Document ODQN81MqDqRRLXYGjrKr7Rzw

DEPARTMENT OF THE NAVY NAVAL RESEARCH LABORATORY 4SSS OVERLOOK AVE SW WASHINGTON DC 20375-5320 3900c-H H C P L V R E F E R T O Ser 6180/0149 %t m From: Commanding Officer, Naval Research Laboratory ' To: Commanding Officer, Naval Facilities Engineering Service Center, Port Hueneme, CA (Code ESC421 R. Lee) Subj: AQUEOUS FILM FORMING FOAM (AFFF) ALTERNATIVES Enel: ( 1) Two copies of subject report 1. Enclosure (1) is forwarded for your information and retention. 2. The Naval Research Laboratory point of contact is Dr. Frederick Williams, Code 6180, (202) 767-2476 and email fwilliam@ccs.nrl.navy.mil. WARREN W. SCHULTZ By d ir e c tio n Copy to: COMNAVSEASYSCOM (Code 05P6 D. McCrory, D. Barylski) OPNAV (Code N762M2 T. Harmon) Distribution Authorized to US Government Agencies and their Contractors Only; All other requests shall be forwarded to: Commanding Officer Naval Research Laboratory, Wash. DC. THIS INFORMATION HAS NOT BEEN APPROVED FOR PUBLIC RELEASE. US00000801 AAQLTUEERONUASTFIIVLEMS FORMING FOAM (AFFF) 180A:FW 1 April 2003 RG.eAo-.CBernotwerns Inc. Lanham, MD APG.lleoAxba.anTldaPrtaaem,peVrAless Solutions C. Whitehurst J. Farley NFC.haWvemy.TiWsetrciylhliDnaomivloissgiyonCenterfor Safety and Survivability Enel (1) to NRL Itr 39000 Ser 6180/0149 Distribution Authorized to US Government Agencies and their Contractors Only; All other requests shall be forwarded to: Commanding Officer Naval Research Laboratory, Wash. DC. THIS INFORMATION HAS NOT BEEN APPROVED FOR PUBLIC RELEASE. US00000802 References (a) Qualified Products List for Military Specification Aqueous Film-Forming Foam (b) Military Specification MIL-F-0024385F, 7 January 1992, Fire Extinguishing Agent, Aqueous Film-Forming Foam (AFFF) Liquid Concentrate, for Fresh and Sea Water Introduction Military Specification Aqueous Film Forming Foam (AFFF) is used worldwide to combat liquid fuel fires. It is the best available agent for rapid fire extinguishing and bum back resistance o f aviation, shipboard, chemical process and petrochemical hydrocarbon fuel fires. The very chemical structures o f the agent that makes it effective for fire fighting also results in potentially undesirable environmental characteristics including: persistence in the environment, potential bioaccumulation in human tissues and toxicity at certain concentrations. Additionally, discharge of foam solution may interfere with waste-water treatment plants. The trend is clearly toward stricter regulation o f the chemicals in AFFF and of the discharge of AFFF into the environment. There are several potential options to address issues related to AFFF impact on the environment. In the short term, there is current technology that appears to be able to reduce the quantities of these environmentally unacceptable chemicals. Additionally, there are other existing agents with potentially less environmental impacts than AFFF that may meet some o f the current dfierteeprmroitneecttihoant rtheqeuseiraegmeennttssc. aAn nmienevtecsutirgraetnitorneoquf itrheemceunrtrse.ntly available agents is needed to The Naval Research Laboratory, in conjunction with Naval Facilities Engineering Service Center, has conducted a test program to evaluate environmentally friendly fire fighting foam candidates as AFFF alternatives. The objective o f this program was to determine the extent to which commercially available or newly developed agents with potentially less environmental impact can meet the current fire protection requirements o f the AFFF military specification. The fire fighting performance, sealability and foamability were evaluated to assess the suitability o f submitted products as alternatives. Product information provided by manufacturers disclosed explicitly and quantitatively the presence o f fluoro-surfactants. No effort has been made to date in this project to substantiate the stated "environmental friendliness" o f the submitted agents. A screening test procedure for fire fighting performance only was conducted at the NRL Chesapeake Bay Detachment with no on-site vendor participation. A representative AFFF agent from the Qualified Products List (QPL) (reference (a)) was tested for comparison with the alternative products. Selective