Document 99VevBmNGewggrBvOba0o54Re

A k SUL6 - 0 7 9 5 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-206. (1 -Octanesulfonic acid) (CAS # 2795-39-3). Remarks: The 3M production lot number was not noted. The test sample is FC-206. Current information indicates it is a mixture of 0.67% PFOS, 17.5% diethylene glycol butyl ether, 78.91% water, 1.33% Hydroxy foamer, 1% sodium octyl sulfate, 0.04% sodium lauryl sulfate, 0.5% polyoxyethylene monooctylphenyl ether, and 0.05% tolyltriazole. 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-206. Data may not accurately reflect the environmental properties o f the fluorochemical proportion o f the 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 W ater 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 001559 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 Fish LCso Daphnia EC so Algae ECso Bacteria inhibition BOD21/COD Results >1000 mg/L >250 mg/L >250 mg/L Inhibited ~7% 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. OTHER________________________________________________ _________ Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 6/26/00 001560 M i . ) TECHNICAL AWARENESS I TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN Dato -z filfn (im portant - Whenever possible, attach a fu ll copy o f the m aterial you have abstracted.) Contributor va /") Division Fric A. Reiner F 1*- Environmental Lab (EE & PC) LocationofOriginal Journal ft Book ft Patent S (Pi.,S^cify)Graft rfpO cy rt Referanca (a.g.. A u th o r, T itle , l*ue D ata, V o lu m e , Paga, ate .): EmployeeNumber 47816 Dr. H. Heilman and D. Muljpr,"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. Dierssen, March 1, 1980). Abstract(givoyourownslantonthosourcedocument) This report compares the environmental acceptability of 6 AFFF Agents including FC 3017 (identified in the report as FC-2otf, 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 competitive 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. , I i Copylist(copiestoliesentbyoriginator) Items submitted on this form art published in the 3 M Technical Awareness Gazette. Q 0 1 5 6 1 Conpllnent to Report of Bundesanstalt fr Gewsserkunde 10. April 1979 i-Mlb/340.22/2596 aiavuvAv Adooisas Study carried pus fbr . Rundesant fur Wehrtechnik und Beschaffung (Govenuoent Agency For Military Technolo|y end Frocurenent) Report: BA 111 1-E/B31E/70145/76066 of October 12 1977. vi .Reporter: Qberreglerungiret Br*J L Rallnaita \ oberregleruagsvet h Miller -, n-V n i -1- Table of Contents. 1. Introduction best c o p y available Page 3 2. Definition of Problem end Task 4 3. Test Results 3.1 Ptqrsleal* Chemical Tests. :\ : 3.2 T M t a for llocfeesilc^ ^gradation 3.3Toslcolot7 Tests '5 ; ; ' V : :'.v' .;' . r 12 ; A. Evaluatlonof Results end Cenelpaien 'jir ** ' t . 7 - " 5. Recommendations for Technical < Ordering Specifications 15 18 V 0. Conclusion 19 Enclosures: Literature list Additions > T 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 car^enhydride fires for instance in refineries (closed systfiin) . 4t'\i^tfi<6sl equipment, high .S.v,;Tjpplications in airports* 0^.:}. - ']*}-. 6. Applications on ships. In the present study it will appear that airport fires take on prefer# reji Importance (1). It is obvious, that a few seconds in time canmake portent difference for saving human lives, and that the question of smvtupi -'V mental endangering especially of waters and streams does assume soem what less importance. But water aafety need not be completely overlooked especially because moet of the actually used fire extinguishing compounds are used loi training. P,-*> f The Bndsssnstslt fqr Gewsserkunde (Sept. of Wate*.. Technology) ip 1973T 'got ~the .task' from the Ministeriums fur Ernhrung, f f stlpfg' M Vo^j|#;| (Ministry of Food Agriculture end Forestry of Nordrhein-Hestfaleq) to jkva) uste 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 ofvseer. Dlfferont HC* brands did vary in degradation and toxicity. Especially the SZ foaa extidpK ' . . guishing solutions used can result in the following damage: !:! 