Document KENgbYgq2j5xyBeOKZNdJQXr

AR 286 -0296 SUMMARY FOR WORK PERFORMED FOR THE GERMAN GOVERNMENT AEXGTEINNCGYUIFSOHRINMGILFIOTAAMRYCTOEMCPHONUONLDOSGYFRAONMD MPURLOTCIPULREEMCOEMNPTAONNIEFSIRE TEST SUBSTANCE Identity: A mixture containing Perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-3017. (1Octanesulfonic acid) (CAS# 2795-39-3) Remarks: The 3M production lot number was not noted. The test sample is FC-3017, referred to in the report as FC-206 freeze protected. Current information indicates it is a mixture of 0.67% PFOS, 20% diethylene glycol butyl ether, 55.41% water, 21% ethylene glycol, 1.33% Hydroxy foamer, 1% sodium oclyl sulfate, 0.5% polyoxyethylene monaoctylphenyl ether, 0.04% sodium lauryl sulfate, and 0.05% tolyltraizole. The following summary applies to a study done by a third party (Dr. H. Hellman and D. Muller) for the German Government Agency For Military Technology and Procurement for purposes of comparing the environmentalproperties of foam extinguishing agents from multiple companies, including 3M's FC-3017. Data may not accurately reflect the environmental properties of the fluorochemical proportion of the test sample. STUDIES Zinc, iron, and copper content; surface tension; Chemical Oxygen Demand; 5-Day Biochemical Oxygen Demand; Toxicity to Fish (species not given); Toxicity to Water flea (Daphnia magna); Toxicity to Algae (species not given); Bacteria inhibition (species not given) Report date: 1977 METHODS: Chemical Oxygen Demand was measured using potassium permanganate and potassium dichromate. Biochemical Oxygen Demand evaluated using a Total Organic Carbon degradation test developed by the Bundesanstalt fur Gewasserkunde. Toxicity to Fish was evaluated according to the German standard process for ~ water testing (DEV) L 15 Toxicity to Daphnia was evaluated according to the German standard process for water testing (DEV) L 11 002832 Toxicity to Algae was evaluated according to the German standard process for water testing (DEV) L 12 The method for evaluating bacterial inhibition was not described. RESULTS [ Th LCs >T1R0e0su0tmgt [DapECh,nia [5250 mg/L Remarks: The above toxicity data did not have test duration information. DATA QUALITY Reliability: Kiimisch ranking = 4. All study values come from a summary list only. No raw data or method documentation was available. The study slouwmmbiaordyegfraaidlaebdiltoitdyiswcalsosoebdsuerravteidonwohfetnoxtichielyprteosdtuicntg.s cIot nitsaniontmcalteearriwalhsytshautch are known to readily biodegrade. The sample purity was not properly characterized and the study fluorochemical proportion in lacks analytical the solution. confirmation of the amount of OTHER Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/27/00 002833 J TECHNICAL AWARENESS [aren TO: TECHNICAL COMMUNICATIONS CENTER -- 201-2CN nsrtnt - Wherpost, tach lopoftemart youhovessi) corre i aEric A. Reinor fA - Environmenp tal e Lab (EE & PC) Couns 0 Book 0 Potent 3 reneSpecity)CGERSE AESTEY pee 47816 Dr. H, Hellman and D. Mulpr, "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 ind Procurement. (Translated by G. Dierssen, March 1, 1980). This report compares the environmental se" 6 AFFF Agents including FC 3017 (identified in the report as FC-206, freeze protected), "FoCx-i2c0i6t,y,andheaFCv-y20m0e.talThceoncreensteraartcihoenr,s maenadsusruerdfacbeiodteegnrsaidona.biliTthye, raepqourattic recommends avoiding use of the 3M AFFF products since all were difficult taore bqiuoedsetgiroandea,bleb.ut tChoempbairoidseongsradoaftiBoOnDs reasnudltCsODansdhowtehdeirthaitntethrepre3Mtatprioo-n ducts 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. subi on is frm rushod inth 3 Tchi AvrnsGz. 002834 CBoumnpdleismaennsttaltto RfierporCtevoafsserkunde 10. April 1979 =N1b/340.22/2596 BEST COPY AVAILABLE ~ Buvironmental Impact of Tire Extinguiebiag Yosm Compounds. Study carried out for Bundesant fur Wehrtechnik und Beschaffung (Government Agency For Military Technolofy and Procurement) Report: BA 111 1-E/B31E/70145/76066 of October 12 1977. Reporter: OObbeerrrreeggtteerruuaaggeevraatt. DDr..Hii,llHearllmama Koblenz 1979 002835 1 Table of Contents. Page 1. Introduction 3 2. Definition of Problem and Task 4 3. Test Results 5 3.1 Physteal- Chemical Tests. 