Experimental determination of growth rate effect on U and Mg partitioning between aragonite and fluid at elevated U concentration

Results are reported from an experimental study in which the partitioning of U and Mg between aragonite and an aqueous solution were determined as a function of crystal growth rate. Crystals, identified as aragonite by X-ray diffractometry and micro-Raman spectroscopy, were grown by diffusion of CO₂ from an ammonium carbonate source into a calcium-bearing solution at temperatures of 22 and 53 °C. Hemispherical bundles (spherulites) of aragonite crystals were produced, the growth rates of which decreased monotonically from the spherulite interiors to the edges and thus provide the opportunity to examine the influence of growth rate on crystal composition. Element concentration ratios were measured using electron microprobe (EMP) and fluid composition was determined by inductively coupled plasma-mass spectrometry (ICP-MS) and atomic absorption (AA). Growth rates were determined directly by addition of a Dy spike to the fluid during the experiment that was subsequently located in an experimentally precipitated spherulite using secondary ion mass spectrometry (SIMS). At 22 °C both U/Ca and Mg/Ca partition coefficients exhibited a strong growth rate dependence when crystal growth rates were low, and became independent of growth rate when crystal growth rates were high. The U/Ca ratios in aragonite increase between 22 and 53 °C; in contrast Mg/Ca ratios show inverse dependence on temperature.     

The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

Nature of the chemical heterogeneity of the continental lithospheric mantle

The paper reports data on the chemical composition of mantle peridotite xenoliths from kimberlites and alkaline basalts that represent the continental lithospheric mantle (CLM) beneath Early Precambrian and Late Proterozoic-Cenozoic structures, respectively. In order to identify compositional trends during the melting of primitive material and propose the most reliable criteria for constraining the conditions of this process and its degree, we analyzed literature data on the melting of spinel and garnet peridotites within broad temperature and pressure ranges. It was determined that the degree of melting (F%) of pristine peridotite of composition close to that of the primitive mantle (PM) can be deduced from the Mg/Si and Al/Si ratios in the residue; an equation was proposed for evaluating F from the Mg/Si ratio. The Ca/Al ratio of residues at low (1–1.5 GPa) pressures and degrees of melting from 2–3 to 20–25% increases several times but decreases with increasing F at pressures higher than 3 GPa. The Na partition coefficient between melt and residue decreases at increasing pressure and approaches one at a pressure close to 20 GPa. Residues after low-degree melting are strongly depleted in Ti, Zr, Y, and Nb but are enriched in Cr. The application of these criteria to the composition of xenoliths brought to the surface from the mantle occurring beneath tectonic structures of various age led us to conclude that compositional heterogeneities of CLM (particularly the variations in the concentrations of major and certain siderophile elements) are controlled, first of all, by the melting of the mantle source material. These processes occurred under various thermodynamic conditions (T, P, and $ f_{O_2 } $ f_{O_2 } ) and differed in their intensity, and this predetermined the compositional diversity of the residual mantle material (its concentrations of Mg, Al, Si, Ca, Na, K, Ni, Co, V, and Cr). Our results are principally consistent with the hypothesis of the global magmatic ocean. It is thought that the early phases of its consolidation were variably controlled by the fractionation of minerals, for example, majorite. Moreover, heterogeneities in the distribution of siderophile elements could be partly predetermined by changes in the properties of these elements at ultrahigh temperatures and pressures. The processes of partial melting were the most intense during the early evolution of the mantle (perhaps, in the Early Precambrian), and hence, the mantle has different chemical composition beneath Archean cratons and Phanerozoic foldbelts.     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Liquid composition-dependence of calcium isotope fractionation during diffusion in molten silicates

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but ⁴⁴Ca/⁴⁰Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al₂O₃, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.     

Hydrochemistry and quality assessment of groundwater in part of NOIDA metropolitan city,Uttar Pradesh

