Document omY4YQ82oKEmyX1Gya8Gx2w6r

NAVAL RESEARCH LABORATORY W ASHING TO N, D.C. 20375 6180-525 IEB?:pij Prob No. 6 1 C 0 5 - 1 9 D From: To : C o m m a n d i n g O f f i c e r , Naval R e s e a r c h Labo r a t o r y Washington, D. C. 20375 Commander, Aeronautical Systems Division (ASD/AEG) Wright Patterson Air Force Base, Ohio 45433 Subj: R&D Final Report on DOD-AGFSRS-76-10 (MIRP FY 7615-76 05064) Improved Environmental Impact Properties for AFFF Materials; forwarding of E n e l : (1) Two copies of subject re p o r t 1. E n c l o s u r e (1) is f o r w a r d e d h e r e w i t h for you r i n f o rmation and retention. 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. , US00000122 618 0-52 5A:H B P :pij 21 O c t o b e r 1976 S u b j : R&D Final Report on D O D - A G F S R S - 7 6 - 1 0 (MIPR FY 7615-76-05063) Improved E n v i r o n m e n t a l Impact Properties for AFFF M aterials E n e l : (1) Work Statement from NRL Contract N00173-76-C-0295 (2) NSRDC/A Itr 2853:AMM 3160 dated 16 July 1976 - 1. A contract was signed, effective 29 June 1976, with the Ansul Co. to perform experimental work pertaining to the environmental characteristics of AFFF formulations and components thereof. A detailed statement covering the program is given in enclosure (1). A copy of Ansul's final report will be forwarded upon receipt at NRL. This is scheduled for December 1976. . 2. Under separate c o n t r a c t w i t h D T N S R D C / A n n a p o l i s , studies were completed on the recen t l y q u a l i f i e d AFF F c o n c e n t r a t e mad e by the Ansul C o . These results are given in enclosure (2). 3. This is a final report on the subject contract. The remaining work to be done at NRL after completion of the Ansul contract will be carried out under the sponsorship of the Air Force Civil Engineering Center. Henry B . Peterson Head - Fire S u p p r e s s i o n Section Chemical Dynamics Branch Code 6180 - Chemistry Division E n d (1) to NRL ltr 6 1 8 0 - 5 2 5 : H B P :pij NRL Prob C 0 5 - 1 9 D 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. US00000123 E n c l o s u r e (1) SECTION F - DESCRIPTION/SPECIFICITIQNS N00173-76-C-0295 Page 7 of 19 F--1. CONTRACTOR'S PROPOSAL PROPOSAL OBJECTIVE a) b) c) 1.2 Tie purpose of this work is to explore the development of experimental AFFF formulations that would exhibit reduced impact on the environment while retaining certin fire sup pression characteristics. In particular it is proposed to examine the effect of the AFFF formulation components on the biological oxygen demand of th concentrate. In light of results previously obtained with available concentrates, fish toxicity is not considered to be a problem and therefore will not be investigated. ~ It is furthermore proposed that the requirements of the MIL-F- 24335 Amendment 8 and the proposed revision thereto will not apply to the present investigation. There will in all probability be a trade off between biological impact and physiochemical characteristics. Fire performance and corrosion characteristics are of primary importance whereas refractive index, pH, viscosity, foam expansion ratio, and surface interracial tension are of lesser importance. ' The generally accepted method for determining proportioned or premixed solution composition is to measure the refractive index of the solution. In order to get acceptable accuracy and precision with field type refractometers, solvent levels of 15-20% are currently used in commercial products. It is assumes that these levels are deleterious from a biological aspect. Sane effort will be expended in evaluating alternate analytical techniques for the measurement of AFFF solution concentration. PROGRAM STEPS a) Raw Material BQD^n Twenty day ODD studies will be conducted on typical fluorocarbon surfactants, hydrocarbon surfactants and solvents. The purpose will be to determine the effect of chemical composition on BODgo Enel (1) to XRL LTR RPT 6180-525A:HB?:pij US00000124 V; . K00173-76-C-0295 Page 8 o f 19 SECTION F - (Cont'd) b) BGD?oDesiqn Experiment Investigate the effect of component concentration and type on BOD20* Candidate formulations will be selected based on this investigation. c) Formulation Design Experiment Formulations will be selected based on the BOD2 0 investigation and screened for fire performance and physiochemical properties. Ibis will include corrosion characteristics, concentrate stability in addition to fire performance. d) Analytical Methods Evaluation An investigation of alternate analytical methods for determining solution concentration will be conducted to determine if a simple method for use in the field is feasible. STATEMENT OF W0?d< (NRL's) ENVIRONMENTALLY IMPROVED AQUEOUS FILM FORMING FOAM (AFFF) F-2. INTRODUCTION The present formulations with respect to fire suppression are highly effective. However, improvements are desired In the environmental area; i.e., development of compositions that have a reduced impact on the environment without loss of fire suppression effectiveness. 2.1 TECHNICAL TASKS a) The Contractor shall explore the development of experimental AFFF formulations that would exhibit a reduced impact: on the environment while retaining fire effectiveness. b) The proposed study will examine the effect of AFFF formulation components on the biological oxygen demand (BOD), chemical oxygen demand (COD), biocegradability, toxicity toward sewage bacteria, fish toxicity, effect of component concentration on selected environmental/biolccical parameters, formulation design experiments, and analytical methods evaluation. US00000125 N0O173-76-C-O295 Page 9 of 19 SECTION F - (Cont'd) .' . 