5 . 3.2 Tests for Mochemicsl Degradation . 7 3.3 Toxicology Tests 12 4. Evaluation of Results and Conclusien 135 5. Recommendations for Technical Ordering Specifications - ". te 18 : 6. Conclusion 19 Enclosures: Literature list Additions N 002836 ae BEST copy AVAILABLE 1. eRobucrIoN For fire extinguishing- foun compounds ome can distinguish six regions: 1. General application (local fire protection) 2. Solvent industry 3. Fighting of carbanhydride fires for instance in refineries 4. Blectrical equipment, Nigh voltage 5. dppiteations ta atrporce. . 6. Applications on ships. application (closed systems) % : . ' In the present study it vill appear that airport fires take on prefers Ted taportance (1). It 1s obvious, that a fev seconds in time cen make important difference for saving human lives, and that the question of @avivesmental endangering especially of vaters and streams doss assume sows vhat Leas importance. But vater safaty nesd not be completely overlooked espaci- | ally because most of `the actually used fire extinguishing compounds sre used 1d tratntng. | The Bendesasstalt fur Gevassarkunde (Dept. of Wate Technology) tn 1975 89F the task from the Miisteriums fur Ernihruns, lasdviftschetc wd Fostsn (4atstry of Food Agriculture and Forestry of Nordrhein-Westfalen) to vals uate the fmpact of fom extiogulshing compounds on the vater quality. Thirty eight foem extinguishing compounds from 8 suppliers vere evaluated chemically, Physicalalnyd biochemically for possible endangering of vatar. Diffarent brands did vary in degradation and toxicity. Especially the 5I'foan extiig- sudshing solutions 5 used can result in the folloving damage: Th [LA o Sasa : : 00283: 3 - Poisoning of natural water purification (in streams) ~ Poisoning or damage to fish and fish food animals. ~ Reduction of oxygen contact by metabolic processes (surface or ground water) ~ Reduction of water quality by organic compounds (general) ~ Undesirable reduction processes in the ground-water. This report was publiciimzpeardk.s (hadin d bd ecei: yps aftentionyfiggh the parties iavolved, such es the manufecturers of foam extisgulehisg compounds and the authorities responsible for water purity. Among others,these consid- erations were taken into account in the DIN- standards. 2. DEFINITION OF PROBLEM AND TASK After several discourses in 1977 between representatives of the Bundesantes fur Vehrtechnik and Beschaffung and the Bundesanstalt fir Gewas- serkunde (BFG), the BFG was authorized om Oct. 12, 1977 to carry out a speed cial study. This study should only cover the products used by the Bundewehr. (W. Garman military) and also products which are considered for possible new introduction. As a first objective, the environmental influence of the following six extinguishing compounds should be determined: 002838 Yo Product 1 Fluor protein 2 L(icgohsttVaptreort,actFeCd)206 5,)y 3 Light ater, FC 206 (normal) 4 L(iagohratalW)ater, FC 200, 5 Protein ToamAld 6 Emrolris oe Manufacturer Fira Dr. R Sthamer, Hamburg Firm 3 M, Neuss Fira 3 H, Neuss Tire 3 N, Neuss Firm Dr. R. Sthamer, Hamburg Firm Eoschat Ag, Frankfurt/Roschat The two types of Light-Water are offered as being "especially safe to the emvironment" (According to BWE). Light Water FC 200 is reported to be out of production, but should be evaluated for comparison. The teat for environmental impact should, if possible, be tested for 5I solutions as used (for Light Water 62) end encompass the folloving parameters: - Surface tension activity ~Toxtetty - Blochentcal degradation - Content of heavy metals : ~ Flame point. The final report should also contain recomendations for the tachatcal procurement specifications (TL). - The final report was