Document La1wpN5ZBx6QV87JZEOBkwY3

Aka&& _ 073? SUMMARY FOR WORK PERFORMED BY THE GERMAN ARMY ON FOAM EXTINGUISHING AGENTS MANUFACTURED BY MULTIPLE COMPANIES TEST SUBSTANCE_______________________________________________ Identity: A mixture containing perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-203. (1-Octanesulfonic acid) (CAS # 2795-39-3). Remarks: The test sample is FC-203. Current information indicates it is a mixture of 1.34% PFOS, 35% diethylene glycol butyl ether, 37.85% water, 20% ethylene glycol, 2.66 % Sultone foamer, 3% sodium octyl sulfate, 0.1% sodium lauryl sulfate, and 0.05% tolyltriazole. The following summary applies to a study done by the German Army for purposes of comparing the environmentatproperties o f foam extinguishing agents from multiple companies, including 3M's FC203. Data may not accurately reflect the environmental properties o f die the fluorochemical component in the test sample. STUDIES________________________________________________________ 10, 20, and 30 minute ECso for Photobacterium phosphoreum (MicrotoxTM), 72-hour EC50 for growth inhibition of Fresh W ater Algae (Scenedesmus subspicatus), 24-hour EC50 for Daphnia magna, 48-hour LC50 to zebra barbling (Brachydanio rerio), Chemical Oxygen Demand and 5-day Biochemical Oxygen Demand METHODS:__________________________ ____________ ________________ Microbics Microtox "BASIC" Procedure Algae growth inhibition per EPA guidelines dated 05-06-1982 Daphnia toxicity according to DIN 38412, Part 11 Zebra barbling toxicity according to DIN 38412, Part 15 RESULTS________________________________________________________ Report Date: 3/29/90 The EC50 for Photobacterium phosporeum was 2500 ppm. It is not clear if this is for the 10, 20, or 30 minute exposure. 000786 The 72-hour E C Growth Inhibition for Scenedesmus subspicatus was 160 ppm. The 24-hour E C for Daphnia magna was 430 ppm. The 48-hour LC for Zebra barbling (Brachydanio rerio) was 1634 ppm. The Chemical Oxygen Demand (COD) was 41,200 mg O2 / L The 5-Day Biochemical Oxygen Demand (BOD5) was 21,500 mg O2 / L DATA QUALITY__________________ _________________ _ __________ Reliability: Klimisch ranking = 4. All study values come from a summary list only. No raw data or method documentation was available. OTHER__________________________________ ________________________ Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/26/00 000787 Q-t/> <>. Investigations of toxic effects and biological degradability of foam extinguishing agents in the waste water by Ekkehard Ising 000788 Investigations o f toxic effects......... in the wastewater 1. Introduction Page 2 On April 15,1985, the Federal Minister for Internal Affairs Introduced a revised and expanded version of the Index of W ater Endangering M aterials *) The Index lists the most important chemical compounds available on the market and divides them into four water endangering categories (W EC) according to their w ater endangering potential: WEC 3 WEC 2 WEC 1 WEC 0 very harmful materials harmful materials mildly harmful m aterials generally harmless m aterials All chemical materials not yet listed in the catalogue, are considered w ater endangering until the authorized Subcommittee fo r "Storage and Transportation o f Water Endangering Materials" at the Federal M inistry for InternalAffairs has decided about their classification. In case of mixtures of materials, the incorporation into a w ater endangering category is decided according to the data measured on the mixture itself. At the focus of the evaluation of a m aterial regarding its endangering potential for the organisms living in water or using it - e.g. as a food - is its acute toxicity, especially for bacteria, algae, small crayfish, fish and mammals. Tests on aquatic organisms (bioassays) are included am ong the procedures prescribed by the legislature for water and w aste w ater evaluation. It is generally accepted: 1. Principally, bioassays cannot be replaced by the chemical analysis. 