Reduction of inorganic compounds in autoclaves by using suspended cellulose

Autoclaves are closed vessels in which liquids can be heated above their ‘normal' boiling points. As a consequence the pressure will rise. This equipment has permitted a variety of processes like the syntheses of organics and the leaching of metal ores. Pressure technologies can be used for accelerating reactions, for specific syntheses or they offer an environmental or economical alternative for existing processes. Wet pressure oxidation of sewage sludge, an organic waste product, has become a proven technology. If less oxygen is added than stoichiometrically required for a complete oxidation, cellulose will break down by a different reaction mechanism, releasing electrons. Under these circumstances reduction of inorganic compounds is possible.     

Water release patterns of heated speleothem calcite and hydrogen isotope composition of fluid inclusions

Speleothem fluid inclusions are a potential paleo-precipitation proxy to reconstruct past rainwater isotopic composition (δ¹⁸O, δD). To get a better insight in the extraction of inclusion water from heated speleothem calcite, we monitored the water released from crushed and uncrushed speleothem calcite, heated to 900 °C at a rate of 300 °C/h, with a quadrupole mass spectrometer. Crushed calcite released water in three not well individualised peaks between 25 and 360 °C, 360 and 650 °C and between 650 and 800 °C while uncrushed calcite released water in two distinct temperature intervals: between 25 and 550 °C and between 550 and 900 °C.Water from two speleothems from the Han-sur-Lesse cave was recovered using three different techniques: i) the crushing and heating to 360 °C technique, ii) the decrepitation by heating to 550 °C and iii) the decomposition by heating to 900 °C technique. Measurements of the δD of water recovered by the decomposition of Han-sur-Lesse calcite heated to 900 °C did not show a 20 to 30‰ offset as found by previous authors. However a difference of 7‰ was observed between water released before and after decomposition of the calcite. Water recovery from the Han-sur-Lesse samples suggests that a simple heating technique (up to 550 °C) without crushing could both (a) recover water with δD representative of that of the drip water and (b) double the water yield as compared to the crushing and heating method.Our study warns for possible contamination of the recovered inclusion water with hydration water of lime, responsible for the recovery of water with very negative δD values.     

Fluid inclusion and cathodoluminescence studies on fluorite from the Kerio valley, Kenya

The Kerio valley lies between the Elgeyo escarpment and the Tugen hills which mark the western margin of the Kenya rift valley. The main fluorite deposits are located in the southern part of the valley at Kimwarer, Choff and Kamnaon.Three types of inclusion fillings were identified: Liquid+Vapour, Liquid+Daughter Minerals and Liquid. The L+V type is dominant. Inclusions occur as clusters, trails along the crystal growth zones and as isolated ones. Low salinities, apparently lower than the 5% wt. NaCl equivalent, were established. Homogenization temperatures suggest that fluorite mineralization took place at different stages and at temperatures between 120 and 180 °C. Isolated readings above 180°C may be referring to the original inclusions in limestone. These measurements and the absence of CO₂ in the inclusions, as well as the occurrence of vugs and crustifications with fluorite, suggest that mineralization took place at relatively shallow depths.Emission spectrum lines representing Eu²⁺, Dy³⁺, Tb³⁺ and Sm³⁺ in fluorite were identified. Sm³⁺ was detected only in the pinkish luminescence of veined fluorite, whereas the pinkish zone in banded fluorite contains Tb³⁺. Eu²⁺ which gives the strongest emission lines in the blue part of the visible spectrum, apparently is responsible for the strong blue cathodoluminescence (CL) in fluorite. The dominance of Eu²⁺ peaks further points to the fact that fluorite mineralization in the Kerio valley took place in an environment that was enriched in Lanthanide Rare Earth Elements (LREE). The presence of rare earths and radioactive elements in fluorite points towards their enrichment in the environment of fluorite mineralization. A juvenile origin of mineral forming solutions is proposed.Two generations of fluorite were established: allotriomorphic fluorite, forming the matrix, and the idiomorphic variety, occurring either in barite or in druzes in early fluorite. Barite in turn forms idiomorphic crystals in allotriomorphic fluorite. Relics of calcite occur in both K-feldspars and in early fluorite. Oxides and hydroxides of Fe, Mn, Ti and Al commonly occur in open spaces in fluorite. Of significance is the presence of gold in fluorite. Fluorite mineralization is of hydrothermal origin in the post-Miocene era and was formed as a result of metasomatic replacement of marble and open space fillings.     

Geochemical and electron paramagnetic characteristics of quartz from a multi-stage vein environment, Cowarra gold deposit, New South Wales

The characterisation of quartz using trace element geochemistry and electron paramagnetic resonance measurements has been tested for different generations of quartz veining in the multi-stage hydrothermal vein system at Cowarra. Quartz closely associated with gold mineralisation can be distinguished from earlier and later quartz generations in the mineralised environment, and both types can be distinguished from regional, barren quartz veins. These separate stages of quartz veins are also recognised from their fluid inclusion characteristics. Geochemical differences in the quartz partly reflect the presence of minor mineral inclusions, particularly sulfides and arsenopyrite.The study highlights the importance of understanding the paragenetic sequence of quartz vein development in a mineralised environment and the need for careful, thorough sampling before attempting geochemical and EPR characterisation of quartz as an exploration technique.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.     