An attempt has been made to study the groundwater geochemistry in part of the NOIDA metropolitan city and assessing the hydrogeochemical processes controlling the water composition and its suitability for drinking and irrigation uses. The analytical results show that Na and Ca are the major cations and HCO₃ and Cl are the major anions in this water. The higher ratios of Na+K/TZ⁺ (0.2–0.7), Ca+Mg/HCO₃ (0.8–6.1); good correlation between Ca-Mg (0.75), Ca-Na (0.77), Mg-Na (0.96); low ratio of Ca+Mg/Na+K (1.6), Ca/Na (1.03), Mg/Na (0.64), HCO₃/Na (1.05) along with negative correlation of HCO₃ with Ca and Mg signify silicate weathering with limited contribution from carbonate dissolution. The hydro-geochemical study of the area reveals that many parameters are exceeding the desirable limits and quality of the potable water has deteriorated to a large extent at many sites. High concentrations of TDS, Na, Cl, SO₄, Fe, Mn, Pb and Ni indicate anthropogenic impact on groundwater quality and demand regional water quality investigation and integrated water management strategy. SAR, %Na, PI and Mg-hazard values show that water is of good to permissible quality and can be used for irrigation. However, higher salinity and boron concentration restrict its suitability for irrigation uses at many sites.     

Geochemistry of sulphate-bearing water of Akra Kaur Dam,Gwadar, Balochistan,Pakistan and its assessment for drinking and irrigation purposes

This paper is an attempt to study the geochemistry of Akra Kaur Dam (AKD) water, north of Gwadar city, southern Balochistan. Representative water samples were collected from AKD reservoir to assess the suitability of water for drinking and agriculture purposes. The major ionic composition is suggestive for freshwater. The average ionic composition demonstrate SO₄ > Ca > Na > Cl > HCO₃ > Mg > K. The plots on Piper diagram reflected Ca–Mg–SO₄ type of water facies. High Ca/SO₄ and Ca/Mg ratios revealed that the water has influence of gypsum dissolution. The negative ratio of chloro-alkaline indices indicated reverse exchange between Ca and Mg in water occurred with Na and K in rocks. The pH, electrical conductivity, total dissolved salts, Ca, Mg, Na, K, HCO₃, Cl and SO₄ concentrations in the dam water were below the permissible limit, however, Na and SO₄ were above the desirable limit, set by the World Health Organization. Important parameters such as residue sodium carbonate, sodium percent, sodium adsorption ratio, permeability index, magnesium content and Kelley’s ratio were calculated to evaluate the suitability of water for irrigation purpose. The result were compared with standard permissible limits and found satisfactory. The health and agriculture hazards of sulphate-bearing water were also discussed.     

Origin and evolution of formation water at the Jujo–Tecominoacán oil reservoir,Gulf of Mexico. Part 1: Chemical evolution and water–rock interaction

The origin and evolution of formation water from Upper Jurassic to Upper Cretaceous mudstone–packstone–dolomite host rocks at the Jujo–Tecominoacán oil reservoir, located onshore in SE-Mexico at a depth from 5200 to 6200 m.b.s.l., have been investigated, using detailed water geochemistry from 12 producer wells and six closed wells, and related host rock mineralogy. Saline waters of Cl–Na type with total dissolved solids from 10 to 23 g/L are chemically distinct from hypersaline Cl–Ca–Na and Cl–Na–Ca type waters with TDS between 181 and 385 g/L. Bromine/Cl and Br/Na ratios suggest the subaerial evaporation of seawater beyond halite precipitation to explain the extreme hypersaline components, while less saline samples were formed by mixing of high salinity end members with surface-derived, low salinity water components. The dissolution of evaporites from adjacent salt domes has little impact on present formation water composition. Geochemical simulations with Harvie-Mφller-Weare and PHRQPITZ thermodynamic data sets suggest secondary fluid enrichment in Ca, HCO₃ and Sr by water–rock interaction. The volumetric mass balance between Ca enrichment and Mg depletion confirms dolomitization as the major alteration process. Potassium/Cl ratios below evaporation trajectory are attributed to minor precipitation of K feldspar and illitization without evidence for albitization at the Jujo–Tecominoacán reservoir. The abundance of secondary dolomite, illite and pyrite in drilling cores from reservoir host rock reconfirms the observed water–rock exchange processes. Sulfate concentrations are controlled by anhydrite solubility as indicated by positive SI-values, although anhydrite deposition is limited throughout the lithological reservoir column. The chemical variety of produced water at the Jujo–Tecominoacán oil field is related to a sequence of primary and secondary processes, including infiltration of evaporated seawater and original meteoric fluids, the subsequent mixing of different water types and the formation of secondary minerals by water–rock interaction. A best fit between measured and calculated reservoir temperatures was obtained with the Mg–Li geothermometer for high salinity formation water (TDS > 180 g/L), whereas Na–K, Na–Ka–Ca and quartz geothermometers are partially applicable for less salinite water (TDS < 23 g/L).     

