Document KR0nqg6x13wREwLJ3dMLEzzyQ

SUMMARY FOR WORK PERFORMED FOR THE GERMAN GOVERNMENT AGENCY FOR MILITARY TECHNOLOGY AND PROCUREMENT ON FIRE EXTINGUISHING FOAM COMPOUNDS FROM MULTIPLE COMPANIES TEST SUBSTANCE Identity:A mixturecontainingPerfluorooctanesulfonatweh,ich may also be referredto as PFOS, FC-95, or as a component ofFC-200. (1-Octanesulfoniaccid)(CAS # 2795-39-3). Remarks: The 3M productionlotnumber was not noted. The test sample is FC-200, a productwhich was out ofproductionpriortothe date the study was conducted in1977. Archivedinformationindicatesitwas a mixtureof 1.8% PFOS, 30.0% diethyleneglycolbutylether,61.5% water, 2.7% Hydroxy foamer,4.0% octylphenoxypolyethoxyethanol. The followingsummary applies toa study done by a thirdparty (Dr. H. Hellman and D. Mutter)forthe German Government Agency For MilitaryTechnology and Procurement forpurposes of comparing the environmental propertiesof foam extinguishingagents from multiple companies, including3M's FC-200. Data may not accuratelyreflect the environmental propertiesof the testsamples with thatof the fluorochemical proportion. STUDIES Zinc,iron,and copper content;surfacetension;Chemical Oxygen Demand; 5-Day BiochemicalOxygen Demand; Toxicityto Fish(species notgiven);ToxicitytoWater flea(Daphnia magna); ToxicitytoAlgae (speciesnotgiven);Bacteriainhibiti(osnpeciesnotgiven) Report date: 1977 METHODS: Chemical Oxygen Demand was measured using potassium permanganate and potassium dichromate. BiochemicalOxygen Demand evaluatedusinga TotalOrganic Carbon degradationtestdeveloped by the BundesanstaltfurGewasserkunde. Toxicityto Fishwas evaluatedaccordingtothe German standardprocess forwatertesting(DEV) L 15 Toxicityto Daphnia was evaluatedaccordingtothe German standard process forwatertesting(DEV) L 11 Toxicityto Algae was evaluatedaccordingtothe German standard processforwatertesting(DEV) L 12 The method forevaluatingbacteriailnhibitiownas notdescribed. RESULTS Fish LC50 Daphnia ECso Algae EC5o Bacteriainhibition BOD211COD Results 100<LC50<1000 mg/L 50<EC50<250 mg/L 25<EC50<50 mg/L Inhibited -12% Remarks: The above toxicitdyata didnothave testdurationinformation. DATA QUALITY ReliabilityK:limischranking= 4. Allstudy valuescome from a summary lisotnly.No raw data or method documentationwas available.The study summary failedtodisclosedurationoftoxicittyesting.Itisnotclearwhy such low biodegradabilitwyas observed when the productscontain materialsthatare known to readilybiodegrade. The sample puritywas not properlycharacterizedand the studylacksanalyticaclonfirmationof the amount offluorochemicalproportioninthe solution. OTHER Submitter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 6/27100 Dot* .'TECHNICAL AWARENESS TO*-T.ECHNICAL COMMUNICATIONS CENTER - 201-2CN (itryportant - Whenever possible,attach a fullcopy of Me materialyou have abstracted.) C,,,,tributor Division I-r'i.c A.. R(-iner 7E@sn'vironmental Lab (EE & PC) ..... Journil- L] Book ocation ol Original 0 Patent 0 (PleaOstehsepr ecifGv) rmtn Age ara t r pt@ Reference (e.g..Author, Title, Issue Date, Volume. Page. etc.): 7 lov*e Number 4@816 Dr. H. Hellman and D. Mul@-r,"Environmental Impact of Fire Extinguishing Foam C(:)mpounds."The study was carried out by the West German Department nf Water Technology for the West German Agency for Military Technology :in(.P]ri-)curemont. (,rranslated by G. Dierssen, March 1, 1980). Al,%tr.irt (giva votif own siint on the source document) 'I'hi.rseport compares the environmental acceptability f 6 AFFF Agents including FC 3017 (identified in the report as FC-20i, freeze protected), FC-206, and FC-200. The researchers measured biodegradability, aquatic NLoxicity,.