Document ByD5pGqdgBgVBzOd4LnrM2V4j

ECOTOXICITY PROFILE OF 1H,1H,2H,2H-PERFLUORODECANOL Voiksr Koch1,William R BertP, Robert C Buck2,John Gannon2, Robert A Hoke2, Hiroyuki iwai3, Mary A Kaiser2, Seiji Shinya4, Ning Wang2 Teiomer Research Program 1Clarlant Germany, 2DuPont USA, 3Daikin Japan, 4Ashai Glass Japan -- AR226-3358 SYNTHESIS OF PERFLQROMiNQLS (TELOMER ALCOHOLS} pH,1H ,2H.2H-Perfluorodecanol, C A S No. 678-33-7 (6-2 Teiomer ilcohol) Is an Important speciality Intermediate. More than 8 0 % of the produced amount of tetomer alcohols are used for the preparation of high molecular weight polymers containing perfHiortnated alcohols. These so-called Tetomer-based Polymeric Products (TBPPs) are used e.g. for the coating of textiles and carpets to achieve resistance against water, oil and stains. The producers of teiomer alcohols are currently investigating In detail the environmental tote and effects properties of tetomer alcohols and especially of 1H,1H,2H,2H-Pertluorodecanol within hie Tetomer Research Program (TRP). ils have in comparison to their hydrogenated counterparts nal physico-chemical properties which are related to the But these properties (e.g. very low water solubility, high volatility) ai :nsiderabte challenges tor ecotoxldty testing. Within TRP testing strategies for this substance which Is difficult to test were developed based on latest methodology. The poster presents basic physico-chemical and tote properties of t H,1H,2H,2H-Perfluorodecanol, applied design tor acute and chronic , .............. ilfsedtm i"t tes`ts and the results tor Ute different t (IFs) Tetrafkioroethylene pF Tetrafluorethylene Ethylene 1H,1H,2H,2H-Pei1kiorodeeanol, C A S No. 678-33-7 (6-2 Teiomer alcohol) Is an Important speciality Intermediate. More than 8 0 % of the produced amount of teiomer alcohols are used tor the preparation of high molecular weight polymers containing perfluonnated alcohols. These so-called Tetomer-based Polymeric Products (TBPPs) ate used e.g. tor the coating of textiles and carpets to achieve resistance against water, oil and stains. Ashai Glass, CSariant. Dalkln and DuPont as major producer of these chemicals have Investigated basic physico-chemical, tote and ecotoxlcty properties of 8-2 Teiomer alcohol which Is the homologue with the highest contera (50-60% wAv) in commercial Teiomer alcohols. Most of the date presented here were established within the Tetomer Research Program (IB P ) funded by the companies mentioned above. will be used In a future Environmental Risk Assessment. 6-2 Teiomer alcohol differsIn some physico-chemical and tote properties from the unftuortnated 1-Oecanol (a table on right hand de on Physico chemical and Fate Properties of 1-Decanol & 6-2 Teiomer alcohol). Whereas these propertiesare responsible tor the desired elfe (hydraphobfctty and oleophobtoity) in articles (e.g textiles and carpets) they are posing a considerable challenge fortesting the ecotoxldty especially In the aquatic compartment ItIs also qufre common to estimate physka-chemdal and fate properties using propert.y.-.p..r.o.p..e.r.t.y..e.s..ti.m..a..t.i.o.n..a.l.g..o.r.i.t.h.m...s./programst,itftto important to note that these programs currently toil to deliverreliable ei tetomeralcohols in most cases and measurements need to be carried < Instead (s. table on right hand de on Physico-chemical and Fate Properties of 1-Decanol 6 8-2 Teiomer Alcohol) in orderte avoid that wrong conclusions were drawn. SmUChjREOP IH.IHHH-PERFLUORODECANOt FFFF FFFF C8 C2 F_ 'Hydrolysis TF n = 3 6-2 Teiomer alcohol n = 4 8-2 Teiomer alcohol 1H, 1H,2H,2H-Pwfluorodecancl 8-2Teiomeralcohol ECOTOXICITY DATA OF 8-2 TELOMER ALCOHOL . PHYSICO-CHEMICAL AND FATE PR O P ER T IES OF t O E C A N p L & B-Z TELOMER ALCOHOL The acuta aquatic ecotoxldty tests were all earned out as limit is with a saturated solution of 8-2 Teiomer alcohol. The test solution v prepared by slow stiring of 8-2 Teiomer alcohol In water to achieve a saturated solution. The solution w as centrifgued and transfered into test vessel which were precoated with toe test substance. Analytical monitoring w as canted out at the beginning and at the end of toe exposure period. For the chronic daphnie test toe stock solution was prepared with methanol a s solvent In tests where aeration Is required (e.g. acute fish test and chronic daphnia test) loss of 6-2 alcohol is very likely and w as observed. successfully appUed