... , ., . A . . . ... ~ ... -. . _, .. . P. ,.. - .. -. . I ., ___.. . .. I. . . . ..-d.”. .. >.-.... I 1 . .I .A,.. . . .. ..-, . I. ... ...,.,.,..., .. ... 

March 17, 2000 

Document Processing Center (7407) 

(Attn: Section 8(e) Coordinator) 

Room G-099 

OPPT 

US EPA 

401 M Street, SW 

Washington, DC 20460 

& EPA-OTS 

000833779X 

RE: TSCA 8(e) SUPPLEMENTAL NOTICE: Sulfonate-based Fluorochemicals - 

Docket Nos. 8EHQ-1180-373; 8EHQ-1180-374 

To Whom It May Concern: 

Enclosed you will find a white paper entitled “Sulfonated Perfluorochemicals in the 

Environment: Sources, Dispersion, Fate and Effects” prepared by 3M. 3M is submitting 

this document as a supplement to our original 8(e) submissions on sulfonate-based 

fluorochemicals. 

If you have any questions, please feel free to contact me. 

Best regards, 

William A. Weppner, Ph.D. 

Director 

Environmental, Health, Safety & Regulatory Affairs 

Specialty Material Markets Group 

3M Center, Bldg. 236-1B-10 

St. Paul, MN 55144 

C: Enc. 

OOOOOS 

J 
Sulfonated Perfluorochemicals in the Environment: 

Sources, Dispersion, Fate and Effects 

Prepared by 

3M 

March 1,2000 

1 
Table of Contents 

1.0 PREFACE 

2.0 EXECUTIVE SUMMARY 

3.0 INTRODUCTION TO FLUOROCHEMICALS 

4.0 PHY S ICA L-C H EM I CAL PROPERTIES 0 F FLU0 ROC H EM ICALS 

5.0 ANALYTICAL TEST METHODS FOR FLUOROCHEMICALS 

6.0 SOURCES OF FLUOROCHEMICALS 

6.1 Manufacturing Waste Streams 

6.1 1 Waste Stream Characterization 

6.12 Air 

6.13 Wastewater 

6.14 Solid Waste 

6.2 Supply Chain Waste Streams 

6.3 Releases from Waste Treatment and Disposal Methods 

7.0 ENVIRONMENTAL TRANSPORT AND DISTRIBUTION 

8.0 ENVIRONMENTAL SAMPLING FOR FLUOROCHEMICALS 

8.1 Environmental Levels 

8.1 1 Historical Data 

8.12 Recent Analyses of Wild Birds and Fish 

8.13 Testing of Fishmeal Used in Rat Studies 

8.14 Plant Site Analyses 

8.15 Biosphere Sampling 

8.2 Human Exposure Levels 

8.2 1 Multi-cities Sampling 

8.22 Carpet Use Studies 

8.23 Paper and Packaging Studies 

8.24 Exposure Scenarios 

4 

5 

9 

13 

17 

19 

20 

22 

22 

22 

23 

24 

24 

25 

27 

27 

27 

27 

31 

31 

32 

32 

33 

33 

33 

33 

2 000003 
9.0 ENVIRONMENTAL TRANSFORMATION/DEGRADATlON OF 

FLUOROCHEMICALS 

9.1 Hydrolysis Studies 

9.2 Photolysis 

9.3 Atmospheric Studies 

9.4 Biodegradation Studies 

9.4 1 Microbial Studies on Perfluorochemicals 

9.42 Biological Transformation 

9.43 Optimizing Conditions for Biodegradation 

10.0 ECOTOXlClTY TESTING OF FLUOROCHEMICALS 

11 .O COMPREHENSIVE PLAN TO ASSESS ENVIRONMENTAL 

EXPOSURE 

11.1 Plan Overview 

11.2 Component 1: Characterize Fate and Transport Properties 

11.3 Component 2: Estimate Releases 

11.4 Component 3: Characterize Distribution in the Environment 

11.5 Component 4: Estimate exposure 

12.0 ECOTOXICITY DETERMINATIONS 

13.0 ECOLOGICAL RISK EVALUATION 

14.0 REFERENCES 

34 

36 

37 

37 

38 

38 

39 

39 

40 

45 

45 

48 

48 

48 

49 

49 

50 

51 

3 000004 
required, along with method validation and oversight at levels comparable to those used 

in the 3M Environmental Laboratory. 

Continual improvements are sought in analytical methods as the ability to detect trace 

quantities is essential for a number of reasons such as: screening laboratory supplies and 

environments prior to initiating toxicity testing, for detecting environmental exposure, for 

determining sources of perfluorochemicals, and for understanding perfluorochemical 

metabolism kinetics. 

