Document 8OzzYjy5VvkGLg4RvYXybmx0d

AR6 - 2 % SUMMARY FOR WORK PERFORMED FOR THE GERMAN GOVERNMENT AGENCY FOR MILITARY TECHNOLOGY AND PROCUREMENT ON FIRE EXTINGUISHING FOAM COMPOUNDS FROM MULTIPLE COMPANIES TEST SUBSTANCE Identity: A mixture containing Perfluorooctanesuifonate, which may also be referred to as PFOS, FC-95, or as a component of FC-3017. (1Octanesulfonic acid) (CAS # 2795-39-3). Remarks: The 3M production lot number was not noted. The test sample is FC-3017, referred to in the report as FC-206 freeze protected. Current information indicates it is a mixture of 0.67% PFOS, 20% diethylene glycol butyl ether, 55.41% water, 21% ethylene glycol, 1.33% Hydroxy foamer, 1% sodium octyl sulfate, 0.5% polyoxyethylene monooctylphenyl ether, 0.04% sodium lauryl sulfate, and 0.05% tolyltraizole. The following summary applies to a study done by a third party (Dr. H. Heilman and D. Muller) for the German Government Agency For Military Technology and Procurement for purposes of comparing the environmental properties of foam extinguishing agents from multiple companies, including 3M's FC-3017. Data may not accurately reflect the environmental properties of die fluorochemical proportion of die test sample. STUDIES Zinc, iron, and copper content; surface tension; Chemical Oxygen Demand; 5-Day Biochemical Oxygen Demand; Toxicity to Fish (species not given); Toxicity to Water flea (Daphnia magna); Toxicity to Algae (species not given); Bacteria inhibition (species not given) Report date: 1977 METHODS: Chemical Oxygen Demand was measured using potassium permanganate and potassium dichromate. Biochemical Oxygen Demand evaluated using a Total Organic Carbon degradation test developed by the Bundesanstalt fur Gewsserkunde. Toxicity to Fish was evaluated according to the German standard process for water testing (DEV) L 15 Toxicity to Daphnia was evaluated according to the German standard process for water testing (DEV) L 11 002832 Toxicity to Algae was evaluated according to the German standard process for water testing (DEV) L 12 The method for evaluating bacterial inhibition was not described. RESULTS F is h L C 5o D a p h n ia E C 50 A lg a e E C 5o Bacteria inhibition B O D 21/C O D >ClPD R esult >1000 mg/L >250 mg/L >250 mg/L Inhibited Remarks: The above toxicity data did not have test duration information. DATA QUALITY Reliability: Klimisch ranking = 4. All study values come from a summary list only. No raw data or method documentation was available. The study summary failed to disclose duration of toxicity testing. It is not clear why such low biodegradability was observed when the products contain materials that are known to readily biodegrade. The sample purity was not properly characterized and the study lacks analytical confirmation of the amount of fluorochemical proportion in the solution. OTHER Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/27/00 002833 4 Dato TECHNICAL AWARENESS -z/i/Sn TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN (im portant - Whenever possible, attach a full copy o f the materia! you have abstracted.) C o n trib u to r .1 D ivisio n Fric A. Reiner Environmental Lab (EE & PC) L o catio n of O riginal 0 J o u r n a l B o o k P a te n t (P|ea S ^ c l f y ) G | r a l t R eference (e.g.. A u th o r, T itle , Issue D ate, V o lu m e , Page, e tc.): ar l p O Em ployee Num ber 47816 Dr. H. Heilman and D. Mul|pr, "Environmental Impact of Fire Extinguishing Foam Compounds." The study was carried out by the West German Department of Water Technology for the West German Agency for Military Technology and Procurement. (Translated by G. Dier.ssen, March 1, 1980). A li*itr;ici (givo yo u r o w n slant o n tho source d ocum o nt) This report compares the environmental acceptability of 6 AFFF Agents including FC 3017 (identified in the report as FC-20fP, freeze protected), FC-206, and FC-200. The researchers measured biodegradability, aquatic 'toxicity,. heavy metal concentration, and surface tension. The report recommends avoiding use of the 3M AFFF products since all were difficult to biodegrade, but the biodegradation results and their interpretation are questionable. Comparisons of BOD5 and COD showed that the 3M pro ducts were more readily degraded than the comp etitive products, yet the authors chose to give more credence to tests measuring dissolved total organic carbon (TOC) concentration over a 21 day period. These tests gave results that were inconsistent with the BOD results. In these tests 3M products inexplicably did not degrade. C o p y L iM (c o p ie s to be sent b y o rig in a to r) Items submitted on this fo rm are published in the 3 M Technical Awareness Gazette. 