Document MJG0gNqX1x3QKNqg8952k7V5a

SUMMARY FOR WORK PERFORMED BY THE GERMAN ARMY ON FOAM EXTINGUISHING AGENTS MANUFACTURED BY MULTIPLE COMPANIES TEST SUBSTANCE Identity:A mixturecontainingperfluorooctanesulfbnawthei,ch may also be referredto as PFOS, FC-95, or as a component of FC-203. (1-Octanesulfoniacc7id()CAS # 2795-39-3). Remarks: The testsample isFC-203. Currentinformatioinndicateist isa mixtureof 1.34% PFOS, 35% diethyleneglycolbutylether,37.85% water,20% ethyleneglycol2,.66 % Sultonefoamer,3% sodium oetyl sulfate0,.1% sodium laurylsulfatea,nd 0.05% tolyltriazole. The followingsummary applies to a swdy done by the Gennan Anny forpurposes of comparing the environmental propertiesof fbam exdnguishing agents from muidpis companies, including3M's FC203. Data may not accuratelyretlectthe environmental propertiesof the the fluorochemical component In the testsample. STUDIES 10,20, and 30 minute EC5o forPhotobacteriumphosphoreum (MicrotoxTm), 72-hour EC50 forgrowth inhibitonofFresh Water Algae (Scenedesmus subspicatus)2,4-hour ECro forDaphnia magna, 48-hour LC5o tozebra barbling(Brachydanior*erioC)h,emical Oxygen Demand and 5-day BiochemicalOxygen Demand METHODS: MicrobicsMicrotox@"BASIC" Procedure Algae growthinhibitiopner EPA guidelinesdated 05-06-1982 Daphnia toxic7iatcycordingto DIN 38412, Part11 Zebra barblingtoxicitayccordingto DIN 38412, Part15 RESULTS Report Date: 3129190 The EC5o forPhotobacteriumphosporeum was 2500 ppm. Itisnotclearif thisisforthe10,20,or 30 minuteexposure. The 72-hour EC5o Growth InhibitiofnorScenedesmus subspicatuswas 160 ppm. The 24-hour EC5o forDaphnia magna was 430 ppm. The 48-hour LCso forZebra barbling(Brachydanio rerio)was 1634 ppm. The Chemical Oxygen Demand (COD) was 41,200 Mg 02 / L The 5-Day Biochemical Oxygen Demand (BOD5) was 21,500 mg 02 / L DATA QUALITY ReliabilityK:limischranking= 4. Allstudyvalues come from a summary lisotnly. No raw data or method documentation was available. OTHER Submitter: 3M Company, Environmental Laboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 6/26/00 ey%y Investigations of toxiceffects and biologicaldegradability of foam extinguishingagents inthe waste water by Ekkehard lsing Investfgatoifotnosxiecffec.t.s...i.nthewastewater 1. lrffoduction Page 2 On Apri1l5,1985,theFederalMinistefrorInternAaflfairisntroduceadrevisedand expanded version of the Index ofWater Endangering Materials The indexlisttshemost importantchemicalcompounds availableon the market and dividesthem into fourwater endangering categories(WEC) accordingtotheirwater endangering potential: WEC 3 WEC 2 WEC I WEC 0 veryharmfulmaterials harmfulmaterials mildlyharmfulmaterials generallyharmless materials Allchemical materialsnot yet listeidnthe catalogue,are considered water endangering untilthe authorized Subcommittee for"Storageand Transportsdonof Water Endangering Materials"attheFederal Minist[yforlntematAflWrs has decided about theirclassification. Incase of mixturesof materialst,he incorporatioinntoa water endangering category isdecided according tothe data measured on the mixtureitself. Atthefocus oftheevaluationofa materialregardingitsendangering potentialfortheorganisms living inwater or using it-e.g.as a food -isitsacute toxicitye,speciallyforbacteria,algae,smallcrayfish, fishand mammals. Tests on aquaticorganisms (bioassays)are includedamong the procedures prescribedby the legislaturfeorwater and waste water evaluation. Itisgenerallyaccepted: 1. Principallbyi,oassays cannot be replacedby the chemical analysis. 