2. Bioassays on the one hand and chem ical/physical procedures on the other, complement each other (see am ong others: Germ an Unified Procedures for W ater, W aste W ater and Sludge Examination, DIN 38412). *) GMBI, Issue A, 36 No. 11 (1985), pages 173-252 000789 Investigations of toxic effects......... in the wastewater During the evaluation of the effects of Page 3 - chemical parameters, e.g. toxic m aterials contained in w ater and - physical parameters, e.g. supply of energy, w ater extraction the attention should be paid to the use of prescribed test organisms and to the conform ance to standard test conditions. The reproducibility and statistical validity of the results should be secured. The following types of test organism s should be used in standardized bioassays in w ater and waste water: - bacteria as chem oheterotrophs - algae as primary producers - protozoans as single primary and secondary consumers - small crayfish as multicell consumers - fish as multicell consumers with a central nervous system. At the sam e tim e, they are th e final members in the aquatic food chains and collect persistent chemicals in their tissues. Additionally, certain saprobic systems can be used in biotests as models of com plete ecosystems. Particularly microcosms and activated sludge systems consisting of various bacteria, fungi, protozo ans and worms. 2. Problem definition According to the definitions in w ater supply law and w aste w ater handling law including pertinent implementation procedures, th e Federal defense forces are frequently quoted as the cause of harmful materials discharges to waters and communal w aste w ater treatm ent plants. Particularly during, e.g. - use of extinguishing foams during trainings and actions - transportation and storage of foam agent concentrates considerable harm can be done to surface and ground waters. 000790 Investigations o f toxic effects......... in the wastewater Page 4 To evaluate the danger potential of th e foam concentrates not vet classified in the w ater endangering categories, their examination and m ilitary-internal tem porary classification into w ater endangering classes is necessary. The Federal Office for D efense Technology and Acquisition in Koblenz, has authorized the defense scientific Service Office of the Federal Army to conduct the necessary research and the subsequent tem porary Arm y-internal W EC classification. The research, leading to establishing w ater endangering categories of foam extinguishing agent concentrates, produces at the sam e tim e values of acute organism toxicities of the, mostly 3%, application solutions. 3- Foam extinguishing agents and their bioassavs 3.1 Total of 16 foam extinguishing agents representing 5 different kinds of foam agents were compara tively evaluated in bioassays (see 3.2) regarding acute toxicity of their application solutions to water organisms and subdivided into w ater endangering categories from the point of view of their concen trates. In particular: - 5 multi-range foam agents - 6 film-forming foam agents - 3 protein foam agents -1 film-forming fuorine-protein foam agent -1 special foam agent for deep-fry pan fires The formulations of the foam extinguishing agents are proprietary information and unavailable to the public. After consultations with m anufacturers, th e following m aterials can be listed as toxic compo nents: - organic surfactants - glycols (e.g. ethylenglycol, butyldiglycol) - preservatives - organic solvents - organic acids - inorganic salts 000791 Investigations o f toxic effects.........in the wastewater Page 5 Presented test results are new and not yet revealed to the m anufacturer com panies. Therefore, product names cannot be published here. Hence, the result tables will have the product names substituted by class descriptions including running item number. 3.2 Listing of the bioassay used (short description of each test with the following result table - see 4.5 through 4.5). 3.2.1 Bioluminescence inhibition test with Photobacteria Phosphoreum in microtox analyzer, model 2055 (Beckman Co.) 3.2.2 Algae growth inhibition test according to the test guidelines of federal EPA dated 05-06-1982. 3.2.3 Daphnia short test according to DIN 38412, Part 11. 3.2.4 Fish test according to DIN 38412, Part 15. 3.2.5 Determination of the biochemical oxygen demand by the application solutions and their dilutions with w ater during 5 consecutive days (BOD 5). Apparatus: Saprom at B12, Voith Co. In comparison to BOD 5, the measurement included: chemical oxygen demand of the application solutions and their dilutions (COD). Apparatus: Dr. Lange digital photometer L P 1 W. 4. Results The results will be described in the following (chapter 4.1 to 4.7) in the form of tables with associated text. 000792 Investigations o f toxic effects......... in the wastewater Page 6 4.1 The biolum inescence inhibition test with Photobacteria Phosphoreum in microtox analyzer, model 2055 by Beckman Co. 4.1.1 Short description of the test The test organism Photobacteria Phosphoreum is a marine bacteria This kind of bacteria is present in immense quantities in the sea layers close to the surface and causes the so called marine phosphorescence. The