0 0 2 8 3 4 Compliment to Report of Bundesanstalt fr Gewsserkunde 10. April 1979 -Nlb/340.22/2596 BEST COPY AVAILABLE ~Environmental Impact of Fire Extinguishing foam Compound#. Study carried out for Bundesamt fur Wahrtachnik und Beschaffung (Government Agency For Military Technology and Procurement) Report: BA 111 1-E/B31E/70145/76066 of October 12 1977. Reporter: Obarregleruagarat Dr. J h Hallmann Oberregleruagsvet D. Mller Koblenz 1979 0 0 .2 8 3 5 Table of Contents 1. Introduction Page 3 2. Definition of Problem and Teak 4 3. Test Results 3.1 Physical- Chemical Taste. 3.2 Tests lor glocheelcsi Degradation 3.3 Toxicology Teats 5 3 -7 12 4. Evaluation of Results and Conclusion 15 5. Recommendations for Technical Ordering Specifications 18 6. Conclusion 19 Enclosures: Literature list Additions 002836 2- - BEST COPY AVAILABLE 1. INTRODUCTION For fir* extinguishing- foam compounds one can distinguish six application regions: 1. General application (local fire protection) 2. Solvent industry 3. Fighting of carfeenhydrlde fires for instance in refineries (closed systems) 4. Electrical equipment high voltage 5.1 Applications in airports. 6. Applications on ships. i In the present study it will appear that airport fires take on prefer i re^d importance (1). It is obvious, that a few seconds in time can make im ' portant difference for saving human lives, and that the question of <onvlcen mental endangering especially of waters and streams does assume some what less importance. But water safety need not be completely overlooked especi ally because most of the actually used fire extinguishing compounds ar used irT training. the Bundesanstalt fqr Gewsserkunde (Dept, of Watet Technology) ip 1975 got the task from the Minis terlums fur Ernahrung, Ian dyijrtschaft <pd Tnrstms (Ministry of Food Agriculture and Forestry of Nordrheln-Westfelen) to eval uate the impact of foam extinguishing compounds on the water quality. Thirty eight foam extinguishing compounds from 8 suppliers were evaluated chemically, physically and biochemically for possible endangering of water. Different brands did vary in degradation and toxicity. Especially the 5Z foam extlpf* guishing'solutions used can result in the following damage: :,VV '< '.Vn' ,V- <. >. - -3- - Poisoning of natural water purification (in streams) - Poisoning or damage to fish and fish food animals. - Reduction of oxygen contact by metabolic processes (surface or ground water) - Reduction of water quality by organic compounds (general) - Undesirable reduction processes in the groundswater. \ This report pas publicise# .!*,pacts d!4>eee4.*%i at|antionHii(|rt that parties involved, such as the manufacturers of foam extinguishing compounds and the authorities responsible for water purity. Among othersthese consid erations were taken into account in the DIN- standards. 2. DEFINITION OF PROBLEM AND TASK ;-t : After several discourses in 1977 between representatives of the Bundesamtes fur Wehrtechnik and Beschaffung and the Bundesanstalt fur Gewasserkunde (BFG), the B7G was authorized on Oct. 12, 1977 to carry out a ape#* d a l study. This study should only cover the products used by the Bundewehr (W. German military) and also products which are considered for possible new introduction. As a first objective the environmental influence of the following sin extinguishing compounds should be determined: 002838 -4- No Product 1 Fluor protein 2 Light Water, FC 206 (frost protected) 3 Light Water, FC 206 (normal) 4 Light