On the acidity and reactivity of HNO in aqueous solution and biological systems

The gas phase and aqueous thermochemistry and reactivity of nitroxyl (nitrosyl hydride, HNO) were elucidated with multiconfigurational self-consistent field and hybrid density functional theory calculations and continuum solvation methods. The pKa of HNO is predicted to be 7.2 ± 1.0, considerably different from the value of 4.7 reported from pulse radiolysis experiments. The ground-state triplet nature of NO− affects the rates of acid-base chemistry of the HNO/NO− couple. HNO is highly reactive toward dimerization and addition of soft nucleophiles but is predicted to undergo negligible hydration (Keq = 6.9 × 10−5). HNO is predicted to exist as a discrete species in solution and is a viable participant in the chemical biology of nitric oxide and derivatives.

Simulation of nutrient loss from soils due to rainfall acidity /

Bibliography: p. 43-44.

Technical report: a technique for studying the dynamic behavior of the soil-plant system, with special reference to the effect of soil acidity and lime applications.

Bibliography: leaves 110-117.

The influence of acidity of cream on the flavor of butter /

"June 10, 1909."

Pulsed EPR studies of a bacterial sulfite-oxidizing enzyme with pH-invariant hyperfine interactions from exchangeable protons

Variable-frequency pulsed electron paramagnetic resonance studies of the molybdenum(V) center of sulfite dehydrogenase (SDH) clearly show couplings from nearby exchangeable protons that are assigned to a (MoOHn)-O-v group. The hyperfine parameters for these exchangeable protons of SDH are the same at both low and high pH and similar to those for the high-pH forms of sulfite oxidases (SOs) from eukaryotes. The SDH proton parameters are distinctly different from the low-pH forms of chicken and human so.

Measurement of exchangeable cations in saline soils

The measurement of exchangeable cations in saline soils is limited by the difficulty in accurately separating soluble cations from exchangeable cations. A method is examined for saline soils in which exchangeable cations are calculated as the total extractable cations minus the concentration of soil solution (soluble) cations. In addition, a further two standard methods were investigated, one which assumes the total soil extractable cations are exchangeable, the other utilises a pretreatment to remove soluble salts prior to measurement of the remaining (exchangeable) cations. After equilibration with a range of sodium adsorption ratio (SAR) solutions at various ionic strengths, the exchangeable cation concentrations of two soils (Dermosol and Vertosol) were determined by these methods and compared to known values. The assumption that exchangeable cations can be estimated as the total soil extractable cations, although valid at low ionic strength, resulted in an overestimation of exchangeable Na and Ca concentrations at higher ionic strengths due to the presence of soluble salts. Pretreatment with ethanol and glycerol was found to effectively remove soluble salts thus allowing the accurate measurement of the effective cation exchange capacity (ECEC), however, dilution associated with the pretreatment process decreased concentrations of exchangeable Ca while simultaneously increasing exchangeable Na. Using the proposed method, good correlations were found between known and measured concentrations of exchangeable Na (Dermosol: y=0.873x and Vertosol: y=0.960x) and Ca (Dermosol: y=0.906x, and Vertosol: y=1.05x). Therefore, for soils with an ionic strength of approximately 50 mM (ECse 4 dS m-1) or greater (in which exchangeable cation concentrations are overestimated by assuming the total soil cations are exchangeable), concentrations can be calculated as difference between total extractable cations and soluble cations.

Identification of the causes of subsoil ammonium accumulations in southeastern Queensland

Unusually high concentrations of exchangeable-NH4+ (up to 270 kg-N/ha) were observed in a Vertisol below 1 m in southeast Queensland. This study aimed to identify the source of this NH4+. Preliminary sampling of native vegetation and cropping areas had found that elevated NH4+was only present under cropped soil, indicating that clearing was linked to the NH4+formation. Mechanisms of NH4+formation that may have occurred in the subsoil after clearing were hypothesised to be a) mineralisation of organic-N; b) NO3- reduction to NH4+; and/or c) the release of fixed-NH4+. In addition it was proposed that nitrification was inhibited in the subsoil, and that this allowed any NH4+formed to accumulate over time. Incubation experiments to examine nitrification rates revealed that nitrification was undetectable, and appeared to be limited by a combination of subsoil acidity and low numbers of nitrifying organisms. Mineralisation studies also revealed that the mineralisation of organic-N was undetectable, and that mineralising organisms were limited by acidity. A small amount of nitrate ammonification could be observed with the aid of a 15N tracer if the soil was waterlogged. However, this NH4+was insufficient to account for the overall NH4+accumulation, and these waterlogged conditions were not observed in the field. Concentrations of fixed- NH4+ measured were also too low to have been responsible for the accumulation of exchangeable-NH4+. It was concluded that none of the proposed hypotheses of NH4+formation could account for the NH4+accumulation observed.

