Document 65RKvDawmvd4nxajbm7D19Kyo

Ar < - 0223 BIODEGRADATION (BOD/COD) TEST SUBSTANCE_____ Identity: A mixture containing perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-600. (1-Octanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-, potassium salt, CAS # 2795-39-3) Remarks: The 3M production lot number was not noted. The test sample is FC-600. Current information indicates it is a mixture of 1.0% PFOS, 81.20% water, 12.00% diethylene glycol butyl ether, 1.00% sodium octyl sulfate, 2.00% propane Sultone foamer, 1.00% sodium decyl sulfate, 0.85% xanthan gum, 0.1% N-(3-chloroallyl) hexaminium chloride, 0.80% starch, and 0.05 % tolyltriazole. The following is an abbreviated summary of multiple biodegradation studies on FC-600. These studies apply to a mixture with incompletely characterized concentration of impurities. Data does not accurately reflect degradation potential of the fiuorochemical component of the test sample. M ETH O D :___________________________________________________ - Methods: OECD 301E and BOD/COD/TOC (summary listing only) Type: Aerobic GLP: No Year completed: 1975, 1983, 1984, 1988 Contact time: 20 days (BOD) and 28 days (OECD 301E) Inoculum: 1984 study used a 50/50 mixture of soil extract and secondary effluent. Sandy loam soils obtained from Ramsey and Washington counties in Minnesota. The secondary effluent sample was supernatant of activated sludge mixed liquor taken from the Metro Wastewater Treatment Plant, St. Paul, MN. Inoculum for the other studies was not noted. RESULTS Chemical Oxygen Demand: Biochemical Oxygen Demand (BOD): 5-Day: 11-Day: 14-Day: 20-Day: 467.000 mg/L* 50.000 mg/L* 255.000 mg/L* 240.000 mg/L* 237.000 mg/L* * Data was available as a summary list only. Total Organic Carbon (calculated for the product): 0.097 g/g 001951 Total Organic Carbon Removal: 90 - 91 % in 28 days Dissolved Organic Carbon Removal: 79.9 - 94% in 28 days** ** Range over 3 separate OECD 301E studies Remarks: Testing was conducted on the mixture as described in the Test Substance Remarks field. The value reported applies to that mixture and not the fluorochemical proportion alone. CONCLUSIONS__________________________________________________ No reliable conclusions can be derived from this study. The indication is that the majority of the product components are readily biodegradable. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY__________________________________________________ Reliability: Klimisch ranking 3. The inoculum is not properly characterized in most studies. The testing was conducted on a mixture with chemicals having varying degrees of biodegradability, leading to potential misinterpretation of the results. The sample purity was not properly characterized and the study lacks analytical confirmation of the amount of fluorochemical proportion in the solutions. REFERENCES__________________________ :______ Testing was conducted by the 3M Company, 3M Environmental Lab, St. Paul, MN, Lab Request Numbers 2874 and 8483. 3M Environment Assessment inquiry #82326, E. A. Reiner, 3M Environmental Laboratory, St. Paul, MN, April 21,1983 3M Technical Report "OECD Biodegradation Testing on FC-600 and FC203." E. A. Reiner, Project 9972410100, 3M Germany, Report Number 001, April 18, 1983 3M Technical Report "Modified OECD Screening Test on FC-203, FC203A, and FC-600." E. A. Reiner, Project 9970010100, International, Report Number 003, July 9,1984. OTHER_____________ Last changed: 6/28/00 Form 1CM20-S-PWO m : LAB REQUEST BOOK - 42-8W RV:'ENVIR. ASSESS. INO. #_ ( PRODUCT: PRODUCT ECOLOGICAL ASSESSMENT REQUEST FOR LABORATORY WORK DIVISION LAB REQUEST NO. Name: V ' ct-*. n . Reauest Date: 4 / / T Protect No. -> 1 Code No : 3 3 c "* SamDle Date: ----. Description: PurDote of Tests REQUESTER j ^ (c PhoneNo. Prob Diite Needed: Zo 3 r tr i LABORATORY A J & 9 l l l k Dote Recaro* Simph Analyst: T W 1 >tfK / th Q ^ R w .a d _____ Data Completed 1 Hours Scant: Y 7S B *L \ P Z B + 1 Plaase Call Reauester If Dalavs Art Encountered. Ay PHYSICAL & CHEMICAL PROPERTIES Heat of Combustion C al/6 (BTU/Lb.) Density Ash Other f C C -c 0 -- ' : - ! `? \ . ; ' WATER POLLUTION pH COO . BOD5 / { sm%\ BOO, Ultimate TOC J 1 da.yA 1-q - A i J s GC 2 . 6 d / y 3 f Oxygen Uptake Dehydt'>gen.ise A ctivity (TTCI Other ' ' * % TC \ 5O O 0O 2 .5 5 f\b O - 2 .3 7 ;rtO I / J V ''**** BIOASSAY Specify Organism and Method: s > Cc* f/V il't, LEACHATE FROM LEACHING TEST pH COD bod5 BOD. Uit imate TOC GC Bioa'isnv Other OTHER Bioaccumulation i . Persistence Degradation Products L-- AVAILb e s t c c py / iB L E -- . _ J '1 . , ;. / ; , ` .A ' :/ r SE 'v FORM tOM--PWO SAMPLE DESCRIPTIQN File: Page No, ENVIRONMENTAL ENGR. LAB - WORK SHEET Date: O e c D Sc#5M AJ& T T o -- 7 -- / i- / --3^ 1 -P i C C-ld S',3.0,2?) F -^ - tW' !/.... - f ^ . ^ ^ j*vr* /j<` __ ] i-- CJ . ^Ca-v'W-' <^)_______ ffftUkbtt* .,.fi.tiief~r\tk^rL_^nr^^t7^j -- ___Z!_>?3ZZ3Ji P P '^.i-- ^ 7 A4. ^ a ,\J s rntoacr fc/H_ T^r / - jtfefi&ny^ji^w><TT'/ /...jlQ A P^ 1 , tm y x y I .* ............. .......... . IT ^ - oo ^ (rfify M ^ e ) 3-0 L y\4^ZK*-&s*~ Aa-f&.'Zcir. ,!,;; ,.i',l|>r>i *)!'i ; . i,? g g ^ ' :T"'; . T / r 3 ^ i ^ Ta < )3 :: V-'i, '-Ni !':?-.'-!rW'*.?;;!A'!"g"1'-?'-V.^-'.-W; - ` ; V .:V'y'3..' . is*i'ffi.'fiii'S!j.'!* 1 ^ '.if.:'.-'?;. V . ... ... i V -!-- $.. O ' 7 "; i ; i j|||jiii.i!|,,y t. :: ! ^C 5W T BEST COPY AVAILABLE Reviewed by: 00195T FORM t010 IW>0 File: Page No. ; - ENVIRONMENTAL ENGR. LAB - WORK SHEET SAMPLE DESCRIPTION 0 ^ C O f a O i > t f ` C D f2 e M < l 4 ar rerr, Date: H (0 ^ Hrs.:Analyst: --"!' - "'.v1 DCC..; LOl;1"S!