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 products were more readily degraded than the competitive products, yet the authors chose to give more credence totests measuring dissolved total orga nic carbon (TOC) concentration over a 21 day period. These tests gave resul* ts that were inconsistent with the BOD results. In these tests 3M products inexplicably did not degrade. Ct)pv L i%t (cupies to tie suni bv originator) Itemssubmittedon thisform we publishedinthe3M TechnicalAwwoness Gazette. Complimmt to Report of Bundesanstalt f*u'rGewasserkunde 10. April 1979 -@.Nlb/340.22/2596 Xwvtrowpmtal Ispect ;if ng* axtiasvu*"$ 1POAMco"ot*40. Study c&rri*4out for flundessatfur Wahrtachnik und Beachaffung ((;ov*rnzmmtAgency For M:LlitaryTecbnoloiy and Procqremmt) Report: RA 111 l-E/B31E/70145/76066 of October 12 1977. Reporter#* Obarregierungstat Dr. 14 .1413VA= Oberregleruagsv*t.u. iallor Koblenz 1979 Table of Contents. 1. Introduction Page 3 2. Definition of Problem and Task 4 3. Test Results 5 .5 3.1 T"ts. T"ts for 410CYA4oiJeml-bos:r*44Um 7 3.3 To*tc*Lw Test$ 12 4. 'Zvaliiatlm.of -R*oults ind c6ntlo8Lolm-: 15 -dations for Tacbnical Ordating Specifications is. conclusion 19 Enclosures: Literature llst Addi tions -2- INTRODUCTION For fire extinguishing- foam compounds one can distia%uish six application rogions: 1. General application (local fire protection) 2. Solvent industry 3. Fighting of c&rW"ydr:Lde fires for lnstance.in refimri" "givamt, Volta$* (closed eye;"@) so Applic4t*mo In 41rports. Appiie*tions on ships. 'In the pys t study it.will appear that airport firas take on Oreferv rep Importance (1). It is obvious, that a few seconds in time can make iwi-portant difference for saving human liv", and that the qu"tion of OWA"Psental ondang*rftg especially of waters and str"us does "sum& some what less Importance. But water safety need not be completely av*ruwked "peci-,'aliy because most of 'the actually used fire extinguishftg compounds ar@ asod@, iritraining. Tlke36ndaemetalt for Gov" "rkunds (Dept. of W&W Tecbmol ogy in 19@@, got the.task from the Mitister:Lme fur Er"hr=S, ("stry- of Food'Agriculture and Forestry of Wordrhain-Wastf4l") to pv4,; uats the Impact of foam extinguishing couppunds on the water quality. Th4vty-. eight foiae*tinguish:Lngcompounds fma 8 suppliers weir*evaluated cheuic&:4Y,, physically and biochemically for possible ondange" of Vater,,.D7if f**rent bran@'s' it@@dvary In dograd atUs and toxicity. lopecially.the 5%*f' bit*@'golutions used can 'resultin the followingda*"; asti*.' -3- Poisoning of natural water purification (in stramm) Poisoning or damage to fish and fish food animals. Reduction of oxygen contact by metabolic processes (surface or ground water) Reduction of water quality by organic compounds (general) Undesirable reduction processes in the groun4wwater, TU# report Vo pubUod-od.@, pa%U. the pairt:k"lav4v*4,, owb tho mmufa.cturm of fo4a, 49tusu:L I" compounds =4. the autbor:Lti"respmsiblt forvttor pur:ity. Auft$ otbitralthesceonsid- *ratio"were taken into account In the DIN- standards. 2. DEFINITION OF PROBLEM AND TASK .After several discourses in 1977 between representatives of 'Bundesautes fur Wohrtachnik and Beschaffung and the Bund"anstalt f'u'Grov". sorkunde (BFG), the BFG was authorized on Oct. 12, 1977 to carry out a spoo'4, cial study. This stuay should only cover the products used by the.Bvnadsrtlehv (W. Gorman military) and also products which are considered for possible um lstrodttctioa. As a first objectivethe euvivo=mental influence of the following six extinguishing compounds should be deterain*d: -4- No Product 1 Fluor protein 2 Light Water, FC 206 Vc3"Oll (frost protected) 3 Light Water, FC 206 (normal) 4 Light Water, Ic 200, 5 tMtOJA Fom "d 6 Zxpyrol 7 15 Manufacturer Firm Dr. R Sth@er, Hmburs Firm 3 M, Nauss Firm 3 M, Nauss IPL= 3 M, Wouis nxv Dr.,R. 