1 . 1 * A'.*r-'i y ' ->v1*-Vr*.*>_>* ;;* . ??..;<: .Jr BEST copy a v a i l 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) i - Undesirable reduction processes in the groundwater. This report plga pubUeixadia, perks parties involved, such as the manufacturer* of foam extinguishing compounds and the authorities responsible for water purity. Among others fthese consid erations were taken into account in the DIM- standards. 2. DEFINITION OF PROBLEM AMD TASK rt r ,. After several discourses in 1977 between representatives of the Bundesamtas fur Vehrtechnlk and Beschaffung and the Bundesanstalt fur Gewas- aSrkunde (BFG), the BFG was authorised on Oct. 12, 1977 to carry out a opnAA. d e l study. This study should only cover the products used by the Bundawehe (W. German military) and also products which are considered for posslble new introduction. As a first objective the environmental influena of the following eiin v->: extinguishing compounds should be determined: s. BEST C O P Y AVAILABLE No Product 1 Fluor protein 2 Light Water, FC 206 (frost protected) 3 Light Water, FC 206 (noraal) 4 Light Watetv W 200, foflpsl) 5 '* Foaa Aid . 6 Bxpyrol F 15 Manufacturer Firm Dr. R Sthaaer, Hamburg Firm 3 M, Neuss Firn 3 M, Neuss Firn 3 M, Neues Firn Dr. /*. 'Sthaaer, Hamburg' ;/ Firn Hoechst Ag, Frsnkfurt/Hoachst The two types 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 coaparison. The test for esvlronaental inpact should, if possible, be tasted for 5Z solutions as uSad (for Light Water 6Z) and anconpass the following parsaeters: - furface tension activity -Toxicity - Biochemical degradation - Content of heavy natals - r is e s p o in t. ... p.y , The final report should also contain recowendatlens for the technical procurement specifications (TL). The final report was scheduled for completion in Sept 1978.;':;Dus" t<h.i.--V.- sicknass-of one of the investigators it was delayed for sons npathsi, ' . sS 3. TEST RESULTS -5\ BESTCOPYAVAILABLE 3.1 Physical- Chemical Taats Tha first tast result gives tha heavy eatal content which was dater1) mined by X-ray fluorescence . Evaluating the figures of Table 1 listing the heavy metal content the two compounds Fluorproteln (Ho 1) and Protein foam- compound (Ho 5) tS G M . eletloe (mixtures) with 40 sod 3 S respectively, is relatively hitf ' -i:- for |he second compound tbs Iron content of 50 mg/1 stands out. All otheT heavy metal concentrations such as the especially recorded levels for coppaf are unimportant. ;-J' Table 1 /?.' ; Heavy metal content in foam extinguishing compounds. Ho. \. C*riginal Products Zn Fa Cu 5 fi Solutions 2 Fa Cu /i ,* 'g * a . v:- 1) Detarmlnad by Dipl. Cham. U. SchlSichert >*.* <i\ ly x 1- ,V'^Q^. ;.'i `f ; , ' v '.{V best copy available When the flame point ia 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 oontain flammable solvents. 3) The surface, or Interphase tensions can be seen from Table 2. The surface tension water/eir generally drops none for concentrations from 50 mg/i to 500 ug/1. Die surface tension is least affected for Ho5 (frotein-foan extinguisher), most effected for two light-Ueter types of fC'206- type. D m reason 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 Interphase} while tensldes 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 2 Interphare activity23 No. Interph iee activity at. 2oC ( dyn/cm) 50 - 1 12 7 S0 ) tl 4 IS % AS A 1 100 750 . mn : so 51 5 so 10 *S AO 05 01 51 It 500 -.y, y' , JO IS 17 00 * i- W 2) Determined according to Abel-Pensky in closed vessel; DIN 51 755, Ed. 966 3) Interphase- Tensiometer, according to Nooy, firm. A. Kross, Hamburg -7 