Water, FC 200, (normal) 5 Protein Foe Aid 6 Expyrol F 15 Manufacturer Firm Dr. R Sthamer, Hamburg Firm 3 M, Neuss Firm 3 M, Neuss Fir 3 M, Neuss Fir Dr. R. Sthamer, Hamburg Firm Hoechst Ag, Frankfurt/Hoechst The two typos of Light-Water are offered as being "especially safe to the environment" (According to BWB). Light Water FC 200 is reported to be out of production, but should be evaluated for comparison. The test for environmental Impact should, if possible, be tested for 5Z solutions as used (for Light Water 6Z) and encompass the following parameters: - Surface tension activity -Toxicity - Biochemical degradation -Content of heavy metals - Flame point. The final report should also contain recoanendations for the technical procurement specifications (TL). The final report was scheduled for completion In Sept 1978. Due to* sickness of one of the investigators it was delayed for sons mpmths. 0^2839 -5- 3. TEST RESULTS 3.1 Physical- Chemical Tests The first test result gives the heavy natal content which was deter1) wined by X-ray fluorescence . Evaluating the figures of Table 1 listing the heavy aetal content, the two compounds Fluorprotein (No 1) and Protein foam- compound (No 5) stood out. For fluorprotein the sine sad iron content of the appliciaation solution (mixtures) with 40 end 55 ng/1 respectively, is relatively high, For the second compound the iron content of 50 mg/1 stands out. All other heavy metal concentrations such as the especially recorded levels for copper are unimportant. Table 1 Heavy metal content in foam extinguishing compound*. No. C'riginal Products Zn Fe Cu PP* '0 too < i 2 7 t + t 3 u 5 6 1 *3 * 2 0. **0 M <1 3 *1 5 In 0 M 0,4 0,1 0,1 0,* 1) Determined by Dipl. Chea. U. Schleichert Solutions Fe cu C/l 15 0,4 0. 0,4 50 0,5 0,02 0,02 0,02 0,02 0,02 0,02 !:i! *:tVV *~----- iii. f 002840 -6- When the flame point la determined, the water content of the sample o must be considered. Flame points above 100 C, the boiling point of water, 2) could not be determined. As could be expected none of the tested samples o did have a flame point below 100 C. It should be obvious that none of the products would contain flammable sblvents. 3) The surface, or Interphase tensions can be seen from Table 2. The surface tension water/air generally drops some for concentrations from 50 mg/1 to 500 mg/1. The surface tension is least effected for No5 (frotein-foam extinguisher), most effected for two Light-Water types of FC'206- type. The reason for this la found In the chemical composition of the extlgulshlng compounds. Protein foam agents can be expected to be generally inactive to the water/air Interphase} while tensides and also so called "synthetic,,pro- ducts are Interphase active. The Interphase activity is less a product specific, but rather a group specific characteristic. Table ? Interebars activity No. Interph ire activity at 2oC ( dyn/cm) 5 100 250 500 ^/1 l a St ss ft tft so 4t It ftft 15 21 St 10 22 ft) a H tft t! to sa If it 2) Determined according to Abel-Pensky in closed vessel; DIN 51 755, Ed. 966 3) Interphase- Tensiometer, according to Nooy, firm. A. Kroas, Hamburg 002841 -7 3.2 Test for Biochemical Degradation To evaluate the water polution characteristics of compounds, it is of (2ft cS<^ ***h*. ck/iKi interest to sum up the chemical parameters, potassium permanganate and C-.o0} 6*0S potassium dichromate uptake, (CSB). The biochemical oxygen uptake (BSB , coo 5 H5 of DSV (4)) can be used especially in combination with CSB to prelimlnar- c<>0 ily evaluate the degradation. When the CSB analytical tent gives reliable results (this* for Instance, is not always true when hydoophoblc compounds r - are being tasted) oaa mat consider positive result derived from the QSB/BSBy r*|io as useful, while negative results can not be counted, since the 5 day .' '6*0 :u incubation period for the BSB-test under same conditions does not encompass sufficient tine for adaptation of the organisms active in the biological . t ` breakdown. It is not certain that toxic inhibitions can be excluded in the , 'f standard BSB (5). To better Insure results concerning the degradatlc^ thgitA is possible by evaluating the CSB/BSB ratio, one must carry out extensive ' :`\1 degradation tests, where the incubation time, the inoculation material and other parameters are determined, so that further breakdown than for the five day BSB'test can be evaluated. At present there are international efforts: underway to Standardise d^i f*1 sradatlon testa. For this Investigation of breakdown of fire extlnsuishinf v -----------------------.