... , ., . 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 awhite 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 andEffects

Prepared by 

# 3M

March 

## 1,2000

1

## Table

## ofContents

1.0 PREFACE 2.0 EXECUTIVE SUMMARY 3.0 INTRODUCTION TO FLUOROCHEMICALS 4.0 PHY SICAL-CH EM

### ICAL PROPERTIES

### 0F FLU0 ROC

### HEM ICALS 5.0 ANALYTICAL TEST METHODS FOR FLUOROCHEMICALS 6.0 SOURCES OF FLUOROCHEMICALS 6.1 ManufacturingWaste Streams 6.1 1Waste Stream Characterization 6.12 Air 6.13 Wastewater 6.14 Solid Waste 6.2 SupplyChain Waste Streams 6.3 Releases from WasteTreatment and Disposal Methods 7.0 ENVIRONMENTAL TRANSPORTAND DISTRIBUTION 8.0 ENVIRONMENTAL SAMPLING FOR FLUOROCHEMICALS 8.1 Environmental Levels 8.11 Historical Data 8.12 Recent Analyses ofWild Birds and Fish 8.13 Testing of FishmealUsed in Rat Studies 8.14 Plant Site Analyses 8.15 Biosphere Sampling 8.2 Human Exposure Levels 8.21 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 

### 0000039.0 ENVIRONMENTALTRANSFORMATION/DEGRADATlONOF 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 Conditionsfor Biodegradation 10.0 ECOTOXlClTYTESTING OF FLUOROCHEMICALS 11.O COMPREHENSIVE PLANTO ASSESS ENVIRONMENTAL EXPOSURE 11.1 Plan Overview 11.2 Component 1: Characterize Fate and Transport Properties 11.3 Component 2: Estimate Releases 11.4 Component3: Characterize Distribution in the Environment 11.5 Component4: 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 

### 000004required, 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 ofreasons such as: screening laboratory supplies and environments prior to initiating toxicity testing, for detecting environmental exposure, for determining sources ofperfluorochemicals, and for understanding perfluorochemical metabolism kinetics.



### 6.0 Sources 

### of Fluorochemicals A few fluorochemicals occur naturally in the biosphere, produced by biological and geochemicalprocesses. 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 producetetrafluoroethylene, sulfur hexafluoride, perfluoromethane and some chlorofluorocarbons in small quantities. Most fluorochemicals in the environment arepresent 

### as a result ofhuman manufacture and use. Releases of fluorochemicals into the environment can occur at each stage 

### ofthe fluorochemical product's life cycle. They can be released whenthe fluorochemical is synthesized, continue during incorporation 

### ofthe 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 approachto estimate environmental releases offluorochemicals.. 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 arelease 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 

### ofthe 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 ofthe product. The assumptions 

### ofcompletebreakdown 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 

### 000019product degradationrates. Somepolymeric products appear to be quite stable in the environment, with long half-lives; otherpolymers hydrolyze quickly. 6. I Manufacturing Waste Streams The assessment ofthe release of sulfonated perfluorochemicals into the environment begins with manufacturing waste generation. Somewaste streams, such as wastewater discharge or disposal ofoff-spec products, can be anticipated and controls provided. Other waste can be generated during any ofthe steps required to produce the fluorochemicals and manufacture the product. The greatest production oftheparent 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. Saltsof PFOS 

### are also manufactured at the facility. Because ofits production volume, the Decatur facility has been the focus of manufacturing waste stream studies. Understanding waste generation and how wastes are managed and disposed ofprovides a better understanding ofpotential releases into the environment. That understanding will help to identify opportunities for reductions in such releases. Themanufacturing process for sulfonated perfluorochemicals 

### is complicated. 

### There are more than 

### 600 intermediate manufacturing steps associated with theproduction ofPOSF and POSF-based products. This translates into hundreds ofprocess steps that require venting orthat 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 oftheprocess could not be analyzed precisely to confiicomposition 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 ofonly one fluorochemical analyte in awastewater 

### matrix. In 1999,improved analytical techniques and methods were developed for additional fluorochemical analytes in awastewater 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 

### Q00020As 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 

### ofthe amounts and kinds offluorochemicals 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 Dischargeto 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 ofPOSF-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 arethe basis for 

