Document MoKE8Y3v5VNVXm6jL070kBq8a

4 /U 6 - 0 6 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 Perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-200. (1-Octanesulfonic acid) (CAS # 2795-39-3). Remarks: The 3M production lot number was not noted. The test sample is FC-200, a product which was out of production prior to the date the study was conducted in 1977. Archived information indicates it was a mixture of 1.8% PFOS, 30.0% diethylene glycol butyl ether, 61.5% water, 2.7% Hydroxy foamer, 4.0% octylphenoxypolyethoxyethanol. 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 o f comparing the environmental properties o f foam extinguishing agents from multiple companies, including 3M's FC-200. Data may not accurately reflect the environmental properties of the test samples with that o f the fluorochemical proportion. 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 000135 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. R E S U L T S _________________________________________________ Fish LCso Daphnia EC Algae EC Bacteria inhibition BOD21/COD Results 100<LCso<1000 mg/L 50<ECso<250 mg/L 25<ECso<50 mg/L Inhibited -12% 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 dear 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. O T H E R _________________________________________________________ Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/27/00 000136 ltn |> TECHNICAL AWARENESS I TO': TECHNICAL COMMUNICATIONS CENTER - 201-2CN Dato (im portant - Whenever possible, attach a full copy o f the material you have abstracted.) C o n trib u to r / A /") D iv is io n F r i c A . R e i n e r t 1*- Environmental Lab (EE & PC) Journal Q Book Patent Location of Original 13 (P |,J ? s c ify > lralt rlpO cy rt Referanca (e g.. A u th o r. T itle , Issue D ata, V o lu m e , Peg, e tc .): Employee Num ber 47816 Dr. H. H e i l m a n a n d D. Muljpr, " E n v i r o n m e n t a l Impact of F i r e E x t i n g u i s h i n g Foam Compounds." The study was carried out by the West German Department of Water Technology for the West German Agency for Military Technology and P r o c u r e m e n t . ( T r a n s l a t e d b y G. D i e r s s e n , M a r c h 1, 1980). Abstract (giva your ow n slant o n the source d ocum ent) This report compares the environmental acceptability of 6 AFFF Agents including FC 3017 (identified in the report as FC-20$, freeze protected), FC-206, and FC-200. The researchers measured biodegradability, aquatic ' t oxicity, .h e a v y m e t a l c o n c e n t r a t i o n , a n d s u r f a c e tension. T h e rep o r t 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 competitive products, yet the a u t h o r s c h o s e to g i v e m o r e c r e d e n c e to t e s t s m e a s u r i n g d i s s o l v e d t o t a l 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. / I sIi I I C opy LiM (copie to be sunt by originator) 0 0 0 1 3 7Items submitted on this form re published in the 3M Technical Awareness Gazette. Conplinent to Report of Bundasanstalt fiir Gewaaserkunde 10. April 1979 ~Mlb/340.22/2596 BEST COPY AVAILABLt Study carried out ft>r Qimdeaaat fur Wehrtachnlk und fieschaffung (Governaent Agency For Military Technology and Frocureaent) Report: BA 111 1-E/B31E/70145/76066 of October 12 1977. .y>r*-Jv*;.1* -j\+ Reporter:' Oberregierungarat Dr.Ht Hallpaaa oberragieruagaratR. Hiller Koblens 1979 '-tVV'yVv; `X 'I t l l -1 - Table of Contenta 1. Introduction Page 3 2. Definition of Problem andTask 4 3. Teat Rsulta .3.1Pkyaleal- Chemical .' 3.2 Teat for gloclMNalcel D|rdetl4ii . 3.3 Toalceloty feet# 5 '3 . .7 U 4. Evaluation of Rsulta SadCnddslen ' i- *.***' iV''* .ri t .***- . 5. Raco-- ndations for Technical < Ordering Speciflestions t-T 6< Conclusion 15 18 19 Bndosurss: Literature list Additions BEST COPY AVAILABLE 1. INTRODUCTION For fir extinguishing- foam compounds one cen distinguish six application regions: 1. General application (local fire protection) 2. Solvent industry 3. Fighting of cargenhydride fires for instance in refineries (dosed sys|||i) 4 Electrical equipment High vdtsgs 3. Applications in airports. 