Document myw7qOXO6g1gk3gX4grq9Kq4

DEPARTMENT OF THE NAVY NAVAL RESEARCH LABORATORY 4555 OVERLOOK AVE SW WASHINGTON DC 20375-5320 So. ^ C . y 3905 ? 1996Ser 6180/0572 From: Commanding Officer, Naval Research Laboratory To: Commander, Naval Facilities Engineering Service Center (Code ESC-421 R Lee), 560 Center Drive, Port Hueneme CA 93043-4327 Subj: ENVIRONMENTAL AND EFFICACY TESTS FOR AFFF SEPARATOR USING ACTUAL FIREFIGHTING WASTEWATERS u Enel: (1) Two copies o f subject report 1. Enclosure (1) is forwarded for your information and retention. This w ork is being conducted under PE DBOF, Work Request N6830596WX00024. 2. There is concern about the potential environmental harm when Aqueous Film Forming Foam (AFFF) constituents spread to the environment or are discharged to waste w ater treatment plants. NRL has developed a prototype AFFF separator. The AFFF separator reduces the AFFF surfactants from typical firefighting waste waters. The presence o f contaminants that would typically be found in firefighting wastes, such as petroleum hydrocarbons and aromatic compounds, do not appear to adversely affect the mechanism o r the efficiency o f the process. In addition, the separator reduces the other pollutants in the waste as measured by BODs, COD, VPH, BTEX and TPH. The concomitant reduction can be significant, e.g., 95 to 100%, particularly for the more volatile species. The overall results are extremely encouraging and continued development o f the AFFF separator is recommended. 3. The NRL Point o f Contact is Dr. F. W. Williams, Code 6180, (202) 767-2002; email, fwilliams@itd.nrl.navy.mil. For furher information about the Navy Technology Center for Safety and Survivability visit the NRL WEB Site at http//chemdiv-www.nrl.navy.mil/6180,htm. Copy to: COMNAVSEASYSCOM (Code 03G Darwin) NFEC (Gott) LANTDIV/NAVFAC (Code 18111 Clark) A001717 A001717 US00007055 6180/0572A,1:FWW 24 September 1996 Environmental and Efficacy Tests for AFFF Separator using Actual Firefighting Wastewaters o \ J^iLeonard F.W. Williams Navy Technology Center for Safety and Survivability Naval Research Laboratory D.P. Verdonik R.E. Bums R J. Ouellette Hughes Associates, Inc. 3610 Commerce Drive, Suite 817 Baltimore, MD 21227-1652 Enel (1) to NRL Ltr 3905 Ser 6180/0572 US00007056 CONTENTS Page 1.0 IN T R O D U C T IO N .................... 1 1.1 Review o f Previous W o rk ............................................................................................... 2 1.2 Environmental Requirements .......................................................................................... 3 2.0 A P P R O A C H ................................................................................................................................. 3 3.0 EX PER IM EN TA L.................................................................... 4 3.1 Source o f Firefighting Test W a te rs ............................................................................... 4 3.1.1 MILSPEC Test W ater........................................................... 4 3.1.2 Waste Tank Water 5 3.2 AFFF Surfactant S ep aratio n .................. 5 3.3 Environmental Tests . . . ............................................................................................ 5 4.0 RESULTS AND DISCUSSION . 4.1 AFFF Surfactant Reduction 4.2 Environmental Tests . . . . . 4.3 MBAS and Drain Time Correlation ....................................................................... 11 4.4 Summary ............................................................................................................... 13 5.0 C O N C L U S IO N ........................................................................................................................... 13 7.0 REFERENCES ........................................................................................................................... 14 ON On On US00007057 Environmental and Efficacy Tests for AFFF Separator Using Actual Firefighting Wastewaters 1.0 INTRODUCTION The U.S. Navy is one o f the world's largest consumers o f aqueous film-forming foam (AFFF). AFFF is currently the agent o f choice for suppressing combustible/flammable liquid fuel fires resulting from aviation and shipboard accidents and battle induced damage. The Naval Air Systems Command (NAVAIR) uses AFFF in essential fire suppression systemsjirotecting ^ aircraft assets. Mobile vehicles (both shipboard and shore side) use AFFF which is discharged through turrets and hand lines. Aircraft carrier flight deck wash down systems can discharge / AFFF in the event o f a serious flight deck mishap. L NAVAIR is not the sole Navy user o f AFFF. The Naval. Sea Systems Cgmmand, the technical manager for the AFFF procurement specification, MIL-F-24385 [1], specifies'AFFF to protect surface ship and submarine machinery spaces through hand lines and fixed sprinkler systems. Deluge sprinkler systems are used to protect aircraft carrier hangar decks. The Naval Facilities Command (NAVFAC) specifies AFFF sprinklers for shore side hangars and other flammable liquid hazards. In addition, AFFF is used by the U.S. Air Force and the civil sector for aircraft crash, fire and rescue, and in hanger