underlying chemical process is a luciferine-luciferase process. D am ages to the Photobacteria, e.g. due to intoxications, result in the inhibition of the luciferine-luciferase activity. The end effect is the reduction of the light emission. This, in itself very simple, principle is used in the microtox analyzer: A light-transparent glass cell is placed in a light-tight measurement head. The glass cell contains 1 ml of a suspension with Photobacteria. The light em itted by the Photobacteria falls on a photoreceptor, is converted into electric energy, amplified, displayed and recorded. The light quantity emitted by a specim en of untreated bacteria is set in the display to the value of 90% . This quantity is tantamount to: "natural, uninhibited light emission". Specim en of equal quantity of bacteria and equal bacteria quality with toxic substances added respond with a reduction of the light emission. Accordingly, the display value lies between 90% and 0%. The 0% -value indicates that the photobacteria of the specimen treated in this way is not capable of light production any more. Fig. 1: Measurem ent arrangem ent of microtox analyzer 000793 Microtox- Analyzer: Measurement configuration Page 6a Printer 000794 Investigations o f toxic effects......... in the wastewater Page 7 4.1.2 The results of the biolum inescence inhibition test with Photobacteria Phosphoreum are assem bled in Table 1. In the first result column are th e effective concentrations of the 16 tested foam agents in p l/l of water leading to a 50% inhibition of the light emission by the light bacteria (= EC50). In the second result column are likewise effective concentrations leading to a 10% inhibition of the light emission (= EC10) and representing the so called toxicity thresholds of th e foam agents to the P h o to b a c te ria The negative decim al logarithms of individual EC10 result after multiplication by the factor of -1 in so called evaluation and endangering figures of the individual foam extinguishing agents to Photobacteria Phosphoreum (see result columns 4 and 5). According to the evaluation schem e of the "Commission for Evaluation of W ater Endangering M aterials", the determ ined evaluation and endangering figures (EE figures) indicate the following toxicity categories: EE figures of 6.0 and higher EE figures 4.0 to 5.9 EE figures 2.0 to 3.9 EE figures under 2.0 : Highly toxic to test organisms : Toxic to test organisms : Low toxicity to test organisms : Generally non-toxic to test organisms 000795 Table 1: Toxicity of foam extinguishing agents Page 7a Acute toxicities as EC 50* and EC10 ** to photbacterium phosphoreum (Photoluminescent bacteria). Criteria: Inhibition of the light power within 1 0 / 2 0 / 3 0 minutes (Classification of the foam agents according to decreasing toxicity) Foam agents (FA) Multirange FA Multirange FA Multirange FA Multirange FA Multirange FA No.2 No.1 No.4 No.5 No.3 EC50 in pl/l of water 6 7.5 15 25 25 EC10 in /Ltl/I and mg/kg of wat<3r Toxicity thres told pl/l mg/kg 0.6 0.61 0.9 0.92 1.7 1.79 1.7 1.75 6 6.0 negative decimal logarithm ofth eE C IO -6.215 -6.031 -5.747 -5.757 -5.222 Evaluation and endangering figures for photobacterium phosphoreum 6.2 6.0 5.7 5.8 5.2 Film forming FA Film forming FA Film forming FA Special FA Film forming FA No.2 No.6 No.1 No.5 2000 300 460 3000 2000 85 30 120 150 460 91 -4.041 32 -4.495 129 -3.889 216 -3.666 479 ; -3.320 4.0 4.5 3.9 3.7 3.2 FC-203 No.4 FC-20&6 No.3 Protein FA No.3 Protein FA No.1 Film forming 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 3.2 2.9 2.6 2.3 2.1 2.0 EC50 = Effective concentration of the foam extinguishing agent lowering the lightpower of the photobacteria by 50% EC10 = Effective concentration of the foam extinguishing agent lowering the lightpower of the photobacteria by 10% 000796 Investigations o f toxic effects.........in the wastewater Page 8 The following evaluation of the bacteria toxicity of the foam extinguishing agents can be concluded from these data: Highly toxic to Photobacteria are the m ultirange foam extinguishing agents No. 1 and 2. Toxic to photobacteria are the multirange foam extinguishing agents No. 3 ,4 and 5, as well as film forming foam agents No. 2 and 6. Low toxicity to photobacteria represent the film-forming foam agents No. 1 ,3 (F C -206,4 (FC-203) and 5, the three protein foam agents, the film-forming fluorine-protein foam agents as well as the special foam agent for deep-fry pan fires. 