Document 5b3kb900EQO1zjBEvkr00roB5

A Review of the Environmental Fate and Effects of Sulfonyl Based Fluorochemicals 3M Environmental Laboratory November 18, 1998 DRAFT 3M Praprictary Information Do Not Copy 1 11/1895 DRAFT 2712.0001 Attorney/Client Privileged Do Not Disclose: Exhibit Table of Contents EXECUTIVE SUMMARY 3 INTRODUCTION 4 PHYSICAL-CHEMICAL PROPERTIES 7 ANALYTICAL TEST METHODS 10 DEGRADATION 13 ECOTOX 7 ENVIRONMENTAL FATE 21 RESEARCH RATIONALE 2 REFERENCES 27 3M Praprictary Information Do Not Copy 11/1895 DRAFT 2712.0002 Atarncy/Cliat Privileged DoNot Disclose 3M_MNOS374965 Executive Summary Adding fluorine atoms to organic molecules produces fluorochemicals, compounds that are quite stabi, chemically inert and nonreactive. Fluorochemicals are produced by an electrofiuorination process which creates a complex and variable mixofchemicals in which fluorine atoms replace hydrogenatomson the organic feedstock and carboncarbon bonds are rearranged. Perfluorochemicals have complete substitutionoffluorine for hydrogen. Fluorochemicals can repel both water and ois, reduce surface tension dramatically, act as catalysts for oligomerization and polymerization, and function under extreme conditions. Major uses for sulfonyl based perfluorochemicals are surface protectors and surfactants, Fluorine's high clectronegativity confers a strong polarity to carbon-fluorine bonds, contributing to the stability and nonreactive characterofperfluorochemical molecules. Unusually, perfluoroalkyl chains arc both olcophobic and hydrophobic. `The addition of charged moieties to the chain can affet the water solubilityof the shorter chains. Reliable `methods for extraction, separation and identificationofperfluorochemicals in tissues and environmental matrices have been developed only in the last five years. New analytical technology i aiding in identification of metabolites and breakdown products. Perfluorocheicals resist degradation by most chemical. physical and biological processes. Research suggests tha the transformationoffluorinated sulfonates requires the presence of hydrogen at the alpha carbon on the fluorinated chain. Perfluorinated molecules arc attacked at non-fluorinated side chains and are transformed into new fluorochemicls, `Sctoumdmieerscsiaulglgyesitmptoharttacnotmppeorufnlduosromcahdeemifcraolmprpoedrfulcutoaronodctiannteersmueldfioantyel,falrueortirdaen,sPfoOrSmFe,d.a during vertebrate metabolism and probabiy by microorganisms to another perfluorochemical, perfluorooctane sulfonate, PFOS. PFOS does not appear to further degrade except in combustion. While progress has been made in identifying metabolites and degradation products, uncertainties remain about the intermediate forms that may exist n the environment in addition to the final degradation product, PFOS. Degradation studies are now focusing on fluorochemicals with hydrocarbon portions to seeifconditions can be optimized to favor the degradationofpartially perfuorinated chemicals and a microorganism developed to alter these compounds. The degradationof polymeric perfluorocheicals through hydrolysis, acrobic and anaerobic bacterial metabolism is being examined. Many perfluorochemicals have been subjected to basic sercening tess for environmental toxicity. Using aquatic organisms, the rangeof toxicity is from an insignificant hazard to 3M Proprictary Information Do Not Copy 3 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0003 IM_MN0S374967 highly toxic. Different species may vary significantly in their response to the same chemical. Lite is known about the environmental fateofperfluorachemicals. Their persistence, which leads to accumulation in the environment, their unusual behavior in partioning and metabolism, and their significant surface activity raise important research issues for environmental dispersion. Uncertainties about the applicabilityof existing models du to etnheviurnounsmueanltaplrodpaetratineeseodfepderffolrumoorodcehlemoipcearlast,ioannadngdavpasliidnaptihoyns,icaalls-occhoemmipclailcaatned cwhhaerracetietraizcactuimounloafteens,vihroonwmeexnptoaslurfaete.to tMhoerleivsintgudayndis nesosnelnvtiianlgocofmipnodnwehnattsoafcctuhmeulates environment transforms the molecules and what effets this exposure has on organisms at all levelsof the ecosystem. 3M has developed a comprehensive plan to gather the necessary information. It will evaluate all releases during the products' lf cycles and all routesofexposure to humans and the environment. The plan identifies taskswhich wil characterize releases from product manufacture and use, characterize the transport and fateofperflurochemicals by addressing the lackofdata and validated models, characterize the distribution of perfluorochemicals in the biosphere though samplingofdifferent habitats and species of concen, and estimate the amounts distributed in populations and the environment. Tasks in the plan are underway. Introduction Fluorochemicals are componentsof several important 3M product lines dueto their cuonimqpuoeneanntdsousfefpurlodpurocptesr,titehse.y Trehpeeyl abroethquwiatteesrtaabnled,oilc,hemriecdaulcleysiunrefratcaentdennsoinorneamctuicvhe.loAwser thanothersurfactants, ata catalysts for oligomerization and polymerization, and function where other compounds would rapidly degrade. 3M has produced sulfonyl based perfluorochemicals commercially for over 40 years. 3M produces fluorocheicals by combining anhydrous hydrogen fluoride with hydrocarbon stock in the presenceofelectrical energy (Simons Electrochemical Fluorination Process). [Figure 1.] The highest production volume fluorochemical is principally perfluorooctancsulfonyl fluoride (POSE) Figure 1. Simons Electrochemical Fluorination Process. 