*S-1 'T. T g-^fife_ ppTAouS Doe CoPCe#JT^A-r/QJ :''; `"0". . Vw.-; V 1W iTiAL s. V P4- P 3" Cl*?*VQCMWtUs') J?3.oAViV I.i'- Xl.*t/M. (_ _ *MAnViaJ "7. --- FWfoQP ( W * ope ------- ,---------- 43,3 /?3,/ /9L.3#__________ i.i .f-*...3>'-?,; ^i- o';'- -" " j"".r:1: r ''V*f - ''.v-`rii '?*! T-^.Ir5s/V*i* :-.;ii.i: ..; ^ ': v .i` BESTCOPY AVAILABLE j r>:; '-'i 3t&*jKf>SM 4 ; -!l !i' g^fPTPI1- :*n1 Reviewed by 00195S: ANALYSIS FOAM I038A b e s t c o p y a v a il a b l e 2( SEC. A^, DAI J V - t f ' f 1 ___ SHEET NO. \ A JV IP tin s -1. 4 r^t44 o ' ^ A/ -- -- _J'fijmPj?l&r, :/*A\ /j y //)y //I ^ *r.7 0 . 2 *?& Ay l% l 1 7.6 l i M 2 o .o 18.0 2.5- 23.3 i/.c. 2 1 .0 A3.7 2.o 2l'7 * i*-- JAp so .; -Y : .S . e 7 E > a tL & T 7 a 9 10 *.r /./ 0 ,0 7.7 r.r y-7 S 4 3.r <5. 3 0.3 0 .1 o . r f , 7 y.y ? 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S' "/ 7 ^ r^**' 0c d SCte&s/tfA -TEST- 3A1 BfJOiiZipMcKir/fc, .rt&b&Ard/iy ,,u 3SB? t)./. --P smtzr DATE &2-~ SHEET ANALYSIS f m \ / V/ v ^ / N/ \ / N / t / / o/o /v /^ /o y ^ fk / / C / B /E I / r / l 7 9 C .9 7 '. r 7 < 3 .* Icrt.k 7 ^*7 7a> iot.3 m * 7 /3 .7 2 /t'ZV'&Z- / 3 4 7*?. 9 L o U K S J+i 4- 7 '--W ' '5 8 / U - f10 P ( & U ( 9 ~ r . C ^ / r ( 1 H { / ? , / ? o . 9 rttM/.S1r 7.7C v > : y C *.8 W t f Li(>, ( It ) _ 12 L d / f a Z t J i / - / i p f c - A t h -- i | ^ - j 13 frA 7 .8 V l , f W.l i f f }7 6 /7 .0 C Y fl.C >3?#f 14 15 16 17 ... 18 19 20 21 22 .. r ., / "fjfzi nt v ^ \ v 6fcvC<- i i / M N i r s f & T c ' I a- J ? F f t A t i e s tef,7 ^ --*> W~\ytA T&? i/ 7 f t f - T W 0 2 , T rr 1 . 23 24 f z z p 25 * 26 27 / fp v E 7. i 7 :6 fr, 3 6 . / 6 / 0 6 'V s 'Y / 28 - 29 V ' ,' 30 . . \ '* ?. v ' ^" flEA31 gp.Q T m P Y a v ; lit 32 33 34 : "; " \ : 35 * ' - 36 - - 37 38 39 a 40 ... *!: -'.V 61 V T' ; . - . : * 42 43 44 45 4 ----------" --.....'!"g ' j y .........-- " ' "S 0(1 ;7Y--t ' 10 f "Ready Biodegradability: Modified OECO Screening Test'* 301 E I. p ,9* 5e A N N E X Sftyte roHM SHEET roe the modified oeco screening test Exp. no.:________________ Dota of start of toot: Tax* Standard eetrlaTT Th*orMcsi test oonc.:_ Inoculum: Carbon analysar: an gse/r !- h >v, A: Controll8 t TOC* I DOC** I II I I IStock ao'ki<} or.the I(1000 ag/i* dilution toat material I I .../loog-Ji-Qf nutrient solution) I B: Carbon det.aei*l*ln,**on>8 "1 V iFiaskl Analyses 1 Culture modi}** !no* | 1 \1 1 1J'1Minorai nutrienti !I solution with 1 1 1 aj Itest Material 1 1 land with II *2 Theor. 1 00C - concentrati one after x daysl cone. 1 mg/1 mg/1 0 (Co) 1rsj 71 -%-/l*l/v/211<i/27l 28 1 / 1! ! 1 tf.l o.o o.*f ! / 2 C .o \ __Ifl.) 0.3 I Iinoculum 11 1l 1 ! ! 1 2 11 '1 1 1 -- r-- 1 1 l(Ct> I 0.06 w i 1 11 i l I 1 bi '/ 1 11 M ji 1.1 -0.1 j 1 1 121 11 b2 / \2 o .o 1__ 1__ 0.5, I 1 11 i 1 | 1 i b x b2 1 |m2 --- 5-- . i, _ ___1 1 l(Ct) - I______________ !_____1__ _________ 11.11 1 1Minarsi nutrienti i ci I/ 1 1solution wlthoutlBlankl 11 test matarlal l l but with i `1 c2 1/ i 1! 1Inoculum 11 1 1 'i . I.Z 1__ 1 1 1 1 e>.x i i i i? JU jii i 1 i 1 1______ II ci C2I / i i v - V 2! ' 1 l(Ct,i) 1 Il 1 11 ox* _____ ! 1__ ____ 1 1 pX<r0.l 1____ ____ I I I * Diaagraomant between DOC and TOC valuaa points towards lnaufflclant solubility of tha tast matarlal. * All DOC valuaa dataxmlnad aftar mambrana filtration. l-fe o I BEST COPY AVAILABLE i "Ready Biodegradability: Modified OECO Screening Test" C: y:.uatlon of r.w d.f. ris.M no. ! 00inCus- coneantratlons blanks (Ox [l - - I I Aif doc tanovsi artar * days i 71 141 211 271 28 -- -*] 100 * ./ fL "1 - *3 J r |p2 ji - -2$-L22L.l. ino i It *2 - J j asn I Ox 02 JO ...... I2 I rar .day x I- i 4 4\%e>\ 11.*/ --H ii \/m I n BEST COPY AVAILABLE "Ready Biodegradability: Modified OECO Screening Test" I 1301 E I Page 11 .1. ANNEX SAMPLE FQHH SHEET FOB THE M001FIE0 9ECO SCREENING TEST Exp. no.; Date of start of teat: Teat Standard eatrlal Theoretical test uonc.i inoculua: Carbon analysers mn o a c /i a8 sassaia i T0C* |c** i IStock solution of the toat Material I I(1000 ag/1, dilution I 1-- ../1000 ! of nutrientsolution) I l* I I I I I Bs Carbon deteralnatlonss ' C - 2Lo3 111 Culture adiua I1IFnoia.ak_1l1AnalyaaalVIlcahogan/1oe.r.110(Cco_-)1acngoj/n17c1en^t1ra4tiIo/vna211f-wie/2r71x Hysl 28 1 '!Il1laetiMnanoiiodanlulctewutriaaloiitailnhatnauriittartilienti11I1 1 I )!1I | ei ao 1!i\11 / / 11 .r T1 11 ^ Si 1 in i i 1 i i i i!11111!111111(lI11otsMinauoioantluctowtriaaloiutainhatnawuriitatrhileonutti|1!i1111111I111Il1_B._la2II_nk|1l!l111111ll1111(_(*_-CC12_tt_-_-))_-b5,`cc-_3Iloici-1_"i_i-_7S_--__tc>_2"o211!11iI11!1|11l1111____/t1__//"__Tl1li_*ii?a,i*_.7.i'..yoj_;*r1_'i1!1111iI1111111____. 1 1111111________1I1____yf..lyo 1 - y.rr ___ 1111!__ __ 1 f-7S| 11 ! ` 7.y i i.tr 1 4 !>S " "r 1 F c- ! 1 I(cbi) 1 .Si] ! ro.i! 1---------------- 1___ L-- __ _ J ____ 1 ___ 1__ !__ ____t Diaagreenent between 0OC and T X valuas pointa towarda inauffioiant solubllity of tha test aatarial. * All 00C valuta datarainad aftar aaabrana filtration. BEST COPY AVAILABLE 001960 kJ kJ i "Ready Biodegradability: Modified OECD Screening Test'* 301 E !.. p* 9* 1 ,' -i,`. S. A N N E X SAMPLE rOHH SHEET FOR THE HOPiriEO PECO SCREENING TEST Exp. no. Data of atart of teat: Test * Standard aatwrlai Theoretical test uone.i________ *** inoeulua: carbon analyser: an oori/i A: Control: , ITOC* j DOC** J IStock solution or tha taat tarisi l . I** I I(1000 /I, dilution II I I .-.-./IQQQ _L_or nutrient solution) I I_____ ;__ I 8: Carbon deteralnatlons: f'C -(,o O 1 iFiaskl Analysas 1 Culture adlu Ino. 1 1 11 1 II 1Minerai nutrisntl 1 ai solution with l i Itast aterll 1 1 2 land wlth II ilnoculu 11 1 iTheor. 