A methodology to estimate odors around landfill sites: the use of methane as an odor index and its utility in landfill siting

The estimation of odor production and dispersion from landfill sites is a very complicated task because of the different chemical species that exist in biogas. To site a new landfill, it is necessary to know the distance that odors can travel around the landfill under atmospheric conditions that increase the concentration of pollutants. Although CH4 is an odorless gas, it can be used as an index to determine the dispersion of low-reactivity odorous species around a landfill site. Methane production rates, estimated by biogas production models, were used by an air dispersion model to determine the spatial distribution of CH4 around landfill sites. By utilizing dispersion models under extreme atmospheric conditions, a maximum CH4 concentration around the landfills was determined. Based on the ratio between CH4 and odorous chemical species, the spatial distribution of the concentration of an odorous species was determined for those species with low reactivity in the atmosphere. For odorous species with high reactivity in the atmosphere, a dispersion-reaction model must be used. In this way, the acceptable distance between new landfills and residential areas can be determined. The proposed methodology could be used as a design tool for those who are interested in landfill siting.     

Spatial and temporal characteristics of urban atmospheric methane in Nagoya City,Japan:: an assessment of the contribution from regional landfills

The spatial and temporal behavior of atmospheric methane (CH₄) in the Nagoya metropolitan area was investigated in relation to the regional meteorological and topographical characteristics. It was found that the daily maximum CH₄ concentrations in the central city area were observed when the northeast wind blew from the foothill of the northeastern mountainous area down into the central city areas, under stable atmospheric conditions. The large and active landfills are the major anthropogenic CH₄ sources and are located at the hill sites in the northeast. Therefore, it was considered that the air mass with the high concentration of CH₄ flowed from the landfill sites into the urban area, and exerted substantial influences on the spatial and temporal variations of atmospheric CH₄ concentrations in the central city area.     

Seasonal Variability in CH4 Emissions from a Landfill in a Cool,Semiarid Climate

ABSTRACT

Methane exchange with the atmosphere was measured during three seasons at the Rooney Road landfill in Jefferson County, CO. Substantial spatial and temporal variability in exchange rates were observed. Mean fluxes to the atmosphere were 534, 1290, and 538 mg CH₄/m²/day, respectively, in the fall of 1994, winter of 1994–1995, and summer of 1995. Median fluxes were 12.42, 8.62, and 5.65 mg CH₄/m²/day, respectively, during those seasons. Forty-three of 177 measurements had small negative fluxes, suggesting methanotrophic activity in the landfill cover soils. Despite probable methanotrophic activity in cover soils, landfills without gas collection systems may emit substantial CH₄ to the atmosphere, with large spatial and seasonal variability.     

Modeling of methane oxidation in landfill cover soil using an artificial neural network

Knowing the fraction of methane (CH₄) oxidized in landfill cover soils is an important step in estimating the total CH₄ emissions from any landfill. Predicting CH₄ oxidation in landfill cover soils is a difficult task because it is controlled by a number of biological and environmental factors. This study proposes an artificial neural network (ANN) approach using feedforward backpropagation to predict CH₄ oxidation in landfill cover soil in relation to air temperature, soil moisture content, oxygen (O₂) concentration at a depth of 10 cm in cover soil, and CH₄ concentration at the bottom of cover soil. The optimum ANN model giving the lowest mean square error (MSE) was configured from three layers, with 12 and 9 neurons at the first and the second hidden layers, respectively, log-sigmoid (logsig) transfer function at the hidden and output layers, and the Levenberg-Marquardt training algorithm. This study revealed that the ANN oxidation model can predict CH₄ oxidation with a MSE of 0.0082, a coefficient of determination (R ²) between the measured and predicted outputs of up to 0.937, and a model efficiency (E) of 0.8978. To conclude, further developments of the proposed ANN model are required to generalize and apply the model to other landfills with different cover soil properties.

Implications:

To date, no attempts have been made to predict the percent of CH₄ oxidation within landfill cover soils using an ANN. This paper presents modeling of CH₄ oxidation in landfill cover soil using ANN based on field measurements data under tropical climate conditions in Malaysia. The proposed ANN oxidation model can be used to predict the percentage of CH₄ oxidation from other landfills with similar climate conditions, cover soil texture, and other properties. The predicted value of CH₄ oxidation can be used in conjunction with the Intergovernmental Panel on Climate Change (IPCC) First Order Decay (FOD) model by landfill operators to accurately estimate total CH₄ emission and how much it contributes to global warming.     

