Document OzLpmGvLy1DZo6x3XmOeGJMJe
A(U2rO51%
PFOA and Associated Salts
Ecotoxicity Elements Title
Activated Sludge R espiration Inhibition T es t - F C -1 0 1 5 -X Acute Toxicity o f F C -1 01 5 to the Fathead Minnow, Pim ephales prom elas Growth and Reproduction Toxicity Test with F C -1 01 5 and the Freshw ater Alga, Selenastrum capricornutum
Acute Toxicity o f F C -1 0 1 5 to the Daphnd, D aphnia m agna
Laboratory or Author
3M Env. Lab T .R . Wilbury Laboratories, Inc, M arblehead, MA T .R . Wilbury Laboratories, Inc, Marblehead, MA T .R . Wilbury Laboratories, Inc, Marblehead, MA
Completion T y p e Date
!
Robust summary,
copies o f data
4/25/96 sheets
5 /1 5 /9 6
Robust summary, final report
5 /1 5 /9 6
Robust summary, final report
5 /1 5 /9 6
Robust summary, final report
Sum m ary Reports
T itle
Technical Report Sum m ary - Final Com prehensive Report: FC 143
Laboratory or Author
3M Env. Lab
Com pletion Date
3 /2 3 /7 9
Type
Robust summary, technical report
i 1
t
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STUDY SUMMARY FOR W ORK PERFORMED DURING 1977-1979
TEST SUBSTANCE
__________________________________________
Id e n tity :
Perfluorooctanoic acid, ammonium salt; may also be referred to as PFOA ammonium salt, Ammonium perfluorooctanoate, PFO, FC116, FC-126, FC-169, orFC -143. (Octanoic acid, pentadecafluoro, ammonium salt, CAS # 3825-26-1)
Rem arks: The subject material is FC-143. It's purity was not sufficiently characterized at the time these tests were conducted, though current information indicates it is a mixture of 96.5 - 100% test substance and 0 3.5% C6, C7, and Cgperfluoro analogue compounds.
The attached is an overview created in 1979 for studies completed from 1977 to 1979. Robust summaries have already been submitted for many o f these studies. Others have not been summarized due to the fact that the original studies were not found.
S T U D IE S
___________________________________________
W ater solubility; degradation; soil sorption; partition coefficient; aquatic tox
Rem arks: The attached document includes a solubility value and an octanol/water partition coefficient value that could not be confirmed through our available archived reports. Their origin is therefore unknown.
DATA QUALITY___________________________________________________
Reliability: These studies have varying Klimisch rankings, though most would be designated a "3". In many cases actual concentrations were not measured. The value was determined by indirect measurement (e.g., bioconcentration analyzing for F-) or using nominal concentrations (e.g., aquatic toxicity). Often the test procedure methodology was not noted. In some cases, the analytical methodology itself was questionable. Additionally, these studies lack sufficient characterization of the test substance purity.
R E F E R E N C E S ____________________________________________________
3M Technical Report "Final Comprehensive Report: FC 143." A. N. Welter, Project 9770612643, Report number 012, March 23, 1979
OTHER___________________________________ ;_______________________
Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133
Last changed: 5/25/00
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TECHNICAL REPORT SUMMARY
Date
Harch 23, 197!
TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN
(Im portant - I f report is printed on both sides o fp eper, send tw o copies to TCC.)
D ivision
Environmental Laboratory (EE & PC)
P roject
Fate of Fluorochemicals
R eport Title
Final Comprehensive Report: FC 143
To
R. A. Prokop
Dapt. N um ber
0535
P roject N um ber
9970612643
deport Number
012
Welter
Notebook Referanca
SECURITY ^
D Open
B Closed
KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.)
CURRENT OBJECTIVE:
Final Report
3M CHEMICAL ^ R E G IS T R Y
09362
No. of Pag* Including C ovar*!eet
11
New Chemicals Reported
Yet
S No
Encompasses all work performed during the period; 1977-1979.
EE&PC - Div. Fluorochemical (Analytical) (Aquatic) (Degradation) (soil) Toxicity
REPORT ABS TRACT: (200-250 words) This abstract information is distributed by the Technical Communications Center ti alert 3M 'ers to Company R A D .
c: D.L. Bacon R.L. Bohon Y.Pothapragada
Information Liaison
lnitials: '"JC<J
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INTRODUCTION
The rationale for performing environmental effects2tudies on fluorochemicals has been discussed previously^ '
The subject fluorochemical of this report is FC 143, a anionic surfactant, which has the potential for widespread distribution in the environment as this material is used by the Teflon(R) coating industry, both domestically and internationally. FC 143 chemically is the ammonium salt of perfluoro-octanoic acid.
This material is a white granular powder having a molecular weight of 431 and the chemical structure shown below.
