Document 0gKxNDypZkeM0zJmpnG4Zv1gx

SUMMARY FOR WORK PERFORMED BY THE GERMAN ARMY ON FOAM EXTINGUISHING AGENTS MANUFACTURED BY MULTIPLE COMPANIES TEST SUBSTANCE Identity:A mixturecontainingperiulorooctanesulfonatew,hich may also be referredtoas PFOS, FC-95, or as a component of FC-206. (1-Octanesulfoniacid)(CAS # 2795-39-3). Remarks: The testsample isFC-206. Currentinformatioinndicateistis a mixtureof 0.67% PFOS, 17.5% diethyleneglycolbutylether,78.91% water,1.33% Sultonefoamer, 1% sodium octylsulfate0,.04% sodium laurylsulfate0,.5% polyoxyethylenemonooctylphenyl ether,and 0.05% tolyltriazole. The followingsummary applies to a study done by the Gennan Army forpurposes of compaiing the environmental properties of foam extinguishing agents from multiplecompanies, including 3M's FC20& Data may not accurately reflectthe environmental properties of the tluorochemical component in the testsample. STUDIES 10,20, and 30 minute EC5o forPhotobacterium phosphorl-um (MicrotoxTm), 72-hour EC50 forgrowth inhibitioonf Fresh Water Algae (Scenedesmus subspicatus),24-hour EC5o forDaphnia magna, 48-hour LC50 tozebra barbling(Brachydanioreiio)C,hemical Oxygen Demand and 5-day BiochemicalOxygen Demand METHODS: MicrobiesMicrotoxS "BASIC" Procedure Algae growth inhibitiopner EPA guidelinesdated 05-06-1982 Daphnia toxicitayccordingto DIN 38412, Part11 Zebra barblingtoxicitayccordingto DIN 38412, Part15 RESULTS Report Date: 3/29190 The EC50 forPhotobacteiium phosporeum was 15,000 ppm. Itisnotclear ifthisisforthe 10,20, Or 30 minute exposure. The 72-hour EC50 Growth InhibitiofnorScenedesmus subspicatuswas 160 ppm. The 24-hour EC50 forDaphnia magna was 2000 ppm. The 48-hour LC50 forZebra barbling(Brachydanio rerio)was 4086 ppm. The Chemical Oxygen Demand (COD) was 24,600 mg 02 / L The 5-Day BiochemicalOxygen Demand (BOD5) was 8700 mg 02 / L DATA QUALITY ReliabilityK:limischranking= 4. Allstudyvalues come from a summary lisotnly. No raw data or method documentation was available. OTHER Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 6/26/00 Ci-el 141Investigations of toxiceffects and biologicaldegradability of foam extinguishingagents inthe waste water by Ekkehard lsing lnvestigatfoofntsoxiecffect.s....i.nthewastewater 1 Introciuction Page 2 On Apri1l5,1985t,heFederaMlinistefrorInternAaflfairisntroduceadreviseadndexpandedversion of the IndexofWater Endangering Materials The indexlisttshemost importantchemicalcompounds availableon themarket and dividesthem into fourwater endangering categories(WEC) accordingtotheirwater endangering potential: WEC 3 WEC 2 WEC I WEC 0 very harmful materials harmful materials mildlyharmfulmaterials generallyharmless materials Allchemical materialsnot yet listedinthe catalogue,are considered water endangering untilthe authorized Subcommittee for"Storageand TfansporWon of WaterEndangering Materials"attheFederalMinisttyforlntemaiAHWrs has decided about theirclassification. Incase of mixturesof materialst,he incorporatioinntoa water endangering category is decided according to thedata measured on the mixtureItself. Atthefocusoftheevaluationofa materialregardingitsendangering potentiaflortheorganisms living inwateror using it-e.g.as a food -isitsacutetoxicitye,speciallyforbacteria,algae,small crayrish, 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. Bioassayson the one hand and chemicavphysicalprocedures on the other,complement each other(see among others:German UnifiedProcedures forWater, Waste Water and Sludge Examination,DIN 38412). GMSI, IssueA, 36 No. 11 (1985),pages 173 -252 Investigatioofntsoxiceffect.s....i.nthewastewater Duringtheevaluatioonftheeffectosf Page 3 -chemical parameters,e.g.toxicmaterialscontained inwater and -physicalparameters,e.g.supply ofenergy,water extraction the attentionshould be paid to the use of prescribedtestorganisms