3M Proprictary Information Do Not Copy 4 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0004 IM_MN0S374968 0 ClHSIF + 17 HE 0I 1-Octanesulforyl fluoride > 4570V 0 GESSFI + 1TH, 0I Perfluoronctanesulfonyl fluoride (POSF) "The fluorinaion process yields about 80% straight chain POSF, and a mixtureofunknown and variable composition containing: other straight chain perfluoroalkyl products, CuFsu.iSOSF,of various chain lengths eg CFiSOF, CSF, CFisSOF "branched chain perfluoroalkyl productsof various chain lengths CFs e.g. CFCE.CE.CRCRC| ECESOF Ch CE CECR| CRCF.CF| CESOF other straight chain, branched and cyclic perfluoroalkyl compounds eg CF: Cie, CiFs, Cio, CiFin, cCiFx "tars" (high molecular weigh fluorochemical byproducts) and other byproducts Becauseofslight differences in process conditions, raw materials, and equipment, the `misture produced by the electrochemical fluorination process varies somewhat from lot to lot and from plant to plant. Four 3M plants currently produce fluoochemicals. These plants are located in: Cottage Grove MN, Cordova IL, Decatur AL. and Antwerp Belgium. During production, many byproducts and waste products are formed. The volatile waste products, such as perfluoromethane, have been vented to the atmosphere in the past but improvements are underway to capture and destroy these releases by thermal oxidation. The tars are incinerated. The byproducts, manyof which are incompletely fluorinated with hydrogen fons still present, are partially degraded in stabilization processes and discharged to wastewater treatment systems. The treatment sludge is cither landfilled or andincorporated. Someofthe non-POSF byproducts are recovered and sold for secondary uses. "The product that results from electrochemicalfluorination is thus nota pure chemical but rather a mix of isomers and homologues. Perfluorochemicals have complete substitution 3M Proprictary Information Do Not Copy 5 11898 DRAFT Attorncy/Clicn Privileged Do Not Disclose 2712.0005 IM_MN0S374969 of fluorine for hydrogen. POSF is usedas a product and is also an important intermediate in the synthesisofsubstances used in many other 3M products. Toa lessr extent, `homologues of POF. [CyF.SO:F where n=anything but 8, principally perfluorohexanesulfony! fluoride, are also intermediates in the formation ofother 3M products. Some of the POSF derived products are relatively low molecular weight (~500 daltons), S`wuerifgahctesaucrtfiavcetamnattseroiralasreanjdoimneodnowmietrhso.theTrhemsoenommoenrosmetrosfoarrem uhsiegdhearsmloolwecmuollaercwueliagrht oligomers and polymers with a mioffluorinated and unfluornated portions. Fluorochemical monomers can also bejoined to phosphates, to polymeric and oligomeric urethane, or o acrylate backbones through ester and other linkages. The majority of 3M fluorochemicals produced are used in polymeric applications. Some products synthesized from POSF and ts homologues are sold as raw materials to customers who use them as intermediates or componentsoftheir products. "The 3M product lines that use sulfonyl based perluorochemicals are summarized below. (Product lincs using fluorochemicals which contain no sulfonyl groups are not listed.) SurfaFceabTrrieca/tUmpehnotlsstery Protector CLaeraptehterPPrrootteeccttoorr Paper Protector Surfactants Specialty surfactants Cleaning applications Electroplating and Fiching Baths Insecticides Paints Inks Photographic Solutions Floor Polishes Fire Extinguishing Foam Concentrates Some paper protectors are mixtures of mono-, di-, and triphosphate estersof2-(Nethylperfluorooctanesulfonamido)ethyl alcohol (N-EtFOSE alcohol). The carpet and texile protectors are based on N-MeFOSE and N-E(FOSE chemistry. The fluorochemicals uscd in fire extinguishing foams arc based on POSF and contain perfluoroalkylsulfonamides, and perfluoroalkylsulfonate salts. 3M Proprictary Information Do Not Copy 6 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0006 3M_MN0S374970 Residuals which are common to all the formulationsofperfluorochemical products arc `perfluorooctane sulfonate (PFOS), N-cthyl (or N-methyl) perfluorooctane sulfonamide (N-EFOSA or N-MeFOSA) and N-cthyl (or N-methyl) perfluorooctane sulfonamidocthyl Efe Table 1. Perfluorochemical Glossary. rr o emo Jfoome e Physical-Chemical Properties : 2712.0007 Fluorinated organics are less well described in the science literature than organic `molecules bearing other halogens, i. bromine, and chlorine, which have been more thoroughly investigated by many rescarchers in published reports. To understand their properties, it is necessary to describe the properties of fluorine. Fluorine has several characteristics which differ from the other halogens and contribute to the unusual properties of fluorochemicals. Fluorine, the most abundant halogen, has a van der Waals radius of 1.47 A, more `comparable to that of oxygen than other halogens, and isosterically similar to a hydroxy] `group. Fluorine has the highest cectronegativity (4.0)ofall the halogens, indeed the highest in the periodic table. This confers a strong polarity 10 the carbon-fluorine bond. "sTthreoncga,rhbiognhleunoerrignyebboonnddciosnotnriebuotfetshetosttrhoensgteasbtiliintynoaftufrleuo(r~o1c1he0mkiecaallsm.ol). This very "The high ionization potentialoffluorine (401.8 kealimole) and its low polarizability implies weak inter- and intramolecular interactions. This is demonstrated in the low boiling points ofperfluorochemicals relative to molceular weight, and their extremely low surface tension and low refractive index. The partitioning behavior of perfluoroalkanes is unusual. Some perfluoroalkanes when mixed with hydrocarbons and water form three immiscible phases, demonstrating that perfluorinated chains are both oleophobic and hydrophobic. A charged moiety. suchas carboxylic acid, sulfonic acid, phosphate or a `quatemary ammonium group, when attached (0 the perflorinated chain, makes the molecule more water soluble becauseofthe hydrophilic natureofthese charged moieties. "Typically, the presenceofthese charged groups on short chain perfluorinated compounds (<C6) noticably increases the solubilityofthe compound in water. Physical data available on fluorochemicals at 3M are principally those parameters needed for quality control use and material handling. Table 2 summarizes the physical data for Tow molecular weight, POSF based fluorochemical products. Someof these products are primarily used as surfactants; others are primarily used as intermediates in the formation of polymeric or oligomeric products. It is important to remember that these data have ben obtained using products that are not highiy refined, and that products may have more than one fluorochemical component. Some may have nonfluorochemical components which enter into determination ofthe values. Additional physical data are available on a few products. These additonal data are typically related to determinationofenvironmental fate e.g. data on sol mobility and partioning coefficients They are summarized in Table 3 Table 2. Physical Data on Fluorochemical Products 3M Proprictary Information Do Not Copy 8 