Document 8RJGJGxK8KxB1wGr4OdnOzwqK

00993/3001/11999599 Procuctosf copie combustion of POSF Based Frochamcals Products of incomplete combustion of POSF Based Fluorochemicals isdocmontsummarizes whats ino shut ocr o reapscomoustn ans This document summarizes what is known about the products of incomplete combustion and frat dorsi ofpausoocansaaryivoce (FOSF) baad worarical of thermal degradation of perfluorooctanesulfonylfluoride (POSF) based fluorochemical rotects POS bases tsochariclars sats f podLrsacana sorts (PROS) nd products. POSF based fluorochemicals are salts of perfluorooctane sulfonate (PFOS) and Senior batted roocy fons. Thpasos parton of104s. primary or substituted ~erftuorooctyl sulfonamides. The perfluorooctyl portion of these Compan 5 pcs Mads of oa Trea nd 30% rchaa srs. compounds is typically a mixture of about 70% linear and 30% branched isomers. Ir~ shan th batons porto, POSK bases sats pasty conan rah addition to the perfluorooctyl portion, POSF based products typically contain a small Saarf horsieh shor on oc Broa chars percentage of homologues with shorter and longer fluoroalkyl chains. Th pros porns of POSEbasroma, snd rary ctr The perfluoroalkyl portions of POSF-based fluorochemicals, and many other SoTicrocaTpoindsare verySane This erlhcansoacrces maoekiey1d perfluorocompounds, are very stable. Thus, perfluoroalkyl chains requires more time and Rho amperes io ty esroped an yirocroon chains. ordera anes higher temperatures to be fully destroyed than hydrocarbon chains. In order to ensure Complore Goon, nGreratorn SH sugges r0sancsa 1% comb.Aten complete destruction, incineration experts at 3M suggest residence times in the combustion nao roster an |Saco and & paar1100 F (526ar-gr0ea) 1 chamber greater than 1 second and a temperature 1,700 F (926 C) or greater. If Combustorchamber mparaires 4% oat LosGopSolowaan vs. combustion chamber temperatures and retention times drop below certain levels, Sasin sencyt can oo pof anpi.Fo orforratedcompounds corsieraie destruction efficiency can drop off rapidly. For nonfiuorinated compounds, considerable artis of nealCOmustn OG, 1 0335 HCPLWTUEs0860D quantities of incomplete combustion products are formed as incinerator temperatures drop 1300. Th ampernehs Is woud 0c pare wo 0 to 1,300F. The temperature at which this would occur for perfluorochemicals would be Semoun ghar Soca of os racer Habit somewhat higher because of their greater stability. Funrochemsals roypicaty norte nh poser of ls ooh organ wastes. Fluorochemicals are typically incinerated in the presence of fuels or other organic wastes. Ur mass condion 1hrary roc of ronan certian 1 hyso3on Under these conditions, the primary products of fluorochemical incineration are hydrogen ido HE 5 CO, Inna Dot os roehamcal 091 poll ores fluoride HF and C02. Incinerators that burn fluorochemicals require pollution control `Samant remote HE otsmove fon he oust HE anscase equipment to remove the HF. If not removed from the exhaust, HF could cause Snatonmantal sto. Th os aly foc roGano1sveguaon. Fide environmental effects. The most likely effects are damage to vegetation. Fluoride orcaniann th 5105 30gconGetsonssegs psd fearhn concentration in the 5-10 ppb range can affect sensitive vegetation exposed for greater then hoes Etec can sacons wi GHEE Nodeexpose x 01060 dips hn 2-4 hours. Effects can also occur with chronic fluoride exposures for 30 to 60 days above 530 eb Hfforma vomburn rochamcas ssoobec io brat. 1 0.3 - 0.6 ppb. HF formed from burning fluorochemicals also affects the incinerator. It aaa rv rd rr onof 1 ck 1%) 0Conus coer fatsof causes more rapid deterioration of the brick lining of the combustion chamber. In parts of a na en yawhat 385 eo do por yor.ast the incirqeration system where