Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils

To determine the effects of intensive cropping of tropical lowland rice (Oryza sativa L.) and the associated long-term soil submergence on chemical properties of soil organic matter, we used solid-state 13C and 15N and solution 31P nuclear magnetic resonance (NMR) spectroscopy to analyze the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions extracted from a series of soils supporting several long-term field experiments in the Philippines. The soils varied mainly in degree of submergence and cropping intensity, ranging from a rainfed rice field without soil submergence to irrigated double- and triple-cropped fields in which soil remains submerged almost all year long. As reported previously, all analyses associated increasing intensity of rice cropping with larger proportions of less humified material in the MHA and CaHA, such as diester phosphorus (P), amide nitrogen (N), and phenolic carbon (C). We established significant correlations between proportions of various spectral areas as well as between some spectral areas and other humic acid (HA) properties such as visible light absorption and free radical concentration (positive indices of humification) and hydrogen (H) concentration (negative index of humification). For example, spectral proportions of heterocyclic N were positively, and proportions of amide N and phenolic C negatively, correlated with visible light absorption and free radical concentration, and each of these spectral proportions had an opposite sign when correlated with H concentration. The correlations of N-alkyl C proportions were the strongest with these properties and with other functional group proportions.     

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.     

Analysis of potentially mobile phosphorus in arable soils using solid state nuclear magnetic resonance

In many intensive agroecosystems continued inputs of phosphorus (P) over many years can significantly increase soil P concentrations and the risk of P loss to surface waters. For this study we used solid-state 31P nuclear magnetic resonance (NMR) spectroscopy, high-power decoupling with magic angle spinning (HPDec-MAS) NMR, and cross polarization with magic angle spinning (CP-MAS) NMR to determine the chemical nature of potentially mobile P associated with aluminum (Al) and calcium (Ca) in selected arable soils. Three soils with a range of bicarbonate-extractable Olsen P concentrations (40-102 mg P kg(-1)) were obtained from a long-term field experiment on continuous root crops at Rothamsted, UK, established in 1843 (sampled 1958). This soil has a threshold or change point at 59 mg Olsen P kg(-1), above which potentially mobile P (as determined by extraction with water or 0.01 M CaCl2) increases much more per unit increase in Olsen P than below this point. Results showed that CaCl2 and water preferentially extracted Al-P and Ca-P forms, respectively, from the soils. Comparison among the different soils also indicated that potentially mobile P above the threshold was largely present as a combination of soluble and loosely adsorbed (protonated-cross polarized) P forms largely associated with Ca, such as monetite (CaHPO4) and dicalcium phosphate dihydrate (CaHPO4-2H2O), and some Al-associated P as wavellite. The findings of this study demonstrate that solid-state NMR has the potential to provide accurate information on the chemical nature of soil P species and their potential mobility.     

Mechanisms of phosphorus solubilisation in a limed soil as a function of pH

Phosphorus (P) quantity-intensity relationships are central to the solubility and release of P from soil to water. Relationships between P extractable by 0.5 M NaHCO extractable P (Olsen P; quantity, Q) and P extractable by 0.01 M CaCl(2) (CaCl(2)-P; possible predictor of soil solution or drainage water P; intensity, I) are curvilinear: above a certain Olsen P concentration, CaCl(2)-P becomes much more soluble than when below it. Aluminium-, Fe- and Ca-P forms (extractable by Olsen's reagent) are thought to control P solubility. Thus, our objectives were to identify P forms in equilibrium with CaCl(2)-P via solubility equilibrium experiments, and the behaviour of CaCl(2)-P in relation to Al, Fe and Ca associated P, determined with 31P high power decoupling magic angle spinning nuclear magnetic resonance spectroscopy (31P HPDec/MAS NMR). Results indicated that two Q-I relationships occurred, one for soils above pH 5.8, and the other for soils below pH 5.8. Above pH 5.8, soils were saturated with respect to hydroxyapatite (Ca(5)(PO(4))(3)OH) and undersaturated with respect to beta-tricalcium phosphate (beta-Ca(3)(PO(4))(2)), while log ion-activity products showed that all soils and pHs were either saturated or in equilibrium with variscite (AlPO(4).2H(2)O) or its amorphous analogue. Using 31P HPDec/MAS NMR, Ca-P was best correlated with CaCl(2)-P in soils above pH 5.8, and with Al-P in soils below this pH. This study demonstrates the value of solid-state NMR in conjunction with wet chemical techniques for the study of labile P and P loss from pasture soils with a wide range of managements.     

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.