3thm*r, iLmbArg 71= Wechst Ag. Frankfurt/Hoechst The two types of Liiht-Water are offered an being 'fespeciallysafe to the wmivonmmt" (According to BWB). Light Water FC 200 in reported to be out of production, but should be evaluated for comparison. The test for onviromantal impact should, if possible, be tested for 5% solutions as used (for Lisht Water 6Z) and encompass the folloving parmeters: furf@4c* tension act:Liiity -Toxicity Blo@b4inical 'dogra"tion Content of heavy metals Flme point. The final report should also contain reco=Aendations for the technical procurement specifications (TL). The final report w" scheduled for completion in Sept 1978. Due't(b, sickness-of one of the investigatorsit w" delayed for am* wa@44. 3. TEST RESULTS 3.1 Physical- Chemical Tests The first test result gives the heavy metal content which w" 1) uln*d by X-ray fluorescence doter- Evaluating the figures of Table I listing the heavy metal content, the two compounds Fluorprotaft (No 1) and Protein foam- eampouqd (So 5) $40 "to Forflvpvprotob the SSUC avA Ins wntqat of th* applic With 40 4*d SS W4911 V""CttVia1Y4.vvlat:L"@y bigb@ Iror Of "CO04 compomd the Ivan Cmt=t Of 50 ag/l stands out. All othiilr heavy metal concentrations such as the especially recorded levels for Copper are unimportant. Table Heavv metal content in foam extinguishing compounds. No. !Iriginal 1.0roducts Zn c@ ppe 700 too 2 7 j 3 5 2 6 3 5 % Solutions zu To Cu 40 08.4 of; all cot 006 091 50 ots 001,02 o02 0902 .0102 0.02 0.02 1) Datormined by Dipl. Chan. U. Schloichart -6- When the flame point is determined, the water content of the sample 0 must be considered. Flame 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 prodetto would contain flammable ablvents. 3) The surface, or interphase tensions can be seen from Table 2. The surfvm tension vater/air generally drops some for concentrations from 50 M'g/i to Sm mg/l. The surface tonsion :Lo least affected for 9*5 (ftatein-foom oxtinguishor), most effected for tva Light-W*ter types of FC'206- t3rpe. Tb* ro"on for this Is found in the chodeal composition of the extiguishing compounds. Protein foam agents can be expected to be generally inactive to the water/air interphasei while tensides and also so called "synthatic"pro- ducts are interphase active. The interphase activity is less a product specific, but rather a group specific characteristic. Tabl-a 2 Inter!)Ii-.t-rieetivity No. Interphise ictivity At ?o0 C dyn/cm) so 100 ?50 Soo 63 ss 6 so 48 36 is 23 10 32 39 2) Determined according to Abel-Pensky in closed vessel; DIN 51 755, Ed. 966 3) Interphase- Tensiometer, according to Nooy, firm. A. Kross, Hamburg -7@ 3.2 Titatfor Biochemical Degradation To evaluate the water polution characteristicsof compounds,it is of Pf,W,,.)A".t%-& @k C(tr-evW-@t"lgC..IU interest to sum up the chem al parameterospotassium permanganate and 0 A.,),c(w- dLC4--.w t(::@o0 ) $00S potassium dichromate uptake, (CSB). Th* biochemical oxygen uptake (BSB coo 5 R5 of DEV (4)) can be used especim",v in combination with CSB to prel4ininar- lly evaluate the degradation. Wbe.u the CSB analyticaltaft gives reliable r"ults (thU. for instance, is not always true when bydeophobic comp6@nds- "a being tooted)mo c lt3 .=wt coa#*"r po*:Lt:Lvroesult derived from the OSB/I$ i44ig," maul,, whue notativo roodts can not be counted, since the tioi2 porud for the BSB-test under *an* conditions dmw not encompass.-. siaificient tim for adaptation of t@he organisms' active in the biological br"kdown. It is not certain that toxic inhibitions can be excluded in 800 standard BSB (5). To better insure results concerning the dogra.datiole tbftl is poF.s-s! ible by evaluating the CSB/BSB ratio, one must carry out extens. ivo,@ i dogradat"n tests, where the Incubation time, the inoculation material ' and, other parameters are determined, so that further br"kd4wn than for the f:tvoi dai UB-test can be evaluated. At present there are internationaloffortalund&rwayto itandardise d4, gradation tests. Fo-r'thisInvestigationof breakdovu of fire extingul foam.,empounds a now T.O.C.