Limits and dynamics of methane oxidation in landfill cover soils

In order to understand the limits and dynamics of methane (CH₄) oxidation in landfill cover soils, we investigated CH₄ oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO₂ concentration. The results indicate a significant difference between the observed soil CH₄ oxidation at field sampled conditions compared to optimum conditions achieved through pre-incubation (60 days) in the presence of CH₄ (50 ml l⁻¹) and soil moisture optimization. This pre-incubation period normalized CH₄ oxidation rates to within the same order of magnitude (112-644 μg CH₄ g⁻¹ day⁻¹) for all the cover soils samples examined, as opposed to the four orders of magnitude variation in the soil CH₄ oxidation rates without this pre-incubation (0.9-277 μg CH₄ g⁻¹ day⁻¹).Using pre-incubated soils, a minimum soil moisture potential threshold for CH₄ oxidation activity was estimated at 1500 kPa, which is the soil wilting point. From the laboratory incubations, 50% of the oxidation capacity was inhibited at soil moisture potential drier than 700 kPa and optimum oxidation activity was typical observed at 50 kPa, which is just slightly drier than field capacity (33 kPa). At the extreme temperatures for CH₄ oxidation activity, this minimum moisture potential threshold decreased (300 kPa for temperatures <5 °C and 50 kPa for temperatures >40 °C), indicating the requirement for more easily available soil water. However, oxidation rates at these extreme temperatures were less than 10% of the rate observed at more optimum temperatures (∼30 °C). For temperatures from 5 to 40 °C, the rate of CH₄ oxidation was not limited by moisture potentials between 0 (saturated) and 50 kPa. The use of soil moisture potential normalizes soil variability (e.g. soil texture and organic matter content) with respect to the effect of soil moisture on methanotroph activity. The results of this study indicate that the wilting point is the lower moisture threshold for CH₄ oxidation activity and optimum moisture potential is close to field capacity.No inhibitory effects of elevated CO₂ soil gas concentrations were observed on CH₄ oxidation rates. However, significant differences were observed for diurnal temperature fluctuations compared to thermally equivalent daily isothermal incubations.     

Implications of the spatial variability of landfill emission rates on geospatial analyses

Accurate methods quantifying whole landfill surface flux of methane are important for regulatory and research purposes. This paper presents the results from the analysis of chamber measurements utilizing geospatial techniques [kriging and inverse distance weighting (IDW)] to arrive at an estimation of the whole landfill surface flux from the spatially distributed chamber measurement points. The difficulties in utilizing these methods will be discussed. Methane flux was determined on approximately 20 m grid spacing and variogram analysis was performed in order to model spatial structure, which was used to estimate methane flux at unsampled locations through kriging. Our analysis indicates that while the semi-variogram model showed some spatial structure, IDW was a more accurate interpolation method for this particular site. This was seen in the comparison of the resulting contour maps. IDW, coupled with surface area algorithms to extract the total area of user defined contour intervals, provides a superior estimate of the methane flux as confirmed through the methane balance. It is critical that the results of the emissions estimates be viewed in light of the whole cell methane balance; otherwise, there is no rational check and balance system to validate the results.     

Influence of Suspended Clay Minerals and Humic Matter on the Solid Phase Extraction Efficiency of Selected Pesticides from Water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and α-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was ≥0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

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.     

Improved methodology to assess modification and completion of landfill gas management in the aftercare period

Municipal solid waste landfills represent the dominant option for waste disposal in many parts of the world. While some countries have greatly reduced their reliance on landfills, there remain thousands of landfills that require aftercare. The development of cost-effective strategies for landfill aftercare is in society’s interest to protect human health and the environment and to prevent the emergence of landfills with exhausted aftercare funding. The Evaluation of Post-Closure Care (EPCC) methodology is a performance-based approach in which landfill performance is assessed in four modules including leachate, gas, groundwater, and final cover. In the methodology, the objective is to evaluate landfill performance to determine when aftercare monitoring and maintenance can be reduced or possibly eliminated. This study presents an improved gas module for the methodology. While the original version of the module focused narrowly on regulatory requirements for control of methane migration, the improved gas module also considers best available control technology for landfill gas in terms of greenhouse gas emissions, air quality, and emissions of odoriferous compounds. The improved module emphasizes the reduction or elimination of fugitive methane by considering the methane oxidation capacity of the cover system. The module also allows for the installation of biologically active covers or other features designed to enhance methane oxidation. A methane emissions model, CALMIM, was used to assist with an assessment of the methane oxidation capacity of landfill covers.     

Biochar: a synthesis of its agronomic impact beyond carbon sequestration

Biochar has been heralded as an amendment to revitalize degraded soils, improve soil carbon sequestration, increase agronomic productivity, and enter into future carbon trading markets. However, scientific and economic technicalties may limit the ability of biochar to consistently deliver on these expectations. Past research has demonstrated that biochar is part of the black carbon continuum with variable properties due to the net result of production (e.g., feedstock and pyrolysis conditions) and postproduction factors (storage or activation). Therefore, biochar is not a single entity but rather spans a wide range of black carbon forms. Biochar is black carbon, but not all black carbon is biochar. Agronomic benefits arising from biochar additions to degraded soils have been emphasized, but negligible and negative agronomic effects have also been reported. Fifty percent of the reviewed studies reported yield increases after black carbon or biochar additions, with the remainder of the studies reporting alarming decreases to no significant differences. Hardwood biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires further evaluation due to the highly skewed feedstock preferences within existing studies. With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security, and energy supplies; biochar may play a role in this endeavor. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits.     

Degradation of methyl isothiocyanate and chloropicrin in forest nursery soils

Recent studies have observed enhanced degradation of methyl isothiocyanate (MITC) from repeated fumigation in agricultural soils. Little is known about fumigant degradation in forest and nursery soils. This study was conducted to determine degradation rates of MITC and chloropicrin (CP) in two forest soils and the impacts of nursery management on degradation of MITC and CP. The half-life values of MITC and CP were evaluated in the laboratory under isothermal conditions (22 +/- 2 degrees C). Three rates representing 0.5x, 1x, and 2x field application rates for each fumigant were used in laboratory incubations. Effect of microbial degradation was determined by conducting incubations with both fresh and sterilized soils. Soil moisture effects were also studied. There was no difference in MITC or CP degradation between fumigated and nonfumigated forest nursery soils. Soil sterilization and high soil moisture content (15% by wt.) reduced MITC and CP degradation. The degradation rates of MITC and CP varied with factors such as nursery history, fumigant application rates, and freshness of tested soils.