2. Bioassays on the one hand and chemical/physicalprocedures on the other,complement each other(see among others:German UnifiedProcedures forWater,Waste Water and Sludge Examination,DIN 38412). GMBI, IssueA.36 No. 11 (1985),pages 173 -252 lnvestigatoffotnosxiecffec.t.s...i.nthewastewater Duringtheevaluatiooftnheeffectosf Page3 -chemical parameters,e.g.toxicmaterialscontainedinwater and -physicalparameters,e.g.supplyofenergy,water extraction the attentiosnhould be paidtothe use ofprescribedtestorganisms and tothe conformance to standardtestconditionsT.he reproducibiliatnyd statisticvaalliditoyftheresultshould be secured. The followingtypesoftestorganisms shouldbe used instandardizedbioassaysinwater and waste water: -bacteriaas chemoheterotrophs -algae as primaryproducers -protozoansas singleprimaryand secondary consumers -smallcrayfishas mufticelclonsumers - fishas mufticelclonsumers witha centralnervous system. At the same time,they arethe final members intheaquaticfood chainsand collecptersistencthemicalsintheirtissues. Additionallcye,rtainsaprobicsystems can be used inbiotestsas models ofcomplete ecosystems. Particularmliycrocosms and activatedsludgesystems consistingofvariousbacteriaf,ungi,protozoans and worms. 2. Problem definifion According to the definitionisnwater supply law and waste water handlinglaw includingpertinent implementationprocedures,thefederaldefenseforcesarefrequentlqyuoted as thecause ofharmful materialsdischargestowatersand communal waste watertreatmentplants. Particulardluyring,e.g. -use ofextinguishinfgoams duringtrainingasnd actions -transportatioand storageoffoam agent concentrates considerableharm can be done to surfaceand ground waters. Investigatoifotnosxiecffec.t.s...i.nthewastewater Page4 Toevaluatehedangerpotentioaftlhefoamconcentratneostv classifiinetdhewaterendangering categoriest,heirexaminationand military-intemtaelmporary classificatiionntowater endangering classesisnecessary.The FederalOfficeforDefense Technology and AcquisitioinnKoblenz,has authorizedthedefensescientifSiecrviceOfficeofthe FederalArmy toconductthenecessaryresearch and the subsequent temporaryArmy-intemalWEC classification. The research,leadingto establishinwgater endangering categoriesoffoam extinguishinaggent concentrates,produces atthe same timevalues of acute organism toxicftioefsthe,mostly3%, applicatiosnolutions. 3. Foam extinguishingacientsand theirUiog@,@ 3.1 Totalof 16 foam extinguishinaggents representing5 differenktindsoffoam agents were comparativeleyvaluatedinbioassays(see3.2)regardingacutetoxicitoyftheirapplicatiosnolutiontsowater organisms and subdividedintowaterendangering categoriesfrom thepointofview oftheirconcentrates. Inparticular: -5 mufti-rangfeoam agents -6 film-forminfgoam agents -3 proteinfoam agents -1 film-forminfguorine-protefionam agent - I specialfoam agentfordeep-frypan fires The formulationosfthefoam extinguishinaggentsareproprietariynformatioannd unavailablteothe public.Afterconsultationwsithmanufacturers,thefollowingmaterialscan be listeads toxiccomponents: -organicsurfactants -glycols(e.g.ethylenglycolb,utyidigtycoq - preservatives -organicsolvents -organicacids -inorganicsafts lnvestigatoffotnos)decffec.t.s...i.nthewastewater Page5 Presentetdestresultasrenew and notyetrevealetdothemanufacturceormpaniesT.herefore, product names cannot be publishedhere. Hence, the resultableswillhave the productnames substitutedby classdescriptionisncludingrunningftemnumber. 3.2 Ustingofthe bioassayused (shortdescriptioonfeach testwiththefollowingresultable-see 4.5 through4.5). 3.2.1 BioluminescenceinhibititoenstwithPhotobacteriaPhosphoreum inmicrotoxanalyzer,model 2055 (Beckman Co.) 3.2.2Algae growth inhibititoenstaccordingtothetestguidelineosffederalEPA dated 05-06-1982. 3.2.3Daphnia shorttestaccordingto DIN 38412,Part11. 3.2.4 Fishtestaccordingto DIN 38412,Pan 15. 