6. Applications on ships* I In the p t study it will appear that airport fires take on prefers r^i Importance (1). It is obvious that a few seconds in time can make 1~ Vportent difference for saving human lives and that the question of isnstltppi . mental endangering especially of waters and streams does assume sous what less importance. But water safety need not be completely overlooked eapeei-v/ ally because most of the actually used fire extinguishing compounds ar used ini training. A:-. fT The Bundesanstalt fr Gevessarkunde (Dept. of Water Technology) ip 1975 got the task from the Mlnlsteriuns fur T, (Ministry of Food Agriculture and Forestry of Nordrhein-Wsstfalsp) to pval* u a t e t h e impact of foam extinguishing compounds on the water quality, thirty; \ eight f o w extinguishlng compounds from 8 Suppliers were evaluated , physically and biochemically for possible endangering of water/'-;Wfferent;;'' sv \y. ' brands did vary in degradation and toxicity. Especially the 5Z foam axtinf shing 'SOlutions used can result in the following damj|gfjt r i l y '*V a.- V;V '.'.-'[ l'-,- b e s t c o p y a v a il a b l e - 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 groundwater. . ;jhl* reportyes p u b U e i * a d i n ^ * ^ i 4 f o * ig ^ partite Involved, euch ss the aeavrfactvrgreof fosn atli|gulhlttg compounds and the authorities responsible to t ueter purity. Among others4these conslderatlons ere taken into account in *ke DIN" etandarda. 2. DEFINITION OF PROBLEM AND TASK rt r i ' Alter several discourses in 1977 between representatives of the Bundesamtes fur Vehrtechnik and Beschaffung and the Bundesanstalt fur Gewae^ serkunde (BFG), the BFG was authorised on Oct. 12y 1977 to tarty out a apeAl d e l study. This study should only cover the products used by the Bundaarebeu (W. German military) and also products which are considered for possible hew introduction. As a first objective the environmental influence of the foliowiag sin * extinguishing compounds should be determined: BEST c o p y a v a il a b l e -4 - No Product 1 Fluor protein 2 Light Water, FC 206 (frost protected) 3 Light Water, FC 206 (normal) 4 Light Vater, FC 200, (normal) 5 Preteia *oem Aid 6 Sxpyrol F 13 Manufacturer Firm Dr. R Sthamer, Hamburg Firm 3 M, Neuss Firm 3 M, Neuss Firm 3 M, Means Firm Or* I. Sthamer, Hamburg : Firm Hoechst Ag, Frenkfurt/Hoschst The two typos of Light-Water ore offorod m being "especially safe ; to the environment" (According to BWB). Light Water FC 200 is reported te be out of production, but should be evaluated for comparison. The teat for environmental inpact 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 M t a l s - Flame point. The final report should also contain recowendations for the technical procurement specifications (TL). Vv",'- : The final report was scheduled for completion in Sept 1978,;-/Duetto' sickness-of one of the investigators it was delayed for some ' ''** ' * m i ;:V.5-r-L- vat, 3. TEST RESULTS -5 - \ BEST COPY AVAILABLE 3.1 Physical- Chemical Tests The first test result gives the heavy metal contest which was deter1) mined by X-ray fluorescence . Evaluating the figures of Table 1 listing the heavy metal content, the two compounds Pluorproteln (Ho 1) and Protein foam- espeund (Ho 5) steed out. .or fluorptotal*' M * if ontent of th* applicleati^ (,>v1`V seletio (mixtures) eith 40 sod 55 eg/l respectively, 1* relatively high., V \ v for tfeo eooood. compound the Iron content of 50 mg/i steads out. All other - heavy natal concentrations such as the especially recorded levels for copper are unimportant. ;;>Table 1 ; Heavy metal content in foam extinguishing compound. No. Original Products 5 % Solutions Zn Fe Cu PP* t >0 too < 27 vi' 3 1 i4 * 5 2 >0 < i 6 3 tm 40 J.4 0,? 0, 0 .* re ne/l Cu -A ,.v. 0.02 - y-sa w H f e nifc::, .f 0.5 0,02 ~ .0,02 .0,02 ' a -,. **>> * - " %Ly 1) Determined by Dipl. Chen. U. Schlelchert *v'fi*. -VyV-:- *': e b j f : ^ v ."VT. yyy.'i:i?V *<V V-. J b e s t c o p y a v a il a b l e -6 - When the flame point ia determined, the water content of the 8ample 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 solvents. 