Document omNRX97oojraqZ5p35mz2BqoD

BIODEGRADATION TEST SUBSTANCE Identity:N-methylperfluorooctanseulfonamidoethanolm;ay also be referredtoas N-MEFOSE Alcohol,FC-790, or FM-3925. (1Octanesulfonamide,N-methyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-N-(2-hydroxyethyClA)S-,# 24448-09-7) Remarks: Materialisan off-whitew,axy solid.Sample purityand lot number were not recorded. METHOD Method: COD/BOD study using3M EnvironmentalLaboratorystandard protocolsmodeled afterthe Standard Methods forthe Examination of Water and Wastewater, 14th EditionA,merican PublicHealthAssociation, 1976. Type: Potassium dichromaterefluxCOD and AerobicBOD GLP: No Year completed: 1979 Contact time (units)S:ee Remarks lnoculum: Not noted. Remarks: The laboratorwyas notabletogenerateuseabledata forBOD due toinsufficieonxtygen depletion. The COD was done inreplicate. RESULTS COD: Analysis1 = 170,000 mg/kg Analysis2 = 156,000 mg/kg Average = 163,000 mg/kg BOD: A twenty-daybiochemicaloxygen demand (BOD) testwith suspended substrateconcentrationsup to 1000 mg/L showed insufficient oxygen depletioninexcess ofthe blankstoallowthe calculatioonf BOD values. ThisresultindicatesthatN-MEFOSE alcoholisnot likeltyo degrade ina non-acclimatedaerobicbiologicatlreatmentsystem. Remarks: A 259 mg/L potassium hydrogen phthalatecontrolr,unning concurrentlywiththe same seed was found to have a BOD5 of231. The mean BOD forthiscontrolsubstrateatthisconcentrationis208 mg/L. This indicatesthattheseed was activeand acceptableforBOD studies. The factthatoxygen depletionratesduringthefirsftourteendays in culturescontainingN-MEFOSE alcoholcloselyfollowedthose ofthe seeded controlsuggests thatthe lackofdegradationisnot due totoxicity to heterotrophimcicroorganisms. DATA QUALITY ReliabilityK:limischranking= 3. The purityofthetestsubstance isnot sufficientclhyaracterizedand the inoculum concentrationisnot described though the controlindicatesitwas active.Study used individuawleights thatexceeded water solubilittyh,us thetestsubstance was notsolubilized and was notavailabletomicrobes. REFERENCES 3M TechnicalReports: "BiodegradationStudieson FM 3925",E.A. Reiner,Project9970012600 PremanufacturingNoticeFC-790, Report No. 0 16,January 8, 1979. "Chemical Oxygen Demand of FM 3925",E.A. Reiner,Project 9970012600 Premanufactudng NoticeFC-790, Report No. 017, January .8,1979. OTHER Submitter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 5/1-7/00 3m, Form6747-11-A TECHNICAL REPORT SUMMARY 1/8/79 TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Important - If report isprinted on both sides of papef, send two copies to TCC.) Di@ision Environmental Project Laboratory Premanufacturing Report Title Notice (EE & PC) FC-790 L)ept. Number 0535 Prolect Num r 9970012600 Report Nu r Biodegradation Studies on FM 3925 To V. Pothapragada AUthor(s) Employee Nurnber(s) E. A. Reiner Notebook Reference 47816 No. of Pvss IncludingCovershoot None See Environmental Lab Request #4197 SECURITY Open El Closed 3M CHEMICAL CompanyConfidential()SpeciAaulthorization) REGISTRY Now ChemicaRlesported Yes No KEYWORDS: (Seletcetrmfsrom3M TheauruSsu.nesotther applicatbelrems.) CURRENT OBJECTIVE: To evaluate the susceptibility biodegradation. of FM 3925 to Biodegradation EE & PC Div. Fluorochemical Degradation BOD REPORT ABSTRACT: (200-250words)Thisabstracitnformatioinsdistributbeyd theTechnicaClommunicationsCenterto aler3tM'erstoCompany R&D. ItisCompany confidentimaalterial. A twenty-day biochemical oxygen demand (BOD) test with suspended substrate concentrations up to 1000 mg/l showed insufficient oxygen depletion in excess of the blanks to allow the calculation of BOD values. This result indicates that FM 3925 is not likely to degrade in a nonacelimated biological treatment system. FM 3422 has previously been found to be resistent to biodegradation even in acclimated aerobic systems. Since it is chemically similar to FM 3422, FM 3925 is probably also resistent cultures. to biodegradation in acclimated microbial InformatLiiopn7 Initial$: -2- BIODEGRADATION STUDIES ON FM 3925 Introduction Previous studies on FM 3422, ethyl fose alcohol (C F SO N(C H C H OH), have shown that this compound is not measgrigl'y RegrRdgd b@ zither acclimated or nonacclimated mixed microbial cultures (1,2). Therefore, it appeared unlikely that the FM 3925, methyl fose alcohol (C F SO 2N(CH )C H OH) because of its chemical similarity, would