Carbon and hydrogen isotope fractionation by microbial methane oxidation: improved determination

Isotope fractionation is a promising tool for quantifying methane oxidation in landfill cover soils. For good quantification an accurate determination of the isotope fractionation factor (alpha) of methane oxidation based on independent batch experiments with soil samples from the landfill cover is required. Most studies so far used data analysis methods based on approximations of the Rayleigh model to determine alpha. In this study, the two most common approximations were tested, the simplified Rayleigh approach and the Coleman method. To do this, the original model of Rayleigh was described in measurable variables, methane concentration and isotopic abundances, and fitted to batch oxidation data by means of a weighted non-linear errors-in-variables regression technique. The results of this technique were used as a benchmark to which the results of the two conventional approximations were compared. Three types of batch data were used: simulated data, data obtained from the literature, and data obtained from new batch experiments conducted in our laboratory. The Coleman approximation was shown to be acceptable but not recommended for carbon fractionation (error on alpha-1 up to 5%) and unacceptable for hydrogen fractionation (error up to 20%). The difference between the simplified Rayleigh approach and the exact Rayleigh model is much smaller for both carbon and hydrogen fractionation (error on alpha-1<0.05%). There is also a small difference when errors in both variables (methane concentration and isotope abundance) are accounted for instead of assuming an error-free independent variable. By means of theoretical calculations general criteria, not limited to methane, (13)C, or D, were developed for the validity of the simplified Rayleigh approach when using labelled compounds.     

Simulation model for gas diffusion and methane oxidation in landfill cover soils

Landfill cover soils oxidize a considerable fraction of the methane produced by landfilled waste. Despite many efforts this oxidation is still poorly quantified. In order to reduce the uncertainties associated with methane oxidation in landfill cover soils, a simulation model was developed that incorporates Stefan-Maxwell diffusion, methane oxidation, and methanotrophic growth. The growth model was calibrated to laboratory data from an earlier study. There was an excellent agreement between the model and the experimental data. Therefore, the model is highly applicable to laboratory column studies, but it has not been validated with field data. A sensitivity analysis showed that the model is most sensitive to the parameter expressing the maximum attainable methanotrophic activity of the soil. Temperature and soil moisture are predicted to be the environmental factors affecting the methane oxidizing capacity of a landfill cover soil the most. Once validated with field data, the model will enable a year-round estimate of the methane oxidizing capacity of a landfill cover soil.     

Induction of enhanced methane oxidation in compost: temperature and moisture response

Landfilling is one of the most common ways of municipal solid waste disposal. Degradation of organic waste produces CH(4) and other landfill gases that significantly contribute to global warming. However, before entering the atmosphere, part of the produced CH(4) can be oxidised while passing through the landfill cover. In the present study, the oxidation rate of CH(4) was studied with various types of compost as possible landfill cover. The influence of incubation time, moisture content and temperature on the CH(4) oxidation capacity of different types of compost was examined. It was observed that the influence of moisture content and temperature on methane oxidation is time-dependent. Maximum oxidation rates were observed at moisture contents ranging from 45% to 110% (dry weight basis), while the optimum temperature ranged from 15 to 30 degrees C.     

Atmospheric emissions and attenuation of non-methane organic compounds in cover soils at a French landfill

In addition to methane (CH(4)) and carbon dioxide (CO(2)), landfill gas may contain more than 200 non-methane organic compounds (NMOCs) including C(2+)-alkanes, aromatics, and halogenated hydrocarbons. Although the trace components make up less than 1% v/v of typical landfill gas, they may exert a disproportionate environmental burden. The objective of this work was to study the dynamics of CH(4) and NMOCs in the landfill cover soils overlying two types of gas collection systems: a conventional gas collection system with vertical wells and an innovative horizontal gas collection layer consisting of permeable gravel with a geomembrane above it. The 47 NMOCs quantified in the landfill gas samples included primarily alkanes (C(2)-C(10)), alkenes (C(2)-C(4)), halogenated hydrocarbons (including (hydro)chlorofluorocarbons ((H)CFCs)), and aromatic hydrocarbons (BTEXs). In general, both CH(4) and NMOC fluxes were all very small with positive and negative fluxes. The highest percentages of positive fluxes in this study (considering all quantified species) were observed at the hotspots, located mainly along cell perimeters of the conventional cell. The capacity of the cover soil for NMOC oxidation was investigated in microcosms incubated with CH(4) and oxygen (O(2)). The cover soil showed a relatively high capacity for CH(4) oxidation and simultaneous co-oxidation of the halogenated aliphatic compounds, especially at the conventional cell. Fully substituted carbons (TeCM, PCE, CFC-11, CFC-12, CFC-113, HFC-134a, and HCFC-141b) were not degraded in the presence of CH(4) and O(2). Benzene and toluene were also degraded with relative high rates. This study demonstrates that landfill soil covers show a significant potential for CH(4) oxidation and co-oxidation of NMOCs.     