3.2.5 Determinationofthebiochemicaloxygen demand by theapplicatiosnolutionsand theirdilutionwsith waterduring5 consecutivedays (BOD 5). Apparatus:Sapromat B12,VoithCo. Incomparison to BOD 5,the measurement included: chemicaloxygen demand oftheapplicatiosnolutionasnd theirdilution(sCOD). Apparatus:Dr.Lange digitaplhotometerLP 1 W. 4. Results The resultwsillbe describedinthefollom(in(gchapter4.l.to4.7)intheform oftableswithassociated text. lnvestigatoffotnosxiecffec.t.s...i.nthewastewater Page6 4.1 The bioluminescenicnehibittieosnwtithPhotobactePrhioasphoreuimnmicrotoaxnalyzemro,del 2055 by Beckman Co. 4.1.1Shortdescriptioonfthetest The testorganism PhotobacteriaPhosphoreum isa marinebacteriaT.hiskindofbacteriaispresent in immense quantitieisnthe sea layerscloseto the surfaceand causes the so calledmarine phosphorescence. The underlyingchemicalprocessisa luciferine-lucffeprraosceess.Damages to thePhotobacteriae,.g.due to intoxicationrse,sultintheinhibitiofnthelucife(ine-lucifearcatsievity. The end effectisthereductionofthelightemission. This,initselvferysimple,principliesused inthemicrotoxanalyzer: A light-transparegnltasscellisplacedina light-tigmhetasurement head. The glasscellcontains1 mi ofa suspensionwithPhotobacteriaT.he lighetmittedby thePhotobacterifaallosn a photoreceptor, isconvertedintoelectriecnergy,amplifiedd,isplayedand recorded. The lighqtuantityemittedby a specimen ofuntreatedbacteriaissetinthe displaytothe valueof90%. Thisquantityistantamountto:"naturalu,ninhibiteldighetmission". Specimen of equal quantityof bacteriaand equal bacteriaqualitywithtoxicsubstancesadded respond witha reductionofthelightemission.Accordinglyt,hedisplayvalueliesbetween 90% and 0%. The 0%-valueindicatetshatthe photobacteriaofthespecimen treatedinthisway isnot capable oflightproductionany more. Fig.1: Measurement arrangement of micratoxanalyzer MicrotoxO-Analyzer:Measurement configuration Light-tigmhetasurement head Glass cellwithspecimen Di Photoreceptor Tempering LUght Amplifier Pr Investigatoifotnosxiecffec.t.s...i.nthewastewater Page7 4.1.T2heresulotfsthebioluminesceinncheibittieosnwtithPhotobactePrhioasphoreuamreassembleidn Table 1. Inthefirsrtesultcolumn aretheeffectivceoncentrationsofthe16 testedfoam agents inuviofwater leadingtoa 50% inhibitiofnthe lighetmissionby the lighbtacteria(= EC50). Inthesecond resulctolumn arelikewiseffectivceoncentrationlseadingtoa 10% inhibitionfthe light emission(= EC10) and representintghe so calledtoxicittyhresholdsofthe foam agents tothe Photobacteria. The negativedecimallogarithmsofindividuaElC1 0 resultaftermultiplicatiboynthefactorof-1inso calledevaluationand endangering figuresofthe individuafloam extinguishinaggents to PhotobacteriaPhosphoreum (seeresulctolumns 4 and 5). Accordingto the evaluationscheme of the "Commission forEvaluationof Water Endangering Materials"t,he determinedevaluatioannd endangeringfigures(EE figuresi)ndicatethe following toxicitcyategories: EE figuresof6.0and higher EE figures4.0to 5.9 EE figures2.0to3.9 EE figuresunder 2.0 Highlytoxicto testorganisms Toxicto testorganisms Low toxicittyotestorganisms Generallynon-toxictotestorganisms Table 1: Toxicityoffoam extinguishingagents Acute toxicitieas EC50* and ECI 0** tophotbacteriumphosphoreum (Photolumineseentbacteria). CriteriaI:nhibitioonfthe lightpower within10 20 /30 minutes (Classificatioofnthefoam agents accordingto d Foam agents (FA) EC50 in pVlofwater ECI 0 inpVl and mg/kg ofwater Toxicitythresiold pi/I mg/kg negative decimal logarithm ofthe ECIO MultirangeFA No.2 6 0.6 MultirangeFA No.1 7.5 0.9 MultirangeFA No.4 15 1.7 MultirangeFA No.5 25 1.7 MultirangeFA No.3 25 6 0.61 -6.215 0.92 -6.031 1.79 -5.747 1.75 -5.757 6.0 -5.222 Filmforming FA No.2 2000 85 91 -4.041 Filmforming FA No.6 300 30 32 -4.495 Filmforming FA No.1 460 120 129 -3.889 SpecialFA 3000 150 216 -3.666 Filmforming FA No.5 2000 460 479 -3.320 FC-203 No.4 2500 600 632 FC-20X(o No.3 15000 2000 2040 ProteinFA No.3 5000 2000 2330 ProteinFA No.1 30000 4000 4570 Filmformingfluorineprotein 30000 7500 8590 ProteinFA No.2 30000 7500 9000 -3.199 -2.690 -2.633 -2.340 -2.066 -2.046 EC50 = Effectivceoncentrationofthefoam extinguishingagent loweringthe lightpowerofthe ph ECI 0 = Effectivceoncentrationofthefoam extinguishingagent loweringthe lightpowerofthe ph Investigatoifotnosxiecffec.t.s...i.nthewastewater Page8 Thefollowienvgaluatiooftnhebactertioaxiciotftyhefoamextinguishaignegntscanbe concluded from these data: Highlytoxicto Photobacteriarethe muftirangefoam extinguishinaggents No. 1 and 2. Toxicto photobacteriarethe muftirangefoam extinguishinaggents No. 3,4 and 5,as wellas filmformingfoam agentsNo. 2 and 6. Lowtoxicittyophotobacteriraepresenttheflim-forminfgoam agentsNo. 1,3 (FC-206,4(FC-203)and 5,thethreeproteinfoam agents,thefilm-forminfgluorine-protefionam agentsas wellas thespecial foam agent fordeep-frypan fires. 4.2 Algae multiplicatiionnhibitiotnest 4.2.1 The investigatioonfsalgaetoxicitwyere conducted accordingtothe assay guideline"Inhibitiofnthe cellmultiplicatioofngreen algaeScenedesmus SubspicatusCHOD" ofthe (German) FederalEPA dated 06.22.1982. Scenedesmus subspicatusisa single-cealultotrophicorganism withvegetativemultiplication. Stockcufturesofalgaewere heldinnourishmentmedia accordingtothetestguidelineandtransferred toa freshmedium once a week. Pre-cufturewsere setup 3 days beforestartinegach assaytoobtain cellsintheexponentialgrowth phase. The experimentswere conducted as statitcests,i.et.hetestedsubstance was added once inthe desiredconcentratioantthe beginningofthe incubation.For each concentratioannd control2 Erienmeyerflaskswith50 mi ofnutritionsaollutionwere setup. The initicaellldensitywas setto the valuebetween 10,000and 15,000cells. The testcultureswere shaken once a day. The cellconcentratiownas determinedon the day 0,3.4 and 7 by means ofan electroniccellcountingdevice.The cellnumbers were used toplotthe growth curves and to calculatethe multiplicatiionnhibitiownhich takes intoconsiderationdays 0,3 and 4 accordingtotheguideline.Day 7 was used foran after-observation. From theconcentration-effeccutrves,the valuesofECI 0 and EC50 were determined. Investigatfoofntsoxiceffect.s....i.nthewastewater Page 9 4.2.2The resultosfalgaegrowthinhibitiaosnsayusingScenedesmus Subspicatuwsere puttogetherin Table 2. The tableisbuiltup according tothe same scheme as table1.The toxicitdyeterminationofindividual foam agents forScenedemus Subspicatuswas conducted inthesame way as thalforphotobacteria. Allfoam agents withthe exceptionoftwo proteinfoam agents should be designated as toxicto Scenedemus Subspicatus. Both ofthe mentioned proteinfoam agents have only weak toxicittyo algae.The specialfoam agents fordeep-frypan firescan be considered a border case between toxic and weakly toxicagents. Itisconspicuous thatone proteinfoam agent which was onlyweakly toxicinrelationtobacteriaisin theupper range oftoxicittyoalgae,whileone highlytoxictobacteriamufti-rangefoam agent has been found inthe mid-range oftoxicitryelativteo algae. Table 2: Toxicityoffoam extinguishingagents Acute toxicitiaess EC50* and EC1 0** to scenedesmus subspicatus (Freshwater algae). CriteriaI:nhibitionfgrowth within72 hours (Classificatioofnthe foam agents accordingto decreasingtoxicity) Foam agents (FA) EC50 in pVlofwater Multirange FA No.3 30 Film forming FA No.6 230 Multirange FA No.1 32 Multirange FA No.4 24 