and to the conformance to standardtestconditions.The reproducibiliatnyd statisticvaalliditoyftheresultsshould be secured. The followingtypes oftestorganisms should be used instandardizedbioassays inwater and waste water: -bacteriaas chemoheterotrophs -algae as primaryproducers -protozoans as singleprimaryand secondary consumers -smallcrayfishas mufticelclonsumers - fishas mufticelclonsumers witha centralnervous system. At the same time,they are the final members inthe aquaticfood chains and collectpersistencthemicalsintheirtissues. Additionallyc,ertainsaprobicsystems can be used inbiotestsas models of complete ecosystems. Particularlmyicrocosms and activatedsludge systems consistingofvariousbacteria,fungi,protozoans and worms. 2. Problem definigon According to the definitionisnwater supply law and waste water handlinglaw includingpertinent implementationprocedures,theFederaldefense forcesarefrequentlyquotedasthe causeof ham-dul materialsdischarges towaters and communal waste water treatmentplants. Particulaqdudng, e.g. -use ofextinguishingfoams during trainingsand actions -transportatioannd storageoffoam agent concentrates considerableharm can be done to surfaceand ground waters. Investigatoifotnosxiecffec.t.s...i.nthewastewater Page4 To evaluatheedangerpotentioaftlhefoamconcentratneotsyetclassirieidnthewaterendangering categoriest,heirexaminationand military-intemtaelmpor'ary classificatiionntowaterendangering classesisnecessary.The FederalOfficeforDefense Technology and Acquisitioinn Koblenz,has authorizedthedefensescientifSiecrviceOfriceofthe FederalArmy toconduct thenecessaryresearch and thesubsequent temporaryArmy-intemalWEC classification. The research,leadingto establishinwgater endangering categoriesoffoam extinguishinaggent concentratesp,roduces atthe same timevalues of acute organism toxicftioefsthe,mostly3%, applicatiosnolutions. 3. Foam exfinquishina-ggentsand theirb"ioassavs 3.1 Totalof 16 foam extinguishinaggents representing5 differenktindsoffoam agentswere comparativeleyvaluatedinbioassays(see3.2)regardingacutetoxicftoyftheirapplicatiosnolutiontsowater organisms and subdividedintowaterendangering categoriesfrom thepointofviewoftheirconcentrates. Inparticular: -5 mufti-rangefoam agents -6 film-forminfgoam agents -3 proteinfoam agents -1 film-forminfguorine-protefionam agent -1 specialfoam agent fordeep-frypan fires The formulationosfthefoam extinguishinaggents areproprietariynformatioannd unavailablteothe publicA.fterconsultationwsithmanufacturers,thefollowingmaterialscan be listeads toxiccomponents: -organicsurfactants -glycols(e.g.ethylenglycolb,utyldiglycoq -preservatives -organicsolvents -organicacids -inorganicsafts lnvestigatoffotnos)decffec.t.s...i.nthewastewater Page5 Presentetdestresultasrenew and notyetrevealetdothemanufacturceormpaniesT.herefore, productnames cannot be publishedhere. Hence,the resultableswillhave the productnames substitutedby classdescriptionisncludingrunningftemnumber. 3.2 Listingofthe bioassayused (shortdescriptioonf each testWiththefollowingresultable- see 4.5 through4.5). 3.Zl BioluminescenceinhibititoenstwithPhotobacteriPahosphoreum Inmicrotoxanalyzerm,odel 2055 (Beckman Co.) 3.2.2Algae growth inhibititoenstaccordingtothetestguidelineosffederalEPA dated 054)6-1982. 3.2.3Daphnia shorttestaccordingto DIN 3841Z Part11. 3.2.4 Fishtestaccordingto DIN 38412,Part15. 3.2.5 Determinationofthebiochemicaloxygen demand by theapplicatiosnolutionasnd theirdilutionwsith waterduring5 consecutivedays (BOD 5). Apparatus:Sapromat B12,VofthCo. Incomparison to BOD 5,the measurement included: chemicaloxygen demand oftheapplicatiosnolutionasnd theirdilution(sCOD). Apparatus:Dr.Lange digitaplhotometer LP 1 W. 4. Results The resultswillbe describedinthefollowin(gchapter4.I.to4.7)intheform oftableswithassociated text. Investigatoifotnos)decffec.t.s...i.nthewastewater Page6 4.1 The bioluminesceinncheibittieosntwithPhotobactePdhaosphoreuimnmicrotoaxnalyzemro,del 2055by BeckmanCo. 