1 DOC - concentrations after x daysl leone. g/1 1 l0/l 0 (Co>1r>J 21 141^/211 n/271 1 / 8o ! 1 / 2 2. * 1 1 I 1 r "7 * -.1 I Il A 1 1 I 1 <1 1 2 l ' p 1____1____ !____ ^ / J i 11 11 j I I .! I .1 ! 1 1 ! . ! '*1 2\ 1 1*1 - -- r -- 1 1 l(Ct> 1 ,,> I.Lbl y1 > 1 1 :1 s'.r | 1 1 1 `1 1 1 bi 1 1 / 1 H.-T 1 III 21.0 1 3.4" . r i ` 1 1 2 1 Bi 17 1 III x.n t n 1 1 1 1 1 11 1 , 1 j bi b2l 1 1 - 2 ----- r " l 1 l(Ct) 1 1 .1 22 It 1 1 3.1 |2-.l i 1______________ !_____1____________ !_____ ___ ______ !_____ ____ ,,1 1Minorai nutritoti \ .ci \ / --/I I 1 solution without 1B l a n k ! * 1 \'*1 1 * - o.Cl Itest tarlai | .1 ,C2 Ibut With 1 |K-Z* I/ 1 | |/.f | | 1 | #.jy./' >>U P:fl linoculu il il 11 1 1 1 11 Cl C2l / 1 11 1 -.IOj 1 1 1 i v - T -- ! 7 L, 1 l(Cbi> 1 !*) ! 1 oSZ 1. 11 1 1 4__ 1____1____ 1___ 1. ! * Olsagraaaent between 00C and TOC values polnti towards Insufficient solubility of the test storiai. ** All 00C values deteralned after aabrane fili ration. AVj 2 A. f BEST COPY AVAILABLE V 001962 F o rm 6 7 4 7 - 1 1-E TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER - 201-2C-12 (Im p o rta nt -- I f report is p rin te d on both sides o f paper, send tw o copies to TCC.) Guidelines on reverse side. D iv is io n 3M Environmental Laboratory (EE & PC) St. Paul Minnesota l*i ujuc l 3M Germany__________________________________ _____________ Roport Title OECD Biodegradation Testing on FC-600 and FC-203 To K, F, Schrqeder, 3M Neuss, Germany____ A u th o r(s ) .. E, A.*'Reiner, Environmental Laboratory N otebook Reference 21-2W-05 None - See 3M Environmental Lab Request 8483 Dopt. Num ber 0535 Project N umbor oe I997241010 Report Number Period Covered or Date 4/18/83 Em ployee Number(s) 47816__________ N o . o f Pages In clu d in g Coversheet 15 SECURITY ^ O Coen RflDort & Summary D Closed Report--Open Summary 3M CHEMICAL R E G IS T R Y - Check box if new chemicals are reported. Use Cl Xcal Registry Form 6092 to report all new substar KEYWORDS: Lab Code Other Keywords CURRENT OBJECTIVE: 1. To measure the biodegradability of two "Light Water" products using the internationally recognized Modified OECD Screening Test. 2. To compare results with those previously obtained using the same test method. REPORT ABSTRACT: This abstract inform ation is distributed by the Technical Communications Center to alert 3M'ei Company R&D. This study used the Modified OECD Screening Test with dissolved organic carbon (DOC) analysis to measure the biodegradability of "Light Water" Brand AFFF products: FC-203 and FC-600. In 28 days, the DOC levels of FC-600 degraded by 80% and 92% for an average of 8 6 % in two parallel tests. In 27 days the DOC of FC-203 degraded by 77% and 81% for an average of 79%. The FC-203 result differed from a similar test done in 1980 in which 93% DO degradation occurred within 21 days. In the present stud parallel sterile controls proved that the DOC loss was no due to chemical or physical processes such as adsorption, volatilization, or precipitation of the organic compounds Inform ation Liaiti iN In itia it: 001964 1*1 vswmtm FC-600/FC-203 Page 2 April 18, 1983 Introduction The 3M Environmental Laboratory undertook this study of the biodegradability of "Light Water" products, FC-600 and FC-203, because of concern expressed by 3M Germany about inconsistencies in past biodegradation test results. Modified OECD Screening Tests conducted in 1980 by the 3M Environmental Laboratory showed that three "Light Water" products were highly biodegradable. FC-203A, FC-206, and FC-3017 (FC-206 F) all were shown to have 90% of their dissolved organic carbon removed in the OECD Screening Test. These results, however, contradict those of H. Hellmann and D. Muller^1 ) using a similar yet not identical test method, the TOC Degradation T e s t (2). in their study. FC-206 and FC-3017 were found to have total organic carbon reductions of only 6 % and 8 %, respectively, in 21 days. These low biodegradation results of Hellmann, however, were also contradicted by his own work. His BOD5 /COD ratios for FC-3017 and FC-206 were 0.5 and 0.4, respectively. This showed that 50% and 40% of the theoretical oxygen demand was expressed within only 5 days. These levels of biodegradation are much greater than the 8% and 6 % TOC removals which he observed in the even longer (21 day) TOC degradation test. This is clearly an inexplicable discrepancy in his work. Hellmann's TOC degradation results are also contradicted by BOD20/COD measurements made by the 3M Environmental Laboratory and other independent laboratories on 3M AFFF products. Such results typically show BOD20 values to range between 60 and 90% of the COD. For example, a collection of such data on 3 U.S. military specification AFFF products made by 3M is shown in Table 1. 001965 - -r,^ ~ Page 3 -- -r - - r '-T -fC M f` U i _ ;___ _ ~-r ~ ~ r -yu.*T*f~iftanrrr TABLE 1 - Ars~yrj BOD, CARBONACEOUS BOD, AND COD DATA ON MIL--SPEC AERE PRODUCT BOD20 C-BOD COD BOD20 C-BODsn Lab (mq/kq) (mq/kq) (mq/kq) ~o d COD FC-203C Lot 501 3M Pace Serco Capsule Galbraith S & W Seed Galbraith Knoxville 500,000 800,000* i 440,000 - 570,000 616,000 670,000 600,000 730,000* 440,000 620,000 671,000 641,000 730.000 740.000 810,000 730,000 737,000 950,000 776,450 776,450 .79 .60 .6 .79 .86 .81 .60 .65 .86 .82 Averaqe S. D. 575,000 594,000 782,000 85,000 90,000 80,000 .73 .12 .75 .12 * Calculated BOD's from different dilutions were very inconsistent. Pace agreed to repeat this work but inadvertently lost their repeated test results as well. We did not request a third testing nor did we include these values in the averages. FC-206C Lot 502 3M Pace Serco Capsule Galbraith S & W Seed Galbraith Knoxville 290,000 350,000 240,000 260,000 416,500 395,500 290,000 370,000 260,000 320,000 411,000 374,000 380.000 360.000 450,000 370,000 410,000 407,250 407,250 0.78 0.78 0.65 0.63 1.02 .97 0.78 0.82 0.70 0.78 1.0 1 .92 Average S. D. 3M Pace Serco Capsule 325,000 73,000 240,000 250,000 210,000 240,000 338,000 396,000 57,00 33,000 FC-78QB Lot 501 230,000 250,000 220,000 230,000 320.000 330.000 350,000 287,000 360,000 .81 .16 .74 .71 .73 .67 H r* .83 .11 ' .71 .77 .64 Average S. D. 235,000 232,000 329,000 17,000 13,000 28,000 .71 .03 .71 .05 001966 FC-600/FC-203 Page 4 April 18, 1983 Methods and Materials 1. Procedure Testing was performed in accordcinco witli the OECD Guideline lor testing of chemicals adopted May 12, 1981. 