6.0 Sources of Fluorochemicals 

A few fluorochemicals occur naturally in the biosphere, produced by biological and 

geochemical processes. Several green plants produce monofluoroacetic acid 

(CH2FCOOH). Some hgi produce monofluorinated organics. All fluorochemicals 

produced biologically contain only one fluorine atom. Volcanoes and other geological 

processes produce tetrafluoroethylene, sulfur hexafluoride, perfluoromethane and some 

chlorofluorocarbons in small quantities. 

Most fluorochemicals in the environment are present as a result of human manufacture 

and use. Releases of fluorochemicals into the environment can occur at each stage of the 

fluorochemical product's life cycle. They can be released when the fluorochemical is 

synthesized, continue during incorporation of the fluorochemical into a product, during 

the distribution of the product to users, during the use of the product by consumers, and 

during disposal practices at all of these stages. 

3M is using a two step approach to estimate environmental releases of fluorochemicals.. 

The initial efforts have focused on determining waste generated; the second step will 

focus on determining releases. Ths two step approach is necessary since not all waste 

produced will result in a release to the environment. Much of the waste that is generated 

is destroyed through treatment or otherwise actively managed to prevent release into the 

environment. Efforts are also being made to further tighten such controls. 

3M has estimated waste generation from each of the following life cycle stages: the 

manufacturing processes, the supply and distribution chains, customer uses and 

producdwaste disposal. 

For ease in comparing waste stream data, wastes are described in term of "PFOS 

equivalents." PFOS equivalents are the weight of C,F,,SOZ present in a sulfonated 

perfluorochemical product. It is the mass of PFOS molecules that would be formed in the 

breakdown of the product. The assumptions of complete breakdown to PFOS of each 

sulfonated perfluorochemical product, in the year in which the product was sold, are 

unlikely "worst-case" assumptions. Various degradation testing finds a broad range of 

19 

000019 
product degradation rates. Some polymeric products appear to be quite stable in the 

environment, with long half-lives; other polymers hydrolyze quickly. 

6. I Manufacturing Waste Streams 

The assessment of the release of sulfonated perfluorochemicals into the environment 

begins with manufacturing waste generation. Some waste streams, such as wastewater 

discharge or disposal of off-spec products, can be anticipated and controls provided. 

Other waste can be generated during any of the steps required to produce the 

fluorochemicals and manufacture the product. 

The greatest production of the parent fluorochemical product, POSF, occurs at the 

Decatur, Alabama plant. Here POSF is created in electrochemical cells and undergoes 

numerous steps to convert it into final products. Salts of PFOS are also manufactured at 

the facility. Because of its production volume, the Decatur facility has been the focus of 

manufacturing waste stream studies. Understanding waste generation and how wastes are 

managed and disposed of provides a better understanding of potential releases into the 

environment. That understanding will help to identify opportunities for reductions in 

such releases. 

The manufacturing process for sulfonated perfluorochemicals is complicated. There are 

more than 600 intermediate manufacturing steps associated with the production of POSF 

and POSF-based products. This translates into hundreds of process steps that require 

venting or that generate wastewater or solid waste. Although the manufacturing process 

attempts to capture, reuse, and recycle most fluorochemicals as desired product material, 

until recently, the unique chemistries created in each step of the process could not be 

analyzed precisely to confii composition and to quantify amounts. The manufacturing 

process is dynamic, with rapidly changing matrices and many process steps. Ongoing 

process optimization activities continuously change the waste stream profile. 

Progress has been made in analytical techniques. In 1997, analytical laboratory 

techmques and methods could quantitatively identify the presence of only one 

fluorochemical analyte in a wastewater matrix. In 1999, improved analytical techniques 

and methods were developed for additional fluorochemical analytes in a wastewater 

matrix. 

Advanced field monitoring technology has been developed based on Fourier Transform 

Infrared spectroscopy (FTIR). This field tool has been used to detect where emissions to 

air are occurring during the manufacturing process and to evaluate whether a process 

change or a control technology can decrease the release. 