scheduled for completion in Sept 1978, Dus to. _ sickness of coe of the fnvestigators it vas delayed forsome paths. I aie Tlie 002839 se 3. mst msws 3.1 Physical- Chemical Tests ined by X-ray fluorescence . The first test result fiver the heavy metal content which was deter1) Evaluating the figures of Table 1 listing the heavy metal conteat, the two compounds Fluorprotein (No 1) and Protein foan- eompound (Ne 5) stand out. Yor Jluorproteis the sinc and irem content of the applicisation olution (aixtures) vith 40 end 55 ag/1 respectivaly, is relatively high, Yor the second compound the irom content of 50 mg/l stands out. All other 1 are misportant. heavy metal concentrations such as the especially recorded levels for copper Table 1 B Heawy motel contentinfoamextinguishingcompounds. w=y Fo. "rigtnal Products 5% Solutions = rn o n 3 Is :0 : 7 p.3 oor4 2 1"0woo oy mn da ! oR on big ay ne+f 0, 0,3 : 1) Determined by Dipl. Chem. U. Schleicher 00 HhAhsr|i we s9em 2 io 002 i i ug! ol FATE 2 002840 oy ev When the flene point is determined, the water content of the sample must be considered. Flame potats above 10C0, the boiling point of water, could mot be deternined. As could be expected none of the tested samples 414 have a Elame pont below 100C. It should be obvious that none of the Products would contain flammable solvents. The surface, or interphase tensions can be seen from Table 2. The surface tension vater/sir generally drops some for concentrations from 50 m/l to 300 mg/l. The surface tension is least effected for KoS (Frotein-fosn extinguisher), most effected for two Light-Vater types of FC 206- type. The reason for this is found in the cheaical composition of the extiguishing compounds. Protein foam agents can be expected to be generally fasctiv to the vater/atr interphase; while tensides and also so called "synthetic'products are interphase active. The interphase activity is less a product specific, but rather a group specific characteristic. Table 2 Interatace sotivity No. Taterphise ctivity ut 20C ( dyn/cm) 50 100 erree-------- w/leme--25--0 -------- 500 a. i 2: 03 " 2 `3 3 $3 s o [5 " 2Ed [3 . . 3 2 8 | 2) Determined according to Abal-Pensky in closed vessal; DIN 51 755, Ed. 966 3) Interphase- Teasiometer, according to Neoy, Pirm. A. Kross, Hamburg 002841 ee 3.2 Test for Bocheatcal Degradation LatasTeortev0alunautmeupthethveatcehrenpfeoallutipoanrRacmeheatmrearacstenproitsectsokie"cssiadoifpeemcroammmpgouuannadstm,e 1ai8atd1ias,ooff Sav) tamniks Coo) 6905 potassium dichromate uptake, (CSB). The biochemical oxygen`uptake (ss, Hg of DEV (4)) can be used especially in combination with 55 to prelintasr- 1ly evaluate the degradation. When the Gh analytical test gives reliable results (this, for instance, is not alvays trus when hydeophobic compoimds : : xd batag tasted) one mist consider porttive result darived fron the Gvrieny x ato as useful, vhile negative results cannotbe counted, since the 5 day incubation period for the SSb-test under seme conditions dose norencimpass sufficient time for adaptation of the organisms active in the biological we rgttin vy vue 54 SV vero, woe sees oe enim breakdown, It 1s not certain that toxic inhibitions can be excluded fn tha `stsadara 3 (5). To better tnsure results concerning the degradation, thea degradation tests, where the incubation time, the inoculationmaterial and other parameters are determined, so that further breakdwn than for the five da} BeB-cast can be evazuated. ' At present there are international efforts wdervay to dtandardire defy gradation tests. Forthtsfavestigecionof breskdowaoffireextinguishing torn' compounds a new T.0.C.