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0008 IM_MNoS374972 Abbreviations: N/D: notdetermined; N/A: not applicable; ~~ approximately [interme TPOSF__---- [Hnt|Ne-MrFOmSeEaldco.hol NEFOSE alcohol EERE [miermed TN-EOSEA [F :: mrof oro [Intermed|N-EWFOSEMA =z T"15ab [<10 [510 [<10 Tneglig[18 [NA | [75-9 m [NA TNA [NA negli [~17 [NA | [1180[<0 [>10 [<i0 [neg [17 [NA| PE|-isob [<io [510 [eto Twi [is [NA | JP f or perH[or JeEf JJeee [cisobT<i0 510 Tio"Toei[15 [NA] Table 3. Physical Data Related to Environmental Fate ET [PrOsKwanTwoso--T-- d0 Tn "Tow Te[1 NEFOSEA [ow | [56| T Teoxioh | [poss Tew 1 11 Tisn@nc posts [TTTTTien | 2712.0009 "The tables illustrate the wide range in values for physical parameters among low `molecular weight, POS based, fluorochemical products. Typically these low molecular weight products tend to have higher water solubility and lower vapor pressure, and tend to `be more mobile in the environmen, than polymeric products containing them. In addition 10 being intermediate in the formationofproducts, some of these low molecular weight fluorochemicals are also likely intermediates in the degradation ofpolymeric compounds. Some can also result from environmental transformationofother low molecular weight Muorochemical products. cEovnitdaeinntinfgroomthtehrectoamblpeosnaernetsthiendaedfdiciiteinocnietso itnhesxeisftliunogrdoacthae.miFcoarlsmuhlaavteedbepernodtuhcetsfocus of data collection. While most ofthe products above consist largely ofone active fluorochemical component, the values obiained for the product are not likely those for the purified fluorochemical alone. Predictionofenvironmental fate and transport requires the useof computer models Existing models require at a minimum the following physical data for operation: molecular weight, boiling/meliing point, pK. octanol/water partition cocfficient, vapor pressure, solubility, Henry's Law Constant, density, evaporation ra, heatof vaporization, bioconcentration factor, and degradation mechanisms in air and water (hydrolysis, photolysis, and biodegradation). Precise values for the parent fluorochemical compound, its intermediate, and the end degradation product are essential for comprehensive predictions about environmental fate and transport "The 3M Environmental Laboratoryi developing the missing physical data on individual fluorochemicals using GuifodrtheeTalstinigofnCheemicsals developed by the `Organisation for Economic Co-operation and Development (OECD). Guidelines exist for the determination of: boiling points,vapourpressures, water solubility. n-octanolivater partition coefficients, soil adsorption/desorption, and hydrolysis as a functionofpH. These methods will provide values reported in a consistent format that is internationally familiar and accepted. This standardization wil id in the review and comparisonofdata on individual flvorochemicals and in model operation and prediction. Analytical Test Methods Procedures for detecting and identifying fluorochemicals in the environment require a very high levelof technical expertise. Most general analytical methods do not provide enough sensitivity or selectivity. "The complex mixtureofpossible components in product, the `multiple matrices in which they could reside (c.. the atmosphere, soils, surface water, groundwater, wastewater, different animal tissues, different animal species, plant species foods, cic.) and trace detection levels require selective extraction and diverse analytical techniques 3M Proprictary Information 10 Attorncy/Clicn Privileged Do Not Copy 11898 DRAFT DoNot Disclose 2712.0010 IM_MN0S374974 Each fluorochemical requires a unique analytical methodology. Reliable methods for extraction, separation and identification have been developed only within the last five years. Prior to that, analysis usually was for "total organic fluoride," which was nonspecific "The analytical techology used in extraction, separation and idenification includes `combinations of high performance liquid chromotography (HPLC), high pressure solvent e(xGtCr)acutsiionng(aHPFSlEa)m,e elloencitzraotsipornayDe(tEeSc)t,orma(sFsIDs)p,eactPrhoomteotrlyon(iMzSa)t,iognaDsetcehertoomro(tPoIgDr)a,phoyr Electron Capture Detector (ECD) and Fourier Transform Infiared spectroscopy (FTIR). For example, analysis of PFOS extracted from tissues requires HPLC-MSMS analysis. "This technique focuses quantitation on five secondary ions ofone primary ion at @ specific HPLC retention time. 3M now has in place Good Laboratory Practice (GLP) methods for several fluorochemicals in several matrices including blood, liver, and several animal tissues and in Soil. These methods arc summarized in Table 4. It has non-GLP analytical methods in place for several fluorochemicals in several matrices such as wastewater sludge, drinking water, and air. Using a combinationofthese methods, the 3M Environmental Laboratory now can detect many fluorochemicals in variety of matrices. "To reach extremely low analytical levels in complicated matrics, the Environmental Laboratory plans 0 expand its analytical technology with the addition ofa tandern timeofflight mass spectrometer. This LC/MSMS instrument will enhance sensitivity for the target fluorochemical compounds by eliminating most interfering fons and reducing bwialclkbgerouusenfdulnoiinsei.denTthifeyiinngstfrluumoernotchpermoivciadlesmehtiagbholmiatsess arensdoliunttieornme(dtioa0t.es00f0o1r awhmiucsh) and so standards are not avaiable "To futher investigate flurochemical degradation/metabalic pathways, particularly those of `polymers, additional new technology will aso include a mlt-inlet MS/MS system. This system will improve characterization of semi-volatile degradation products. 