United States Environmental Protection Agency Hazardous Waste Engineering Research Laboratory Cincinnati OH 45268 Research and Development EPA/600/S2-87/090 Feb 1988 Project Summary Municipal Landfill Gas Condensate Jeffrey Briggs New regulations or air emissions from municipal landfills may require installing gas collection systems at landfills. As landfill gas (LFG) is collected, water and other vapors in the gas invariably condense in the system or are purposely removed in the normal treatment of the gas. Condensate production can amount to more than 5000 liters per day con- sisting of two liquid phases: an aqueous phase and a hydrocarbon phase. The management of LFG condensate con- tinues to be a problem for the solid waste landfill owner or operator because options for proper disposal are limited. Liquid disposal to solid waste landfills is virtually banned, and current regulations may identify condensate or one of its phases as a hazardous waste if it fails the Toxicity Characteristics Leaching Procedure (TCLP) Toxicity Test. EPA's Office of Solid Waste desired a baseline study to identify physical/chemical characteristics and hazardous properties of condensate from LFG collection sys- tems at solid waste landfills. This study involved the collection and analysis of condensate samples from four U.S. landfill sites with active gas migration or gas production systems. The characteristics of both the hydro- carbon phase and the aqueous phase of the condensate were compared against EPA hazardous waste criteria. Results indicated that neither phase exhibited properties of corrosivity or reactivity. However, the hydrocarbon phase was ignitable, as was the aqueous phase in one sample. No pesticides, PCBs or priority pollutant metals were detected in any sample. A list was developed of 94 organic compounds found in LFG condensate, 49 of which are priority pollutant compounds. Most condensate samples obtained at the four sites were identified as hazardous according to the proposed regulatory limits of the TCLP Toxicity Test. Eleven compounds were present in the hydrocarbon phase at concentra- tions exceeding the proposed limits and five compounds exceeded the limits in the aqueous phase. However, the four sites varied considerably and definite correlations could not be made between site characteristics, the LFG collection systems, and the resultant condensate properties. It is possible that the low levels of organics found in the con- densate from the aerobic LFG control site may result from the aerobic bio- degradation of some of the compounds present. This correlation may be biased by other factors and should be tested by collecting data from more sites, both aerobic and anaerobic. This Project Summary was developed by EPA's Hazardous Waste Engineering Research Laboratory, Cincinnati, OH, to announce key findings of the research project that Is fully documented In a separate report of the same title (see Project Report ordering Information at back). Introduction Landfill gas (LFG) condensate is a liquid produced in landfill gas collection sys- tems. The condensate is removed as the LFG is withdrawn from landfills. Produc- tion of condensate may be through natural or artificial cooling of the gas or through physical processes such as volume ex- pansion. Condensate is composed prin- cipally of water and organic compounds. Often the organic compounds are not soluble in water and the condensate separates into a watery (aqueous) phase and a floating organic (hydrocarbon) phase. This organic fraction may comprise up to five percent of the liquid. The purpose of this project was: (1) to review existing background information ------- on the chracteristics of condensate; and (2) to obtain and analyze condensate samples from LFG collection systems at four landfills nationwide. The condensate samples were sampled and analyzed under prescribed conditions in order to qualitatively and quantitatively describe condensate characteristics. Specifically, the analyses were to determine baseline properties of LFG condensate from a limited number of samples and establish if either condensate phase is hazardous, and if so, on the basis of which con- stituents. In addition, LFG collection system information was collected to assess possible impacts due to system operations. Procedure Landfill sites for condensate sampling were chosen on the basis of size, geo- graphic location, and cooperation of the site owners/operators. The sites chosen had to be of sufficient size to produce several hundred gallons of condensate per day to ensure representative samples of newly formed condensate. Landfill sites with either gas control systems or gas production systems were considered for selection. Similarly, it was desirable to consider sites that contained only mu- nicipal refuse versus those sites that combined municipal and commercial waste. Finally, landfill sites were selected based on the owners/operators willing- ness to allow site access and supply background information on site develop- ment and operation. Those owners who agreed to participate, did so with the understanding that their sites would not be identified. Four landfill sites were selected; three of the sites had gas re- covery systems for processing and ulti- mate sale for production purposes, and the other had a collection system for purposes of methane migration control. Landfill gas condensate was sampled from fresh accumulations in closed stor- age containers or directly from the gas collection pipelines. All samples were taken under vacuum from the last point in the system prior to treatment, pro- cessing, or blower equipment. This sampling point was the "knock-out" pot storage tanks at the production sites and from a low point in the collection system pipe at the control system. All samples were fresh and volatilization of trace organics was minimized during sampling. Where possible, condensate samples were obtained