Scaling methane oxidation: from laboratory incubation experiments to landfill cover field conditions

Evaluating field-scale methane oxidation in landfill cover soils using numerical models is gaining interest in the solid waste industry as research has made it clear that methane oxidation in the field is a complex function of climatic conditions, soil type, cover design, and incoming flux of landfill gas from the waste mass. Numerical models can account for these parameters as they change with time and space under field conditions. In this study, we developed temperature, and water content correction factors for methane oxidation parameters. We also introduced a possible correction to account for the different soil structure under field conditions. These parameters were defined in laboratory incubation experiments performed on homogenized soil specimens and were used to predict the actual methane oxidation rates to be expected under field conditions. Water content and temperature corrections factors were obtained for the methane oxidation rate parameter to be used when modeling methane oxidation in the field. To predict in situ measured rates of methane with the model it was necessary to set the half saturation constant of methane and oxygen, K_m, to 5%, approximately five times larger than laboratory measured values. We hypothesize that this discrepancy reflects differences in soil structure between homogenized soil conditions in the lab and actual aggregated soil structure in the field. When all of these correction factors were re-introduced into the oxidation module of our model, it was able to reproduce surface emissions (as measured by static flux chambers) and percent oxidation (as measured by stable isotope techniques) within the range measured in the field.     

Assessment of the methane oxidation capacity of compacted soils intended for use as landfill cover materials

The microbial oxidation of methane in engineered cover soils is considered a potent option for the mitigation of emissions from old landfills or sites containing wastes of low methane generation rates. A laboratory column study was conducted in order to derive design criteria that enable construction of an effective methane oxidising cover from the range of soils that are available to the landfill operator. Therefore, the methane oxidation capacity of different soils was assessed under simulated landfill conditions. Five sandy potential landfill top cover materials with varying contents of silt and clay were investigated with respect to methane oxidation and corresponding soil gas composition over a period of four months. The soils were compacted to 95% of their specific proctor density, resulting in bulk densities of 1.4-1.7 g cm⁻³, reflecting considerably unfavourable conditions for methane oxidation due to reduced air-filled porosity. The soil water content was adjusted to field capacity, resulting in water contents ranging from 16.2 to 48.5 vol.%. The investigated inlet fluxes ranged from 25 to about 100 g CH₄ m⁻² d⁻¹, covering the methane load proposed to allow for complete oxidation in landfill covers under Western European climate conditions and hence being suggested as a criterion for release from aftercare. The vertical distribution of gas concentrations, methane flux balances as well as stable carbon isotope studies allowed for clear process identifications. Higher inlet fluxes led to a reduction of the aerated zone, an increase in the absolute methane oxidation rate and a decline of the relative proportion of oxidized methane. For each material, a specific maximum oxidation rate was determined, which varied between 20 and 95 g CH₄ m⁻² d⁻¹ and which was positively correlated to the air-filled porosity of the soil. Methane oxidation efficiencies and gas profile data imply a strong link between oxidation capacity and diffusive ingress of atmospheric air. For one material with elevated levels of fine particles and high organic matter content, methane production impeded the quantification of methane oxidation potentials. Regarding the design of landfill cover layers it was concluded that the magnitude of the expected methane load, the texture and expected compaction of the cover material are key variables that need to be known. Based on these, a column study can serve as an appropriate testing system to determine the methane oxidation capacity of a soil intended as landfill cover material.     

The influence of atmospheric pressure on landfill methane emissions

Landfills are the largest source of anthropogenic methane (CH4) emissions to the atmosphere in the United States. However, few measurements of whole landfill CH4 emissions have been reported. Here, we present the results of a multi-season study of whole landfill CH4 emissions using atmospheric tracer methods at the Nashua, New Hampshire Municipal landfill in the northeastern United States. The measurement data include 12 individual emission tests, each test consisting of 5-8 plume measurements. Measured emissions were negatively correlated with surface atmospheric pressure and ranged from 7.3 to 26.5 m3 CH4 min(-1). A simple regression model of our results was used to calculate an annual emission rate of 8.4 x 10(6) m3 CH4 year(-1). These data, along with CH4 oxidation estimates based on emitted landfill gas isotopic characteristics and gas collection data, were used to estimate annual CH4 generation at this landfill. A reported gas collection rate of 7.1 x 10(6) m3 CH4 year(-1) and an estimated annual rate of CH4 oxidation by cover soils of 1.2 x 10(6) m3 CH4 year(-1) resulted in a calculated annual CH4 generation rate of 16.7 x 10(6) m3 CH4 year(-1). These results underscore the necessity of understanding a landfill's dynamic environment before assessing long-term emissions potential.     