temperatures drop below the dew point, the hydrofluoric acid Corton condadn caevesncosdea ron damoge. HFaos om bn containing condensate can cause considerable corrosion damage. HF formed from burning rte Tar han arpa Ses encahs o 4ce waste with a higher than expected fluorochemical concentration can cause the pH of the Suing soon 5 hoppac Thusacecne, Hi 403 00t 2orion scrubbing solution to drop precipitously. When this occurs, HF and other combustion ros tarssro morscompile 1 aland ba oon il ose 50 products that are scrubbed more completely in neutral and basic solutions will escape to the mosphere Ti 2a 840 uta o rmodon of3. iewhta 8 0 0sack atmosphere. This can also cause the formation of a visible white tail on the stack plume Sorecfhss rolescanbe rizedby owlmedPOSFEase nd er Some of these problems can be minimized by slowly metering POSF based and other fluorochemicals into incineration waste streams. Fornston of Dion a Fears Formation of Dioxin and Furans Dianormataniamot haytoaceding he cargitecombustonof ogensiod Dioxin formation is most likely to occur during the incomplete combustion of halogenated roman sin 14 Coeted phone. Chris romeo and foes wos, aromatics, such as chlorinated phenols. Chlorinated, brominated and fluorinated aromatics, 102010vr 51 wciarTeaanguTrd of Gon, 5 ely ie TCLs require very little molecular rearrangement to form dioxins, so relatively large amounts are adhom comcme.Foromerbsdf ensad comps oh38 formed from incomplete burning. For other types of halogenated compounds, such as oi or. oer a oun sy 18 ur me Pay polyvinyl chloride, researchers have found that relatively little dioxin is formed. Particularly ae tPrao 4Sorptiriomne rd CoysConttration Made Available by 3M for Inspection and Copying as Confidential Information: Subject to Protective Order In Palmer v, 3M, No. C2-04-6309 pr-- 3MA01412209 6116155..00000011 EEx1xh6hi1ibb5iitt 1615 State of Minnesota v. 3M Co., Court File No. 27-CV-10-28862 0099/0301/9t95999 3scos, th conditionsofth nner.nt hlocrboncoraion iy he in this case, the conditions of the incinerator, not halocarbon concentration, play the Fradaes dnunnafartt To scent rst srsviel mere predominant role in dioxin formation. The scientific literature contains vastly more imation about fo ormaton of chormtodsnd imines sen an Sook ersten information about the formation of chlorinated and brominated dioxins than about formation rr doin. of fluorinated dioxins. Tost aveshown orntes din an sa appar ob otoe ancrores Tests have shown fluorinated dioxins and furans appear to be less toxic than chlorinated ins Fo rarple bara Hagonmatr cranial credoaon and dioxins. For example Weber and Hagenmaier found that octafluorodibenzodioxin and 237B1avaorsanachrwane respecivaly, 1000-34 ossactiacvtse 2,3,7,8-tetrafluorodibenzofuran were, respectively, 1000-fold less active or inactive in a CYP acy i EROD ast han COD ans TCOF nti. ast nas inducing CYP1A activity in the EROD test than TCDD and TCDF. Induction, in this test, has ouncoroltodwih unancaantoric (Weber 1596)One usesshow 1010 ss been correlated with dioxin and furan toxicity (Weber 1995). Other studies show 10-fold less CVPR cto by 237ba5n by7237087C000 Thi coremad csssay at CYP1A induction by 2,3,7,8-TFDD than by 2,3,7,8-TCDD. This confirmed bioassays that Sionednoocay 62: 5.TFDDto AI i at 10-100 oo. (Ho fnwadeTCD showed no toxicity of 2,3,7,8-TFDD to NMRI mice at 10-100 ug/kg. (How toxic would TCDD be tisconcaaton?)Flucntad ous85shave ie ropries htmise om. be at this concentration?) Fluorinated dioxins also have other properties that make them aushar, Thoshowpas Shandon of tid 33. 