2. Chemicals The reference material used was laboratory grade sodium benzoate (C7 H5NaC>2 ) F.W. = 144.11. A 30.3 mg sample of this compound was diluted to 1 . 0 liters with the nutrient solution described by the method to yield a theoretical DOC of 20 mg/1. The "Light Water" samples used were supplied by G. Piessens, E.T.S.L. and consisted of FC-203 and FC-600. Lot numbers were not provided. Nutrient solutions of the "Light Water" products with DOC's of approximately 20 mg/ 1 (based on calculations from the formulation) were prepared by bringing both 527 mg of FC-600 and 153 mg of FC-203 to 2.0 liters with nutrient solution. 3. Inoculum The inoculum was a 50/50 mixture of the soil and secondary effluent inocula each prepared in accordance with the OECD procedure. The soil used was fresh loamy sand garden soil obtained from White Bear Lake, Minnesota, and the water for the soil extraction was chlorine-free well water. The secondary effluent sample was the supernatant from an activated sludge aeration basin at the St. Paul Metro Wastewater Treatment Plant. The combined inoculum was passed through Whatman 54 filter paper prior to usage. 4. Sterile Controls Replicate vessels containing 400 mg/1 HgCl2 served as sterile controls for both test materials and the reference compound. The sterile controls were handled in the same way as the viable cultures. 5. Instrument The organic carbon analyzer used was a Dohrmann DC-52A. Its sensitivity limit is approximately 2 mg of carbon per liter. 6 . Sample Handling and Storage The sample preservation method used was that prescribed by the TOC manufacturer. The method involved adding 1 drop of concentrated HC1 per 10 ml of filtered sample. This brought the samples to less than pH 2. The samples were then stored under refrigeration in vials with aluminum foil-lined caps. Dohrmann literature indicates that the method can stabilize potassium hydrogen phthalate, a readily biodegradable material, for several months. 001967 FC-600/FC-203 l'ago 5 April 18, 1983 Due to problems with the sensitivity of the TOC analyzer, only half of the samples were analyzed within a month after sampling. Following 4-5 months of storage, all of the samples were reanalyzed. Comparison of the TOC analyses done within 1 month with those done after 4-5 months of storage showed that in only one stored sample had the TOC changed significantly. This sample was discarded. Results and Discussion Table 2 summarizes the resul'ts of this study. Appendices 1 and 2 contain the actual data sheets and plots of the degradation as a function of time. Table 2 shows that the sodium benzoate reference compound was nearly completely degraded within 14 days. Degradation of both FC-600 and FC-203 continued throughout the course of the 28-day test period without plateauing. At 28 days the average TOC removal for FC-600 was 8 6 % and at 27 days the average TOC removal for FC-203 was 79%. The test procedure recommends that chemicals giving a result greater than 70% loss of DOC (within 28 days) should be regarded as readily biodegradable. These 3M formulated AFFF products are thus even more completely degraded than is necessary for a chemical to be considered readily biodegradable. TABLE 2 Biodegradation (% DOC removal) of Sodium Benzoate, FC-203 and FC-206 Product Sodium Benzoate Sodium Benzoate Duplicate 7 94.4 92.3 % Degradation at Day; li 21 21_ 28 94.7 96.3 93.2 99.6 93.5 97.7 94.5 100.0 FC-203 FC-203 Duplicate 37.4 43.0 59.2 54.6 68.4 66.0 76.7 81.3 78.0 * FC-600 FC-600 Duplicate 46 47.2 63.5 67.1 73.5 80.2 82.1 88.7 79.9 92.1 Sample discarded due to probable contamination. The sterile control data in Table 3 provide further substantial evidence that soluble TOC loss from the test samples is not due tophysical modes such as adsorption, volatilization, or precipitation. These samples were handled identically to the test vessels, except that they contained HgCl2 to prevent microbial growth. At the end of 28-day test period, these controls contained all of the initial DOC. 001968 FC-600/FC-203 Page 6 April 18, 1983 TABLE 3 Percent of Initial DOC in Sterile Controls at 28 days Product % DUC Remaining FC-203 98.1 FC-600 101.3 Conclusion The present study demonstrates that Light Water products FC-203 and FC-600 are "readily biodegradable" according to the recommended 70% DOC removal criteria of the Modified OECD Screening Test. FC-203 and FC-206 had average losses of DOC of 79% and 8 6 %, respectively. References 1. Dr. H. Hellmann and D. Muller, "Environmental Impact of Fire Extinguishing Foam Compounds (Uroweltgefahrdung durch Feuerlosch-Schaummittell)." The study was carried out by the West German Institute of Hydrology (Bundesanstalt fur Gewsserkunde), April 18, 1979. 