Temperature effects on the calcite skeletal composition of deep-water gorgonians (Isididae)

We test for and calibrate a proxy for ocean temperature based on the skeletal composition of the widely distributed, deep-sea gorgonians in the family Isididae (bamboo corals), through use of three complementary methods: a short-term comparison of element/Ca ratios to a four-year temperature record, a long-term comparison with oceanographic records spanning forty years, and a geographic comparison of Isidids collected at sites ranging from the tropics to Antarctica. The assays consistently support a temperature-dependency for Mg/Ca ratios and suggest S/Ca is indirectly affected by temperature, but indicate little or no effect of temperature on P/Ca and Sr/Ca. The consensus relationship between Mg/Ca and temperature for Isidid calcite from the comparisons with the temperature time-series is T = −0.505 + 0.048 Mg/Ca, where T is in °C, Mg/Ca is in mmol/mol, and the applicable range is 3-6 °C. The results of the geographic assay, though imprecise, suggest the applicable range extends to temperatures below freezing. The scatter of data points around the regression of temperature and Mg/Ca is wide in all assays. This could reflect the effect of factors other than temperature on Mg/Ca ratios, but is also likely to reflect limitations of the field data, the effects of assumed constant growth rates in the corals and instrumental analytical error. The combined effects of micro-scale variability in growth rates and wide confidence intervals for each data point suggests that environmental reconstruction from Isidid internode calcite from sparse data or at time scales less than decades be done with caution. Comparisons within and among colonies do not indicate strong vital effects on ontogenetic variability in the corals, other than possibly close to the central pore of the coral. However, similar Mg/Ca ratios for Isidids from Antarctic and more temperate regions suggest adaptation to local conditions and hence a role for physiology at higher taxonomic levels, at least. Taxonomically higher level vital effects are also suggested by large differences between gorgonian families in their regressions between Mg/Ca and temperature, by Mg/Ca ratios that overlap over a wide temperature and habitat range, and for a non-linear relationship between temperature and the slope of the Mg/Ca-temperature relationship across the order.     

Absorbed complex of riverine solid substances and its role in geochemical balance of the ocean

Data on the composition of the absorbed complex of riverine solid substances and its transformation in marine environments obtained from field observations and experimental investigations are systematized and generalized. Average values of the specific surface of the riverine suspended particulates (~20 m²/g) and the total exchange capacity of solid substances of the continental runoff (~28 mg-equiv/100 g or 280 g-equiv/t of the transported terrigenous material) are determined. It is shown that the composition of the absorbed complex in the riverine suspended particulates, as well as bottom sediments of rivers and inland water bodies differs principally from that of bottom sediments in oceans and seas: Ca dominates in the first case; Na, in the second case. When the riverine terrigenous material enters oceans and seas, the composition of the absorbed complex is subjected to the ion-exchange transformation reflected in the replacement of exchange Ca (~80%) mainly by Na and also by K and Mg of seawater. This process is responsible for the influx of 45.5 Mt/yr of dissolved Ca to ocean and the removal of 37.3, 12.8, and 3.9 Mt/yr of Na, K, and Mg, respectively. The relative transport of Ca, Na, K, and Mg to ocean with the river runoff is +7.5,–12.3,–22.4, and–2.6%, respectively.     

黑龙江东宁金厂金矿土壤离子电导率异常特征、离子成份及找矿预测

为了解黑龙江东宁金厂金矿体土壤离子的电导率异常特征,查明金矿体中土壤离子电导率成分的离子组成以及不同种类离子的含量变化关系对电导率的贡献大小,初步探讨矿区土壤离子电导率异常的形成机理,本文对金厂金矿开展了土壤离子电导率测量,取得以下认识:(1)发现多个具有成矿远景的离子电导率异常区,经深部工程验证具有隐伏的金矿体;(2)组成土壤离子电导率异常的离子成分主要是HCO-3、SO2-4、Ca2+、Cl-、K+、Na+、F-、Mg2+、Mn2+等一套水可溶性离子,经过相关分析得出金矿电导率异常与各离子的相关系数为HCO-3>Ca2+>SO2-4>Cl->K+>Na+>F->Mg2+>Mn2+。     

