Document n9w6RQVXB7QrVgOJ2RejZaVez

SUMMARY FOR WORK PERFORMED FOR THE GERMAN GOVERNMENT AGENCY FOR MILITARYTECHNOLOGY AND PROCUREMENT ON FIRE EXTINGUISHING FOAM COMPOUNDS FROM MULTIPLE COMPANIES TEST SUBSTANCE IdentityA:mixturceontainiPnegrfluorooctanesulfwohniacthem,ay alsobe referredtoas PFOS, FC-95, oras a component ofFC-3017. (1Octanesulfoniaccid)(CAS # 2795-39-3). Remarks: The 3M productionlotnumber was not noted.The testsample isFC-3017, referredtointhe reportas FC-206 freezeprotected.Current informationindicatesitisa mixtureof0.67% PFOS, 20% diethyleneglycol butylether,55.41% water,21 % ethyleneglycol,1.33% Hydroxy foamer, 1% sodium octylsulfate0,.5% polyoxyethylenemonooctylphenylether,0.04% sodium laurylsulfatea,nd 0.05% tolyltraizole. The followingsummary applies to a study done by a thirdparty (Dr.H. Hellman and D. Muller)forthe German Govemment Agency For Military Technology and Procurement forpurposes of comparing the environmental propertiesof fbam extinguishingagents from multiple companies, including 3M's FC-3017. Data may not accurately reflectthe environmental properties of the fluorochemical proportion of the test sample. STUDIES Zinc,iron,and copper content;surfacetension;Chemical Oxygen Demand; 5-Day BiochemicalOxygen Demand; ToxicitytoFish(speciesnotgiven); ToxicitytoWater flea(Daphniamagna); ToxicittyoAlgae (speciesnotgiven); Bacteriainhibitio(nspeciesnot given) Report date: 1977 METHODS: Chemical Oxygen Demand was measured usingpotassium permanganate and potassium dichromate. BiochemicalOxygen Demand evaluatedusinga TotalOrganic Carbon degradationtestdeveloped by the BundesanstaltfurGewasserkunde. ToxicitytoFishwas evaluatedaccordingtothe German standardprocess for watertesting(DEV) L 15 Toxicityto Daphnia was evaluatedaccordingtothe German standardprocess forwatertesting(DEV) L 11 ToxicitytoAlgae was evaluatedaccordingtothe German standardprocess forwatertesting(DEV) L 12 The method forevaluatingbacteriailnhibitiwoans not described. RESULTS Fish LC50 Daphnia EC50 Algae EC50 Bacteria inhibition BOD21/COD Result >1000 mg/L >250 nig/L >250 mg/L lnhibfted -9% Remarks: The above toxicitdyata didnot have testdurationinformation. DATA QUALITY ReliabilityK:limischranking= 4. Allstudy valuescome from a summary list only. No raw data or method documentationwas available.The study summary failedtodisclosedurationoftoxicittyesting.Itisnot clearwhy such low biodegradabilitwyas observed when the productscontainmaterialsthat are known to readilybiodegrade.The sample puritwyas not properly characterizedand the studylacksanalyticaclonfirmatioonfthe amount of fluorochemicalproportioninthe solution. OTHER Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St. Paul,Minnesota,55133 Last changed: 6/27/00 Date 'TECHNICAL AWARENESS TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (jiiiportant-Whenever possible,attach a fullcopy of the material you have abstracted.) C, Ir ibijtor ivision ,:ricA. R(iiner TEn'vviis'roo' nmental Lab (EE & PC) U Journal0 Book LocatioonfOriginal Other Garmin Aie C] Patent 13 (Pleasepecify) ra t r pt? Referenc(ee.gA.u.thor,TitleI,ssuDeate,Volume,Page.ate.), P OV ae Number 477Z0 16 Dr. H. Hellman and D. Mui@r,"Environmental Impact of Fire Extinguishing Foam Compounds." The study was carried out by the West German Department of Water Technology for the West German Agency for Military Technology :tn(iPr(-)ctjreni(-n(t,.rranslated by G. Diersson, March 1, 1980). Al)@ir;(igci.v1Vfottiorvvnsiinotn thesourcdeocument) 'I'hi.rcesport compares the environmental acceptability f 6 AFFF Agents including FC 3017 (identified in the report as FC-200p,freeze protected), FC-206, and FC-200. The researchers measured biodegradability, aquatic @@oxicity,.heavy metal concentration, and surface tension. The report recommends avoiding use of the 3M AFFF products since all were difficult to biodegrade, but the biodegradation results and their interpretation are questionable. Comparisons of BOD5 and COD showed that the 3M pro(lucts were more readily degraded than the competitive products, yet the authors chose to give more credence totests measuring dissolved total organic carbon (TOC) concentration over a 21 day period. These tests gave results that were inconsistent with the BOD results. In these tests 3M products inexplicably did not degrade. C,)Pv L i%l(cup.esto tiesont Uv originator) Itemssubmittedon thisform we publishedinthe3&4T*6nical Awmenon Gazette. Compliment to Report of Bundesanstalt f@r Cewasserkunde. 