Estimation of mass transport parameters of gases for quantifying CH4 oxidation in landfill soil covers

Methane (CH(4)), which is one of the most abundant anthropogenic greenhouse gases, is produced from landfills. CH(4) is biologically oxidized to carbon dioxide, which has a lower global warming potential than methane, when it passes through a cover soil. In order to quantify the amount of CH(4) oxidized in a landfill cover soil, a soil column test, a diffusion cell test, and a mathematical model analysis were carried out. In the column test, maximum oxidation rates of CH(4) (V(max)) showed higher values in the upper part of the column than those in the lower part caused by the penetration of O(2) from the top. The organic matter content in the upper area was also higher due to the active microbial growth. The dispersion analysis results for O(2) and CH(4) in the column are counter-intuitive. As the upward flow rate of the landfill gas increased, the dispersion coefficient of CH(4) slightly increased, possibly due to the effect of mechanical dispersion. On the other hand, as the upward flow rate of the landfill gas increased, the dispersion coefficient of O(2) decreased. It is possible that the diffusion of gases in porous media is influenced by the counter-directional flow rate. Further analysis of other gases in the column, N(2) and CO(2), may be required to support this hypothesis, but in this paper we propose the possibility that the simulations using the diffusion coefficient of O(2) under the natural condition may overestimate the penetration of O(2) into the soil cover layer and consequently overestimate the oxidation of CH(4).     

Methane mass balance at three landfill sites: What is the efficiency of capture by gas collection systems?

Many developed countries have targeted landfill methane recovery among greenhouse gas mitigation strategies, since methane is the second most important greenhouse gas after carbon dioxide. Major questions remain with respect to actual methane production rates in field settings and the relative mass of methane that is recovered, emitted, oxidized by methanotrophic bacteria, laterally migrated, or temporarily stored within the landfill volume. This paper presents the results of extensive field campaigns at three landfill sites to elucidate the total methane balance and provide field measurements to quantify these pathways. We assessed the overall methane mass balance in field cells with a variety of designs, cover materials, and gas management strategies. Sites included different cell configurations, including temporary clay cover, final clay cover, geosynthetic clay liners, and geomembrane composite covers, and cells with and without gas collection systems. Methane emission rates ranged from -2.2 to >10,000 mg CH(4) m(-2) d(-1). Total methane oxidation rates ranged from 4% to 50% of the methane flux through the cover at sites with positive emissions. Oxidation of atmospheric methane was occurring in vegetated soils above a geomembrane. The results of these studies were used as the basis for guidelines by the French environment agency (ADEME) for default values for percent recovery: 35% for an operating cell with an active landfill gas (LFG) recovery system, 65% for a temporary covered cell with an active LFG recovery system, 85% for a cell with clay final cover and active LFG recovery, and 90% for a cell with a geomembrane final cover and active LFG recovery.     

Use of a biologically active cover to reduce landfill methane emissions and enhance methane oxidation

Biologically-active landfill cover soils (biocovers) that serve to minimize CH4 emissions by optimizing CH4 oxidation were investigated at a landfill in Florida, USA. The biocover consisted of 50 cm pre-composted yard or garden waste placed over a 10-15 cm gas distribution layer (crushed glass) over a 40-100 cm interim cover. The biocover cells reduced CH4 emissions by a factor of 10 and doubled the percentage of CH4 oxidation relative to control cells. The thickness and moisture-holding capacity of the biocover resulted in increased retention times for transported CH4. This increased retention of CH4 in the biocover resulted in a higher fraction oxidized. Overall rates between the two covers were similar, about 2g CH4 m(-2)d(-1), but because CH4 entered the biocover from below at a slower rate relative to the soil cover, a higher percentage was oxidized. In part, methane oxidation controlled the net flux of CH4 to the atmosphere. The biocover cells became more effective than the control sites in oxidizing CH4 3 months after their initial placement: the mean percent oxidation for the biocover cells was 41% compared to 14% for the control cells (p<0.001). Following the initial 3 months, we also observed 29 (27%) negative CH4 fluxes and 27 (25%) zero fluxes in the biocover cells but only 6 (6%) negative fluxes and 22 (21%) zero fluxes for the control cells. Negative fluxes indicate uptake of atmospheric CH4. If the zero and negative fluxes are assumed to represent 100% oxidation, then the mean percent oxidation for the biocover and control cells, respectively, for the same period would increase to 64% and 30%.     