~degradation test(6)_daveloped bytheBundesanstalt fur Gewasserkunde was used. Its test-criteria is thecompletebreakdownof > tha total organte carbon (100). For the test procedure the test compound sarves as the only source of carbon. Inorganic mineral salts are added in sdvaice. The incubation takes Plac1ea screv-cep Esk vith sir space, placed fn a shaker. ha dogreda- Pr for the fire extinguishing fosn compounds were carried out at 20C ta'ehe dark, in deviation from the stated test procedures. : Tnee 002: 842- *7 BEST COPY AVAILABLE ---8- When the percentage breakdown according to the TOC-test 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 cerain circumstances a high degradation can be simulated which actually 1s based upon physical processes such as, forinstance,absorp tion of solids which has no relation to completebiologicalbreakdownsnd atsaralization. : "According to the experiences gathered by participation in o roundrae oe TC reeulte for completely soluble compounds are somevhat lower than sic vie the breakdown is measured by the "modified OECD-dgreening test" (7). This "mod#fied OECD -screening test" vas tested by international round tests. Te has some disadvancages csmpametdo: the 20.dagradat ibn test.sdoun weri used for tasting of emlsions and suspensions. Stace the products tested here are mixtures the results of theadgrad- atlon cast 1s only well defined hex a total breakdown is recorded. In cases Vhere particla breskdovi 1s observed, this cen be dus to the fact that only Part of the product can be broken down, while other parts can mot. The breakdown ofmixture can thenbemanipulated by the manufacturer by addition : of compounds which are easily brokendovn,but othervise without function. "Even though, it is useful to test the breakdown of the present mixture products,because it gives a prelintaary ranking of the products. For future tests, vhich could be carried out after a period of a fev years of uss, 1'should be attempted to test the braskdown of the single components of the - -- products. . 002843 a ResuTs: -- BEST COPY AVAILABLE Hate the percentage of degradation of the aplication solutions afcer a period Table 3 does list the measurement results obtained for the orginal products, to evaluate the Potential for endangering of the water. Table 4 otf days together with other degradation parameters of interest. TOC- degradation curves are incorporated ia attachments 1-6. The specific "me Values veryiag smuats obtained from Table 3 of organte compounds. show that Ofcourse the one different productscontain should count a lovcontent of organic materials and of organic carbon found in products 1,4 and 5 as Positive factors vhen water endangering 1s to be Judged. Tor the application solutions (table 4) the 35 and fn are listed to gether with the ratio between these two factors and can be used inaddition tothe TOC the product degradation o 6 should results for-the `evaluations. According to the ratio be considered easy to degrade. For the products 1 #24 (48 3, Which according to sloo established fron the che TOC- degradation test matabolism test), the appeys mediumdegradable wtevorabiecas/ass at10 could poastbly be dus to the chemical oxidation of fron salts the 383, Tedapradacion of each Jrodust, Separately, is evaluated as follows: Tom extinguishing compound Nok 40n/ XyCrp0; consumption, and shows shova a favorable ratio good bacteria action in of 1040, consump the metabolism test, together with a 472 307.44 Product No 2 shove a Toc- degradation. favorable CSB/38B; It must be rated as mediumdegradable. - ratio, but stace the other teats ct" a0" sot tadteate a good ot TWdagradetton of degradation race 16 18 product 3 te even less classified as difficult them that of product 2, to 50 degrade. 1 fet 1 cluseitind as difficult to degrade. ' = 002844 i Hee though thedegradation during the TOC-test vasSucshuy,Advanced iia {ae zonle wi- BEST COPY AVAILABLE Poten'isl for endangering of waters by original products No WO, E010, ora. 50 Organic ' used used content dontent 8) part b) w/t wl kao 1 2 1 0.203 152s os * 10,7 #3000 2 0,098 3.438 0.23 EI "= Forol 3 0.085 19% 0,22 7" 3 fezeo 8 00m tn [X]) El s 0.408 2m ""e * " ------a--ee--re----4--,08--------uN--------"--------2------ a) only approximate values ; ) only approximate values, burnoff values at 600C and variable duration Table 4 Blochegioal derredation Of application ready solutions (5%) Sol myn men No Bate of Cf a, Bs 2 w$88m, Dinograd. Daegrad. Foivnala,l a0, (me E20) B05 503 TE pgtnavor. tou PF) Fluor patny 5.000 12.00 4.08 31 0) . FO) 2 2.50036268). 