Power Sources NTIS DTIC. Conference

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1 DISPOSAL CHARACTERISTICS OF SELECTED MILITARY BATTERIES Louis F. Soffer U.S. Army Communications-Electronics Command Safety Office presented at Q ' JPAA 36th Power Sources NTIS DTIC Conference Accesion For CRAM TAB Unannounced Justification... Hyatt Cherry Hill Availability Codes Cherry Hill, New Jersey Avail and / or June 6-9, 1994 Dist Special By Distribution I Sponsored by the Power Sources Division Electronics & Power Sources Directorate U.S. Army Research Laborator U.S Arm Approved for public release; Distribution Unlimited

2 Form Approved REPORT DOCUMENTATION PAGE OMB No. 0704"0188 Public reporting burden. for this collection of information is estimated to average 1 hour per resp~onse. includingj the time for reviewing, instructions, searching existing data sources. gathering and maintaining th da.ta needed, and.completing and. reiwing the col~lection of inrformation. Seed Om.merits re~arding this,burden estimate or. any other_ aspect.of this collection of informa tion, incu ding sugge stons for reu cong thi b0urden, to w as hnmg ton He d urters SJervices. Directorate to r In formatio nl Operations and Re port., Jefer o Davis Highway. Suite Arlington. VA and to the Office of Managemenft and Budget. Paperwork Reduction Project ( ), Washington. DC AGENCY USE ONLY (Leave blank) 2. REPORT DATE 3. REPORT TYPE AND DATES COVERED 6 Jun 94 Technical: TITLE AND SUBTITLE 5. FUNDING NUMBERS DISPOSAL CHARACTERISTICS OF SELECTED MILITARY BATTERIES 6. AUTHOR(S) Louis F. Soffer 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION US Army Communications-Electronics Command (CECOM) REPORT NUMBER CECOM Safety Office CECOM-TR-94-6 ATTN: AMSEL-SF-REE (Soffer) Fort Monmouth, NJ SPONSORING /MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING/MONITORING AGENCY REPORT NUMBER US Army Research Laboratory (ARL) Electronics and Power Sources Directorate Power Sources Division Fort Monmouth, NJ SUPPLEMENTARY NOTES Presented at 36th Power Sources Conference sponsored by ARL, June 6-9, Cherry Hill, NJ, 12a. DISTRIBUTION /AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE Approved for public release; distribution is unlimited. 13. ABSTRACT (Maximum 200 words) Considerable work has been done to assess the disposal characteristics of CECOM procured military batteries under current U.S. Environmental Protection Agency hazardous waste identification regulations, and State bioassay requirements. This paper presents test results for alkaline, carbon-zinc, magnesium, lithiummanganese dioxide, lithium-sulfur dioxide, and lithium-thionyl chloride batteries. Present findings indicate that: (1) lithium-thionyl chloride and magnesium batteries with greater than 50 percent remaining charge exceed the federal regulatory limit of 5.0 mg/l for chromium, (2) alkaline, carbon-zinc, lithium-maganese dioxide, and lithium-thionyl chloride batteries fail California bioassay toxicity requirements with 96-h LC 50 of less than 500 mg/l. Assay methods, findings, disposal requirements, and design implications are discussed. 14. SUBJECT TERMS 15. NUMBER OF PAGES Military batteries; alkaline, magnesium, lithium batteries; toxic 8 characteristic leaching procedure; bioassay; hazardous wastes; 16. PRICE CODE Resource Conservation and Recovery Act (RCRA) regulations 17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACT OF REPORT OF THIS PAGE OF ABSTRACT Unclassified Unclassified Unclassified UL NSN Standard Form 298 (Rev. 2-89) Prescribed by ANSI Std. Z