Film forming FA No.2 37 Protein FA No.2 225 Film forming FA No.3 FC-206 160 Film forming FA No.4 FC-203 160 Filmforming FA No.5 105 Film forming FA No.1 355 Muftirange FA No.2 Film forming fluorineprotein Special foaming agent Protein FA No.3 Protein FA No.1 68 80 105 435 6200 EC 10 iniii/aind mg/kg ofwater Toxicitythreshold PVI mg/kg 8 8.0 8 8.4 9 9.2 9 9.5 9 9.7 10 12.0 16 16.3 16 16.9 22 23 36 39 38 39 35 40 56 81 202 235 509 581 EC50 = Concentrationinhibitintghe growth by 50% after72 hours EC1 0 = Concentrationinhibitintghe growth by 10% after72 hours negative decimal logarithm ofthe EC10 -5.097 -5.076 -5.036 -5.022 -5.013 -4.921 -4.788 -4.772 -4.638 -4.409 -4.409 -4.398 -4.042 -3.629 -3.236 Investigatoifotnosxiecffect.s....i.nthewastewater 4.3 Resuftsofthe Daphnia shon-termassay Page10 4.3.1Testorganisms inthiscase a 6to 24-hoursoldinstarofDaphnia Magna. The toxiceffectofsubstances containedinwateron Daphnia Magna ismeasured as thesolutionlevelorconcentration(ppm, ppb) ofthe testedsubstancesinwhich,aftertestingc,ertainpercentageofDaphnia became immobile (effecticvoencentrationfsor10% and 50% oftheanimals= EC1 0 and EC50). Testconfiguration Ina. 25 mi beakerflask5, mi ofstandardwater (socalleddilatiownater)were filledT.hen,2 oldanimals areput inlefto themselvesfor24 hours withoutfood. Afterthattime,theoldanimalsare removed. The neonates releasedinthemeantime,were counted and theevaporatedwaterreplenished.Now, 5 ml ofthetoxicantsolutioanreadded intothebeaker glass.Thisresultisnthesolutionof10 ml and thereforerepresentsthe firsltevelofdilatioonfthe testedsubstance inwater. Furtherlevelsare obtainedinthe same way. To inhibitthenaturalswimming activitoyftheanimalsand tosecure a possiblyequalsubstance intake inalllarvaet,hetestmaterialislefitndarkness forthe next24 hours;the countingofthestilmlobile instarfsollowsthereafter. Controlbreed Inparalletlo each assay seriesa, determinatioonfthe EC1 0-valueisconducted withthe reference substance potassiumdichromate.The quantitieussed inthiscase are0.9-1.9mg/iofstockwater. Thetestresultisvalidwhenlessthan10% ofDaphnia neonates became immobileinthiscontrolassay. lnvestigatoffotnosxiecffec.t.s...i.nthewastewater Page 11 4.3.2The resultsofDaphnia short-termtestarecollectedinTable 3. The configuratioonfthetableagainfollowsthescheme used inTable 1.Alsothe determinationofthe toxicitoyfindividuafloam agentstoDaphnia isconducted justlikeinprevioustestswithPhatobacteria and green algae. Allmulti-rangefoam agents,film-forminfgoam agentsup totherunningNo.3 and thespecialfoam agentfordeep-drypan firesa,retoxicto Daphnia Magna The remainingfoam agents,i.et.hefilmformingFA No. 3,thethreeproteinFA and the film-formifnlguorine-proteFiAnhave low toxicittyo Daphnia. Generally,the mufti-rangaend the film-forminfgoam agents are lesstoxicto Daphnia than to the bacteria. Table 3: ToxicitVoffoam extinguishinaggents Acute toxicitieas LC50* and LCl 0** to Daphnia Magna (Water flea); CriteriaL:oss ofabilittyo swim within24 hours (Classificatioofnthe foam agents accordingto decreasingtoxic .Foam agents (FA) LC50 in pVl of water LC 10 inpVl and mg/kg ofwater Toxicitythres,old PI/I mg/kg negative decimal logarithm ofthe LCLO Multirange FA No.3 75 12 Multirange FA No.4 58 13 Multirange FA No.2 75 20 Film forming FA No.1 600 20 Multirange FA No.1 120 30 12.0 13.7 20.4 21.6 30.5 -4.921 -4.863 -4.690 -4.666 -4.516 Film forming FA No.2 200 30 Film forming FA No.4 FC-203 430 30 Film forming FA No.6 1500 45 Special foam agent 75 45 Multirange FA* No.5 250 75 32.2 31.6 47.3 65.0 77.4 -4.492 -4.500 -4.325 -4.188 -4.111 Film forming FA No.5 Protein FA No.3 Film forming FA No.3 FC-206 Protein FA No.1 Protein FA No.2 Film forming