Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

The Nordic geological surveys： Geology for society in practice

Since the mid-nineteenth century., when the first of the Nordic Geological Surveys were established, they have generated a substantial amount of information on the Earth＇s crust, its natural resources, its processes, and on the geological history of Nordic areas. The collective mission of the geological surveys is to carry out ＂Geology for Society＂, by doing research and providing services, and by making geological information and data easily accessible to all the varied end users in industry, government agencies, government institutes, public administrations, technical offices, academia and research institutes, as well as for private individuals. The present paper gives a brief overview of a few, selected, research areas and projects currently undertaken by the Nordic geological surveys. These serve as practical examples of how the Nordic geological surveys address important societal problems and challenges that require geological input for their solution.     

An experimental study of Fe–Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt \(X_{{{\text{Ni}}}}^{{{\text{Sulfide}}}}=\frac{{{\text{Ni}}}}{{{\text{Ni}}+{\text{Fe}}}}\) (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of \({f_{{{\text{O}}_{\text{2}}}}}\) on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0?±?1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ ??1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients \(K_{{\text{D}}}^{{}}=\frac{{(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}/X_{{{\text{Fe}}}}^{{{\text{sulfide}}}})}}{{(X_{{{\text{Ni}}}}^{{{\text{olivine}}}}/X_{{{\text{Fe}}}}^{{{\text{olivine}}}})}}\) are small, averaging 10.0?±?5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K_D (21.1–25.2). Compared to previous determinations at 100 kPa, values of K_D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (\(X_{{{\text{Ni}}}}^{{{\text{sulfide}}}}\)?~?0.28)?>?140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.     

Trace element zoning in pyroxenes from ODP Hole 735B gabbros: diffusive exchange or synkinematic crystal fractionation?

Major and trace element profiles of clinopyroxene grains in oceanic gabbros from ODP Hole 735B have been investigated by a combined in situ analytical study with ion probe, and electron microprobe. In contrast to the homogeneous major element compositions, trace elements (REE, Y, Cr, Sr, and Zr) show continuous core to rim zoning profiles. The observed trace element systematics in clinopyroxene cannot be explained by a simple diffusive exchange between melts and gabbros along grain boundaries. A simultaneous modification of the melt composition is required to generate the zoning, although Rayleigh fractional crystallization modelling could mimic the general shape of the profiles. Simultaneous metasomatism between the cumulate crystal and the porous melt during crystal accumulation is the most likely process to explain the zoning. Deformation during solidification of the crystal mush could have caused squeezing out of the incompatible element enriched residual melts (interstitial liquid). Migration of the melt along grain boundaries might carry these melt out of the system. This process named as synkinematic differentiation or differentiation by deformation (Natland and Dick in J Volcanol Geotherm Res 110(3–4):191–233, 2001) may act as an important magma evolution mechanism in the oceanic crust, at least at slow-spreading ridges.     

The spatial pattern and dynamics of a Sahelian agro-ecosystem

The spatial pattern and dynamics of a Sahelian agro-ecosystem are analyzed. Approaches and methods suitable for land use systems analysis are discussed. The importance of combining various spatial and temporal scales in a multi-disciplinary framework is stressed. An analytical framework focusing on the land use system at the village level is presented. It pays specific attention to the integration of georelated data with those describing the socio-economic decision-making units (households). It is intended as a basic component in a land use analytical model which meets the requirements of being multidisciplinary as well as hierarchical.Selected results from a case study in northern Burkina Faso, are presented. Mainly issues with a spatial dimension, taking advantage of the georelated observations, are dealt with in this context. They reveal, for instance, that field pattern dynamics appear to be much more complex than generally believed and that the commonly held notion that fields are expanding cannot be confirmed by this case. The land use dynamics constitute a complex pattern, determined by household specific parameters as well as by the natural resource base. Furthermore, the experience from the application of a differential GPS for detailed land use studies in the Sahel is presented and discussed.     