4.1.1Shortdescriptoifotnhetest ThetesotrganisPmhotobactePdhaosphoreuimsa marinbeacteriTah.iskindofbacterisapresent inimmensequantitiientshesea layercslosetothesurfacaend causestheso callemdarine phosphorescencTeh.eunderlyicnhgemicaplrocesissa lucledne4uclerparsoecessD.amagesto thePhotobacterei.ag,d.uetointoxicatiroenssu,ilnttheinhibitoiftohnelucffedne-lucfafcetriavsiety. Theendeffecitsthereductioofnthelighetmission. Thisi,nitsevlefrysimplep,rincipilsuesedinthemicrotoaxnalyzer A light-transpgalraesncstelilsplaceidnalight-tmiegahsturemenhtead.Theglascselclontain1smi ofa suspensiownithPhotobacterTihae.lighetmittebdythePhotobactefrailalosna photoreceptor, isconverteidnteolectreincergya,mplifideids,playaenddrecorded. Thelighqtuantietmyittebdya specimeonfuntreatbeadcteriissaetinthedispltaoythevaluoef90%. Thisquantiitsytantamountto:"naturauln,inhibiltiegdhetmission". Specimenofequalquantitoyfbacteriaand equalbacterqiuaaliwtiythtoxiscubstanceasdded responwditha reductioofnthelighetmissioAnc.cordingtlhye,displvaayluleiebsetween90% and 0%.The0%-valuiendicattehsathephotobacteorfitahespecimetnreateidnthiwsayisnotcapable oflighptroductiaonymore. Fig1.: Measuremenatrrangemenotfmicrotoaxnalyzer MicrotoxO-Analyzer: Measurement configuration Light-tighmteasurement head Glass cellwithspecimen Di Photoreceptor L Tempering L Light Amplifier Pri Investigatoifotnosxiecffec.t.s...i.nthewastewater Page7 4.1.2The resultosfthebioluminescenceinhibititoenstwithPhotobacteriaPhosphoreum areassembled in Table 1. In the firsrtesultcolumn are the effectiveconcentrations of the 16 testedfoam agents inliVIofwater leading to a 50% inhibitioonf the lightemission by the lightbacteria(= ECSO). Inthe second resultcolumn are likewiseeffectiveconcentrationsleading toa 10% inhibitioonfthe light emission (= EC10) and representing the so called toxicitythresholds of the foam agents to the Photobacteria. The negative decimal logarithms of individualEC1 0 resultaftermultiplicatiobny the factorof -1 inso calledevaluationand endangering figuresof the individualfoam extinguishingagents to PhotobacteriaPhosphoreum (see resultcolumns 4 and 5). According to the evaluationscheme of the "Commission for Evaluation of Water Endangering Mate(ials",the determined evaluationand endangering figures(EE figures)indicatethe following toxicitcyategories: EE figuresof 6.0 and higher EE figures4.0 to 5.9 EE figures2.0 to 3.9 EE figuresunder 2.0 Highlytoxicto testorganisms Toxic to testorganisms Low toxicittyo testorganisms Generallynon-toxicto testorganisms Table 1: Toxicityoffoam extinguishinaggents Acute toxicitieas EC50* and EC 10** to photbacteriumphosphoreum (Photoluminescentbacteria). CriteriaI:nhibitioonfthe lightpower within10 20 /30 minutes (Classificatioofnthefoam agents according to Foam agents (FA) ECSO in pl/Iof water EC 10 inpllland mg/kg ofwater Toxicitythresiold PI/I mg/kg negative decimal logarithm of the ECIO Multirange FA No.2 6 0.6 Multirange FA No. 1 7.5 0.9 Multirange FA No.4 15 1.7 Multirange FA No.5 25 1.7 Multirange FA No.3 .25 6 0.61 0.92 1.79 1.75 6.0 -6.215 -6.031 -5.747 -5.757 -5.222 Film forming FA No.2 2000 85 91 -4.041 Film forming FA No.6 300 30 32 -4.495 Film forming FA No.1 460 120 129 -3.889 Special FA 3000 150 216 -3.666 Filmforming FA No.5 2000 460 479 -3.320 FC-203 No.4 FC-20Ato No.3 Protein FA No.3 Protein FA No. 1 Filmforming fluorineprotein Protein FA No.2 2500 15000 5000 30000 30000 30000 600 2000 2000 4000 7500 7500 632 2040 2330 4570 8590 9000 -3.199 -2.690 -2.633 -2.340 -2.066 -2.046 EC50 = Effectivceoncentrationofthefoam extinguishinaggent loweringthelightpowerofthe pho EC1 0 = Effectivceoncentrationofthe foam