Methane oxidation in a landfill cover with capillary barrier

The methane oxidation potential of a landfill cover with capillary barrier was investigated in an experimental plant (4.8 m x 0.8 m x 2.1m). The cover soil consisted of two layers, a mixture of compost plus sand (0.3 m) over a layer of loamy sand (0.9 m). Four different climatic conditions (summer, winter, spring and fall) were simulated. In and outgoing fluxes were measured. Gas composition, temperature, humidity, matrix potential and gas pressure were monitored in two profiles. CH4 oxidation rate within the investigated top cover ranged from 98% to 57%. The minimum was observed for a short time after irrigation. Temperature distribution, gas concentration profiles and lab-scaled batch experiments indicate that before irrigation the highest oxidising activity took place in a depth of about 30 cm. After irrigation the oxidising horizon seemed to migrate upwards since methanotrophic bacteria develop better there due to an adequate supply with oxygen. It can be assumed that the absence of oxygen is one of the most important limiting factors for the CH4 oxidation process. Abrupt cross-overs between horizons of different soil material may lead to zones of increased water saturation and decreased soil respiration.     

Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO₂ levels: the added value of the isotope (δ¹³C and δ¹⁸O CO₂; δ¹³C and δD CH₄) approach

We are presenting here a multi-isotope approach (δ¹³C and δ¹⁸O of CO₂; δ¹³C and δD of CH₄) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO₂ levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH₄ oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH₄ is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH₄ oxidation by the methanotrophic bacteria. δ¹³C of CO₂ samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.     

USING ISOTOPIC AND MOLECULAR DATA TO MODEL LANDFILL GAS PROCESSES

Using a large data set, a preliminary investigation has been made to evaluate the usefulness of stable isotope ratios for improving our understanding of methane and carbon dioxide generation in landfills. Included are approximately 130 landfill gas samples from across the U.S.A., and 18 recent samples from: (1) an Argonne Laboratory study area in the Brea-Olinda Landfill, Orange County, California (U.S.A); and (2) several Los Angeles County landfills, California (U.S.A). The following isotope ratios were examined: δ¹³C for methane, δ¹³C for carbon dioxide and δD for methane. Using simple ratio plots supplemented by mass-balance calculations, these data show promise for indicating the relative contributions of the four major carbon cycle processes in landfills, namely: (1) direct oxidation of organic material to carbon dioxide; (2) methane generation from fermentation (acetate cleavage); (3) methane generation from carbon dioxide reduction; and (4) methane oxidation to carbon dioxide by methanotrophic bacteria. Both the methane generation and oxidation reactions are central to an explanation of the trends discussed herein. The data also suggest that direct oxidation of organic matter in the refuse may be contributing to the observed isotopic ratios in some cases. The trends observed at the Brea-Olinda site were similar to trends using the large U.S. database, suggesting that isotopic techniques may be useful to better constrain carbon cycle processes common to all landfill settings.     

Above- and below-ground methane fluxes and methanotrophic activity in a landfill-cover soil

Landfills are a major anthropogenic source of the greenhouse gas methane (CH(4)). However, much of the CH(4) produced during the anaerobic degradation of organic waste is consumed by methanotrophic microorganisms during passage through the landfill-cover soil. On a section of a closed landfill near Liestal, Switzerland, we performed experiments to compare CH(4) fluxes obtained by different methods at or above the cover-soil surface with below-ground fluxes, and to link methanotrophic activity to estimates of CH(4) ingress (loading) from the waste body at selected locations. Fluxes of CH(4) into or out of the cover soil were quantified by eddy-covariance and static flux-chamber measurements. In addition, CH(4) concentrations at the soil surface were monitored using a field-portable FID detector. Near-surface CH(4) fluxes and CH(4) loading were estimated from soil-gas concentration profiles in conjunction with radon measurements, and gas push-pull tests (GPPTs) were performed to quantify rates of microbial CH(4) oxidation. Eddy-covariance measurements yielded by far the largest and probably most representative estimates of overall CH(4) emissions from the test section (daily mean up to ～91,500μmolm(-2)d(-1)), whereas flux-chamber measurements and CH(4) concentration profiles indicated that at the majority of locations the cover soil was a net sink for atmospheric CH(4) (uptake up to -380μmolm(-2)d(-1)) during the experimental period. Methane concentration profiles also indicated strong variability in CH(4) loading over short distances in the cover soil, while potential methanotrophic activity derived from GPPTs was high (v(max)～13mmolL(-1)(soil air)h(-1)) at a location with substantial CH(4) loading. Our results provide a basis to assess spatial and temporal variability of CH(4) dynamics in the complex terrain of a landfill-cover soil.     