20 

Q00020 
As better analytical techniques become available, efforts are being made to: 

- characterize the major manufacturing processes generating fluorochemical 

- evaluate the effectiveness of fluorochemical removal technologies; and 

- provide better estimates of the amounts and kinds of fluorochemicals released to 

the environment from manufacturing processes and from waste treatment and 

disposal. 

waste streams; 

Waste Type 

Air Emissions 

Wastes sent off-site to Incineration 

Wastes sent off-site to Landfills 

Discharge to River after Wastewater Treatment 

Information currently available on waste streams generated during manufacturing 

processes at Decatur is derived from engineering calculations, air emissions modeling, 

and limited testing. An overall site materials balance was developed in the mid- 1990's 

using the amount of POSF-based solids initially created in the electrochemical cell and 

the amount of POSF contained in final products sold. The difference was an estimate of 

total waste streams generated during processing. The emission factors derived fiom this 

balance are used to calculate waste streams from production throughput. They are the 

basis for the estimates in Table 5. These estimates derived from the material balance are 

not precise, as this methodology can produce only rough approximations. 

Estimated PFOS Equivalents, Ibs 

19,000 

657,000 

380,000 

10.000 

The estimates in Table 5 reflect the most current information available and combine data 

derived from several sources: information from the mid-90s site balance, wastewater 

testing, waste disposal records, process models and supplemental information from 1997, 

1998 and 1999. Several changes in waste disposal and processing have been 

implemented since the mid- 1990s in order to reduce potential releases to the 

environment. Wastewater sludges that were once land applied on site are now sent to a 

municipal landfill for disposal. Off-spec materials that were discharged to wastewater are 

now shipped off-site to be incinerated. 

Table 5 helps to demonstrate the vast difference between volumes of wastes generated 

and volumes of releases to the environment, since the vast majority of wastes sent to 

incineration are destroyed in the incineration process and most material sent off-site to 

landfills will be effectively managed to prevent release to the environment. 

Table 5. Estimated 1998 Wastes Generated (in PFOS Equivalents) at the 

Decatur Manufacturing Plant 

- I 

Total Wastes 1 1,066,000 

Note: The 10,000 Ibs/yr of PFOS equivalents in the discharge to the river are estimated releases to the 

environment after wastewater treatment, not the Ibs/yr generated prior to treatment. 

21 000021 
More explanation of the estimates and efforts currently underway in air, wastewater and 

waste management follows. 

6.11 Waste Stream Characterization 

Updating material balances for the manufacturing process is an ongoing effort. Today 

process engineers use a model of process steps to calculate air emissions. New 

information is being compiled to aid with model operation and waste calculations. The 

effort to determine physicaUchemical properties for sulfonated perfluorochemicals will 

improve model inputs and waste stream calculations. Analytical technology is improving 

understanding of process chemistry 

Data from the process engineers' available material balances in the plant's reporting 

system have been used to supplement the earlier site balance in estimating air emissions. 

Initial reports fiom th~s system indicate that most site waste and air emissions result from 

fewer than 10 key steps in the early stages of POSF production. Process experts are 

examining these steps for ways to reduce or eliminate the impurities and wastes generated 

in the steps. 

In 1999, the Decatur plant installed a discotherm unit which heats the process materials, 

vaporizing and capturing the fluorochemicals. It will significantly reduce the 

organofluorides in the wastewater. This technology will operate to reduce emissions and 

waste at the source. It will make it easier to segregate waste streams and recycle 

fluorochemical wastes back into the process. 

6.12 Air 

3M engineers have reviewed specific process steps to determine what air emissions 

testing is feasible and appropriate. Testing of complex batch-processing systems is 

difficult due to quickly changing process conditions, venting pressures, and difficulty in 

isolating processes; however, characterization testing may be possible. The technical 

feasibility of performing this testing for two major processes is now under evaluation. 

Any emissions testing will require modifications to process vents and mitigation of 

potential safety hazards. About 80 separate venting points are associated with the 

equipment used to make sulfonated perfluorochemicals. 

6.13 Wastewater 

Analytical methods have been developed during the past year to better characterize the 

wastewater discharge from the site. The first testing of wastewater before and after 

treatment for specific fluorochemicals occurred at Decatur early in 1998. The testing was 

22 

000022 
limited and reflected operating conditions for a relatively short period of time (24 hour 

composite samples of influent and effluent for one week.) Some of the compounds that 

were identified in the wastewater were: a diester of EtFOSE alcohol, EtFOSE alcohol, 

MeFOSE alcohol, PFOS, FOSA, PFOSAA, PFOA and PFHS. 

In 1998 an interim carbon adsorption treatment system was installed as part of 

wastewater treatment. Data for the effluent estimate in Table 5 reflects this change. This 

treatment system treats the largest single source of fluorochemical-containing wastewater 

in order to remove PFOS and other sulfonated perfluorochemicals fiom the wastewater. 

