M4E COLEMAN: ISOTOPIC IDENTIFICATION 95° nen Isotopic Identification of Landfill Methane DENNIS D. COLEMAN,” CHAO-LI LIU, KEITH C. HACKLEY,+ and STEVEN R. PELPHREY* ‘tstech Laboratories, In, 1208 Parkland Cour, Champolgn, 1L 618211826 Sitinos Stote Geological Survey, 615 East Peabody Drive Chompuien, IL 1820-6964 7 r i ABSTRACT @ offers, Hutchinson (1993) has pointed out that landfills ‘Analysis of stable and radiogenic isotopes of earboo and hhydrogen in methane provides ‘natural gas, coalbed gas, and glacial where stable sotope analysis is not definitive, the radiogenic isotopes, radiocarbon (C), GD generally is defiitive. Methane formed from the microbial decomposition of recent organic materials such ‘as wood, paper, yard waste, and food scraps contains clevated "°C concentrations that reflect the above-normal Landfill gasis| typically 40% carbon dioxide and 60% methane, The potential changes in global climate caused by increased carbon dioxide have been well publicized, but thousands of ears play bas lower“ concettions th potential eet of amosphere methane hve recived duct radiusive der Mebane formed alongwith col INTRODUCTION @ Landfill methane has: tion not only because cerns but also because Etta See Smtr a 8 landfill gas.vo °56 ENVIRONMENTAL GEOSCIENCES microbial methane are present in ocean sediments. Rice and Claypool (1981) have estimated that more than 20% of the world’s known natural gas deposits were at least Sources of Methane ‘mogenic origin (Rice and Claypool, 1981), and this type of gas predominates in natural gas pipelines and storage reservoirs throughout the country. Thermogenic natural 25 deposits are commonly associated with ol, but meth- ane is also formed as a pat ofthe coaification process. In some coals, this gas became trapped within the pores ‘gas has been produced from coalbeds for mé tially as a means of degassing the coal pr changes tht have occurred ‘or mixing with gases from other Xeameta = ((Ranple ~ Raandard)/Ruanaw) » 1000 (1) where BX = the isotope of interest (8C, 8D, 80, ete) R = the ratio of "C/"C, *A/'H, or "0/0, ete. ing its isotopic ratio on a ratio mass-spectrometer.COLEMAN: ISOTOPIC IDENTIFICATION 97” ‘ported by the Inara Nise Eney Agen AEA: AR 9, ine iso, Bas my Using standard nomenclature, '“C concentrations are unit (TU) is equal to one atoms. Because both concentrations, or radicactivities, can be measured in ¢i- ther liquid scintillation or gas proportional counters. DISTINGUISHING GASES FROM DIFFERENT SOURCES of subsurface gas, gases from different do not have identical compositions. The chemical and isotopic composit provide information on the ori ‘timescan even provide insights ‘a gasis not of microbial origin (and thus not because bacteria and other microbes prod ‘amounts of these components (Bernard, is apparent from these data that concen- 100 ppm are quite common in landfill gas. ‘San Francisco Bay sediments, and levels an order of mag nitude higher than this were generated in laboratory cul- tures. Therefore, the presence or absence of trace amounts, a0 Ethane (ppm) FIGURE 2 Eihane and propane cocennston ia ea eames of these components does not conclusively indicate ‘gas mixture can change as it migrates. Higher molecular ‘weight hydrocarbons such as ethane, propane, and butane can be removed during migration (Coleman et al, 1977), and itis probable that removal can occur with other vola- tile organic compounds frequently used to identify land- fil gas (eg. ketones and halogenated hydrocarbons). As the presence of high concentrations of centration increased, thus making a thermogenic ga look ‘more like a microbial gas.°98 ENVIRONMENTAL GEOSCIENCES Identifying Gases Using Stable-Isotope ful information for distinguishing gases from different sources, Other work, more specifically related to the study ‘of methane formed by microbial processes, has shown that hydrogen isotope analysis of methane can even help to 50,000 years old, the drift gases formed from organic ‘materials in these deposits would be expected not to con- tain detectable “C.°T00 ENVIRONMENTAL GEOSCIENCES ‘upon the average age of the org it was formed. Only limited available, and these are m from swamps and thus are biased towards higher “Ccon- centrations; subsurface samples would be expected to have as from other types Figure 5 does not show sewer gas is defined as that formed ied by human activities, such aping operations). Data for these two gases were Sewer gas would be expected to have a *C very similar to that of landfill gases. Com- fill and that in the compost. ‘Tritium analysis of methane provides another method of identifying landfill gas and also has potential for dis tinguishing sewer gas and compost gas from lan ‘The hydrogen in methane generated by acetate fe all of the water in precipitation in the early 1960s when at of tritium were at a maximum, radioactive decay would hhave decreased the level to below what was observed for some samples. One source maybe tracers in biochemical |uminous paints, used on some watch and instrument dials and “glow-in-the-dark” signs, are the most probable source of tritium in a municipal landfill. The authors are not proposed that tritium analysis ishing landfill gas from sewer gas on Tandfil gas would reflect the tiiumCOLEMAN: ISOTOPIC IDENTIFICATION IOI” Light hydrocerbons in marine sed issertation, Texas A&M University, Col- Bogner, J. E. (1990). Energy potential of modern landfill In Proceedings of the Minois energy conference. Chicago, sis of methane generally requires at least 5 ‘methane, SUMMARY @ Conventional molecular (chemical) analyses are very Iie! Reports ofthe Deep Sea Dring Pro 579-884, >. D. (1979). The origin of drifts deposits as ters of gas, can generally allow landfill gas to be distinguished from thermogenic gas (such as natural gas ‘and coalbed gas) and glacial-drift gas. However, this anal- ysis does not allow differentiating landfill gas from will sometimes indicate whe ‘Although it generally gas (these thermogenic gases contain no "*C analyses will also generally allow distinguish- subsurface. In Proceedings of the ual landfill gas symposium (pp. is of methane may be a particularly use- , and Further research in this area is warranted. REFERENCES @ Alperin, M. J, Reebargh, W.S, and Whiticar, M, J. 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