applications. There is concern about the potential environmental harm when the AFFF constituents spread to the environment with run-off from fire fighting operations or are discharged to wastewater treatment plants [2], The primary component o f AFFF solution is water. Other components include non-fluorinated surfactants (e.g., hydrocarbon surfactants), glycol ethers, and fluorinated surfactants. The environmental issues which have been raised include persistence o f AFFF fluorosurfactants, discharge o f glycol ethers used in foam formulations, and the potential for upsetting the balance o f biodegradation mechanisms in wastewater treatment facilities when foams are discharged and treated in this manner. It is suspected that some o f the compounds used to create the highly effective characteristics o f AFFF do not readily breakdown in the environment. Thus, the very elements which apparently make AFFF an effective agent have a detrimental, o r at least an unknown, impact on the environment. Based on these perceived problems, local authorities may severely restrict or prohibit the discharge o f AFFF into the local wastewater stream. This is currently the case with several wastewater treatment plants in the Maryland/Virginia area. 1 US00007058 1.1 Review of Previous Work In response to these problems, the Naval Facilities Engineering Service Center sought an economical way to separate AFFF from the wastewater at fire training facilities. The project resulted in a proof-of-principle device that lowered the AFFF in water solutions [3], A brief summary o f that work follows. The first task was to develop a simple test that could be performed in the field that would correlate with the AFFF concentration. The method developed is based on drain times. The AFFF MILSPEC requires that drain time be determined for all AFFF solutions [1], The drain time is defined as the amount o f time required for a specific amount o f generated foam to return to a specific amount o f liquid. The MILSPEC test required specific procedures and equipment that was not readily adaptable to a small-scale field test. An inexpensive test to measure drain time was developed. Drain time is measured using a 2.54 cm (l-in) diameter by 10.2 cm(4 in) high test tube with a screw cap. The tube is filled with 5.2 cm(2 in) o f solution and shaken 50 times. The time to reduce 90 percent o f the foam back to liquid is recorded. Several problems still exist with this manual method: sensitivity to how vigorously the sample is shaken, the temperature and the amount o f liquid. To overcome some o f these problems a single operator was used. Acceptable repeatability was then achieved. The drain time results were correlated against a property o f the AFFF that could be accurately measured, surface tension. The results were in excellent agreement and provide a good measure o f the relative decrease in the amount o f AFFF in the solution. This proof-ofprinciple work only used one AFFF concentrate, 3M brand 6% MILSPEC AFFF foam concentrate (FC-206 CF). With a method to measure the relative concentration o f AFFF in solution, a series o f breadboard AFFF separators were developed. The basic design concept was to use air bubbles to create,a foam. Water alone can not form a bubble, but the surfactantsjn the AFFF allow a foam to form. The foam shouId~Fe~fIch mTurfactants~compared~with the averagew ater solution. This effectively concentrates the surfactants into the foam which can be subsequently removed by mechanicaljpeans. _The method was shown to be capable o f separating the surfactants from AFFF-water solutions down to a concentration o f 1000 ppm, or lower, o f surfactants. In summary, previous development work proved 1) the feasibility for using foam creation to concentrate and remove the AFFF fluorosurfactants, 2) the basic design features for the separator unit, and 3) a simple field test that correlates the reduction in surfactant levels to a laboratory measurement technique. All o f these results, however, were obtained on `standard' or pure AFFF-water solutions that would be typical from AFFF discharge tests, e.g., testing fire trucks. There are two other scenarios for creating wastewater containing AFFF that still needed to be evaluated in the separator unit: Standardized Fire Tests (e.g., AFFF MILSPEC Qualification Tests) Actual Fire events (Firefighter Training) 2 T US00007059 1.2 Environmental Requirements In addition to the other types o f wastewaters, the effluent from the separator needed to be evaluated in terms o f environmental impacts. Seven tests were chosen based on requirements o f Hampton Road Sanitation District and the wastewater treatment plant at the Chesapeake Beach Detachment (CBD) o f the Naval Research Laboratory (NRL) [4,5]: 1. Biological (Biochemical) Oxygen Demand, 5 day (BOD5) 2. Chemical Oxygen Demand (COD). 3. Volatile Petroleum Hydrocarbons (VPH) 4. Total Petroleum Hydrocarbons (TPH) 5. Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) 6. Methylene Blue Active Substances (MBAS) 7. pH The BOD test measures the amount o f dissolved oxygen that is consumed by bacteria in breaking down the organics present in the sample. The higher the BOD the greater the extent o f pollution. The COD test measures the amount o f oxygen that is required to oxidize the organics present under certain conditions of oxidizing agent, temperature and time. It is a separate measure from the BOD test and has no direct relationship to the results o f the BOD test [5,6]. The ratio o f BOD to COD however, is often used as an indication o f the degree o f biodegradability o f a sample. A BOD/COD ratio equal to one means that all o f the organics that can be oxidized, as indicated by the COD test, are oxidized by the microbes in the water, as indicated by the BOD test. The petroleum hydrocarbon content is tested in three ways. The BTEX test is exactly as its name implies. It measure the concentration o f benzene, toluene, ethylbenzene and xylenes. The VPH test covers the organic range C4 through C l2, commonly referred to as the gasoline range. The BTEX and gasoline range tests can be run together. The TPH tests measures organics CIO and up. This effectively covers the diesel range (CIO to C24) and the oil and grease range. These three tests in combination, should adequately characterize the fuel concentration/contamination of the wastewater [6], The MBAS test is used to measure the concentration o f detergents and surfactant type materials that react with methylene blue to form a blue colored salt. It is only applicable to anionic surfactants measured as linear alkyd sulfonates (LAS) [5], 2.0 APPROACH W astewater from a standard AFFF QPL test, and from the 660,000 I (20,000 gal) wastewater tanks at CBD were tested using the AFFF separator to determine the ability to reduce 3 US00007060 the AFFF surfactants. The drain time versus concentration plots developed under the previous work were used to determine the effectiveness o f the separator with these wastewaters [3], Before and after samples o f the two wastewaters were sent to an EPA approved environmental laboratory for the required tests. All samples were tested for BOD, COD, pH, MBAS, BTEX, and VPH. Only the wastewater from the storage tanks was tested for TPH. The wastewater from the QPL test uses gasoline so there should not be any heavy hydrocarbons present that would require the TPH tests. Standard samples o f AFFF-water solution were prepared for 1000 ppm, 500, ppm, 100 ppm and 10 ppm. These `standards' were sent to the same environmental laboratory to undergo MBAS tests to determine how well the MBAS results compare with the drain time results. 3.0 EX PERIM EN TA L 3.1 Source of Firefighting Test W aters The test waters came from the live-fire facilities at the CBD. The complex consists o f office, laboratory, and indoor and outdoor fire testing spaces. All o f the live-fire testing facilities use potable water, generally from the fire hydrant system, and are designed to collect and store all resulting wastewater. There are three basic scenarios for fire tests run at CBD that result in wastewater: Qualified Purchase List (QPL) test for Aqueous Film Forming Foam (AFFF), as described by M3L-F-24385[1,7] Small-scale tests performed in Burn Building. Mid-scale and large-scale tests performed on the flight simulation outdoor fire mat or other outdoor fire test areas. 3.1.1 MILSPEC Test Water The waste from the QPL fire tests is the easiest to characterize because there is a specific standard test method. The purpose o f this test is to determine if the specific product meets the requirements for AFFF listed in the MILSPEC. The resulting waste, hereafter referred to as MILSPEC TEST will contain gasoline and AFFF, and may also contain products from the fire. The fire products o f concern are the aromatic hydrocarbons such as those measured by the BTEX test. The AFFF concentrates and, therefore, the resulting solutions used in these tests will contain fluorinated surfactants, hydrocarbon surfactants, and glycol ethers. The precise make-up o f each AFFF concentrate is proprietary and will vary from vendor to vendor. The QPL test requires using salt water to simulate the effects o f using ocean water. The waste may also contain the salts used to generate the artificial sea water, 4 US00007061 3.1.2 Waste Tank W ater The two waste tanks collect all o f the effluents from the three types o f testing: QPL Tests, Small-scale tests in the Bum Building, and Medium- and Full-scale Tests. The resulting waste, hereafter referred as W ASTEWATER can contain any or all o f the constituents used: heptane, JP-5, JP-4, Diesel, AVGAS, MOGAS, fire combustion products, MILSPEC and non-MILSPEC AFFF, CLASS A foam extinguishing agents, PKP and salt (used to simulate sea water). There is no way to predict the concentrations o f the various elements. Samples taken at different times may result in considerably different composition depending upon the fire testing that is taking place at any given time. 3.2 AFFF Surfactant Separation A MILSPEC TEST was performed using Angus MILSPEC 3% foam. Instead o f discharging the effluent to the waste collection system it was collected in a 2091 (55 gal) drum. The drum was turned on its side and let stand for seven days. Approximately 571(15 gal) was drained from the bottom o f the tank and placed into the 