extinguishinaggent loweringthe lightpowerofthe pho Investigatioofntsoxiecffect.s....i.nthewastewater Page 8 The followinegvaluatioofnthebacteritaoxiciotfythefoamextinguishianggentscanbe concluded from these data: Hi-ghltyoxicto Photobacteda arethe muftirangefoam extinguishingagents No. I and 2. Toxicto photobacteriaare the muftirangefoam extinguishingagents No. 3,4 and 5,as wellas filmformingfoam agents No. 2 and 6. Low toxicittyophotobacteriarepresentthefilm-forminfgoam agents No. 1,3 (FC-206,4 (FC-203)and 5,the threeproteinfoam agents,thefilm-forminfgluodne-proteifnoam agents as wellas the special foam agent fordeep-frypan fires. 4.2 Algae multiplicatiionnhibitiotnest 4.2.1 The investigationosfalgaetoxicitwyere conducted according totheassay guideline"Inhibitionfthe cellmultiplicatiofngreen algae Scenedesmus SubspicatusCHOD" ofthe (German) FederalEPA dated 06.22.1982. Scenedesmus subspicatusisa single-celalutotrophicorganism withvegetativemultiplication. Stock culturesofalgaewere @eldinnourishment media according tothetestguidelineand transferred toa freshmedium once a week. Pre-cufturewsere setup 3 days beforestartinegach assay toobtain cellsinthe exponentialgrowth phase. The experimentswere conducted as statictests,i.e.the testedsubstance was added once inthe desiredconcentrationatthe beginningof the incubation.For each concentrationand control2 Erlenmeyer flaskswith50 mi ofnutritionsaollutionwere set up. The initicaellldensitywas settothe value between 10,000and 15,000 cells. The testcultureswere shaken once a day. The cellconcentrationwas determinedon the day 0,3,4 and 7 by means ofan electronicellcounting device.The cellnumbers were used toplotthegrowth curves and to calculattehe multiplicatiionhibitiownhich takes intoconsiderationdays 0,3 and 4 according tothe guideline.Day 7 was used foran after-observation. From the concentration-effecutrves,the values ofEC 10 and EC50 were determined. Investigatfoofntsoxfecffect.s....i.nthewastewater Page 9 4.2.2The resultosfalgaegrowthinhibitiaosnsayusingScenedesmus Subspicatuswere puttogetherin Table 2. The tableisbuiltup accordingtothesame scheme astable1.The toxicitdyeterminationofindividual foam agents forScenedemus Subspicatuswas conducted inthesame way as thatforphotobacteria. Allfoam agents withthe exceptionof two proteinfoam agents should be designated as toxicto Scenedemus Subspicatus. Both ofthe mentioned proteinfoam agents have only weak toxicittyo algae.The specialfoam agents fordeep-frypan firecsan be considered a border case between toxic and weakly toxicagents. Itisconspicuous thatone proteinfoam agent which was onlyweakly toxicinrelationtobacteriaisin the upper range oftoxicittyoalgae,whileone highlytoxictobacteriamufti-rangefoam agent has been found inthe mid-range oftoxicitryelativteoalgae. Table 2: Toxicityoffoam extinicuishinganents Acute toxicitieas ECSO* and EC1 0** to scenedesmus subspicatus(Freshwater algae). CriteriaI:nhibitioonfgrowth within72 hours (Classificatioofnthefoam agents accordingtodecreasingtoxicity) Foam agents (FA) ECSO in pVl ofwater 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 forrhingFA No.4 FC-203 160 Film forming FA No.5 105 Film forming PA 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 ECI 0 inpVl and 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 = Concentrationinhibititnhgegrowth by 50% after72 hours ECI 0 = Concentratioinnhibftitnhgegrowthby 10% after72 hours negative decimal logarithm ofthe ECIO -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 Investigatoifotnosxiecffec.t.s...i.nthewastewater 4.3 ResuftsoftheDaphnia short-termassay Page10 4.3.1Testorganisms inthiscasea 6to24-hoursoldinstarofDaphnia Magna. The toxiceffecotfsubstances containedinwateron Daphnia Magna ismeasured as thesolutiolnevelorconcentratio(nppm, ppb) of