-degrgdation toot (6) developed by the Bunda"n'*'Ul.t'" fur 04massark=da was used. Its test,-aftteriaIn the complete br"kdoim of the total organic carbon (TOC). ,'Forthe test procedure the test compound serves as the only source of carbon. Inorganic mineral salts are added in advaice. The incubatioit,takes place in'a screw-cap flask with air space, placed In a shaker. tiki"'do'grada- tion tests for the fire extingulaWkAg foam compounds war* carried out.at 20 C In the dark, In deviatiou from the stated test procedures, 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 fro the solution is often considered as degradation. Under carain circumstances a high degradation can be simulated which actually in based upon physical processes such asfor instanc%aboorptlon of ooli" which has no relation to couplet* biological breakdown and A4oot4lM to the ex"rione" gathor" by particip*tum la a round t"t Abi VbC mwults for completelsyolwas compoundsaresalwamtlowerthan when the breakdoiwsnmeasurebyd the "modifieOdECD-drreenintgest" This"mod&fiOoEdCD-screenitn"gt"wastootebdy internatiornoaulndt'ests*' It'hassomedisadwa&Ugen usedfor testing of emulsions and suspensions. Since the products tested here are mixtures the results6f the de"gradati@n test is only well defined when a total breakdown is rocor4ed. In c"os where partie]Abreakdownin observodthdacan be due to the fact that;'only part of the product can be broken down, while other parts can not.- The breakdown of mixture can ;hen 0* man:ipulatedby the nimufacturerby addition, of compounds which are easily broken dow% but otherwise without function. Even though,it is usefulto test the breakdown of the prosent.sixt@re productsibecauseit gives a preliminaryrankingof the products. For future teits, which could be carrw -outafter a period of a few years of U94i, it's@ouldbe attmptad to test the breakdownof the single components-ofthe products. -9- RESULTS: Table 3 does list the measurement results obtained for the orginal products, to evaluate the potential for -endangering of the water. Table 4 lists the percentage of degradation of the application solutions after a period of 2 days together with other degradation parameters of interest. The specific TOC- dogra4atUm curves are Incorporated in attachments 1-,6. The v4mw obtained fma Table 3 ohm that the 41fforeat products conta:Li..'@ voryug 4mmts of organic compounda. Ofcourse on* abould count 4 low content of orgodc w&torialo and of organic carbon found In products 1,4 and 5 as positive factors when water endangering Is to be judged. For the application solutions (table 4) the eiBLand BSB5 are listed tic@- gothor with the ratio between these two factors and can be used in addition, to the TOC- degradation results far-th*,4m*luatl4M. According to the ratio the product No 6 should be considered easy to degrade. For ttkaproducts I and 5, which according to the TUC- degradation test appeor sodium degradable also established from the metabolism test), the unfavorable CBS/BSi ratio could possibly be due to the chemical oxidation of izvn salts provint In the products. The Iron salta would increase the CSS without Lncr"sln tb* BSB 54 The degradation of each product, separately, is evaluated as foll9"lt Fo@ extinguishing compound No* shown a favorable ratio of KHNO .:Con#WW- 4 tion/ 112CriO.consumption, and shows good bacteria action in the metabolism. test$ together with a 47% TOC_ degradation. It mot be rated as u"iua dogr@;t@kbit. -3ot7 -Product No 2 shows a favorable CSB/BSB5 - ratio, but since the other t@ do not Indicate a good degradation rat* It is classified as diffic@itto degr*14 UK-fttadatAsa of product 3 is even less tbM Is ci"siftedas difficultto dagmde* that of product 2.9so It ftim thoiqh the de$rsdat:Londuring the TOC-tast woo @urther,advwxad Pot.enl-i:i"lor end.