Methane flux and oxidation at two types of intermediate landfill covers

Methane emissions were measured on two areas at a Florida (USA) landfill using the static chamber technique. Because existing literature contains few measurements of methane emissions and oxidation in intermediate cover areas, this study focused on field measurement of emissions at 15-cm-thick non-vegetated intermediate cover overlying 1-year-old waste and a 45-cm-thick vegetated intermediate cover overlying 7-year-old waste. The 45 cm thick cover can also simulate non-engineered covers associated with older closed landfills. Oxidation of the emitted methane was evaluated using stable isotope techniques. The arithmetic means of the measured fluxes were 54 and 22 g CH(4) m(-2)d(-1) from the thin cover and the thick cover, respectively. The peak flux was 596 g m(-2)d(-1) for the thin cover and 330 g m(-2)d(-1) for the thick cover. The mean percent oxidation was significantly greater (25%) at the thick cover relative to the thin cover (14%). This difference only partly accounted for the difference in emissions from the two sites. Inverse distance weighing was used to describe the spatial variation of flux emissions from each cover type. The geospatial mean flux was 21.6 g m(-2)d(-1) for the thick intermediate cover and 50.0 g m(-2)d(-1) for the thin intermediate cover. High emission zones in the thick cover were fewer and more isolated, while high emission zones in the thin cover were continuous and covered a larger area. These differences in the emission patterns suggest that different CH(4) mitigation techniques should be applied to the two areas. For the thick intermediate cover, we suggest that effective mitigation of methane emissions could be achieved by placement of individualized compost cells over high emission zones. Emissions from the thin intermediate cover, on the other hand, can be mitigated by placing a compost layer over the entire area.     

Spatial variability of soil gas concentration and methane oxidation capacity in landfill covers

In order to devise design criteria for biocovers intended to enhance the microbial oxidation of landfill methane it is critical to understand the factors influencing gas migration and methane oxidation in landfill cover soils. On an old municipal solid waste landfill in north-western Germany soil gas concentrations (10, 40, 90 cm depth), topsoil methane oxidation capacity and soil properties were surveyed at 40 locations along a 16 m grid. As soil properties determine gas flow patterns it was hypothesized that the variability in soil gas composition and the subsequent methanotrophic activity would correspond to the variability of soil properties. Methanotrophic activity was found to be subject to high spatial variability, with values ranging between 0.17 and 9.80 g CH₄ m⁻² h⁻¹_. Considering the current gas production rate of 0.03 g CH₄ m⁻² h⁻¹, the oxidation capacity at all sampled locations clearly exceeded the flux to the cover, and can be regarded as an effective instrument for mitigating methane fluxes. The methane concentration in the cover showed a high spatial heterogeneity with values between 0.01 and 0.32 vol.% (10 cm depth), 22.52 vol.% (40 cm), and 36.85 vol.% (90 cm). The exposure to methane raised the oxidation capacity, suggested by a statistical correlation to an increase in methane concentration at 90 cm depth. Methane oxidation capacity was further affected by the methanotroph bacteria pH optimum and nutrient availability, and increased with decreasing pH towards neutrality, and increased with soluble ion concentration). Soil methane and carbon dioxide concentration increased with lower flow resistance of the cover, as represented by the soil properties of a reduced bulk density, increase in air capacity and in relative ground level.     

Soil atmosphere concentration profiles and methane emission rates in the restoration covers above landfill sites: Equipment and preliminary results

In an investigation into the microbial oxidation of methane in soils, a simple and robust sampling device for the collection of small samples of soil atmosphere was used. The method has the potential for determining small-scale variations in depth profiles of gases, without the potential problems of sample migration during collection. Measurements of methane concentration profiles at a number of points along a transect in a restored landfill site in Essex correlated well with the measured emission of landfill gas from the surface of the soil. Emissions were only detected where methane concentrations reached the soil surface.     