13.00 ~1y 08 - eel yg Boysen 0.00 3) 0 - FC raw 16.500 4430 34 0) - 5 1100 20.000 3.2% 60 02 + " | msdsun . alftiouls . diffionls " auteioult medium ------ 6 2-- .500----36-- .000---- 41.0e 00 e 08 1,e 0 . e"te oeadsiyr nto x) Bvaluation of biochemical degradation in TOC- test (at standard temporature of 250) 0 - 2 % difficult to degrade 40-75% medium degradable 20 = 40 elightly degredadle 75 - 100 % very degradable . ' esa -1- BEST copy AVAILABLE for product 4 than for products 2 and 3, it vas classified as difficult todegrade. For fire extinguishing fom compound 5, the metabolism test indicates that it can be the TOC test. broken down. The product A fs finding which classified as 1s confirmed by the mediua degradable. Tesults of For product 6 one finds a complicated degradation behavior whichmight originate from the high toxic effect of this product. After 7 days degrada- tion already 102 of the TOC 1s broken down. Further degradation doesresults. only after 14 testing days, but then sn intensive degradation leading to breake : down of 602 ofthe starting TOCdoestakeplace. The slowdown1a breakdown organten involved. after 7 test days can be evaluated as an `adaptation period for the micro- 3:3 Toxicologytesting METHOD In the "Evalustion of the Water Endangering by Fosm Extinguishing Compounds (2), the results concerning toxic effects towards algae and bacteria were discussed. In this evaluation which is concerned with tests for products that possibly could be used in large amounts, the toxicology testsware intensified. In addition to the incorporation- metabolism tests, also teste with emall crabs and fish were carried out. confiraed. This way the previous results could be further The toxicolgy test 1s carried out according to the German standard pro- cess for water testing (DEV) (4) L 11, L 12, and L 15. For these,the latest Feat procedures vere used as published by the responsible working comittess . For fish-tests the concentrations used were from 0 to 10,000 mg/l, where 002846.; a2 BEST cory AVAILABLE a large grauation of dilutions vas used. The further torologlcal test vere carried out with smaller gradations from 0 to 210 mg/l to iasure, that the Products could ba differentiated as well as possible. REsuLTS: In the enclosures 1 to 6, the results of the toxicology tests sre, presented "aa dose- resction curves and the results are calculated and preseated fn Teble 5. : Product o1, "Tluorecheungeist (Enclosure 1) is so toxic at concentrations :' of 10,000 ng/1 that all test animale did te (xc, = 10000 mg/1). Bat for the concentration 1000 mg/l the product Le not datrimeatal (20, 1000 ng/1). (50 affective concentracton vith respect to the corrempontiag tant. BE, ds the lovest tested concentration for which a 1007 result with respect to the test criterias is recorded. For the fish test, this is the concentration at Which all animals die; EC, is the highest tasted concentration at vhich no significant reaction 1s observed with respect to the test criteria), * Tovards thesaal1'CPah Daphnia magna (vater fle), the product 1s not detrinental at the highest concentrations tested (ECs 250 mg/l) "Tha photoanthaste activicy of algss is esstly effected by Fluorichase- Selst. The effect is still balov the critical duit at concentrations of 50 mg/L; but at 100 mg/l it is significant. The bacteria oxygen uptake during break down of peptone is increased by the product. This makes the biochemical break down of the product itaslf plausible This result 1s aloo confirmed by the TOC - degradation test (sec. a. "The product Moz, Light Vater, FC 206, frost-insured (enclosure 2), rescts aiailar to product No 1 in the fish and dephnis tests. Aleo the Tesut of the facorporation test Ls sinilar