thetestedsubstancesinwhich,aftertestingc,ertainpercentageof Daphnia became immobile (effecticvoencentrationfsor10% and 50% ofthe animals= ECI 0 and ECSO). Test configuration Ina. 25 mi beakerflask5, mi ofstandardwater (socalleddilatiownater)Were filledT.hen,2 oldanimals areput inleftothemselvesfor24 hours withoutfood. Afterthattime,theoldanimalsareremoved. The neonates releasedinthemeantime,were counted and theevaporatedwaterreplenished.Now, 5 mi ofthetoxicanstolutioanreadded intothebeaker glass.Thisresultisnthesolutionof10 mi and thereforerepresentsthefirsltevelofdilatioonfthe testedsubstance inwater. Furtherlevelsare obtainedinthe same way. To inhibitthe naturalswimming activitoyftheanimalsand tosecure a possiblyequalsubstanceintake inalllarvaet,hetestmaterialislefitndarkness forthenext24 hours;the countingofthe stimlolbile instarsfollowsthereafter. Controlbreed Inparalletlo each assay series,a determinationofthe ECIO-value isconducted withthe reference substance potassiumdichromate.The quantitieussed inthiscase are0.9-1.9mgA ofstockwater. The testresulitsvalidwhen lessthan 10% ofDaphnia neonates became immobileinthiscontrolassay. lnvestigatoffotnosxiecffec.t.s...i.nthewastewater 4.3.2 The resultsofDaphnia short4erm testare collectedinTable 3. Page 11 The configurationofthetableagain followsthe scheme used inTable 1.Alsothedeterminationofthe toxicitoyfindividuafloam agents toDaphnia isconducted justlikeinprevioustestswithPhotobacteria and green algae. Allmutt!-rangefoam agents,film-forminfgoam agents up totherunning No. 3 and the specialfoam agent fordeep-dry pan firesa,re toxicto Daphnia Magna. The remainingfoam agents,i.et.hefilmforming FA No. 3,the threeproteinFA and the film-forminfgluorine-proteFiAn have low toxicittyo Daphnia. Generally,the mufti-rangeand the film-forminfgoam agents are lesstoxicto Daphnia than to the bacteria. Table 3: Toxicityof foam extin_quishina-gqents Acute toxicitiaes LC50* and LCl 0** toDaphnia Magna (Waterflea); CriteriaL:oss of abilittyo swim within24 hours (Classificatioofnthe foam agents accordingtodecreasingtoxic .Foam agents (FA) LC50 in ptA of water LC 10 inliVIand mg/kg ofwater Toxicittyhre old PVI mg/kg negative decimal logarithm ofthe LCl 0 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 animalswithinthe testperiod LCl 0 = Concentrationcausing 10% immobilityofthe animalswithinthe testperiod Investigatioofntsoxiecffect.s....i.nthewastewater 4.4 Resultsofthefishtoxicittyest Page 12 4.4.1 The investigatioonfthefishtoxicitays wellas fishholdingand water qualitywere inagreement with theOECD guidelinesT.he zebra barblings(BrachydanioXerio)had an average body lengthof3.0 0.5cm. The mortalitdyuringthe lasttwo weeks ofthe stock holdingwas 0%. The 02 contentand pH ofthetestsolutionswas determined att= Oh,t = 48h and t= 96h (end ofthe experiment).Duringtheexperiment,therewas no noticeablechange ofthe 02 content.The pH ofthe testsolutionswas 7.8 0.2 atthe beginningofthe test. The food supplywas suspended 24 hours beforethe startofthetesl The temperature ofthesolution was 28*C O.E@Cwithconstantlightaerationthrough a glasscapillaryand a light/darckycleof16/8 hours. In each concentrationlevel,10 fisheswere put inthe 10 litetrestsolutionina 15 litefrullglass bowl under statictestconditionsand the number of dead determined after24, 48, 72 and 96 hours. Uncertaintiedsuringtheexperimentwere recorded. The LC50 were calculatedwitha computer program according to Uchtfieldand Wilcoxon 1949; LCO and LCloo resulteddirectlfyrom the test. 4.4.2 The resultsofthe fishtox7icitte@stare compiled inTable 4. The resultrepresentatioannd determinationof the toxicitoyf individuafloam agents to fishagain followsthe bacteriatest(see4.1.2). Clearly,toxictofishareonlymufti-rangefoam agents No. 2 and 4. The remaining mufti-rangefoam agents No. 1 and 3,as wellas