3.2 Test for Bloch-- leal Degradation BEST COPY AVAILABLE To evaluate the water polutlon characteristics of compounds, It Is of P c / *>* eiit/ -.h*. c J L i (,<-- C Interest to sum up th ch-- leal parameters) potassium permanganate and <JjkY)i~ K -C io O ) 6<iOS potassium dlchromate uptake, (CSB). The biochemical oxygen uptake (BSB , ci c 5 H5 of DEV (4)> can be uad especially In combination with CSB to preliminary c*0 lly evaluate the degradation. lib-- the CSB analytical ta*t gives reliable resulta (this, for Instance, le not always true when hydeophobic compo-- d '".ri'': . ' ,k C* / Q i j k re being tasted) one moat consider positive result derived from the ssa/i*- ^ ratio as useful, while negative results can not be entintad, since the i ^ vM incubation period for the BSB-t-- t under same conditions do-- not enc auiflci-- t time for adaptation of the organisms active la the biological breakdown. It la not certain that toxic Inhibitions can be excluded in / I- ' -, & o o ' >, standard BSB (5). To better insure results concerning the degradation^ C -, la possible by evaluating the CSB/BSB ratio, one a-- t carry out extensive ' ' . degradation tests, where the Incubation time, the Inoculation material and.; t' other parameters are determined, so that further breakdown than for the five f day BSB-C-- t can be evaluated. ! M . i . . At pr-- t there are International effects: underway to itandardlz* dslf . vf' : . ... .. gradation t-- ta. For this lav-- tlgatlon of breakdown of fire rtinynfnhlnf ^ fo-- compounds a new T.O . C d e g r a d a t i o n test <6) developed by the B u n d e s i M ^ ^ i t ^ fur 6-- -- serkunde v -- used. Its t-- t e M t e r l a is the complete breakdown'o f ' . ; the total org-- ic carbon (TOC). 'For the t-- t procedure the t-- t compound serves as the only source of carbon* Inorganic mineral salts are added in advance. The Incubation tak-- v :' : ` . " place in a screw-cap flask with air space, placed in a shaker. ' kfcadegrada- f t'!- ^ '. " O ' ' . ' - V tlon t-- ts for the fire -- tlngulshftng foam compounds were carried out -at 20 /;!. In the dark, in deviation from the stated t-- t procedures. 1-V , r' ._:'' .v r>' *Ij "i o iiS -8CQP'* Whan the percentage breakdown according to the TOC-teet is compared to -results from other 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 m l i u w l 1tit W - According to the experiences gathered hy participation in a round test| - ,k 1; A | e l6C results for completely soluble compounds are somewhat lower thin *'>&*** when the breakdown is measured by the "modified OECD-Screening test" (?). This "modified OECD -screening test" was tested by international round testa.'' It has some disadvantages - *. i' used for testing of emulsions and suspensions. Since the products tested here are mixtures tin results Of the dejprad- ; 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 1 *. - - . > breakdown of mixture can then bn 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. Fot future tests, which could be carried out after a period of a few years of usd, it* should ge attempted to test the breakdown of the single components of the products. BESULTS: -9- BEST COPY AVAILABLE Table 3 does list the measurement 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 solutiona after a period of 2 days together with other degradation parameters of interest. The specific^' TOC- degradation curves are Incorporated in attachments W . t .. _' The values ebtalned from table 3 show that the different products contain v , varying amounts of organic compounds. Ofcourse one should count a low content *. ' 1 . ^ . of organic materials and of organic carbon found in products 1,4 and 5 an v positive factors when water endangering is to be judged. ^ r0 & oC ' For the application solutions (table 4) the CSB and BSBj are listed to- gether with the ratio between these two factors and can be used in addition - to the TOC- degradation results forrthe evalnetloan. 