Speciation of Cu in MSWI bottom ash and its relation to Cu leaching

In Flanders, recycling of bottom ash is mainly inhibited by the high leaching of Cu. Although it has been proved that dissolved organic C plays a major role in the Cu leaching, the possible role of inorganic Cu mineral speciation has never been experimentally examined. In this study the speciation of Cu is investigated using a combination of optical microscopy and electron microprobe –WDX/EDX. Several Cu species were determined. Metallic Cu (with or without an oxide shell), CuO and Cu₂O were the most abundant. These particles were most likely present in wire-like structures. Copper also occurred as alloy (brass, bronze, zamak), and was found frequently together with typical elements such as Ca, Cl and S. Finally, small metallic Cu particles seemed to be trapped in or precipitated on oxides and silicates. Based on this Cu speciation study, pure Cu minerals were selected and leached as a function of time. The solubility after equilibrium of all studied Cu minerals never exceeded 20 μg/L (which equals 10% of the total Cu leaching).The effect of heating (2 h at 400 °C) on the speciation of Cu was investigated using the same combination of techniques. Results show that metallic Cu seemed to be converted to Cu oxide (mostly CuO) and that the particles were more porous after heating. These conclusions were verified by XRD analysis of the heated pure Cu minerals. After heating, the Cu minerals were also leached as a function of time, to study the impact on Cu leaching. Results indicate that their leaching had slightly increased in comparison with the non-heated Cu minerals. However, the major decrease in Cu leaching in heated bottom ash, more than neutralizes this effect and thus can be attributed to the destruction of organic matter and not to the (small) change in Cu speciation.     

高铝粉煤灰中部分主微量元素的分布规律研究

本文旨在研究部分主微量元素在高铝粉煤灰中的分布规律,从而为其资源化利用提供科学依据。首先根据高铝粉煤灰的物相组成特点采用新的分离方法将之分离为三个相(或相组合):铁质微珠、莫来石-刚玉相以及玻璃相;然后分别用化学分析和ICP-MS测试主微量元素在高铝粉煤灰、铁质微珠以及莫来石-刚玉相中的含量,并结合相关数据计算出这些元素在玻璃相中的含量。结果表明,除Al、Mn外,其他元素均在玻璃相中有不同程度的富集;除Al外,其他元素则在莫来石-刚玉相中有不同程度的贫化;除Ti以外的铁族元素以及除Ga、Pb以外的金属成矿元素均在铁质微珠中富集,其他元素则在其中贫化。     

Temporal transport of major and trace elements in the upper reaches of the Xijiang River,SW China

This study investigated the temporal variations of major and trace element contents and controlling factors in the upper reaches of the Xijiang River, SW China. The results showed the major ions principally derived from the weathering of carbonate and silicate rocks, with a seasonal variation impacted by the monsoonal climate. The contents of dissolved trace elements also varied seasonally in the two main tributaries: the Nanpan and Beipan rivers. Most dissolved trace elements such as Mn, Zn and Pb being affected by anthropogenic contributions displayed a large seasonal variability, from onefold to hundred-fold, while V, Rb and U show a relative stable trend uncorrelated with the different seasons, suggesting a natural origin by rock weathering. Suspended particle matter in the Nanpan and Beipan rivers was depleted in Ca, Mg, Na, K and Sr, but enriched in Al, Fe and Sb compared to the upper crust (UC) values. A binary mixture of silicate-rich and carbonate-rich sources dominates the behavior of elements such as Ca and Sr in riverine sediments, while a third end-member with an anthropogenic signature influenced the content of trace elements like Mn, Sb, Pb, Zn, Cd, Cr and Cu. The enrichments of Sb relative to the UC would be related to the mining activity in the studied area. The study highlights the importance of investigating temporal variations of major and trace element contents of rivers controlled by the monsoon climate and impacted by human activity.     

