Document 93nnbXD6n2EMzya8ongKj5BQ3

TECHNICAL REPORT SUMMARY TO; TECHNICAL COMMUNICATIONS CENTER - 201-2CN BACK TO MAIN Dale 8/31/81 (Im portant -- I f report sprinted on both sides o f paper, send two copies to TCCJ D iv is io n Dept. Num ber Environmental Laboratory (EE & PC) Projcjr.l Commercial Chemicals R eport T itle Chemical Oxygen Demand of CS-2151 To 0535 Projoct N um hor 9970012600 Report Num ber OS* 7 D. R. Ricker, Commercial Chemicals Division, 53-4N A u th o r(s ) Em ployee Num ber(s) Eric A. Reiner, Environmental Laboratory/EE & PC, 21-2W-5 47816 N otebook Refuronco N o. of Pagos In clu d in g Covorshool None (See Environmental Lab Request #6260S) s e c u r it y ^ 3 Open (Company Confidential) Q Closed (Special Authorization) 3M CHEMICAL w REGISTRY w New Chemicals Reported Yes 3 No KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.) CURRENT OBJECTIVE: To determine the chemical oxygen demand of CS-2151 Chemical Oxygen Demand <con ) ixig/'atia'Lion Oxidation EE&PC Div. Fluorochemical Surfactant REPORT ABSTRACT: (200-250 words) This abstract inform ation is distributed by the Technical Communications Center alert 3M `ers to Company R&O. It is Company confidential material. The chemical oxygen demand (COD) of CS-2151 was determined in accordance with the Standard Methods reflux method and according to the Standard Ampule COD Method of Oceanography International. The reflux protocol gave a COD of 66,000 mg/kg. The ample method gave a ODD of 81,000 mg/kg. Experience with a wide variety of perfluorinated organics has shown that the perfluorinated portions are not oxidized under the conditions of the COD test. The potassium salt of the perfluorinated portion of the subject material was previously tested and showed no chemical oxygen demand. Thus the observed COD appears to be due to the diethanol amine portion of the chemical. The theoretical oxygen demai of CS-2151, assuming complete oxidation of only the diethanolamine portion is 77,000 mg/kg. Info rm a tion Liaison Initials: COD OF CS-2151 BACK TO MAIN Introduction The chemical oxygen demand (COD) test measures the oxygen equivalent of a chemical under strong oxidizing conditions. When compared to theoretical oxygen demand, COD can give an indication of the stability of the component to chemical oxidation. Since most organic compounds are completely degraded in the COD test, this test is frequently used for comparison with the biochemical oxygen demand (BOD) test. For those materials degraded by the COD test, the BOD/COD ratio gives an indication of the completeness of biodegradation. This report describes the test performed on CS-2151 to evaluate its COD. It provides the data generated in this study and compares the chemical oxygen demand to the theoretical oxygen demand. Methods and Materials The 3M Environmental Lab-received the test substance on 11/4/80. The sample was a light, yellow liquid. It was reported to contain 25% solids in water. Solid portion of this product is designated CS-2070. Wade Schiel performed the chemical oxygen demand test in accordance with the standard Environmental Laboratory Protocol (attached) this protocol is based on the Standard Methods chemical oxygen demand procedure. The COD was also measured according to the Oceanography International Standard Ampule COD Method (copy attached). For both procedures, COD's were also run in parallel on potassium hydrogen phthalate (KHP) reference samples. Results and Discussion Duplicate determinations by the reflux method gave COD for CS-2151 of 67,000 mg/kg and 66,000 mg/kg. A potassium hydrogen pthalate standard run in parallel with a theoretical COD of 405 mg/l was determined to have a COD of 392 mg/1* Duplicate COD measurements on CS-2151 by the ampule protocol were both 81,000 mg/kg. The parallel standard with a theoretical COD of 176 mg/1 was determined to have a COD of 170 mg/1. Previous studies on FC-98, which is the same fluorochemical except that potassium replaces the diethanolamine, showed that FC-98 had no chemical oxygen demand. Therefore, it appears that the chemical oxygen demand of CS-2151 is due only to oxidation of the diethanolamine portion of the molecule. The theoretical COD of the CS-2151 solids (CS-2070), assuming its fluorochemical portion and NH3 are not oxidized, is 307,000 mg/kg. Thus, the theoretical COD of CS-2151, which is a 25% aqueous solution is 77,000 mg/kg. Conclusion The measured COD values are consistent with the hypothesis that only the diethanolamine portion of the molecule is degraded in the COD test. BACK TO MAIN * Lab Req. No. (d 2-(O ^jvh) Environmental Lab Data Sheet AMPULE C.O.D. Date analyzed Analyst 0 , 4 - S U A A 7 OCEANOGRAPHY INTERNATIONAL COD PROCEDURE Sample D e s c rip tio n I Lo "X-Co o Spec. 20 No. A >OOnwi Blank X T /o v ...................... -z.