Measured versus estimated total porosity along structure-stability gradients of coarse-textured tropical soils with low-activity clay

Soil total porosity is, rather than measured by water desorption method, more often estimated from bulk density (BD) and assumed particle density. Measured and estimated total porosities of even kaolinitic tropical soils (which have low tendency to expand upon wetting) usually differ by an extent that depends on soil structural stability, but such differences are scarcely documented. Seventy samples of coarse-textured soils under different fallow- and cultivation-management systems in the southeastern region of Nigeria were analyzed for texture, mean-weight diameter (MWD) of aggregates, BD and organic matter (OM) concentration. Soil total porosities measured by water desorption method were compared with those estimated from BDs (with particle density fixed at 2.70 g cm^?3), after grouping the soils by structural stability, assessed by OM/(silt + clay) for 50 of the samples from fallowed plots (BD > 1.48 g cm^?3) and MWD for the rest from cultivated plots (BD < 1.48 g cm^?3). The fallowed plots showed a wider stability range than the cultivated plots. Irrespective of land use, structural stability tended to increase with decreasing soil BD. Measured total porosities were consistently higher than their estimated counterparts, with the differences closing up with increasing soil structural stability up till a mean BD of 1.41 ± 0.05 g cm^?3 (corresponding to MWD of 2.66 ± 0.12 mm), beyond which the trend reversed. These results suggest that, as the soil structural stability increases, soil particle density decreases while entrapped air and transitory drainage of saturated samples at weighing increase. Estimating total porosity with a fixed particle density of 2.70 g cm^?3 appears suitable only in highly stable soils, with BD of ≤1.40 ± 0.08 g cm^?3 and/or MWD of ≥2.92 ± 0.05 mm [corresponding to OM/(silt + clay) of ≥16.38 ± 0.28 %].     

A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.     

Stability of titanian clinohumite: Experiments and thermodynamic analysis

Reversed hydrothermal experiments on a natural titanoclinohumite [Ti-Cl; approximate formula Mg_7.5FeTi_0.5O₁₆(OH)] show that it breaks down at 475°±11° C (3.5 kbar), 620°±11° C (14 kbar) and 675°±8° C (21 kbar) to the assemblage olivine +ilmenite+vapor. An internal-consistency analysis of the data yields _r G _s ^/0 (298 K, 1 bar)=36,760±3,326 cal (mole Ti-Cl)^–1. _r S _s ^/0 (298 K, 1 bar)=34.14±5.91 cal deg^–1(mole Ti-Cl)^–1. Linear correlation coefficient r _G–S 1.0. A solution model that accounts for TiO₂-M(OH)₂ and F-OH substitution shows that the results for our nearly F-free Ti-Cl are in reasonable agreement with the unreversed breakdown experiments of Mer-rill et al. (1972) on a F-bearing Ti-Cl.Because fluorine is necessary to stabilize Ti-Cl under mantle conditions, we suggest that Ti-Cl is much more likely to be a storage device for fluorine than for water in the mantle.     

Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes

Ab initio STO-3G molecular orbital theory has been used to calculate energy-optimized Si-O bond lengths and angles for molecular orthosilicic and pyrosilicic acids. The resulting bond length for orthosilicic acid and the nonbridging bonds for pyrosilicic acid compare well with Si-OH bonds observed for a number of hydrated silicate minerals. Minimum energy Si-O bond lengths to the bridging oxygen of the pyrosilicic molecule show a close correspondence with bridging bond length data observed for the silica polymorphs and for gas phase and molecular crystal siloxanes when plotted against the SiOSi angle. In addition, the calculations show that the mean Si-O bond length of a silicate tetrahedron increases slightly as the SiOSi angle narrows. The close correspondence between the Si-O bond length and angle variations calculated for pyrosilicic acid and those observed for the silica polymorphs and siloxanes substantiates the suggestion that local bonding forces in solids are not very different from those in molecules and clusters consisting of the same atoms with the same coordination numbers. An extended basis calculation for H₄SiO₄ implies that there are about 0.6 electrons in the 3d-orbitals on Si. An analysis of bond overlap populations obtained from STO-3G* calculations for H₆Si₂O₇ indicates that Si-O bond length and SiOSi angle correlations may be ascribed to changes in the hybridization state of the bridging oxygen and (d – p) π-bonding involving all five of the 3d AO's of Si and the lone-pair AO's of the oxygen. Theoretical density difference maps calculated for H₆Si₂O₇ show a build-up of charge density between Si and O, with the peak-height charge densities of the nonbridging bonds exceeding those of the bridging bonds by about 0.05 e Å^?3. In addition, atomic charges (+1.3 and ?0.65) calculated for Si and O in a SiO₂ moiety of the low quartz structure conform reasonably well with the electroneutrality postulate and with experimental charges obtained from monopole and radial refinements of diffraction data recorded for low quartz and coesite.     