3) The surface, or Interphase tensions can be seen from Table 2. The surfsc tension water/air generally drops some for concentrations from 50 mg/i to 500 ttg/1. The surface tension is least effected for Ho5 (trotein-foam extinguisher), most effected for two Light-Water types of fC'204- type. The resn for this is found in the chemical composition of the extlgulshlng compounds. Protein foam agents can be expected to be generally inactiv to the water/air interphasej while tensides and also so called "aynthtic,,pro- ducts are interphase active. The Interphase activity is less a product specific, but rather a group specific characteristic. Table 2 Inte ri)h.ire activity . No. Interphaee activity at 2oC ( dyn/cm) 50 - 1 42 ) ! 4 ft! S 4! 4 ! 100 50 !! !i 51 4! 250 500 -, ;/ E' V' 44 14 5 2! . % 10 22 .: 4t 24 ` 42 n 40 * ... -, M: : , m-r- 2) Determined according to Abel-Pensky in closed vessel; DIN 51 755, Ed. 966 3) Interphase- Tensiometer, according to Nooy, firm. A. Kross, Hamburg . ...0.00144 -7 BEST c o p y a v a il a b l e 3.2 Test for Biochemical Degradation To evaluate the vater polutlon characteristics of compounds, it ia of kf c l y ^ i interest to sun up th chemical parameters, potassium permanganate and OAV)'' C_10.) 4aOs potassium dichromate uptake, (CSB). The biochemical oxygen uptake (BSB , coo Bj of DEV (4)) can be usd especially in combination with CSB to preliminar-: C0 lly evaluate the degradation. Bhen the CSB analytical tatt gives reliable results (this, for instance, if not always true when hydeophobic compound# .-*:? V Co/<3k% are being tested) ooa must consider positiva result derived from the B S B / h ^ A Y.r as useful, while negative results can not be counted, since the i day PM?s: i `- . .. . . !,, intubation period for the BSB-test under sens conditions does not encapes# sufficient time for adaptation of the organisms active in the biological ,,, t- breakdown. It is not certain that toxic inhibitions can be excluded in thg. / i r . &oO ' i ' standard BSB (5). To better Insure results concerning the degradation thgj|< L *v / is possible by evaluating the CSB/BSB ratio, one must carry out extensive `it- degradation tests, where the incubation time, the inoculation material and other parameters are determined, so that further breakdcjvn than for the five day BSB'test can be evaluated. .i At present there are International effects: underway to Standardise gradation tests. For this investigation Of hrmmkdmn of firm mytiwyifmhfmf -AV foam-compounds a new T .0 .C.~degradation test (6) developed by the Bundesamiv&it<; 'i f fur ftewaaserkunda was used. Its testatitarla is the complete breakdown' of. 'KN.';G 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 t-ft; .:.>. >V' place in a screw-cap flask with air space, placed in e shaker, fekadegrada- , t,!" '' '<?. . o tion tests for the fire extinguishing foam compounds were carried out at 0 in the dark, in deviation from the stated test procedures. 1" - : ..' ' Il A, . - r*' . . . ii . . ' ; ' I '. r !>' ' ;r.vMU1V1 ' V5'-- A b e s t c o p y AVAILABLE -8 - When the percentage breakdown according to the TOC-test Is compared to results from other degradation teats, 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 mineralisation. . >* "' , . :V According to the experiences gathered by participation in a round test, - , v jp|e ttC results for completely soluble compounds are somewhat lower then iJJ, ' .V when the breakdown Is measured by the "modified OECD-dpreanlng test" (V) This "modified OECD -screening test" was tested by International round, tests. It'has soma dlMdvaarageseeng*.nod^*o-'tbe'<4KIC/dagradatibtt*teet.->ndd^nMMi9f6 ' * "*'s * * l used for testing of emulsions and suspensions ation test Is only well defined whea a total breakdown is recorded. In cases where particle breakdown la observed,this can be due to the fact that'only part of the product can be broken down, while other parts can hot. The breakdown of mixture can then be manipulated by the manufacturer by addition 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 t h e ? products. v ' T ` rr v 7 0 :0 Q i 4 ^ i | RESULTS: b e s t COPY AVAILABLE ---- Table 3 does list the aeasurenent results obtained for the orglnal products, to evaluate the potential for endangering of the water. Table 4 lists the percentage of degradation