separately for both the aqueous and hydrocarbon phases. Analyses of condensate were per- formed using EPA Standard Methods for hazardous characteristics, priority pol- lutant metals (EPA SW-846), priority pol- lutant organic compounds, (EPA 624 and 625), and pesticides (EPA 608). Con- ventional wastewater parameters, BOD, COD, TOC, pH, nitrate nitrogen, and hydrogen sulfide were also measured using Standard Methods. (16th Ed., 1985). Duplicates, spikes and surrogates were used to determine precision and accuracy of the analyses. The GC/MS analyses were performed with a Hewlett Packard GC/MS 5995* with a HP1000 data sys- tem using a packed column of 1 percent SP-1000 on 60/80 carbopack B. Results and Discussion There is little published information on the characteristics and quantities of con- densate produced in LFG collection sys- tems. Some owner/operators of these systems have performed sampling and analysis of condensate for their own use but these results remain unpublished. Data obtained from nine landfills samples (a total of 24 samples) indicated a large variability for various parameters. Table 1 compares BOD, COD, and TOC analysis from 24 condensate (unpublished data) to typical values from the literature for sewage and leachate. However, the sampling and analytical procedures em- ployed for the unpublished data may not valid. In addition, results from condensate sampling under this study from the four landfills are included in Table 1. Site information was obtained from the four landfill sites selected for LFG con- densate and gas sampling. These sites are designated as "Northeast," "Mid- west," "Northern California," and "Southern California." The amount of condensate collected from the four sites varies from about 2,700 to 7,500 liters per day. There was * Mention of trade names or commercial products does not constitute endorsement or recommenda- tion for use. no apparent correlation between climate and condensate volume. The warm, dry Southern California site produces up to 7,500 liters per day from about 85,000 cubic meters of LFG, while the cool, moist Midwest site produces only about 4,200 liters per day from over 85,000 cubic meters of LFG. The operating data from each of the four LFG collection systems were col- lected at the time of sampling. Data included gas temperature, composition (percent methane and oxygen), and average BTU content. Methane and oxygen contents varied according to the type of gas collection system at the site. At the Northeast site, methane content was low (22 percent), due to the opera- tion of the extraction system which allows air intrusion in order to control gas migration at the landfill perimeter. At the remaining three sites with gas production systems, methane contents ranged from 54 to 63 percent. Gas temperatures were measured on the inlet side of the vacuum pumping equipment at each site and ranged from 17° C at the Northern California site to 36.7° C at the Northeast site. In two of the three production sites, LFG condensate samples were obtained as two distinct phases, principally in aqueous phase and a small volume of floating organic (hydrocarbon) phase. Both aqueous and organic phases were sampled at the two California sites with the organic phase comprising approxi- mately 0.5 percent of the condensate volume. At the Midwest site two phases were produced but sampling access was provided only to the aqueous phase by the site operator. The Northeast site produced an oily film of insufficient quantity to analyze separately as the organic phase. The samples from the four sites are compared on the basis of the four stan- dard EPA hazardous waste characteristics below: Ignitablllty Of six condensate samples analyzed Table 1. Comparison of BOD, COD, and TOC Values for Condensate, Domestic Sewage and Landfill Leachate Landfill Gas Condensate Parameter BOD COD TOC Unpublished data (mg/l) 1.000-31,250 476 - 14,720 575- 4,900 Data from this study (mg/l) 4,000- 17.500 1,042 - 30,500 94 - 23.500 Domestic sewage fmg/l) 100- 500 25O - 1.000 100- 300 Typical leachate (mg/D 1.050 - 32.400 800-50.700 700 - 68.000 ------- (four aqueous and two organic), three were ignitable. The organic phase samples from the California sites were ignitable. CorrosMty and Reactivity No condensate samples were hazard- ous on the basis of corrosivity. Con- densate from the Northeast site was slightly alkaline (pH 7.6), while the three production systems produced acidic con- densate ranging from pH 4.21 to 5.03. Similarly, no condensate samples were hazardous on the basis of reactivity. TCLP Toxlclty Test EPA has proposed to amend the EP Toxicity Test replacing the old leaching procedure with the new Toxicity Char- acteristics Leaching Procedure1. Part of this proposal includes expanding the list of toxic compounds from 14 to 52. The condensate analytical results were compared to this proposed list. Condensate samples were analyzed for pesticides, PCBs, and priority pollutant metals and organic compounds. No pesti- cides, PCBs, or priority pollutant metals were detected in any samples. The or- ganic constituents in the condensate samples were analyzed in three major groups for each phase sampled (4 aqueous and 2 hydrocarbon): the priority pollutant volatile organic compounds, the priority pollutant base/neutral and acid extractable compounds, and other organic compounds. These latter compounds were detected by GC/MS techniques but not quantified. A total of 94 organic compounds was identified as present in LFG condensate, 49 of which are priority pollutant com- pounds. Eleven of these priority pollutant compounds were found in every con- densate sample in either the aqueous or organic phase: benzene, toluene, phenol, ethyl benzene, benzyl alcohol, bis (2- chloroisopropyl) ether, bis (2-ethylhexyl) phthalate, naphthalene, N-nitrosodi- methylamine, 2,4-dimethylphenol, and 4-methylphenol. Fifteen compounds found in the condensate samples are on the proposed TCLP Toxicity List. These are listed in Table 2, with their occurrence in each of the two phases (aqueous and organic phase) and the proposed regula- tory level. Eight of the compounds were found exceeding the proposed regulatory levels in the organic phase, three in both the organic and aqueous phases, and two in only the aqueous phase. In addition to the compounds on the proposed TCLP Tabl« 2. Priority Pollutant Organic Compounds Found In LFG Condensate Exceeding Regulatory Levels In The TCLP Toxicity List Presence Regulatory Regulatory Level Level* Exceeded Compound Volatile Organic Compounds 1. Benzene 2. Toluene 3. Methylene chloride 4. Trichloroethylene 5. 