1. 0. April 1979 rNlb/340.22/2596 snvtroawmtal impact Fire xxtingu:tobtn Foss Cowo=4*. Study carried out for ilundassat fur W*hrtochnik und Beachaffung (Mm*rnmnt Agency For Nilitary Tocbnoloiy and Proci4roment) Report: RA 111 l-E/B31E/70145/76066 of October 12 1977. Reporter: Obarr*gierungerat Dr. R@ Val3wA= Obarreglov=ssvot.D. iallor Koblenz 1979 Table of Contents. 1. Introduction Page 3 2. Definition of Problem and Task 4 3. Test Results 5 3.1 -"1"1- CBMIC" T"te. 3.2 Tests for liacho""I vogr&"tt" 7 3.3 toxteolosyTests 12 4. Bva3L@eati1omf ,Raoulto imd C6ntlual6u;- 15 S. Re, datlons for Technical Orderin Specifications 18 Conclusion 19 Enclosures: Literature list Additions -2- 1. INTRODUCTION For fir* extinguishing- foam compounds one can distio4clob six application rogions: 1. General application (local fire protection) 2. Solvent industry 3. Fightlag of cxr%lnhy4rido fires for instance In rofUwri" 4. sio@,-tciw equip@t, tub voltage (closed sypgw'w) s.' 'Appliestums In airports. 60 Applications on ships. In the.pro@t study it will appear that airport fire@ take on Oreforti rap Importance (1). It Is obvious, that a few seconds In time can make In- portant difference for saving human liv", and that the question of owdlvqok- mmtal endangering especially of waters and streams does "sum* soma what leis Importance. But water safety need not be completely ov*ru*ked **peel-..- ally because most of'the actually used fire extin"Ublng iti@training. compounds ar@ used.. I%* 26ndawastaLlt fisrCm""rkunde (Dept. of Watot Technology) in 19 75@.@ got the took from the Mlitintoriumsfur Ernihrms bat wd fimmoai*@. ("stry of Food Agriculture and Forestry of iiordrha:Lu-W"tf4loo)to PV84- uat* the Impact of foam extinguishing couppunds on the water quality. Th$rty-. eight foam e*tlng"shug compounds from 8 suppliers Vero avaluatikdch":Lc&Uy@ physically and biochemically for possible ondangeriqg of water. @.'Kff'*!rent br'an@s"d:id vary In degradation and toxicity. lopecially.tha SZ'foau exti*-; "solutions used can result In the following dmwgp: -3- - Poisoning of natural water purification (in streams) - Poisoning or damage to fish and fish food animals. - Reduction of azygen contact by metabolic processes (surface or ground water) - Reduction of water quality by organic compounds (general) - Undesirable r*4uction processes In the ground-,@water. This report pas pubuti. ..4w..ParuW,4,A,@149-4@4."-kwwo$."11.49,"t:Lo**"t*he Pettis* :Lnvolv*4,such " the mmufacturors of fow qxtftSuiobi4 compottade an4.the autbor:tti" responsible for vtter pur:ity. Ann$ otheralthese conalderatio" were taken Into account In the DIN- standards. 2. DEFINITION OF PROBLEM AND TASK After several discourses in 1977 between represen%ativ" of the Bundeomtes fur Vehrtachn:Lkand Beachaffung and the Bundosanstalt f*u*Grovasserkunde (BFG), the BFG v" authorized an Oct. 12, 1977 to carry out a @POMA cial study. This study should only cover the products used by th&,Bun4ovehr'. (W. German military) and also products which are considered for possible U" lntrodttction. As a first objectivethe eavivanamtal Influence of the following six. eztlnguiahing compounds should be datermft*d: -4- NO Product I Fluor protein 2 Light Water, FC 206 P30/7 (front protected) 3 Light Water, FC 206 (normal) 4 Light Water, FC 200, (normal) 5 ftvt"x fo4a "d 6 Lxpy"l 7 15 Hanufacturer Firm Dr. R Sthamer, Hamburg Firm 3 M, Neuse Firm 3 M, Nouns Flra 3 M, *me* nX* Dr.