Spatial variability of soil organic carbon in grasslands: implications for detecting change at different scales

Extensive data used to quantify broad soil C changes (without information about causation), coupled with intensive data used for attribution of changes to specific management practices, could form the basis of an efficient national grassland soil C monitoring network. Based on variability of extensive (USDA/NRCS pedon database) and intensive field-level soil C data, we evaluated the efficacy of future sample collection to detect changes in soil C in grasslands. Potential soil C changes at a range of spatial scales related to changes in grassland management can be verified (alpha=0.1) after 5 years with collection of 34, 224, 501 samples at the county, state, or national scales, respectively. Farm-level analysis indicates that equivalent numbers of cores and distinct groups of cores (microplots) results in lowest soil C coefficients of variation for a variety of ecosystems. Our results suggest that grassland soil C changes can be precisely quantified using current technology at scales ranging from farms to the entire nation. (C) 2001 Elsevier Science Ltd. All rights reserved.

Grassland management and conversion into grassland: effects on soil carbon

Grasslands are heavily relied upon for food and forage production. A key component for sustaining production in grassland ecosystems is the maintenance of soil organic matter (SOM), which can be strongly influenced by management. Many management techniques intended to increase forage production may potentially increase SOM, thus sequestering atmospheric carbon (C). Further, conversion from either cultivation or native vegetation into grassland could also sequester atmospheric carbon. We reviewed studies examining the influence of improved grassland management practices and conversion into grasslands on soil C worldwide to assess the potential for C sequestration. Results from 115 studies containing over 300 data points were analyzed. Management improvements included fertilization (39%), improved grazing management (24%), conversion from cultivation (15%) and native vegetation (15%), sowing of legumes (4%) and grasses (2%), earthworm introduction (1%), and irrigation (1%). Soil C content and concentration increased with improved management in 74% of the studies, and mean soil C increased with all types of improvement. Carbon sequestration rates were highest during the first 40 yr after treatments began and tended to be greatest in the top 10 cm of soil. Impacts were greater in woodland and grassland biomes than in forest, desert, rain forest, or shrubland biomes. Conversion from cultivation, the introduction of earthworms, and irrigation resulted in the largest increases. Rates of C sequestration by type of improvement ranged from 0.11 3.04 Mg C.ha(-1) yr(-1), with a mean of 0.54 Mg C.ha(-1).yr(-1) and were highly influenced by biome type and climate. We conclude that grasslands can act as a significant carbon sink with the implementation of improved management.

Environmental factors controlling soil respiration in three semiarid ecosystems

Previous research suggests that soil organic C pools may be a feature of semiarid regions that are particularly sensitive to climatic changes. We instituted an 18-mo experiment along an elevation gradient in northern Arizona to evaluate the influence of temperature, moisture, and soil C pool size on soil respiration. Soils, from underneath different free canopy types and interspaces of three semiarid ecosystems, were moved upslope and/or downslope to modify soil climate. Soils moved downslope experienced increased temperature and decreased precipitation, resulting in decreased soil moisture and soil respiration las much as 23 acid 20%, respectively). Soils moved upslope to more mesic, cooler sites had greater soil water content and increased rates of soil respiration las much as 40%), despite decreased temperature. Soil respiration rates normalized for total C were not significantly different within any of the three incubation sites, indicating that under identical climatic conditions, soil respiration is directly related to soil C pool size for the incubated soils. Normalized soil respiration rates between sites differed significantly for all soil types and were always greater for soils incubated under more mesic, but cooler, conditions. Total soil C did not change significantly during the experiment, but estimates suggest that significant portions of the rapidly cycling C pool were lost. While long-term decreases in aboveground and belowground detrital inputs may ultimately be greater than decreased soil respiration, the initial response to increased temperature and decreased precipitation in these systems is a decrease in annual soil C efflux.