Comparison of the results from sampling done in February 1998 with sampling done in 

the end of 1998 indicates the quantity of PFOS discharged to the Tennessee River 

declined by about half. In addition to the carbon adsorption system, in-process 

operational changes were made in off-spec product discharge procedures that also 

contributed to the reduction in PFOS content of the discharge to the river. 

The carbon system has been incorporated as a permanent upgrade of the wastewater 

treatment system. Monitoring indicates that with proper operation, carbon adsorption 

removes better than 99% of PFOS. Removal efficiency of other sulfonated 

perfluorochemicals varies, but the treatment appears to provide a high degree of removal 

for most. A number of wastewater streams currently going to sewers are in the process of 

being diverted to thermal treatment facilities for disposal. This will result in a reduction 

in the values listed in Table 5. 3M has conducted an extensive review of state-of-the-art 

technology for wastewater treatment. Various upgrades are currently being evaluated. 

The long term goal of wastewater treatment at the plant is to utilize source control and 

end-of-pipe treatment to remove nearly all sulfonated perfluorochemicals fiom 

wastewater prior to discharge to the river. 

6.14 Solid Waste 

An effort to identify all waste streams and their disposal methods is underway. Existing 

waste tracking is done on a site basis, so it is difficult to distinguish the particular streams 

with POSF chemistry. The mid-1990s emission estimates did not distinguish fmal 

disposal of the material lost fiom production, so site records were used in combination 

with the existing emission estimates to create the current picture of potential releases 

resulting from disposal. 

A review of plant records for 1998 has been completed to determine primary waste 

disposal locations for the site. According to Decatur plant records, 63% of the 

fluorochemical containing wastes are sent to incinerators, 33% of the wastes are disposed 

in hazardous waste landfills and 4% in non-hazardous waste landfills. 

23 

000023 
6.2 Supply Chain Waste Streams 

Waste Stream 

Air 

Wastewater 

Solid Waste 

Using sales data, 3M identified key products that contain a majority of the fluorochemical 

solids used in products. These products represent 89% of PFOS-equivalents sold by 3M 

in 1997 in the United States. Most commonly, these products were sold to commercial 

users who applied them or incorporated them into their products. 

Supply Chain Use Disposal 

2,600 3,300 0 

112,000 18 1,000 0 

59,000 377.000 1,262,000 

Using the information developed from sales, 3M estimated customer and end user waste 

streams (Table 6). These estimates are imprecise and based on several assumptions, but 

provide qualitative information. Using the chemical formula for PFOS, the 

fluorochemical solids were converted to "PFOS equivalents" for ease in estimating and 

comparing total losses of sulfonated perfluorochemicals and in comparing losses. The 

assumptions of complete breakdown to PFOS of each sulfonated perfluorochemical 

product, in the year in which the product was sold, are unlikely "worst case" assumptions. 

Product waste stream estimates are based on conservative, worst case assumptions about 

the generation of waste streams at supply chain facilities. These are often based on 

operator experience or engineering estimates rather than laboratory tests and can result in 

wide ranges in waste stream calculations. In estimating wastes, these data do not include 

loss of product residuals in the waste streams because information on the properties of 

residuals and processes at supply chain facilities and end user locations is inadequate to 

estimate this loss. 

Initial estimates associate waste streams generated from uses and disposal of the products 

by customers of each business unit. These estimates are helping to focus efforts in 

improving customer stewardshp practices and 3M product reengineering. As is evident, 

most of the waste generated is in the form of solid waste. 

Table 6. Customer and End User Waste Stream Estimates, 

PFOS equivalents, Ibs in 1997 

6.3 Releases from Waste Treatment and Disposal Methods 

3M and its consultant are gathering information on treatment and waste handling at 

several landfills and wastewater treatment plants which receive wastes containing 

sulfonated perfluorochemicals from the supply chain facilities and 3M manufacturing 

24 

000024 
facilities. Information is also being compiled on some of the largest wastewater treatment 

facilities and landfills in the United States in order to estimate the potential 

perfluorochemical releases to the environment fiom municipal disposal facilities not 

associated with the supply chain or manufacturing. 

Incineration is a favored disposal method because of its high rates of destruction of 

sulfonated compounds. 3M and its consultant are further evaluating the effectiveness of 

incineration for this purpose. The basic bond breaking chemistry of thermal destruction 

of POSF-based fluorochemicals, the destruction efficiencies of various 

technologies/situations such as municipal incinerators, and the products that could result 

from incomplete combustion are elements of the study. The study involves a review of 

3M and external literature to compile information on the formation and properties of 

thermal transformation products of sulfonated perfluorochemicals. 