4.2 Algae multiplication inhibition test 4.2.1 The investigations of algae toxicity w ere conducted according to the assay guideline "Inhibition of the cell multiplication of green algae Scenedesm us Subspicatus CHO D" of the (German) Federal EPA dated 06.22.1982. Scenedesm us subspicatus is a single-cell autotrophic organism with vegetative multiplication. Stock cultures of algae were held in nourishment m edia according to the test guideline and transferred to a fresh medium once a week. Pre-cultures were set up 3 days before starting each assay to obtain cells in the exponential growth phase. The experiments were conducted as static tests, i.e. the tested substance was added once in the desired concentration at the beginning of the incubation. For each concentration and control 2 Erlenmeyer flasks with SO ml of nutritional solution w ere set up. The initial cell density was set to the value between 10,000 and 15,000 cells. The test cultures were shaken once a day. T h e cell concentration was determ ined on the day 0 ,3 ,4 and 7 by means of an electronic cell counting device. The cell numbers were used to plot the growth curves and to calculate the multiplication inhibition which takes into consideration days 0 ,3 and~4 according to the guideline. Day 7 was used for an after-observation. From the concentration-effect curves, the values of EC 10 and EC 50 were determined. 000737 Investigations of toxic effects.........in the wastewater Page 9 4.2.2 The results of algae growth inhibition assay using Scenedesm us Subspicatus w ere put together in Table 2. The table is built up according to the same scheme as table 1. The toxicity determ ination of individual foam agents for Scenedemus Subspicatus was conducted in the sam e way as that for photobacteria. All foam agents with the exception of two protein foam agents should be designated as toxic to Scenedem us Subspicatus. Both of the mentioned protein foam agents have only w eak toxicity to algae. The special foam agents for deep-fry pan fires can be considered a border case betw een toxic and weakly toxic agents. It is conspicuous that one protein foam agent which was only weakly toxic in relation to bacteria is in the upper range oftoxicity to algae, while one highly toxicto bacteria multi-range foam agent has been found in the mid-range of toxicity relative to algae. 000798 Table 2: Toxicity of foam extinguishing agents Acute toxicities as EC 50* and EC10 ** to scenedesmus subspicatus (Fresh water algae). Criteria: Inhibition of growth within 72 hours (Classification of the foam agents according to decreasing toxicity) Page 9a Foam agents (FA) EC50 in pl/l of water Multirange FA Film forming FA Multirange FA Multirange FA Film forming FA No.3 No.6 No.1 No.4 No.2 30 230 32 24 37 Protein FA Film forming FA Film forming FA Film forming FA Film forming FA No.2 No.3 FC-206 No.4 FC-203 No.5 No.1 225 160 160 105 355 Multirange FA No.2 Film forming fluorineprotein Special foaming agent Protein FA No.3 Protein FA No.1 68 80 105 435 6200 E C 10in p l/l.and mg/kg of water Toxicity thre! bold m 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 negative decimal logarithm o fth eE C IO -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 EC50 = Concentration inhibiting the growth by 50% after 72 hours EC10 = Concentration inhibiting the growth by 10% after 72 hours Evaluation and endangering figures for S. subspicatus 5.1 5.1 5.0 5.0 5.0 4.9 4.8 4.8 4.6 4.4 4.4 4.4 4.0 3.6 3.2 000799 Investigations o f toxic effects.........in the wastewater 4.3 Results of the Daphnia short-term assay Page 10 4.3.1 T est organisms in this case a 6 to 24-hours oid instar of Daphnia M agna. The toxic effect of substances contained in w ater on Daphnia M agna is measured as the solution level or concentration (ppm, ppb) of the tested substances in which, after testing, certain percentage of Daphnia becam e immobile (effective concentrations for 10% and 50% of the animals = EC10 and EC50). Test configuration In a 25 ml beaker flask, 5 ml of standard w ater (so called dilation water) were filled. Then, 2 old animals are put in left to themselves for 24 hours without food. After that tim e, the old animals are removed. The neonates released in the meantime, were counted and the evaporated w ater replenished. Now, 5 ml of the toxicant solution are added into the beaker glass. This results in the solution of 10 ml and therefore represents the first level of dilation of the tested substance in w ater. Further levels are obtained in the sam e way. To inhibit the natural swimming activity of the animals and to secure a possibly equal substance intake in all larvae, the test material is left in darkness for the next 24 hours; the counting