3 DISPOSAL CHARACTERISTICS OF SELECTED MILITARY BATTERIES Louis F. Soffer US Army Communications-Electronics Command Fort Monmouth, New Jersey Introduction or toxic (D004-D043) in accordance with (IAW) established Over the past ten years analytical procedures under this considerable work has been done regulation. RCRA toxicity to assess the disposal regulations became more severe in characteristics of CECOM-procured 1990, when test Method 1311 was military batteries using current changed from the Extraction US Environmental Protection Procedure Toxicity (EP Tox) test Agency (EPA) hazardous waste (HW) to the Toxicity Characteristic identification regulations, and Leaching Procedure (TCLP). This state bioassay requirements. change means, in many cases, that This paper presents previous and a higher concentration of a TCLP current test methods, results, contaminate may be extracted from disposal requirements and design the sample, than was the case implications for six classes of utilizing the EP Tox methodology. military batteries procured by A solid waste is determined to be the US Army Communications- a HW when the extract Electronics Command (CECOM). concentration under TCLP for a particular contaminate is equal We have assessed the disposal to or greater than the characteristics of Army batteries "regulatory level (mg/l)" in under Resource Conservation and "Table 1, Maximum Concentration Recovery Act (RCRA) regulations of Contaminants for the Toxicity administered by EPA, and state Characteristic" of 40 CFR bioassay requirements. This paper presents findings and All states must utilize RCRA regulatory management guidance requirements as a minimum for the for CECOM-procured alkaline determination of HW. In addition (ALK), zinc-carbon (LCE), to RCRA's TCLP the states of magnesium (MG), lithium-manganese Alaska, California, Minnesota, dioxide (Li-MnO 2 ), lithium-sulfur Rhode Island, and Washington dioxide (Li-S0 2 ) and lithium- utilize bioassay techniques to thionyl chloride (Li-SOC1 2 ) determine toxicity for HW batteries. identification. Bioassay test utilizes an organism's response Background to a chemical insult to assay toxicity. The measure of RCRA regulations define HW toxicity is inversely either by listing specific waste proportional to the amount of streams, or by the identifying chemical substance to which the specific characteristics under 40 organism is exposed. A typical Code of Federal Regulations (CFR) criteria is the lethal Part 261 Subpart C. Batteries concentration (LC) 500 mg/l, are not listed; and therefore, in which is fatal to 50% of the test order for them to be identified organisms, i.e. LC 50, during a 96 as HW under RCRA, they must be hour (96-h) test period. found to be ignitable (DO01), corrosive (D002), reactive (D003) Previous Findings 180

4 CECOM has analyzed MG and Li- methodology and results are shown SO 2 military batteries 1, 2 prior to below under analysis 2. TCLP requirements. MG batteries were found to be non-hazardous Analysis 1 4 solid waste (NHSW). Li-So 2 batteries were found to be Method 7 ' 8 ignitable (DO01), and reactive (D003) under RCRA. The A random sample, n=42 management recommendation for Li- (7/type), of ALK, LCE, MG, Li- SO 2 batteries suggested that the MnO 2, Li-SO 2 and Li-SOCl 2 military complete discharge of the battery batteries were selected from would eliminate D001 and D003 depot stock. Prior to analysis characteristics, thereby allowing ALK, LCE, MG Li-MnO2 batteries for its disposal as a NHSW. US were discharged to 50% of Army Laboratory Command (LABCOM) capacity to simulate field analysis of Li-SOCl 2 military conditions prior to disposal. batteries 3 yielded results and IAW solid waste management management recommendations guidance 2 ' 3 Li-SO 2 and Li-SOCl 2 similar to those for Li-SO 2 batteries should be totally batteries, discharged prior to disposal; therefore, these batteries were Current Efforts totally discharged prior to analysis. When the TCLP methodology replaced EP Tox we undertook a TCLP: The battery samples major study 4 to evaluate ALK, LCE, were then reduced to <9.5mm MG, Li-MnO 2, Li-So 2 and Li-SOC1 2 particle size, and 100g aliquots military batteries for the were extracted IAW TCLP toxicity characteristic under methodology. The extracted TCLP. The other RCRA leacheates were analyzed for characteristic tests for metals, volatile organic ignitability, corrosivity and compounds and semi-volatile reactivity were not affected by organic compounds, except for this 1990 regulatory change. In pesticides and herbicides, IAW addition, we decided to analyze SW as required by Method these batteries utilizing Metal leacheate samples California's (CA) bioassay were analyzed using atomic methodology. The methodology and absorption spectrometry or results are shown below under inductively coupled plasm analysis 1. technique. Volatile organic compounds and semi-volatile A finding of analysis 1 organic compounds were analyzed below, indicated that MG using gas chromatography/mass batteries discharged to 50% spectrometry or high performance capacity should be characterized liquid chromatography as as toxic HW for Cr (D007) under appropriate. RCRA. This finding was challenged by a major battery Bioassay: Aquatic bioassays supplier. 5 The supplier's were conducted to further findings suggested that the TCLP characterize HW. CA's sensitivity for Cr was dependent on the battery's state of charge. This P rompted an additional TCLP study to clarify this issue. The 181