Effect of leachate irrigation on methane oxidation in tropical landfill cover soil

The effect of leachate irrigation on methanotrophic activity in sandy loam-based landfill cover soil with vegetation was investigated. Laboratory-scale experiments were conducted to investigate the methane oxidation reaction in cover soil with and without plants (tropical grass). The methane oxidation rate in soil columns was monitored during leachate application at different organic concentrations and using different irrigation patterns. The results showed that the growth of plants on the final cover layer of landfill was promoted when optimal supplement nutrients were provided through leachate irrigation. The vegetation also helped to promote methane oxidation in soil, whereas leachate application helped increase the methane oxidation rate in nonvegetated cover soil. Intermittent application of leachate (once every 4 days) improved the methane oxidation activity as compared to daily application. Nevertheless, the adverse effects of organic overloading on methane oxidation rate and plant growth were also observed.     

Improving the aeration of critical fine-grained landfill top cover material by vegetation to increase the microbial methane oxidation efficiency

The natural methane oxidation potential of methanotrophic bacteria in landfill top covers is a sustainable and inexpensive method to reduce methane emissions to the atmosphere. Basically, the activity of methanotrophic bacteria is limited by the availability of oxygen in the soil. A column study was carried out to determine whether and to what extent vegetation can improve soil aeration and maintain the methane oxidation process. Tested soils were clayey silt and mature compost. The first soil is critical in light of surface crusting due to vertical erosion of an integral part of fine-grained material, blocking pores required for the gas exchange. The second soil, mature compost, is known for its good methane oxidation characteristics, due to high air-filled porosity, favorable water retention capacity and high nutrient supply. The assortment of plants consisted of a grass mixture, Canadian goldenrod and a mixture of leguminous plants. The compost offered an excellent methane oxidation potential of 100% up to a CH₄-input of 5.6 l CH₄ m⁻² h⁻¹. Whereas the oxidation potential was strongly diminished in the bare control column filled with clayey silt even at low CH₄-loads. By contrast the planted clayey silt showed an increased methane oxidation potential compared to the bare column. The spreading root system forms secondary macro-pores, and hence amplifies the air diffusivity and sustain the oxygen supply to the methanotrophic bacteria. Water is produced during methane oxidation, causing leachate. Vegetation reduces the leachate by evapotranspiration. Furthermore, leguminous plants support the enrichment of soil with nitrogen compounds and thus improving the methane oxidation process. In conclusion, vegetation is relevant for the increase of oxygen diffusion into the soil and subsequently enhances effective methane oxidation in landfill cover soils.     

CHANGES IN MAJOR AND TRACE COMPONENTS OF LANDFILL GAS DURING SUBSURFACE MIGRATION

A gas plume emanating from the Foxhall Landfill in Suffolk (U.K.) has been defined within unsaturated ferruginous sands on the basis of elevated concentrations of methane, carbon dioxide and volatile organic compounds (VOCs). The plume is relatively narrow, extends more than 100 m from the landfill boundary, and lies mainly between 2 m bgl (below ground level) and the water table at 9.5 m bgl. With increasing distance along the axis of the plume, the ratio of methane to carbon dioxide gradually decreases, while nitrogen increases. Oxygen appears beyond 80 m from the landfill boundary. Stable carbon and hydrogen isotope ratios in methane become heavier with distance, while carbon dioxide becomes isotopically lighter with respect to stable carbon. This provides strong evidence for microbially mediated methane oxidation. Zones of black reduced sediment near the landfill suggest that ferric iron [Fe(III)] may be acting as an electron acceptor for oxidation. No thermal anomaly was observed, thus suggesting that the rate of oxidation/flux of methane is low. Volatile organic compounds in the plume were trapped using a combination of sorbants (Tenax GR, Haysep Q and Carbosieve S-III), and desorbed thermally into a GC/MS for semi-quantitative analysis. The 79 VOCs identified were similar to those found in other landfills, and their concentrations, both in the landfill and in the soil gas, were broadly related to their volatility. Only two compounds (vinyl chloride and dichlorofluoromethane) approached or exceeded the long-term exposure limit (LTEL, as defined by the U.K. Health and Safety Executive, 1992) outside the landfill. Halogenated compounds (dichlorodifluoromethane, dichlorofluoromethane and trichlorofluoromethane) were found to be most mobile but their concentration profiles suggest that they may have been flushed out of the landfill during its early stages. It is suggested that the association of volatile halogenated compounds with methane is good evidence that they are derived from a landfill.