35.6 cm(14 in) by 35.6 cm (14 in) by 91.4cm(36 in) high separator unit. Air was supplied at an initial rate o f 1132 1/hr (40 S C F H ) and the foam was removed every five minutes. The air flow rate was increased to 2 2 6 4 1/min (80 SCFM) when the drain time dropped to approximately 1.5 seconds to further reduce the surfactant concentration. The test was stopped when the drain time dropped below one second, approximately 5 hours and 40 minutes from beginning o f test. In a second test 76 1(20 gal) o f WASTEWATER was removed from the CBD storage tanks and placed into the separator unit. A sump pump with a two stage w ater filter was also placed into the tank to attempt to remove some o f the heavier particles present. Air flow was set at 11321/min (40 SCFM) and the foam was initially removed every 4 minutes. The test was stopped when the drain time dropped to about 2.75 seconds, approximately 12 hours and 30 minutes from start o f test. 3.3 Environmental Tests Before and after water samples from the AFFF QPL tests and the storage tank were tested for COD, BODs, TPH, BTEX, pH and MBAS. Additionally, standard samples o f AFFF solution were also tested for MBAS to determine if the MBAS test was suitable for the AFFF-type surfactants. All o f these tests were run in accordance with EPA approved methods as follows: TEST BODj COD MBAS * BTEX t VPH t TPH pH EPA METHOD 405.1 ppm 410.4 ppm 425.1 ppm 8020 ppb 8015-M ppb 418.1 ppb N/A 5 US00007062 4.0 RESULTS AND DISCUSSION 4.1 AFFF Surfactant Reduction The concentration o f the AFFF surfactants was calculated from the drain time measurements using the drain time versus concentration plots previously developed and provided in Figures 1 and 2 [3], The drain time at the start o f the MILSPEC TEST sample was 10.93 seconds representing a concentration o f approximately 1350 ppm. The drain time at the end o f the test was 0.83 seconds representing a concentration o f approximately 240 ppm. The initial drain time o f the WASTEWATER sample was 17.13 seconds or about 1800 ppm. After running through the separator the drain time was reduced to 2.77 seconds corresponding to about 500 ppm o f AFFF surfactants. These tests confirmed that the separator adequately reduces the AFFF surfactant concentration with both o f these types o f firefighting wastes. 4.2 Environmental Tests The results o f the environmental tests and the separator tests are provided in Table 1. The same headings for MILSPEC TEST and WASTEWATER are used. Samples captured for environmental testing just prior to running the AFFF Separator are labeled BEFORE. Samples taken after AFFF separation are labeled AFTER. The values given as `less than' using the "<" symbol are at or below the detection limits for that analysis, as provided in the Report o f Analysis from Gascoyne Laboratories, Inc., Appendix A. An analysis o f the BEFORE and AFTER samples from the MILSPEC TEST and the WASTEWATER indicate that all measured quantities are decreasing. The effluent from the AFFF separator contains considerably less AFFF surfactants and is less polluting as measured by the environmental tests. The reductions can be significant. This is particularly true for the more volatile species measured in the BTEX and VPH tests versus the heavier organics measured in the TPH test. This result is expected with the aeration technique used in the AFFF Separator. The MILSPEC TEST BEFORE sample was extremely high in VPH and BTEX, and had the highest COD o f the group. There is good rationale for the observed high value o f the COD test from the results o f BTEX and VPH. However, this same reasoning does not hold true for the concentration o f BTEX and VPH versus the BOD5results. The BOD5 was not very high which was unexpected based on the composition o f the wastewater. Further analysis revealed that the BO D 5test that is prescribed by the wastewater treatment plants and recommended for this study is not suitable for this type o f w astew ater. The BOD20test is apparently needed to provide enough time for the particular organics present to react with the bacteria. All future testing should require the 20 day BOD test instead o f the 5 day test to more adequately characterize these wastes. 6 US00007064 Fig. 1 - Average Drain Time vs. Concentration for A1TT {6%) Solutions t Fig. 2 - Average Drain Time vs. Concentration for AIT'F (6%) Solutions j_i _ 600 It is typical when making comparisons between the environmental tests that it is difficult to assign particular concentrations to particular results between different wastes. To overcome this problem the BEFORE and AFTER data is compared by percent reduction. The percent reduction is defined as: (initial concentration - final concentration) / initial concentration The results in Table 1 that are below the detection limits are assigned the value o f the detection limit. This assumption provides the maximum percent reduction that is possible. The results that are given as None Detected (ND) are given a value o f 0 also reporting the maximum percent reduction possible. Table 2 lists the results o f this analysis for the AFFF surfactant and the environmental tests. Table 1 - Results of Environmental Tests