Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between (12)CH(4), (13)CH(4), and (12)CH(3)D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7vol% in the concentration and a RMSD of 0.8 per thousand in the delta(13)C value, with delta(13)C the relative (13)C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.     

Levels of PCDDs, PCDFs and dioxin-like PCBs in raw cow's milk collected in France in 2006

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) are widespread environmental contaminants. A French national survey was carried out in April 2006 to assess the concentrations of PCDD/Fs and dioxin-like PCBs (DL-PCBs) in raw cow's milk. A random sampling scheme stratified by region was applied to collect 239 raw milk samples from 93 plants belonging to 17 dairy companies. Compared to a previous survey led in 1998 analyzing half-skimmed drinking milk in France, the PCDD/Fs level was cut by half, with an average concentration of 0.33 pg toxic equivalent (TEQ)/g fat in 2006. The mean DL-PCBs concentration was 0.57 pg TEQ/g fat and subsequently the sum of PCDD/Fs and DL-PCBs was 0.90 pg/g fat, values below the thresholds defined by the European Union regulations.     

Indicators of deforestation in the Southern Brazilian Pre-Amazon

In recent years, Amazonian deforestation has become a question of global concern. Deforestation in Amazon is a complex phenomenon in nature and has been related to traditional agriculture expansion. In this work, land use, socioeconomic and conservation indicators, combined with statistical analysis, were used to understand forces associated with patterns of deforestation. This approach was applied in Southern Brazilian Pre-Amazon in Mato Grosso State, which represents an extensive rain forest-savanna ecotone, located in the south border of Amazon biome. Based on data from the last two agricultural censuses (1995/1996–2006), we compared agricultural expansion in this area and Mato Grosso state. Results have shown that 85 % of state deforestation was concentrated in Southern Pre-Amazon and was closely related to increase in number of cattle and pasture area. PCA results pointed that population (92 %), number of cattle (86.5 %), pastures (84.2 %) and tractors (78.4 %) were variables with highest positive correlation to deforestation. It showed that GDP contributes to an individual axis and has a low correlation to deforestation (37.8 %). Conservation units and indigenous reserves also contribute to a single axis and were negatively correlated to temporary crops area. Results revealed a significant reduction in production and commercialization of extractive products in the region, revealing that the main, almost only conservation policy in Mato Grosso remains the creation of Special Areas. We suggest that further studies are necessary to screen development alternatives to simple cutting trees down. It is important to diversify strategies for deforestation control, and development aspects must be more seriously considered to reach a sustainable deforestation control policy.     

Effects of compost biocovers on gas flow and methane oxidation in a landfill cover

Previous publications described the performance of biocovers constructed with a compost layer placed on select areas of a landfill surface characterized by high emissions from March 2004 to April 2005. The biocovers reduced CH₄ emissions 10-fold by hydration of underlying clay soils, thus reducing the overall amount of CH₄ entering them from below, and by oxidation of a greater portion of that CH₄. This paper examines in detail the field observations made on a control cell and a biocover cell from January 1, 2005 to December 31, 2005. Field observations were coupled to a numerical model to contrast the transport and attenuation of CH₄ emissions from these two cells. The model partitioned the biocover’s attenuation of CH₄ emission into blockage of landfill gas flow from the underlying waste and from biological oxidation of CH₄. Model inputs were daily water content and temperature collected at different depths using thermocouples and calibrated TDR probes. Simulations of CH₄ transport through the two soil columns depicted lower CH₄ emissions from the biocover relative to the control. Simulated CH₄ emissions averaged 0.0 g m^?2 d^?1 in the biocover and 10.25 g m^?2 d^?1 in the control, while measured values averaged 0.04 g m^?2 d^?1 in the biocover and 14 g m^?2 d^?1 in the control. The simulated influx of CH₄ into the biocover (2.7 g m^?2 d^?1) was lower than the simulated value passing into the control cell (29.4 g m^?2 d^?1), confirming that lower emissions from the biocover were caused by blockage of the gas stream. The simulated average rate of biological oxidation predicted by the model was 19.2 g m^?2 d^?1 for the control cell as compared to 2.7 g m^?2 d^?1 biocover. Even though its V_max was significantly greater, the biocover oxidized less CH₄ than the control cell because less CH₄ was supplied to it.     

Use of Pb blast furnace slag as a partial substitute for fine aggregate in cement mortar

The technical properties of cement mortars containing natural fine aggregate that is replaced by lead blast furnace slag at 25 and 35% level were assessed at fixed water-to-cement (W/C) ratio and at fixed flow table value. The leachabilities of some toxic elements from the cement mortars were also assessed to test the environmental suitability of the slag for use in preparation of cement mortar. At fixed W/C ratio, the strength of the mortar decreased with increase of the slag content. On the other hand, at fixed consistency, strength increased with increasing slag content in the mortar composition. The concentrations of some toxic elements in the leachates collected from the mortars containing slag were slightly higher than for the control mortar, but the concentrations in the leachates remained within the regulatory limits for recycling in construction applications. For most elements, leaching from a mortar containing 35% of slag was similar to that from a mortar containing 25% of slag. Therefore, 35% of natural sand can be beneficially replaced with Pb slag to produce cement mortar without affecting the mechanical and leaching properties studied in this work.     

Biosorption and retention of orthophosphate onto Ca(OH)2-pretreated biomass of Phragmites sp.

The biosorption of phosphorus in the form of orthophosphate(Po) from wastewater using biomass as the sorbent is of potential importance because the Po-loaded biomass could be applied in the agricultural sector as fertilizer and soil conditioner. However, biomass generally displays a very low affinity for Posorption and therefore biomass surface modification is required. In the present study, the biomass(as model grinded leaves of Phragmites sp. were used)was pretreated with Ca(OH)2to enhance Pobiosorption capacity(qe). The results indicate that the alkaline pretreatment resulted in a modification of surface functional groups. It was concluded that the main sorption mechanisms were ligand exchange and electrostatic attraction. A series of experiments were conducted to investigate the performance of the pretreated biomass for Pouptake under various conditions. Isotherm and thermodynamic studies were also applied and analyzed. The biosorption process was best described by the pseudo-second order kinetic model and Langmuir isotherm, which gave a qmaxof 12.27 mg P/g at 25°C and p H 7. The Ca(OH)2treated Phragmites biomass applied in this study for Porecovery may present some potential advantages in terms of costs and environmental impact.     

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.