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 appeigr medium degradable (as also established from the metabolism test), the unfavorable CBS/BSB. ratio could possibly be due to the chemical oxidation of iron salts present in the products. The iron salts would Increase the CSBwithOut Increasing 1 the B8Bj. Th degradation of each product, separately, is evaluated as follwyrt ? 1 . : `v `i Foam extinguishing compound Non shows a favorable ratio of KMUO, c o n m U p ? r 4 .k tion/ consumption, and shows good bacteria action in the metabolism test, together with a 47Z TOC- degradation. It must be rated as medium degradable I'.', . ' ' Y Product No 2 shows a favorable CSB/BSBj - ratio, but since t h e o t h e r tents do not indicate a good degradation rate it is classified as difficult to degrade* 4, Tbidagradatiee of product 3 is even less them that of product 2, so it J "n. V'- is'classified as difficult to degrade. V-v. Even though the degradation during the TOC-test was further'^ advanced I?;. fm . Tab\e } - 10- Potencial Tor sndang(rin =i of waters by orid.oe%* AVAll-ABLE No nnO,, 4 used K 2Cr7 used Org.C content V Oontent a) Organic part b) -- k*' k / | k*'* X X \ fe 3 o n i ft fC Z o 5 4 5 4 0 . 20J 0 , 09 O.OOV 0 ,0 5 0 0,41* . 0J41 J,5 2 5 1.43 M 30 r.t;i 2iH I 4.a* a) only proxiaata valuta 0 ,|5 0 ,? 4 0 ,2 2 0 9I 0 te# tetl 89 53 17 ` o O*. . t ; 0 ,? 4 . 23* 20 . rl M b) only approxlmata valuta, b u m o f f valuta ai 6ooC and varlblt duration Tabla 4 Bloobamloal dagradatlon Qt ap p lioaU on rta d y aom U ona (5rf) No Bate of Sol? Mn04 (m. KgCrO^V fti5 1 tj/l m Oj/1 m Oj/t flsi c 0 Sagrad. Sagrad. in ia matbabol . TO# taat taat Pial aval. *) s.o o o ^ 12.300 ^c>7 2 f?c-2-C ) 2 t00(t.H)24.|Alr t c `ld0 4 r 250 14.300 i 5 1.500 20.000 4 2.500 34.000 // 4 .0 3 0 M 3.000 ^ 10.000 4.450 tel 3,4 3.250 0*1 *1.000 M 0.5 t.i 0,2 ,1 4 " - 4? 0 '0 2 3? 42 madium ' dlffioult diffiat diffibUi^ .madium aaa'y to [Radium z) Bvaluation of bioohemioal dagradatlon in TOO- taat (at thda*4 ' temperatura of 2$0) o - 2o jt dlffioult to dagrada 4o - 75 % mdium dagradabla 2o - 4o f i aligbtly dagrudable 75 - loo % verydtgradable -11- BEST COPY AVAILABLE for product 4 than for products 2 and 3, It vaa 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 behavior which night originate from the high toxic effect of this product. After 7 days degradetion already 101 of the toe is broken down. further dagcadatioo doe restj6t| aly i f U testing days but thes es intensive degradation a e d ^ ' tv braefc- * dove of 601 of the starting TOC dobs take place* The Slav down in breakdown; after 7 tost days can be evaluated as an adaptation period for the Micro-. organism Involved. 33 t.aatins METHOD In the "Evaluation of the Water Endangering by Foam Extinguishing (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 lerge anounts the toxicology' test* w e r e l * tendIfled. In; addition to the Incorporation- metabollam tests a l W t a s u with snail 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 these the latest ~ pest procedures vers used as publlshsd by the responsible working conUitteea . For fish-tests the concentrations used were from 0 to 10,000 ng/1, where & -12- BEST COPY AVAILABU a large grauatlon of dilutions was 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. RESULTS: In the enclosures 1 to 6, the results of the toxicology tests ere.".presented," nsvdoee- reaction curves and the results are calculated and presented fn Table s, ; . . . .Vf. Frodnet Me 1 "Fluorscheumgelst (Knclosure 1) la as toxic at concentrations ]r of 10,000 ng/1 that all teat animals did die (EC * 10000 mg/1). Bqt for 100 the concentration 1000 mg/1 the product la not detrimental (BCV* 1000 mg/1)* O '*. ;' '' ( E O effective concentration with respect to the corresponding test.' EC is I0Q 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, Daphnia magna (water flee), the product Is not detrimen tal at the highest concentrations tested (ECq* 250 mg/1) < The photosynthesis activity of algae is easily effected by Fluorschatsm- geiat. The effect Is still below the critical limit at concentrations of 50 mp/1; but at 100 mg/1 it le significant.