2. D. Muller and T. Tittizer, "The TOC Degradation Test - A Process to Test Organic Materials for Complete Biodegradation (Per TOC Abbautest - ein Verfahren zur Prfung von Organbischen Substanzen auf Vollstndigen Biologischen Abbau)," Developed at the Bundesanstalt for Gewsserkunde, Koblenz, Z. F. Waser-und Abwasser-Forschung (1979). 3. Organization for Economic Cooperation and Development, Guidelines For Testing of Chemicals, Section 301 E, Ready Biodegradability: Modified OECD Screening Test, May 12, 1981. 4. Dohrman DC-52A Operating Manual, 4th Ed., 1978. .Page 7 Appendix 1 BEST COPY AVAILABLE annex SAMPLE FQNM SHEET FQft 1HE HOPI H EP PECO SCBEEMIMC TEST Exp. n o . ; L A. & f t H ? 3 _____ Oote o f s t a r t o t t o s t ; In - 3 n - jfaT Wa* ' ' ondard rc e ta r la l TheoreM?**.! t e s t u o n c .:_ inoculun: ^ d id za f Laroon . . t l y w r C l t t m i M f r i m . U t , j A At C o n tro ls ; I TOC* I 00C ** II stock solution or the tost tarlai I(1000 ao/1, dilution - I .../IQttO al of nutrlant solution! -- --- 8` Carbon dotaflnatlons; >Sop)_U M B-CfJ=gLOA~} ______ .flask|'Analyaaa Ithsor.l DOC concentrations aftar x days . Cultura aodiu Ino. I ! II Icone. I g/1 Minorai nutrlantl aolutlon vlth 1 1 | j 1 taat aatarial and vlth Inaoulua I 1 1 I I 2 1 l 1 \mi 1 2* *2 1 l(Ct) ) / U * AV ai.i ^ av ii on|/ , f h i A r 0 .7 A A ! i . o !/. / } / . i 11 1 1 1 J ^i5 i 1 1 11 12 1 11 bl *2 ________ i_____ 1 ' I / . 7 . 3 o > . 7 | C . </ l A y ! A y ! / 1,2<5.0 , 2 , 0 / , y L>.r A i ~ ! 11 1 ...... 1" " III i 1 1 bl b3 1 1M2 . ------- ; ----- 1 1<Ct ) 1 , 1. J I I I n . r: / . i r />.i>c o.K 1 _M__in__o_r_a_i__n__u_t_r_i_e__n_ti1______ aolutlon without 1Blankl taat aatarial Put vlth inaaulua *1 1 I Cl 02 M '3 j<7 o.i - D j ! / H 0.1 0.3 Q.I 1 ______ 1 0} * 02 4 J 11 (Cpi) / A 0 A 7 i f a s' 0.3 0.0 \ .....j kintrai nutnant aolutlon without lank taat aatarial out g u n InaaSXS *1 1 a A 4 ' i o . / 0 . 7 A O j / t f * i f / r 0.1 i f l , Q.% 1 I1 s* *'>____ i V ,n" * ..... (C ai) / A os' 0 .7 a 3 i '1.74' f . T _______ 1 Pa*aa? M C and TOC valuta paint a tavarda Inaufflaiant aalublllty f tha taat aatarial. JU1 M C valuta dataralnad afta rana filtration. $ /W ittib e 0 f * 1 *wj>*2. p o c - AfTei? X PAI -- 07 w 2. ( r .l7.. ______ / . o % 0.7 >.3r 0 -H ST 0019^0 / / EPage '8 / J111 12 "Ready ttiodeyradability: Modified OECD Screening Test" LJ fcyg? "-- ! J. IOOC - concentration*! lolnua I blank* i I <I I IT l0i T - SoD ILtM NJ:g_oA-re, I 'BM raaovalarter flays I 71 141 211 271 21 -I-- I-- h - h H -- III - ajt 1 II I ` j - 100 a|fc*j?y.y I I-- I iaaan I 1i0 II I l . i-7 - *5 J 100 U I,, I j^.3| %.l I>1 0j for bay a In l i e /OO.O BEST COPY AVAILABLE * 001971 'age "Heady UiodegracJubi1ity: Modified OECD Screening Test" 301 E BEST COPY AVAILABLE ANNEX SAMPLE rOUM SHEET FOH 1HE HOOlflEU UEC SCOEENlMC TEST Exp. no.: L # -fr Date of start of test: __ aar xY_U_ E'endord R s t n r l e l i Sc.pim r * \ Thoor^t test cone.:, inoculum Caroon ana1yxai-: bow E MlMtJ fc -EJ ttlrNy Page 11 fumali: j TOC* 1 00C* 1 11 .-/l 1 1Stock solution or tho tost aatarlal ! 1 1 1(1000 ao/l, dilution 11 1 1 .../IMO al of nutrient solution) 1..J_____ 9 l .^ag IQ I "Ready Biodegradability: Modified OECO Screening Test" C: Eva: u U o n o f ra d a ta : ! 1 ' Iflaskl " Ino. ! IOOC - conoantratlonal 1 Inus blanks I| i 1 1 _ I 1 ..... . . njt 1 fC- Zo3 1* o!C rtmo\rsl arter x doys 1 1 71 1 211 271 28 1 t 1 h - + -- 1------ ! 11 11 1 11 11 1 1 12 1I 1 1f l'f*- -U i . --Muj4.3------M-JtM 1 j- 1 1 m o 1jV,.3,C C H X ii i 1 1i 1 in ----- 1---- 1---- 1 i lasan 1 . "* * 01 i iii i 1 1 1 IDI ----------------- :__1' i___fo_r_d_a_y _x_________ \i_t_fOdi_^_7_ It7l77l 7? ! i__ L__j____i * Pi^ i o r T R C S u l t s h (> f& Ail -TO S*+ou) S A m P L C M T / W hlM p o c A kM c y s e (1 ) UAtdC- S A s C - ^ O M o M 'E T 'e S 'T SoLVLTiOiJ &Suc'T, BEST COPYAVA,LASLE *$ t Page il "Heady Uiodegradubil ity : Modified OECO Screening Test'1 301 E Page li BEST COPY AVAILABLE * o, ..* sample r a w SHEET r m THE H Q f i l f l il j Q.ECP. S C M K tlJ M .IC S I Exp. no. ! L- A . ^ V ? 3 Dote o f s ta r t o f to s t : ' j o - j - i - X ' *- E^andord naturlnli TheoraMrsl test uonc.: inoculuai , U l Caroon a.ialrver: D C - <53- A '( T i m s r*A W * ' Saaixsdi- I TOC I Istock solution of the teat tarlai l 1(1000 ag/1, dilution I I-- -HMfl J> of nutrient solution) I 00C* H___ Sorten fl8lTtg>Qv.HaoT! I _____ T e sr iF i aMtAkti-rreApniatHly.ses I Culture e d lu Ino. I I II I. t r iMineral nutrient eolutlon alth 1 F A - Goo IIThaor.I OOC - concentrations after x days Icone. I - ng/l l g / l 10 ( C o ) l. e 7 l m a il* I 2 1 1 * 271 28 I ' j2i.tjg.rr.ejt.2jy;?|y.? test atorial end with 2 Inecluuilua I |*1 1 *2 III 1-- 1 12 1 1 1 l 1 1. "l | m ,o M 7ri M t U l 1 1______ 1_______1_______ 1 2 1 ,7 1/3. M i A i r , . i {,?.<?{ j , i b j b jl 2 - ------- 5-- 1 (Ct ) j . aur M i Y 4 {\ 3 '1 M ineral n u trie n t! e e lu tlo n v tth e u tllla n k l 1 ta a t a a ta ria l C] tu t liit i in te u iw " 1 C l CJ 3 . ------- j ----- ) f / 1 i 1 _____ i_____ -- <Cb l> m M e rti n u trie n t ta lu tle n a lth a u t C lank ta a t a te rle i tu t v lth in a a u lu t *1 1 / 1 i 1 * / <Cbl) ___ Oiaetreeeent tetaeen OOC and TOC valuta tainte teaerde Ineuffieient solubility er tea test aatarlai. ** M l M C valuta datatulnad after M a tta n e flltretien. se'e s o d i u m f c e / J e o ^ e m & e b l A M k. l 001974 \ 1 /ag.e 1 2 : I 1 1 / E .1 /1 ,4* 12 1 .1 "Ready Biodegradability: Modified oeco Screening Test" C* * y tlon of row ditii I ruki I no. ! I IOOC - eenoontrotlon lolnuo jblonko !* [* - fc-Goo |K DiX roaovsl aftor x dayt I 71 141 211 271 20 +-+ II III t00|/,o|3,rj73<5|53,;j T !p- - f l -- I >' 1 . ino I - *3 J .I Mon I Ol 02 IO I for boy V7.