be rgaa?ly degridaglg. @he following work was conducted to check the susceptibility of FM 3925 to biodegradation. Ultimate Biochemical Oxygen Demand A twenty-day biochemical oxygen demand (BOD) was conducted on FM 3925.according to the standard Environmental Laboratory protocol (attached), except that FM 3925 was placed in the BOD bottles in solid form and that the bottles containing FM 3925 were continuously stirred for the entire incubation period. Stirring was done using a Hach Model 2173 with magnetic stirring bars. The seeded controls and reference compounds were not stirred. The results of this study are shown in TABLE I and are plotted in Figure 1. No biodegradation of FM 3925 was observable by this method. Th6 method requires that the dissolved oxygen depletion in a test culture exceed the oxygen depletion of the seeded control by at least 2 mg/l. This did not occur. Thus the BOD cannot be calculated. The BOD at each time is therefore considered to be less than 2000 mg of oxygen per kg of this compound. A 259 mg/l potassium hydrogen phthalate control run concurrently with the same seed was found to have a BOD of 231. The mean BOD for this control substrate at this concentiation is 208 mg/l. This indicates that the seed was an active acceptable seed for BOD studies. The fact that the test substrate did not degrade to a detectable level in this study suggests that these compounds would not degrade significantly in a nonacclimated waste treatment system. Whether or not microbial populations can acclimate to degrade, this compound cannot be determined from this study. However, since FM 3925 is structurally very similar to FM 3422, which has been shown not to degrade in acclimated cultures, we anticipate that FM 3925 will resist degradation by even acclimated microbial cultures. The fact that oxygen depletion rates (Figure 1) during the first fourteen days in cultures containing FM 3925 closely followed those of the seeded controls suggests that lack of degradation is not due to toxicity to heterotrophic microorganisms. 9 8 bD 7 0 -W 6 Cd ;-4 5 0 4 x 0 3 ,a w > ri 2 0 Figure 1: Oxygen Concentration of Culture Bottles During Ultimate BOD Study of FM 3925 L Average Seeded Cont 10 mg/l FM 39 100 mg/l FM 39 1000 mg/l FM 39 %&-now ...... i.LtL. 0 3 5 7 10 14 Time (Days) Description and Concentration Seeded Control #1 Seeded Control #2 Seeded Control #3 Seeded Control #4 Avg. Seeded Control FM 3925: 10 32 100 560 1000 mg/l mg/l mg/l mg/l mg/l Potassium hydrogen phthalate: 2.6 mg/l 4.3 mg/l 6.1 mg/i 7.8 mgll Day 3 8.9 8.9 8.9 8.9 8.9 8.4 8.7 8.5 8.7 8.7 6.5 5.0 3.3 1.7 TABLE 1 ULTIMATE BOD DATA FOR FM 3925 Day 5 8.7 8.9 8.8 8.9 8.8 Dissolved 02 Concentration Day 7 Day 10 8.4 8.3 8.6 8.5 8.5 8.4 8.6 8.5 8.5 8.4 Day 14 7.8 7.9 7.7 8.1 7.9 8.3 7.9 7.7 7.4 8.3 8.0 7.7 7.4 8.3 7.7 7.7 7.5 8.4 8.1 8.0 7.6 8.5 8.1 8.1 7.7 - - -5- References: (1) Reiner, E. A., Biodegradation Studies of Fluorocarbons, 3M Technical Report 8/12/76. (2) Reiner, E. A. . Biodegradation STudies of Fluorocarbons-I I, 3M Technical Report 1/9/78. EAR/cen Aw@ C.@MET,.RA@TI LiLTiKh-rE BOD DA-RA -Si4EET I?ZS"(fUSA, S F-'PKiZes s 0 met11;@S4AfAPLe ]3bD3@ B-OD.T l@@o SC)DIO BOD 3Z 00- A e--rUt- 0 L> L/,4 146;S PLACCO i@j 1-146 F30.b BOTTL.ES l@) THE Sc3L-I.D FOIZM- s 4C@,PLA C 6 P,..'t,4O.A,,at4l-iq'LAOIAS S-rIRZIW(a LLN IT6 C@14 t-AODE.LZ'117:3)wi-r !BTiR.P iN4 @BA Ps ;,-TiAeISA PAPLF-S WE.RP- MI)CF-D@ I>IARNI(4 7t4S FNT IRE iNe- 10 VV -A -7-t.rooo, ,Form 6747-1 i-A TECHNICAL REPORT SUMMARY Date 1/8/79 TO- TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Importan-t Ifreporitsprinteodn bothsideosfpaper,sendtwocopiestoTCC.) Division Project vxronmentAl-.L Report Title Prema.nufacturing Chemical Oxygen To Author(s) V. Pothapragada Notebook E. Reference A. Reiner abbr- atory (EE & PC)Notice FC-790 Demand of FM 3925 Dept. Number 0535 Project Number 9970012600 Report Number 017 Employee Number(s) 47816 No. of Pages Including Covershoot SECURITY None - See Environmental Lab Request #4197 .1Open 11 Closed 100 (Company Confidential) (SpecialAuthorize t-on CHEMICAL 13 REGISTRY P' New Chemicals Reported Yes gg No KEYWORDS: (Select terms from 3M &-4 Thesaurus. Suggest other applicable terms.) Cl@emical Oxygen Demand (COD) CURRENT OBJECTIVE: To determine the extent to which FM 3925 is oxidized by refluxing in the presence of potassium dichromate under strongly acidic