TEST DRAIN TIME in PPM BIOCHEMICAL OXYGEN DEMAND in mq/l (PPM) MILSPEC TEST MILSPEC TEST WASTEWATER WASTEWATER BEFORE AFTER BEFORE AFTER 1350 240 1800 500 <1000 220 1,100 870 CHEMICAL OXYGEN DEMAND in mq/l (PPM) 13000 2400 4,700 3,100 METHYLENE BLUE ACTIVE SUBSTANCES in mq/l (PPM) 13 3.7 98 29 TOTAL PETROLEUM HYDROCARBON in mo/i (PPM) Not Taken Not Taken 140 94 VOLATILE PETROLEUM HYDROCARBONS in ua/l (PPB) 2 .000.000 m ooo 300,000 65,000 BTEX BENZENE In ua/I (PPB) TOLUENE in ua/l (PPB) ETHYLBENZENE in uq/i (PPB) XYLENES in ua/l (PPB) _P_H 20,000 32,000 3200 17,000 8.1 200 <100 ND ND 8.5 700 2000 500 2400 5.6 200 ND ND <300 5.6 9 US00007066 The M3LSPEC TEST samples contained volatile organic compounds that are effectively removed by the aeration process in the separator. The BTEX and VPH are reduced by over 95%. The MBAS, BOD5and COD are reduced by 78 - 82%, providing excellent agreement. This would seem to imply that the COD and BOD, tests are adequately taking into account the AFFF surfactants. The results o f the WASTEWATER samples are not as straight forward. While the percent reduction o f the more volatile organics as evidenced by the BTEX and VPH results is still quite large, they do not correlate well with the change in COD. There may be several reasons for this. The starting concentration for VPH and BTEX are considerably lower for the WASTEWATER samples than for the MILSPEC TEST samples. As such they do not contribute as much to the COD results. The concentrations for BTEX and VPH for both AFTER samples are in the same concentration range. Using the values for VPH from Table 1 for AFTER samples o f MILSPEC TEST and WASTEWATER, the results are 300,000 ppb and 65,000 ppb respectively. There may be a lower limit to the reduction o f VPH using the AFFF separator so that the percent reduction analysis is misleading. Lastly, the presence o f heavy hydrocarbons that are not as effectively removed by the aeration process may be more responsible for the COD than the volatile hydrocarbons for the WASTEWATER samples. The percent reductions between the TPH, COD and BOD, are in better agreement than any other tests o f the WASTEWATER samples. This would seem to imply that the AFFF surfactants are not affecting the changes in the BOD, or COD very much, if at all. This discrepancy between the MILSPEC and WASTEWATER samples is not explainable at the current time with the limited test data available. Table 2 - Percent Reductions between BEFORE and AFTER Samples TEST DRAIN TIME BOD, COD MBAS TPH VPH BTEX BENZENE TOLUENE ETHYLBENZENE XYLENES MILSPEC TEST WASTEWATER % REDUCTIONS % REDUCTIONS 82% 72% 78% 21% 82% 34% 72% 70% NA 33% 95% 78% 99% 100% 100% 100% 71% 100% 100% 88% 10 US00007067 4.3 MBAS and Drain Time Correlation To determine if the MBAS test could be correlated to the drain time results, four standard samples o f Angus 3% MILSPEC AFFF were prepared: 1000 ppm, 500 ppm, 100 ppm, and 10 ppm. These samples were prepared using the same concentration assumptions used in the previous work [3]. The drain time for the standards were measured and the concentrations determined using the drain time versus concentration plots provided in Figures 1 and 2. The results are provided in Table 3. The drain time concentration values for the two samples below drain time detection limits are estimated using the average values from the drain time data and are shown in italics. Table 3 - Drain Time anc Concentration o f AFFF Standard Solutions CONCENTRATION DRAIN TIME CONCENTRATION BY DILUTION. PPM SECONDS BY DRAIN TIME, PPM 10 ND 7 100 ND 68 500 2.29 360 1000 4.34 670 The concentrations based on drain time are approximately 30% lower than predicted from dilution. This is not unexpected. Firstly, there were considerable assumptions made in the previous w ork in determining the concentration o f the AFFF surfactants. Secondly, the AFFF used for this study is different than the one used for the previous study, Angus 3% MILSPEC AFFF versus 3M 6% MILSPEC AFFF (FC-206 CF), respectively. It is reasonable to expect that there are different concentrations o f surfactants between the two proprietary formulations. These four standard solutions and a control blank with the same water used to dilute the standards were sent for MBAS analysis. The results are provided in Table 4 with the results for the MILSPEC and WASTEWATER samples. Table 4 - Drain Time Concentration versus MEIAS Results CONCENTRATION MBAS SAMPLE BY DRAIN TIME, PPM PPM S-2 fCONTROL BLANK) S-1 S-5 00 7 0.05 70 0.44 360 4.4 S-3 670 7.4 MILSPEC BEFORE MILSPEC AFTER 1350 240 13 3.7 WASTEWATER BEFORE WASTEWATER AFTER 11 1800 500 98 29 US00007068 The intent was to determine if the MBAS results could be used to determine the concentration o f AFFF surfactants. A Correlation Factor was developed by dividing the drain time concentration by MBAS. The results are provided in Table 5. The results for the standards and the MELSPEC TEST samples all appear to be in the same range. However, the WASTEWATER results are an order o f magnitude higher for similar drain time concentrations. Possible explanations for this discrepancy are provided later in the report. The average Correlation Factor o f 