-R. Sthmor, Rmburs 71= ftoebst As, Frankfurt/Hoechst The two types of Liibt-Water are offered as being "*specially safe to the environmmt" (According to BWB). Light Water FC 200 is reported to be out of production, but should be evaluated for comparison. The to4t for environmental Impact should, if possible, be tested for 52 solutions as used (for Light Water 6%) and encompass the following paramters: turfeco tension actlvity -Toxicity - Biothmlcal degradation - Content of heavy metals - Flame point. The final report should also contain recommendations for the technical procuremmt specifications (TL). The final report was scheduled for completion In S*pt 1978. Due to,@ sicknase-of one of the investigators It was delayed for son* amths. -5- 3. TEST RESULTS 3.1 Physical- Chemical Tests The first test result gives the heavy metal content which was deter1) mined by X-ray fluorescence Evaluating the figures of Table 1 listing the heavy metal content, the two o.oupomde Floorprotein (No 1) and Protein foaa- eampouqd (He 5) st4W Out. POV floorproteft the zinc and :Jrm contest of the applici"tift (N$Xtam) V:Lth40 OW 55 wg/l respoet:Lvoly,is rout:Lvol for the 4ocft4 couromd the ivon content of 50 as/I stands out. All othiv hOW7 Metal concentration$ such as the especially recorded levels for copper.' are unimportant. Table Heavy metal content in foam tiniz!ishniR compounds. No. "%riginal @yjroducts Zo Fe cu ppe Igo 7 3 03 6 1 2 970 6 3 9 5 zu solutions Fe tu 40 006 0 4:1 so eel ots 0,02 00'02 00 00022 9 0 02 0:02 1) Datorm4ned by Dipi. Ches. U. Schl*:Lchart -6- When the flame point is determined, the water content of the sample 0 must be considered. Fl-a points above 100 C, the boiling point of water, 2) could not be determined. As could be expected none of the tested samples 0 did have a flame point below 100 C. It should be obvious that none of the products would cmtaln fImmeAble -ablvents. 3) The surface, or interphase tensions can be seen from Table 2. The surface tension water/air gcnerally drops *me for concentrations from @O mg/l to $00 ag/l. The surface tension Is least affected for N*5 (ftotein-foan extinguisher), most effected for two Ught-Water types of FC-206- type. 7b& reason for this Is found in the chemical composition of the extiguishing compounds. Protein foam agents can be expected to be generally inactive to the water/air interphase; while tensides and also so called "synthetic"pro- ducts are interphase active. The lnterphase activity is less a product specific, but rather a group specific characteristic. Tabl.p. 2 .Inter!)I,-.-tircetivitv lio. Interphpe @-ctivity --Lt'.,)Oco ( dyn/cm) so too 250 Sao 62 2 is ss Is 6 so 48 ss Is 23 is at 62 2) Determined according to Abel-Peusky in closed vessel.; DIN 51 755, Ed. 966 3) Interphase- Tonsiometer, according to Nooy, rlrm, A. Krona, Hamburg -7@ 3.2 Tikotfor Biochmical Degradation To evaluate the water polution characteristics of compounds, it is of interestto sun up the chem cal parameters@potassium permanganate and a A.-/c)@- tc-00) 4 a DS potassium dichromate uptake, (CSB). The biochemical oxygen uptake (BSB 5 Colo R5 of DEV (4)) can be used especially In combination with CSB to prel4m4nar- ily evaluate the degradation. Wbou the CSB analytical taft gives reliable results (thU, for Instance, Is not always true when hydeophobic compounds are being tested) one mot emal4or pos:Lt:Lve mmult c /-3a,0-3 der:tved from the OSB/BSS ratio maul, whao astat:Lvorowdts can nOt be co:mtod, since the bmubatlon period for the BSB-t"t under same conditions do" not oncoap"o s4f:Lc:Lenttime for adaptation of the organILe" active in the biological breakdown. It Is not certain that toxic inhibitions can be excluded In tho 600 standard BSB (5). To better insure results concerning the dogradat C.0 P.0 Lou In possible by *valuating the CSB.7BSB ratio, one must carry out extensive dogradatd*n toots, where the Incubation time, the inoculation material and. other parameters are determined, so that further broakd*m A day UB-test can be evaluated. than for the fiv* At present there are International affort4 underway to itandardits di*' gradation tests. For this Investigation of breakdown of fire SaLt*Mdsh;!4 foam.