3700 ha a rf of less hazardous. The slow phase elimination of fluorinated 2,3,7,8-TFDD has a half-life of appGamat & Sheu uc wee hn in 6.5.3 8inaon E1 of or0th approximately 4.5 hours, much lower than the 8.5-day elimination half-life of clqlorinated Z375TCDD (visor 1955) Adstonaly. hohrsanegeyvd l (oer 2,3,7,8-TCDD (Weber 1995). Additionally, fluorinated dioxins are highly volatile (Weber 565) Tsaap means is hywea ors easly ore te imaspnes haher 1995). This perhaps means that they would more readily enter the atmosphere, higher PUOrtage fTar 20Spar woul a 1 as rac, 15a hy151 3 percentages of that in the atmosphere would be in the gas phase, It is also likely that a Rar rapotormous shtoon ce resp 1 fs oro 06 higher proportion would photodegrade in the atmosphere and less would return to the pci ppiniiend surface soil or waterways. Chior dos an rar htwopatil fuorrsted kospear to bamuch ss Chlorinated dioxins and furans that are partially fluorinated also appear to be much less or.Wane:anaHagonmlr oun 0ao order mace roses toxic. Weber and Hagenmaier found that a four order of magnitude increase in Concannon us aadcausecampersEROD alywhanhin ons concentration was required to cause comparable EROD activity when fluorine atoms pla2c37aTCOdD tatihn stoo Tey asoshowed halrobcsan replaced two 2,3 7,8-TCDD chlorine atoms. They also showed that organisms can hb 30dslo enesio ontoddoneeand ran ar 35 on hearte metabolize and eliminate fluorinated dioxins and furans more rapidly than their chlorinated ansogs (ReerncaVieoe R ana. Haganmaer. Syne andaraoyfisssd analogs. (Reference Weber, R. and H. Hagenmaier. Synthesis and analysis of mixed Cea uredGoa consand brio san 4 ossessrert of amalon chlorinated-fluorinated dibenzo-p-dioxins and dibenzofurans and assessment of formation ndorton fh redond cholo FuadSours Gra nd and occurrence of the fluorinated and chlorinated-fluorinated dibenzo-p-dioxins and maracas. Cramo41s99n)1r3.5s8) dibenzofurans. Chemosphere 34 (1997) 13-28.) Voast f (Cramesprae 300), 626.631995)wokingwihdtoctn isinhtno Weber et al. (Chemosphere, 30(4), 629-639,1995), working with detection limits in the range 0pot. dlacind no formatoofPED and PDFs arahasi copaurd. 300. of 10 ppt, detected no formation of PFDDs and PFDFs from heating copper fluoride, sodium Furi, 22 y an an a ar, cows 30C an 50 C. Un osecorns, fluoride, and fly ash in an air stream between 300C and 500 C. Under these conditions, Campari mickras oTahand cn obi sa orn danse an comparable mixtures of fly ash and chlorine or bromine salts form dibenzodioxin and arashTroaurorsscpons 1 1a asso ff Sosa ofFortnd Gon 40d dibenzofuran. The authors propose that the reason for the absence of fluorinated dioxin and fur formation coud bh oon C.Fbond omsn. .saecransya furan formation could be the lack of C-F bond formation. C-F bonds form only at amperessors500C. 3meres twh ox 1gossTh 49m temperatures above 900 C, a temperature at which dioxins are destroyed. The same Tsouposs 445earsty ord Goinssr ans 6 00d24 BY reasons possibly also explain why fluorinated dioxins and furans are not formed as by Fro of som pion ven as CF os re orm. products of aluminum production even though C-F bonds are formed. oarfund harbin polyialrontylons (PTFE)casesrocecaPEdDDsor Webber found that burning polytetrafluoroethylene (PTFE) causes no detectable PFDD or PROF maton ASScthyaanns.ccomblustyion cath. and ass 50ers ciaoh PFDF formation. Additionally calculations, combustion data, and mass spectral data all Suggest i a abo lsBondsof 1 los axaSnesiPaOSl505y00 suggest that the carbon-sulfur bonds of the less extensively studied PFOS based Compasarmo otear ask kr 0Croncoon ors ne ara compounds are more labile and break before the carbon-carbon bonds in the perfluoroaikyl ceAtte a3 ofro eprcatornerrdoi yBreCeorstcrts . Made Available by 3M for Inspection and Copying as Confidential Information: Subject to