106 for the four standards and the MELSPEC tests is used to calculate concentrations based on the MBAS. The results are also provided in Table 5 with the percent difference between the two concentrations. Table 5 - Drain Time-based Concentration versus MBAS-based Concentration in ppm SAMPLE S-2 S-1 S-5 S-3 DRAIN TIME CONCENTRATION 0 7 70 360 670 MBAS CORRELATION MBAS FACTOR CONCENTRATION DIFFERENCE 0 NA 0 NA 0.05 139 5 23% 0.44 158 47 33% 4.4 82 468 -30% 7.4 91 787 -17% MILSPEC BEFORE M1LSPEC AFTER 1350 240 13 3.7 104 65 1382 393 -2% -64% WASTEWATER BEFORE WASTEWATER AFTER 1800 500 98 29 18 10421 -479% 17 3084 -517% The results for the standard samples are the best with absolute value percent differences ranging 17 to 33 % but the values for the others are not as good (i.e., 2 - 64% for MELSPEC TEST samples and 479 to 517% for WASTEWATER samples) and would not provide an adequate estimation o f the AFFF surfactants. There are several possibilities why this may be occurring. The MBAS test that is specified by the wastewater treatment plants is for anionic surfactants only. However, AFFF is a complex mixture o f surfactants that may include anionic, non-ionic and cationic surfactants, and therefore only an unknown portion o f the surfactants may be accounted for in this test. Secondly, the test was developed for typical surfactants used as detergents and is reported as LAS [5], In calculating the results in a certain molecular weight is assumed that is almost certainly different from the molecular weight(s) o f the AFFF surfactants. The results, therefore, would not be linear. Lastly, there may be chlorides in the WASTEWATER samples that are interfering with the results [5], Chlorides may be present in the wastewater because the QPL test 12 US00007069 requires testing AFFF formulations with simulated salt water. The MBAS test alone does not appear to be adequate to determine the concentration o f AFFF surfactants. There is another environmental test that may be used to measure non-ionic surfactants, Cobalt Thiocyanate Active Substances (C T A S ). It is recommended that future work include both the MBAS and CTAS tests to determine if the combined results correlate to the drain time concentrations. There does not appear to be an EPA test method for cationic surfactants. The rationale is that the cationic surfactants represent only a small fraction o f the total quantity o f surfactant manufactured in the U.S. Unfortunately, the percent o f cationic surfactants within AFFF formulations may be considerably higher than the U.S. average. 4.4 Summary The AFFF separator is reducing the AFFF surfactants for these typical firefighting waste waters as well as it performed with `pure' AFFF- water solutions. The presence o f contaminants that would typically be found in firefighting wastes, such as petroleum hydrocarbons and aromatic compounds, do not appear to adversely affect the mechanism or the efficiency o f the process. In addition, the separator is reducing the other pollutants in the waste as measured by BODj, COD, VPH, BTEX and TPH. The concomitant reduction can be significant, e.g., 95 to 100%, particularly for the more volatile species. The overall results are extremely encouraging and continued development o f the AFFF separator is recommended, as discussed below. 5.0 CONCLUSION 1. The AFFF separator is able to reduce the AFFF surfactant concentrations o f the firefighting wastewaters tested. Typical contaminants such as petroleum fuels and volatile aromatic compounds do not have an adverse effect on the final surfactant reduction process or final concentration. 2. The AFFF separator is also reducing the volatile petroleum hydrocarbons and aromatic compounds through the aeration process. The results from all o f the environmental tests indicate that the effluent from the AFFF separator is less polluting than the original wastewater as based on COD and BOD5. 3. The BODj test is not adequate to characterize the typical firefighting wastewaters tested. A longer residence time is apparently needed for the bacteria to consume the organics. It is recommended that the BOD20 test be specified for all future testing. 4. The tests did not lend any insight into whether or not the AFFF surfactants are breaking down in the BOD or COD tests. The limited data does not provide any insight to this question. 13 US00007070 5. The MBAS test alone does not adequately correlate to the AFFF concentrations as measured by drain time. The environmental test for CTAS should also be included in any further testing. 6. It is not possible to determine whether these wastewaters would be acceptable to the wastewater treatment plants at CBD or Hampton Roads as direct influent. The degree o f dilution with other influent wastewaters will impact this decision. However, the separator is improving the wastewater and should assist in making these effluents acceptable. 7. The results are extremely encouraging and continued development o f the separator suitable for field testing is recommended. 6.0 REFERENCES 1. Military Specification, "Fire Extinguishing Agent, Aqueous Film-forming Foam (AFFF) Liquid Concentrate, for Fresh and Seawater," MIL-F-24385F, 7 January 1992. 