conditions. Degradation Fluorochemical EE & PC-Div. REPORT ABSTRACT: (200-250 words) This abstractinformationisdistributedby the TechnicalCommunications Center tc alert3M'ers to Company R&D. ItisCompany confidentialmaterial. The chemical oxygen demand (COD) of FM 3925 was determined according to the 3M Environmental Laboratory's standard protocol which is modeled after the Standard Methods procedure. The COD was determined to be 163,000 mg/kg. This is 35% of the total theoretical oxygen demand (assuming N is not oxidized) and 71% of the oxygen demand calculated assuming that only the nonfluorinated portion of the molecule is degraded. InformationLiaio Initials: -2- CHEMICAL OXYGEN DEMAND OF FM 3925 The chemical oxygen demand of FM 3925 was calculated according to the standard protocols of the Environmental Laboratory (attached). These protocols are modeled after the procedure described in Standard Methods (1). The results of two replicate analyses are shown in TABLE 1. TABLE 1 COD of FM 3925 Analysis 1 Analysis 2 Average 170,000 156,000 163,000 mg/kg mg/kg mg/kg This COD is 35% of the total theoretical oxygen demand assuming complete oxidation to.F , co so NH and H 0. It is 71% of 2t 12 the oxygen demand calculated assaling i@at on y the nonfluorinated portion of the molecule is degraded as in the following reaction: c F so N(CH )C H OH 8 17 2 3 24 + 4 0 --;NC F 2 8 17 SO NH 2 2 + 3 CO 2 + 3 H 2 0. (MW 557) Reference: (1) Standard Methods' 'for'the' Ekahiih*at'ibho'f* Water 'an'dWastewater, 14th Edition, American Public Health Association, 1976. EAR/cen Attachment 3M ENVIRONMENTAL.LABORATORY CHEMICAL OXYGEN DEMAND PROTOCOL (Used prior to January 4, 1979) EAR 1/4/79 Chemical oxygen demand is determined by a modification of the method described in Standard Methods for the Examination of Water and Wastewater,, American Public Health Assocation, p. 550554, (1976). Procedure Modifications The reflux apparatus differs from that described in Standard Methods in that 500 ml round-bottomed boiling flasks with groundglass 24/40 neck are used in place of comparable ground-glass Erlenmeyer flasks. In addition, electric heating mantles, which are capable of adequately boiling the contents of the reflux flasks, are used in place of a hot plate. The silver sulfate catalyst is added directly to each COD flask prior to refluxing the sample-sulfuric,acid-dichromate mixture. The ferrous ammonium sulfate titrant is standardized against the blank. It is assumed that no dichromate is reduced in the blank during the reflux procedure. Sample Size and Reagent-Quantity and Normalities Sample size is 50 ml. The reagent quantities and normalities are those prescribed for this sample size in Table 508:1 of the 14th Edition of Standard Methods, except that A92SO4 is added in 0.12 g quantities and is not dissolved in the concentrated sulfuric acid reagent. Procedure for Low COD Samples The alternate Standard Methods COD procedure for low-COD samples is used when COD values of 50 mg/l or less have to be determined. In this procedure the sample size and reagent quantities remain the same, but the normalities of the dichromate and ferrous ammonium sulfate solutions are reduced to 0.025 N and 0.01 N,. respectively. EAR 1/4/79 3M ENVIRONMENTAL LABORATORY CHEMICAL OXYGEN DEMAND PROTOCOL Chemical oxygen demand is determined according to the method described in Standard Methods for the Examination of Water and Wastewater, erican Public Health Association, p. 550--5-5-4-,--ff976). Procedure Modifications The reflux apparatus differs from that described in Standard Methods in that 500 ml round-bottomed boiling flasks with groundglass 24/40 neck are used in place of comparable ground-glass Erlenmeyer flasks. In addition, electric heating mantles, which are capable of adequately boiling the contents of the reflux flasks, are used in place of a hot plate. Sample Size and Reagent Quantity and Normalities Sample sizes of 50 ml are used with the reagent quantities and normalities given in Standard Methods, Table 508:1. Procedure for Low COD Samples The alternate Standard Methods COD procedure for low COD samples is used when COD values of 50 mg/l or less have to be determined. In this procedure the sample size and reagent quantities remain the same, but the normalities of the dichromate and ferrous ammonium sulfate solution are reduced to 0.025 N and 0.01 N,. respectively.