Protective Order In Palmer v. 3M, No, C2-04-6309 swore 3MA01412210 11661155..00000022 osname 09/30/1999 an on ste ns mn ts 08 chain. These pieces of information are relevant to the likelihood of POSF based compounds ony forming dioxins. The fluoroalkyl radicals formed from breakage of the C-S bond in POSF etaTor ome retter based products would be on average shorter but otherwise analogous to those formed from Be em aa aro PTFE. Since these fluoroalkyl radicals do not rearrange to form dioxins or furans when sity PTFE is burned, there is no reason to believe these same radicals would form dioxin during emer the combustion of POSF based products. For the same reason burning other compounds DT with perfluoroalkyl groups should not form dioxins. roe PED che tas tr Polyfluoroethylenepropylene (PFEP) is another fluoropolymer that has been studied more ripe eA Cenc eee extensively than POSF based products. The perfluoroalkyl radicals formed from thermal ore ratte degradation of this polymer would have a structures analogous to radicals formed from the ar ea om burning of POSF based fluorochemicals with branched fluoroalkyl chains. e218 Pr va oe fcrt st The a U.S. EPA Peer Review Draft on health risks of combustion facilities states that ea available data suggests that fluorinated dioxins and furans are not likely products of eer ee sRorEa LrS incomplete combustion from incineration facilities. There is some concern (EPA530-D-98- 001A) that fluorine in combustion gases may increase the formation of chlorinated dioxins. I ---- POSF based fluorochemicals, when burned in the presence of paper and presumably other ia Orr td hydrogen containing organic materials are destroyed by combustion and the major product re er of combustion is HF. HF was the only fluorine product detected when ra ts rc mains rnccrn' have are by in large One of the questions about fluorochemical incineration is Pere scary ie ic dint gt irs Perfluoromethane CF4 is a particularly stable molecule due to the strength of its CF bonds. er Its complete destruction in incineration virtually insures the complete destruction of other ean, Fo Was Cr wr Tend 8. organic compounds in the same stream. (Tsang, W, et at., Combust. Sci. Technol. !998, Ee 139(1-6), 385-402.) 0 0 Pe oct ry Et cs 1, ** In 1992, Philip H. Taylor of the University of Dayton Environmental Sciences Group, who oe at the time was involved in studies of CFCs and SFe, told us that anything including A oe Oc fluorochemicals that goes directly through the flame is destroyed. For this reason, there is Teor t ra e i Ton, no point in doing flame work. It is the materials that bypass the flame that could form partial i a RT degradation products Another important point of our conversation with him is that it is the reere ee kinetics that limit the reaction as opposed to the thermodynamics. The important thing to Teoma study is the reaction kinetics in secondary combustion. pr ton ems pr ** Another problem with the combustion of fluorochemicals is that regulations may restrict ee the amounts of HF that can be emitted. For example, we have had this problem with an en oman industrial customer in Germany (15-Jan-!992 memo from Dr. Sik Toh Ting). =Senet reg Pot arts raatrs ** 3M fluorochemicals, including PQSF based products, contain no fluorinated aromatic ee es nt compounds. Thus, fluorinated dioxins would have to be formed by a total rearrangement of SRR Made Available by 3M for Inspection and Copying as Confidential Information: Subject to Protective Order In Palmer v. 3M, No. C2-04-6309 3MA0141221t 16150003 1615.0003 o0s9r/3o0r/1t9s9s9e 70combustion oducts nha ncvraionaxbaust. Ths, Bunsincswkedso. the combustion products in the incineration exhaust. Thus, fluorinated dioxins would be found at most at trace levels. 