the film-forminfgoam agents No. I and 2 can be assigned to a toxic/ weakly toxictransitiornange. Weakly toxictofishare the film-forminfgoam agents No. 3 (FC-206,4 (FC-203),5 and 6,the proteinfoam agents No. 2 and 3,as wellas the specialfoam agent fordeep-fry fires.The film-forminfgoam agent No. 1 as wellas the flim4ormingfluorine-protefionam agent are generallynon-toxicto fish Table 4: Toxicityoffoam extinguishinaggents Acute toxicitiaes LC50* and LCO** (48hours)toBrachydanio rerio(zebrabarbling); CriteriaM:ortalitoyfthetestanimalswithin48 hours (Classificatioofnthefoam agents accordingto decreasin@ Foam agents (FA) LC50 in pillof water, LC 0 inpilland mg/kg ofwater Toxicitythre 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 forr.ilinFgA SpecialFA , Filmforming FA No.1 No.3 No.4 FC-203 No.3 FC-206 173 1369 1634 1880 4086 Filmforming 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 = Highesttestedconcentrationinmglkg, atwhich 50 % ofthetestanimals died LC 0 = Highesttestedconcentrationinmg/kg, atwhich no testanimalsdied Investigatoffotnos)decffec.t.s...i.nthewastewater 4.5 Determinationofbiochemicaldegradabilfty Page13 InTable 5,thefiguresofthechemicaloxygen demand (COD) and thebiochemicaloxygen demand duringthe fiveconsecutivedays (BOD 5),expressedinmg 02 per Ifteorfwater,were collectefdor3% applicatiosnolutionosfthefoam agents. The levelofthe biochemicaldegradabilitoyfthetestedsubstancescan be sufficientalcycurately determinedfrom the ratiofCOD toBOD S. Inan idealcase theCOD to BOD 5 would be l.:1. Such ratiowould describean nearlyquantitativbeiodegradationofa testedsubstance.RatiosofCOD to BOD 5 ofI :0.5signalan insufficiebiochemicaldegradation. The valuespresentedinTable 5 pointto the insufficiebnitochemicaldegradationofthe mufti-range foam agentsNo. I and 4 as wellas thefilm-forminaggent No.3 (FC-206).Duringthecategorization ofthe concentratesofthesefoam agents intoa water endangeringcategory,thecharacteristiocfs insufficiebnitochemicaldegradabilitiysconsideredas negative("Malus")and resulteidnassignment tothe nexthigherwaterendangeringcategory(see4.7). Table 5: COD and BOD 5 offoam extinguishinaggents Foam extinguishinagent Multirangefoam agent No.1 No.2 No.3 No.4 No.5 film-forming coam agent No. 1 No.2 No.3 FC-206 No.4 FC-203 No.5 No.6 Film-formingfluor-protF.A Proteinfoam agent No.1 No.2 No.3 COD ofthe3% solutioinn mg of0211 ofwater 43700 47400 40300 52800 30100 21000 34300 24600 41200 29700 21900 19600 15000 14100 17100 BOD5 ofthe3% solutioinn 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 Evaluation degradabil insufficient probably insu sufficient insufficient sufficient sufficient sufficient insufficient probably insu sifricient sufficient sufficient sufficient sufficient Specialfoam agent notmeasured 4600 no biochem. degr. N/A T N/A Investigatfoofntsoxiecffect.s....i.nthewastewater Page 14 4.6 Determinationofthe water endangering figuresand classificatioofnthe testedfoam extinguishing agent concentratesintowater endangering categories. 4.6.1 As alreadyexplainedinthe introductiont,he "Commission forEvaluationof Water Endangering Materials"considered theacute toxicittyoselectedtestorganisms as a primarycriterifaorclassfflcationofa substance or a substance mixtureintoa water endangering category.A furtherimportant evaluationcriteriwaas the biochemicaldegradabilftoyfthe substance or substance mixtureunder consideration. Afterconsultationwsithsome ofthemembers ofthe"Commission forEvaluationofWater Endanger- ingMaterials"regardingthe classificatioofn16 foam extinguishinaggent concentrates,the determinationofthe mammals toxicit(yLDSO orao,has been waived. Instead,inadditiontothe prescribed considerationofthe -acute bacteriatoxicitaynd the -aciae fishtoxicity, the acute toyjcftietso -algae and -water flea were taken intoconsiderationduringthe classfflcatioofnthe testedfoam extinguishingagent concentratesintowater endangering categories. 