Modeling will be used to determine to the extent practical, the releases to the 

environment from the amount of material sent to incineration, wastewater treatment 

plants, and landfills. 

The goals of the life cycle release studies are: 

- to identify important fluorochemicals based on volume of release, mode of 

- to provide values for use in modeling the distribution of fluorochemicals in the 

- to determine sampling sites and substantiate sampling results; 

- to predict which fluorochemical releases may result in exposure to humans and 

- to identify fluorochemicals that require further study as to their transport, fate 

release and chemistry; 

environment; 

the environment; and 

and exposure potential. 

7.0 Environmental Transport and Distribution 

The transport and fate of chemicals in the environment depends on many factors but 

principally on the interaction between environmental conditions (e.g. water, temperature, 

sunlight), and chemical properties (e.g. partitioning and reactivity). In the environmental 

area, eleven important fate and transport mechanisms for sulfonated perfluorochemicals 

have been identified for further study. These are: 

1. Partitioning between air and product, i.e. volatilization fiom product to air; 

2. Indoor air deposition; 

3. Accumulation on airborne particulates; 

4. Fate and transport to the stratosphere; 

25 

000025 
5. 

6. 

7. 

8. 

9. 

10. 

11. 

Accumulation at the surface water microlayer; 

Degradation (includes hydrolysis, photolysis and biodegradation); 

Dissociation in water; 

Uptake in plants; 

Uptake in fish; 

Uptake in birds; 

Efficiency of wastewater treatment systems. 

All of these fate and transport mechanisms have been linked to models. Modeling uses 

mathematical equations to simulate and predict real events and processes. Many types of 

models will be considered for use in this effort to evaluate sulfonated perfluorochemicals. 

Simple models of ecosystems, indoor air, and treatment systems (wastewater, landfills) 

are being used to screen for possible fate mechanisms, possible exposures, and possible 

sample detection limits. For example, one preliminary screening model suggests that top 

trophic level species such as fish eating birds and sea mammals should be examined. 

This finding was incorporated into the design of the biosphere sampling plan. 

Chemicals differ greatly in their behavior. The major differences in behavior of organic 

chemicals in the environment are due to physical-chemical properties. Although 

laboratory studies are underway on physicallchemical properties of PFOS, EtFOSE 

alcohol and MeFOSE alcohol, models are being developed to estimate the 

physical/chemical properties of other sulfonated perfluorochemicals. Ths will reduce the 

time and testing required to gather these data for use in environmental fate models. 

Fugacity is a concept that is used to describe the tendency of a compound to migrate in 

and between one environmental medium and another. Different media include air, water, 

soil, sediment, and biota, all of which together compose a dynamic, interactive system-- 

an ecosystem. Predictions about movement of a chemical must incorporate both its 

physical/chemical properties and the environment the chemical is in. For example, a low 

vapor pressure does not mean a chemical is not present in air. It may evaporate 

appreciably from water despite a low vapor pressure if it has low solubility in water. By 

entering the physical-chemical property data on a chemical into a fixgacity model of a 

generic or specific environment, it is possible to estimate general features of a chemical's 

likely behavior and fate. The output of these calculations can be presented numerically 

and pictorially. (6) 

Fugacity models will be used to predict fate and transport of sulfonated 

perfluorochemicals. Existing fixgacity models typically are based on experience with 

chlorinated organics. An internationally recognized modeling expert is developing/ 

adapting models to consider the unique properties of fluorochemicals. The goal of this 

modeling effort is to have a multimedia model or models to predict the fate of sulfonated 

perfluorochemical products and associated byproducts in a variety of ecosystems. 

26 

000026 
8.0 Environmental Sampling for Fluorochemicals 

8.1 Environmental Levels 

8.11 Historical Data 

In the late 197Os, 3M conducted a very limited number of studies to assess the 

distribution of fluorochemical constituents in the environment. Several freshwater fish 

species were tested for a number of fluorochemical compounds. In reviewing the data 

obtained from these studies in context of the current knowledge of the behavior of these 

materials, 3M has concluded that these historical data are highly questionable and may be 

misleading. Therefore, they are not included in this paper. The sections following 

present more reliable data and information collected using validated sampling and 

analytical methodologies. 

8.12 Recent Analyses of Wild Birds and Fish 

In analysis in 1999 of the plasma of ten fish eating birds, albatross nestlings at Midway 

Island in the Pacific Ocean and eagle nestlings in Minnesota and Michigan, PFOS was 

detected in each of the samples from eagles. The samples were collected in 1989, 92, and 

93 by Dr. John Giesy of Michigan State University as part of other surveys. Three of the 

albatross adults showed no detectable levels of PFOS (< I ppb detection level). 