5 Table 1 Summary of TCLP Results by Battery Chemical Type n=42 1, Mean (mq/l) TCLP TCLP Type Regulatory Contaminant ALK LCE MG Li-MnO 2 Li-So 2 Li-SOCI 2 Limit Arsenic < Barium < <0.10 < Cadmium < < < Chromium < < Lead < <0.050 <0.050 <0.050 < Mercury N/A 4 N/A N/A N/A 0.2 Selenium < <0.050 < Silver < <0.010 <0.010 <0.010 < Notes: 1. Sub-sample, n=7, for each battery chemistry type. 2. Mean value exceeds regulatory limit. 3. Upper 95% confidence limit around mean exceeded regulatory limit. 4. Lithium and MaQnesium batteries do not contain mercury. methodology was selected as a TCLP: No volatile organic representative test. 8 The TCLP compounds nor semi-volatile method uses an acetate buffer, organic compounds were found that which is toxic to some aquatic exceeded the regulatory limits biota. In order to eliminate (RL) established by 40 CFR 261 this confounding variable, Method criteria. The results for "EPA 1312 from SW-846 was utilized for Contaminant" metals are found in extraction, which is not toxic to Table 1. Fifty percent capacity the Fathead minnow and MG batteries exceeded the 5.0 Ceriodaphnia, utilized in CA's mg/l RL for Cr. The upper 95% methodology. The organisms confidence limit around the mean utilized represent vertebrate for totally discharged Li-SOC1 2 and invertebrate species, batteries exceeds the 5.0 mg/l RL respectively. Preliminary 48-h for Cr. Under EPA's LC 5 0 acute toxicity tests were interpretation Li-SOC1 2 failed the conducted to establish dilution TCLP RL. Therefore, 50% capacity ranges. Acute 96-h LC 50 toxicity MG batteries, and totally tests were conducted. The LC 50 discharged Li-SOC1 2 batteries are concentrations (mg of battery/l) considered HW. reported will kill 50% of the test animals in the specified Bioassay: Table 2 summarizes time period. the 96-h LC 5 0 acute toxicity results for MG, Li-So 2, Li-MnO 2 Results and ALK batteries. LC 5 0 of <

6 mg/l are identified as HW. exceeded the RLs established by Preliminary 48-h acute LC CFR 261 criteria. toxicity tests for LCE (LC 50 =289 mg/l) and Li-SocI 2 (LC 5 0 =2.5 mg/l) Chromium (mg/l) batteries identified them as HW under this criteria. 96-h LC 50 testing for these later two classes of batteries was not required. Li-Mn0 2, ALK, LCE and Li-SOCI 2 batteries are HW under this bioassay criteria. 3 Table 2 2 Acute 96-h LC 5 0 Toxicity i by Battery Tvoe (ma of batterx/l) pan Battery Test Organism I Type Fathead Ceriodaphnia o 0 & IC 0 Minnow Capacity (%) MG 22,928 18,067 Figure 1. TCLP Analysis of Li-SO MG Batteries Li-MnO Discussion ALK Methods Analysis 26 The EP Tox method uses a Method 7 structural integrity test (SIT) to determine the particle size A random sample, n=20 prior to extraction. During (5/condition), of military MG previous analysis many battery batteries were selected from cells survived the SIT intact, independent government test and internal battery/cell samples previously obtained, structures could not be extracted Prior to analysis the samples prior to analysis. This model is were assigned and pre-conditioned inadequate as eventually to four state of capacity batteries/cells lose integrity in conditions: 100% (un-discharged), a landfill disposal site. The 50% (50% capacity), 10% (10% TCLP does not utilize a SIT. capacity), and 0% (totally TCLP requires all components to discharged). be "crushed, cut, or ground", such that, the sample particles TCLP: The samples were will pass through 9.5mm sieve prepared and analyzed IAW prior to extraction and analysis. procedures described under Solids and liquids are amenable Analysis 1, above, to extraction as well as volatiles in a "zero-headspace Results: MG batteries extractor" utilized by this discharged to <50% capacity did method. not exceed RCRA RL for Cr, see There is a great difference volatile Figure 1. organic No compounds, other metals, nor between twee EPA's Is a TCLP great and bioassay bioassay semi-volatile organic compounds tests to identify HW. Bioassay is independent for the chemical 183