|^r77 ^ $c> -r BEST COPY AVAILABLE t 9 I 0019 Page 13 Appendix 2 TO1977 Page 14 Page 15 W1978 F o rm 6 7 4 7 -1 1-D TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER - 201-2C-12 (Im p o rta nt -- I f report is p rin te d on both sides o f paper, send two copies to TCCJ Guidelines on reverse side. Division epL Number Rnvi rrmmsnhal_Lahorat-nry (ER & PC)_S t ._Paul . Minnesota P ro je c t . , 0535 Proiact Num ber ff3rtajren a t i0 n a l --------------------------------------------------- riRPn finrssn ing Tpst- on Fr~?r>T To FC-203A. and Q Q 7nm m nn Report Number FC-600 tr c o Z Period Covered or Date D._Reese,_Tox ico-l.any,_3M Carmany______ Author(s) 3 E m p loJyyeMe ^mv) E . A-- Reiner m -En-uironmental_r.ahnrat-nry - 2 1 - 2W - Q 5 Notebook Reference 47 816 -None -...Sea Environmental Lab Request #9 i l l --------------- ____________ I______ ____________________________ 9 DSECURITY Open Report, Summary Closed Report--Open Summary 3M CHEMICAL Check box if new chemicals are reported. Use Chemi REGISTRY " cal Registry Form 6092 to report all new substances. KEYWORDS: Lab Code Other Keywords CURRENT OBJECTIVE: To test the repeatability of the modified OECD Screening Test in measuring the biodegradability of Light Water products. _ j_ I ,, La. Llj_ I.. REPORT ABSTRACT: This abstract inform ation is distributed by the Technical Communications Center to alert 3M'ers to Company R&D. This study again used the modified OECD Screening Test to evaluate the biodegradability of Antwerp Light Water products. The products studied in this set of tests were FC-203, FC-203 NFP (equivalent to FC-203A), and FC-600. Also tested was U.S. FC-203 Lot 3072. One of these products, FC-203 NFPf was also included in the previous set of tests done in 1980. The results of this testing were consistent with previous OECD Screening Test studies on Light Water products. The results indicate that all of the tested products are readily biodegradable. j ) I cc : R.L.Bohon-21- 2W-05 D.R.Ricker-23 5-1B-10 D.W.Kent-236- 2A-04 001979 MODIFIED OECD SCREENING TEST ON FC-203, FC-203A, AND FC-600 INTRODUCTION This study was undertaken to demonstrate the biodegradability of two Light Water (L/W) products, FC-600 and FC-203, using the internationally recognzied Modified OECD Screening Test' . This testing was requested by 3M Germany because of inconsistency in the results of past biodegradation tests done on these products. Modified OECD Screening Tests conducted in 1980 by the 3M Environmental Laboratory showed that three L/W products were highly biodegradable' . The products tested were FC-203A (previously identified as FC-203 NFP), FC-206, and FC-3017 (FC-206 freeze protected). Greater than 90% of the dissolved organic carbon (DOC) of these 3 products was removed during the 1980 testing. See Table 1 for a summary of these results. Table 1 Results of 1980 Testing on Light-Water Products Product % Degradation at Day: 2 14 21 27 28 FC-203 NFP1 13 85 93 91 93 FC-206 , 23 90 94 93 92 FC-3017^ - 37 94 96 96 95 Hydroquinone-3 89 92 97 94 93 Footnotes: 1 FC-203 NFP is nonfreeze protected FC-203 and is equivalent. to 2 FC-203A. 2 FC-3017 is freeze protected FC-206. Hydroquinone was the reference product. These 1980 results contradict those of H. Hellmann and.D. Muller (3) who used a similar test method, the TOC Degradation Test' . Hellmann1s TOC (total organic carbon) test results, however, are an exception from normally obtained results. His finding of 8% TOC removal for FC-3017 and 6% TOC removal for FC-206 in the 21-day long TOC Degradation Test contradict his own BOD5/COD data. His 5-day biochemical oxygen demand (BOD) results were 50%'>and 40% of the chemical oxygen demand (COD) of FC-3017 and FC-206, respectively. This is a significant level of degradation for a 5-day BOD test. These opposite results within his own paper clearly are an inexplicable discrepancy. Hellmann's TOC Degradation Test results are also inconsistent with BOD2Q/COD measurements made by the 3M Environmental Laboratory and by other independent laboratories on 3M AFFF products. Such results typically show BOD2Q values to range between 60% and 90% of the CGD.~ For example, a collection of such data on 3 U.S. military specification AFFF products manufactured by 3M is shown in Table 2. 001980 3 OECD Screening Page 2 July 9, 1894 Table 2 BOD, Carbonaceous BOD, and COD Data on Mil-Spec AFFF Product C-BODon COD C-BOD,,_ Lab (mq/88 ) (mq/kqj (mg/kq) ^ 8 COD4*0 FC-203 C Lot 501 3M Pace Serco Capsule Galbraith inoculum #1 Galbraith inoculum #2 580,000 800,000* 440,000 570,000 616,000 600,000 730,000* 440,000 620,000 671,000 730.000 740.000 810,000 730,000 737,000 950,000 776,450 670,000 641,000 776,450 .79 .60 .6 .79 .86 .81 .60 .65 .86 .82 Average S. D. 575,000 594,000 782,000 85,000 90,000 80,000 .73 .12 .75 .12 * Calculated BOD's from different dilutions were very inconsistent. FC-206C Lot 502 3M Pace Serco Capsule Galbraith inoculum #1 Galbraith inoculum #2 290,000 350,000 240,000 260,000 416,500 395,500 290,000 370,000 260,000 320,000 411,000 374,000 380.000 360.000 450,000 370,000 410,000 407,250 407,250 0.78 0.78 0.65 0.63 1.02 .97 0.78 0.82 0.70 0.78 1.01 .92 Average S. D. 325,000 338,000 396,000 73,000 57,000 33,000 .81 .16 .83 .11 FC-780B Lot 501 3M . Pace Serco Capsule 240,000 250,000 210,000 240,000 230,000 250,000 220,000 230,000 320.000 330.000 350,000 287,000 360,000 .74 .71 .73 .67 .71 .71 .77 .64 Average S. D. 235,000 232,000 329,000 17,000 13,000 28,000 .71 .03 .71 .05 001981 OECD Screening Page 3 July 9, 1984 METHODS AND MATERIALS 1. Procedure Testing was performed in accordance with the.OECD Guidelines for testing of chemicals adopted May 12, 1981. 