to the first product. But the inbiBieion of the photosynthesis activity a less and becomes significant only at the ha ighesyt concestration 250 mg/l. : = Tesalt of the mtabolim ratsarmupiet0it2e'saT. im BEST copy AVAILABLE - definitely different than for the first product: There ia no methabolic increase which could be interpreted as a sign of break down. The T0C degradation test also doas show a bresk down of less than 10%. The results of the biological teats carried out concerning product Wo. 3 "bight Water, FC 206, normal," are nearly indeatical to the results obtained for product No. 2 Light Water, frost protected. The only difference 18; that the toxic effects tovards alge indicated for product 2 are mot found for product Bo. 3. . i Product No, 4, "Light Vater, FC 200, normal," 1s different from the ro foam agents discussed previously by having a definite toxic effect tovards f- e1an, oPiE aod algan. For fam the cent antasle die already at 1000 my/t (EC, = 100 ug/1, ECygq = 100pag/1). Tn the daphne test, 33% of the animals dled within 24 hours at 100 g/l, at 250 ng/L about 75% of the animals dled (Cg = 50 mg/1, EC1g0 = 500 mg/1). Thedacorporation tast for this product is already surpassed at concentratdons of 5 mg/l; at '250 mg/l a complete inhibition of alges activity is recorded (EC, = 2 mg/l, EC = 250 mg/1). Product No. 5, Protein Foun Agent, a sll biological tests is squil 0 product Ma. 1. No significant toxic effects vere found tovards algae at | concentration of about 250 mg/l. For the methabolien test an increase in bacteria oxygen corporation vas recorded, but it vas less then for product No. 1. The result of the methabolism test corresponds to a relatively. l Positive reaction towards the break dovn test. Product No. 6, Expyrol, 1s exceptionally high in toxicity andihdelgy of break dows. The toxicity sgaiast fish a a8 high as for prduct Ho. i (ECo = 00mg/1 and XC); = 1000 mg/1). For small crab this product. 1s a 002846 ET BEST coPY AVAILABLE especially toxic (EC, = 25 mg/l and ECjgp = 500 mg/1). : The tncorporation test shovs an inhibition at 10concentrations above 10 mg/l. For 250 mg/l there is a 65% inhibition. lke astro ae wok 94 tents srpossin. The metabolism curve of this product indicates that it contains meta- Table 5 Resulte of toxicology test ( exiressod in order of poison classes) Le No Fish pret(DVL 1 ur ? mn 3 m "n s mn e6 e n Potern claer Daphne 15) (DEVAL 11) un A et itis Sky Algae Bacteria (DSVL 12) inhibit. (DBVL 12) enhance. Total evaluation x) 1 ur . m1 ur n/a nr - mr 3807 mr m m n t ur - mr -- 206 - IY " ur ur nr . nr enw ene e nr e. e n 1 Proven inhibition on ter! animils at concentrations below 5 mg/ 1 Prison class 11 t Ae in 1, Tesion 5 to Pod mg/l Potro clase 1111 No duiags at concontrations below 259 ug/l pgtar evaluation: Calculated hy weirhted avarage. The test result with lowest critical limit of concentration in multipiied bySe 4. Evaluation of Results and Conclusions . Summarizing the single criteria of the test, one can obtain differedt xesults, depending upon what importance 1s given to the diferent criteria. The ortgtasl products constitute a threat to biological systems such as the life in streams and biological systems of purification plants, due to their high toxic level to which the surface tension, and for product 1, 002849 BEST copyAVAILABLE =15- the content of zine 1s added. The drinking water supply could be endangered by the content of just the organic material in the original compounds. Also the application strength 5-6 % solutions of all products tested can lead to danger for biological systems due to their physical, chemical and toxic characteristics. ay the further dilution by a factor of 20 to 80, which is active in the application of foamfiive-extinguisebing compounds'sh toxis level of iainc (2 mg/1 for bacteria, 10 ~ 25 mg/l for fish) 1s not exceeded and also the surface tension activity can loose its importance. ' `Itthenwesms reasonable to evalusts the vater