-------------------------------- ----------------------------- ---------- ----------------------------------- - foam compounds a new T.O.C.-degradation test (6) developed by the Bundesanstelt fur Cewasserkunde was used. Its test criteria is the complete breakdown of _' i' ;i the total organic carbon (TOC). 'For the test procedure the test compound serves as the only source *of carbon. Inorganic mineral salts are added in advance. The incubation takes place in a screw-cap flask with air space, placed in a shaker, the degrada- r tn ' /0 tion tests for the fire extinguishing foam compounds were carried out at 20 C k in the dark, in deviation from the steted test procedures. i" BEST COPY AVAILABLE -8- When the percentage breakdown according to the TOC-test is compared to results from ocher degradation tests, it must be taken into account, that the disappearance of one material from the solution is often considered as de gradation. Under ceraln circumstances a high degradation can be simulated which actually is based upon physical processes such as>for instance^absorp tion of solids which has no relation to complete biological breakdown and . i ' ' ** *' 'r mineralisation. '\ According to the experiences gathered by participation in a round test. |e TC results for completely soluble compounds are somewhat lower than v '-.Vh v ;j-`- _ when the breakdown is measured by the "modified OECD-Spresning test" (?). This "modified OECD -screening test" was tested by international round tests. It'has some disadvantages oompanedto tfae>^KIC.'degradation*test^sdd<c*n i ' - * i. used for testing of emulsions and suspensions. Since the products tested here are mixtures the results Sf the degrad- ation test is only well defined when a total breakdown is recorded. In cases where particle breakdown is observed, this can be due to the fact that only part of the product can be broken down, while other parts can not. The breakdown of mixture can then be manipulated by the manufacturer by addition ~ ... ............- i ' of compounds which are easily broken down,but otherwise without function. Even though, it is useful to test the breakdown of the present mixture products;because it gives a preliminary ranking of the products. For future tests, which could be carried out after a period of a few years of use, it' should he attempted to test the breakdown of the single components of the - products. (0Q243 -9- BEST COPY AVAILABLE RESULTS: Table 3 does list the measurement results obtained for the orglnal products, to evaluate the potential for endangering of the water. Table 4 H a t s the percentage of degradation of the application solutions after a period S' of 2 days together with other degradation parameters of Interest. The specific TOC- degradation curves are Incorporated In attachments 1-6. The values obtained frost Table 3 show that the different products contain varying amounts of organic compounds. Ofcourse one should count a low content of organic materials and of organic carbon found in products 1,4 and 5 as positive factors when water endangering Is to be judged. roO For the application solutions (table 4) the CSB and BSB^ are listed to gether with the ratio between these two factors and can be used in addition to the TOC- degradation results forrthe evaluations. According to the ratio r the product No 6 should be considered easy to degrade. For the products 1 ' and 5, which according to the TOC- degradation test appegr medium degradable (as also established from the metabolism test), the unfavorable CBS/BSBy ratio could possibly be due to the chemical oxidation