Metal Oxides Remove Hydrogen Sulfide from Landfill Gas Produced from Waste Mixed with Plaster Board under Wet Conditions

Abstract

Hydrogen sulfide (H₂S) is a major odorant in landfills. We have studied H₂S production from landfill residual waste with and without sulfur-containing plaster board, including the influence of the water content in the waste. The laboratory experiments were conducted in 30-L polyethylene containers with a controlled water level. We also studied how different materials removed H₂S in reactive layers on top of the waste. The organic waste produced H₂S in concentrations of up to 40 parts per million (ppm) over a period of 80 days. When plaster board was added, the H₂S concentration increased to 800 ppm after a lag period of approximately 40 days with a high water level, and to approximately 100 ppm after 50 days with a low water level. The methane (CH₄) concentration in the initial experiment was between 5 and 70% after 80 days. The CH₄ concentration in the second experiment increased to nearly 70% in the container with a high water level, slowly declining to approximately 60% between days 20 and 60. The CH₄ concentrations during the experiments resembled normal landfill concentrations. Metallic filter materials were very efficient in removing H₂S, whereas organic filter materials showed poor H₂S removal.     

Methane emissions from 20 landfills across the United States using vertical radial plume mapping

Landfill fugitive methane emissions were quantified as a function of climate type and cover type at 20 landfills using U.S. Environmental Protection Agency (EPA) Other Test Method (OTM)-10 vertical radial plume mapping (VRPM) with tunable diode lasers (TDLs). The VRPM data were initially collected as g CH₄/sec emission rates and subsequently converted to g CH₄/m²/day rates using two recently published approaches. The first was based upon field tracer releases of methane or acetylene and multiple linear regression analysis (MLRM). The second was a virtual computer model that was based upon the Industrial Source Complex (ISC3) and Pasquill plume stability class models (PSCMs). Calculated emission results in g CH₄/m²/day for each measured VRPM with the two approaches agreed well (r ² = 0.93). The VRPM data were obtained from the working face, temporary soil, intermediate soil, and final soil or synthetic covers. The data show that methane emissions to the atmosphere are a function of climate and cover type. Humid subtropical climates exhibited the highest emissions for all cover types at 207, 127, 102, and 32 g CH₄/m²/day, for working face (no cover), temporary, intermediate, and final cover, respectively. Humid continental warm summers showed 67, 51, and 27 g CH₄/m²/day for temporary, intermediate, and final covers. Humid continental cool summers were 135, 40, and 26 g CH₄/m²/day for the working face, intermediate, and final covers. Mediterranean climates were examined for intermediate and final covers only and found to be 11 and 6 g CH₄/m²/day, respectively, whereas semiarid climates showed 85, 11, 3.7, and 2.7 g CH₄/m²/day for working face, temporary, intermediate, and final covers. A closed, synthetically capped landfill covered with soil and vegetation with a gas collection system in a humid continental warm summer climate gave mostly background methane readings and average emission rates of only 0.09 g CH₄/m²/day flux when measurable.

Implications The OTM-10 method is being proposed by EPA to quantify surface methane emissions from landfill covers. This study of 20 landfills across the United States was done to determine the efficacy of using OTM-10 for this purpose. Two recently published models were used to evaluate the methane flux results found with VRPM optical remote sensing. The results should provide a sense of the practicality of the method, its limitations at landfills, and the impact of climate upon the cover's methane flux. Measured field data may assist landfill owners in refining previously modeled methane emission factor default values.     

Effect of biogas generation on radon emissions from landfills receiving radium-bearing waste from shale gas development

Dramatic increases in the development of oil and natural gas from shale formations will result in large quantities of drill cuttings, flowback water, and produced water. These organic-rich shale gas formations often contain elevated concentrations of naturally occurring radioactive materials (NORM), such as uranium, thorium, and radium. Production of oil and gas from these formations will also lead to the development of technologically enhanced NORM (TENORM) in production equipment. Disposal of these potentially radium-bearing materials in municipal solid waste (MSW) landfills could release radon to the atmosphere. Risk analyses of disposal of radium-bearing TENORM in MSW landfills sponsored by the Department of Energy did not consider the effect of landfill gas (LFG) generation or LFG control systems on radon emissions. Simulation of radon emissions from landfills with LFG generation indicates that LFG generation can significantly increase radon emissions relative to emissions without LFG generation, where the radon emissions are largely controlled by vapor-phase diffusion. Although the operation of LFG control systems at landfills with radon source materials can result in point-source atmospheric radon plumes, the LFG control systems tend to reduce overall radon emissions by reducing advective gas flow through the landfill surface, and increasing the radon residence time in the subsurface, thus allowing more time for radon to decay. In some of the disposal scenarios considered, the radon flux from the landfill and off-site atmospheric activities exceed levels that would be allowed for radon emissions from uranium mill tailings.