danger by the products `according to their toxicity at the concentrations which can be reached during application, and according to their biochemicaldegradation,even though there at present are only degradation results available for the finished nied pro- ducts. For none of the compounds the degradation is so easy as & classify them as enviromentally friendly compounds. In the selection one then must differ- entiate relatively better products from relatively worse products. When fire-extinguishing foam compounds are applied, the about 5 I solu- "tions areas previously stated diluted by a factor of 20 to 80. They then are in a region of concentration betwean 125 to 500 mg/l. At this concen- tratton thecompounds of araduce to the test organten. Pooduct o. 1oSandanNdo.to23 loasreetwhiatrhouttexatceuraeffdeacctei- nsme ateir further dilution by a factor of 2 to 5. Such dilution fe tb buen pected in the pre-flood tank of the purification systems. For the vary ov toxic products or Vea No. 6, ancsdditional dilution by a factor of batvesn 50 and 200 is necessary to get below the toxic level. Such`af1uttons at s 002850; 16 BEST copy AVAILABLE . are not certain in : practice. Fe2o Product No. 4 shows in. addition a low degree of degraTdahtiaornudaand sh7oueldntno3tacbeeofusedtfeolrcathoat nreasswohnee. Cont properis ars taken fato account. But both products are difficult to degrade and could thus disturb and Gupatr the drinking water supply) and the use of thesepro- ducts therefore should be avoided. Of the remaining products the foam compound No.:l has a telatively! gh toute level towards algae due to the high content ofstad uteines thats properties are lost to 4 large extent dus to the dilution during usage, end since the product is relatively easy to degrade, the endangering Of the vaters dus to this product appears to be of little importance. `The grouping of the 6 products proposed here does take biological and cheaical results into account, but dbes not consider application technical characteristics. If it fa notpossible,due to application technical, reasons to avoid the use of products which are difficult to degrade or are especially toxic, then it vould be advisable totecsttoheimrsipngloe nenfot r des- sraadndatoxticaiffo ectns. Further it should be attempted to replace components especially biologically damaging by less damaging materials of #imilar effect. `Such approach has been successful for other materials of A environmental concern. : 5. Recommendations for technical ordering specifications (on ott dapataton caractarestso she srpate cmon Based upon the investigations as`Wiscussed,'the following require- - ments can be nade of the manufacture of foam fire-extinguishing compounds: Praseat 1n foun compounds should be vel established.) The break down should be as easy as possible, right mov it ie considered 002851 : -17- BEST COPY AVAILABLE 22fair,whena50%breakdown farecordedinthemodifiedORCD-Sereentng- Test (7). For a test which records complete chemical degradatios such as "the T0C-degradation test (6), a 40 I break down shoyld be the minimum required. 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. " "Tua oxic effects of the foe compounds tovards vater orgeties, apecially Seitacta, sigas, wllPEASS mt ria should be io small as porstblen & subfictently nontoxtc range can be set 1f the KCsq for bacteria, algas, daphas and fish is above 1500 mg/l foam agent in water. For toxicology test, L 11, L 12, and L!15 of DEV (4), or similar Procedure for vhich aqual type results can be proves, are to be used. "The heavy metal content should not exceed 1 % stag, or forother matal an' amount for which a corresponding degree of bacteria toxic effects fe recorded. ` 6. Conclusion "According to the task the following six foam compounds, deterained by the "Bundesant fir Wehrtechnik und Beschaffung" in Koblenz,vare evaluated vith relation to possible endmmgering of vaters: Plogrprotetn; Light Vater 76 206, noraal; Light Vate`FrC 