C 7 F_15_ COO'NH,4
-PC 143
This report consolidates all available information in the areas of water solubility, partition coefficients, degradation, soil sorption and aquatic toxicity. The probable environmental risk of FC 143 is defined.
METHODS
Water solubility, biodegradation and soil sorption methodology's have been the subject of technical reports'1-3 .
A) Aquatic Toxicity Testing
The testing protocols utilized for this study were modeled after that described by TISEPA (1975)' .
1. Bluegill Sunfish
The bluegill sunfish (Lepomis maarochirua) used in this study were obtained from a private hatchery.a Stock fish were held in fiberglass holding tanks filled with carbon-filtered well water maintained at 14-15C. A daily photoperiod of 16 hours light and 8 hours dark, with a 30-minute transition period, was maintained throughout the acclimation and testing period. The fish were fed Tetra-MinD daily, food being withheld 48 hours prior to and throughout the test period. Fish were acclimated for 14 days prior to testing.
Acute short-term (96-hour) static aquatic bioassays were performed on FC 143, lot 340. Carbon-filtered well water of known composition was used as the diluent. All glass aquaria, 35 x ?0 x 70 cm, containing 16 liters of water or water plus FC 143 comprised a study chamber.
^ a l e Fattig Fish Farm, Brady, Nebraska Commercial fish food of known composition.
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Twenty bluegill sunfish, (Lepomis maoroohirue) , uniform in size and weight, were tested at each concentration of FC 143. Test fish were randomly assigned to various test chambers within 30 minutes following FC 143 addition. Test temperatures were maintained at 1 9 - 1C. Mortality, temperature, dissolved oxygen level, and pH of all test solutions were measured at 24-hour intervals or until total mortality had occurred. General observations relative to behavioral or erratic swimming patterns were similarly recorded when appropriate. Organisms used in this study were considered to be generally healthy and free of disease.
2. Aquatic Invertebrates - 48 hour Static LCg^
i Daphnia magna, twenty organisms per test chamber, were exposed to FC 143, lot 340 at varying concentrations for 48 hours. " F i r s t instars were counted and placed in carbon-filtered well water, with chemical added and solubilized prior to the addition of the Daphnia magna.
Invertebrate test concentrations were 7.5, 10, 18, 32 and 56 mg/1 while vertebrate test concentrations were 420, 560, 750, 1000, and 1350 mg/1.
LC50 values with 95% confidence limits were calculated using theuUSEPA (Duluth) Probit computer program on the 3M Trac system.
RESULTS
Table 1 lists water solubility and partition coefficient data obtained using FC 143, lot 340. This material is extremely water soluble, >20 g/1. FC 143 where added to water appeared to form a gel although further additions of FC 143 were similarly absorbed. This material is slightly lipophilic as evidenced by a partition coefficient of 5. Based on these data it can be concluded that FC 143 would not biocogcentrate to an appreciable extent in the environment. Chiou e al'0 ' have described an empirical relationship between the water solubility of a chemical and its bioconcentration factor. In their system, the ascribed error is considered to be approximately one order of magnitude. When applying data generated for FC 143 to this proposed relationship, this material would be projected to possess a bioconcentration factor of approximately 10.
TABLE 1
Water Solubility and Partition Coefficient of FC 143
Parameter
Test
Results
Solubility
Coarse method
>20 g/1
id
Partition Coefficient n-octanol/water
5
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FC 143 was found to be completely resistant to biodegradation under the test conditions employed1 . The 2 1/2 month shake culture biodegradation study utilized microbial test cultures derived from activated sludge inocula obtained from the Chemolite, Decatur and Twin Cities Metro Plan waste treatment system. During the time course of this study a strain of microbes which could degrade FC 143 did not develop, hence this material would be expected to persist in the environment for extended periods of time unaltered by microbial catabolism.
Soil sorption studies have shown that approximately 5%,
(range 2-7%), of the FC 143 present in a water solution was
adsorbed to Brill sandy loam soil (Table 2)1 . Conversely,
approximately 80% of the amount of FC 143 adsorbed to this soil would be desorbed after three (3) desorption trials (Table 2). Mobility ,gf_ FC 143 was calculated using the scheme
described by Hamaker1 ' whereby adsorption coefficients are converted to a constant, K , which reflects the organic
content of the soil. Thiso c investigator has shown that the
relative mobility of a group of pesticides could be determined in this fashion and that the K value could be correlated
with pesticide mobility. In applying this test, FC 143 had
a K value of 17, being slightly less mobile than chloramben,
8f 12-8, wjj^h was the most mobile pesticide based on
Haffiaker's work10J.