Solar thermal decomposition of desalination reject brine for carbon dioxide removal and neutralisation of ocean acidity

Desalination plants could become net absorbers (rather than net emitters) of CO2. Thermal decomposition of salts in desalination reject brine can yield MgO which, added to the ocean, would take up CO2 through conversion to bicarbonate. The process proposed here comprises dewatering of brine followed by decomposition in a solar receiver using a heliostat field.

Qualidade do solo da camada de cobertura final em área de disposição de resíduos no semiárido tropical

The final disposal of municipal solid waste in unsuitable areas without an infrastructure that meets the health measures and environmental protection, coupled with the lack of technical criteria in phase and decommissioning of the dump can promote environmental degradation. Alternatively to minimize the impacts of this activity for the stabilization of the area by isolating the massive waste with implementation of an adequate and finished by a layer of soil for plant growth final cover system. In this context, the present study aimed to evaluate the quality of the final cover in the area of a disabled dump the tropical semi-arid region in order to assist the process of recovery of these areas. The study area is located in the tropical semi-arid region in São João do Sabugi /RN. Soil samples were collected in the dump area and bushland as a benchmark of quality. To which they were subjected to analysis of physical attributes (particle density, bulk density, grain size and porosity), chemical properties (pH, K + , Na+ , Ca2 + , Mg2 + and Al3 + exchangeable, potential acidity, available phosphorus, sum of bases, CEC, base saturation, aluminum saturation, saturation Na + and adsorption ratio sodium, total organic carbon and total nitrogen) and total and soluble concentrations of heavy metals (Mn, Pb, Zn, Cd, Cu, Mo, Co, Cr, Ba and Ni). The differences between physical and chemical soil under native forest and final cover showing reduction of soil quality in the area off to the dump, which hinders the development of native vegetation and the recovery of the area. The absence of superior waterproofing to allow vertical transfer between the solid waste and the final cover promoted enrichment by chemical elements and heavy metals in excess can impair revegetation. Deficiencies found in the construction process of the final cover point to the need for intervention to accelerate the process of stabilization and recovery of the area of the local ecosystem

Hardpan and maize root distribution under conservation and conventional tillage in Agro-Ecological Zone IIA, Zambia

Hardpans (plough/hoe pans) are commonly believed to restrict plant root growth and crop yields under conventional small-scale agriculture in sub-Saharan Africa. This study questions the notion of widespread hardpans in Zambia and their remedy under conservation tillage. Soil penetration resistance was measured in 8x12 grids, covering 80 cm wide and 60 cm deep profiles in 32 soil pits. Large and fine maize roots were counted in 8x6 grids. Soil samples from mid-rows were analysed for pH, exchangeable H+, exchangeable Al3+, cation exchange capacity, total N and extractable P (Bray 1) at six depths from 0-10 to 50-60 cm. Cultivation-induced hardpans were not detected. Soils under conservation tillage were more compact at 5 cm depth than soils under conventional tillage. No differences in root distributions between conservation and conventional tillage were found. Maize ( Zea mays L. ) roots were largely confined to a relatively small soil volume of about 30 cm x 30 cm x 30 cm. Root growth appeared to be restricted by a combination of low concentrations of N and P. Soil acidity and Al saturation appeared to play a minor role in root distribution. L-shaped taproots in soils under manual tillage reported earlier were not necessarily due to hardpans, but may rather be caused by temporarily dry, impenetrable subsoils early in the rain season. There is no scientific basis for the recommendation given to farmers by agricultural extension workers to “break the hardpan” in fields under manual or animal tillage in the study areas.

Shifting Processes with Cyclically Exchangeable Increments at Random

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