Spatial distribution and geochemical baselines of major/trace elements in soils of Medak district,Andhra Pradesh,India

Regional-scale variations in soil geochemistry were investigated with special reference to differences among soil groups and lithology in an area of 9,699 km² in Medak district, Andhra Pradesh, India. The concentrations of 29 elements (major: Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, P and trace: As, Ba, Cd, Co, Cr, Cu, F, Mo, Ni, Pb, Rb, Se, Sr, Th, U, V, Y, Zn, Zr) in 878 soil samples collected (557-topsoil, 321-subsoil) at a sampling density of 1 site/17 km² from 557 sites representative of all the soil types present in studied area were determined, and their elemental composition are discussed. The baseline levels of these elements in soils are determined over different lithological units for the identification of anomalous values relative to these. For the first time, geochemical maps for Medak district are prepared on 1:50,000 scale and the lithogeochemical database generated provides information on the lateral and vertical distribution of elements in soil. The spatial variations in the distribution of elements reflect underlying geologic characteristics. Box-plots reveal that the concentration of most of the elements in soils were not strongly dependent on the soil group but the soil-geochemistry abruptly changes with the change in the soil parent materials indicating that the distribution of elements is mostly influenced by the bedrock lithology and other natural processes acting on them. For instance, the concentrations of Co, Cu, Fe, Mn, Ti, V and Zn are high in soils developed on basaltic terrain while the soils developed on granitic and gneissic terrain exhibit high elemental concentrations of K, Pb, Rb, Si, Th and Y. Alfisols had relatively high contents of elements while entisols had lower concentrations of most of the elements. The database can be used in the chemical characterisation of different geological units as well as applications in various environmental and agricultural fields. The results indicate that regional geology is an important determinant of soil geochemical baselines for soil pollution assessment and further emphasizes the importance of determining background levels locally. The defined baselines can be used to establish background values for future soil surveys.     

Determination of some trace elements in geochemical standards by X-ray fluorescence

The following trace elements Cr, Cu, Nb, Ni, Pb, Rb, Sr, Y, Zn, and Zr were determined by X-ray fluorescence in some geochemical standards from Japan and France. The internal standard method was applied using a Philips PW 1410 X-ray spectrometer. The results were compared with the published data.     

Scenario of particulate trace metal and metalloid transport during a major flood event inferred from transient geochemical signals

High-resolution sampling (every 3 h) of SPM was performed during a major flood event in a heterogeneous, medium scale watershed of the Garonne-Gironde fluvial-estuarine system (the Lot River; A = 10,700 km²; Q = 151 m³/s). Particulate metal and metalloid (Cd, Zn, Pb, Co, Cr, Ni, Mo, V, U, As, Sb, Th) concentrations were compared with monthly data of the same site (Temple site) obtained during 1999–2002. During the flood event, suspended particulate matter (SPM) concentrations closely followed river discharge with a maximum value (1530 mg/L) coinciding with the discharge peak (2970 m³/s). Trace metal/metalloid concentrations showed significant temporal variations and very contrasted responses. Particulate concentrations were similar to baseline values at the beginning of the flood and mostly increased during the event, showing anticlockwise and complex shape hystereses. Comparison of SPM yield (440,000 t) and particulate metal/metalloid fluxes during the flood with annual fluxes (1999–2002) highlights the great importance of major flood events in fluvial transport. Adequate sampling frequency during floods is necessary for reliable annual flux estimates and provides geochemical signals that may greatly improve our understanding of fluvial transport processes. The scenario of SPM and metal and metalloid transport during the flood are reconstructed by combining variations of Zn, Cd and Sb concentrations, concentration ratios (e.g. Zn/Cd, As/Th, Cd/Th) and hysteresis loops. Changes in SPM and metal/metalloid transport during distinct key stages of the flood were attributed to successive dominance of different water masses transporting material from different sources (e.g. industrial point source, bed sediment from reservoirs, plain erosion). Flood management (dam flushing) clearly enhanced the remobilization of up to 30-a old polluted sediment from reservoir lakes. Sediment remobilization accounted for ∼185,000 t of SPM (i.e. 42% of the total SPM fluxes during the flood) and strongly contributed to particulate metal/metalloid transport for Cd (90%), Zn (83%) and Pb (61%). Therefore, flood management needs to be taken into consideration in future models for erosion and pollutant transport.     

A coupled non-isothermal reactive transport model for long-term geochemical evolution of a HLW repository in clay

A numerical model of coupled saturated/unsaturated water flow, heat transfer and multi-component reactive solute transport is presented to evaluate the long-term geochemical evolution in bentonite, concrete and clay formation for a potential geological radioactive waste repository. Changes in formation porosity caused by mineral dissolution/precipitation reactions are taken into account. Simulations were carried out with a general-purpose multicomponent reactive transport code, CORE^2D V4. Numerical results show that pH in the bentonite porewater can vary from neutral to up to 13 over a time scale of 1 Ma although dissolution of silica minerals and precipitation of secondary calcium silicate hydrate (CSH) minerals in bentonite buffer the effect of the hyperalkaline plume. Mineral precipitation reduces the volume of pore space in bentonite close to the bentonite–concrete interface due to the precipitation of CSH minerals. Model results indicate that bentonite porosity decreases less than 25%. The hyperalkaline plume from the concrete only extends to a distance of 0.7 m in the clay formation over the time range of 1 Ma.     