of the still mobile instars follows thereafter. Control breed In parallel to each assay series, a determination of the EC10-value is conducted with the reference substance potassiumdichromate. The quantities used in this case are 0.9 -1 .9 mg/l of stock water. The test result is valid when less than 10% of Daphnia neonates becam e immobile in this control assay. ooosoo Investigations o f toxic effects......... in the wastewater Page 11 4.3 .2 The results of Daphnia short-term test are collected in Table 3. The configuration of the table again follows the scheme used in Table 1. Also the determ ination of the toxicity of individual foam agents to Daphnia is conducted just like in previous tests with Photobacteria and green algae. All m ulti-range foam agents, film-forming foam agents up to the running No. 3 and the special foam agent for deep-dty pan fires, are toxic to Daphnia Magna. The remaining foam agents, i.e. th e filmforming FA No. 3, the three protein FA and the film-forming fluorine-protein FA have low toxicity to D ap h n ia. Generally, the multi-range and the film-forming foam agents are less toxic to D aphnia than to the b a c te ria 000801 Table 3: Toxicity of foam extinguishing agents Acute toxicities as LC50* and LC10 ** to Daphnia Magna (W ater flea); Criteria: Loss of ability to swim within 24 hours (Classification of the foam agents according to decreasing toxicity) Page 11a Foam agents (FA) LC50 in pl/l of water LC10 in pl/l and mg/kg of water Toxicity thres hold pl/l mg/kg negative decim al logarithm o fth eL C IO Multirange FA Multirange FA Multirange FA Film forming FA Multirange FA No.3 No.4 No.2 No.1 No.1 75 58 75 600 120 12 13 20 20 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 Film forming FA No.4 FC-203 430 Film forming FA No.6 1500 Special foam agent 75 Multirange FA No.5 250 30 30 45 45 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 3000 Protein FA No.3 600 Film forming FA No.3 FC-206 2000 Protein FA No.1 7500 Protein FA No.2 Film forming fluorineprotein 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 LC50 = Concentration causing 50% immobility of the animals within the test period LC10 Concentration causing 10% immobility of the animals within the test period Evaluation and endangering figures for daphne magna 4.9 4.9 4.7 4.7 4.5 4.5 4.5 4.3 4.1 4.1 4.1 3.6 3.5 2.7 2.4 2.4 000802 Investigations of toxic effects......... in the wastewater 4.4 Results of the fish toxicity test Page 12 4.4.1 The investigation of the fish toxicity as well as fish holding and w ater quality w ere in agreem ent with the OECD guidelines. The zebra barblings (Brachydanio j<erio) had an average body length of 3.0 0.5 cm. The mortality during the last two weeks of the stock holding was 0%. The 0 2 content and pH of th e test solutions was determ ined at t = Oh, t = 48h and t = 96h (end of the experiment). During the experiment, there was no noticeable change ofthe 0 2 content. The pH ofthe test solutions was 7.8 0.2 at the beginning of the test. The food supply was suspended 24 hours before th e start ofth e test. The tem perature of the solution was 23C 0.5C with constant light aeration through a glass capillary and a light/dark cycle of 16/8 hours. In each concentration level, 10 fishes w ere put in th e 10 liter test solution in a 15 liter full glass bowl under static test conditions and the number of dead determ ined after 24, 48, 72 and 96 hours. Uncertainties during the experiment were recorded. The LCgo w ere calculated with a computer program according to Lichtfield and Wilcoxon 1949; LC0 and LC100 resulted directly from the test. 4.4.2 The results of the fish toxicity test are compiled in Table 4. The result representation and determination of the toxicity of individual foam agents to fish again follows the bacteria test (see 4.1.2). Clearly, toxic to fish are only multi-range foam agents No. 2 and 4. The remaining multi-range foam agents No. 1 and 3, as well as the film-forming foam agents No. 1 and 2 can be assigned to a toxic/ weakly toxic transition range. Weakly toxic to fish are the film-forming foam agents No. 3 (F C -206,4 (FC-203), 5 and 6, the protein foam agents No. 2 and 3, as well as the special foam agent for deep-fry fires. The film-forming foam agent No. 1 as well as the film-forming fluorine-protein foam agent are generally non-toxic to fish 000803 Table 4: Toxicity of foam extinguishing agents Acute toxicities as LC50* and LCO** (48 hours) to Brachydanio rerio (zebra barbling); Criteria: Mortality of the test animals within 48 hours (Classification of the foam agents according to