information for the agents that were tested is listed in Table 1. Information includes the recommended working solution concentration, advertised use, and whether the agent is fluorinated or not. The listing is coded so as not to specifically identify products but to Tpraobvleid. e a means for comparing their relative fire fighting performance to the QPL agent in the 1 TABLE 1. Agents tested Aeent # 1 2 Concentration 3 %/ 6 % 3% Fluorinated Yes Yes 3 4 3% 3% Yes Yes 5 6 7 8 9 10 11 12 13 14 15(QPL) 3% 3% 6% 6% 0.3 % / 1 % 1%/ 3 % 3% 6% 6% 3% 6% Yes Yes No No No Yes No No No Yes Yes Test Procedure The tests used for screening to evaluate fire extinguishing performance were based on the Military Specification MIL-F-24385F(SH) dated 7 January 1992, "Fire Extinguishing Agent, Aqueous Film Forming Foam (AFFF) Liquid Concentrate, for Fresh and Sea Water" (reference (b)). The 28-ft2fire extinguishment test described in the MIL-SPEC was used to evaluate extinguishment capability. All agents were mixed full strength in fresh water using the vendor suggested mixing ratio. Ten gallons of unleaded gasoline fuel were used that conformed to ASTM D439. The fuel was poured within a 30-sec period, ignited within 30 sec o f fueling and allowed to bum freely for 10 sec. After the prebum period, the fire was attacked and extinguished as expeditiously as possible, continuing foam application for a total o f 90 sec even if the fire had been extinguished. All fire tests were continued until extinguishment occurred if extinguishment could be accomplished safely. The actual fire extinguishing time was recorded. If the agent extinguished the fire, the MIL-SPEC bumback test procedure was performed to evaluate foam blanket resistance to degradation, followed by the expansion and drainage test (foamability) to evaluate the quality o f the foam, and the film and seal test to evaluate the effective sealing of the surface of the fuel to prevent re-ignition. The following bumback procedure was done according to the MIL-SPEC: A burning pan (1-foot in diameter with 2-in. sides) containing 1 gal o f unleaded gasoline was placed in the center o f the 28 sq ft pan and a time started. When it appeared that the fire had spread outside the pan so that burning would continue after the pan was removed, the pan was removed. The bumback time is that time at which it is estimated that 7 sq ft (25 percent) of the total area is involved in flames. The bumback time was also recorded. The purpose o f each o f these tests was to provide data for cSoPmEpCarcrisitoenrioa.f the agents being tested, and not to determine if they would pass or fail the MIL 2 US00000804 Test Results tTehsterMesIuLlt-sS.PEC criteria given in reference (b) are listed to give perspective when comparing the BFiurme ebxatcinkgtuimiseh:m3en60t time: 30 seconds seconds maximum (6 minutes) minimum Expansion: 5.0 minimum Drainage time: 150 seconds (2 minutes 30 seconds) minimum Film & seal: Pass / Fail (no sustained ignition) TarheeliesxtteidnginuiTshambleen2t.tIefsttshewaegreendtofnaeileind at least duplicate; to extinguish the the best times or performance figures fire, then the bumback, expansion and drainage, and film and seal tests were not performed. A "+" sign following the "Fire Out" time wptAihnreFedorFivQeciFadnuteeaeedxclsiteftifsinhoesgaeadumrfPioysraahfompoedprrubsleicecxatiastnnitdnLigo/giontsuertisosafthfienxd4mde:dde3hni0awdtd.tanopItoen4rtre:te4vshx5piootrsi(uane(ysmgtleuynisnoipts:zshas,zselttscehhe)seedbof1eain0rflloetghrtaaheenlelbdpoMeenairnsIlitmLgeor-efeSntxaPeahgrtEaeiovCnueftsttcmmehrdeieitx.te2her8Aoidadgs.fsqeonr(fptteo#afru1cteh5albtipleseasftnQr)oPmL Table 2. Test Results. Agent # 1 1 CToe6ns%ete. d% 3% Fire Out (seconds) 90 + 220 + 23 3% 3% 31 79 45 3% 3% 42 36 6 3% 32 7 6% 210 + 8 6% 289 + 9 9 10 331%%% 136 290 + 30 11 3% 287 + 12 6% 160 + 13 6% 50 Bum Back Time (seconds) 455 420 353 424 505 30 680 475 Expansion 8.7 3.6 8.9 7.7 8.5 9.1 10.3 14 3% 29 485 8.6 15 6% 32 555 Drain Time (min:sec) 8:50 2:50 3:35 5:30 8:10 34:00 No drainage observed 6:20 Film Suggested I & Seal Use Pass PPPFaaaasssislss Pass Fail Pass QPL DISCUSSION Comments/observations are given below for each o f the agents: 3 US00000805 Agent #1 This agent