- -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 ' - - '-H; ' This result Is also confirmed by the TOC - degradation teat (sec. 3.2). ;v- The product Bo2. Light Water. FC 206. froat-lnaurad (enclosure 2), reacts Similar to product No 1 In the fish and daphnia tests. Also tbe neeuit of I*. ' ' i , the Incorporation teat Is similar to the first product. But the lnhbitlon Vi of thephotosynthesis activity la less and becomes significant only at the -T~ < . . highest concentration 250 mg/1. \ The result of the metabolism rater 1. ft . \ :;v- - ' -V/fcSt'A BEST COPY AVAILABLE -13- deflnitely different than for the first product: There Is no methabollc increase which could be Interpreted as a sign of break down. The TOC degradation test also does show a break down of less than 102. The results of the biological teats carried out concerning product So. 3 "hltht Water. FC 206. normal," are nearly Inden tlcal to the results obtained for product So. 2 Light Water, frost protected. The only dlfferencf " Is; that tho toxic offsets toward algos indicated for product 2 ora .not fj*Md;1 lot product So. 3. Product So. 4, "Light Veter, PC 200, normal," is different fron the /V \ v foam agents discussed previously by having a definite toxic effect towards f* >: , .-VC fish, small crabs and algaa. For fish the test animals die already at 1000 mg/1 (BC0 - 100 ng/1, BC^q q - loqtag/l). In the daphne test, 332 of the animals died within 24 hours at 100 mg/1, at 250 mg/1 about 752 of the anlnsls died <EC^ - 50 mg/1, EC100 - 500 mg/1) . The incorporation test for this product Is already surpassed at concen trations of 5 mg/1; a t '250 mg/1 a complete inhibition of algae activity is recorded (EC0 2 mg/1, EC 250 mg/1). Product No. 5. Protein Foam Agent. ln ell biological teats if aquhl to product Kb. 1. No significant toxic offsets were found towards algaa at concentration of about 250 ng/1. For the nethabolisn test an increase1in bacteria oxygen corporation was recorded, but it was less than for product So. 1. The result of the nethabolisn test corresponds to a relatively -: positive ^reaction towards the break down test. ^ Product No. 6. Exovrol. is exceptionally high in toxicity and ^ d l ^ . o f ;. break down. The toxicity against fish is as high as for product No 4 (ECft 10Oag/l and 1C100 - 1000 ng/1). For snail crab this produ^'is. *"if- i +W ''v '>: -i*- BEST COPY AVAILAB especially toxic (EC0 25 ng/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 1e 5 Results of toxicology test ( expressed in order of poison classes) No Fish Daphne Algae Bacteria (DBVL 12) Total (DEVL 15) (DSV1 11) (DEVL 12) inhibit* enhance* evaluation x) III 111 II 7 III III Il/Ill III III III a- 11 11 l 5 in in III 6 II It 11 Ul III III lit HI III 11/1*1 - III 3 * '? - Ill -- m in x % m ' tt - P o i n n class 1 ! Proven inhibition on tost, animals at concentrations b e 'ow 5 mg/ 1 Poison class 11 * As in 19 region 5 to 2oo mg/l Poison class 111 No dareago at concentrations below 25? me/i 'Total evaluation* Calculated by weighted avaragei The test result with lov.ept critical limit 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 systems such as the life in streams and biological systems of purification plants, due to their high toxic level to which Jfhe surface tension, and for product 1, -is- BEST COPY AVAILABLE the content of zinc is added. The drinking veter supply could be endangered by the content of just the organic material in the original compounds. Also the application ftrength 5-6 it 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 * factor of 20 to 80, which Is active in the application of f o a m ^ l r e ^ t i a g elshingptps ^ U n d e g h f r t ^ t l e v s l o f atnc ' ' .. v ;.