### the estimates inTable 

### 5. These estimates derived from the material balance are not precise, 

### asthis 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-1990sin order to reduce potential releases to the environment. Wastewater sludgesthat 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 ofwastes generated and volumes ofreleases to the environment, since the vast majority ofwastes 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 10,000Ibs/yrof PFOS equivalentsin the discharge to the river are estimated releases to the environment afterwastewater treatment, not the Ibs/yr generated prior to treatment.
21 

## 000021More explanation ofthe 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 amodel ofprocess steps to calculate air emissions. New information is being compiledto 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 ofprocess chemistry Data 

### from the process engineers' availablematerial balances in the plant's reporting system have been used to supplement the earlier sitebalance in estimating air emissions. Initial reports 

### fiom th~s system indicate that most site waste and air emissions result from fewer than 10key 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 theprocess materials, vaporizing and capturing the fluorochemicals. It will significantly reduce the organofluoridesin 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 stepsto determine what air emissions testing 

### is feasible and appropriate. Testing ofcomplex batch-processing systems 

### is difficult dueto quickly changing process conditions, venting pressures, and difficulty in isolating processes; however, characterization testing may be possible. The technical feasibility ofperforming 

### this testing for two major processes is now under evaluation. Any emissionstesting 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 fromthe site. The first testing 

### ofwastewater before and after treatment for specific fluorochemicals occurred at Decatur early in 

### 1998. The testing was 

### 22 

### 000022limited and reflected operating conditions for a relatively short period 

### oftime 

### (24hour composite samples ofinfluent and effluent for one week.) Someofthe compounds that were identified in the wastewater were: a diester ofEtFOSE alcohol, EtFOSE alcohol, MeFOSE alcohol, PFOS, 

### FOSA, PFOSAA, PFOA and 

### PFHS. In 1998an interim carbon adsorption treatment system was installed aspart of wastewater treatment. Data for the effluent estimate in Table 

### 5 reflects this change. This treatment system treats the largest single source offluorochemical-containing wastewater in order to remove PFOS and other sulfonatedperfluorochemicals fiomthe wastewater. Comparison ofthe results from samplingdone in February 1998 with sampling done in the end of 1998 indicatesthe quantity ofPFOS discharged to the Tennessee River declined by about half. In addition to the carbon adsorption system, in-process operational changeswere made in off-spec product discharge procedures that also contributed tothe reduction in PFOS content of the discharge to the river. The carbon system has been incorporated as a permanent upgrade ofthe wastewater treatment system. Monitoring indicates that with proper operation, carbon adsorption removes better than 99% of

### PFOS. Removal efficiency ofother sulfonated perfluorochemicals varies, but the treatment appears to provide a high degree ofremoval 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 areduction in the values listed in Table 

### 5. 

### 3Mhas 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 ofthe material lost fiom production, so siterecords were used in combination with the existing emission estimates to create the current picture ofpotential releases resulting 

### from disposal. A review ofplant records for 1998 has been completed to determine primary waste disposal locations 

### forthe site. According to Decatur plant records, 

### 63% ofthe fluorochemical containing wastes are sent to incinerators, 33% ofthe wastes are disposed in hazardous waste landfills and 

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



### 23 

## 0000236.2

### Supply Chain Waste Streams



### Waste Stream Air Wastewater Solid Waste Using sales data, 3M identified key products that contain a majority ofthe fluorochemical solidsused in products. These products represent 

### 89% ofPFOS-equivalents sold by 

### 3M in 1997in 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 

### 0 112,000 181,000 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 solidswere 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 onconservative, worst case assumptions about the generation 

### ofwaste streams at supply chain facilities. These are often based on operator experience or engineering estimatesrather than laboratory tests and can result in wide ranges in waste stream calculations. In estimating wastes, these data do not include 

### loss 

### ofproduct residuals in the waste streamsbecause 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 

### ofthe products by customers of eachbusiness unit. These estimates are helping to focus efforts in improving customer stewardshppractices 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 Treatmentand DisposalMethods 

### 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 

### 000024facilities. Information is also being compiled on some ofthe largest wastewater treatment facilities and landfills in the United States in order to estimatethe 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 ofdestruction 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 

### ofvarious technologies/situations such as municipal incinerators, and the products that couldresult from incomplete combustion are elements ofthe 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 ofmaterial sent to incineration, wastewater treatment plants, and landfills. The goals ofthe life cycle release studies are:



## - to identify important fluorochemicalsbased 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 samplingresults;

- to predict which fluorochemical releases may result 

### in exposure to humans and



### - to identify fluorochemicalsthat require further study asto their transport, fate

release and chemistry; environment;

the environment; and and exposure potential.