of the application solutions after a period S' of 2 days together with other degradation paraaeters of Interest. The specific TOC- degradation curves are Incorporated in attachments 1-6. v ' . ' /. ' ' - . .. . Th| values Obtained from Table 3 show that the different products contain /, , varying snounts of organic conpounds. Ofcourse one should count 0 T o w content ' of organic neterlals and of organic carbon found in products 1,4 and 5 as/ o positive factors when water endangering Is to be judged. r*o 6o0 For the application solutions (table 4) the CSB and BSBj are listed to- . gather with the ratio between these two factors and can be used In addition to the TOC- degradation results forrthe evaluations* According to the ratio ; :' 1 the product No 6 should be considered easy to degrade. For the products 1 and 5, which according to the TOC- degradation test appeigr pedlun degradable '' ,`<r / : . i (as also established fro the netsbollsa test) the unfavorable CBS/BSB^ , ratio could possibly be due to the chenlcal oxidation of iron salts nreaamt in the products. The iron salts would increase the CSB without increasing ' the B8B5< Th degradation of each product, separately, la evaluated as follgw|| '` ' 1 ',' \ Fosa extinguishing coapound Nofc shows a favorable ratio of KMnO. :onsdhP":: r 4. tlon/ K2 Cr2<>7 consumption, and shows good bacteria action in the aetabollsm test, together with a 47Z TOC- degradation. It nust be rated as editai d e g a ^ ^ | n . `Traduci Ho 2 shows a favorable CSB/BSB5 - ratio, but since the other do'not indicate a good degradation rate it is classified as difficult to degrade* TIM degradation of product 3 is even less is'classified as difficult to degrade, that of product 2 so it . '; -T :Vyiv, V-V oQoaslii Byen though the degradation during the TOC-test was furthetr^addyvaerhc^e d ^ j r ; ^ . ^ ^ tf y '-r; -'.f -10- BEST COPY AVAILABLE Potential Cor endangering of waters by original oroducta No On04 used K 2Cr07 used Org.O content B0 Content a) Organic part b) -- k*' kgl X I fc 3 11 ft fC t 0.20* ,525 2 0,09 1.438 * 0.08V 4 0,050 r.o;i ' 1.4 2,H> * . e. lei 4.W .. .. '*t T- a) only approximate values 0,15 0,?4 0,12 0,90 *# 89 55 m 80 /* 8 20,? d. 21* . 20 il n. b) only approximate values, buraoff value at 6ooC and variable duration Table 4 Bioohemloal degradation of applloatlon ready eolutione (5f0 Vo Rate of W mn(>4 (m. V g C r O ^ H **T5 j/l m V ** V * Ql Ivo*"* fit'll ni 5.000 ^ 12.100 4*010 ! 2 1 . ^ ) 0 . 1 1 1 1 *5.008 ' t b 1 2 00(4.5*.)24.100/" 10.000 M r.250 14.100 4.450 .4 5 MOO 6 2.500 20.000 38.000 S.210 41.OOO t M JSV co 1 tf M 1.) 0,1 Regrad. Degrad* in in setbabol. TO test teat Final aval* x) 42 am 0 medium ' difflOttlt 4 diffiomlt 12 difficult 32 .medium 41 eaey to ^edlum x ) Bvaluation of bioohemioal degradation in TOC- test (at Standard ' temperature of 250) a - 2o Jt difficult to degrade 2o - 4o jC slightly degradable 4o - 75 % medium degradable 75 - loo % very degradable 000148 -1 1 - b e s t c o p y a v a il a b l e 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 he broken down, A finding which is confined by the results of the TOC- test. The product is classified as medium degradable. For product 6 one finds a complicated degradation behavior which might originate from the high toxic effect of this product. After 7 days degrade- ' " ' . ' '.<:/i'V.- . tom. already 101 of the TOC is broken down* Further 4o*rMetion 4oes resi4Jt^ i ly after 14 testing days, but tliga a intensive degradation l ^ 4 ^ to k |r ^ - - down of 601 of tits starting TOC doss take plans The slew down fabraakdown after 7 toot days can be evaluated as an adaptation period for the micro organism involved. 3.3 TSxicolQgy testing METHOD In the "Evaluation of the Veter Endangering by Foam Extinguishing Compounds" (2), the results concerning toxic effects towards algae and bacteria were discussed; . In this evaluation which la concerned with tests for products that possibly * . could bs used in large amounts, the toxicology' test* vereiaceadifled. In addition to the incorporation- metabolism tests, 'also''teats with snail crabs..' *. .'