$ ( 2 ntJ t lor bacteria, 10 - 25 mg/1 for fish) la not exceeded and also A- the surface tension activity can loose its importance* m It theneeeme reasenableto 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 b ' ' . at present are only degradation results available for the finished mixed pro- f ducts. For none of the compounds the degradation is so easy ns CO classify them as enviromentally friendly compounds. In the selection one then must differ entiate relatively better products from relatively worse products. Whan fire-extinguishing foam compounds arm applied, the about S I Olu- -giona.aseas previously stated diluted by a factor of 20 to 80. ^ e y than''T are in a region of concentration between 125 to 500 mg/1. At this cojjcan- fYzoG ------ --- " tratlon the compounds of product MO. 3 and Bo. 5 are without acute detriment ~ " '' fc T ^ ? ~~ : : :" ' to the test organism. Product No. 1 and No. 2 Isms their toxic effect . -- after further dilution by a factor of 2 to 5. Such dilution is to be ex- . pected in the pre-flood tank of the purification systems. For the very toxic products No. 4 and No. 6, am^kdditional dilution by a factor of' between 50 and 200 is necessary to get below the toxic level. . 4 . , j. Such dilutions it # BESTcopy available are not certain In practice. Product No. 4 shove 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 end could thus disturb and (impair the drinking water supply^ and the use of these pro ducts therefore should be avoided. Of the remaining products the foae coeipound No.r:1 .has atelStivelyt-tfiVhigh tsetc level towards algae due to the high contest ofjdne, |ug since thage 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 des not consider application technical characteristics. If it l not possible,due to application technical,reasons to avoid the use of products which are difficult to degrade or are especially toxic, than it would be advisable to teat their single components for de gradation and toxic effect. Further it should be attempted to replace components especially biologically damaging by less damaging nsterials of similar effect. tUch approach has been Successful for other materials of environmental concern. 5. Recoimsendations for technical ordering specifications Based upon the investigations as discussed*' the fBUowigg require ments can be isade of the manufacture of foam fire-extinguishing compounds: ^ T h e 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 ft is considered r--* . . . -J:: s >... . . r * .0015 8 sr c o p y avails as fair, when a 50 X break down la recorded in the modified OKO8er*ai*<ns- Teat (7). For a teat which recorda complete chemical degradation ouch as the TOC-degradation teat (6), a 40 X break down should be the minimum required. Other teata can be uaed ip replacement of the abovementioned, if it has been proven, that equal reaulte are obtained aa for the teata according to (6) and (7), when thaae producta are tested. ; ^ . . \ -v iv'V- tha tonic effects o f .the foam coapounds towards water orgadlsm, especially bacteria, algae, a^(l?9e n & a end flab should be as small as possible.< A %. sufficiently nontoxic range can be set if the BC^q for bacteria, algae, daphni and fish is above 1500 mg/1 foam agent in water. For toxicology teat, L 11, L 12, and L115 of DEV (4), or aimllar ' 1` . ' procedure for which equal type results can be proven, are to be used. i:- " ' The heavy metal content should not exceed 1 X zinc, or fop other metal : . V" ' / ;: an amount for which a corresponding degree of bacteria toxic effects is f*. . recorded. `i* *C . 