fluorineprotein 3000 600 2000 7500 7500 7500 85 200 300 1900 3700 3700 88.5 233 305 2170 4440 4240 -4.053 -3.633 -3.516 -2.664 -2.353 -2.373 L(jSo= Concentrationcausing 50% immobilityofthe animalswithinthetestperiod LC 10 = Concentrationcausing 10% immobilityofthe animalswithinthetestperiod Investigatoifotnosxiecffec.t.s...i.nthewastewater 4.4 Resufts of the fishtoxicittyest Page12 4.4.1 The investigatioonf the fishtoxicitays well as fishholding and water qualitywere in agreement with the OECD guidelines.The zebra barblings(Brachydanio$,erio)had an average body length of3.0 0.5 cm. The mortalityduring the lasttwo weeks of the stock holding was 0%. The 02 content and pH ofthetestsolutionswas determined att = Oh. t = 48h and t = 96h (end ofthe experiment). During the experiment,therewas no noticeablechange ofthe 02 content. The pH ofthe testsolutionswas 7.8 0.2 at the beginning of the test. The food supply was suspended 24 hours beforethe startof the test.The temperature ofthe solution was 237C 0.!5@Cwith constant lightaerationthrough a glass capillaryand a light/darkcycle of 16/8 hours. Ineach concentration level,10 fisheswere put inthe 10 litetrestsolutionin a 15 lftefrullglass bowl under statictestconditionsand the number of dead determined after24, 48, 72 and 96 hours. Uncertaintiesduring the experiment were recorded. The LC50 were calculatedwith a computer program according to Lichffieladnd Wilcoxon 1949; LCO and LCloo resulteddirectlfyrom the test. 4.4.2 The resultsof the fishtoxicitt@estare compiled inTable 4. The resultrepresentafionand determinationof the toxicityof individualfoam agents to fishagain followsthe bacteriatest(see 4.1.2). Clearly,toxicto fishare only mufti-rangefoam agents No. 2 and 4. The rema7iningmufti-rangefoam agents No. 1 and 3, as wellas the film-fonningfoam agents No. I and 2 can be assigned to a toxic/ weakly toxictransitionrange. Weakly toxicto fishare the film-formingfoam agents No. 3 (FC-206,4 (FC-203),5 and 6,the proteinfoam agents No. 2 and 3, as wellas the special foam agent fordeep-fry fires.The film-formingfoam agent No. I as well as the film-formingfluorine-proteifnoam agent are generallynon-toxicto fish Table 4: Toxicityoffoam extinguishingagents Acute toxicitiaes LCSO* and LCO** (48 hours)toBrachydanio rerio(zebrabarbling); CriteriaM:ortalitoyfthe testanimalswithin48 hours (Classificatioofnthefoam agents accordingtodecreasing Foam agents (FA) LCSO in pillofwater LC 0 inpilland mg/kg ofwater Toxicittyhres,old negative decimal logarithm Multirange FA No.4 68 Multirange FA No.2 109 Multirange FA No.3 131 Film forming FA No.2 141 Film forming FA No.1 161 Multirange FA Protein FA Film forming FA Special FA Filmforming FA No.1 No.3 No.4 FC-203 No.3 FC-206 173 1369 1634 1880 4086 Film forming FA No.5 Film forming FA No.6 Protein FA No.2 Filmforming flourineprotein Protein FA No.1 3075 3075 6524 10000 1000 52 87 100 100 100 100 500 1000 1000 2000 2000 2000 4472 10000 10000 55 89 100 107 108 102 582 1053 1442 2036 2082 2100 5370 10000 10000 -4.260 -4.051 -4.000 -3.971 -3.967 -3.991 -3.235 -2.978 -2.841 -2.691 -2.682 -2.678 -2.270 -2 -2 LC50 = Highesttestedconcentrationinmg/kg, atwhich 50 % ofthe testanimalsdied LC 0 = Highesttestedconcentrationinmg/kg, atwhich no testanimalsdied Investigatfoofntsoxiecffect.s....i.nthewastewater 4.5 Determinationofbiochemicaldegradability Page 13 InTable 5,the figuresofthe chemicaloxygen demand (COD) and the biochemicaloxygen demand duringthe fiveconsecutivedays (BOD 5),expressed inmg 02 per lfteorfwater,were collectedfor3% applicationsolutionsofthe foam agents. The levelof the biochemicaldegradabilityofthe testedsubstances can be sufficientalcycurately