-- r r --^ r . v .rjp ml Sample D ilution Factors Z.tuu-9 lootij jo,c ^ t.o ^ f z.ltl /. X T w .f Graph Readout (e % C .O .D . mg/1 $ I } CT>Z> , L. Q,2>oo u . 6 3 .6 3 U 1 , rJ? " - J L >,o /, i?o7j (.0 m * if 1,007 1(0 `i I.P7+. -9/ o .w 00 /.oc? * r t,OZ1-^tOOtyJ 100 j . r SA b o .r b > 1,03e! ! sn > *3f ? -----------7--.-0--------m------*-/px------- 2-S ----- . ^ (p 30^ t-A T2S 5 > 9*0 2 i 8 ^ | , ft'*** a A - ' q b tjc p * w . & !o 290/O ft) 9LA-flC~ 7^00 ' ifrrvr.PtG S?2 > a if.p Y `2~Y(5t - fy&tDiPf /vt' mirTUCJ ,<t H )~i O ( J --_ BACK TO MAIN ..... TECHNICAL REPORT SUMMARY Date 8/31/81 TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (Im portant -- I f report is printed on both sides o f paper, send two copies to TCC.) D iv is io n Environmental Laboratory (EE & PC) P ro je c t Commercial Chemicals Division Report Title Biodegradation of CS-2151 (CS-2070) To Don Ricker, Commercial Chemicals Division, 53-4N A uthor(s) Eric A. Reiner, Environmental Laboratory(EE & PC), N n to h o o k Roforonco None (see Lab Request #6260S) Dept. Num ber 0535 Project N u m b er 9970012600 Report Num ber CSS E m ployee Num ber(s) 21-2W-! A 2 S 1 6 N o. of Pagos In c lu d in g C ovor shoot s e c u r it y 1 Open (Company Confidential) O Closed (Special Authorization) 3M CHEMICAL w REGISTRY w New Chemicals Reported Yes S No KEYWORDS: (Select terms from 3M Thesaurus. Suggest other applicable terms.) CURRENT OBJECTIVE: To evaluate the susceptibility of CS-2151 to biodegradation. Biodegradation EE&PC Div. (Env. Lab) BOD Fluoroehemical Surfactant REPORT ABSTRACT: (200-250 words) This abstract inform ation is distributed by the Technical Communications Center to alert 3M'ers to Company R&D. It is Company confidential material. A 20-day biochemical oxygen demand (BOD^q ) test using concentrations of CS-2151 ranging from 60 to 540 mg/1 gave a BOD20 for CS-2151 of 69,400 mg/kg (278,000 mg/kg for CS-2070;. Oxygen demand is presumed to be due to the diethanolamine portion of the molecule since a previously conducted BOD,,q test on the sodium salt of the fluoroehemical portion of CS-2151 showed no oxygen uptake. The BODgQ was equivalent to 90% of the theoretical oxygen demand for the diethanolamine portion of the molecule assuming its complete conversion to C02 , H20, and NHL. The possibility of partial degradation oi the^fluorochemical portion of CS-2151 cannot be eliminated by this testing. However, experience with a wide variety of similar compound indicates that the perfluorinated portion of this molecule will not biodegrade. In fo rm a tion Liaison In itia ls: BACK TO MAIN BIOCHEMICAL OXYGEN DEMAND OF CS-2151 Introduction The objective of this study was to obtain an indication of the biodegradability of CS-2151, which is the diethanolamine salt of perfluoro ethylcyclohexane sulfonic acid. Its intended use is as a surfactant for mist suppression in anodizing, electroplating, and etching baths. As a result of these uses, it will be dragged out with parts and will enter the environment with the water used to rinse these parts. When used in strong-acid, etching systems, the ethanolamine portion of the molecule would likely be partially or completely oxidized prior to its entry into the environment. Methods and Materials The Environmental Laboratory received the test sample on 11/4/80. The sample was a light, yellow liquid. It was reported to contain 25% solids in water. W. A. Sohiel and M. Roberts performed the 5, 10, and 20-day biochemical oxygen tests according to the attached standard Environmental Laboratory protocol. In this testing, four concentrations were used ranging from 68 to 540 mg of CS-2151 per liter of BOD dilution water. There was little oxygen depletion during the first five days, but at 10 and 20 days only the BOD bottle containing 68 mg/1 of CS-2151 contained greater than 0.5 mg/1 of oxygen residual. The oxygen depletion due to the samples is shown in Table 1 below: Table 1 - Oxygen depletion due to CS-2151 (i.e., oxygen depletion in sample bottle corrected for oxygen depletion due to seed and water). CS-2151 Cone.