decreasing toxicity) Page 12a Foam agents (FA) LC50 in /i|/l of water LC 0 in /jI/I arid mg/kg of water Toxicity thres hold negative decimal logarithm Evaluation and endangering figures for brachydanio rerio Multirange FA Multirange FA Multirange FA Film forming FA Film forming FA No.4 No.2 No.3 No.2 No.1 68 109 131 141 161 Multirange FA Protein FA Film forming FA Special FA Film forming FA No.1 173 No.3 1369 No.4 FC-203 1634 1880 No.3 FC-206 4086 Film forming FA No.5 Film forming FA No.6 Protein FA No.2 Film forming 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 1 -2.691 -2.682 -2.678 -2.270 -2 -2 LC50 = Highest tested concentration in mg/kg, at which 50 % of the test animals died LC 0 = Highest tested concentration in mg/kg, at which no test animals died 4.3 4.1 4.0 4.0 4.0 4.0 3.2 3.0 2.8 2.7 2.9 2.7 2.3 2 2 000804 Investigations o f toxic effects......... in the wastewater Page 13 4.5 Determ ination of biochemical degradability In Table 5, the figures of the chemical oxygen demand (COD) and the biochemical oxygen demand during the five consecutive days (BOD 5), expressed in mg 0 2 per liter of water, were collected for 3% application solutions of the foam agents. The level of the biochemical degradability of the tested substances can be sufficiently accurately determ ined from the ratio of COD to BOD 5. In an ideal case the COD to BOD 5 would be 1,: 1. Such ratio would describe an nearly quantitative biodegradation of a tested substance. Ratios of COD to BOD 5 of 1 : 0.5 signal an insufficient biochemical degradation. The values presented in Table 5 point to the insufficient biochemical degradation of the multi-range foam agents No. 1 and 4 as well as the film-forming agent No. 3 (FC-206). During the categorization of the concentrates of these foam agents into a water endangering category, the characteristics of insufficient biochemical degradability is considered as negative ("Malus") and resulted in assignment to the next higher water endangering category (see 4.7). 000805 Table 5: COD and BOD 5 of foam extinguishing agents Page 13a Foam extinguishing agent COD of the 3% solution in mg of O j/I of water Multirange foam agent No.1 No.2 No.3 No.4 No.5 43700 47400 40300 52800 30100 Film-forming foam agent 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-prot. FA Protein foam agent No.1 No.2 No.3 19600 15000 14100 17100 BOD5 of the 3% solution in mg of Og/I of water 17500 25900 30500 15200 25800 15700 23200 8700 21500 21100 -A*) 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 of biochemical degradability within 5 days insufficient probably insufficient sufficient insufficient sufficient sufficient sufficient insufficient probably insufficient sifficient sufficient sufficient sufficient sufficient Special foam agent 4600 no biochem. degr. N/A N/A O * ) ./. = not measured 00 Investigations o f toxic effects......... in the wastewater Page 14 4.6 Determination of the water endangering figures and classification of the tested foam extinguishing agent concentrates into w ater endangering categories. 4.6.1 As already explained in the introduction, the "Commission for Evaluation of W ater Endangering M aterials" considered the acute toxicity to selected test organisms as a primary criteria for classifica tion of a substance or a substance mixture into a water endangering category. A further important evaluation criteria was the biochem ical degradability of the substance or substance mixture under consideration. After consultations with some of the members of the "Commission for Evaluation of W ater Endanger ing Materials" regarding th e classification of 16 foam extinguishing agent concentrates, the determ i nation of the mammals toxicity (LD50 oral), has been waived. Instead, in addition to the prescribed consideration of the - acute bacteria toxicity and the - acute fish toxicity, the acute toxicities to - algae and - water flea were taken into consideration during the classification of the tested foam extinguishing agent concentrates into water endangering categories. 4.6.2 In Table 6, the evaluation figures of th e acute toxicities of the foam extinguishing agents to the test organisms, are presented in columns 2 through 5. According to the methods em ployed by the "Commission for Evaluation of W ater Endangering Materials", the arithmetic averages of the evalu ation figures result in the so called w ater endangering number (W EN) of the material under consideration (6th column). From the w ater endangering numbers determ ined in this way, the w ater endangering categories (W EC) are derived according to the following scheme: W EN 6 and higher W EN 4.0 to 5.9 W EN 2.0 tp 3.9 W EN 1.9 and lower - WEC 3 -W EC 2 -W EC 1 -WEC0 The classification of the tested foam extinguishing agent concentrates into the w ater endangering categories can be taken from th e last column of Table 6. 