稳定同位素和微量元素在多源多汇体系中地球化学行为的理论模拟

根据地质体系多源多汇的特点,引进了一种新的定量地球化学理论模型,适用于模拟稳定同位素和微量元素在具有多个物质来源和多种分馏途径的地质体系中的变化规律。运用本文多源多汇模型研究岩浆同化-分异结晶过程中微量元素和稳定同位素的行为,所得的结果与前人AFC模型结果一致。运用此多源多汇模型对岩浆水与大气水混合过程中结晶出的石英进行模拟计算,发现其氧同位素组成随着结晶温度的降低而变大。大气中甲烷的产生和消耗有多种途径,是一种多源多汇体系,运用此模型研究它的碳同位素组成,发现其值随着甲烷总量的增多而变大。多源多汇模型不仅从更高的层次上包含了简单分馏模式、多元混合模式和AFC模式,而且可以研究这些模式不能解决的复杂地球化学过程。     

Distribution and geochemical significance of trace elements in shale rocks and their residual kerogens

There is a dearth of information about the distribution of trace elements in kerogen from shale rocks despite several reports on trace element composition in many shale samples. In this study, trace elements in shale rocks and their residual kerogens were determined by inductively coupled plasma–mass spectrometry. The results from this study show redox-sensitive elements relatively concentrated in the kerogens as compared to the shales. This may be primarily due to the adsorption and complexation ability of kerogen, which enables enrichment in Ni, Co, Cu, and Zn. For the rare earth elements (REEs), distinct distribution characteristics were observed for shales dominated by terrigenous minerals and their kerogen counterparts. However, shales with less input of terrigenous minerals showed similar REE distribution patterns to their residual kerogen. It is speculated that the distribution patterns of the REEs in shales and kerogens may be source-related.     

华南红土主元素表生地球化学特征

华南红土从其母岩到表土,普遍表现为主元素SiO2、K2O、Na2O淋失,Fe2O3、Al2O3、N、S富集。红土饱和水含量最高的是D2型红土,最低的是老红沙型红土。在岩石与上层红土风化特征中,风化强度以γ型红土最强,而灰岩型红土最弱;淋溶系数最大的是灰岩型红土,最小的为γ型红土;变异系数最大的为灰岩型红土,最小的为Q2型红土。从空间上看,红土的表生地球化学特征、红土成分的变异系数、红土的淋溶系数、红土的风化率和风化强度、红土湿度和温度等均受母岩、气候纬度效应制约。相关分析表明,华南红土中的水含量和土温与Fe2O3含量呈正相关关系。初步研究表明,华南红土的表生地球化学特征是长期和多种环境变化的真实记录。     

Composition of estuarine colloidal material: major and trace elements

Colloidal-sized material from the Patuxent River estuary, Maryland, was analyzed for more than 30 elements by instrumental neutron activation analysis. Sample data from stations ranging in salinity from 0.04 g/kg to 12 g/kg indicate that the winter colloidal material is dominated upstream by poorly crystallized clay minerals and iron oxide, but above a salinity of 10 g/kg, it consists primarily of carbonaceous material. Winter colloidal material decreases non-conservatively seaward from 29 to 0.6 mg/l. The summer colloidal material, however, is carbon-rich throughout the estuary and the amount of colloidal material in the upper water column does not change appreciably with increasing salinity. Many trace elements (Cs, Hf, Rb, Se, Th, V and the REE) covary with Al and probably are associated with the clay component. Other elements (As, Ba, Sb, Se, U and Zn) are considerably enriched relative to Al and may covary with the organic component. The results suggest that the freshwater winter colloidal system is a product of continental weathering processes, whereas the summer colloidal material is derived primarily from estuarine biological processes.     