2. 1.1 TASK I - Raw Material BQD70 and OOP _ Twenty-day BOD studies shall be conducted on typical fluorocarbon surfactants, hydrocarbon surfactants and solvents. The purpose will be to determine the effect of chemical composition on BOD2 0 * Chemical oxygen demand (COD) ^ measurements, toxicity toward sewage bacteria, and fish ^ toxicity (kill fish) will also be made on the above materials. 2 .1.2 TASK II - Biodegradability and BOD?n Design Experiment . Investigate the effect of component coneentration on biodegradability and BOD2 0 Candidate formulations will be selected based on this investigation. 2.1.3 TASK III - Formulation Design Experiment Formulations shall be selected based on the BOD20 biodegradability investigation and screened for fire ^ performance and physiochemical properties. This will include corrosion character istics, concentrate stability in addition to fire performance. . In the event that a more highly concentrated material (to be used in less than a 6% solution) is desired, all environmental properties shall be adjusted to a 6% datum base. 2.1.4 TASK IV - Analytical Methods Evaluation An investigation of alternate analytical methods for determining solution concentration shall be conducted to determine if a simple method for use in the field is feasible. 3. PERFORMANCE FIRS MEASUREMENTS 3.1 Compare fire performance of the new formulation with that of formulation currently manufactured and employed in the field by the same test methods. Fire performance test procedures shall conform to Paragraph 4.7, Mil-F-24385 (NAVY) Amendment 8 , as applicable. US00000126 SECTION F - (Cont'd) ND0173-76-C-0295 Page 10 o f 19 4. RECORDS 4-1 Processing, formulations, method of preparation, aging, stabilization, and other pertinent parameters shall be maintained so that your process and materials can be later accurately duplicated, so that future programs may be coordinated or compared to the results and conclusions of your current study. These records shall be available for perusal by NRL Scientific Officer for a period of 1 year following completion of the work. 5. . 5.1 DELIVERABLES 1. The contractor shall provide NEIL a final summary report on all tasks and sub-tasks of this study. It shall consist of summaries of all studies and experiments along with theoretical or experimental based conclusions or recommendations. 2. 100 gallons of experimental concentrate of the final selected formulation, . SECTION G - PRESERVATION/PACKAGING AND PACKING 1 Material shall be crated in accordance with best domestic commercial practices to assure safe delivery to the Naval Research Laboratory. 2 Marking: Receiving Officer, Naval Research Laboratory, Washington, D. C ., 20375, Contract Number N00173-76-C-0295. 3 The Contractor shall nark all shipments under this contract in accordance with the edition of MIL-STD-129 "Marking for Shipments and Storage", in effect on the date of the contract. A The Contractor shall comply with FED STD 313 (Symbols for Packages and Containers for Hazardous Industrial Chemical and Materials) to the extent applicable. . US00000127 DEPARTMENT OF THE NAVY NAVAL SHIP RESEARCH AND DEVELOPMENT CENTER HEADQUARTERS BETHESDA, M AR YLA N D 20034 ANNAPOLIS LABORATORY A N N A P O LIS , MO 21402 CARDEROCK LABORATORY BETHESDA, MO 20034 IN REPLY R EFER TO: 2853:Ai'W 3160 1 6 J U L 1976 From: Commander, David Vi. Taylor Naval Ship R&D Center To: Director, Naval Research Laboratory, Code 6180 Subj Ansul, AFFF, Ansul Co., Marinette, 'Wisconsin 54143, 6% concentrate, DOT Formulation No. A-71108, Bioassay of Ref: (a) Work Request No. N00173-76-WR-60166 Enel: (1) Report TM-23-76-29, "DTMSRDC Standard Static Marine Bioassay Procedure for Shipboard Chemicals" 1. In compliance with reference (a), listed below are the results of the bioassay tests of Ansul: A. Fundulus sp. Killifish B. Artemi a salina Brine Shrimp C . Pseudomonas nigrifaciens Bacterial Species D. Thai assiorira pseudonana LC5q = 4,287 ppm in 96 hrs LC50 = 3,937 ppm in 72 hrs Bactericidal = 50,000 ppm in 95 hrs Bacteriostatic = 40,000 ppm in 95 hrs LC = <4000 ppm in 96 hrs 2. The results of the Biochemical Oxidation Demand (BOD) and the Chemical Oxidation Demand (COD) tests along with a comparison of the BOD test in saline and non-saline waters are listed on page 2. These tests ware _ performed by Code 2850 according to the 13th Edition, 1971 of "Standard Methods for the Examination of Water and Waste-Water." E n e l (2) to N R L L T R R P T 6180-525A:HBP:pij US00000128 2853 :AMM 3160 Subj: Ansul, AFFF, Ansul Co., Marinette, 'Wisconsin 54143, 6% concentrate, DOT Formulation No. A-71108, Bioassay of . RESULTS OF BIOCHEMICAL OXYGEN DEMAND (BOD) AND CHEMICAL OXIDATION DEMAND (COD) STUDY OF ANSUL TEST DURATION (DAYS) 5 10 DILUTION 1:30,000 1:100,000 1:30,000 1:100,000 BOD (mg./I.) With NaCl 1.8 5.4 X 104 1.2 1.2 X 105 1.4 4.2 X 104 Without NaCl 1.4 4.2 X 104 0.9 0.9 X 104 oxygen depleted 1.9 1.9 X 105 4.3 4.3 X 105 COD = 4.09 X 105: mg./I. 3 . The results of the "In Vivo" tests indicate that Ansul has a relatively low level of toxicity and the BOD and COD test results indicate a reason ably high level of biodegradability. . Copy to: NAVSEC (SEC 6101) By diisoi-t.-.-.- 2 US00000129