3Mhasconcn wo patsycn caution of FG07. (3 W. Wier, ** 3M has conducted a two part study on the combustion of FC-807. (J. W. Miller, 3M Capote ResauchLabor, 1968 ha star vcecon sn sson pacer Corporate Research Laboratories, 1986.)The first part involved combustion studies on paper sa7gio cost wihheSCOTCHBAN rodcts. In ase fst, orgarine samples coated with the SCOTCHBAN products. In these tests, no organic fluorine orn Hu OSo WA Gn es ThSly Le1aprd SLIe containing combustion products were detected. The analyst suggested that a possible Teas iwas as octry ve ehClowdetects concartaic reason for this was that combustion products may have been below detectable concentration Gortonvr owSori wei oF FC507onpar Aociet ose ansha due to the very low coating weight of FC-807 on paper. Another probable reason is that Vo lil G01 couscn oductwou 5 eced1 ure kl very little organofluorine combustion product would be expected to survive the likely CosrmStecospnoo conditions as is discussed below. 01 nar combustionpron fn sty.combs prodcs of SCOTCHBAN In the "neal" combustion portion of the study, combustion products of SCOTCHBAN usrochemicls weemessedaehingheFC.207 uoachericl olds 0450C. fluorochemicals were measured after heating the FC-807 fluorochemicat solids to 450 C. Thsrosuco sly Gelocion onocrarolucnn doyoaanprods. Shy parce This produced easily detectable levels of organofluorine degradation products. Sixty percent 1 1 pod olncind 3 Sl araG07SG00NSSS HOSA of the initial product was collected as volatile thermal degradation products. Measured Gpradaion procs acai nay 40% of ralGALWe. A degradation products accounted for nearly 40% of the original product weight. A uirocharic alcohol (OSE)sccouetad oagprortayhl f 0Gees fluorochemical alcohol (EtFOSE) accounted for approximately half of the detected Gratatonpockets Nayacater of 1Gayaon 10%, corssedofC31 C7 degradation products. Nearly a quarter of the degradation products consisted of C3 to C7 iadshares conanng aSle ycogen om.Oier gradation prods fluorinated alkanes containing a single hydrogen atom. Other degradation products Ddpace as ndpfyosslnamdes (He 1 shoreschin included perfluorocarboxylic acids and perfluorosulfonamides. (Were there shorter chain atescauoranses)Nofu ool: Sr wars Sle 300s tors Perfluorosulfonamides?) No fluoroolefinic materials were detected suggesting that otefins 010s ly doraondo odatos.Th wa on m fgr cous Som are less likely degradation in~e nediates. This was an important finding because some roouire a5. Sens fluoroolefins, e.g., F, , : ..outylene, 2thesedcrarsdsahdotnro eles ohcr ra SC TCHBANecu, As these degradation products had struct,.~res related to the original SC ~TCHBAN ~roducts, hoy es it oyconn 1 ayer iidsacaotne they were initial or early degradation int,;rm ~ .~~' v likely acc~ ~ted because the ro capac of nfo sos ans haan nome heat capacity of the fluorine ~toms and the format~o~ .... h~sti ~qating Paindeanape trons ---- fluorochemical radicals pm -~ [emperature ,f~ ;v~: ~.m~erature ohn acarson fotos) cami Torco. to which the combustion ~ heated to ini . ~com# 1 process, icoe 20C in this case 450 C Rowancosonse co concoofnprvt adetgdoatncnsr ct .pmcsto As was observed 're concentrations of partial degradation pr ::Jucts is e~,~t.e'd~e.~ to om ra SbimingofSCOTCveHstBedAagNer PenSCOTCHBAN be much reducr ~e burning of SOOTOHBAN treated paper. '.qhen SCOTOt~'.AN Vossapige mc no nyfredfurnerraeacdaocl rok treated pap~: ~rn~d, the initially formed fluorochemical thermal decor'~ ,,~ 9ro~i~cts sagan nai sackonzone Ser seer ame would pas~ :~h the f!~-~e reaction zone of the ~" ..... ataer as tb -~d: This Tone ai emerson ons. zone ' ;~ave a [,.~: Ror camera oun on ait fluc :~ner,q~cals w.c.:,~id re in the range of .