-compoundsa now T.O.C.-dogradation test (6) de"loped by the Bunde---..& it fur Mw"serkunds was used. Its test:-aftteriato the complete breakdown of t" total organic carbon (TOC). ,'Forthe test procedure the test compound sorv" as the only sourc;eof carbon. Inorganic mineral salts are added in advance. The Lncubatio@'takes . . place in a screw-cap flask with air space, placed In a *Mkor. thi'.a.sdrad a- 0 tilontests for the fire extingulaWtAg foam compounds were carried out @'at 20 C In the dark, In deviation from the stated test procedures. r When the percentage breakdown according to the TOC-t"t is compared to results from other degradation tests, It must be taken into account, that the disappearance of one material from the solution is often considered as degradation. Under carain circumstances a high degradation can be simulated which actually is based upon physical processes such as,,forinstance,,aboorpt:iouof solids which has no relation to complete biological breakdown and t Acoordlm 1, tlii' TOC results to the experience@ gathered by particlpotlm for completely soluble compounds aire sourobat vhen-the breakdown Is measured by the "modified OECD-04:r"ning la a round t"t lower than test,, This ''modified 090 -screening it has some dl"dvaaftgea test" was tested by International round'test's.' used for testing of emulsions and suspensions. Since the products tested here are mixtures the results 6f the diiradati@m test Is only wall defined when a total breakdown is rocor4ed. tu where partle]A br"kdowi is observed,,thda can be due to the fact that@@'only part of the product can be broken down,'while other parts can note The breakdown of uizture 00 manipulated by the nimuf4teturerby addition of compounds wh:Lchare easily broken dov% but otherwise without function. Even though, It.is useful to test the breakdown of the prosent.vaxt@re productsibecau" It giv&s a preliminary ranking of the products. For future . tests, which could be cartw -out after a period of a few years of ua4. :itstaouldlaeattempted to test the breakdown of the single components of the products. --MEN= -9- RESULTS: Table 3 does list the measuremut results obtained for the orginal products, to evaluate the potential for.;mdangering of the water. Table 4 lists the percentage of degradation of the application solutions oftar a period of 2 days together with other degradation parameters of Interest. The spocifle TOC- degradation curves &re Incorporated In attachumts 1-,6. The valaw obtaumd from Table 3 ohm that the differentproducts C*Ut&u. varyus owints of orgaule cowpomde. Ofcourse one Should count a low content of organic materialsand of orgmlc carbon found In products 1,4 and 5 as positivefactorswhen water endangeringIs to be judg*d. Sao For the applicationsolutions(table4) the EIB'and BSB5 are listed togather with the ratio between these two factorsand can be used In addition to the TOC- degradationresults for,the.-ev&luatl4M. According to the ratio the product No 6 should be consideredeasy to degrade. For the productsI and 5, which according to the TOC- degradation test app*W medium degradable (as alsoestablishedfrom the metabolismt"t), the unfavorableCBS/BSB 5 ratio could possiblybe due to the chemicaloxidationof Iran salts pre#"t In the products. The Iron salts would Increasethe CSB without lncreasft$ the BSB 5@ The degradationof each product, separately,to evaluated as follow.o;.. .Foam 1 extinguishing compound No'*&bows a favorable ratio of KMAO .:Conauqp- 4 t'an/ K2Cr2P7 consumption,and shown good bacteria action In the metabolism test,togetherwith a 4n TOC- degradation. It must be rated N"Iun degj!,@4fLb@s. -30,".t7''.A':'A-i ProducSto 110: 2 shows a favorableCSB/BSB 5 - ratio, but since the other t0'$;Lf L nioit'ludicaategood degradationrate It is classifiedas difficultto d*gradee- Tbikdfticad4tAeo&f product 3 is even less tbft thatof product 2.g so It Is.