Modeling the stepped potential discharge of primary alkaline battery cathodes

A novel model for the potentiostatic discharge of primary alkaline battery cathodes is presented. The model is used to simulate discharges resulting from the stepped potential electrochemical spectroscopy (SPECS) of primary alkaline battery cathodes cathodes, and the results are validated with experimental data. We show that a model based on a single (or mean) reaction framework can be used to simulate multi-reaction discharge behaviour and we develop a consistent functional modification to the kinetic equation of the model that allows for this to occur. The model is used to investigate the effects that the initial exchange current density, i00, and the diffusion coefficient for protons in electrolytic manganese dioxide (EMD), DH+, have on SPECS discharge. The behaviour observed is consistent with the idea that individual reduction reactions, within the multi-reaction, reduction behaviour of EMD, have distinct i00 and DH+ values.

Application of chemometrics to analysis of soil pollutants

This overview focuses on the application of chemometrics techniques for the investigation of soils contaminated by polycyclic aromatic hydrocarbons (PAHs) and metals because these two important and very diverse groups of pollutants are ubiquitous in soils. The salient features of various studies carried out in the micro- and recreational environments of humans, are highlighted in the context of the various multivariate statistical techniques available across discipline boundaries that have been effectively used in soil studies. Particular attention is paid to techniques employed in the geosciences that may be effectively utilized for environmental soil studies; classical multivariate approaches that may be used in isolation or as complementary methods to these are also discussed. Chemometrics techniques widely applied in atmospheric studies for identifying sources of pollutants or for determining the importance of contaminant source contributions to a particular site, have seen little use in soil studies, but may be effectively employed in such investigations. Suitable programs are also available for suggesting mitigating measures in cases of soil contamination, and these are also considered. Specific techniques reviewed include pattern recognition techniques such as Principal Components Analysis (PCA), Fuzzy Clustering (FC) and Cluster Analysis (CA); geostatistical tools include variograms, Geographical Information Systems (GIS), contour mapping and kriging; source identification and contribution estimation methods reviewed include Positive Matrix Factorisation (PMF), and Principal Component Analysis on Absolute Principal Component Scores (PCA/APCS). Mitigating measures to limit or eliminate pollutant sources may be suggested through the use of ranking analysis and multi criteria decision making methods (MCDM). These methods are mainly represented in this review by studies employing the Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) and its associated graphic output, Geometrical Analysis for Interactive Aid (GAIA).

Regional field measurement of soil moisture content with neutron probe

The neutron logging method has been widely used for field measurement of soil moisture content. This non-destructive method permitted the measurement of in-situ soil moisture content at various depths without the need for burying any sensor. Twenty-three sites located around regional Melbourne have been selected for long term monitoring of soil moisture content using neutron probe. Soil samples collected during the installation are used for site characterisation and neutron probe calibration purposes. A linear relationship is obtained between the corrected neutron probe reading and moisture content for both the individual and combined data from seven sites. It is observed that the liner relationship, developed using combined data, can be used for all sites with an average accuracy of about 80%. Monitoring of the variation of soil moisture content with depth in six months for two sites is presented in this paper.

Effects of dry density and grain size distribution on soil-water characteristic curves of sandy soils

The unsaturated soil mechanics is receiving increasing attention from researchers and as well as from practicing engineers. However, the requirement of sophisticated devices to measure unsaturated soil properties and time consumption have made the geotechnical engineers keep away from implication of the unsaturated soil mechanics for solving practical geotechnical problems. The application of the conventional laboratory devices with some modifications to measure unsaturated soil properties can promote the application of unsaturated soil mechanics into engineering practice. Therefore, in the present study, a conventional direct shear device was modified to measure unsaturated shear strength parameters at low suction. Specially, for the analysis of rain-induced slope failures, it is important to measure unsaturated shear strength parameters at low suction where slopes become unstable. The modified device was used to measure unsaturated shear strength of two silty soils at low suction values (0 ~ 50 kPa) that were achieved by following drying path and wetting path of soil-water characteristic curves (SWCCs) of soils. The results revealed that the internal friction angle of soil was not significantly affected by the suction and as well as the drying-wetting SWCCs of soils. The apparent cohesion of soil increased with a decreasing rate as the suction increased. Further, the apparent cohesion obtained from soil in wetting was greater than that obtained from soil in drying. Shear stress-shear displacement curves obtained from soil specimens subjected to the same net normal stress and different suction values showed a higher initial stiffness and a greater peak stress as the suction increased. In addition, it was observed that soil became more dilative with the increase of suction. A soil in wetting exhibited slightly higher peak shear stress and more contractive volume change behaviour than that of in drying at the same net normal stress and the suction.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.