'
Table 2 Soil Sorption Tests on FC 143
Parameter
Test
Solution
Results
Soil Sorption Adsorption
Water
^ 5%, range 2-7%
Desorption
Water
80% of amount adsorb
Koc 17
Results of the acute static aquatic tests are tabulated (Table 3). Based on the aquatic toxicity criteria established by NIOSH, FC 143 would be considered practically non-toxic to the vertebrates and invertebrates used in this test^ . It is to be noted that the invertebrate data correlate well with those data obtained when testing fresh warm water^species. This correlation has been observed repeatedly115"1 .
Egg-fry studies were contracted to EG&G Bionomics Laboratory and their results comprise Tables 4 and 5. These studies were undertaken to assess the effect of FC 143 at sublethal levels on hatchability, survival, weight and length changes (Table 4). It is generally accepted that the immature or young stages of an aquati.c species are quite sensitive indicators
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Table 3 FC 143, Results of 96 Hour Acute Static Testing
Limits
Test Organisms
96 Hr.LC,n Lower, mg/1 Upper mg/1 mg/1 50
Bluegill Sunfish
569
500
636
Daphnia magna
63?.
570
699
63? 570
698
Table 4 Percentage Egg Hatch, Percentage Survival, Total Length and Wet Weight of Fathead Minnow Fry (Pimephale8 promelae) during Exposure to varying concentrations of FC 143 ' 30 Days Post Hatch
Concentration Hatch % Survival % Length mm Weight mg mg/1
100
96 85
20.5
59.5
50
92.5
94
20
62.5
25
99
92.5
21
72
12.5
90.5
97.5
21
71
6.2
94.5
93
?1
69
Control
96.5
93.5
20.5
68.5
aWork performed by EG&G Bionomics Laboratory, Inc.
^Summary table submitted to Environmental Laboratory, 3M, St. Paul, as part of final report.
of chemically induced toxicity. In the parameters under investigation no statistically significant differences were obtained. At the highest FC 143 concentration tested, 100 mg/1, reductions were recorded in survival percent and weight 30 days post hatch. Although these data are suggestive of a latent onset in the development of cumulative toxicity, the dose levels of FC 143 at which these phenomina were observed far exceed, (several orders of magnitude), the environmental concentrations of FC 143.
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Based on the results of the histopathological examination, a 30-day exposure to 100 mg/1 FC 143 did not contribute to abnormal histopathology (Table 5). Both groups of organisms exhibited fatty liver changes, 6/10 controls and 5/10 treated organisms. Similarly, gill hyperplasia was seen in both groups, 3/10 controls and 2/10 treated fry.
Table 5
Histopathological Examination of Fathead Minnow Fry (Pimephales prometas) exposed 30-days to 100 mg/1 FC 143a D
Test Material
Numbet of Observations
Histopathological Findings
Control
10 6/10 fatty liver changes 3/10 normal 3/10 gill hyperplasia
100 mg/1 FC 143
10
5/10 normal 5/10 fatty liver changes 2/10 gill hyperplasia
DISCUSSION
The primary purpose of this report is to provide a single source for all environmental data generated relating to FC 143 and to provide an analysis of potential environmental risk.
In developing this analysis two model types will be discussed: (1) a schematized closed system environment and 2) a practical model based on use of FC 143 at a manufacturing site and consumer product usage.
1. Closed System
The environment can be considered to be a closed system, schematically represented as:
Chemicals entering this system might establish an equilibrium between two or all three compartments, remain confined within a single compartment or pertubate all phases of the depicted cycle.
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Specifically we can represent the Impact of FC 143 in the following manner:
No Photodegradation Air
Volatility.
Soil
No degradation
Volatility Rate?
rain
80%
fater? of adsorb
5% adsorbed
_ Water >20 g/1 (gel)
Sediment, No biodegradation sorption phenomena as seen in soil
As illustrated, FC 143 enters the environment primarily by means of the waterways and secondarily via the terrestrial ecosystem and atmosphere. This material does not adsorb permanently to either soil and/or sediment, remaining however in the water compartment. It is not known whether FC 143 is volatile, a fact which assumes importance in light of.the finding that FC 143 does not undergo photolysis. * Based on the foregoing, the waterways apparently are the environmental sink for FC 143. Intermediate receptors have not been identified.
2. Manufacturing and Consumer Model
The following construct illustrates various pathways wherein FC 143 may enter the environment at the processing site.
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PC 143 Anionic Surfactant
l
Manufacturer
l' R
Photographic Industry---Process Teflon Coating
Constmer
Liquid
Waste Treatment I I Effluent
Outfall t
Wastes
Sludge
Landfill
Leach Volatile
I M r / I Soil **2 HgO
Solid
incinerate
L
Ash
Landfill
l
Soil l'
Food Chain
I
2
ZTvQO
8
The above figure depicts projected pathways wherein FC 143 might enter thevenvironment. In discussing use of FC 143 by the Teflon' `'coating and photographic industries with Dr. M. Pike, Commercial Chemical Division, I was informed that to their.knowledge no FC 143 wastes would be generated by the Teflon^ ^coating process. Based on this information, I have depicted this no waste situation by the following Sign;
In discussing the manufacture of FC 143 with Jerry Hoffer, Chemolite, a similar observation to that outlined above was made.