Alternative water management options to reduce vulnerability for climate change in the Netherlands

Urbanization, land subsidence and sea level rise will increase vulnerability of the urbanized low-lying areas in the western part of the Netherlands. In this article possibilities are explored to reduce vulnerability of these areas by implementing alternative water management options. Two main water management fields are distinguished, water supply and flood control. A four-component vulnerability framework is presented that includes threshold capacity, coping capacity, recovery capacity, and adaptive capacity. By using the vulnerability framework it is shown that current water supply and flood control strategies in the Netherlands focus on increasing threshold capacity by constructing higher and stronger dikes, improved water storage and delivery infrastructure. A complete vulnerability decreasing strategy requires measures that include all four capacities. Flood damage reduction, backup water supply systems and emergency plans are measures that can contribute to increasing coping capacity. Recovery capacity can be increased by multi-source water supply, insurance, or establishing disaster funds. Adaptive capacity can be developed by starting experiments with new modes of water supply and urbanization. Including all four components of the vulnerability framework enables better understanding of water and climate related vulnerability of urban areas and enables developing more complete water management strategies to reduce vulnerability.     

The fusion crust of the Winchcombe meteorite: A preserved record of atmospheric entry processes

Fusion crusts form during the atmospheric entry heating of meteorites and preserve a record of the conditions that occurred during deceleration in the atmosphere. The fusion crust of the Winchcombe meteorite closely resembles that of other stony meteorites, and in particular CM2 chondrites, since it is dominated by olivine phenocrysts set in a glassy mesostasis with magnetite, and is highly vesicular. Dehydration cracks are unusually abundant in Winchcombe. Failure of this weak layer is an additional ablation mechanism to produce large numbers of particles during deceleration, consistent with the observation of pulses of plasma in videos of the Winchcombe fireball. Calving events might provide an observable phenomenon related to meteorites that are particularly susceptible to dehydration. Oscillatory zoning is observed within olivine phenocrysts in the fusion crust, in contrast to other meteorites, perhaps owing to temperature fluctuations resulting from calving events. Magnetite monolayers are found in the crust, and have also not been previously reported, and form discontinuous strata. These features grade into magnetite rims formed on the external surface of the crust and suggest the trapping of surface magnetite by collapse of melt. Magnetite monolayers may be a feature of meteorites that undergo significant degassing. Silicate warts with dendritic textures were observed and are suggested to be droplets ablated from another stone in the shower. They, therefore, represent the first evidence for intershower transfer of ablation materials and are consistent with the other evidence in the Winchcombe meteorite for unusually intense gas loss and ablation, despite its low entry velocity.     

Developing a building policy for the erosion zone: Solutions to some key (Dutch) questions

In those coastal communities where the most seaward strip of mainland consists of dunes, these dunes often serve as a flexible sea defence. In addition, this strip offers large potential for housing and commercial enterprises. Unfortunately, due to severe storm surges part of this strip (the erosion zone) is subject to erosion, and as a result of which any buildings or infrastructure located here, are destroyed. Therefore, as we will illustrate in this paper, a building policy for this zone should reflect a compromise between two opposite interests: exploitation of the existing potential and, prevention of an unacceptable high risk due to erosion. Accordingly, the authors have developed a framework for such a building policy on the basis of which the desirability of various different types of investments and the location within the erosion zone of such investments can be determined. The examples that are used to illustrate this framework in this paper are limited to experiences in The Netherlands as relevant data and experiences are available and relatively easy accessible here. Nevertheless, the approach as is described is generic and applicable worldwide suggesting that the discovered unused potential for exploitation is not just limited to The Netherlands.     

Greening international shipping through private governance: A case study of the Clean Shipping Project

This article aims to generate insights into both private governance and partnerships within the shipping industry, but also tries to improve understanding of the complex process of institutionalisation.This is achieved through a case study of the Clean Shipping Project, a public/private partnership that aims to promote sustainability in the shipping industry. A set of enabling and constraining factors are examined that shape the institutionalisation process and determine to what extent the Clean Shipping Project can establish and expand authority as an industry norm.Overall, the Clean Shipping Project cannot yet be considered a full-fledged private governance institution, because of an insufficient level of collaborative advantage mainly due to weak system robustness and unfavourable market characteristics and conditions. However, institutionalisation is an ongoing process and the future outlook for the Clean Shipping Project remains promising. The Clean Shipping Project is certainly a relevant supplement to existing regulations and there is a basic level of commitment and cohesion within the partnership, so it is not unlikely that in the future this initiative may help to uncouple growth in shipping activities from environmental harm.