3M Proprictary Information Do Not Copy n 11898 DRAFT 2712.0011 Attorncy/Clicn Privileged DoNot Disclose IM_MN0S374975 Table 4. GLP Methods for Extraction and Analysis of Fluorochemicals [rm eer 1. EE few ee 1 EEEr fRees Eese 2712.0012 Avysis | saunritoancaFnsC_|| RBaotvisneerusmerum alEkFoOhoSlECI PFOS.DEA PrOSEA 25s0 Toheyrmal desopion sampler | 0.26 cNoSupdlaedcc1i0oGnCafnodr aqunaanliytrsieopnaration;| 0.5 oor Degradation Because thecarbon fluorine bond is one of the strongest in nature, with high bond energies. is cleavage requires large amountsofenergy. Most chemical and physical processes nawrally occurring in the biosphere lak the required energy. Perfluorolkyl chains are not degraded in the chemical oxygen demand (COD) test, nor in total organic carbon (TOC) analyzers that use very reactive chemical and ultraviolet degradation `mechanisms. Photodegradationofthe carbon-fluorine bond and the carbon-carbon bonds within perfluorinated portions has not been demonstrated. Combustion does destroy uorochemicals an degradation s found in high temperature TOC analyzers. A few fluorochemicals occur naturally in the biosphere, produced by biological and `cochemical processes. Monofluoroacetc acid (CH:FCOOH) is produced by several hpelxaanft.luoSriodme,epfeurnguiorproomdeutcheanmoenaonfdlusoorimneatcehdloorrogfalniucosr.ocaTrebtornasflauroeropertohdyulecneed,bsyulvfourlcanoes orother geological processes in small quantities. However, all biologically produced fuorochemicals contain only one fluorine atom. No perfluoro moieties or similar `molecules have been found within biological systems. In perfluorinated molecules, the fluorine surround the carbon chain completly, shiciding the carbon-carbon bonds from attack. The fluorine atoms confear "rigidity" to the `molecule. This rigidity could obstruct the conformation required for a fit with enzymes, thereby blocking biological attack ofhe carbon-carbon bond. As a molecule becomes `more fluorinated, carbon-carbon bonds, carbon-hydrogen andcarbon-fluorine bonds all typically increase in strength. Because fully uorinated organic molecules have a molecular structure different from anything ese known to be present in nature, it is not surprising that no microorganisms as yet have been found that can degrade perfluoroalkyl chains. Work at Michigan State University by Blake Key under the direction of Dr. Craig Criddlc used a laboratory isolate ofa bacterium. a Pseudomonas species, to investigate the potential for biodegradation of fuorinated sulfonates. The researchers used model fluorinated sulfonate compounds 3M Propricary Information DoNot Copy 13 11898 DRAFT AttorneyClient Prive DoNot Disclose 2712.0013 3M_MNOs374977 difluoromethane sulfonate (DEMS), triflaoromethane sulfonate (TEMS), 2.22wifluorocthanesulfonate (TES). PFOS and H-PFOS (1H,1H,2H 2H-perfluorooctane sulfonate). (riddle et al. demonstrated that the microorganism degraded those fluorochemical `compounds containing hydrogen and used them as sulfur sources for growth under sulfurYimiting, acrobic conditions. They later found that such degradation occurred in soi even when sulfur was not limiting. The organism completely defluorinated DEMS. It used DEMS as the sole sourceofsulfur, but not as a sourceof carbon or energy. TES and HPROS were partially defluorinated. Six volaile products were detected for H-PFOS, all containing oxygen and fluorine but not sulfur. Where the carbons were fully fluorinated, i.e. TEMS and PFOS, no degradation was found. Criddic etl. concluded that the twansformation offluorinated sulfonate required the presenceofhydrogen at the alpha carbon on the fluorinated alkyl chain. They theorized that when hydrogen is present at the alpha carbon, a site for attack is provided and the carbon-sulfur bond becomes more accessible. Perfluorinated compounds have a rigidity conferred by the fluorine: Substitution and no structures tha are susceptible to electrophilic or nucleophilic attack. Results of standardized degradation test that have been performed with perfluorochemical products reflcct tha the products show lite susceptibility to biodegradation. (See Table 5.) Fluorochemicals lacking nonfluorinated organic portions have essentially no biochemical oxygen demand (BOD). Those with ionically bonded organics show BODs close (0 that which would be expected fiom their organic portion alone. Fluorochemical surfactants with covalently bonded organic portions have mixed. result. In aerobic degradation work in the laboratory,a few perfluorochemicals appeared 0 demonstrate some biodegradation over time but 10 analysis was done to determine. `what compounds were present a the conclusionofthe tests. See Table 6 When perfluorinated organic molecules do degrade, it is not the fluorinated portion that is affected. They are only attacked at non-fluorinated side chains. Rather than complete. degradation, the molecule undergoes transformation. The transformed product is another fluorinated compound. CiFiSO-F, + HO ------ CFiSOr POSF PFOS CFSOR ------ ------ ------ CiFiSOs POSF derivative PROS 3M Proprictary Information Do Not Copy 14 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0014 IM_MN0S374978 Table 5. Results of Standard Degradation Tests on Fluorochemicals FPlruoodruoccthsemPircianlciple [psf [N-NM-EeIFFOOSSEEaallcoohhaol cmoKne Tseom0 Ti26630o.0000 [ENFEFOOSSEAA [poser [PPOROSSiKtsaaltn use Jee Tsao [prN-OESFDOESEAsalacainol clylens|| 71s07o0o0000 oxide adder [Ew me] SWtoapy | 1[0B-odpay | 2[0o-dDay Other Ke | moke | me Tat Twi fw | | 1 Twit Tat1 OS24u0p0iaTkheO=D: Nwoodnetgishnake a7dsakysatcutdiiveastoerd sda sues TaTno lw[10000 f|[ w200 7 or ready biodegradable |TT 1 Ta0 io| Ts0a7.o000 | winoWdaergrbaudragti3on| tmronstuhdyshoark2e.5 ak study T So emonal| Bins COD means Chemical Oxygen Demand. It is a measure of the oxygen equivalent of the organic matter content oaf sample tha is susceptible oxidation by a strong chemical oxidant such as potassium dichromate. BOD means Biochemical Oxygen Demand. Its the amount of oxygen consumed by `microbial processes while breaking down a known amount ofa test substance. ThOD means Theoretical Oxygen Demand. I isthe theoretical quantityofoxygen used when the test compound is filly mineralized. This valueis calculated using the structure ofthe test chemical BIAS means Bismuth Active Substances. These are materials, such as water soluble polyethoxylates, that precipitate with barium tetraiodobismuthate. 