206, Frost protected; Light Water C 200, noraals Protainsshaumitcel; Bxpyrol F 15. The test includes interphase activity, coxteology, biochemical degradation, heavy metal content and flame point. The results vere presented and dlecussed and a conelusion reached. The } products Tiwompioteta and Protetnschaumittel were recommended due to relatively favorable biologic characteristics. The final conclusions swe Sven as recomendations for techatcal delivary terns (TL) to be red by the contract agency. I a - oo : 002952 - LimsmaruRs vst Deutache Torschunge- und Verachaanstale. fur Luft (1) Fiala, R.: Study "Mittelschaum fur Flugzeugbrandbekampfung" und Raumfahrt e.V., K5la-Wahn 1977, (2) Bundesanstalt fur Gewasserkunde: Gutachten uber die Wasserge- fahrlichke{t von Schaumloschmitteln, Koblenz 1975. - (3) Hellmann, H.:TenSsicdheaumDletsecrhgaeintttse1l3- (1i9h7r6e),mig2l7i0ch-e2W7a3.ssergefahrdung, (4) Deutsche torent, Einheitsverfahren VzeutrshWaaisnsyer-T,igAmbrwmagsesetri-stuontdunSschlTaomgm.- (5) Zahn, R. undbHi.slWoeglilsecnhse:n AbEbianubeairnkfearcthesvonVerFfraohdruekntenzuurnPdriAivfuengsder sSeoroinh2a52l.tsstoffen. Chemiker Zeitung 98 (1974), (6) Miller, D. und T. Tittizer: Der TOC-Abbautest - ein Verfahren * zur Prifung von organischen Substanzen suf voll- Freep Eig ae Wasser- und Abwasserforschung 12 (1979), 14-21. (1) Fischer, W..: Mebvertahren sur Bestimmung der biologtache Abbaubarkeit von wasserloslichen, organischen Usweltchemikalien mit Kohlenstoffanalytik (DOC) (Modified : OECD Screening ) Test). X manu script o the form Renked Ki Sispeldort, sang oo the E.G..as recommended process. (21,2. 1978). Enclosures : Toxicology - concertration/reaction curves and degradation curves. 1 to 6. JTinnecolelil C.v7 Glprese Sflecte /, GF : 002853 lS 100 Nr.1 Fluorprotein wD = ec 0 & 50 = "0 ww -40 = "0 Ia 2 E00 T 1T T T 1 1 rT& [1 1 TT 71 T 1 rr =v 11 becca LL Lp [ ~~ T r T mx I ITTTT=.l I~ 1 bb pbb I 1 1 \--1 r= rrr r= rt ] rrr = ( | 1 [+11 1 =] 5 0 25 S50 100 250 1000 10000 Kongentration mg/l RC 1 ,a 60 -- SS ] I I ee fool ---- . 0 _-- ee 7 1% n Dgmeletion Time, Guys 002854 Nr. 2 Light water, FC 206, frostgeschitzt 40 280{ TOXIrCOaLOtGYiToSTn tort DVL 12 Ze Mothsholirm tert DVL 12 460 D= Daphne teat DEVL 11 P= Vish tost DEVIL 165 eb rrrttt Sef y -- rrrrrr 2fp de Ab Rr t E 3 T r Tr T e Is y_--] -0 r TT r] ] :a A r] r _--] fz w r rr r ] 3 Zn SE EYSN ESS SE 4 5 0 2% S50 100 250 1000 10000 Tongentration mg/l Wr1] -- 1" I Sa I * 1 0 0 a j TT 1 7 1% un Degmaletion, Tree,Gyo 02855 | : Nr. 3 Light water, FC 206, normal 100 +80 w50] TA-=OXIDICensOciLonOrcGpYortaTetrSiiTonDatorta DVL 12 : PZae KBoitchhabtoeltirm fDoVsLt 15DAV, 17 * r Tr1 TT TT 3 +4 rT r TT :2 0 TT a TT. ---- | 8 0 Lemma NN 1 = Mt eh "20 1 -- [1 . a = ee & I -- CP w ee === r Z 5 0 2% 50 100 250 1000 10000 onzentration mg/l n-- 1 _-- 1 -- 82 : -- l -- L] i" 2A e 20 , 0 oo . re --------] -- pre . Test of P0C- degradntion 1] -- 7 1% 2 Degmelation ime, ys 02856 Nr4. Light water, FC 200, normal +100 +80 so] PTNOAEOICSOOLEOCYTHTST ont, DVL 12 EGe Euethsrholis mfosttDOL 12 v s WI--o rrt r t tT tt ] s FC lm -- l a--r -- -- TT -- --] .A as Fe ~~ = E e Ie Ne e er-- 1 1 Pzoa -- S -- f1] Hi 5 NT iEER o.w , P I Ye N o s 5 10 2% S00 100 250 1000 10000 &oneentration mg/l T ----3 i" ow : -- 0 0 --_------ I EE I 1 1 7 1% n Dgmdatien Fmee, Guye | 002857 | ) Nr.5 Proteinschaummittel +100 pBdY h BaPrianeth DW 1 gFeoreesnnetToieon ovesre 18pan 1 540 r ta r r1r tg o T F rpr r 1 ] ] A We SE5go --] ---- --] fw F Ew TT -- 5 10 25 50 100 250 1000 10000 Koneentration mg/l LE Bal |, 0 - reTente6 700- ----] degradation L -- L] | 1] | 7 1% a Degmcdle tron Fine, Gus 02858 Nr.6 Expyrol F15 0 80 tl Ti=oATTnocLarOnrorPasLhP Sepia tert Boi Ta RR2 4ze +vemniorin " 1 cE wl -- or trr r r EO af rer m o da r m -- |m N ed *= 20 T See s e 5TW Le Cr Nr N1 E2a y=]1 : a) yo r= r ] I EY SASE " S 0 25 S50 100 250 _ 1000 10000_| Concentration mg/d ig sol &5 40 ) _-- 0 LT NC] TN] -- 1N0]] 1 =1 ' Dymda*tien Frm,Gy+ st