Genetic techniques for livestock breeding: Restructuring institutional relationships in agriculture

This paper explores some of the key institutional transformations in livestock breeding associated with the increasing significance of genetic techniques, situating this within an assessment of an emerging agricultural bioeconomy. Focusing on beef cattle and sheep breeding in the United Kingdom, the paper examines how a move towards the involvement of international and corporate interests in livestock breeding is restructuring the network of institutional interests affecting the knowledge and decision making of individual breeders. The paper suggests that the structural transformation of beef cattle and sheep breeding is complicated by the need for negotiation between breeders’ ‘traditional’ knowledge-practices and the ‘geneticised’ techniques being made available to them. We are thus seeing the emergence of new and complex interactions between the major actors which are reconfiguring power relationships in the UK livestock breeding sector.     

A modeling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite

Several computer models of quartz were developed and tested. A simple model based on a potential energy function, derived in large part from quantum mechanical calculations on the molecule H₆Si₂O₇, was found to reproduce the compressibility curve for quartz up to pressures of 8 GPa. The potential includes quadratic expressions for the SiO bond lengths, the OSiO angles and a parameter spanning the SiOSi angle together with an exponential OO repulsion term for non co-dimer O atoms. The variations in the cell edges and in the SiOSi angle, as a function of pressure, parallel observed trends when the bond lengths and angles calculated for the molecule are used as rgressor values. Poisson ratios calculated using the model match those observed. Two configurations for quartz related by the Dauphiné twin law are generated as minimum energy structures of the model with about equal frequencies as observed in nature. It is shown that the model, devised for quartz, can also be applied to the silica polymorph cristobalite, giving reasonable estimates of its compressibility curve, structural parameters and its negative Poisson ratio. When the observed bond lengths and angles are used as regressor values, the model generates the absolute coordinates of the atoms and the cell dimensions for quartz to within 0.005 Å and those of cristobalite to within 0.001 Å, on average, both at zero pressure. When applied to coesite, the model yields a zero pressure structure that is close to that observed but which is significantly softer than observed. The resulting SiO bond lengths are linearly correlated with f _s (O), as observed for coesite, despite the use of a single bond length and a single SiOSi angle as regressor values in the calculation. When the structures are optimized assuming P1 space group symmetry and triclinic cell dimensions, the resulting frameworks of silicate tetrahedra exhibit the translational, rotational and reflection symmetries observed for quartz, cristobalite and coesite. The fact that the resulting frameworks exhibit observed space group symmetries is evidence that the symmetry adopted by the silica polymorphs can be explained by short ranged forces.     

Climate impacts of environmental degradation in Sudan

There exists an impressive amount of work for Sudan showing the anthropogenic degradation of natural vegetation cover. However, there are few examples of consequent climatic changes in literature. This work, thus, seeks to assess such effects of environmental forcing on various climatic patterns over the past few decades. Within the frame of the present analysis, the results are quite striking and are in concordance with scientific contentions that such land degradation could result in climatic modification. Higher temperature and less rainfall, sunshine duration and global radiation have been noticed. Evapotranspiration has responded more to the warming and drying conditions, thus showed signs of increasing rates, especially during the wet season. However, the extent of increase seems to have been suppressed by the decrease in sunshine duration and solar radiation as well as the inconsistent behaviour of wind speed. Changes in the variability of the within-year monthly observations have also occurred, thus suggesting an increase in the occurrence of extremes. The observed climatic modification in the country has exaggerated the insidious drought conditions. The present findings are hoped to contribute to our understanding of the effects of environmental problem and assist in considering policy responses. This revised version was published online in July 2006 with corrections to the Cover Date.     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.