3M Proprictary Information Do Not Copy 1s 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0015 IM_MN0S374979 Table 6. Aerobic Biodegradation Test Results on Sulfonate- based Perfluorochemicals. Chemi CFSON (CH) CHCOOK) C4FrSON(C:H: XCHLCH,O)r:CH, CF 1SON(CiH: (CHIH) H cro CCHHLNCCHH,:C)0,0 Hi Bi don Test, B 57% of T0h.eorueptiiackael Oxygen Demand in 625 hrs. 2D5-i33%sOirngs2adniuocsCalrbovnReemovdal 09% emoBriaslmuth Activ Substance pn oftheoretical in days From studiesof vertebrate metabolism using rats, 3M researchers have found that derivativoefs POS breakdown (0 perfluorooctane sulfonate (PFOS). Exactly how derivativoefs POSF are attacked and what intermediates are formed in the transformation process to produce PFOS is not completely known, but significant progress has been made in identification In rats it appears N-EFOSE-OH is metabolized to PFOSA and PFOSAA and other intermediates as it is degraded to form PFOS. "The eliminationofmetabolite via urine and feces is very slow. Intravenous administration of potassium "C-PFOS showed ''C present in liver and plasma ofmale ats for several weeks. Concentrations in fat and other tissues were lower (<5%of iver.) Chromatographic analysis showed no biotransformationof PFOS. Afiera single oral doseofPFOS, 25% was i the liver 89 days post dose. Inthe degradation of Me-FOSE-based compounds, several metabolites have been OcoHn.firTmheedseinwiesrseueidsentaifmicpdoulfsietnegsstHPaLnCimcalosu. plTheedsetoineclleucdter:osPprFaOyS,MSPFaOnSd AverainfdicMdea-gaFiOnsStEstandard material. (See Analytical Methods.) Other metabolites hase been tentatively identified but not yet confirmed duc to a lack of standards. In other studies, animals dosed with PFOS showed no metabolites other than PFOS, "Thus PFOS appears o be the end productof vertebrate metabolism ofPOSF based products. tis also the likely final productofdegradation by microorganisms. PFOS 3M Proprictary Information Do Not Copy 16 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0016 3M_MN0S374980 therefore enters the environment in multiple ways: as a product, as a residual in another fluorochemical product, as a metabolite as a degradation product resulting from hydrolysis or microbial breakdownofother fluorochemicals. Once in the environment, PFOS has not been shown to degrade any further under any. `natural conditions except combustion. Resistant to chemical and biological attack, PFOS persists and accumulates, but exactly in what amounts, and where is not well understood. Whether PFOS is the form that is most important in the dispersalofperfluorochemical `compounds in the environment or it s other intermediates that are mobile and arc converted to PFOS over time is unknown. Although some luorochemicals with hydrocarbon portions have demonstrated resistance 0 biodegradation under standard test conditions, i.. aerobic microbial degradation using a wastewater inoculum, existing studies did not examine all combinationsofconditions `which could be optimized to favor the degradationofpartially perfluorinated chemicals. "These include slowly preacelimating microorganisms to the fluorochemical and using these: acclimated microbes in degradation testing and using longer biodegradation test periods New studies initiated at the Environmental Laboratory are now exploring the possibility that a microorganism could eventually be enriched that could metabolically ater these low molecular weight luorochemicals. These studics are investigating anacrobic as well as acrobic degradation. Additionally, a programofstudies has been initiated to examine how polymeric perfluorochemicas, the most common perfluorochemical products, degrade. "This program includes studiesofpolymer hydrolysis, photolysis, and acrobic and anaerobic biodegradation. Ecotox `Pmearyflvuaorryocshigenmiifciaclanstlpyroindutcheeira rveasrpieotnysoef1r0etshpeonssaemseicnhaemqiucaatli. orTgyapniicsalmlsy., pDoilfyfmeerreintc sfpoercmises do not cause significant toxic effects. Surfactants as a class, both fluorinated and unfluorinated, tend to be likely to demonstrate aquatic toxicity. Basic environmental toxicity screening data are available for many sulfonated perfluorochemicals (sce Table 7). In considering the toxicity testing, it is important to note the year of the test. Older test protocols are not comparable to current bioassays which follow accepted, standardized test methods (OECD/USEPA). Almost al testing used products and not purified perfiuorochemicals. In old tests, the fluorochemical product used was likely more variable, with more impurities because manufacturing processes and product purity have significantly improved overtime. Several tests were hampered by the insolubiityofthe perfluorochemical and results arc expressed as greater than the measured solubility. 3M Proprictary Information 7 Attorncy/Clicn Privileged Do Not Copy 11898 DRAFT DoNot Disclose 2712.0017 IM_MN0S374981 In describing environmental toxicity data, the 3M Environmental Laboratory uses six levelsofdescriptors on its Product Environmental Data Sheets. These levels are similar to definitions used by the National Institute for Occupational Safety and Health (NIOSH). where X= the lDoewfeisntitLiCoSn0s,ofECToSx0icoirtyIC50 in mg/L (ppm) Environmental Lab NIOSH Insignificant hazard Minimal Hamiful Toxic Very Toxic Extremely Toxic X> 1000 100< X<1000 10<X<100 1<X<10 01<X <1 X<01 Insignificant hazard Practically nontoxic Slightly toxic Moderately toxic Highly toxic "Two perfluorocompounds have more toxicity test data than others becauseof their use as insecticides in ant and roach bait stations. These perfluorochemicals arc N-E(FOSA and PFOS Li salt. The manufacturerof the insecticide using PFOS Li salt, in addition to the aquatic toxicity data, supplied data on wildlife toxicity. These arc Malad: Acute Toxicity ~~ LDSO= 81 my/ke NOEL<12.5 make Subacute Toxicity, NLCO5E0C=<39244 ppppmm Northem: Acute ToxicityLDS0-42 mg'kg Bobwhite NOEL=<11.7 mgrkg SubacuteToxicity 1.C50-220 ppm NOEC<04 ppm "The insecticide N-E(FOSA and ts metabolite PFOSA have been reported to be potent uncouplesof oxidative phosphorylation in rabbit renal mitochondria. 3M Proprictary Information Do Not Copy 18 11898 DRAFT 2712.0018 Attorncy/Clicn Privileged DoNot Disclose IM_MNoS74982 [oe [oo [op To | Table 7. Aquatic Toxicity Testing on Perfluorochemical Products [POSE 1 Pimcphalespromelas |96hLCSO [1000 Ta LL [[-NE-WEOOSSEEMAA ||Piimmeepphhaalleesspprroommeellaass |o9s6bhrriLCC5S0O T|1>0100000 T[8s4 ]| , 2712.0019 [E rom T 1 prwi . 