In view of the above we can project the environmental concentration under conditions wherein all FC 143 manufactured is lost to the environment.
Since waterways are the environmental sink for FC 143, a simplistic model utilizing a single point source for FC 143 and a river would enable one to project an estimated environmental concentration for FC 143 under a worst case situation.
We have made several assumptions which are considered basic to this simplistic model:
1) Total production is at Chemolite and all FC 143 produced is discharged.
2) No FC 143 is removed by the treatment facility.
3) All effluent is discharged into the Mississippi River.
4) FC 143 is discharged uniformly.
5) River flow and all other parameters are constant * hence not subject to seasonal and/or climatic perturbations.
The formulae used in these projections include:
1) MG/min
(River Flow, CFM)(Conversion,gal/ft^)(Time,min) Production, per annum
2) MG/min X 1440 MG/Day
3) Lbs/day = (mg/1 x wt. lbs. HgO per gal)(MG/Day)
Mississippi River flow at Hastings, MN, based on a 10 year low flow record is 10,000 CFS.
The total 5 year production figures were provided by D.R. Ricker, Commercial Chemicals Division. In utilizing these figures an estimated environmental concentration of FC 143 in the Mississippi River below Chemolite was calculated. During the period 1973-1978, the EEC for FC 143 was calculated
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to be 1.6 Hg/1 at Hastings, Mn., while the EEC projected for the period 1978-1983 is projected at 2.4i/g/l. Since the water compartment is the environmental sink for FC 143, it is determined that at the present and projected levels of production FC 143 will not present an unreasonable environmental risk under worst case situations.
CONCLUSIONS
Under the test conditions employed in characterizing selected physicochemical and environmental properties of FC 143 it has been determined that this material
1) is extremely water soluble, forming a gel at 20 g/1. 2) has an n-octanol/water partition coefficient o f ^ S 3) is resistant to microbial degradation 4) is extremely mobile in Brill sandy loam soil 5) in an egg-fry study did not affect hatchability,
survival, length or weight following a 30 day exposure to FC 143 at sublethal levels to a statistically significant degree. Similarly, no adverse effect was noted on tissues examined for evidence of chemical induced pathology. 6) is to be found primarily in the water compartment, hence its environmental sink. No specific intermediate receptors have been identified. 7) would have an estimated environmental concentration of approximately 1.6-2.4j7g/l, under conditions wherein all FC 143 were manufactured at Chemolite and discharged into the Mississippi River. 8) will not present an unreasonable environmental risk based on present and projected production levels, usage patterns etc.
BIBLIOGRAPHY
1. Mendel, A., Technical Report: "Analytical Methodology and Support", January 17, 1979.
2. Reiner, E . A . , Technical Report: "Biodegradation Studies of Fluorocarbons - III", July 19, 1978.
3. Welsh, S.K., Technical Report: "Adsorption of FC 95 and FC 143 on Soil", February 27, 1978.
4. US/EPA - Methods for Acute Toxicity Test with Fish, Macro-invertebrates and Amphibians, Ecological Research Series 660/3-75-009, 1975.
5. Chiou, Cary T . , Virgil H. Freed, David W. Schmedding, and Rodger L. Kohnert: Partition Coefficient and Bioaccumulation of Selected Organic Chemicals, Environmental Science and Technology, 11(5): 475-478, 1977.
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6. Hamaker, J.W., "Interpretation of Soil Leaching Experiments" in Chemicals, Human Health and the Environment, A Collection of Dow Scientific Papers, Vol. 1, Dow Chemical USA Midland, Michigan 48640.
7. Registry of Toxic Effects of Chemical Substances, '76 Edition, Christensen, H.E., and E.J. Fairchild, Eds. p.xv and Ci, US Department of Health, Education, and Welfare; National Institute for Occupational Safety and Health, Washington, D . C . , June, 1976.
8. Welter* A . N . , Technical Report: Aquatic Toxicity Studies, FC 214-30 lot 566, February 16, 1979.
9. Welter, A . N . , Technical Report: Aquatic Toxicity Studies, FC 232 lot 610, January 17, 1979.
10. Welter, A . N . , Technical Report: Final Comprehensive Report, FC 95 March, 1979.
11. Todd, J.W., Technical Report: FC 143 Photolysis Study using Simulated Sunlight, February 2, 1979.
12. Welter, A.N. Technical Report: Final Comprehensive Report on FM 3422, February 2, 1979.
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