^v 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 thesethe latest pest procedures were used as published by the responsible working coemittees . For fish-tests the concentrations used were from 0 to 10,000 mg/1, where BEST COPY AVAILABLE a large grauatlon of dilutions vas used. The further toxologlcal test were carried out with smaller gradations from 0 to 210 mg/1 to .insure, that the products could be differentiated as well as possible* ''vV RESULTS: In (he enclosures 1 to 6, the results of the toxicology test* ere..fresitedp- -ssv^ose- reaction curves and the results ere calculated sad presented fn Table Froduet Ms 1, "Fluorachawsgslst (Enclosure 1) is es texte st concentrations of 10,000 ag/1 that ell test entasis did die (EC " 10000 ag/1). But for JLtAJ t - the concentration 1000 ag/1 the product is not detrimental (EC. 1000 ag/1) f ( E O effective concentration with respect to the corresponding test. ECU is '* 0 0 the lowest tested concentration for which a 100X result with respect to the s *1i m .; . i -` . test criteria is recorded; For the fish test, this is (he 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 saall crab, Daphnia magna (water flee), the product is not r. ' < detrim ental at the highest concentrations tested (ECq 250 ag/1) The photosynthesis activity of algae is easily effected by Fluorschaua- geist. The effect is still below the critlcal limit at concentrations of .Vi > 50 ag/1; but at 100 ag/1 if is significant. ` .. "` ,V-.'t. ' The bacteria oxygen uptake during break down of peptone is increased by the product. This aakes the biochemical break down of the product itself plausible This result is also confirmed by the TOC - degradation test (see; 3.2), 1. The product No2, Light Water. FC 206. frost-insured (enclosure 2), reacts similar to product Mo 1 in the fish and daphnls tests. Also theresult of i the incorporation test is similar to the first product. But the inhibition of the photosynthesis activity la less and becomes significant o n l y a t the highest concentration 250 ag/1. \ The result of tbs metabolism'radar -1 3 - BEST COPY AVAILABLE definitely different than for the first product: There le no methaboilc increase which could be Interpreted as a sign of break down. The TOC degradation test also does show a break down of less than 10X. The results of the biological tests carried out concerning product Ho. 3 "Light Water PC '206. normal," are nearly indentlcal to the results obtained for product No. 2 Light Water, frost protected. The only difference is; that the toxic effects towsrds algae indicated for product 2 ere tujt fpued t o t product No, 3. Product No. 4, "Light Water, PC 200, nornal," is different from the foan agents discussed previously by having a definite toxic effect towards , fish, anal? crabs and algae. For fish the test animals die already at 1000 ng/i^ (EC0 - 100 ng/1, EC100 " lOflpjhg/1). In the daphne test, 33X of the animals ^ died within 24 hours at 100 ng/1, at 250 ag/1 about 75X of the anlnals died (EC^ - 50 ng/1, EC^q o 500 ng/1). The incorporation test for this product is already surpassed at concen trations of 5 ng/1; at '250 ng/1 a couplets inhibition of algae activity is recorded (EC0 2 ng/1, EC - 250 ng/1). Product No. 5. Protein Foan Ayent. In all biological teats is squill to product NO. 1. No significant toxic offacts'were foundtowardsalgae at concentration of sbout 250 ng/1. For the nethabolisn test an increase' i n .*? bacteria oxygen corporation was recorded, but it was less than for product No. 1. The result of the nethabolisn taSt corresponds to a relatively positive ^reaction towards the break down test.' rv, Product No, 6. Exnyrol. is exceptionally high in toxicity and dehpfc.of' --; v ; ' iti.- V '..' / break: downn,. The toxicity against fish la as high as for prduct No 4 : (EC^ iOOng/1 and SC:100 " 1000 ng/1). For snail crab this produqtis r4 _14_ BEST COPY AVAILABLE especially toxic (EC0 25 mg/1 and EC^q q 500 mg/1) The incorporation test shows an inhibition at lOZconcentrations above 10 mg/1. For 250 mg/1 there is a 65Z inhibition. The metabolism curve of this product indicates that it contains meta bolic active as well as toxic compounds. Tab!e 5 Results of toxicology test ( expressed in order_of poison classes) No Pish Daphne Algae Bacteria (DEVL 12) Total (DBVL 15) (D3V1 11) (DBVL 12) inhibit. . enhanoe. evaluation x) in 111 n ? in 111 i i / u i S It! III in A- ii 11 i 5 in 6n HI It iu n UI III 111 lit III III II/UI - H I 3 1? Ill -- T-oi - l/lt III % n Poison class. 