-inge-rino@f waters by ,)ripinalproducts No KI@NO 4 USO(I x2 CrO 7 used Org.0 content H 2 dontent a) Orizanic part b) 0,203 lts2s osls 89 30 (7 2 0,098 3.436 0,24 $3 to( 3 0.065 4930 otil '77 r- 00050 is$?) Otto so 0,41'F 11301 4o tool 23 la a) only op"xiasto values b) only approximate valueng burnoff values at 6oooG and variable duration To.ble 4 Biochemical-dogradation of &.D-plioationready so]-utions No Rate of B mo 4 (m. 1 cro 2I "40 L s.ooo 1 -'Lao 4 2 f.2so 5 1.100 61 2.mo 13*go 400* 20.00 36.mw 3.230 41-M CBS r.L70 Dograd. Dograd. in ta nothabolo- TOb test too* Vinal *Val, x) )$I 603 0 taI Mai= dif floal dif fiftlt- 594 12 dif f$Oiiiit 691 092 4 37 madi= I ost lei 4 62 easy to. X) Ivaluation of biochemical degradation temperature of 2500) o - 2o % diffioult to depTa6do 40 75 % sodium degradable in TOC- test(at standard 2o - 4o % elishtly degradable 75 loo % very dogn@"ble for product 4 than for product's2 and 3, it was classifiedas difficult to degrade. For fire extinguishing foam compound 5, the metabolim 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 sodium degradable. For product 6 one finds a complicated degradation bolpvtor which might originate from the high toxic affect of this product. After 7 days dogr&4tim. 4r*ady 1OX of Ow TOC Is brok" 4mo rurtbw 4ftyra4atUM4fte o!Llyaft*v 14 teotfts days* but thm on Si@tmaivedftroutum lo*41n to dow# of 6OX of the startiag TOC 4o*s take puco. The slim down In br"kdowii after 7 test days can be evaluated as so mkpt4tion period for the'nicro-. organism involved. 303 ToxicoloSi testing METHOD In the "Evaluation of the Water Endangering by Foam Extinguishing Co"ouuds" (2)0 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 toxicolo'gyt,est* addition to the incorporation- metabolism tests, also tests with =all crabs and fish were carried out. This way the previous results could be further confirmed. The toxicolgy test In carried out according to the ftruan standard procass for water testing (DEV) (4) L 11, -L 12, and L 15. For th"etthe ist"t post procedures were used an publtshad by the responsible worklng'conkitte".0 For fish-tests the concentrations used 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 differentiated as well as possible. RESULTS: -In the enclosures 1 to 6, the results of the toxicology tests &ra,".presented,.'' .-4a:oose-r"ctu* curves and the results are calculated and presentedfn Table 50 Pr*4*et lb 1. *Yluorocbaumteist(Ikelosure1) is so toxic at concentrations of 109000 94/1 that all test aulmle did die (IC 10000 mg/1). Bqt for. 100 thik concentration 1000 mg/l the product is not detrimental (EC 1000 mg/1).: (EC- effective concentrationwith respect to the corresponding tdst,' SC is too. the lowest tasted concentration for which a 100% result with respect to the', test criteriais roeord*d For the flsh@test, this is the concentrationat which all animls die; EC0 is the highest tested concentrationat which no significantreaction in observed with respect to the test criteria). exlvk,,ae. Towards the small crab,Daphnia nagua (water flee),the product is not detrimental at the highest concentrations tested (ECom 250 mg/1) The photosynthesisactivity of algae is easily affected by Fluorschaot- gaist.