torthe Acute Daphnia test, whereas for fish toe substance concentration at the end of toe test was below LOD. But despite considerable efforts itwas not possible to Sowtrough ryriamestablish a reliable and still cost-effective which would ensure constant concentration during the whole exposure period and which would be the test system ofchoice for acute fish and chronic daphnia testing. For the chronic daphnia test a semi-static test design was used and substance toss due to volatility was carefully monitored in 3 testing Intervals (see graph below). The test substance was dissolved In methanol and mixed thoroughly with quartz sand. The solvent was evaporated in a hood arto the substance concentration verified by reextracting from the sand (96% recovery). The quartz sand was then mixed with toe aritltical sediment and toe soli Sediment and soil samples were taken at toe beginning and at toe end of tire exposure and an analysis canted out to determine toe total fluorine content (Total Organic Fluorine TOF) In order to ensure that there was no considerable loss by volatilisation during tire test period (3d, 14d or 21d). Analytical methods Q Q M Sfor84 Takm orttocM (Aqw fc uitipM liw nt) mlzGC: CP-6800 Varion Fused Silica CP-SIL8 Capillary column MS: Saturn 2000, Vartan; = 463 and 395 Calibration curve: r2= 0,9984; LOD = 9 pg/L, LOQ = 27 pg/L W ktooU Toth M otiodlbrM om tuSan atToUOrgwteFluortMfTOF) (Sodknantw xiS otcanpwtnont} Combustion of the analyte In an oxyhydrogen flame (ca. 1200 C) (details see (9j). The physico-chemical and fate properties of C8-2 Teiomer alcohol differ In various aspects considerably from the properties of toe unffuorinated 1-Decanol (e.g. density, water solubility, volatility). It Is Important to note that property property estimation methods deliver reasonable results for 1-Decanol but are In most cases not suitable to derive properties for 8-2 Tetomer alcohol. This can be seen easily when comparing measured and estimated results for 8-2 Teiomer alcohol (e.g. water solubility, vapour pressure, volatility, sorption The tow water solubility, high volatility a s well a s sorptive propertiesof 6-2 alcohol mates testing especially oftoe Aquatic Ecotoxldty difficult. ___________ if i! W M iA iO ______ iwsamrm r~- BMB.ttqp) la. hl ,,.Mm Minn i i 1 iiiiiiM _E5tSaJ3_ twtSpw CCNC.JS ONS solution w as effective observing almost no loss due to volatility. The jlfce phyco-chem properties of 1H,1H,2H,2H- 'ferfluorodecanol, C A S No. 678-39-7 (8-2 Teiomer alcohol) require and careful analytical monotortng In order to derive data. The low water solubility and high volatility g In the aquatic compartment difficult e . quested for the test e.g. fish (acute test) and daphnia quartz sand coaled with 8-2 Teiomer alcohol can be mixed with soil and sediment and during toe exposure period of toe tests (3d. 14d or 21d) no toss of Total Organic Fluorine (TOF) was observed. TOF w as determined with the WickboId Torch Method (9|. In the Aquatic compartment 8-2 Teiomer alcohol has shown no effect at the concentrations which could be achieved In water tor acute and chronic ). Testing Is also difficult for algae a s during the test the teste. i&es considerably. Due to the sorptive properties of 8-2 In the Terrestrial compartments toe NO EC for earthworm was 32 mg/Kg >1 toe concentration In water drops in toe algae test by dw. and for toe most sensitive plants species rape and the endpoint fresh weight toe N O EC was 25 mg/Kfl dw. aTesting 8-2 Tetomer alcohol in the solid compartments (sediment and The nematode Caenorhabditls elegans abundant In soil and sediment soli) w as found less difficult as coating of quartz sand with metoanolic showed no effects on growth and reproduction at 1000 mg/Kg dw (WWMWMWMWMMMM/MAMMMMWilWWtfMWMMMWWWWWMNWWWMIWMWWMI REFERENCES; B IU C U D Oafeaet '1-Docanof, http-J/ecfejrcit Safety Date Sheet, FJoowet EA800 AMrieii, Mafisrtai Safety Date Sheet. 1-Oecsnol Ulm, K. & Uttbig, H, Cham. 29g.1976,99 (12), 477-68 EPI: U S E P A O P F T E PI S u l * Property Estimation Software, Version 3.10, htip^/www.epe.aov/opptlnWexpoaureMocs/epIsuiteJitm Cfeftant. Unpublished measuamenfa, FkiowetEASOO DuPont, 8 E T A C 2003, Ham bug Sweeter, P A , Decomposition of Organic Fluorine Compound byWWdrokl Oxytiydrogen H Analytics!Chemtofry, 1968,28,1788-1768 _ Tratfwpnjger, W ,, Hsfcfer. M., Hiles, B., Bator, S.. Ahif, W., Bivkon. Tox. and Chem. 1997,18.246-250