2. Chemicals The reference materials used were laboratory grade sodium benzoate, (C7 H5 Na02) F.W. = 144.11 and linear alkylbenzene sulfonate (LAS). The LAS Solution used was a 5.68% active solution supplied by the U.S.Environmental Protection Agency as a reference material for biodegradation testing. The Light Water (L/W) test mateials used were U.S. FC-203 Lot 3072 provided in 1983 by the Commercial Chemicals Division, FC-203 and FC-600 samples provided by E.T.S.L. Antwerp in 9/82 and FC-203 NFP provided by E.T.S.L. in 1980. Antwerp provided no lot numbers with their samples. FC-203 NFP (nonfreeze protected) is equivalent to FC-203A. Prior to testing, the L/W and reference materials were dissolved in the OECD nutrient solution and brought to the following initial DOC concentrations: sodium benzoate 20 mg/1, LAS approximately 15 mg/1, and L/W products approximately 40 mg/1. The L/W TOC was higher than that used in previous testing (20 mg/1 ) because our experience has shown that L/W at 40 mg/1 is not toxic. Also higher concentrations improve the accuracy of the TOC analysis. For this study, nutrient solutions were prepared using both vitamin sources allowed by the OECD Screening Test, yeast extract and synthetic vitamin solution. This was done to determine if the vitamin source affected the extent of L/W degradation. INOCULUM The inoculum was a 50/50 mixture of soil extract and secondary effluent prepared in accordance with OECD procedures. The soil, which was extracted, was a mixture of fresh, sandy loam garden soils obtained from Ramsey and Washington Counties in Minnesota. The secondary effluent sample was the supernatant of an activated sludge mixed liquor sample taken from an aeration basin at the St. Paul Metro Wastewater Treatment Plant. The combined inoculum was passed through Whatman 54 filter paper prior to usage. INSTRUMENT The organic carbon analyzer used was a Dorhman DC-52A. Its sensitivity limit is approximately 2 mg of carbon per liter. 001982 OECD Screening Page 4 July 9, 1984 5 SAMPLE HANDLING AND STORAGE The sample preservation method used was that-prescribed by the manufacturer of the organic carbon analzyer. The method involves adding 1 drop of concentrated HC1 per 10 ml of filtered sample. This brings the samples to less than pH 2. The samples were stored under refrigeration in vials with aluminum foil lined caps. Our experience is that this storage method can preserve L/W containing samples for several months without affecting the DOC. All DOC analyses on samples from this study were done within one week of its completion. RESULTS AND DISCUSSION Table 3 summarizes the results of this study. This table shows that sodium benzoate, the reference compound, was_nearly completely degraded (95%) within 7 days. Every replicate of all of the L/W products showed greater than 80% TOC removal within the 28-day test period. Seven of the ten test flasks containing the various L/W products showed greater than 90% TOC removal. The average DOC removal for all four L/W product was greater than 90%. The results of this testing are shown graphically in Figures 1 and 2. These results are averaged, and because of this, do not show the actual pattern of degradation in the individual cultures. Figure 3 is an example graph of 2 cultures degrading the same product, FC-203 NFP. It shows that once degradation of this product began that it was very rapid, but that the lag prior to the onset of degradation was variable. The reason for this variability between the duplicate cultures was not known nor was it expected. It may have been due to the fact that the cultures received different levels of viable microorganisms capable of degrading the major components of the Light Water products. Thus, the population of bacteria with these capabilities had to build up in the cultures prior to the onset of rapid (exponential) degradation. Review of the data in Table 3 indicates that results of replicate testing of the other L/W products also varied considerably at days 7, 14, and 21. Again, this variation appears to be due primarily to the length of the lag phase prior to the onset of biodegradation. However, due to the small number of samples taken, one frequently could not tell how long biodegradation of individual L/W containing cultures took following the initial lag. 001983 4 OECD Screening Page 5 July 9, 1984 Table 3 Biodegradation of LIGHT WATER Products and Refernce Materials Product/Vitamin Source Sodium Benzoate/Yeast-1 Sodium Benzoate/Yeast-2 2 j Sodium Benzoate/Vit.-1' Sodium Benzoate/Vit.-2 Mean FC-203(3)/Yeast-l FC-203/Yeast-2 FC-203/Vit.-1 FC-203/Vit.-2 Mean U.S. FC-203/Yeast-l U.S. FC-203/Yeast-2 Mean FC-203A(5)/Yeast-l FC-203A/Yeast-2 Mean FC-6003/Yeast-l FC-600/Yeast-2 Mean LAS/Yeast-1 LAS/Yeast-2 Mean _________ % DOC Removal After X Days 7 14 17 21 27 28 98.8 99.6 94.4 88.6 95 11.7 29.5 29.4 24.8 30.5 29.1 32.6 88.6 _(4 ) -- --- 28.4 27.0 27.7 90.2 89.8 91.0 80.5 95.6 95.3 92.1 83.6 95.2 92 26.9 64.3 25.1 90.8 -- 79.2 90.7 95.5 96.0 96.5 97.5 97 12.6 13.2 8.5 89.1 -- 6 . 6 75.5 -- 7.7 10.5 1 1 . 0 86.4 85.1 92.5 _(6 ) 89.3 76.3 87.0 87.2 96.0 92 94.2 88.8 91 22.8 5.9 7.8 8.8 25.1 20.4 49.1 29.7 52.1 33.4 43 Footnotes: Used yeast extract as vitamin source. Used OECD synthetic vitamin solution as vitamin source. ;.; From Antwerp 1982. 