1 s Proven inhibition on tost, animals at concentrations be'ow 5 mg/ 1 Poison class 11 t As in 1) re-jion 5 to 2oo mg/l Poison class lilt No damage at concentrations below 2$o ng/l . 'Total evaluation Calculated by weighted avrage. The test result with lowest critical liait of concentration is multiplied by 5 4. Evaluation of Results and Conclusions Summarizing the single criteria of the test, one can obtain different results, depending upon what importance is given to the different criteria. ' The original products constitute a threat to biological systme such as the life in streams and biological systems of purification plants, due to their high toxic level to which J:he surface tension, and for product 1, -1 5 - BEST COPY AVAILABLE 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. iI . ly the further dilution by a factor of 20 to 80, which is active in -the application of foam -^Ite^ttmiwftHtngec^wyoagd^-tliK.' levelsof ;tnc ( 2 mg/1 for bacteria, 10 - 25 mg/1 for fish) is not exceeded and also ; > theeurfaee tension activity can loose its importance* It thaawtens reasonable to evaluate the water danger by the products i; according to their toxicity at the concentrations which can be reached during ' application, and according to their biochemical degradation, even though there at present are only degradation results available for the finished mixed pro- f ducts. ' For none of the compounds the degradation is so easy an to classify them as eavlromentally 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 1 SOlu- -gionsare as 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 cpcen- f-c z o C ' tration the compound of product HO. 3 and Wo. 5 are without acute detriment ---- fc to the teat organism. Pcoduct No. 1 and No. 2 lema their toxic effect . - after further dilution by a factor of 2 to 5. Such dilution is to be ex- -- . , ;;;;: .-/i pactad in the pre-flood teak of the purification systems. Fer the very fS C-t^Ov) ` . ; . toxic products No. 4 and No. 6, an*zddltlonal dilution by a factor of i between 50 and 200 is necessary to get below the toxic level. Speh dftutioiut,, i"?j are not certain In practice. Product Mb. 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 (inpair the drinking water supply^ and the use of these pro- ducts therefore should be avoided. Of the remaining products the foam compound Ko.ilhas tigh t*** level towards algs* due to the high content of sine. gut since the** properties are lost to a large extent due to the dilution during ** *' * '. * usage, and since the product is relatively easy to degrade, the endangering of the waters due to this product appears to be of little Importance. The grouping of the 6 products proposed here does take biological a n d .. chemical results Into account, but dhea not consider application technical characteristics. If It ii 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 thal* w y w nata for de gradation and toxic affects. Further it should be attempted to replace components especially biologically damaging by less damaging materials of similar effects inch approach has been successful for other materials of environmental concern. 5. Recommendations for technical ordering specifications Based upon the Investigations as discussed^ the'fdllewigg require ments can be made of the manufacture of foam fire-extinguishing compounder- < yThe biological degradation characteristics of the organic components present In foam compounds should be well established^ The break down should be as easy as possible, right now it is considered u 9* H 000154 BEST COPY AVAILABLE -1 7 - aa fair, when a 50 Z break down la racordad In the modified OgO-ScreeiH^g- Taat (7). For a taat which records complete chemical degradation auch as the TOC-dsgradatlon test (6), a 40 Z break down ahopld be the minimum required. Other tests can be used in replacement of the abovsmentloned, if it baa been : i f proven, that equal results are obtained aa for the teats according to (6) ` and (7), when those products are tested. The toxic efffcte of the foam compounds towards water orgaAlsm, especially beeterls, algae, s a s a d fish should be aa small as possible.