of iron salts present in the products. The Iron salts would Increase the CSB without increasing " -- the BSB,. The degradation of each product, separately, la evaluated as follows: Foam extinguishing compound r 1 shows a favorable ratio of KMnO, conaunp- * tion/ KjCrjOy consumption, and shows good bacteria action in the metabolism test, together with a 47Z TOC- degradation. It must be rated as medium degradable i; ' ^ Product Mo 2 shows a favorable CSB/BSB^ - ratio, but since the other tests ; v Y~ do not indicate a good degradation rate it is classified as difficult to degrade. ^ life degradation of product 3 is even less than that of product 2, so it is classified as difficult to degrade. 002844 Even though the degradation during the TOC-test was further advanced v- . -XO- BEST COPY AVAILABLE Potential for endangcLrin of waters by original products No KKnO. 4 used K 2 Cr07 used Org.C content V Oontent a) Organic part b) kft/J kftM XX ft 3 o n Ft zt> fc Z o \ 0 ,20? f,125 1 0,098 2.438 3 0.089 4 o.ow 5 9,415 8 . 0 ,|0 1 " " 1,1 i n . n n i l l i l .il 1,9 f,t;i 2.31) 4iM ,) only approximate values 0,|5 0,24 0 ,2 2 0 ,2 0 0 ,0 o.n 89 52 u 00 4 8 0,7 44- - ` 2 1* 20 9 11 b) only approximate values, burnoff value* at 6ooC and variable duration Table 4 Biochemical degradation o t applioation ready e o l u U o n e (5ft) No Rate of ! M n 0 4 (m. XgCrO^V * 305 w5 5 . rbrf* 8 Oj/i fg Oj/t g Oj/l k `\ CSl Cj O Cl wo** /wfcn| f-t y *j j | f t - 100 4 5 6 & 1.000 2.100 2. SOflftU**) 28 1004 2 iOO(Mfr)24.t80r r.250 U.lOO MOO 20.000 2.100 98.000 4.01i 5.000 10.000 4.410 9.210 41.OOO 1. 0,1 ,> 0 .1 MM ! o.l 8, 0,2 0,0 ,1 Degrad. Degrad. in in ethabol . TOO test teat Final eval. *) 47 medium 8 difficult 8 difficult 12'm difficult 17 medium 82 eaey to | jiedium x) Evaluation of bioohemioal degradation in TOC- test (at Standard ' temperature of 250) ^ o - 2o difficult to degrade 2o - 4o H slightly degradable 4o - 75 1* ediua degradable 75 - loo very degradable 002S45. - . ' - l .'4 BEST COPY available for product 4 than for products 2 and 3, It was classified as difficult to degrade. For fire extinguishing foam compound 5, the metabolism test indicates that it can be broken down. A finding which is confirmed by the results of the TOC- test. The product is classified as medium degradable. For product 6 one finds a complicated degradation bel|evior which might originate from the high toxic effect of this product. After 7 days degrade.* tion already 10Z of the TOC is broken down. Further degradation does resultai, only after 14 testing days* but than an intensive degradation leading to b***!*- ` down of 60Z of the starting TOC does take place* The slow down in breakdown after 7 test days can be evaluated as an adaptation period for the micro organism involved. 3.3 Toxicology testing METHOD In the "Evaluation of the Water Endangering by Foam Extinguishing Compounds" (2), the results concerning toxic effects towards algae and bacteria were discussed. In this evaluation which is concerned with tests for products that possibly could be used in large amounts, the toxicology teate were iAtendlfidd. In addition to the Incorporation- metabolism tests, also tests with small crabs and fish were carried out. This way the previous results could be further confirmed. The toxicolgy test is carried out according to the German standard pro cess for water testing (DEV) (4) L 11, L 12, and L 15. For thsaS|the latest pest procedures were used as published by the responsible working conmittee* . For fish-tests the concentrations used vers from 0 to 10,000 mg/1, where 002846 -12- BEST COPY AVAILABLE a large grauatlon of dilutions was used. The further toxological test were carried out with saaller gradations from 0 to 210 mg/1 to .insure, that the products could be differentiated as well as possible. RESULTS: In the enclosures 1 to 6, the results of the toxicology test* ere. presented as dose- reaction curves end the results ere calculeted end presented JLn Table 5* , Product Ho 1, "Fluorschaumgeist (Enclosure 1) la so toxic at concentrations ^ of 10,000 ng/1 that