### 7.0 Environmental Transportand Distribution The transport and fate ofchemicals in the environment depends on many factors but principally onthe 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 fiomproduct to air; 2. Indoor air deposition; 3. Accumulation on airborne particulates; 

### 4. Fate and transport to the stratosphere; 

### 25 

### 0000255. 6. 7. 

### 8. 9. 10. 11. Accumulation at the surface water microlayer; Degradation (includeshydrolysis, photolysis and biodegradation); Dissociation 

### in water; Uptake in plants; Uptake in fish; Uptake in birds; Efficiency ofwastewater treatment systems. All ofthese fate and transport mechanisms have been linked to models. Modeling uses mathematical equations to simulateand predict real events and processes. Many types of models will be considered for use in this effort to evaluate sulfonated perfluorochemicals. Simple models ofecosystems, indoor air, and treatment systems (wastewater, landfills) are being used to screen forpossible fate mechanisms, possible exposures, and possible sample detection limits. For example, one preliminary screeningmodel suggests that top trophic level species such 

### as fish eating birds and sea mammals should be examined. 

### This finding was incorporated into the design ofthe biosphere sampling plan. Chemicals differ greatly in their behavior. The major differences in behavior oforganic chemicals 

### in the environment are due to physical-chemical properties. Although laboratory studies are underway on physicallchemical properties ofPFOS, EtFOSE alcohol 

### andMeFOSE alcohol, models arebeing developed to estimate the physical/chemical properties of other sulfonated perfluorochemicals. 

### Thswill reduce the time and testing required to gather these data for use in environmental fate models. Fugacity is aconceptthat 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 andthe 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 vaporpressure 

### ifit has low solubility in water. By enteringthephysical-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 ofthese 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 ofecosystems.

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 offluorochemical 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 ofthe current knowledge ofthe behavior ofthese 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 

### ofWild Birds and Fish In analysis in 1999of the plasma 

### often fish eating birds, albatross nestlings at Midway Island in the Pacific Ocean and eagle nestlings in Minnesota and Michigan, PFOS was detected in each 

### ofthe 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 

### ofthe albatross adults showed no detectable levels of

### PFOS (< 

### I ppb detection level). Detectable, but not quantifiable levels ofPFOS were found 

### in the remaining albatross samples, both collected frombirds less than a year old. All albatross sampleswere collected in 1992-93. See Table 7. These data are semi-quantitative, screening quality. As only a small amount (< 

### ImL)ofplasma 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 onwild bird plasma, the plasma

### from a second set of wild birds was examined forthe presence ofPFOS. (See Table 7.) The source ofthe plasma was three seaeagles 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 ofthe eagleplasma 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

AIbatross Albatross Albatross SeaEagle SeaEagle Sea Eagle Bald Eagle Bald Eagle Bald Eagle Bald Eagle Bald Eagle Bald Eagle

Bald Eagle 13 Dec 92 Midway atoll 8 years BLD 13Dec 92 Midway atoll 15 years BLD 28 May 93 Baltic, Sweden nestling 125 18May 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 NorthAmerica 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, 371 8 Jun 92 CarrollTwp, OH nestling 374 BLQ= Below Limit of Quantitation (10 ppb) BLD= Below Limit of Detection (approximately 1ppb) Following the bird plasma studies, sixty liver samples collected by the U.S. Fish & Wildlife Service from various species 

### ofbirds 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 

### ofthe analyses 

### was to determine ifthe presence 

### ofPFOS could be detected in these sample matrices. 

### 3Mbelieves that these sets ofdata are insufficient to draw conclusions with any statistical merit. The 

### PFOS data in Table 

### 8 are semi-quantitative, screening quality, with 

### a margin oferror estimated at 

### - 

### + 30%. The limit ofquantitation for 

### PFOS is 

### 6 ppb.



### 28 

### 000028

### Table 8. 

### Analysis of Wild Bird Livers.

SampleNo. BLQ= Below limit ofquantitation (6ppb) 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 SanDiego, 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 -.