2-Butanone (MEK) Aqueous X X X X X Organic X X X X (mg/liter) 0.07 14.4 86 0.07 72 Aqueous X X Organic X X X X 6. Chlorobemene X** X 1.4 X 7. Tetrachloroethylene X X 0.1 X X 8. 1,1,1-Trichloroethane X X 30 X 9. Chloroform X" X 0.07 X 10. Carbon tetrachloride X 007 X Acid and Base/Neutral Compounds 11. Phenol X 14.4 12. 1,2-Dichlorobenzene X X 4.3 X 13. 1,4-Dichlorobenzene X X 10.8 X 14. Nitrobenzene X 0.13 15. Bisf2-chloroisopropy)ether X X 0.05 X X * Regulatory level according to proposed TCLP Toxicity List'. ** Detected, but at levels too low to reliably quantify. ' Federal Register. Vol. 51, 114, June 13, 1986 Toxicity List, many other organic com- pounds were detected. Conclusions and Recommendations Conclusions This investigation obtained and analyzed condensate samples from selected nationwide landfill sites with operating LFG collection systems. Due to an absence of published literature on condensate, this work serves as a baseline effort to identify condensate characteris- tics. Conclusions and recommendations from this investigation are based on a limited sampling program that indicates that site-specific variability is to be ex- pected. However, they are presented below as guidance to landfill owner/ operators, landfill design engineers and regulatory agencies for implementing practical measures to collect and properly dispose LFG condensate. • Landfill gas condensate is a two- phase liquid containing an aqueous phase and an organic phase (which often separates as a float). The organic phase varies in volume and composition among sites, and may range from less than one percent to five percent (by volume) of the total mixture. In general, the aqueous phase is mostly water and trace organic compounds. The organic phase consists principally of hydro- carbons, xylenes, chloroethanes, chloroethenes, benzene, toluene, other priority pollutants, and trace moisture. Condensate production from three sites with LFG recovery systems ranged from 44 to 162 liters gen- erated per 1000 cubic meters of unprocessed LFG. Condensate wastewater parameters (e.g., BOD, TOC, COD, etc.) vary among sites and is similar to typical landfill leachate. The major organic components of LFG condensate were identified using standard EPA analytical methods for priority pollutants in water samples. The frequency of detection and concentrations are compared to regulatory levels in the proposed TCLP Toxicity Test. Of the 49 priority pollutant compounds detected in condensate, 15 are listed in the proposed TCLP contaminants, list. Ten VOCs and three acid and base/neutral priority pollutants were found in condensate at levels ex- ceeding the proposed regulatory limits. Condensate quality, as measured by the organic priority pollutants pre- sent, differs according to each phase (i.e., aqueous versus organic) and the type of priority pollutant (VOCs versus acid and base/neutral frac- tions). Similar VOCs are found in ------- both the aqueous and organic phases; however, a larger number of acid and base/neutral compounds are present in the aqueous than in the organic phase of the condensate. Concentration levels may be orders of magnitude higher in the organic phase than the aqueous phase. • Landfill gas condensate samples from the four sites contained no pesticides, PCBs, or priority pollutant metals and did not exhibit hazardous characteristics when tested for cor- rosivity or reactivity. 229 Based on hazardous characteristics tests for ignitability and TCLP toxicity, LFG condensate, and particularly the organic phase, may be a hazardous waste. Eleven priority pollutants were detected in the organic phase at levels that exceed the proposed regulatory limits. Recommendations 1. The composition of LFG condensate is variable and is likely influenced by many site-specific variables. Future field testing efforts should include a sufficient number of samples at 20 to 30 nationwide LFG collection sites to help deter- mine the key environmental and design variables that affect con- densate composition. 2. This study was directed principally towards identifying the priority pol- lutants present in condensate. Future analytical efforts should fully characterize LFG condensate and in particular, the organic phase, for other (i.e., nonpriority pollutants) organic and inorganic constituents. Analytical problems experienced on the oil-like organic phase caused by the complicated matrix suggests the need for analytical protocol develop- ment and testing. Regulatory decisions regarding whether or not condensate must be treated and disposed as a hazardous waste may impact available capacity for treatment and the economic viability of gas recovery systems. Further studies should address the nature and extent of these impacts. Jeffrey Briggs is with SCS Engineers, Reston. VA 22090. Paul de Percin is the EPA Project Officer (see below). The complete report, entitled "Municipal Landfill Gas Condensate," (Order No. PB 88-113 246/AS; Cost: $12.95, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Hazardous Waste Engineering Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES PA EPA PERMIT No G-35 Official Business Penalty for Private Use S300 EPA/600/S2-87/090 0001961 LIBRARY REGION V US EPA 230 S OIARBCRN ST CHICAGO 60604 ------- |