2. Darwin, R. L., Ottman, R.E., Norman, E.C., Gott, J.E, and Hanauska, C.P., "Foam and the Environment: A Delicate Balance," NFPA Fire Journal, Vol. 89 No. 3, May/June 1995, pp. 67-73. 3. Beitel, J. J., Bums, R.E., Ouellette, R, and Szepesi, D., "Tests for Mechanical Separation o f AFFF in Firefighting Waste Water," draft, 15 December 1995. 4. Hampton Roads Sanitation District, "Industrial Wastewater Discharge Regulations,", November 1, 1990. 5. Kopp, J:F. and McKee, G.D., "Methods for Chemical Analysis o f Water and Wastes," United States Environmental Protection Agency, March, 1983. 6. Gascoyne Laboratories, Inc,, "Client Reference Guide,", January 1, 1995. 14 o m pa n n ipii.nl* 1"... . i ' .iiiii.ijl.iiji>w w d US00007071 7. Department o f the Navy, "Qualified Products List o f Products Qualified under Military Specification MIL-F-24385 Fire Extinguishing Agent, Aqueous Film Forming Foam (AFFF) Liquid Concentrate, for Fresh and Sea Water," Naval Sea Systems Command QPL-24385-25, Washington, DC, 21 May 1992. , /(J IX jJ & r FTW. WILLIAMS, Director"" Navy Technology Center for Safety and Survivability Code 6180 D. P. VERDONIK Hughes Associates, Inc. Baltimore MD Robert E. BURNS, President Hughes Associates, Inc. Baltimore MD Ralph J. OUELLETTE Hughes Assp coates. Inc. Baltimore MD 15 US00007072 ( f e a s c i T n t ' J z b a v u i v w s , H in t. F /y ' T\r sHSGiff ' A .;r5 j Report No. 96-03-124 Baltimore. MD 21224-5697 G; v"--*.; 4 ; 0 i~ '\p! L. oil3 -Oi533-`SCC . tC'GAS-CCV! -AXMG i 533E AJ Report Date : March 20, 1996 Report To : Hughes Associates Page : 1 of 15 Sample I.D. Submitted Water: CBD/K-09, WWI, dated 03/06/96 (0815} . Benzene Toluene Ethylbenzene Total Xylenes Volatile Petroleum Hydrocarbons . (reported as gasoline, C4 to C12) Results 700 2,000 500 2,400 300,000 Detection Limits 100 100 100 300 10,000 Surrogate Recovery (%) Tri fluorotoluene 99 Dilution Factor: ' 100 Notes (1) Results expressed as ug/1 (ppb). (2) Analysis performed according to method EPA 8020/8015-M. (3) Analyst(s): CPB; Date Test Completed: 03/12/96. Laboratory Director APPENDIX A US00007073 ( fe a stamir r a a n e s5 , 4 l ln r . Report N o . 96-03-124 3aitimore, VD 21224-6697 E?0 ~ T OF '\M AL vTF3 5aooi G A -C rAXNO. -ITO 6 32- 5^ Report Date: March 20, 1996 Report To : Hughes Associates Page : of 15 Sample I.D. Submitted Water: CBD/K-09, WWII, dated 03/06/96 (0830) Benzene Toluene Ethylbenzene Total Xylenes Volatile Petroleum Hydrocarbons (reported as gasoline, C4 to C12) Results 200 ND ND <300 65,000 Detection Limits 100 100 100 300 10,000 Surrogate Recovery {%) Trifluorotoluene 117 Dilution Factor: 100 Notes (1) Results expressed as ug/1 (ppb). ( 2 ) Analysis performed according to method EPA 8020/8015-M. (3) Analyst(s): CPB; Date Test Completed: 03/12/96. ' Z" Z Willxdm L. LOCI?: Laboratory Director A-2 US00007074 \-^r m i n t j C h i a r N j j r ' Report To : Sample I.D. 96-03-124 Baltimore. MD 21224-6697 \ N A L V 3 ;.i -W ' t \ * *_ 1 -'Oi 632-'too 5001 GA5 -CCYN FAX NO. . -101633-5 Report Date: March 20, 1996 Hughes Associates . Page: 3 of 15 Submitted Water: .CBD/K-09, MSI, dated 03/06/96 (0840) Benzene Toluene Ethylbenzene Total Xylenes Volatile Petroleum Hydrocarbons (reported as gasoline, C4 to C12) Results Detection Limits 20,000 1,000 32,000 1,000 3,200 1,000 17,000 3,000 2,000,000 100,000 Surrogate Recovery (%} Trifluorotoluene 98 Dilution Factor: 1000 Notes (1) {2} (3) Results expressed as ug/1 (ppb). Analysis performed according to method EPA 8020/8015-M. Analyst(s): CPB; Date Test Completed: 03/12/96. ......------------------------------------------------------------------------------------------------------------------------------------------------ ___________________ William L. Lock Laboratory Director A-3 US00007075 I Report No. 96-03-124 -iiQl532-1300 300)GAS-COVN FAX NO -*101633-5F4-3 Report Date: March 20, 1996 Report To: Hughes Associates Page: 4 of 15 Sample I.D. Submitted Water: CBD/K-09, MSII, dated 03/06/96 (0850} ' Benzene Toluene Ethylbenzene Total Xylenes Volatile Petroleum Hydrocarbons (reported as gasoline, C4 to C12) Results 200 <100 ND ND 100,000 Detection Limits 100 100 100 300 10,000 Surrogate Recovery (%) Trifluorotoluene 95 Dilution Factor: 100 Notes (1} Results expressed as ug/1 (ppb). (2 ) Analysis performed according to method EPA 8020/8015-M. (3) Analyst(s): CPB; Date Test Completed: 03/12/96. A- 4 Laboratory Director US00007076 (ctBCXJnz IC a iirrru ia r B S , Report N o . 