SandhillCrane Valenica Co.,NM BLQ Sandhill Crane Valenica Co., NM BLQ Sandhill Crane socorro co., NM BLQ Sandhill Crane socorroco.,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 32SampleNo. Species Location PFOS ppb

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

### ofPFOS. The fish were collected in 

### 1997-98fiom 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 

### ofthe 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 samplingprograms. 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 (approximately7ppb) 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 

### 00003108.13 

### Testing of

### Fishmeal Used 

### in Rat Studies

Sub-surface water, inppm PFOS PFOS homologues Surface films. inpprn PFOS PFOS homologues Sediment,inpprn PFOS PFOS homolowes While performing human health toxicity studies (see Perfluorooctane Sulfonate: Current Summary 

### ofHuman Sera, Health and Toxicology Data, January 1999), 

### 3Mfound "endogenous" levels 

### ofPFOS in some ofthe 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 15ppb. 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 ofPFOS. 

### 3Mdeveloped a complex analytical method to analyze fishmeal samples collected from different fish stock. At a detection limit of2 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 SiteAnalyses In March 

### of 1998,3Mconducted screening level sampling forPFOS around the Decatur plant. 

### The outfall ofthe Decatur wastewater treatment plant is at a bay nearthe mouth of Baker's Creek. Baker's Creek flows into the Tennessee River, a largeriver 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 ofthe sampling was to experiment with samplingtechniques 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 Nearthe Decatur Wastewater Discharge SampleLocations: UP1 & UP2:Tennessee River, upstream of discharge BC1: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 filmsamples were skimmed from the top ofthe water, at the aidwater interface. Sediment sampleswere collected from the river bed using an Ekman Dredge. Sampleswere taken atthe water collection point or, if sedimentwas lacking there, as close aspossible to it.



### 31 

### 000031Based onthis initial sampling, a more extensive sampling was conducted. Sampling locations extended fromabout 

### 10miles upstream of the facility to 25 miles below the facility. As 

### aresult of analytical techniques being developed to lower detection limits, analyses ofthese samples is pending.

8.15 Biosphere Sampling 

### 3M is building onrecent information with advances in technology to design aprogram that could detect traces of sulfonated perfluorochemicals across a range of species, environmental habitats and geographic locations, including soil, water and organisms. 

### 3M’sapproach 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 onthe geographic regions where sulfonated perfluorochemicals are currently found, identify areasthat shouldreceive more investigation, and eliminate some general environments from Mer sampling in the immediate future. Key ecosystems and species ofconcern surrounding manufacturing plants are being tested aswell 

### as ecosystemsremote from manufacturing and use locations. Where possible, synoptic samples 

### of soil, sediment, air orwater are also being taken, but theprimary focus ofinitial studiesis 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 ofthe general 

### U.S. population will be assessed in phases through a “Multi-Cities Study.” 

### This involves field investigation of paired cities, onewith 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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### 0000328.21 

### 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 

### onpotential sources of

### humanexposure. The cities were selected to represent urban locations

### withvarious levels offluorochemical releases and various types ofmunicipal 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 foodproducts will be sampled. Theseinclude: beef, pork, chicken, hot dogs, catfish, eggs, milk, bread, green beans, apples from three grocery stores and, ifpossible, produce from local farmers' markets.

8.22 

### CarpetUse 

### Studies The carpet study will estimate any loss of fluorochemical from normal use of carpets. If a pilot study ofcarpets finds significant releases, then the study will assess human exposurethat may occur via inhalation, dermal and ingestion routes.


### 8.23 Paper andPackaging Studies Results 

### ofpast studies 

### on the migration of fluorochemicals from packaging into food have been submitted to the FDA, and FDA has cleared the use 

### ofpaper and packaging protectors for food 

### as indirect food additives. Current work focuses on the development of new methodologiesto extract various fluorochemicals frompaper and several foods, then perform quantitative, 

### low level analyses (< 1ppb).


### 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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