Loon NC
B.B. Gull NC
G. Egret FL
B.C.N.H. CA
Osprey FL
Cormorants Japan
N=219
TRV= 0.6
50
Frequency
Minimum = 0.001
Maximum = 1.740
Geomean = 0.0697
60
40
30
20
10
0
0.001 0.01
0.1
1.0 10.0
PFOS (mg/kg ww)
Bird Blood Plasma
Minimum = 0.001
Maximum = 2.57
Geomean = 0.108
MOS
Minimum = NIL (0.38)
Geomean = 8.98
Exceedence
Bald Eagles
AL, WI, SC
Frequency
16
N = 61
TRV 0.97
12
8
4
0
0.001 0.01 0.1 1.0 10.0
PFOS (mg/kg, ww)
Water vs. Bird TRV
60
MOS
Minimum = NIL (0.022)
Mean
= 2.80
Exceedence
FL, AL
Lake Ontario Canada
TRV = 50.0
50
Frequency
Minimum = 0.00004
Maximum = 2210
Mean
= 17.87
40
30
20
10
0
0.001 0.1 10 1000
PFOS (ng/L)
Sampling in South Bohai coastal rivers of China.
PFCs in Estuarine and Coast of North Bohai Sea
North Bohai Bay, especially
Liaoning Province
PFCs in Water from North Bohai Bay
Potential Ecological Risk to Aquatic Animals
General Conclusions PFCs-China
 Significant concentrations of PFCs were found in water
(mean: 18.4 ng/l) and biological samples (fish: 265 ng/g dw).
 While concentrations of PFCs in soils and sediments were
less.
 The predominately detected compound was PFOS, with a
maximum of 30.9 ng/l in water and 791 ng/g dw in fish.
 PFCs were significantly greater in Liaohe River system, which
suggests point sources in this urbanized and industrialized
region.
 PFOS concentrations in water and biota were both less than
the reported threshold concentrations.
General Conclusions
Concentrations in water or tissue are generally
less than the thresholds
Thresholds are exceeded only in a few
industrial areas
Thresholds are conservative (protective) such
that exceedences do not necessarily indicate the
potential for population level effects
Nanjing
Questions ???????
Thank You!!!!! Questions????
 John P. Giesy, Ph.D.
 Professor & Canada Research Chair in Environmental
Toxicology
 Dept. Veterinary Biomedical Sciences & Toxicology
Centre
 University of Saskatchewan
 Saskatoon, SK, Canada
 Tel: (306) 966-2096 Fax: (306) 931-1664
 Email: John.Giesy@usask.ca
 WebSite:
http://ww.usask.ca/toxicology/faculty_profiles/giesy_john.html
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