- A ' sufficiently nontoxic range can be set if the BC^q for bacteria, algais', daphneand fish is above 1500 mg/1 foam agent in water. For toxicology test, L 11, L 12, and L115 of DEV (4), or similar procedure for which equal type results can be proven, are to be used. ' *i The heavy metal contant should not axceed 1 Z zinc, or fop other metal ' an amount for which a corresponding degree of bacteria toxic affects is :. recorded. 4. .V " 6. Conclusion ,,. fAccording to the task the following six foam compounds, determined by the "Bundesaat Fur Wehrtechnlk und Beschaffung" in Koblenz, were evaluated with- relation to possible endangering of estate: Floorprotein; Light Water FC 206, normal; Light Water FC 206, Frost protected;tight Water FC 20Q, normal; ..a, ' ' t. '' Protelnabhaumaittel; Expyrol F 15. The test includes lnterphasa activity, -- b;` .; toxicology, biochemical degradation, heavy metal content and flams point. .t ' ', The results were presented and discussed and a conoluslon reached,- The' .'' <A . V v-t - "> products Floorprotein and Proteinschaunmlttel were recommended ir relatively favorable biologic characteristics. The final conclusions e m m given aa rscoBBsndatlons for technical delivery terms (Tt) to be used by the contract agency. '.:rS ' -jA -1 8 - LITERATURE LIST . (1) Fiala, R.: Study "Mittelschaum fr Flugzeugbrandbekampfung" Dautacha Forschungs- und Varschsanatalt fr Luftund Raumfahrt e.V., Koln-Wahn 1977. <2> Bundesanstalt fr Gewsserkunde: Gutachten ber dla Wassergefahrllchkait von Schaumloachmlttaln, Koblenz 1975. (3) Hallmahn, H.; Schaumloschmittel - ihre mgliche Vassergefahrdng, Tenside Detergents 13 (1976), 270 - 273. (4) Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlahmuntersuchung. Weinhelm, Erganzungslleferung 1972. (5) Zahn, R. und H. Vellens: Ein einfaches Verfahren zur Prfung der biologischen Abbaubarkeit von Produkten und Abwas serinhaltsstoffen. Chemiker Zeitung 98 (1974), 228- 232. (6) Mller, D. und T. Tittlzer: Der TOC-Abbautest - ein Verfahren zur Prfung von organischen Substanzen auf voll stndigen biologischen Abbau. Zeitschrift fr Wasser- und Abwasserforschung 12 (1979), 14-21. (7) Fischer, W.K.; Meverfahren zur Bestimmung der biolpglschenv Abbaubarkeit von wasserlslichen, organischen Umveltchemlkallen mit Khlenstoffattalytik (DOC) \ (Modified OECD Screening Test). JN. , .A i:mahtt-;-', acript ot the ferm Henkel KU Dsfeldort, seht to theg.G. .a# recommended process. (21,2. 1978). Enclosures Toxicology - concertration/reactlon curves and degradation c u r v e s . J t o 6. 000156 / 000157 Nr. 2 Light water, FC 206, frostgeschutzt *00 11 + 00 ^60 TOXICOLOG Y TIsiST A= Incorp orati on tos?ib Di-nIL 12 __ D= Daphne tep.t DEVL 1LI 1 1 Z- & ethaholiFin tes>t DBVI, 12 Tf. !ish tost DBVL 15 c 20 01 a t-i 0 Moc -20 -40 'E*. C -60 c I >80 \o 1 -100 00 80 oo e a) 60 + H C O 40 c. oo e-i ?0 ---- Sar- 4 10 25 50 100 250 * \ \ V. v to \ -% \ _____ ;________ 1000 10000 Concentration mg/1 .] Tent of TOC- degradation 14 21 9 c ir Increase in Nr. 3 Light water, FC 206, normal 100 80 ^60 40 TT T TOXICOLOGY T3ST A Incorporation tost DiiVL 12 Do Daplino teet DISVL 11 Z Koth.abolipm t e s t Di-JYT 12 P Vih ioi'.t DiiV I 1*5 20 0 ^ fWVttfflMewA 20 -40 m -60 80 100 10 25 50 100 250 1000 10000 Concentration mg/1 Inhibition in 80 .' oo a) H 4 60 C fc! o 's*. 40 fi Oo 2P Test*of TOC- degradation 0 14 1 c r o i 59 TOC in jo of initial TOC Inhibition in Increase in Nr. 5 Proteinschaummittel 0 0 1 G1 Nr. 6 Exp yro l F 15 00 1 " T 80 -- tP. c 60 cai 40 u oc 20 TOXICOLOGY "PS:T A= Incorporaioi tes t D= DapVino tesi mvi 11 i ___ ___ __________ ____________ 0 DE VL \2 Z> 1ethaoolipn toFt D'iVI 12 F. :'ieh tort D m . is fA ^ -- s y "r"< __________________ -i B T f g --- * `20 C CO 40 -fHr* ri rO 60 H 80 00 H - --1 N 1 \V \ y i-- 1 flB __________ 1,Oj i - IF F 10 25 50 100 250 1000 _.... 1QQQEL. Concentration mg/l 00 oo6 80 T + n c H H 60 i-i O cH 40Ou/s &< 20 t n t f O & x o