was designed for application at 3% and 6%, suggesting 3% usage with Easaprilryataepdpnliocazztiloens.o thick layer o f foam f the that afopapmeartoedatdoirdeicmteindisahretaheo ffitrheeibnutrhnaitnlgimfuiteeldsuarrfeaac. eRperdoivriedcetdioan o f the foam in an attempt to control the fire allowed it to increase to its full intensity bpageeracfaionur.smeBaoonftchteh.tehTeinh6te%en6s%aintydteo3sft%twhsaeosfliucroteinoadnnusdcwtheeadrzeafortdresootunesdlycwoanitsdhhiotnirootndpseiscrcrieoerdantoeibdfltefiomdrieftfh(e9er0efi+nrceseecin) fighter. The foam quality prior to application to the fire appeared to be "good". Agent #2 "Good" quality foam blanket was produced. Agent #3 The foam quality was "soupy". Very little foam blanket build-up. There did not appear to be a seal forming on the surface and the splashing of the new foam being applied broke the surface coating and caused substantial flare up o f the fire. Agent #4 The foam appeared "wet" compared to other foams generated. The extinguishment time was marginal with fire flaring again when the fire was almost extinguished. The fire was more difficult to extinguish following the bumback. This could be due to the fuel being heated by the bumback process. Agent #5 When the fire was nearly out, small flickering flames were difficult to extinguish and added approximately 5 seconds to the "Fire Out" time. During the bumback, the surface resealed without extinguishing the fire completely and the bumback time was extended significantly. Agent #6 The foam blanket and effectiveness were "good". Small flames at the pan edge persisted, adding a few seconds to the "Fire Out" time. 4 Asent #7 Foam was applied with no noticeable suppression of the fire. At 90 seconds the heat was so intense the fire fighter backed away and the water nozzles on the edge of the pan were briefly turned on. The water was secured and foam application was continued after a few seconds. This happened again briefly at approximately 60 seconds later. The foam application was initiated again until 3:50 (min:sec) had elapsed with no noticeable suppression of the fire. Portable extinguishers with an AFFF from the QPL were used to extinguish the fire. Aeent #8 The foam did not extinguish the fire. The overall intensity and heat release rate of the fire were diminished but a seal on the surface did not seem to form to extinguish the fire. Where the foam blanket was "piled" up at the edges, some suppression occurred, but when the foam was redirected to other areas on the flaming fuel surface, the initially suppressed flames quickly returned to full intensity. At 4:49 (min:sec) the foam in the system reservoir (10 gallons) was exhausted and the fire was not extinguished. At 5:07 (min:sec) portable extinguishers were used to extinguish the fire. Tafigrheee.netfbfeecintgotfetshteedQoPrLthAeFtFemFpwearastduirme ionfisthheedf,upelerfhroampstbheeclaounsge boufrmniinxgintgimweitohftthhee Aeent #9 At 60 seconds the fire was out over 6% o f the surface. At 90 seconds the fire was out over 75% of the surface. At 2:16 (min:sec) the fire was extinguished. The foam blanket looked good The foam seemed to form a seal on the surface, but its resistance to bumback wasn't effective. When the bumback pan was inserted the fire reached 5% to 10 % o f the surface immediately and the pan was removed at 26 seconds. In 30 seconds 50% o f the surface was burning. In 60 seconds 100% o f the surface was burning. Agent #9 was reapplied. Alotw2:in15ten(msitiyn.:sec) after starting the bumback, fire covered 50% o f the surface at a Aovte3r:3109%(moifnt:hseecs)utrhfeacfeo.am in the reservoir was exhausted and fire still covered At 3:40 (min:sec) the portable extinguishers were used to extinguish the fire. At 4:30 (min:sec) the fire was extinguished with the portables. In a separate test, in which Agent #9 was mixed at 3% (note this was higher than the manufacturer's recommendation), it failed to extinguish the fire by 290 seconds, at which time the system reservoir was exhausted and portable extinguishers were used to extinguish the fire. 5 US00000807 Agent #10 The The sfouarmfacleoorkeseedal"egdowodh"en(stimheilbaurmtobMacIkLf-iSrPe EpaCnAwFaFsFr)emanodvepderaftor6m:0e0d(wmeinll:.sec) and the fire re-extinguished. Agent #77 After 60 seconds of foam application, about 50% of the surface was out. After 96 seconds of foam application, about 60% was out. The flame intensity and heat release rate foam application was redirected to other were areas doinmtihneisfhueedl by this foam, but surface, control o when the f the fire was lost. Tthheefifroea.m blanket seemed to control the fire but did not seal the surface to extinguish Aquti4ck:4ly7.