2712.0020 ECS0~ Median Effective Concentration. It is the concentration ofa test substance which causes a 50% effect on a specific characteristicofthe test organisms (c 2. immobilization of 0%ofthe Daphnia, reduction in algal ell growth by 50% as compared to the controls) afer a specified exposure period. Iti the usual endpoint in a toxicity test with Daphnia and other smallorganisms where death is hard to determionre in tests wheere growth is measured. LCS0= Median Lethal Concentration. It is the concentration ofa substance which kill 50% of the test organisms exposed to it ina specified time. It s the usual endpoint in an acute toxicity test with fish. 1CS0= Median Inhibitory Concentration. Its the concentration ofa test substance which inhibitsa biological process ofa test after a specified exposure period organism by 50% (e.2. ight production, respiration) NOEL= No Observed Effect Loading NOEC=No Observed Effect Concentration EL=Effective Loading, LL=Lethal loading. These are used where the test substance is not completely water soluble. A water accomodated fraction (WAF) is prepared. The test substance is loaded into water at different loadingsto prepare each test concentration. "The solutions are mixed and the liquid fraction i decanted to use as the test water. Environmental Fate "The release of perfluorocarbons into the environment begins with the manufacturing process. Unintentional releases can occur during anyof the steps required to produce the fluorochenical and manufacture the product. 3M applies strict industrial hygiene and safety practices to aid in minimizing production releases. Some releases such as disposal of waste products, are expected and controls provided. Within the last five years, the Environmental Laboratory has developed advanced technologybasedon Fourier Transform Infrared spectroscopy (FTIR) and applied it to the field monitoring of luorochemicals at plant stcs. Using this technology, p`meirnfilmuiozreocrheleemaisceaslorfelleuaosreoscchaenmibcealchsatrhacrtoeurgihzeodptainmdizqiuanngtitfhieedo.perIat thiaosnobfeesnteupssedi ttohe pcrqoudiupcmteinotnipnrorceemsosv.alItofhafsluaolrsoocbheeemnicuaslewdatsotemoenmiitsosriotnhse. effectivenessofpollution control In addition to releases during production and at manufscturing plants, perfluorochemicals enter the environment with product usage. After starting with the manufacturing process. 3M Proprictary Information 2 Attorncy/Clicn Privileged Do Not Copy 11898 DRAFT DoNot Disclose 2712.0021 IM_MN0S374985 the releaseofperfluorocarbons into the environment continues through product handling and distribution in the commercial sector, through the application of the perfluorochemical product e.g. textile protection, and during wear, abrasion and useofarticles treated with product. The release ends during the final disposition or disposalofperfluorachemically treated products "The fateofperfluorochemicals released to the environment is largely unknown. The characterization of fat is complicated by uncertainties about the full angeof intermediate forms of perfluorachemicls that may cxist in the environment in addition to PFOS, the final degradation product. Very le basic physical, chemical and biological data have. ben collected on the environment near the plants. Gaps in physical, chemical, and environmental monitoring data hinder model prediction and validation "The quite limited biological data thatdo exist consistofscattered, one-time testing and `pioneer sampling involving very smal numbersoforganisms. These are reported below. Laboratory studies done i the late 1970s detected the presenceofcertain fluorochemicals in fish. Early studics used N-EtFOSE alcohol. Aquatic testing was hampered by the insolubiltyofthis material and the actual concentration fish were exposed to was disputed (reported solubility: 50 ppby; reported aquarium concentration: 500 ppb). Both 3 bluegill and 2 channel catfish were found to rapidly take up the chemical and have a whole body burden of N-E(FOSE alcohol up to 400 times that in the water. The amounts in th fish declined rapidly when the fish were placed in clear water. Two channel catfish were dissected to determine concentrations in organs. The gal bladder concentrated the chemical more than any other organ (26,550 ppm). Concentrations i the brain and gastrointestinal tract exceeded 1000 ppm. The skin, skeleton, liver and ills contained the chemical at a level similar to the whole organism In 1979, thirty bluegill sunfish exposed to effluent froam manufacturing plant were found to contain N-EtFOSA (10 ppm), N-EFOSF: alcohol (7 ppm), and PFOS. Thirty more. exposed to water from a nearby river tested negative for fluorochemicals.. When four fish (2 channel catfish, | white bass, and 1 white crappie) were collected from the river, inital testing reported the presence ofN-EtFOSA, N-E{FOSE alcohol and N-MeFOSE alcohol in the fish. On further examination of test methodology. this finding was reported as incorrect. No volatile luorochemicals were found. Non-volatile luorochemicals, . PFOS, appeared to be present, but could not be identified. In recent testsof the bloodof 10 fish eating birds, albatross nestlings in the mid-Pacific and eagle nestlings in the Midwest, PFOS was detected in the eagles at an average of 41 pdebt.ectTehdeinalhbuatmraonssbslhooodwecdollveecrtyedlitftreoomrnthoe gdeetneecrtaalbUl.eS.levpeolpsuolfatPiFoOnS(.30-P4F0OpSpbh)a.s been These data support speculation about biological amplification. A reliable method for `measuring fluorochemical concentration in fish tissu has recently been developed in the 3M Proprictary Information Do Not Copy 2 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0022 IM_MN0S374985 Environmental Laboratory, but very few data currently exist on amounts presen afier cither laboratory or field exposure to a fluorochemical. Extrapolation from existing `physicalichemical data is problematic. Many perfluororganics have quite different properties from other chemicals that are known to bioconeentrate. For example, the hydrophobic and lipophilic propertiesofchlorinated hydrocarbons differ from perfluorinated chains which are both oleophobic and hydrophobic Vertebrates may also metabolize perfluorochemicals differently from the way known bioaccumulaive chemicals are metabolized. Metabolic studies at 3M suggest that after ingestion, PFOS is readily adsorbed into the blood from the gut. Once i the blood, it appears 10 bind to albumin and circulates in the blood until i reaches the liver where it c`omlalnecutfsa.ctuIrnetdhebiklei.verT,hPeFbOilSe cisitthheernbisntdosr,edcoimnptlheexgeasllobrlabdedecro,mbeeaisngcoenxjpurgeastseeodfinnteowlthye duodenal areaofthe intestine. Here PFOS may again be readsorbed into the blood and recirculated inthis loop. This proposed mechanism explains the long half life of fluorochemicals in the vertebrate body. Models are critical to determining environmental fate, but models currently in use are typically derived from