@-The affectis still below the criticallimitat concentrations of 50 us/I; but at 100 ug/l it is significant. @The bacteria oxygen uptake during break down of paptone in increased by tha'product. This makes the biochemical break down df tb* product Itselfplausible. This result is also confirmed by the TOC - degradationtest (see. 3.2)* @The product No2, Light Water, FC 206, frost-insured (enclosure'-2@9'reacto similar to product No 1 in the fish and daphnia tests. Also the roodt of the Lueorporation test is similarto the first product. But the intd$ition of the,photosyntb"isactivityis I"s and become elvific=t only'&t.the hisbast concestratim 250 mg/i. CTba result of the gotawlist, -vW*@001 -13- definitely different than for the first product: Th*re is no methabolic increase vhich could be interpreted as a sign of break down. The TOC degradation test also does show a break down of less than 102. The results of the biological tests carried out concerning product No. 3 ".Usht Water, PC 206, normal, 11 are nearly indentical to the results obtained for product No. 2 Light Water, frost protected. The only difference is;thatthe tozftof feet@ towards alpm la4icatod for pro*wt 2 are not d for pro4uet No. 3. Pro4uct No. 4t, "Lisht Water, FC 200, normal," Is different from the foam agents discussed previously by having a definite toxic *fa'acttdvards fish, smcallcyrab* and algae. For fish the test animals die already at 1000 (Eco 100 ua/l, Ecioo 10OP-Mg/1). In the dapbn* test, 33% of tha animals died vith:Ln 24 hours at 100 mg/l, at 250 mg/l about 75% of the animals died- (EC@ - 50 mg/l, EC,oo - 500 mg/1). The 4.n--rp-orationtest for this product is already surp"aed at cancan- trattons of 5 mg/l; at'250 mg/l a complete Inhibition of algae activity is recorded (EC, - 2 mg/l. EC - 250 mg/1). Product No. 5, Protein Foam Agent, In all biological tests to equhl to product tb. 1. No significant toxic effects vere found toward* algae at concentration of about 250 u$tl. For the methabou= test an lner"se@ in b&6teria oxygen corporation w" recorded, but it vas less thm for product No. 1. The result of the nothabouss t"t corresponds to a relatively positive.r*action towards the break down test. Product No. 61_Expyrol, is exceptionally high in toxicity and break down'. The toxicity against fish Is &ishigh as for prgduct No@@'4 (Eb9 !'Mai/I and ZC ioo 1000 ug/1). For amll crab tUs -14- especially toxic (ECO 25 mg/l and ECloo 500 mg/1). The incorporation test shows an inhibition at 10%concentrations above 10 mg/l. For 250 ag/l there is a 65% inhibition. The metabolism curve of this product indicates that it contains met&- bolic active as well as toxic compounds. T-a'Ibe 5 Results of toxicolo,&X test exi)res.sedin order of poison classes) No Fish Daphne Aleae Bacteria (DEVL 12) Total (D"L'VL 15) (DZ-VL 11) (DEVL 12') inhibit. enhance. evaluation x) III tit III III til III III 6 IT III Poipin cl.ass 1 Proven iniiibition on tf-st.-@-inim-iiast cnricentr.-Ltions be'o-m mg/ 1 lliifinel.iss 11 As in 1) re.-,-io5n to 2o-imir,/l Poi!@on clasp lllt No dir,-.aga-t3 concentrations below @)-5?mg/l X)Total evaluatiin: C--ilcu'Latebdy weir,-hted iv-%r!ige.The test rbsult witb I.o,;;Ec-r;irttical limit of concentr.-itioinq Mltiplied by 5' 4. Evaluation of Results and Conclusions S--grizing the single criteria of the test, one can obtain different results, depending upon what importance Is given to the differani criteria. The original products constitute a threat to biological systems such as the life in stroams and biological systems of purification plants, due to their bigh toxic level to which,,@hesurface tension, and for product 1, 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 strength 5-6 % solutions of all products tested can lead to danger for biological system due to their physical, chemical and toxic characteristics. By tho furtherdilution by a factor of 20 to 80, vhigh is active in the appl:Lcatim of foam,--Otwe-o* -"NPDIOU 2 *$/1 for bftteri4, 