~ pose m~~ more .~itions, why ail of cae ca al t!-..]etectable ii ~oi~:~ch ,~t~ical w: PTFE bogs egacer aTuomchameatpor ase ** PTFE begins "~ degrade r. o. ~e fluorochemical po~t~ ased Prone Cosr | am _stenp0s8u3 adseen oF fluorochemic~ '~,e~ir. ~.:,~ at ~s temperature as is eviden~ ~0~ Sr oC oT manawoav aca Songmin con~ersior" ~ ~o CS f.o C7 ~onohydrogenated ftuor:~;:~ .'ii'licsls along w~h TE prod 0 i HGH chan, ThaPYRococrncoaPOnSE ms produc[s ,,.: ;:tie still **~:~ct C6F! 7 chain. the hydroca,~bon portion of PO~;I~ nA eAviart nby Coee pcioansrs4coptgongEssAConLtam orn Made Available by 3M for Inspection and Copying as Confidential Information: Subject to Protective Order In Palmer v. 3M, No. C2-04-6309 swore 3MA014!2212 6161155..00000044 o0s9r/3o0r/t1e99s9s asadurocnaricls wih Pyrosprionswilbg 1 degrade over 8 based fluorochemicals with hydrocarbon portions will begin to degrade at lower as is areas oy lowe os Secompasnon ana evidenced by the following initial decomposition temperatures. ream me FC-171 Fer 20C FC-135 Fein we FC-430 Feo Sec FC-99 i we FC-129 Fare x0 FC-170C 350 C 260 C 450 C 535 C 450 C 300 C arbor ordis oun 0b 1 mainuatepyrolysis rocof PIFE a ghar Carbonyl fluoride is found to be the main oxidative pyrolysis product of PTFE at higher moar.CarboyPu Corea SaAES Sorta ot Gre35. temperatures. Carbonyl fluoride concentrations decreases significantly as temperature drop 1051500andBeappasswhe empress p155000.Whe water var prose to at 550 C and disappears when temperatures drop to 500C When water vapor is present necarr ga, carson ar0 cov CO2aaHF in the carrier gas, carOonyl fluoride is converted to CO2 and HF. Ory inha soa ruses tn maton otc vyfxscclaorssoions Oxygen in the air stream prevents the formation of toxic very toxic octafluoroisobutylene HOMPTFED105.Gynwou esas 855rent 4omen10m90 ofPOSE from PTFE pyrolysis. Oxygen would presumably also prevent its formation from 3M of POSF Cane urnacss based fluorochemicals. =GaAS0RogerG. PrMiTocsnsiosay1Tre expos dinfeor ** 02/09/90, Roger G. Perkins 3M Toxicology 1. The 31Vl exposure guideline for poruarcobere0'01spatspe ono 8 Coun aos. 1418ied perfluoroisobutylene is 0.0! pads per million as a ceiling value. It is not a time-weighted ricogovaun (3s sh15 eDxpo ue) average value! (Is this still the exposure guideline?) =TisBasicwashshui coor th PFI dso inthe idphase ** This basic wash should destroy the PFIB dissolved in the liquid phase. Vi Gscussed ow10dtomin th formation ofdeasaton proses dungactvates ** We discussed how to determine the formation of degradation products during activated cabonregurraion. Aero call 1ahas sn Hte 35he6lcom3arsat0on.| carbon regeneration. After our call, I talked to John Hunter. Based on that conversation, I Conuied rtmars 1c 3 3rartnod10 avoutcn ageareionTh reasis concluded that there is not a significant need to evaluate carbon regeneration. The reason is FalTonal con acnaedcoon om ou 0 51 ow SesO1od 0 that fluorochemical containing activated carbon from our plant site is now destroyed in Comrie. Viaar ot egenrsi oaSpar Catan. nma yKIOWo eGDs. 400 cement kilns. We are not regenerating of the spent carbon, and to my knowledge, we are Pots Seiad cabo Hedirento ro amcalwists rao 100 not advocating activated carbon treatment of fluorochemical waste streams to our Trh cnondtpoonshcf.heTchemsenctokniinownsu4scSeFa (1lLy5c2Ca) sthhsfsuoovsrhtasroiccaltotan customers. The conditions of the cement kilns would certainly fully destroy the fluorochemical to inorganic products, These conditions are 2700F (1482C) with a several second retention time rma re Liceyom Made Available by 3M for Inspection and Copying as Confidential Information: Subject to Protective Order In Palmer v, 3M, No. C2-04-6309 sw 3MA01412213 11661155..00000055