Implications: Increased development of hydrocarbons from organic-rich shale formations has raised public concern that wastes from these activities containing naturally occurring radioactive materials, particularly radium, may be disposed in municipal solid waste landfills and endanger public health by releasing radon to the atmosphere. This paper analyses the processes by which radon may be emitted from a landfill to the atmosphere. The analyses indicate that landfill gas generation can significantly increase radon emissions, but that the actual level of radon emissions depend on the place of the waste, construction of the landfill cover, and nature of the landfill gas control system.     

Natural and anthropogenic methane sources in New England

We have recently completed a methane emissions inventory for the New England region. Methane emissions were calculated to be 0.91 Tg yr^-1, with wetlands and landfills dominating all other sources. Wetlands are estimated to produce 0.33 Tg CH₄ yr^-1, of which 74% come from Maine. Active landfills emit an estimated 0.28 Tg CH₄ yr^-1, 60% of which are generated from twelve landfills. Although uncertainty in the estimate is greater, emissions from closed landfills are on the same order of magnitude as active landfills and wetlands; 0.25 Tg CH₄ yr^-1. Sources of moderate magnitude include ruminant animals (0.05 Tg CH₄ yr^-1) and residential wood combustion (0.03 Tg CH₄ yr^-1). Motor vehicles, natural gas, and wastewater treatment make only minor contributions. New England is heavily forested and the soil uptake of atmospheric methane in upland forests, 0.06 Tg CH₄ yr^-1, decreases emissions from soils by about 18%. Although uncertainties remain, our estimates indicate that even in a highly urbanized region such as New England, natural sources of methane make the single greatest contribution to total emissions, with state totals varying between 8% (Massachusetts) and 92% (Maine). Because emissions from only a few large landfills dominate anthropogenic sources, mitigation strategies focused on these discrete point sources should result in significant improvements in regional air quality. Current federal regulations mandate landfill gas collection at only the largest sites. Expanding recovery efforts to moderately sized landfills through either voluntary compliance or further regulations offers the best opportunity to substantially reduce atmospheric methane in New England. In the short term, however, the large contribution from closed, poorly regulated landfills may make the attribution of air quality improvements difficult. Mitigation efforts toward these landfills should also be a priority.     

Greenhouse Gas Dynamics of Municipal Solid Waste Alternatives

ABSTRACT

Previous greenhouse gas studies comparing landfilling with combustion of municipal solid waste (MSW) are limited to examinations of the emissions weighted by their relative radiative activity. This paper adds another dimension by analyzing the atmospheric response to these emissions. The heart of the analysis is a time-dependent model using a perturbation analysis of the IS92a results of the Intergovernmental Panel on Climate Change (IPCC). Using as inputs the emissions from the two technologies, the model calculates atmospheric concentration histories. Scenarios for a landfill and a combustor envision each accepting 1000 Mg refuse/day for a 30-year operating period followed by a 70-year postclosure period. The baseline scenario examines the basic greenhouse impact of each technology. The other scenario adds active gas collection at the landfill and energy offset credits for avoided power plant carbon emissions. For both scenarios, CH₄ and trace gases from the landfill persist in the atmosphere, and they are relatively potent at forcing IR heating. The combination of these features place the landfill much higher than previously expected on the greenhouse impact scale. For the baseline scenario, the time-integrated radiative forcing from landfilling is 115 times that of combustion, and this ratio is 45 for the second scenario.     

Modeling landfill gas potential and potential energy recovery from Thohoyandou landfill site,South Africa