@cia.seltiaesd difficultto degrade. F."m though the degradationduring the TOC-t"t W" further advanead 70101f, 3 -ILO- Pot,enlial 'or endange-rin--a-f, wa ters by -)ripinalprodue to No K]KNO 4 ust-,rl K 2 GrO 7 used Org.0 content H2 bontent a) Organic part b) 01203 los2s Otis 89 Fe 0 17 2 0,098 3.434 012.4 rc -10( A olosv Z.9930 0622 C> 4 otoso let?) otio so 0 o4 I'F 19391 of,* is 6 selelloon 49*6 sell .7 only op"xinato values b) only apprOximSts values,'I)urnoffvalues at 6o*OC and variable duration Table 4 Biochemical dogradationi2f Uglio&tion ro&gz solutions (5%) No Rate of mino 4 04 sail C-00 083 3 (me K laro1 8 -'*,Os 2I *all 94%11 CBS C..,O Degrade Dogred, in nothabol. T(@b test test Final oval, x) 5.00 4.9* sodium eL 3r%%7 2. soontio) as -z.L 1 2 IS-00 ty oo!F diffima-k diffiftlt 4 t.2%0 16.m 4.450 3o4 093 12 dif fifti @t 5 1.100 20-000 3.250 Got 093 37 madim 6 2.wo *.on ql.m ost $*1 4 402 easy to l'isdium x) Ivaluation of bioohomioal dogr&4ation in TOO- test (at standard temperature of 250C) o - 2o % diffioultto deprade 40 - 75 % sodium degradable 2o - 40 % elightly degradable 75 - loo % Y*ry dogr"i%*olo for product 4 than for products 2.and 3, it was classified as difficult to degrade. For fire extinguishing foam compound 5, the metabolism test indicates that It can be broken down. A finding which Is confirmed by the results of the TOC- test. The product is classified as medium degradable. For product 6 one finds a complicated degradation belpvtor which might originate from the high toxic effect of this product. After 7 days d*gradatim already 102 of the TOC Is brok4m 4mo. ftrthw 4ogra4*tloudoes r""Itt@, only aftow 14 testing days, but tWo an Satowive dftr*4atum lowift to breakdown of 6OX of the starting TOC does take p3L*coq The slow down In br"kdow,ii, after 7 test days can be evaluated as on &&pt4tion period for the microorganism Involved. 3.3 TbxlcoloO testinit NRTBOD In the "Evaluation of the Water Endangering by Foam Extingulshftg Co"omds" (2), the results concerning toxic effects towards algae and bacteria were discu*mW.. In this evaluationwhich in concerned with tests for products that possibly could be used :inlarge amounts, the toxicologyaddition to the Incorporation-notabo]Llamtests,,also tests with small crabs and fish were carried out. This way the previous results could be further confirmed. The toxicolgy test In carried out according to the Germm standard procase for water testing (DEV) (4) L 11, L 129 and L 15. For tmee,the latest post procedures were used an publtshed by the responsible working comitte". For fish-taste the concentrations us*d were from 0 to 10,000 mg/l, where -12- a large grauation of dilutions was used. The further toxological test were carried out with smaller gradations from 0 to 210 mg/l to Insure, that the products could be differentiatedas well as possible. USULTS: ..Inthe enclosures 1 to 6, the results of the toxicology tests &ra@ presented. ..-40:.Ooser-eaction curves and the results are calculated and presented @n Table 5,. Product No 1, *Yluorscmmg"st (Inclosure 1) La so toxic at concentrations of 10,000 mg/i that all test anlmls did die (SC 10000 mg/1). Bqt for 100 the concentration 1000 mg/l the product Is not detrimental (Ec looo mg/1),@, (EC- effective concentrationwith respect to the correspondingtest. Ec is . 