The pathway of trace elements during oil shale combustion—A clue to their availability for leaching processes

A model for the pathway of some trace elements during fluidized-bed combustion of israeli oil shale is suggested, based both on pilot plant and laboratory tests. This model demonstrates the role of carbonate matrix in suppressing the volatilization of trace elements due to fixation of most elements in new-formed silicates. The quality of leachates derived from oil shale combustion wastes can be predicted on the basis of the proposed model.     

REE distribution in the resin-asphaltene fractions as a geochemical criterion for identification of sources of trace elements in oil

This paper reports REE data on resin-asphaltene components of oil from six oil-gas-bearing provinces and on bitumoids from inferred oil-source rocks (domanikites and bazhenites). It was shown that, regardless of geological-tectonic structure of the regions, oil composition, depth of reservoirs, and host lithologies, oil exhibits significant REE fractionation, and, unlike bitumoids, positive Eu anomaly. The (Eu/Sm)_n ratio increases from asphaltenes to resins and further to oils. Based on REE distribution in oil, source rocks, and bitumoids, it was concluded that deep-seated fluids were one of the possible sources that defined the trace element composition of oil.     

Silicate perovskite-melt partitioning of trace elements and geochemical signature of a deep perovskitic reservoir

We have determined the partitioning of a wide range of trace elements between silicate melts and CaSiO₃ and MgSiO₃ perovskites using both laser ablation-ICPMS and ion microprobe techniques. Our results show that, with the exception of Sc, Zr, and Hf, all trace elements we considered are incompatible in MgSiO₃ perovskite, from highly incompatible for U, Th, Ba, La, Sr and monovalent elements to slightly incompatible for heavy rare earth elements. MgSiO₃ perovskite-melt partition coefficients increase slightly with Al content in the perovskite. These observations contrast strongly with partitioning between CaSiO₃ perovskite and silicate melts. In the latter case, all rare earth elements are clearly compatible as are U and Th. Our data also suggest that, contrary to pressure and temperature, melt composition can significantly affect CaSiO₃ perovskite-melt partitioning; partition coefficients for rare earth elements and U and Th increase with decreasing CaO melt content. The presence of ∼0.4 wt% water in melt makes little difference, however. Partitioning of trace elements into the large site of both MgSiO₃ and CaSiO₃ perovskites follows the near-parabolic dependence on ionic radius predicted from the lattice strain model. The peaks of the parabolae are much higher for the CaSiO₃ phase, perhaps suggesting that the mechanisms of charge compensation for heterovalent substitution are different in the two cases. Our partitioning data have been used to assess the potential effect of perovskite fractionation into the lower mantle during early Earth history. Crystallisation of less than 8% of a mixture of CaSiO₃ and MgSiO₃ perovskites could have led to a ‘layer’ enriched in U and Th without disturbing the chondritic pattern of refractory lithophile elements in the primitive upper mantle. The resultant reservoir could have high Sm/Nd, U/Pb, Sr/Rb, Lu/Hf ratios similar to the HIMU component of ocean island basalts, but would not balance the observed depletion of the primitive upper mantle in Si and Nb.     

Temporal and spatial patterns of trace elements in the Patuxent River: A whole watershed approach

Trace element distributions, partitioning, and speciation were examined at 15 sites in the Patuxent River watershed from May 1995 through October 1997 to determine possible sources of trace elements to the river and estuary, to examine the relationship of the trace element discharges to freshwater discharges as well as to land use and geographic region, to validate previous estimates of loadings to the river, and to provide baseline data for trace elements in the Patuxent River watershed and estuary. Six freshwater sites were examined, representing different basins and geographic provinces, and nine sites along the estuarine salinity gradient. Subregions within the watershed varied considerably in concentrations and areal yields for some elements. Concentrations of As, Cd, Ni, Pb, and Zn were elevated in the Coastal Plain sites compared to the Piedmont sites, while Cu and Hg were more evenly distributed. Cadmium, Cu, Hg, Ni, Pb, and Zn showed overall positive correlations with river flow while As and methylHg (meHg) showed negative correlations with river flow. Concentrations of trace elements in the estuarine portion of the river were generally low, and consistent with mixing between Patuxent River water with elevated concentrations and the lower concentrations of the Chesapeake Bay. Interesting features included a local Cd maximum in the low salinity region of the estuary, probably caused by desorption from suspended sediments, and a significant input of water containing high As concentrations from the Chesapeake Bay and from As being released from bottom sediments in summer. Comparisons between the estimated annual flux of trace elements and the estimates of suspected source terms (atmospheric deposition, urban runoff, and known point sources) suggest that, except for Hg, direct atmospheric deposition is small compared to fluvial loads. Current estimates of trace element inputs from point sources or from urban runoff are inadequate for comparison with other sources, because of inappropriate techniques and/or unacceptably high detection limits. A complete examination of trace element dynamics in the Patuxent River (and in other coastal systems) will require better data for these potential sources.     