96-03-124 Baltimore. MD 21224-6697 t 1 :f o r t o f A N A L Y S IS 40] 6 3 3 -I8Q0 3001 GAS-CCYN PAX NO 4101 633-5443 Report Date: March 20, 1996 Report To : Hughes Associates Page: 5 of 15 Sample I .D . Submitted Water: CBD/K-09, WWI, dated 03/06/96 (0815} Test Detection Results Limits Method Biochemical Oxygen Demand Chemical Oxygen Demand Detergents (MBAS) pH 1,100 4,700 98 5.6 300 1,000 4 NA EPA 405.1 EPA 410.4 EPA 425.1 EPA 150.1 Date Test Analyst Completed RAH 03/12/96 PBK 03/13/96 PBK 03/07/96 GB 03/06/96 Notes (1) Results expressed as mg/1 (ppm). A-5 William L. Lock Laboratory Director US00007077 zscm nw Chiorimiribs, 4lnr. }V 3aitimore. MO 21224-5697 HPOFiT OF AM AL'.'SIS -`0,5j3 '`B00 300-GAS-GOVN 96-03-124 " A X -MO A'Ci633-3A Report Date: March 20, 1996 Report To : Hughes Associates Page: 6 of 15 Sample I.D. Submitted Water: CBD/K-09, WWI, dated 03/06/96 (0815} Total Pet. Hydrocarbons Test Detection Results Limits Method 140 1 EPA 418.1 Date Test Analyst Completed PRM 03/15/96 Notes (1) Results expressed as mg/1 (ppm) William L. Lock Laboratory Director A-6 US00007078 0asrnmu' IChiinraiirris, -dint. Report To : Sample I.D. 96-03-124 Baltimore. MD 21224-6697 \ i-- I V i l i OF MALVS3 - Q i 33-*5C- 3001 -AX NO. -10! S33-A-3 Report Date: March 20, 1996 Hughes Associates Page : of 15 Submitted Water: CBD/K-09, WWII, dated 03/06/96 (0830) Test Detection Results Limits . Method Biochemical Oxygen Demand Chemical Oxygen Demand Detergents (MBAS) PH 870 3,100 29 5.6 300 1,000 2 NA EPA 405.1 EPA 410.4 EPA 425.1 EPA 150.1 Date Test Analyst Completed RAH 03/12/96 PBK 03/13/96 PBK 03/07/96 GB 03/06/96 Notes (1) Results expressed as mg/1 (ppm). William L. Lock Laboratory Director A -7 US00007079 (Hascutnii' Caiioraiant's, 3 n t #7 - -v 1*7 u s r Report No. Report To: Sample I.D. 96-03-124 ^ L- 07 ! Or A M A L Y 313 4`G.S23-1S 3001GA5-CQYN AAXNO -:0i633-54-13 . Report Date : March 20 r 1996 Hughes Associates Page : 8 of 15 Submitted Water: CBD/K-09, WWII, dated 03/06/96 (0830) Total Pet. Hydrocarbons Test Detection Results Limits Method 94 1 EPA 418.1 Date Test Analyst Completed PRM 03/15/96 Notes (1) Results expressed as mg/1 (ppm) William L. Lock Laboratory Director A-8 US00007080 fe a st umto jUctbarziarizs, -dint- Report No. 96-03-124 Baltimore. MD 21224-6697 E P 0 7 OP ANALYSIS -101 633-'300 3.001 GAS-CCYN CAX NO. -101 633-5--3- Report Date: March 20, 1996 Report To: Hughes Associates Page: 9 of 15 Sample I.D. Submitted Water: CBD/K-09, MSI, dated 03/06/96 (0840) Test Detection Results Limits Method Biochemical Oxygen Demand Chemical Oxygen Demand Detergents (MBAS) pH ND 13,000 13 8.1 1,000 1,000 1 NA EPA 405.1 EPA 410.4 EPA 425.1 EPA 150.1 Date Test Analyst Completed RAH 03/12/96 PBK 03/13/96 PBK 03/07/96 GB 03/06/96 Notes ' (1) Results expressed as mg/1 (ppm). William L. Lock Laboratory Director A-9 US00007081 I :33 '8GG 5001: -S-CCYN -X NO. -t"C1 r^ 1j-'j Report Date: March 20, 1996 Report To: Hughes Associates Page : 10 of 15 Sample I.D. Submitted Water:. CBD/K-09, MSII, dated 03/06/96 (0850} Test Detection Results Limits Method Biochemical Oxygen Demand Chemical Oxygen Demand Detergents (MBAS) pH 220 2,400 3.7 8.5 50 500 0.5 NA EPA 405.1 EPA 410.4 EPA 425.1 EPA 150.1 Date Test Analyst Completed RAH . PBK PBK GB 03/12/96 03/13/96 03/07/96 03/06/96 Notes ( 1 ) Results expressed as mg/1 (ppm) ........ Willxanv^L. Lock Laboratory Director A-10 US00007082 C ^ im r a iu r it's , Baltimore. MD 21224-6697 \MAi CDI -iOi 633-:8C0 3001 GA5 -COYN PAX NO . 41)633-5-J-3 Report Date: March 20, 1996 Report To: Hughes. Associates Page: 11 of 15 Sample I.D. Submitted Water: CBD/K-09, S2, dated 03/06/96 (0900) , Detergents {MBAS} Test Detection \ Results Limits Method ND 0.02 EPA 425.1 Date Test Analyst Completed PBK 03/07/96 Notes (1) Results expressed as mg/1 (ppm). ^ili^m^lj. Lock Laboratory Director A-ll US00007083 (fcigrijmt iLhimraiiirirs Report N o . 96-03-124 Baltimore. MD 21224-6697 : ! - O h ! O h A N A L . Liil li0 ;S3 3 iSCC 30IGAS -CCVN "AX NO iiOi 633-5AA3 Report Date: March 20, 1996 Report To : Hughes Associates Page: 12 of 15 Sample I.D . Submitted Water: . CBD/K-09, SI, dated 03/06/96 (0900) Detergents (MBAS) Test Detection Results Limits Method 0.05 0.02 EPA 425.1 Date Test Analyst Completed PBK 03/07/96 Notes (I! Results expressed as mg/1 (ppm) "William L. Lock Laboratory Director A-12 US00007084 m r m t ji u ;a r r o r a i o r i t ' s 3 n t- Report N o. 96-03-124 Baltimore. MD 21224-6697 ! 1U< , 1 ? t" A L V 315 4101 633-1800 8001 GAS-COYN FAX MO . 4101 633-5443 . Report Date: March 20, 1996 Report To : Hughes Associates Page: 13 of 15 Sample I.D. Submitted Water: CBD/K-09, S3, dated 03/06/96 (0900) Detergents (MBAS) Test Detection Results Limits Method 7.4 0.5 EPA 425.1 Date Test Analyst Complte PBK 03/07/96 Notes (1) Results expressed as mg/1 (ppm) William If. Lock Laboratory Director A-13 US00007085 a s c x n m b iilcth a ru i ries, 4 l n c . 96-03-124 Baltimore. MD 21224-6697 REPORT OF ANALYSIS 410i533-1300 soci g a s -c c y n FAX NO. '4101 633-5443 Report Date: March 20, 1996 Report To : Hughes Associates Page: 14 of 15 Sample I .D . Submitted Water:. CBD/K-09, S4, dated 03/06/96 (0900) Detergents (MBAS) Test Detection Results Limits Method 0.44 0.04 EPA 425.1 Date Test Analyst Completed PBK 03/07/96 Notes ( 1 ) Results expressed as mg/1 (ppm). A-l 4 Laboratory Director US00007086 Hsrmjiu' H a b o r a t i i r i t ' s , 3 m r . 96-03-124 Baltimore. MD 21224-6697 ! 1 I-- I M I- ' ' ' OF ANALY5I: 4101 S 3 3 - - ; : 0 3001 GAS-CCVN FAX NC 4101 633-344 3 , Report Date: March 20, 1996 Report To : Hughes Associates Page: 15 of 15 Sample I.D . Submitted,Water : CBD/K-09, S5, dated 03/06/96 (0900) Detergents (MBAS) Test Detection Results Limits Method 4.4 0.2 EPA 425.1 Date Test Analyst Completed PBK 03/07/96 Notes (1) Results expressed as mg/1 (ppm) A-15 William L. Lock Laboratory Director US00007087