100 the lowest tested concentration for which a 10OZ result with respect to the: test criteria Is recordod...Forthe flab@test,this Is the concentrationat which all animals die; EC is the highest tested conc4mtration at which no 0 significantreaction Is observed with respect to the test cri.taria). Towards the small crab,Daphnia magna (water floe),the product La not detrimental at the highest concentrations tested (ECo- 250 mg/1) The photosynthesisactivity of algae Is easily off*ctad by Fluorsibago- gaint. The effect is still below the criticallimit at concmtratlons'of 50 ft/1,; but at 100 ux/l it is significant. ,4 'The bacteria oxygen uptake during break down of p*ptone in increased by the product. This makes the blochanical break down of the product Itself plausible. This result Is also confirmed by the TOC - degradation test (sec. 3*2)o The product No2, Light Water, FC 206, frost-:Lneurod(enclosure2io reacts similar to product No I in the fish and daphnia tests. Also the roadr, of the incorporation test in similar to the first product. But the lnt@iltion of the photosynthesisactivity Is less and become significantoply.ot,the highest concentration 250 mg/l. [Tbe result of the astabolim -vv*o@fi*t t -13- definitely different than for the first product: There Is no methabolic increase which could be interpreted as a sign of break down. The TOC degradation test also does show a break down of less than IOZ. The results of the biological tests carried out concerning product No. 3 "Uzht Water, FC 206, normal,ifare nearly lndentical to the results obtained for product No. 2 Light Water, frost protected. The only differeniis Is; that the tozle effects towards &IS" indicated for product 2 or* not @for product No. 3. Product No. 4,,"Ugbt Water, PC 200, nonial,*'I* different from the foam agents discussed previously by having a definite toxic of-&'actowards fish, and algae. For fish the test animals die already at looo (Eco 100 ue/l, RCIOO IOCP ft/1). In the daphne test, 33% of th* animals died within 24 hours at 100 mg/l, at 250 mg/l about 75Z of the animals died (EC@ - 50 mg/l, EC,oo - 500 mg/1). The Ancorporatlon test for this product Is already surp"sed at concentratxlonsof 5 mg/l; at*250 mg/l a complete inhibition of algae activity is recorded (ECO - 2 mg/l, EC - 250 mg/1). Product No. 5. Protein Foam Agent. la all biological tests to equhl to product Nb. 1. No significant toxic effects were found . towar 4* algae at concentration of about 250 a$fI. For the usthabollon test on fter"se@ ltt .becter:Laoxygen corporation was recorded, but it was less than for product No. 1. The result of the nothabol:Lsotest corresponds to a re]At:Lvflly positive.r"ction towards the break down test. Product No. 6. Expyrol, is exceptionally high in toxicity and i%,Ooln.of break down. The toxicity against fish Is high as for pr6duct No.', 100"/l and IC ioo 1000 ug/1). For =all crab tb" product .:Lo -14- especially toxic (ECO - 25 mg/l and ECIOO - 500 mg/1). The incorporation test shows an inhibition at 1O%concentrations above 10 mg/l. For 250 ag/l there is a 65% inhibition. The metabolism curve of this product indicates that it contains meta- bolic active as well as toxic compounds. Ta@)le5 Results of toxicologz test ( exiiressed in order of poison classes) No :,'ish Daphne Algae Bacteria (D,-6VL15) (DZVL 11) (DEVL 12)N inhibit, III III III ILI it tit 6 IT iri fit (DBVL 12) Total enh.,ince. eviluation X) III Poip-)n el.asr 1 Proien inliibitionon tf-ptf,inim-il.a-t@ c,)n(!entr.@itions be'3-,v5 mg/ lliirincliss 11 As in 1,1re.--io5n to ?o-)mt7,/l Poiron class 111: No at concentrations betow '15? TT]9/1 x) Tot-tlevaluati-)n: C-ii.cu'Litebdy weiflhted -tv.%rage.The test result .vith lo,.,;Fc;rrittical limit of concentrttion in multipiied by 4. Evaluation of Results and Conclusions Summarizingthe single criteria of the test, one can obtain different results, dependingupon what Importance is given to the different criteria. The original products constitutea threat to biological systems such an the life in streams and biological systems of purification plants, due to their high toxic level to which ;he surface tension, and for product 1, -15- the content of zinc is added. The drinking water supply could be endangered by the content of just the organic material in the original compounds. Also the application Itrann.th5-6 Z solutions of all products tested can lead to danger for biological system due to their physical, chemical and toxic characteristics. By the further dilution