Effect of pH on the uptake of arsenate and vanadate and the stability of these anions in alkaline solutions – a Raman spectroscopic study

Hydrotalcites have been synthesised using three different pH solutions to assess the effect of pH on the uptake of arsenate and vanadate. The ability of these hydrotalcites to remove vanadate and arsenate from solution has been determined by ICP-OES. Raman spectroscopy is used to monitor changes in the anionic species for hydrotalcites synthesised at different pH values. The results show a reduction in the concentration of arsenate and vanadate anions that are removed in extremely alkaline solutions. Hydrotalcites containing arsenate and vanadate are stable in solutions up to pH 10. Exposure of these hydrotalcites to higher pH values results in the removal of large percentages of arsenate and vanadate from the hydrotalcite interlayer.

Influence of hydrocarbon contamination on clay soil microstructure

Microstructural (fabric, forces and composition) changes due to hydrocarbon contamination in a clay soil were studied using Scanning Electron Microscope (micro-fabric analysis), Atomic Force Microscope (forces measurement) and sedimentation bench test (particle size measurements). The non-polluted and polluted glacial till from north-eastern Poland (area of a fuel terminal) were used for the study. Electrostatic repelling forces for the polluted sample were much lower than for the non-polluted sample. In comparison to non-polluted sample, the polluted sample exhibited lower electric charge, attractive forces on approach and strong adhesion on retrieve. The results of the sedimentation tests indicate that clay particles form larger aggregates and settle out of the suspension rapidly in diesel oil. In non-polluted soil, the fabric is strongly aggregated – densely packed, dominate the face-to-face and edge-to-edge types of contacts, clay film tightly adheres to the surface of larger grains and interparticle pores are more common. In polluted soil, the clay matrix is less aggregated – loosely packed, dominate the edge-to-face types of contacts and inter-micro-aggregate pores are more frequent. Substantial differences were observed in the morphometric and geometrical parameters of pore space. The polluted soil micro-fabric proved to be more isotropic and less oriented than in non-polluted soil. The polluted soil, in which electrostatic forces were suppressed by hydrocarbon interaction, displays more open porosity and larger voids than non-polluted soil, which is characterized by occurrence of the strong electrostatic interaction between clay particles.