Detectable, but not quantifiable levels of PFOS were found in the remaining albatross 

samples, both collected from birds less than a year old. All albatross samples were 

collected in 1992-93. See Table 7. These data are semi-quantitative, screening quality. 

As only a small amount (< ImL) of plasma was available to conduct the analyses, no 

matrix spikes were possible to estimate the method's recovery efficiency, but the methods 

used have been characterized in other, similar matrices. 

After the initial screening results on wild bird plasma, the plasma from a second set of 

wild birds was examined for the presence of PFOS. (See Table 7.) The source of the 

plasma was three sea eagles collected from the Baltic Sea and seven bald eagles collected 

from North America. The samples were collected in 1992-93 and again by Dr. John 

Giesy. PFOS was detected in all of the eagle plasma screened. These data are semiquantitative, screening quality. Two matrix spikes (250 ppb) prepared from eagle plasma 

were extracted and analyzed. Both showed >8O% recovery. 

27 

000027 
Table 7. Levels of PFOS in the Plasma of Wild Birds 

A I batross 

Albatross 

Albatross 

Sea Eagle 

Sea Eagle 

Sea Eagle 

Bald Eagle 

Bald Eagle 

Bald Eagle 

Bald Eagle 

Bald Eagle 

Bald Eagle 

Bald Eagle 

13 Dec 92 Midway atoll 8 years BLD 

13 Dec 92 Midway atoll 15 years BLD 

28 May 93 Baltic, Sweden nestling 125 

18 May 93 Midway atoll 0 BLQ 

27 May 93 Baltic, Sweden nestling 93 

23 May 93 Baltic, Sweden nestling 215 

23 Jun 92 L. Superior ONT nestling, F 494 

26 Jun 92 North America nestling 165 

28 Jun 93 North America nestling 198 

5 Jun 92 North America Adult, F 1047 

26 Jun 92 Devil’s Is., WI nestling, F 226 

22 Jun 92 Mud Creek,OH nestling, 37 1 

8 Jun 92 Carroll Twp, OH nestling 3 74 

BLQ= Below Limit of Quantitation (10 ppb) 

BLD= Below Limit of Detection (approximately 1 ppb) 

Following the bird plasma studies, sixty liver samples collected by the U.S. Fish & 

Wildlife Service from various species of birds were analyzed. The dead birds were 

collected at a variety of sites across the United States. They were not part of a controlled 

research study, but were selected for their location and diet. All but sandhill cranes are 

fish eating species. The sandhill cranes are an insect eating species. The purpose of the 

analyses was to determine if the presence of PFOS could be detected in these sample 

matrices. 3M believes that these sets of data are insufficient to draw conclusions with 

any statistical merit. The PFOS data in Table 8 are semi-quantitative, screening quality, 

with a margin of error estimated at - +30%. The limit of quantitation for PFOS is 6 ppb. 

28 

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Table 8. Analysis of Wild Bird Livers. 

Sample No. 

BLQ= Below limit of quantitation (6 ppb) 

Species Location PFOS ppb 

1 

2 

3 

4 

5 

Sandhill Crane Kearney, NE 41 

Sandhill Crane Keamey, NE BLQ 

Sandhill Crane Keamey, NE BLQ 

Sandhill Crane Kearney, NE BLQ 

Sandhill Crane Kearneir. NE BLO 

16 

17 

18 

19 

20 

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

31 

32 

33 

34 

35 

36 

37 

38 

39 

40 

41 

42 

43 

44 

45 

000029 

Brandt's Cormorant San Diego, CA 53 

Brandt's Cormorant San Diego, CA 46 

Brandt's Cormorant San Diego, CA 46 

Brandt's Cormorant San Diego, CA 80 

Brandt's Cormorant San Diego, CA 205.5 

Dbl. Crested Cormorant St. Martinville, LA 59 

Dbl. Crested Cormorant St. Martinville, LA 145 

Dbl. Crested Cormorant St. Martinville, LA 333 

Dbl. Crested Cormorant St. Martmville, LA 76 

Dbl. Crested Cormorant St. Martinville, LA 170 

Brown Pelican Miami, FL 106 

Brown Pelican Miami, FL 134 

Brown Pelican Miami, FL 125 

Brown Pelican Miami, FL 159 

Brown Pelican Miami, FL 48 

-. 