4.6.2 InTable 6,the evaluationfl4uresofthe acutetoxicftieosfthe foam extinguishingagents to the test organisms,are presented in columns 2 through S. 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 consideratio(n6thcolumn).From thewaterendangeringnumbers determinedinthisway, thewater endangeringcategorie(sWEC) arederivedaccordingtothefollowinsgcheme: WEN 6 and higher WEN 4.0to5.9 WEN 2.0tp3.9 WEN 1.9and lower -WEC3 -WEC2 -WEC1 -WECO The classificatioofnthetested foam extinguishingagent concentratesintothe water endangering categoriescan be takenfrom the lastcolumn ofTable 6. Table 6: 1)Determinationofwater endangerin-qfigures(WEF) as an arithmeticaverage ofthe evaluationfigures fortheacute toxicitaygainstbacteria,algae,water fleaand fish. 2)The resultincglassificatiionntowater endangerin_qcategories(WEC Foam extinguishingagent Evaluationfiguresforthe acute toxicitaygainst p Bacteria Algae a..atmyfiskl 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 4.1 N/A 4.7 4.1 4.5 4.0 4.9 4.0 4.5 4.0 4.7 4.0 4.3 2.7 4.5 3.0 4.1 2.9 4.1 2.8 3.5 2.7 3.6 3.2 2.4 2.3. 2.4 2.0 2.7 2.0 5.0 5.2 4.9 4.9 4.8 4.4 4.3 4.2 3.9 3.7 3.7 3.5 3.3 3.0 2.72.6" Investigatfoofntsoxiecffect.s....i.nthewastewater Page 15 4.6.3Under the pressureofthegeneralactiveenvironmentalconsciousness,the questiondiscussedtodate is: Should classificatioonfthe substance concentrate intoa water endangering category be based on acute toxicittyo the most sensitivemember of a food chain? Shouldthis bethe case,the categorizationofthe 16foam extinguishingagent concentrates presented inTable 7 intowater endangering categorieswould be the result. 4.7 The biochemical degradabilityofthe - mufti-rangefoam materialNo. I and - mufti-rangefoam agent No. 4 isnot sufficient. This factleads to a downgrading of the concentrates from the water endangering category 2 (see Table 6) to the water endangering category 3. Incase ofthe insufficientbliyochemicallydegradable film-formingfoam agent No. 3, the downgrading takes place from the water endangering category 1 (see Table 6) to the water endangering category 2. Table 7: 1)Determinationofwaterendangerin-qfigures(WEF) based on the evaluationfiguresforthe most sensitive group oftestorganisms. 2)The resultincglassificatiionntowaterendangering categories(WEC) Foam extinguishinaggent Evaluationfiguresforthe acutetoxicitaygainst Bacteria Algae D,c4oh-u-.- srii-alrcraytish 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 4.4. 4.0 3.6 3.2 47 45 4.1 4.9 4.9 4.3 4.5 2.4 4.5 3.5 4.7 4.1 2.4 4.1 3.6 2.7 4.1 4.0 N/A 4.3 4.0 2.7 4.0 2.3 3.0 2.7 4.0 2.9 2.0 2./8 3.2 2.0 Water endangering figure(WE 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 Investigatfoofntsodceffect.s....i.nthewastewater 5. Finaclonsiderations Presented Page 16 -dataoftheacutetoxicitoyftheapplicatiosnolutionsoffoam extinguishingagentstowaterorganisms -data concerning biochemicaldegradabilitoyffoam extinguishingagents - classificatiofn the testedfoam extinguishingagent concentratesintothe water endangering categoriesbase'd on o artthmeticaverages ofthe evaluationfiguresofthe actae toxicfties o evaluationfiguresofthe actae to)dcftietsothe most sensitiveorganism Ineach case have to be checked by the "Commission forEvaluationofWater Endangering Materials". The Commission willevaluatethe toxicitdyata establishedby the army and indicateifitshould be considered complete orinneed offurtherinvestigations. The examinationwillalsoprovidea determinationconcerningthe procedures used fortheclassfflcationoffoam extinguishinaggents intothe water endangering categories. Especialltyhe latterresultisofinteresittislikeltyoseta precedence thatcould affecthe commercial law ofthe European Community startingin1992.