ell test animals did die (EC 10000 mg/1). But for 100 th concentration 1000 mg/l the product is not detrimental (EC. 1000 ng/1)* 0' ( E O effective concentration with respect to the corresponding test. E C is too the lowest tested concentration for which a 100Z result with respect to the teat criteria is recorded. For the fish test, this is the concentration at which all animals die; ECq is the highest tested concentration at which no significant reaction is observed with respect to the test criteria). Towards the small crab, Daphnie magna (water flse)j the product is not detrimental at the highest concentrations tested (ECq** 250 mg/1) * The photosynthesis activity of algae is easily effected by Fluorschaum- geist. The affect is still below the critical limit at concentration of 50 ng/1; but at 100 mg/1 it is significant. i v The bacteria oxygen uptake during break down of peptone is Increased by the product. This makes the biochemical break down of the product itself plausible i >. >* This result is also confirmed by the TOC - degradation test (sec. 3.2). The product Ho2, Light Water, FC 206. frost-insured (enclosure 2), reacts similar to product Ho 1 in the fish and daphnie tests. Also the result of the Incorporation test is similar to the first product. But the inhibition of the photosyntheais activity is less and beconss significant only at, the highest concentration 250 mg/'11.. \^TTbhe result of the Mtabollsn rstsr|es|;:>'ie' b e s t c o p y a v a il a b l e definitely different than for the first product: There is no methabolic Increase which could be Interpreted as a sign of break down. The TOC degradation test also does show a break down of less than 10Z. The results of the biological tests carried out concerning product No. 3 "bight Water. FC '206. normal," are nearly lndentlcal to the results obtained for product No. 2 Light Water* frost protected. The only difference la; that the toxic effects towards algae Indicated for product 2 are not fpuad for product So. 3. Product No. 4 "Light Water, FC 200, normal," is different from the /'> foae agents discussed previously by having a definite toxic effect towards fish, S M l f crabe and algae. For flah the teat animals die already at 1000 ng/1 (ECq - 100 mg/1, EC10o 10Cpmg/l). In the daphne test, 33Z of the animals died within 24 hours at 100 mg/1, at 250 mg/1 about 75Z of the animals died (EC^ 50 mg/1, EC^q q 500 mg/1). The -incorporation test for this product is already surpassed at concen trations of 5 mg/1; at 250 mg/1 a complete inhibition of algae activity Is recorded <ECQ 2 mg/1, EC 250 mg/1). Product No. 5, Protein Foam Ayent, in all biological tests is equhl to product NO. 1. No significant toxic effects were found towards algae at concentration of about 250 mg/1. For the methabollsm test an Increase in bacteria oxygen corporation waa recorded, but it was less than for product No. 1. The result of the methabollsm test corresponds to a relatively V ` positive .reaction towards the break down test. .' .I Product No. 6, Bxpyrol. is exceptionally high in toxicity and ifc delfp of break down. The toxicity against flah la as high as for product No. 4 (ECq 10Oag/l and EC10Q 1000 mg/1). For small crab this product is .1A' '-V- \\ t. 6vk``'-UiP-i-0 2 848: ';> i : i -14- BEST COPY A VAILA BLE especially toxic (ECQ - 25 mg/1 and EC100 - 500 mg/1). The Incorporation test shows an inhibition at 10%concentrations above 10 mg/1. For 250 *g/l there is a 65% inhibition. The metabolism curve of this product indicates that it contains meta bolic active as well as toxic compounds. Table 5 Results of toxicology test ( expressed in order of poison classes) No ?ish Daphne Algae Bacteria (DEVL 12) Total (DE'/L 15) (DSV1 11) (DEVL 12) inhibit. enhance. evaluation x) 1 III 1 111 5 ni k 11 5 in 6 11 111 III III II HI IT u Il/Ill 111 l 1X1 11 in in 111 in in 111 II/llI - III III - 2 . 0 6 - i/n in n Poison class 1 : Proven inhibition on tost, animals at concentrations be! ov/ 5 mg/ 1 Pointi c'ass 11 s As in lj region 5 to ?oo mg/l Poison class 111! No damugo at concentrations below 25p tng/l 'Total evaluations Calculated by weighted avarage. The test result with lowest critical limit of concentration is multiplied by 5 . 