Modelling of major elements in mantle-melt systems using trace element approaches

Major elements can be modelled in ways similar to the quantitative petrogenetic modelling used for trace elements. In contrast to modelling with trace elements, however, modelling with major elements is constrained by the stoichiometry of the solid phases. Within these constraints, the same equations for partial melting and crystallization which have been used to such advantage for trace elements may be used for major elements.Calculated MgO and FeO abundances in a mantle-melt system are used as an example of the modelling technique. Such modelling yields limited fields of permissible melts and residues for a given parent composition, but does not give the paths of melting. It does allow the temperature and extent of melting which gave rise to a melt to be determined from the MgO and FeO abundances of the melt or residual solid. Applying the results of the modelling to igneous rocks and ultramafic nodules leads to the following conclusions, which are subject to the uncertainties in the available distribution coefficients. Least differentiated basalt glasses from the ocean floor are derived from parent melts with less than 15.5 weight % MgO and 8.2 wt. % FeO. Komatiites may be derived by less than 60% melting of a pyrolite source leaving a residue of olivine and pyroxene. Many nodules from the subcontinental mantle appear to be residues of large fractions of melting (>30%) at high temperature and pressure, whereas ultramafic nodules from oceanic basalts appear to be residues of smaller fractions of melting (<30%) at lower temperatures and pressures.     

A sequential partly iterative approach for multicomponent reactive transport with CORE2D

CORE^2D V4 is a finite element code for modeling partly or fully saturated water flow, heat transport, and multicomponent reactive solute transport under both local chemical equilibrium and kinetic conditions. It can handle coupled microbial processes and geochemical reactions such as acid–base, aqueous complexation, redox, mineral dissolution/precipitation, gas dissolution/exsolution, ion exchange, sorption via linear and nonlinear isotherms, and sorption via surface complexation. Hydraulic parameters may change due to mineral precipitation/dissolution reactions. Coupled transport and chemical equations are solved by using sequential iterative approaches. A sequential partly iterative approach (SPIA) is presented which improves the accuracy of the traditional sequential non-iterative approach (SNIA) and is more efficient than the general sequential iterative approach (SIA). While SNIA leads to a substantial saving of computing time, it introduces numerical errors which are especially large for cation exchange reactions. SPIA improves the efficiency of SIA because the iteration between transport and chemical equations is only performed in nodes with a large mass transfer between solid and liquid phases. The efficiency and accuracy of SPIA are compared to those of SIA and SNIA using synthetic examples and a case study of reactive transport through the Llobregat Delta aquitard in Spain. SPIA is found to be as accurate as SIA while requiring significantly less CPU time. In addition, SPIA is much more accurate than SNIA with only a minor increase in computing time. A further enhancement of the efficiency of SPIA is achieved by improving the efficiency of the Newton–Raphson method used for solving chemical equations. Such an improvement is obtained by working with increments of log concentrations and ignoring the terms of the Jacobian matrix containing derivatives of activity coefficients. A proof is given for the symmetry and non-singularity of the Jacobian matrix. Numerical analyses performed with synthetic examples confirm that these modifications improve the efficiency and convergence of the iterative algorithm. Changbing Yang is now at The University of Texas at Austin, USA.     

A global approach to reactive transport: application to the MoMas benchmark

Water resource management involves numerical simulations in order to study contamination of groundwater by chemical species. Not only do the aqueous components move due to physical advection and dispersion processes, but they also react together and with fixed components. Therefore, the mass balance couples transport and chemistry, and reactive transport models are partial differential equations coupled with nonlinear algebraic equations. In this paper, we present a global method based on the method of lines and differential algebraic system (DAE) solvers. At each time step, nonlinear systems are solved by a Newton-LU method. We use this method to carry out numerical simulations for the reactive transport benchmark proposed by the MoMas research group. Although we study only 1D computations with a specific geochemical system, several difficulties arise. Numerical experiments show that our method can solve quite difficult problems, get accurate results and capture sharp fronts.