determined from the ratiofCOD toBOD S. Inan idealcase the COD toBOD 5 would be 1,:1. Such ratiowould describean nearlyquantitativbeiodegradationofa testedsubstance. RatiosofCOD to BOD 5 of 1 :0.5signalan insufficienbtiochemicaldegradation. The values presented inTable 5 pointto the insufficiebnitochemicaldegradationofthe mufti-range foam agents No. 1 and 4 as wellas thefilm-forminaggent No. 3 (FC-206).During the categorization ofthe concentratesofthese foam agents intoa water endangering category,the characteristicosf insufficiebnitochemicaldearadabilitiysconsideredas negativeC'Malus")and resultedinassignment tothe nexthigherwater endangering category(see 4.7). Table 5: COD and BOD 5 offoam extinguishinaggents Foam extinguishingagent COD ofthe 3% solutionin mg of02/1 ofwater Multirangefoam agent No.1 No.2 No.3 No.4 No.5 43700 47400 40300 52800 30100 Film-forming Toam agen No.1 No.2 No.3 FC-206 No.4 FC-203 No.5 No.6 21000 34300 24600 41200 29700 21900 Film-forming fluor-protF.A Proteinfoam agent No.1 No.2 No.3 19600 15000 14100 17100 BOD5 ofthe 3% solutionin mg of02/1 ofwater 17500 25900 30500 15200 25800 15700 23200 8700 21500 21100 12300 13300 8700 14500 Ratio COD:BOD5 1 0.40 1 0.55 1 0.76 1 0.29 1 0.86 1 0.75 1 0.68 1 0.35 1 0.52 1 0.71 1 0.6 1 0.89 1 0.62 1 0.85 Evaluationol degradabilk insufficient probably insuffi sufficient insufficient sufficient sufficient sufficient insufficient probably insuffi sifficient sufficient sufficient sufficient sufficient Special foam agent 4600 no biochem. degr. N/A N/A not measured Investigatfoofntsoxiceffect.s....i.nthewastewater Page 14 4.6 Determinationofthe water endangering figuresand classificatioofnthe testedfoam extinguishing agent concentratesintowater endangering categories. 4.6.1 As already explainedin the introductiont,he "Commission forEvaluationof Water Endangering Materials"considered theactae toxicittyo selectedtestorganisms as a primary criterifaorclassificationofa substance or a substance mixtureintoa water endangering category.A furtherimportant evaluationcriteriwaas the biochemicaldegradabilkyofthe substance or substance mixtureunder consideration. Afterconsuftationswithsome ofthe members ofthe "Commission forEvaluationofWater EndangeringMate(ials"regardingthe classificatioofn16 foam extinguishingagent concentrates,the determinationofthe mammals toxicit(yLD50 oraq,has been waived. Instead,inadditionto the prescribed considerationofthe -acute bacteriatoxicitaynd the -acute fishtoxicity, the acute toxicititeos -algae and -water flea were taken intoconsiderationduring the classificatioofnthe testedfoam extinguishingagent concentratesintowater endangering categories. 4.6.2 InTable 6,the evaluationfl4uresofthe acute toxicftioefsthe foam extinguishingagents tothe test organisms,are presentedin columns 2 through 5. According to the methods employed by the "Commission forEvaluationofWater Endangering Materials"t,he arithmeticaverages ofthe evaluationfiguresresultin the so calledwater endangering number (WEN) of the materialunder consideration(6thcolumn). From thewaterendangering numbers determined inthisway, thewater endangering categories(WEC) are derivedaccording tothe followingscheme: WEN 6 and higher WEN 4.0 to 5.9 WEN 2.0tp 3.9 WEN 1.9and lower -WEC 3 -WEC 2 -WECI -WECO The classificatioofnthe testedfoam extinguishingagent concentratesintothe water endangering categoriescan be taken from the lastcolumn ofTable 6. Table 6: 1)Determinationofwater endangering figures(WEF) as an arithmetiacverage ofthe evaluationfigures forthe acute toxicitaygainstbacteria,algae,water fleaand fish. 2)The resultingclassificatiionntowater endangerin-qcate-gorie(sWEC Foam extinguishingagent