17-day samples were only taken for LAS. From Antwerp 1980. Originally labelled FC-203 NFP. ' Sample contaminated, not used. 001984 X'xyuxe 1 DY BIODEGRDBILITY: Modified Screening Tesi OECD 30IE -- Adopted 12 May 81 Environmental Lab Request No. 9611 100 90 60 70 60 50 40 30 20 10 0 iMguj_e z DY BIODEGRRDABILIT Y : Modified Screening Test OECD 301E -- Adopted 12 May 81 Environmental Lab Request No. 9611 100 THIS SERIES WAS RUN USING 90 STANDARD NUTRIENT SOLUTION 80 70 60 50 40 30 20 Legend 10 A SODIUM BENZOATE REFERENCE X FC-203, ANTWERP 9/82 0 Figure J DY BIODEGRRDflBILITY: Modified Screening Test OECD 301E -- Adopted 12 May 81 Environmental Lab Request No. 9611 100 THIS SERIES HRS RUN USING 90 'STANDARD' NUTRIENT SOLUTION CONTAINING YEAST EXTRACT. 80 70 60 50 40 30 20 10 Legend A F0-203. ANTWERP *80 NFP (FLASK NO. 11 X F0-203. ANTWERP *80 NFP (FLASK NO. 2) 0 Figure 4 DY BIODEGRBDBBILITY: Modified Screening Test OECD 301E -- Adopted 12 Mag 81 Environmental Lab Request No. 9611 100 90 00 70 60 50 40 30 20 10 0 t-- r Cj OECD Screening Page 9 July 9, 1984 II The modified OECD Screening Test is intended for use on single chemical substances. L/W products, on the other hand, are aqueous solutions containing a mixture of chemicals. Pure chemicals, which have greater than 70% loss of DOC within 28 days, are regarded by the OECD guidelines as being readily biodegradable. Also, this result has to be reached within 10 days of the DOC removal first exceeding 10%. Only one of the replicates of each of the four L/W products tested met this second OECD requirement of 70% degradation within 10 days of first reaching 10% degradation. This requirement, however, is not realistically applicable to L/W or other formulated products (mixtures). The chemicals within mixtures will frequently have differing susceptibilities to biodegradation. Readily degradable chemical components of such products may start to degrade immediately, while the onset of degradation of other chemicals in these products may be delayed. Thus, disregarding this second criteria, which is not reasonable for mixtures of chemicals, the results show that the mixture of chemical components in each of these products is readily biodegradable. Cultures tested with the synthetic vitamin solution showed, on average, a slightly lower level of DOC removed than cultures using yeast extract as the vitamin source. Future OECD screening tests should thus use yeast extract since the synthetic vitamin solution is more difficult to prepare and does not give improved degradation. LAS, which is a readily biodegradable and commonly used surfactant in detergents, did not degrade fully under these test conditions. This occurred in spite of the fact that its concentration was only 15 mg/1 of DOC compared to the 40 mg/1 of DOC used for the Light Water products. The reason for the slow rate of LAS biodegradation appears to be that LASginhibited microbial degradation at the test concentration1 . To check this hypothesis, at the end of the 28-day test period, the remaining LAS containing test cultures were split and half were diluted to twice their volume with fresh inoculated nutrient media. At this point, the rate of degradation in the diluted cultures increased substantially. Seventy percent of the DOC remaining at the time of dilution was removed within 15 days. Results of this work on LAS are shown graphically in Figure 4. Another researcher, has similarly reported a low level of biodegradation of LAS in the modified OECD screening test. D. Liu found that Marlon A (dodecylbenzene sulfonate) had a half life of 39 days. CONCLUSIONS The present studies repeated the findings of previous OECD Screening Tests on Light Water products done by the 3M Environmental Laboratory. Both sets of tests showed that L/W products are "readily biodegradable." In all cases, the average DOC removal for L/W products was greater than 90% after 28 days. L/W products were much more degradable than the very commonly used and "readily biodegradable" surfactant, LAS. 001989 OECD Screening Page 10 July 9, 1984 n REFERENCES Organization for Economic Cooperation and Development, Guidelines For Testing of Chemicals, Section 301 E, Ready Biodegradability: Modified OECD Screening Test, May 12, 1981. E. A. Reiner, Biodegradation of "LIGHT WATER" Products in OECD Test 6/80, 3M Technical Report No. 40, Dept. 0535, Project 9970012600, 6/30/80. ( 3 ) Dr. H. Hellmann and D. Muller, "Environmental Impact of Fire Extinguishing Foam Compounds (Umweltgefahrdung durch Feuerlosch-Schaummittell)." The study was carried out by the West German Institute of Hydrology (Bundesanstalt fur gewasserkunde), April 18, 1979. (4) D. Muller and T. Tittizer, "The TOC Degr-adation Test - A Process to Test Organic Materials for Complete Biodegradation (Per TOC Abbautest - ein Verfahren zur Prfung von Organbischen Substanzen auf Vollstndigen Biologischen Abbau)." Developed at the Bundesanstalt for Gewasserkunde, Koblenz, Z. F. Waser-und Abwasser-Forschung (1979). Dohrman DC-52A Operating Manual, 4th Ed., 1978. R. D. Swisher, Surfactant Biodegradation, pages 16-17 and 147, Marcel Dekker, Inc., 1970. (7) D. Liu, Study on Biodegradation of Aniline and Marlon A, Biodeterioration 5, Edited by T. A. Oxley and S. Barrry, 1983. 001990 L/W TOC of FC-600 % i n Prod Components Empeiical Formula MW MWofC T X 2 Sultone foamer C16 H23 F 1 3 S 2 0 6 N2 650 192 0.0059 1 Filmer (FC -95) C8 F 1 7 S 0 3 K 522 128 0.0025 1 Ha octyl sulfate C8 H 1 7 0 4 S Na 232 96 0.0041 1 Na decyl sulfate C10H21 0 4 S Na 260 120 0.0046 0.1 DovicideA C12 H 1 7 05 Na 264 144 0.0005 0.05 Benzothazol C6 H5 N3 119 72 0.0003 0.8 Kelco Keltrol assume C6 H10 0 4 146 72 0.0039 0.8 Stanley H -2 7 7 Starch assume C6 H10 0 4 146 72 0.0039 12 Butyl Carbitol C8H1803 162 96 0.0711 81.25 Dl Water H20 18 0 0 Product TOC= 0.097 Page 1 001.991