Improved salinity management for the Nebine / Mungallala / Wallam catchment

The low stream salinity naturally in the Nebine-Mungallala Catchment, extent of vegetation retention, relatively low rainfall and high evaporation indicates that there is a relatively low risk of rising shallow groundwater tables in the catchment. Scalding caused by wind and water erosion exposing highly saline sub-soils is a more important regional issue, such as in the Homeboin area. Local salinisation associated with evaporation of bore water from free flowing bore drains and bores is also an important land degradation issue particularly in the lower Nebine, Wallam and Mungallala Creeks. The replacement of free flowing artesian bores and bore drains with capped bores and piped water systems under the Great Artesian Basin bore rehabilitation program is addressing local salinisation and scalding in the vicinity of bore drains and preventing the discharge of saline bore water to streams. Three principles for the prevention and control of salinity in the Nebine Mungallala catchment have been identified in this review: • Avoid salinity through avoiding scalds – i.e. not exposing the near-surface salt in landscape through land degradation; • Riparian zone management: Scalding often occurs within 200m or so of watering lines. Natural drainage lines are most likely to be overstocked, and thus have potential for scalding. Scalding begins when vegetation is removed, and without that binding cover, wind and water erosion exposes the subsoil; and • Monitoring of exposed or grazed soil areas. Based on the findings of the study, we make the following recommendations: 1. Undertake a geotechnical study of existing maps and other data to help identify and target areas most at risk of rising water tables causing salinity. Selected monitoring should then be established using piezometers as an early warning system. 2. SW NRM should financially support scald reclamation activity through its various funding programs. However, for this to have any validity in the overall management of salinity risk, it is critical that such funding require the landholder to undertake a salinity hazard/risk assessment of his/her holding. 3. A staged approach to funding may be appropriate. In the first instance, it would be reasonable to commence funding some pilot scald reclamation work with a view to further developing and piloting the farm hazard/risk assessment tools, and exploring how subsequent grazing management strategies could be incorporated within other extension and management activities. Once the details of the necessary farm level activities have been more clearly defined, and following the outcomes of the geotechnical review recommended above, a more comprehensive funding package could be rolled out to priority areas. 4. We recommend that best-practice grazing management training currently on offer should be enhanced with information about salinity risk in scald-prone areas, and ways of minimising the likelihood of scald formation. 5. We recommend that course material be developed for local students in Years 6 and 7, and that arrangements be made with local schools to present this information. Given the constraints of existing syllabi, we envisage that negotiations may have to be undertaken with the Department of Education in order for this material to be permitted to be used. We have contact with key people who could help in this if required. 6. We recommend that SW NRM continue to support existing extension activities such as Grazing Land Management and the Monitoring Made Easy tools. These aids should be able to be easily expanding to incorporate techniques for monitoring, addressing and preventing salinity and scalding. At the time of writing staff of SW NRM were actively involved in this process. It is important that these activities are adequately resourced to facilitate the uptake by landholders of the perception that salinity is an issue that needs to be addressed as part of everyday management. 7. We recommend that SW NRM consider investing in the development and deployment of a scenario-modelling learning support tool as part of the awareness raising and education activities. Secondary salinity is a dynamic process that results from ongoing human activity which mobilises and/or exposes salt occurring naturally in the landscape. Time scales can be short to very long, and the benefits of management actions can similarly have immediate or very long time frames. One way to help explain the dynamics of these processes is through scenario modelling.

Effect of biochar amendment on the soil-atmosphere exchange of greenhouse gases from an intensive subtropical pasture in northern New South Wales, Australia

We assessed the effect of biochar incorporation into the soil on the soil-atmosphere exchange of the greenhouse gases (GHG) from an intensive subtropical pasture. For this, we measured N2O, CH4 and CO2 emissions with high temporal resolution from April to June 2009 in an existing factorial experiment where cattle feedlot biochar had been applied at 10 t ha-1 in November 2006. Over the whole measurement period, significant emissions of N2O and CO2 were observed, whereas a net uptake of CH4 was measured. N2O emissions were found to be highly episodic with one major emission pulse (up to 502 µg N2O-N m-2 h 1) following heavy rainfall. There was no significant difference in the net flux of GHGs from the biochar amended vs. the control plots. Our results demonstrate that intensively managed subtropical pastures on ferrosols in northern New South Wales of Australia can be a significant source of GHG. Our hypothesis that the application of biochar would lead to a reduction in emissions of GHG from soils was not supported in this field assessment. Additional studies with longer observation periods are needed to clarify the long term effect of biochar amendment on soil microbial processes and the emission of GHGs under field conditions.

Thermal stability of the soil minerals destinezite and diadochite Fe3+2(PO4)(SO4)(OH)·6H2O - implications for soils in bush fires

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the soil minerals destinezite and diadochite. These two minerals are identical except for their morphology. Diadochite is amorphous whereas destinezite is crystalline. Both minerals are found in soils. It is important to understand the stability of these minerals because soils are subject to bush fires especially in Australia. The thermal analysis patterns of the two minerals are similar but not identical. Subtle differences are observed in the DTG patterns. For destinezite, two DTG peaks are observed at 129 and 182°C attributed to the loss of hydration water, whereas only a broad peak with maximum at 84°C is observed for diadochite. Higher temperature mass losses at 685°C for destinezite and 655°C for diadochite, based upon the ion current curves, are due to sulphate decomposition. This research has shown that at low temperatures the minerals are stable but at high temperatures, as might be experienced in a bush fire, the minerals decompose.

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)•6H2O – implications for soil science

The two minerals diadochite and destinezite of formula Fe2(PO4,SO4)2(OH)•6H2O have been characterised by Raman spectroscopy and complimented with infrared spectroscopy. These two minerals are both found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill-defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.