ABSTRACT

The increase in solid waste generation has been a major contributor to the amount of Greenhouse gases (GHGs) present in the atmosphere. To some extent, a great chunk of these GHGs in the atmosphere is from landfill. This study assesses two theoretical models (LandGEM and Afvalzorg models) to estimate the amount of landfill gas (LFG) emitted from Thohoyandou landfill site. Also, the LFGcost Web model was used to estimate the cost and benefits of the implementation of an LFG utilization technology. The Thohoyandou landfill started operations in the year 2005 and it is proposed to reach its peak at approximately in the year 2026. The LandGEM calculates the mass of landfill gas emission using methane generation capacity, mass of deposited waste, methane generation constant and methane generation rate. Meanwhile, the Afvalzorg model determines the LFG emissions using the Methane correction factor, yearly waste mass disposal, waste composition, Degradation Organic Carbon, methane generation rate constant, LFG recovery efficiency. The study findings indicate that the methane (CH₄) and carbon dioxide (CO₂) emitted from the landfill estimated from LandGEM will peak in the year 2026 with values of 3517 Mg/year and 9649 Mg/year, respectively. Results from the Afvalzorg model show that CH₄ emission will peak in the year 2026 (3336 Mg/year). The LandGEM model showed that the total LFG, CH₄ and CO₂ emitted from the landfill between 2005 and 2040 are 293239.3 Mg/year, 78325.7 Mg/year and 214908.6 Mg/year, respectively. The simulation from the Afvalzorg model found that the CH₄ emitted from the years 2005– 2040 is 74302 Mg/year. The implementation of an LFG utilization technology was economically feasible from consideration of the sales of electricity generated and Certified Emission Reductions (CER) (carbon credits).     

Secular trends of atmospheric methane (CH4)

Due partly to human activities the present yearly emissions of CH₄ exceed the atmospheric sinks, thus leading to a 1.2–1.9% per year atmospheric increase in the concentration of CH₄. New evidence based on studies of polar ice cores suggests that several hundred years ago the concentrations of CH₄ were perhaps only half of current values. These diverse findings are tied together in a single unified logistic model of atmospheric concentrations past, present and future. Using realistic growth rates of the sources of CH₄ caused by human activities, the model explains the concentrations and current growth rates. It also predicts that a doubling of CH₄ relative to present levels is possible given the long (9-year) atmospheric lifetime. Such increases of CH₄ concentrations may have already perturbed our global environment and may continue to do so in the future. The environmental effects include increased surface temperature of the earth, additional O₃ and CO in the clean non-urban atmosphere, depletions of tropospheric OH radicals, but perhaps also protection of the stratospheric ozone layer from destruction by man-made fluorocarbons.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

A comparison of CH4, N2O and CO2 emissions from three different cover types in a municipal solid waste landfill

High-density polyethylene (HDPE) membranes are commonly used as a cover component in sanitary landfills, although only limited evaluations of its effect on greenhouse gas (GHG) emissions have been completed. In this study, field GHG emission were investigated at the Dongbu landfill, using three different cover systems: HDPE covering; no covering, on the working face; and a novel material-Oreezyme Waste Cover (OWC) material as a trial material. Results showed that the HDPE membrane achieved a high CH₄ retention, 99.8% (CH₄ mean flux of 12 mg C m^-2 h^-1) compared with the air-permeable OWC surface (CH4 mean flux of 5933 mg C m^-2 h^-1) of the same landfill age. Fresh waste at the working face emitted a large fraction of N₂O, with average fluxes of 10 mg N m^-2 h^-2, while N₂O emissions were small at both the HDPE and the OWC sections. At the OWC section, CH₄ emissions were elevated under high air temperatures but decreased as landfill age increased. N₂O emissions from the working face had a significant negative correlation with air temperature, with peak values in winter. A massive presence of CO₂ was observed at both the working face and the OWC sections. Most importantly, the annual GHG emissions were 4.9 Gg yr^-1 in CO₂ equivalents for the landfill site, of which the OWC-covered section contributed the most CH₄ (41.9%), while the working face contributed the most N₂O (97.2%). HDPE membrane is therefore, a recommended cover material for GHG control.

Implications: Monitoring of GHG emissions at three different cover types in a municipal solid waste landfill during a 1-year period showed that the working face was a hotspot of N₂O, which should draw attention. High CH₄ fluxes occurred on the permeable surface covering a 1- to 2-year-old landfill. In contrast, the high-density polyethylene (HDPE) membrane achieved high CH₄ retention, and therefore is a recommended cover material for GHG control.     

Alternative carbon dioxide modelling approaches accounting for high residual gases in LandGEM

High Canadian waste disposal rates necessitate landfill gas monitoring and accurate forecasting. CO₂ estimates in LandGEM version 3.02 currently rest on the assumptions that CO₂ is a function of CH₄, where the two gases make up nearly 100% of landfill gas content, leading to overestimated CO₂ collection estimates. A total of 25 cases (five formulas, five approaches) compared annual CO₂ collection at four western Canadian landfills. Despite common use in literature, the 1:1 ratio of CH₄ to CO₂ was not recommended to forecast landfill gas collection in cold climates. The existing modelling approach significantly overestimated CO₂ production in three of four sites, resulting in the highest residual sum of squares. Optimization resulted in the most accurate results for all formulas and approaches, which had the greatest reduction in residual sums of squares (RSS) over the default approach (60.1 to 97.7%). The 1.4 Ratio approach for L _o:L _o-CO2 yielded the second most accurate results for CO₂ flow (mean RSS reduction of 50.2% for all sites and subsection models). The annual k-modified LandGEM calculated k’s via two empirical formulas (based on precipitation) and yielded the lowest accuracy in 12 of 20 approaches. Unlike other studies, strong relationships between optimized annual k’s and precipitation were not observed.