Sandhill Crane Valenica Co., NM BLQ 

Sandhill Crane Valenica Co., NM BLQ 

Sandhill Crane socorro co., NM BLQ 

Sandhill Crane socorro co., NM BLQ 

Sandhill Crane Valenica Co., NM BLQ 

Dbl. Crested Cormorant Naples, FL 212 

Dbl. Crested Cormorant Naples, FL 10 

Dbl. Crested Cormorant Naples, FL 52 

Dbl. Crested Cormorant Naples, FL 100 

Dbl. Crested Cormorant Naples, FL 152 

Brown Pelican Calipatria, CA BLQ 

Brown Pelican Calipatria, CA 16 

Brown Pelican Calipatria, CA 36 

Brown Pelican Calipatria, CA 6 

Brown Pelican Calipatria, CA 32 
Sample No. Species Location PFOS ppb 

In addition to wild birds, some fish from the wild were tested for the presence of PFOS. 

The fish were collected in 1997-98 fiom sites in Michigan as part of surveys conducted 

by Dr. John Giesy. They were stored frozen and analyzed in 1999. Six species were 

tested. Low levels of PFOS were detected in four of the twelve samples. Since no 

sample matrices were available for matrix spike studies, these data are of screening 

quality only. No clear meaning can be drawn from the data. They are being used to 

develop sampling programs. Table 9 reports the findings. 

56 

57 

58 

59 

60 

Table 9. PFOS Screening in Fish. 

Brown Pelican Ft. Lauderdale, FL 194 

Brown- Pelican Ft. Lauderdale, FL 71 

Brown Pelican Ft. Lauderdale, FL 31 

Brown Pelican Ft. Lauderdale. FL 91 

Brown Pelican Ft. Lauderdale, FL 75 

BLD= Below Limit of Detection (approximately 7ppb) 

BLQ=Below Limit of Quantitation (approximately 70 ppb) 

Sample 

No. 

1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

12 

Species Location Test Matrix Test Result 

carp Pine River, MI whole body BLD 

Lake Trout Siskiwit Lake, Isle Royale, MI whole body BLD 

Lake Trout Siskiwit Lake, Isle Royale, MI whole body BLD 

Lake Trout Lake Superior whole body BLD 

Walleye Detroit River, MI whole body BLD 

Ciscowet Lake Superior, Marquette, MI muscle BLD 

Brown Trout Detroit River, MI muscle BLD 

Channel Catfish Lake St. Claire, MI muscle BLD 

Lake Trout Pine River, MI whole body BLQ 

Brown Trout Rouge River, MI liver BLQ 

Channel Catfish Lake St. Claire, MI egg BLQ 

Channel Catfish Lake St. Claire, MI egg BLQ 

30 

0000310 
8.13 Testing of Fishmeal Used in Rat Studies 

Sub-surface water, in ppm 

PFOS 

PFOS homologues 

Surface films. in pprn 

PFOS 

PFOS homologues 

Sediment, in pprn 

PFOS 

PFOS homolowes 

While performing human health toxicity studies (see Perfluorooctane Sulfonate: Current 

Summary of Human Sera, Health and Toxicology Data, January 1999), 3M found 

"endogenous" levels of PFOS in some of the naive rats used in the studies. The levels 

found in the rat livers ranged from 29 ppb to 300 ppb. Livers of rats from one supplier 

showed no PFOS above the detection limit of 15 ppb. Further investigation revealed 

fishmeal to be an ingredient in the rat chow fed to the rats in which PFOS was detected. 

Fishmeal was not a dietary component of the rats that had no detectable levels of PFOS. 

3 M developed a complex analytical method to analyze fishmeal samples collected from 

different fish stock. At a detection limit of 2 ppm, PFOS was detected in three samples of 

fishmeal and not detected in three samples. At this time, these data are not conclusive. 

<.010 <.010 0.44 0.025 0.012 <.010 c.010 

c.010 c.010 0.10 c.010 c.010 <.010 c.010 

N/C N/C 1.60 1.00 0.28 N/C N/C 

N/C N/C 0.02 c.010 <.010 N/C N/C 

0.177 <.050 31.1 N/C N/C c.050 <.050 

<.050 <.050 <.050 N/C N/C x.050 c.050 

8.14 Plant Site Analyses 

In March of 1998,3M conducted screening level sampling for PFOS around the Decatur 

plant. The outfall of the Decatur wastewater treatment plant is at a bay near the mouth of 

Baker's Creek. Baker's Creek flows into the Tennessee River, a large river that supports 

barge traffic. About 25 miles downstream is Wheeler Dam. The samples tested were of 

water surface film, subsurface water and sediment. A goal of the sampling was to 

experiment with sampling techniques and analytical methods. Therefore, the analytical 

data are of screening quality only. Data on PFOS from the sampling are in Table 10. 