(min:sec), the foam in the reservoir was exhausted and the fire intensity grew At 5:00 (min:sec), the portable extinguishers were used. The performance o f the QPL AFFF seemed diminished, due perhaps to mixing with this non-fluorinated AFFF or the temperature of the fuel. Agent 12 At 160 seconds there was no discemable suppression o f the fire, and the portable extinguishers were used to extinguish the fire at 180 seconds. The fire intensity and heat release rate were very intense. Agent #13 Thick foam and "good" foam blanket. Flickering flames persisted and extended the extinguishment time a few seconds. For the expansion and drainage test there was no drainage from the foam observed by 12 minutes, at which time the test was halted. Agent #14 Good foam blanket and performance. Agent #15 Small flickering extended the fire-out time a few seconds. Good foam blanket and performance. 6 CONCLUSIONS Agents 2, 5, 6, 10, and 14 are recommended for further evaluation. They performed well in the fire extinguishment test and met or exceeded the requirements for bumback, expansion and drainage, and film and seal criteria. All contain fluoro-surfactants. Agent 4 is recommended for further evaluation. It performed marginally in the fire extinguishment test, and marginally the bumback test, but met or exceeded the requirements for expansion, drainage, film and seal. It contains fluoro-surfactant also. Agent 13 is recommended for further evaluation. Although it performed poorly in the foamability and sealability test, and gave only marginal extinguishment time, it gave good bumback protection, expansion ratio and drainage time. It shows promise because o f its stated improved environmental impact (no fluoro-surfactant content). Agents 3 (fluorine-containing) is not recommended for further evaluation, because the fire seexatilningguiushsemdefnotrteimvaeluwaatisonm.arginal and it failed the MIL-SPEC criteria for expansion ratio and Aangdenvter9yipsonoort bruecmobmamckenpdreodtefcotirofnurther evaluation as it gave a very long extinguishment time tAhgeetnetsst f1i,re7., 8T,h1e1oatnhder1c2riaterreinaowterreeconmotmteesntdeded. for further evaluation. They did not extinguish dSouwmnmsaerliezcitnegd, tthoeselivsetnofca1n4dciadnadteidsafotersfionliltoiwal-loynsupbrjoegcrtaemd .to fire performance testing has been RECOMMENDATIONS The immediate follow-on should be a more detailed evaluation o f the environmental issues and benefits o f the alternative firefighting foams compared to MIL-SPEC AFFF. The seven down selected products have demonstrated sufficient performance to warrant more detailed investigation of their claimed environmental benefits. They are being analyzed for Chemical Oxygen Demand (COD) and Biological Oxygen Demand (BOD) to assess their biodegradability. A number o f additional factors must also be considered in ascertaining a product's environmental impact. These include adquatic toxicity to various species, compatibility with wastewater treatment plants, presence and concentration o f solvents (e.g. glycols and glycol ethers) as well as the proportion and composition o f the fluorine-containing components. This iancfcoerpmtaabtiloenalwteirllneantiavbelfeirmefeiagnhitninggfuflofaumrtsh.er down selection for achieving environmentally A more general appreciation o f the technical issues involved in AFFF reformulation, and correlation between the physical properties (such as dynamic surface tension, viscosity, propensity to produce foam) and the performance tests (such as fire extinguishment time, bumback resistance and drainage rate), should be established. This technology.base will greatly tfhaceisleitmatoerceadndetiadialetedesvtualduiaestiownilal nbde fguitvuerne iinmaprsoepveamraetnetrse.poDrits.cussion on the proposed details of 7 US00000809