Mid-infrared imaging of WL 16: the spatial distribution of the hydrocarbon emission features

We present arcsec-resolution images at 8.2, 10.0 and 11.3 μm of the unusual young object WL 16 in Ophiuchus, which has an extended envelope of fluorescing hydrocarbon molecules. To the limit of achieved sensitivity, the faint 10.0-μm continuum has a surface-brightness distribution that is not distinguishable from those at 8.2 and 11.3 μm, where the luminosity is known to be dominated by the polycyclic aromatic hydrocarbon (PAH) emission features. We conclude that the 10-μm continuum either arises from non-equilibrium heating of small dust grains that are well mixed with the hydrocarbons or is quasi-continuous emission from the PAH particles themselves, rather than thermal equilibrium emission from macroscopic dust grains, and that there is no significant silicate absorption variation across the source. The extended hydrocarbon emission may trace a flattened, equatorial distribution of circumstellar material or arise in bipolar lobes. The former case is slightly favoured, based on currently available data, and would imply that WL 16 is a relatively evolved Herbig Ae star, the equatorial plane of which has been almost cleared of normal dust, leaving only fluorescing hydrocarbons and larger coagulated particles as a possibly transient fossil of the original circumstellar disc.     

Impact of wildfire on source water contributions in Devil Creek,CA: evidence from end‐member mixing analysis

A geochemical and end‐member mixing analysis (EMMA) is undertaken in Devil Canyon catchment, located in southern California, to further understanding of watershed behaviour and source water contributions after an acute and extensive wildfire. Physical and chemical transformations in post‐fire watersheds are known to increase overland flow and decrease infiltration, mainly due to formation of a hydrophobic layer at, or near, the soil surface. However, less is known about subsurface flow response in burned watersheds. The current study incorporates EMMA to evaluate and quantify source water contributions before, and after, a catchment affected by wildfires in southern California during the fall of 2003. Pre‐ and post‐fire stream water data were available at several sampling sites within the catchment, allowing the identification of contributing water sources at varying spatial scales. Proposed end‐member observations (groundwater, overland flow, shallow subsurface flow) were also collected to constrain and develop the catchment mixing model. Post‐fire source water changes are more evident in the smaller and faster responding sub‐basin (interior sampling point). Early post‐fire storm events are dominated by overland flow with no significant soil water or groundwater flow contribution. Inter‐storm streamwater in this smaller basin shows an increase in groundwater and a decrease in soil water. In the larger, baseflow‐dominated system, source water components appear less affected by fire. A slight increase in lateral flow is observed with only a slight decrease in baseflow. Changes in the post‐fire flow regimes affect nutrient loading and chemical response of the basin. Relatively rapid recovery of the chaparral ecosystem is evidenced, with active re‐growth and evapotranspiration evidenced by the fourth post‐fire rainy season. Copyright © 2008 John Wiley & Sons, Ltd.     

Temporal and spatial variability of cation and silica export in an alpine watershed,Emerald Lake,California

A reaction set of possible mineral weathering reactions is proposed to explain observed cation and silica export for the Emerald Lake watershed, a small Sierra Nevada, California catchment. The reaction set was calculated through a stoichiometric mole‐balance method, using a multiyear record of stream flow and snowpack chemical analyses and site‐specific mineral compositions. Reaction‐set calculations were intended to explore how the processes controlling stream cation and silica export depend on differing bedrock mineralogy across the catchment as snowmelt and runoff patterns change over the year. Different regions within the watershed can be differentiated by lake inflow subdrainages, each exhibiting different stream‐flow chemistry and calculated weathering stoichiometry, indicating that different silica and cation generation processes are dominant in wet steep portions of the catchment. Short‐term differences in stream concentrations were assumed to reflect ion exchange equilibria and rapid biological processes, whereas long‐term persistent stream concentration differences in different areas of the catchment were assumed to reflect spatial variability in mineral weathering stoichiometry. Mineralogical analyses of rock samples from the watershed provided site‐specific chemical compositions of major mineral species for reaction calculations. Reaction sets were evaluated by linear regression of calculated versus observed differences between snowmelt and stream‐flow chemistry and by a combined measure. Initially, single weathering reactions were balanced and evaluated to determine the reactions that best explained observed stream chemical export. Next, reactions were combined, using mineral compositions from different rock types to estimate the dependence of ion fluxes on lithology. The seasonal variability of major solute calculated fluxes is low, approximately one order of magnitude, relative to the observed three orders of magnitude variability in basin discharge. Reaction sets using basin‐averaged lithology and Aplite lithologies gave superior explanations of stream chemical composition. Copyright © 2004 John Wiley & Sons, Ltd.     

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