     

N2O emissions at municipal solid waste landfill sites: Effects of CH4 emissions and cover soil

Municipal solid waste landfills are the significant anthropogenic sources of N₂O due to the cooxidation of ammonia by methane-oxidizing bacteria in cover soils. Such bacteria could be developed through CH₄ fumigation, as evidenced by both laboratory incubation and field measurement. During a 10-day incubation with leachate addition, the average N₂O fluxes in the soil samples, collected from the three selected landfill covers, were multiplied by 1.75 (p < 0.01), 3.56 (p < 0.01), and 2.12 (p < 0.01) from the soil samples preincubated with 5% CH₄ for three months when compared with the control, respectively. Among the three selected landfill sites, N₂O fluxes in two landfill sites were significantly correlated with the variations of the CH₄ emissions without landfill gas recovery (p < 0.001). N₂O fluxes were also elevated by the increase of the CH₄ emissions with landfill gas recovery in another landfill site (p > 0.05). The annual average N₂O flux was 176 ± 566 μg N₂O–N m^?2 h^?1 (p < 0.01) from sandy soil–covered landfill site, which was 72% (p < 0.05) and 173% (p < 0.01) lower than the other two clay soil covered landfill sites, respectively. The magnitude order of N₂O emissions in three landfill sites was also coincident by the results of laboratory incubation, suggesting the sandy soil cover could mitigate landfill N₂O emissions.     

Effects of ammonia on methane oxidation in landfill cover materials

The effects of ammonia (NH₃) on CH₄ attenuation in landfill cover materials consisting of landfill cover soil (LCS) and aged municipal solid waste (AMSW), at different CH₄ concentrations, were investigated. The CH₄ oxidation capacities of LCS and AMSW were found to be significantly affected by the CH₄ concentration. The maximum oxidation rates for LCS and AMSW were obtained at CH₄ concentrations of 5 % and 20 %(v/v), respectively, within 20 days. CH₄ biological oxidation in AMSW was significantly inhibited by NH₃ at low CH₄ concentrations (5 %, v/v) but highly stimulated at high levels (20 % and 50 %, v/v). Oxidation in LCS was stimulated by NH₃ at all CH₄ concentrations due to the higher conversion of the nitrogen in NH₃ in AMSW than in LCS. NH₃ increases CH₄ oxidation in landfill cover materials.     

Gas phase reactions of unsaturated esters with Cl atoms

Background, aim, and scope  

Acrylate and methacrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon (CH₂=CHCOO– and CH₂=CCH₃COO–, respectively) and are widely used in the polymer plastic and resin production. Rate coefficients for Cl reactions for most of the unsaturated esters have not been previously determined, and a good understanding is needed of all the atmospheric oxidation processes of these compounds in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of photo-oxidants and therefore on health and environment.     

T-S模糊神经网络在厌氧反应器预测中的应用

3个厌氧反应器运行稳定后,用三氯甲烷和2、4-二硝基酚作为毒物负荷对它们进行了冲击试验.利用负荷冲击试验所得的数据集建立了T-S模糊神经网络,并用其预测了反应器的容积产气率、挥发性脂肪酸和CH4体积含量.研究结果表明,基于某一反应器建立的T-S模糊神经网络可以很好地预测毒物负荷冲击下该反应器的容积产气率、挥发性脂肪酸和CH4变化规律,实测值与预测值的相关系数均＞0.850;但是基于某一反应器建立的模糊神经网络用来预测其他反应器时,其预测能力较差,预测值和实测值的相关系数基本上＜0.500.     

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands

GOAL, SCOPE AND BACKGROUND: [corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. METHODS: A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm.The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). RESULTS: Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. DISCUSSION: The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. CONCLUSIONS: Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. RECOMMENDATIONS AND PERSPECTIVES: The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.     

Measurement of methyl halides in the marine atmosphere

An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH₃Cl, CH₃Br, and CH₃I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH₃Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH₃Cl concentration amounted to as high as 1400 pptv and indicated that CH₃Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH₃Br and CH₃I, suggesting a common source in the area.