Evaluationfiguresforthe acute toxicitaygainst Bacteria Algae PA-Ph4,41 9m6gtmyfisb- Fish Water endangering figure(WEF) Multirange FA No. 4 5.7 Multirange FA No. 5 5.8 Multirange FA No. 2 6.2 Multirange FA No.1 6.0 Multirange FA No. 3 5.2 Film-forming FA No. 2 4.0 Film-forming FA No. 1 3.9 Film-forming FA No. 6 4.5 Film-forming FA No. 4 FC-203 3.2 Film-forming FA No. 5 3.2 Special FA 3.7 Film-forming FA No. 3 FC-206 2.9 Protein FA No. 3 2.6 Protein FA No. 2 2.0 Film-formingfluorine-protein 2.1 Protein FA No. 1 2.3 5.0 N/A 4.4 5.0 5.1 5.0 4.4 5.1 4.8 4.6 4.0 4.8 3.6 4.9, 4.4 3.2 4.9 4.3 5.0 4.1 N/A 5.2 4.7 4.1 4.9 4.5 4.0 4.9 4.9 4.0 4.8 4.5 4.0 4.4 1 4.7 4.0 4.3 4.3 2.7 4.2 4.5 3.0 3.9 4.1 2.9 3.7 4.1 2.8 3.7 3.5 2.7 3.5 3.6 3.2 3.3 2.4 2.3. 3.0 2.4 2.0 2.7 2.0 2.7 2.6' Investigatioofntsoxiceffect.s....i.nthewastewater Page 15 4.6.3Underthepressureofthegeneralactiveenvironmentaclonsciousnesst,hequestiodniscussedtodate is: Should classificatioofnthe substance concentrateintoa water endangering categorybe based on acute toxicittyothe most sensitivemember ofa food chain? Should thisbe thecase,thecategorizatioonfthe16foam extinguishinaggent concentratespresented inTable 7 intowater endangering categorieswould be the result. 4.7 The biochemicaldegradabilitoyfthe -mutti-rangefoam materialNo. 1 and - multi-rangefoam agent No. 4 isnot sufficient. This factleadsto a downgrading ofthe concentratesfrom the water endangering category2 (see Table 6)to the waterendangering category3. Incase ofthe insufficientbliyochemicallydegradablefilm-forminfgoam agent No.3, thedowngrading takes place from the water endangering category 1 (see Table 6) to the water endangering category 2. Table 7: 1)Determinationofwater endangering figures(WEF) based on the evaluationfiguresforthe most sensitive group oftestorganisms. 2) The resultincglassificatiionntowaterendangering categories(WEC) Foam extinguishingagent Evaluationfiguresfortheacute toxicitaygainst Bacteria Algae Sm"al?cotirsh Fish Multirange FA No. 2 6.2 Multirange FA No. 1 6.0 Multirange FA No. 5 5.8 Multirange FA No. 4 5.7 Multirange FA No. 3 5.2 Film-forming FA No. 6 4.5 Film-forming FA No. 2 4.0 Protein FA No. 2 2.0 Film-f6rming FA No. 4 FC-203 3.2 Film-forming FA No. 3 FC-206 2.9 Film-forming FA No. 1 3.9 Film-forming FA, No. 5 3.2 Film-form.fluorine-protein 2.1 Special FA 3.7 Protein FA No. 3 2.6 Protein FA No. 1 2.3 4.4 5.0 N/A 5.0 5.1 5.1 5.0 4.9 4.8 4.8 4.4 4.6 4.41 4.0 3.6 3.2 4.7 4.1 4.5 4.0 4.1 N/A 4.9 4.3 4.9 4.0 4.3 2.7 4.5 4.0 2.4 2.3 4.5 3.0 3.5 2.7 4.7 4.0 4.1 2.9 2.4 2.0 4.1 2./8 3.6 3.2 2.7 2.0 Water endangering figure(WEF 6.2 6.0 5.8 5.7 5.2 5.1 5.0 4.9 4.8 4.8 4.7 4.6 4.4 4.1 3.6 3.2 lnvestigatoffotnosxfecffec.t.s...i.nthewastewater 5. Finalconsiderations Page16 Presented -dataoftheacldetoxicitoyftheapplicatiosnolutionsoffoam extinguishinaggerttstowaterorganisms -data concerningbiochemicaldegradabilitoyffoam extinguishinaggents - classificatioofn.thetestedfoam extinguishinaggent concentratesintothe water endangering categoriesbased on o arithmetiacverages oftheevaluatiofniguresoftheacLAetoxicities o evaluatiofniguresoftheactaetoxicititeosthe most sensitivoerganism ineach case have to be checked by the "Commission forEvaluationofWater Endangering Materials". The Commission willevaluatethetoxicitdyata establishedby the army and indicateffitshould be consideredcomplete or inneed offurtherinvestigations. The examinationwilallsoprovidea determinatiocnoncerningtheproceduresused fortheclassificationoffoam extinguishinaggents intothewater endangering categories. Especialltyhelatterresulitsofinteresittislikeltyoseta precedence thatcouldaffectthecommercial lawoftheEuropean Community startinign1992.