7 compound(s) present. TCLP looks important concept. We have for a particular concentration recently commented regarding (mg/l) level of a specific Docket # F-93-SCSP-FFFFF 1 0, which element or chemical compound affects the recycling and present, which is defined as a reclamation of batteries. HW. Bioassay is only concerned, Presently New Jersey's code if the test animal dies at the requires battery recycling. It LC 50 <500 mg/l. These methods is important that industry provide two different means of continues to take positive steps assessing toxicity. It is quite to ensure a means to recycle and possible that more states may market spent batteries/cells to adopt bioassay in the future, reduce the HW stream. particularly those with fragile and extensive wetlands. Design Findings We have already incorporated a complete discharge device in Our findings support the military procured Li-SO 2 and Limanufacturer's data, which SOCI 2 batteries to eliminate their indicate that available chromium reactivity prior to disposal. is affected bý the battery's Since MG batteries with <50% state of charge. It appears that capacity are not HW under RCRA, MG batteries with <50% charge do we may consider the same approach not exhibit Cr in excess of the in the future for the MG RCRA RLs. Management guidance batteries. has been provided to user activities, so that, users may Conclusion test battery capacity prior to disposal. The challenge for the future is to identify, isolate, and Environmental Regulations properly manage hazardous waste to prevent its entering the waste The characterization of HW stream. We should and must for disposal depends on your minimize waste in order to location and its applicable protect our environment and that regulations. Findings aside, we of our children. This is called must deal with "NIMBY", that is pollution prevention, which is the Not in My Back Yard syndrome. the thrust of the Pollution I can only suggest that it must Prevention Act of We be dealt with on a case-by-case should strive to reduce the waste basis. It is important to get to at its inception, that is by know your regulator. Even if designing our commodities for findings indicate that the reuse, remanufacture or material for disposal is a NHSW, recycling. We should attempt to the county officials may not use less hazardous components. allow the waste at the landfill We have reduced the mercury site without a special permit, content in LCE and ALK batteries. And with regard to permits, the Maybe we can reduce chromium in disposal site's permit must MG batteries, or increase the include your waste stream, or life or cycles of secondary your organization may not use the batteries. This will help meet site. the requirements of Executive Order Only your Waste minimization is another innovation can achieve these 184

8 aims. (8) Polisini, J.M., and Miller, R.G. (1988), Static Acute References Bioassay Procedures for Hazardous Waste Samples, (1) Diem, M. and Rosak, D. California Department of Fish (1983), Hazardous Waste Special and Game, Water Pollution Study No , Control Laboratory. Evaluation of Magnesium Batteries Report, US Army (9) Test Methods for Evaluating Environmental Hygiene Agency Solid Wastes, SW-846 (Jan. (AEHA), Aberdeen Proving Ground 1990), Rev. 3d Ed., US (APG), MD Environmental Protection Agency, Office of Solid Waste and (2) Rosak, D. (1985), Hazardous Emergency Response, Wash., D.C., Waste Study No , Evaluation of Lithium Sulfur Dioxide Batteries, AEHA, APG, MD (10) Federal Register, 2/11/93, V. 58, No. 27, Subject: Part 260-Hazardous Waste Management (3) Kulkarni, R.K., and System: Subpart C-General Rosencrance, A.B. (1986), Rulemaking Petitions. Technical Report 8507, Safety And Health Hazards Of Disposal Of Lithium Thionyl Chloride Batteries In Sanitary Landfills, US Army Medical Bioengineering Research & Development Laboratory, Ft. Detrick, MD (4) Hanson, M., et al. (1992), Toxicity Study of Selected Military Batteries, Martin Marietta Energy Systems Inc., Contract DE-AC05-840R21400, Oak Ridge, TN (5) Letter, Rayovac Corp., 5 September 1991, Subject: TCLP Analysis of BA-4386/U Magnesium Battery. (6) Painter, P.P. (1993), TCLP Study of Army Procured Magnesium Batteries, Northeastern Analytical Corp. (NAC), NAC Job Final, Marlton, NJ (7) Title 40, Code of Federal Regulations, Part 261, Appendix II (1991), Method 1311 Toxicity Characteristic Leaching Procedure (TCLP). 185