Table IO. Sampling Near the Decatur Wastewater Discharge 

Sample Locations: 

UP1 & UP2: Tennessee River, upstream of discharge 

BC 1 : Baker's Creek below outfall 

Q 1 & 42: Baker's Creek, downstream of discharge, in quiet waters near Tennessee River 

WD1 & WD2: Tennessee River below Wheeler Dam 

IUP1 /UP2 IBC1 IQ1 142 IWD1 IWD2 1 

N/C = not collected 

Surface film samples were skimmed from the top of the water, at the aidwater interface. 

Sediment samples were collected from the river bed using an Ekman Dredge. Samples were taken at the 

water collection point or, if sediment was lacking there, as close as possible to it. 

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Based on this initial sampling, a more extensive sampling was conducted. Sampling 

locations extended from about 10 miles upstream of the facility to 25 miles below the 

facility. As a result of analytical techniques being developed to lower detection limits, 

analyses of these samples is pending. 

8.15 Biosphere Sampling 

3M is building on recent information with advances in technology to design a program 

that could detect traces of sulfonated perfluorochemicals across a range of species, 

environmental habitats and geographic locations, including soil, water and organisms. 

3M’s approach is to use existing, scientifically recognized, sampling and data collection 

programs in order to minimize the time needed to obtain information. The goal is to set 

some bounds on the geographic regions where sulfonated perfluorochemicals are 

currently found, identify areas that should receive more investigation, and eliminate some 

general environments from Mer sampling in the immediate future. Key ecosystems 

and species of concern surrounding manufacturing plants are being tested as well as 

ecosystems remote from manufacturing and use locations. 

Where possible, synoptic samples of soil, sediment, air or water are also being taken, but 

the primary focus of initial studies is tissue samples from biological receptors, especially 

those in upper trophic levels. The information obtained in the initial studies will be used 

to determine appropriate studies for ascertaining critical pathways. 

8.2 Human Exposure Levels 

Studies to investigate human exposures take several approaches: 

1. Environmental exposure of the general U.S. population will be assessed in 

phases through a “Multi-Cities Study.” This involves field investigation of 

paired cities, one with significant manufacturing or commercial fluorochemical 

use, matched with a city without known significant use. The study will involve 

direct sampling for dietary and environmental presence. 

2. Residential exposure will be assessed through a product’s use and controlled 

measurements of the product’s releases. This study will measure releases of 

fluorochemical residuals and total PFOS from carpets. 

3. The migration of sulfonated perfluorochemicals used in food packaging to the 

food is being quantified for several foods. 

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8.21 Multi-cities Sampling 

The multi-cities study pairs a city having significant manufacturing or commercial use of 

fluorochemical products based on customer sales with a city that does not. Initially six 

cities, (three pairs) are being examined. This may be expanded, depending on initial 

results. The multi-cities sampling will yield environmental distribution data as well as 

data on potential sources of human exposure. The cities were selected to represent urban 

locations with various levels of fluorochemical releases and various types of municipal 

water supplies. The samples to be obtained, where possible, are: urban air, surface water 

column and surface microlayer, sediment, river fish, drinking water intake, treated 

drinking water, tap water, the influent and effluent to publicly owned waste treatment 

works, sludge, and municipal landfill leachate. Additionally a "market basket" of several 

food products will be sampled. These include: beef, pork, chicken, hot dogs, catfish, 

eggs, milk, bread, green beans, apples from three grocery stores and, if possible, produce 

from local farmers' markets. 

8.22 Carpet Use Studies 

The carpet study will estimate any loss of fluorochemical from normal use of carpets. If 

a pilot study of carpets finds significant releases, then the study will assess human 

exposure that may occur via inhalation, dermal and ingestion routes. 

8.23 Paper and Packaging Studies 

Results of past studies on the migration of fluorochemicals from packaging into food 

have been submitted to the FDA, and FDA has cleared the use of paper and packaging 

protectors for food as indirect food additives. Current work focuses on the development 

of new methodologies to extract various fluorochemicals from paper and several foods, 

then perform quantitative, low level analyses (< 1 ppb). 

8.24 Exposure Scenarios 

These scenarios will be developed using data from release, fate and distribution studies. 

Their purpose is to prioritize exposure pathways for further study by developing 

quantitative estimates of specific exposures under known conditions in a specific 

location. 

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