4. Evaluation of Results and Conclusions Summarizing the single criteria of the test, one can obtain differentresults, depending upon what importance is given to the different criteria. The original products constitute a threat to biological systems such as the life in streams and biological systems of purification plants, due to their high toxic level to which |he surface tension, and for product 1, 002849 BEST COPY AVAILABLE -15- the content of zinc Is added. The drinking water supply could be endangered by the content of just the organic material In the original compounds. Also the application strength 5-6 X solutions of all products tested can lead to danger for biological systems due to their physical, chemical and toxic characteristics. \ By the further dilution by e factor of 20 to 80, which is active in the application of foam flre-extingulshingcompodads efcfr-tbxic l e v a l o f a t n c < 2 ng/1 for bacteria 10 - 25 mg/1 for fish) ~ie not exceeded and also I the surface tension activity can loose its Importance. It then seems reasonable to evaluate the water danger by the products according to their toxicity at the concentrations which can be reached during application, and according to their biochemical degradation, even though there L, at present are only degradation results available for the finished mixed pro ducts. For none of the compounds the degradation Is so easy as Ct> classify them as envlromentally friendly compounds. In the selection one then must differ entiate relatively better products from relatively worse products. When fire-extinguishing foam compounds are applied, the about 5 X aolu- -glons areas previously stated diluted by a factor of 20 to 80. They then are in a region of concentration between 125 to 500 mg/1. At this concen- ec zo 6 ------------- tration the compounds of product Ho. 3 and No. 5 are without acute detriment ~~ fc ~ : to the test organism. Product No. 1 and No. 2 leas their toxic effect ' after further dilution by a factor of 2 to 5. Such dilution is to be ex pected in the pre-flood teak of the purification systems. For the very u toxic products No. 4 and No. 6, am^Addltional dilution by a factor of -* * between 50 and 200 Is necessary to get below the toxic level. Sueh dilutions ! ' -^ t *.-n 0O2S5G, BEST COPY AVAILABLE -16- are not certain in practice. Product No. 4 shows in. addition a low degree of degradation and should not be used for that reason. The products 2 and 3 are of little concern when toxic properties are taken into account. But both products are difficult to degrade and could thus disturb and impair the drinking water supplyj and the use of these pro- ducts therefore should be avoided. Of the remaining products the foaai compound N o . l has . telltirelpi high M s i e level towards algae due to the high'content of ilnc. Jut since theta properties are lost to a large extent due to the dilution during v **... usage, and since the product is relatively easy to degrade, the endangering of the waters due to this product appears to be of little importance. The grouping of the 6 products proposed here does take biological and chemical results into account, but dOes not consider application technical characteristics. If it lh not possible,due to application technical,reasons to avoid the use of products which are difficult to degrade or are especially toxic, then it would be advisable to test their alnfle components for de gradation and toxic effects. Further it should be attempted to replace components especially biologically damaging by less damaging materials of similar effect. tUch approach has been successful for other materials of environmental concern. 