by a factor of 20 to 80, which Is active in the applicatum of foam 2 mg/l for bacteria, 10 - 25 ug/l for fish) Is not exceeded and also tbitsurface tension activity can Umse Its Importance. ',Ittbau:veem reasonable-.toevaluate the water danger by the products, according to their toxicity at the concentrations which can be reached during application, and according to their biochemical dagradaticn@even.thou$h there at present are only degradation reau3Ltsavailable for the finished mi@" pro- For none of the compounds the degradation Is so easy se eb c-lassifythen as eaviromentally friendly compbunds. In the selection one then must differonilate relatively better products from relatively!voroe products. When fIre-aztinguishing foam compounds are applied, the about 5 Z goiu@.VLons.,areas previously stated diluted by a factor of 20 to 80. They than are in a region of concentration between 125 to 500 mg/l. At this concentratton the compound-9of product No. 3 and No. 5 are rithoutacute detriment 17 to the test organism. Pwoduct No. 1 and No. 2 lo" their toxic affect after further dilution by a factor of 2 to 5. Such dilution in'to bo'expectod in the pro-flood tank of the purification systems. For the very toxic products No. 4 and No. 6, aftgmltlonal dilution by a factor of' betwoo 50 and 200 Is necessary to got below the toxic I&vel. Such Aiiutlfts-:.. -16- are not certain in practice. Product No. 4 shows in,addit:Lona low degree of degradatilon and should not be used for that reason. The roducto 2 and 3 are of little-concarn when toxic pro22rties are taken into accotm-t. But both products are difficult to deitradeand could thus dintyarb-and (@RP&irthe drinkluit-water supply@-.and the use-of these vroducts therefor* should be avoided. Of the rematalas products the fom compound no..@l.h" Ugb tftdc level tmords alg" *m to the high content of zinc. jut since theft properties are lost to a -largoextent due.to the dilution during usage, and aftco the product in relatively easy to degrade, the endangering of the waters due to this product appears to be of little importance. The grouping of the 6 products proposed here does take biological and chemical results into account, but dbeo not consider application technical character:Lstics. If It ti not possibledue to application technical,reasons to avoid the use of products which are difficult to degrade or are especially toxic, then It would be advisable to test their slnalo nat&Afor dde- gradation and toxli-affects. Further It should be attempted to replace components especially biologically damaging by less damaging materials of similar effect..- ftch approach has been successful for other materials of environmental concern. 5. Recomandations for technical ordertnit s"clficat!tons Based upon the Investigations liscuseed,@,the,-f#llowftgrequire- mmto can be made of the manufacture of foam firo-extingu:Ls Ing compounds; CThe biologlcal.dogradation characteristics of the organic components present in foam compounds should be well established The break down Would be as "my as possible, right now It In considered -17- as fair, when a 50 % break down is recorded in the modified OgCD-Scroming- Test (7). For a test which records complete chemical degradation such as the TOC-dogradation test (6), a 40 % break down shoyld be the minimum r*quired. Other tests can be used in replacement of the abovementioned, If it has been proven, that equal results are obtained as for the tests according to (6) and (7). when these products are tested. The -t*3de efflgts of the foam compo.ands towards water argailem, 4spec,14;y era;8 and fInk sb*ul4 be as moll as poss:ibile.i A suititiontly nontoxic range can be set If the IC50 for bacteria, allgas'. daohi%aand fish is above 1500 mg/l foam agent in water. .For toxicology test, L 11, L 12, and L"15 of DEV (4), or obdlar procedure for which equal type results can be proven, are to be used. The heavy metal content should not exceed 1 % zinc,,orfor other natal an amount for which a corresponding degree of bacteria toxic effects to recorded. 