(mg/1) Oxygen Depletion Due to Samp Day 5 Day 10 Day 2 68 0.06 4.17 4.69 140 0.16 >7.65 -- 270 0.20 >7.65 -- 540 0.31 >7.6 BACK TO MAIN - 2- When there is less than 2 mg/1 oxygen depletion, the Environmental Laboratory Protocol calls for reporting BOD as less than the BOD value which would have been calculated if the highest test material concentration had shown an oxygen depletion of 2 mg/1. The 5-day BOD was thus reported to be less than 3,700 mg/kg. The BOD at 5 and 10 days was calculated based on the oxygen depletion of the 68 mg/1 culture in accordance with the attached protocol. The reported BOD values are, therefore: BOD5 - <3,700 mg/kg BOD^o - 62,000 mg/kg BOD20 - 69,000 mg/kg BOD tests have also been done on the potassium salt of perfluoro ethylcyclohexane sulfonic acid. The 20-day BOD was found to be less than 3,800 mg/1. These results indicate that under these conditions that the perfluorinated portion of the molecule is unlikely to degrade. Assuming no nitrification and no biodegradation of perfluorinated portion of the molecule, the theoretical biochemical oxygen demand would be 77,000 mg/kg (307 mg/kg for the 100% solids material). The observed BOD value was, thus, 90% of the theoretical assuming that only the diethanolamine was biodegraded. Since BOD values rarely reach theoretical oxygen demand, these results indicate essentially complete degradation of the diethanolamine portion of the molecule. Discussion The results of this testing when evaluated in conjunction with BOD results on the potassium salt of the fluorochemical portion of this molecule indicate that the fluorochemical portion of the molecule would not biodegrade under the test conditions, while the diethanolamine portion would be completely degraded. The 20-day biochemical oxygen demand test (BOD20) is a test for ready biodegradability. This test alone cannot exclude the possibility that the fluorochemical portion of the molecule may biodegrade after longer periods of acclimation or under more favorable conditions. Such degradation is, however, very unlikely. Literature studies conducted on an ongoing basis for several years have not uncovered articles that describe the biodegradation of a completely perfluorinated organic material. The 3M Environmental Laboratory has also not seen the biodegradation of any 3M perfluorinated organic materials. ''environmental Laboratory BOO Work Sheet Samples BACK TO MAIN Lab Req. No. t < 2 . G 0 Analyst 3aek A . S Data Started n ~ i< b X BOD Run N o .| * $ 0 - 3 ^ Analyst - Day BOD Readings Date Sample Description Initial Dilution Initial Dilution Factor "" to ........... V " " C S T - I S 'I . LIQ U ID FORM f Sample diluted to ml with Dl water 1 -- ............. -- ........-- :------------------------ -- -- --- ----------------------------------------------- (Dilution factor = 1 if undiluted) Bottle No. Cone, of Sample1 12 3 I (p 72 .S ' (Ho X lo 54-0 Sample Size2 Initial D.O. (D ,) Present D.O. <D2 ) /,<? l.c V. o <?`0 y .ir 2 .1 C 7 .n< %no 2 .5 ^ S '.Y < r S '. 3 jr If - -- Total D.O. Depletion (D , D2) .2_ o o. 3 o .HO 0 .HZ' Depletion Due *'+ 0.0 O J Z D.I (9, Z Z 0 .*(, 0 . 3 * 0 -3 I 0 - 3 7 5 ^ -Dav * 5" S -D av BOD 1 3/ K ?'*1 ''1' Note: 1. Cone. = Concentration of sample (ml/l or mg/l) in BOD bottles. 2. Sample Size = ml or g of sample or diluted sample added to BOD Bottle. SAVE S !$ tiS '&<0y77DEEGSRAIEDATTHE/oRtEi>__IS__A_M__Y Form 19756 PWO BACK TO MAIN Shvtronnwntat Laboratory BOD Work Shost - A .......... - ......... ...... ...; ..... . ..V.,i LabR*q. No. % 2. 0 $ Analyst C ' aA A , S c iu J ? 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SA\j 'EerrrfjEs if rttERE is auy b E G M b f lT t o M '____________ .k. \f /o-tL. hc> ^ Vo ^ ^ fU*. .&trdL sAsfasOZJ(? 7^-- .....----;----------:--- Form 19756 PWO (SnvironmBntaf Loborotory 1 0 D Work Shoot * tem pi .1 ' I S | | r --------------------------------:---------- ^ -- -- 4^ 1 Ubftaq.No.+ ^ 2 G 0 S * A rw ytt . Date Sterted C-tuU A , S c L J ? n/ihXo ample Description BODflun No.| ' 5%j - 3 7 ' 2 Q ` DayBQDReadings . Analyst . . * ;: .... ; _ : . . (a), &, v . Date ''H-ru Initial Dilution Initial Dilution Factor ,, A . 0 3 4A4 e W of Sample diluted to J&0 \ ml with D l water , . (jF- >i ----------- "f -- - -- 7------------------- ----- -----------*----------- ---------------------------------- ---- ; (Dilution factor - 1 if undiluted) Bottle No. Cone, of Sample1 J SI (* JU J y tH o X Io S4o Semple Ste3 /,0 1 .0 V. <j Initial D.O. (D, I % .1C Zn< S r7 0 Present D.O. (D2) X rfo < o tC <Or<T : Total D.O. Depletion (D, - D jI S'%$ ----------- m Depleteen Due ' . 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