6. Conclusion rAccording to the teak the following six foam compounds, determined . \ by the "Bundesamt fttr Wehrtechnlk und Beachaffung" in Koblenz, ware evaluated withrelation to possible endangering of waters: Flnarproteln; bight Water ;> f=c*7 " . FC 206, normal; Light Water FC 206, Frost protected;Light Water FC 20Q, normal; Protelnabhaumlttal; Expyrol F 15. The test Includes Interphase activity, -- h >* toxicology, biochemical degradation, heavy metal content and flame point. The results were presented and discussed end a conclusion r a a c h s d . T h a . ,V / v products Fluorprotein and 'Proteinschaunmlttel were racoamandad due tp ' V t --' v.. . *'v--.\ f : ;' relatively favorable biologic characteristics. The final conclusions, a m m r / \C _rW,i- given as recommendations for technical delivery terms (TL) t o b t u H d b y ' the contract agency. -18- BEST COPY AVAILABLE LITERATURE LIST . (1) Flala, R.: Study "Mittelschaum fr Flugzeugbrandbekampfung" Dautscha Forachunga- und Varachsanatalt fr Luftund Raumfahrt e.V. Kln-Wahn 1977, (2> lundaaanatalt fr Gewsserkunde: Gutachten ber die Waasergefahrlichkalt von Schaumloschmitteln, Koblens 1975. (3) Hallmahn, H.: Schaumlschaittel - ihre mgliche Wassergefahrdung, Tenalde Detargenta 13 (1976), 270 - 273. (4) Deutache Einheitsverfahren zur Wasser-, Abwasser- und Schlamnuntersuchung. Weinheim, Erganzungslleferung 1972. (5) Zahn, R. und H. Wellens: Ein einfaches Verfahren zur Prfung der biologischen Abbaubarkeit von Produkten und Abwas serinhaltsstoffen. Chemiker Zeitung 98 (1974), 228- 232. (6) Hller, 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 biolqgiachetK Abbaubarkeit von wasserlslichen, o r g a n i s c h e n ^ Umweltchemikalien mit Khlenstoffabalytik (DOC) V (Modified OECD Screening Test). .A ::mah-;-''. script ox the ferm Henkel KG Dusfeldorft seht t the .G..es recommended process. (21,2. 1978) . - Enclosures Toxicology - concertratIon/reactIon curves and degradation curves. 1 to 6. OOlSrtO 001531 TOC in o of initial TOC Inhibition in Increase in Nr. 3 Light water, FC 206, normal i ----;-- I TOXICOLOGY T3ST i A Incor p o rat ion tor<t DiVL 12 I) Laphno ten t DKVL 11 z ti'ietlvibolip m t e s t DiiVT, 1? F - Fish to n t DiVIi 15 Increase in i Inhibition in $ -- -- 100 1 jpMB 4 m :pfijii iiiiiiii V\ *- 1 FJ----------- -- ------ \ \% ii 10 25 50 1[10 250 1C100 10300 Concentration mg/l 31 80 oo B* cd H -P 60 H C Vl o 40 c oo B* Test'of TOC- de/radation I U 21 01S83 Nr. 4 Light water, FC 200, normal 1 +UJ0 1 i1 +80 +60 POXICLO}Y T3SST A= IncorjjoratiLon tos t DC VL 12 D= ])aphn<3 torib D13VL 11 1 Z- 1vietha'oolipra tort D'lVIi 12 ,P 'ish. tort DiiVI. 1*5 \R c +40 I a + 20 o u oc 0 MinfT.n.ir.1 nril r-irtr^ -20 \ \ , c -40 co -60 H H -80 c <100 L \ %L V _ \ \ "53 \ \ T Vi.J ... .3 10 25 50 100 250 1000 10X0 Concentration mg/1 60 oo I--I 1 rl 60 + H C H O 'R 40 c H oo ' 1-- -------------------_____________________ __ __________ - T o r.t oT TOC-- lo ffr a d n tio n ' ___ . 1 ---- L. ............................................n.. 14 21 tie w f (b f 00158 Nr. 5 Proteinschaummittel 1 Increase in $ Inhibition in # TOC in % o? initial TOC / / e */ 'f y j r i t / (J a y c 00158 Nr. 6 Expyrol F 15 00- i i 00- ToXICOLOijY TE;iT __ A.= Incor<oratJioi tes t DE VL 1? '? . c 60- D= Da pan tesib Davi 11 H Z- Ilethabol irn tcpt D-VI, 12 - :'ish tort D m . i5 ' 40 ce O c 20- M y Sjs^-H ____________ g* -- < t X * "'Z-- 0h r s, 20 c H c 40 H H 60rO H .0 C M eo \1 \ 1 L LV_______ m~ v v j --- V- <x 1jn>j X , ' (F) 00 -------- i 10 25 50 100 250 1000 _ .. 1Q0Q_ Concentration* m/l 00 O O 80fr* 'S -f H C H 60 O c H O 40 fri 1 1 20 0- .--* T er. 1 o TOC- clojN id a tio n .r ftx Ai ^ 1 ; _ ________ ____________________ ~ U -- - k ^ t o t e t i f * J v + r i t f m. . 01$6