10 25 mg/i for fish) Is not oxce*4@ thi surface temlon activity can Uwse its Inportance. &180 and '-Ittwm@memn roaaemtble-.teovaluato the water danger by the products according to their toxicity at the concentrationswhich can be reached during application, and according to their biochemical dogradatici@even,though there at present are only degradation results available for the finished mi"d pro',meta. For none of the compounds the degradation Is so easy 4* classify then as onviromentallyfriendly compbunds. In the selection one then must differ- anilate relativelybetter products from relatively!worseproducts* . When fire-extinguishing foam compoundo aro applied, the about 5 2 tolu.@. Vtons.,ave previously stated diluted by a factor of 20 to 80., They then' are in a region of concentrationbetween 125 to 500 mg/l. At this concen- r-C7-0 4 tratton the compounds of pratit,-Ncot. 3 and No. 5 are without acute detriumt to the test organism. P;voductNo. 1 and No. 2 lose their toxic effect aftar furtherdilutionby a factor of 2 to S. Such dilutionis't6 be-'expected in the pre-flood tank of the pur:Lfleation system. For the'very toxic products No. 4 and No. 6, &nLAMitional dilution by a factor of' betw"0.50 and 200 in necessary to got below the toxic level. speb -16- C are not certain in practice. Product No. 4 shows in,addition a low degree of degradation and abould not be used for that reason. The products 2 and 3 are of little concern when toxic properties are taken into account. But both products are difficult to destradeand could thus distysrband (impairthe drinking vater supply@ and the use of these products therefor* should be avoided. of the ressialas pro4ucts the f*A.mcompound No...I.h" up "sk Lev" tmor4a alg" 4" to tbo high content of xinc. jut since th*Aiaproperties are lost to a large extent due-to the dilution during usage, and since the product Is 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 dbes not consider application technical characteristics. If it ti not possible,,dusto applicationtechnical,reasons to avoid the use of products which are difficult to degrade or are *SpecW ly toxic, then it would be advisable to test their sinzll------------- nonts for de- Further it should be attempted to replace components especially biologically damaging by lose damagim noter:Lalsof similareffect.. gbcb approach has been successful for other materials of environmental concern. 5. Recomandations for technicalordotins mocificatifte Based upon the Investigationsas 'discu*mWi,t'he.-f&Lhowftrgequire- mmto can be made of the manufacture of foam fire-extingu:Lsh:Lncgoqpomdo: CThe biological destradationcharacteristicsof the organic components present in foam compounds should be vall established The break dowu swuld be as easy &a possible, right am It Is considered -17- as fair, when a 50 X break down is recorded in the modified ORCO@-Sr-rafting- Test (7). For a test which records complete chemical dtgradatiossuch as the TOC-dogradation test (6), a 40 Z break down shopld 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. Tb* gM&e gfflets of the fom eavoikads t.ow*rds water arga"smg 4004CI4;7,. 0 and fish sboul4 be as small as possIL6&*.,A suificientlynontoxic range can be set If the IC50 for bacteria,,algab, daob"'and fish to above 1500 mg/l foam agent in water. For toxicologytest, L 11, L 12, and LtlS of DEV (4), or oftilar procedure for which equal type results can be proven, are to be used. The heavy metal content should not exceed 1 Z zinc,,orfor other metal an mount for which a corresponding degree of bacteria toxic effects Le recocded. L 6. Conclusion raccording to the task the following six foam compounds,,dateralnod by the,"Bundessat fdr Wohrtechnik und B"chaf fung" in Koblenz'w$are evaluat*4 with,relation to possible endangering of waters: Flearprotoin;Light ita'terl. FC 2060 norml; Light Water FC 206, Frost protect*d;;Light Water FC 20Q* notiAl;:Protein&Wml-lttel; Expyrol F 15. The test includes interph"a actlvltyl toxicology, biochemical degradation, heavy metal content and flame point. The results were presented and discussed and a conalusion r"chod..