experience with chlorinated hydrocarbons. Mode assumptions may not apply to or inadequately consider fluorochemical behavior. For example, do the unusual surface activity and partitioning propertiesoffluorochemicals lead to concentration in the micro-layer between surface water and air? Ifso, what docs this mean for the communityoforganisms that routinely inhabit his area? For organisms that feed on surface inhabitants? Will measurements of PFOS in organisms resultfroma classi biological amplification through trophic levelsorbe the result ofa hitherto unknown bioconcentration mechanism? Reservoirs and sinks for perfluorocarbons are yet to be documented. The dynamics regulating living systems evolved without the experienceofthese chemicals, and it is uncertain how they are incorporating these molecules. A substantial amountof additional researchi needed to adequately characterize their fate. It will equire more direct testing. inference from detected ambient levels, and modeling. More study s essential to find what accumulates, where it accumulates, how exposure to the living and nonliving components ofthe environment transforms the molecules and what effects this exposure has on organisms at all levels of the ecosystem Research Rationale Assessing the environmental fate and effectsofperfluorochemicals is a challenging task. As described above, these chemicals have unusual properties which distinguish them from other persistent chemicals, c.g. chlorinated hydrocarbons, which now form the basis for understanding and predicting environmental fate. Extrapolations and assumptions based 3M Proprictary Information 23 Attorncy/Clicn Privileged Do Not Copy 11898 DRAFT DoNot Disclose 2712.0023 IM_MN0S374987 on historical understandings of fute could introduce error and bias into research designed 0 evaluate uniquely perfluorochemical behavior. Basic information gathering similar to that gathered in the first studiesof environmental faei required. The physical-chemical. degradative, temporal and geographic nature of releases throughout the flurochemical products lie cycles must be understood. Representative questions that must be answered include How much human and ecosystem exposure is due to releases from plans, from the applicationofproducts, from the use and disposalofproducts? environ`mWehnatt?are the major sourcesoffluorochemical exposure through the natural `What happend to fluorochemicals as they pass through wastewater treatment systems? When discharged to the air? Do polymeric flurochemical products diffe in stability and environmental behavior fiom the low molecular weight perfluorochemical intermediates? How and in what forms are perfluorochemicals transported through environmental `media e.g. air, soil, ground water, surface water, the surface filmofwater? `What i the distributionoffluorochemicals throughout the biosphere? near `manufacturing plants? in remote areas? Could the concentrationsoffluorochemicls detected in the environment affect the functioningofany partofthe ecosystem? "To answer these questions and many others like them, significant additional background information must be generated. After considering the current and historical information availableon the physical, chemical and biological behavior of perfluorochemicals, 3M and its consultant, Batelle Memorial Institute, have developed a research plan to gather the necessary data. The plan has four research components. Its diagrammed in Figure 2. 1. Characterize releases. The fate and dispersionofperfluorochemicals in the environment is determined by the quantity and rate oftheir release from processes and products. Quantitative information about releases will be used to estimate environmental burden, both present and historical, and may be used to forcast changes that result from changes to products and processes. The plan provides for measuring the amounts and Kindsofperfluorochemicals released during the full ie cycle ofa perfluorochemical product. Testing will start when the perfluorochemicals are first created, continue through the distribution and conversion stages where perfluorochemicals are sold or made into products, extend to the commercial and residential us ofthe products and includ the final disposal of the product. Several different environmental compartments for releases will be sampled. These include: indoor and outdoor air (3M manufacturing, customer facility, commercial establishment, and residential), floor dust and soil, wastewater, wastewater shudge and municipal landfil. The measurements wil come from direct testing, engineering estimates, and simulations. 3M Proprictary Information Do Not Copy 2 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0024 IM_MN0S374988 2. Characterize the transport and fateofperfluorochemicals. Ful characterization ofintermediate formsofperfluorochemicals that may exist in the environment in addition to PFOS will ake some time. Initial priritics wil be established by: rinevveisetwiignatgienxgihstoiwngesxtiusdtiicnsg ocnommpualrttimmeendtiaaltfruagnascpoirtty;models can be adapied to consider the propertiesofperfluoracheicals, developing a set ofdata needs for physical-chemical properties and environmental parameters o support modelingof ate and transport mechanisms; screening available data, both estimated and measured, ambient and laboratory, to develoap plan to address data gaps. 3. Characterize distributionofperfluorocheicals inthe biosphere. To determine `where perfluorochemicals accumulate in ecological systems, levels will be measured in the Soil, water and speciesof three different kindsofhabitat. Key ecosystems and species of concern surrounding a manufacturing plant will be identified and listed. Habitat types and location with respect to the 3M plant and cfiluent streams will be described. Samples will be collected from representative habitats and biological receptors a different trophic levels. Missing data will be predicted using computer models which have been thoroughly evaluated. 