1 5. Reconmendations for technical ordering specifications Based upon the investigations as discussed*' the fallowing require- ments can be made of the manufacture of foam fire-extinguishing compounds: (^The biological degradation characteristics of the organic components present in foam compounds should be well established .j The break down should be as easy as possible, right now it is considered -17- BEST COPY AVAILABLE as fair, when a 50 Z break down la recorded la the modified OgCB-Scrsordng- Test (7). For a teac which records complete chemical degradation such as the TOC-degradation test (6), a 40 Z break down shopld be the ain-fsHTM required. Other tests can be used in replacement of the abovementioned, If it has been proven, that equal results are obtained as for the tests according to (6) and (7), when these products are tested. The toxic effects of the fosa compounds towards water orgadlsm, especially bacteria, algae* s^l^erabs and fish should be a~s small as possible* A sufficiently nontoxic range can be set if the BC^q for bacteria* algae* daphne and fish is above 1500 mg/1 foam agent In water. For toxicology test, L 11, L 12, and Li 15 of DEV (4), or stellar procedure for which equal type results can be proven, are to be used. : - -i The heavy metal content should not exceed 1 Z sine, or fop other metal an amount for which a corresponding degree of bacteria toxic effects is i recorded. , 6. Conclusion rAccording to the task the following six foam compounds, determinad by the "Bundesamt fur Wehrtechnlk und Beachaffung" in Koblenz,wars evaluated l/ with' relation to possible endangering of waters: FloQtrproteln; Light Water : fC FC 206* normal; Light Water FC 206, Frost protected;Light Water FC 20Q, normal; ProtelnsOhaummittel; Expyrol F 15. The test includes Interphase activity, - h; -. toxicology* biochemical degradation, heavy metal content and flame point.- The results were presented and discussed and a coneluslon reached. The . . V-t - products Fluorprotein a n d 'Proteinschaumalttel were recommended doe to - relatively favorable biologic characteristics. The final conclusions',sms* given as recommendations for technical delivery terms (TL) to be used by the contract agency. :M)02SS2 -18- LITERATURE LIST (1) Fiala, R.: Study "Mittelschaum fr Flugzeugbrandbekampfung" Deutsche Forschung*- und Verschsanstalt fr Luftund Raumfahrt a.V., Koln-Wahn 1977, (2) Bundaaanatalt fr Gewsserkunde: Gutachten-ber die Wassergefahrllchkeit von Schaumloschaitteln, Koblenz 1975* (3) Hellmann, H.: Schaumlschmittel - ihre mgliche Wassergefahrdung, Tenside Detergents 13 (1976), 270 - 273. (4) Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung. Weinheim, Erganzungslleferung 1972. (5) Zahn, R. und H. Wellens: Ein einfaches Verfahren zur Prfung der biologischen Abbaubarkeit von Produkten und Abwas serinhaltsstoffen. Chemiker Zeitung 8 (1974), 228- 232. (6) Mller, D. und T. Tittizer: Der TOC-Abbautest - ein Verfahren zur Prfung von organischen Substanzen auf voll 12stndigen biologischen Abbau. Zeitschrift fr Wasser- und Abwasserforschung (1979), 14-21. (7) Fischer, W.K.: Meverfahren zur Bestimmung der biologischer Abbaubarkeit von wasserlslichen, organischen Umweltchemikalien mit Khlenstoffahalytik (DOC) (Modlfied OECD Screening Test). A manuseript ox the ferm Henkel KG Onsfeldorf * sent to the E.G. as recommended process. (21, 2. 1978). Enclosures Toxicology - concertration/reaction curves and degradation curves. 1 to*6. 002853 Nr. 1 Ftuorprotein I 100 80 60 40 c aaC>ij 20 tn o c 0 >20 TOXICOLOGY T3ST A= Incorporation test DiiVL 12 D= Daphne tort DiiVL 11 Z= Methaholism tort D:-'.VT, 12 F= Pish tort DiiVI, lr) so- LTT^.Tfe -d > -40 oc -60 -P -80 M -100 H 10 25 50 100 250 1000 10000 002854 TOC in o o initial TOC Inhibition in Increase in Increase in Inhibition in fi Nr. 3 Light w ater, FC 206, normal 100 T T 80 TOXICOLOGY TUST A= Incorporation test Di)VL 12 Z Ivlethaholif-m test DKVL 1 ? 60 D Daphne tort DKVL 11 P- Pish tcc-.t DKVL lr) 40 20 0i 20 -40 * 60 80 100 100 i 2EE 10 25 50 100 250 1000 10000 Concentration mg/t 80 O O Eh fHlj -P 60 Ci O 40 c Oo e Z'i \ Test1of TOC- degradation 0 7 . 14 2 S / f f t 7 *7 s r t O & f 002856 TOC in % of initial TOC Inhibition in % Increase in Nr. 5 Proteinschaummittel 00 TOC in fo of initial TOC Inhibition in $ GD O) Ni Increase in $ NJ i" O) CD CD Nr. 6 Expyrol F15 maooi I