*,@T@e* products.Fiuorprotein and*Protainschaumittal we're recoumud*4 4ge to. relativelyfavocable biologic characteristics. The final conclusime, ow- given "''rewmmmdations the contr"t &Soucy. for technical delivery terms (TL) to be v4qd Uy. -18- LITERATURE LIST. (1) Fiala, R.: Study "Mittelachaum fur Flugzeugbrandbekampfung" Deutsche Forschungs- und Veracheanstalt fur Luftund Raunfahrt a.V., Y-6la-Wahn 1977. (2) bu@desaustalt fur Gow4searkunde: Cutachten uber die W"sergefahrlichkalt von Schausloacbmittoln, Koblenz 1975. (3) Hellmann, H.: Schaual'o'schnitto-l ihro m@gliche Wassorgofahrdung, Tenside Detergents 13 (1976), 210 - 273. (4) Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlatemuntersuchung. Weinheim, Erganzungeliefertmg 1972. (5) Zahn, R. und H. Wellens: Ein sinfaches Verfahren zur Prfifungder biologischen Abbaubarkeit von Produkten und Abwasserinhaltsstoffen. Chemiker Zeitung 98 (1974), 228- 232. (6) M@ller, D. und T. Tittizer: Der TOC-Abbautest - ain Verfahren zur PrUfung von organischen Substanzen auf vollstand igen biologischen Abbau. Zeitachrift fur Wasse*r- und Abvasserforschung 12 (1979), 14-21. (7) Fischer, W.K.: HeBverfahren zur Bestimmung der biol.o.gischeu\ Abbaubarkeit von wasserl'o*alichen,organischen Umweltchemikalien mit Koblenstoffabalytik (DOC) (Modified OECD Screening Test). A menu-.\. script ox the firm Renkei KU Mofis"ldortbsent to the-g.G..ap recommended process. (21.2,.1978). Enclosures Toxicology concertration/reaction curves and degradation curves.. I to 6. N 1 Fluorprotein +80 #60 TOXI(;OLOG Y TL,;ST A=!Inc.-)rporationtest D"7 IVL 12 D= Daphne tort DEVL 11 Z= lletli:,.'t)oltio!s,tm Di-.VT1,2 rm Fish tr-.rt Di,'V1, 1 r) 1640 -20 0 ----------- A 140 -40 -60 0 -80 -ioo. 100 5 10 25 @o ibo z'50 1000 10000 Concentrationmg/l 80 - E- r--4 .ri 60 0 40- 20 Test of' TOC- (Ioe;r,)AaLion 0 7 14 21 Nr.2 Lightwater,FC 206,frostgeschotzt 400 460 TOXICULDO Y TEST A= Inearporzition toot D7'VL 12 D= Daphno ter-.tDL,'VL11 Z= D!ethabolism toft Dl,"VT1,2 tost D--.,f1V,1 r) L.P. r_ 20 Cl- 0 - 20 -40 -60 Iz loo ioo 5 10 2@ @O 160 2@C *% mow 1600 .10000 Concentratiomng/i 80. 0Erc-l@4i 60 0 40 To-..--o-fL TOC- f 14 21 N 3 Lightwater,FC 206,,normal 100 -80 W60 - TO;@ICULOGY TTIST Az@ Incorporation test Dil-"V1L2 D- D@Lplino to.-.tDL,VL 11 c +40 - <D ocuc 20 - ----------- ------ Z- D!ethabolipm test D"-:VT1,2 Ps Vish tu:,t Dl-,VIi,r) ----T ----- 60. .80 100- %- io 25 @o ibo 2@o 1000 10000 Concentrcitiomng/l 100 0 E- 60 0 40- E-4 zq 00 TOC- 7 14 21 Nr.4 Lightwater,FC 200, normal + +80 To,@.ICUIjOGY '.P@;ST A= Ine3rporation test DOVL 12 Z= I.,;etha7oolirtmest Dl,',I1I2T, D- Daphne tort DEVL 11 r- Yish tcrt D.@V.,1, 1 440 C-1 + ZO - 0 -20 -40. 0 -50-80-100 100 olk, I* *% %-. % o so- 5 lo 2@ @o ibo i5o 1600 iooo-o Concentrationmg/i Cd 60 0 40- E- 20 0 Tost of'TOC- 14 21 SO N r.5 Proteinschaummittel #100 Inc D "Vi, @12 D= D*tihne t,::t.D-ZV, 11 660 #40 Z- 1'etl)--')Dl.ipm t D',"r,, Fm '-'ishtcrt D*'JV;. 117, 20 0 ----------- 0 ------------ -20 %* - 40 0 - 50 80 ioo 5 10 25 50 100 250 1000 10000 Concentrationmg/l 100 80 C0.> Er-I 60- 0 40 0 E- ?n Test -)fTOC- deeradation 0 1"4 2@ Nr.6 Expyrot F 15 00 go. 60 cl@ 40 ZO.0.4 -20 0 :40 @a Incorporatioo test DEVI, D= Dap'rine -vest D-,-.,VL1.1 Z- 1-:eth@'n;)I.iptmept IP= Yish"tert D; L. '04 go 00 00 5 10 25 50 100 % % Ni (F) 250 1000 ini)(I[L- Concentritioit, mg/i 0E-4 80- 60 40- 20 TeriL a.C TUC- @".L 6@ A' 0 7 0 14 21