4. Estimate amounts of perfluorochemicals distributed in populations and environments. The methods used to estimate human exposure include collection of samples during scenarios which demonstrate use patterns and exposure pathways, ``ppoeprusloantailonmso.nitTohreinmge,tqhuoedsstiounsneadirfeosr,escuorlvoegyisc,alaenxdptoessutrinegoasfsesstastmiesntitcsalwliyllvableidbsausbesdetosnoUf.S. Environmental Protection Agency (USEPA) ecological isk assessment guidelines. Figure 2. Overview of Project Plan 2b)) SPruopdpulcytcuhsaein ) Disposiion inthe Environment 2B)ioEsmpphierirceablassaemdploinng b) Predictive modeling 331 Proprictary Information -- DoNot Co 111y595 DRAFT 2712.0025 Attorncy/Clicn Privileged DoNot Disclose IM_MN0S374989 aEE)staHiomgmataaenErxposure Disirbuton: "The plan has been implemented and the needed information s being collected or developed. 3M has for many years been working on reducing and minimizing releases of the products as part ofits overall focus on product stewardship and pollution prevention. A corporate policy formalized in 1975 commits the company to safe and environmentally responsible practices in the development, manufacture, distribution, use and disposalofall 3M products. One initiative established under this policy is Product Life Cycle Management (PLCM). This initiative is designed to assure awareness ofpotential impacts at every stageof a product's life cycle. 3M business unis seling fluorochemical products have evaluated their products, listing those ofgreatest concern, the significant routes of exposure, information gaps and what testing is needed. In the environmental area, twelve important fate and transport mechanisms have been identified. These are 21.. aiinvdfoporrodauicrtdeppaorstiittiioonning 3. accumulation on airborne particulates 4. fate and transport to the stratosphere 5. accumulation at the surface water microlayer 6. degradation (includes hydrolysis, photolysis and biodegradation) 7. dissociation in water 8. uptake in plants 9. uptake in fish 10. uptake in birds 1. toxicity to wastewater treatment systems 12. efficiencyofwastewater treatment systems All twelve of these fate and transport mechanisms have been linked to three modeling categories: ecosystem, indoor ai and wastewater treatment systems. Models and adaptations of mods arc hing evaluated in cachofthese categories for usc ina screening process which will identify areas requiring more detailed modeling. The `physical/chemical parameters necessary to support model operation have been identified and are being developed. The degradation testing now underway will aid in determining which chemical specics need further examination "The plan provides a comprehensive approach to answering the questions about perfluorochemical fate and effects. These new exposure studies supplement existing. `ongoing research at 3M. To provide information quickly, the project components will proceed simultaneously and independently. Givinag high priority to developing the information th estimated timeftame for completion ofthese studies is two years. 3M Proprictary Information Do Not Copy 2 11898 DRAFT Attorncy/Clicn Privileged DoNot Disclose 2712.0026 3M_MN0S374990 References 1 Published Literature Flynn,R L. in "Industrial Applicationsof Organochlorine Compounds," Proceedings of the Symposium on Electrochemistry in the Preparation of Fluorine and lis Compounds. Childs and Fuchigami, Eds, The Electrochemical Society, Inc.: Pennington, NJ, 1997; 9715:51. Guidelines for the Testingof Chemicals, vol. 1, Section 1, "Physical Chemical Properties." `Organisation for Economic Co-operation and Development (OECD), Paris, France. Key, BLL; Howell, RD; Criddic, C.S. "Fluorinated Organics in the Biosphere," Environ. Sci. Technol, 1997,31: 2445-2454. Key, BLL; Howell, R.D.; Criddle, CS. "DefluorinationofOrganofluorine Sulfur `22C6o7m.pounds by Pseudomonas Sp. Strain D2," Environ. Sei. Technol, 1998, 32: 2283Schnellmann, R. and Manning, R, "Perfluorooctanc sulfonamide: a structurally novel uncouplerofoxidative phosphorylation," Biocim Biophys. Acta, 1990. 10/6: 344-345, 11 3M Confidential Reports "Exposure Assessment Plan for Fluorochemical Products, Version 3," Battelle Memorial Institute, Columbus, OH, May 18, 1995. "MPaeyrf2l6u,or1o9o9c5t.ane Sulfonate in Human Sera: Current Summary," 3M Medical Department, Gagnon, J.E., "Bioaccumulation of Fluorochemicals in Tennesee River Fish," Environmental Laboratory, Technical Report, May 22, 1979. Gagnon, J.E., "Fluorochemicals in Tennessee River Fish." Environmental Laboratory, Technical Report, December 28, 1979. Hansen, K.J, "Identification and characterizationoffluorochemical metabolites of Me- FOSE-based compounds - Summary Report," Environmental Laboratory, October 23, 1998 -HaSnusmemn,arKy_Jr.e,po"rItd,e"ntEinfviicartoinomnenatnadlchLaarbaocrtaetroirzya,tiOocnotofbfelruo2r3,och19e9m5i.cal metabolites ofPFOS 3M Proprictary Information 27 Attorncy/Clicn Privileged Do Not Copy 11898 DRAFT Do Not Disclose 2712.0027 IM_MNoS374991 Johnson, 1.0, "Absorption and BiotransformationofN-Ethyl FOSE and Tissue Distribution and Eliminationof Carbon-14 after AdministrationofN-Ethyl FOSE-'*C in Feed." Riker Laboratorics, Drug Metabolism Department, January 19, 1983. Johnson, 0, "Biotransformationof 'C-N-Ethyl FOSE in Rats after Adminsiration in Feed for One Week," Riker Laboratoris, Drug Metabolism Department, January 28, 1983. Johnson, J.D, "Extent and Route of Excretion and Tissue Distributionof Total Carbon 14 in Rats after a Single IV Doseof [PFOS "C Product], December 28, 1979. Johnson, 1.0, "Perluorooctanesulfonate and Perfluorooctanoate Metabolism in Rats." Riker Laboratories, Drug MetabolismDepartment, June 1, 193. Purdy, R., "Research Planfor 3M Fluorochemicals," Environmental Laboratory, April 1998 Purdy, R., "OccurrenceofPerfluorooctaneSulfonate (PFOS) in Wildiie, Part I. Eagles and Albatrosses," Environmental Laboratory, October 16, 1998 Reiner, E.A., "Environmentally Relevant Properties of3M Fluorochemicals, Environmental Laboratory, April 27, 1995. Reiner, E.A. Editor, "Fate of Fluorochemical-s Phase 11." Environmental Laboratory. May 20, 1983 Smith, 1 K., "Ealuation and PrioritizationofData Needs Related to Fluorochemical Fate and Transport." Battelle Memorial Institute, Columbus, OH, October 6, 1995. Vraspir, GA. and Mendel, A., "Analysis for Fluorochemicals in Bluegill Fish." Environmental Laboratory Technical Report, May 1, 1979. Welter, AN., "Evaluation of the Bioconcentration Poteofn[Nt-Ei(FaOSlE product]," Environment Laboratory Technical Report, August 16, 1978. Welter, A.N., "Final Comprehensive Report on [N-EtFOSE product)" Environmental Laboratory Technical Report, February 7, 1979. 3M Proprictary Information Do Not Copy 2 11898 DRAFT 2712.0028 Attorncy/Clicn Privileged DoNot Disclose IM_MNoS374952