000807 000808 Table 6: 1) Determination of water endangering figures (WEF) as an arithmetic average of the evaluation figures for the acute toxicity against bacteria, algae, water flea and fish. 2) The resulting classification into water endangering categories (WEC Foam extinguishing agent Evaluation figures for the acute toxicity against Bacteria Algae 'p J ./p h A U J -' m att-crayfisb. Fish Multirange FA No. 4 5.7 5.0 Multirange FA No. 5 5.8 N/A Multirange FA No. 2 6.2 4.4 4.9 4.3 4.1 N/A 4.7 4.1 Multirange FA No. 1 Multirange FA No. 3 Film-forming FA No. 2 6.0 5.2 4.0 5.0 4.5 4.0 5.1 4.9 4.0 5.0 4.5 4.0 Film-forming FA No. 1 Film-forming FA No. 6 Film-forming FA No. 4 FC-203 3.9 4.5 3.2 4.4 4.7 4.0 5.1 4.3 2.7 4.8 4.5 3.0 Film-forming FA No. 5 Special FA Film-forming FA No. 3 FC-206 3.2 3.7 2.9 4.6 4.1 2.9 4.0 4.1 2.8 ' 4.8 3.5 2.7 Protein FA Protein FA No. 3 No. 2 2.6 2.0 3.6 3.6 3.2 4.9 2.4 2.3 Film-forming fluorine-protein Protein FA No. 1 2.1 2.3 4.4 2.4 2.0 3.2 2.7 2.0 W ater endangering figure (WEF) 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 2.7 2.6 Page 14a W ater endangering class (WEC) 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 1 Investigations o f toxic effects......... in the wastewater Page 15 4.6.3 Under the pressure of the general active environmental consciousness, the question discussed todate is: Should classification of the substance concentrate into a w ater endangering category be based on acute toxicity to the most sensitive member of a food chain? Should this be the case, the categorization ofthe 16 foam extinguishing agent concentrates presented in Table 7 into w ater endangering categories would be the result. 4.7 The biochem ical degradability of the - m ulti-range foam material No. 1 and - m ulti-range foam agent No. 4 is not sufficient This fact leads to a downgrading of the concentrates from the w ater endangering category 2 (see Table 6) to the w ater endangering category 3. In case of the insufficiently biochemically degradable film-forming foam agent No. 3, the downgrading takes place from the w ater endangering category 1 (see Table 6) to the water endangering category 2. 000809 Table 7: 1) Determination of water endangering figures (WEF) based on the evaluation figures for the most sensitive group of test organisms. 2) The resulting classification into water endangering categories (WEC) Page 15a, Foam extinguishing agent Evaluation f gures for the acut3toxicity against Bacteria Algae S m alrcrayfish Fish Multirange FA Multirange FA Multirange FA No. 2 No. 1 No. 5 6.2 6.0 5.8 Multirange FA No. 4 Multirange FA No. 3 Film-forming FA No. 6 5.7 5.2 4.5 Film-forming FA No. 2 Protein FA No. 2 Film-forming FA No. 4 FC-203 4.0 2.0 3.2 Film-forming FA No. 3 FC-206 Film-forming FA No. 1 Film-forming FA No. 5 2.9 3.9 3.2 Film-form, fluorine-protein Special FA 2.1 3.7 Protein FA Protein FA No. 3 No. 1 2.6 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 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 1 4.7 4.0 4.1 2.9 2.4 2.0 4.1 2./8 3.6 3.2 2.7 2.0 W ater 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 W ater endangering class (WEC) 3 3 2 2 2 2 2 2 2 2 2 2 2 2 1 1 000810 Investigations o f toxic effects......... in the wastewater 5. Final considerations Page 16 Presented - data ofthe acute toxicity ofth e application solutions of foam extinguishing agents to w ater organisms - data concerning biochemical degradability of foam extinguishing agents - classification of the tested foam extinguishing agent concentrates into th e w ater endangering categories based on o arithmetic averages of the evaluation figures of the acute toxicities o evaluation figures of th e acute toxicities to th e most sensitive organism in each case have to be checked by the "Commission for Evaluation of W ater Endangering Materials". The Commission will evaluate the toxicity data established by the army and indicate if it should be considered com plete or in need of further investigations. The examination will also provide a determ ination concerning the procedures used for the classifica tion of foam extinguishing agents into th e w ater endangering categories. Especially the latter result is of interest it is likely to set a precedence that could affect the commercial law of the European Community starting in 1992. 000811