6. Conclusion r-According to the task the following six foam compounds.,determined by the "Bundesamt fUr Wahrtochnik und Beachaffung" in Koblahz.,were evaluat*4' with,relation to possible endangering of waters-. Flourprotein; Light Water. FC 206, normal; Light Water FC 206, Frost protoct*d;;Light Water FC 20Q, not!=* l-, Proteinsbhaummittel; Expyrol F 15. The test Includes interphase activity, toxicology. biochemical degradation, heavy metal content and flame palnt. The results were presented and discussed and a conalusion r"ched. Tfis' products noorprotein and'Protainschaumittal we're roconomdad 4as to. relatively favorable biologic characteristics. The final cone4gslo=, given as recommendations for technical delivery terms (TL) to.bs used by the contra4t agency. LITERATURE LIST. (1) Fiala, R.: Study "Mittelachaum fur Flugzeugbrandbekampfung" Deutsche Forschungs- und Veracheanstalt fur Luftund Raunfahrt o.V., 1WIn-Wahn 19.77. (2) Sundesanstalt fur Cow""rkunde: Cutachten uber die Wasserge- fahrlichkalt van Schnualoschnittaln, Koblenz 1975. (3) Hellmann, H.: Schauml'o'schmittel - ihre m@gliche Wassergofahrdung, Tenside Detergents 13 (1976), 270 - 273. (4) Deutsche Einheiteverfahren tur Wasser-, Abwasser- und Schlammuntersuchung. Wainheim, Erganzungelieferung 1972. (5) Zahn, R. und H. Wellens: Ein einfaches Verfahren zur Prifung der biologischen Abbaubarkait von Produkton und Abwasserinhaltestoffen. Chemiker Zeitung 98 (1974), 228- 232. (6) Maller, D. und T. Tittizer: Der TOC-Abbautest - ein Verfahren zur PrGfung von organischen Substanzen auf vollstand.igenbiologischen Abbau. Zeitachrift fur Wasser- und Abwasserforschung 12 (1979), 14-21. (7) Fischer, W.K.: MeBverfahren zur Bestimmung der biologischen\ Abbaubarkeitvon wasserl'o*alichoerng,an'ischen Umweltchemikallemnit Kohlenstoffanalyti(kDOC) (ModifiedOECD ScreeningTest). A manuscriptor the fi= RenkeiKU Obuipeldortsbent to the F,.G..aorecommendedprocess. (21.2,1.978). Enclosures Toxicology concertration/reaction curves and degradation curves. I to 6. N r.1 Fluorprotein 100 +60 *60 *40 - TOXIUOLOG Y T"!-ST A.-@I!nc.-)r' poration test D.-;VL12 D- Daphne tort DL-VL 11 -20- Z= Pm Fish tort tost D@-',V1T2, D .'V1, 1 r) -20 -40 0 -60 H 100 100 A 5 10 2@ @O 160 2iO % 1600 10000 Confeentratiomng/i 80 - C> E- r-4 CA .@ll 60 .rq C,: C> 40- C0.) E- 20 Tet;t of' TOC- (Iogr,)AaLion now 14 21 Nr.2 Lightwater,FC 206,frostgeschotzt .-+80 460 TOXICULOG Y TNST Az!Inez)rporzitiontest D:;VL 12 D- Daphne test DL,;VL11 Z- le-ethabolipmtest D!-'Vl1,2 P". ',@ishtcjs:t D -.@,1.,V 1 r) ,40 4) 20- 0 20 -40 60 0 80 10 100- ,00 ---------:@ -00 5 10 25 50 100 250 % go- 1000 10000 Concentratiomng/l 80 - E- 60 0 40- 0 E- Ter.-L TOC- Lion 0 14 N r.3 Lightwater,FC 206, normal 100- -80 #60 *40 4) co .0 20 C-1 TO-,tlC;ULOGY TEST A= IncorPOration teft D--'VL12 D- 1).Lptinotopt DEVI, 11 zu D!ethabolipm to.Qt D@-;VT1,2 F- Fish -20 V, r. - 40 0 -60 H 100 100 'It % % 5 10 25 50 160 2'50 1000 10000 Concentrationmg/i C> EH 40- E-4 TOC- de,,,IridrL-tion 0 14 2 Nr.4 Lightwater,FC 200, normal +80- +60440. Cl- +20- 0 -20 -40. -60- 4@ -80 -100 100 TO,@l(;UJOGY.. 'f@;ST A= Inearp oration test D,-,@'1V2L D- Daphne tort DEVL 11 Z= D:.eth-.bol.iptmest D,-;VT1,2 P= ?ish % % ........... % h, - 5 10 25 @O 100 250 1000 10000 Concentrationmg/i 0 E- 60- 0 40. 0 E20 Ti:@nt I' TOC- 14 De Nr 5 Proteinschaumm ittel +100- -go- D= 060 .Lnc jr.)or-if, t::rL DEVI -o40 +20 0 -20 -40 0 50 D Vi'j Z= -'ish 80 100 1'0 25 5'0 100 250 100 D ',VT,1 CF) 1000 10000 Concentrationmg/i 80 0 Er-4 ai 60 - 0 40- E-4 ?n Test if TOG- dearadation 0 21 7,/@te,e Nr.6 Expyrot F 15 00 go 17'kXL-Co&o(ly r? L,;;@T IncorPOratiO4 test DEVI, 1;? D= Dapline test D:3VL 11 Z- t.:etli@'r)al.tioFm 12 60 (D 40 20 - 0.4 Zo -\--.L a0 40 +3 60- Iw 00 -..4 5 10 25 50 160 2-50 1000 Con(jentr;itiOlt,m&,/l 00 C.) E-4 80 r-i Cd 600 40- E- 20 Ter%L aC TOC- (lo,,.,rtcl:tl;ion 0 t 0 14 21 f