熔体-溶液体系中元素分配系数:新资料及其研究方向

基于近几年来国内外学者测得的熔体-溶液体系中F、Cl、P、CO_2、B、Au、Pb、Zn、Cu、Fe、Mg、Li、Rb、Cs、K、Na、Ca、Sr、Ba、Co、Ni、Be、Mo、W、Si、Al、REE、Sc、Ti、U、Th、Zr、Hf、Nb、Pt、Ir、Pd等元素的分配系数,从元素性质、溶液成分(阴离子和阳离子)、熔体成分和物理化学条件等方面进一步分析总结了分配系数变化规律,并提出了预测未知元素分配系数的元素性质准则、溶液成分准则、熔体成分准则和物理化学条件准则,最后指出了这一研究领域今后的研究方向。     

Hydrogeochemistry and sensitivity to acidification of streamwaters in crystalline areas of northern Fennoscandia

About 6,400 water samples were collected from small catchments in northern Finland and Norway above 66° N latitude as a part of the Nordkalott Project carried out jointly by the Geological Surveys of Finland, Norway, and Sweden. Electrical conductivity (EC) was measured in situ and Ca, Mg, Sr, Ba, Na, K, Si, Fe, Mn, Al, and Zn concentrations were determined from filtered and acidified samples by the ICAP method. The relative abundance of mafic, ultramafic, and carbonate rock components in the catchments is the most influential factor controlling the EC values and the main cation concentrations (Ca, Mg, Sr). These components also determine the HCO₃ alkalinity or acid-neutralizing capacity (ANC) of streamwater. In the northern coastal belt, Na is derived largely from airborne sea salts, but in the southwestern corner of the research area it may be derived partly from relict sea salts in sediments. The concentrations of Na, K, and Si do not depend solely on the lithological environment. Fe and, to a lesser extent, Mn and Al occur in the highest abundances in the low-lying, intensely paludified southern part of the area, suggesting that these metals tend to go into solution and are transported in complexed forms with dissolved and colloidic humic matter. The areal distribution patterns of the main cations (Ca, Mg, Sr) and of some heavy metals (Fe, Mn) in streamwater are fairly consistent with those of till and minerogenic stream sediments, although, in a statistical approach, only a few significant correlation coefficients were established.     

Interdiffusion of Na,K,and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coefficient of net-work modifiers (mainly Na, K, and Ca) in a two-phase melt-NaCl system, in which the melts are granitic and the system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 – 1400°C, pressures of 0.001 × 10⁸ – 2 × 10⁸ Pa, and initial H₂O contents of 0 wt% –6.9 wt% in the granitic melts. The diffusion coefficients of Fe and Mg were difficult to resolve. In all experiments a NaCl melt was present as well. In the absence of H₂O, the diffusion of net-work modifiers follows an Arrhanious equation at 1 × 10⁵ Pa: lgD_ca=−3. 88−5140/T, lgD_k =−3. 79−4040/T, and lgD_Na, =−4.99−3350/T, where D is in cm² /s andT is in K. The diffusion coefficients of Ca, Na, K, and Fe increase non-linearly with increasing H₂O content in the melt. The presence of about 2 wt% H₂O m the melt will lead to a dramatical increase in diffusivity, but higher H₂O content has only a minor effect. This change is probably the result of a change in the melt structure when H₂O is present. The diffusion coefficients measured in this study are significantly different from those in previous works. This may be understood in terms of the “transient two-liquid equilibrium” theory. Element interdiffusion depends not only on its concentration, but also on its activity co-efficient gradient, which is reflected by the distribution coefficient, of the two contacting melts.     

Crystal-chemistry and cation ordering in the system diopside-jadeite: A detailed study by crystal structure refinement

The Nybö eclogite pod in Norway is characterized by a great variety of clinopyroxene compositions with Jd contents ranging from less than 5% up to nearly 80%, whilst Ac+Hd contents remain almost constant (mostly within 10±5%).Unconstrained X-ray structure refinement has been carried out on 16 pyroxene crystals (8 with C2/c and 8 with P2/n space group) from the Nybö eclogite, and also on one omphacite crystal (from Lago Mucrone in the Sesia-Lanzo Zone, Western Alps) which displays the highest degree of cation ordering yet described. The final discrepancy factors range from 0.014 to 0.029. The population of the sites has been determined on the basis of bond length considerations and of the results of the site occupancy refinement. Six of these crystals were subsequently analysed by electron microprobe.The tetrahedral sites are occupied by Si with negligible amounts of Al. Al, Mg, Fe³⁺ and Fe²⁺ occur at the octahedral sites; in the ordered P2/n crystals Al and Fe³⁺ are concentrated at the M11 site, whilst Mg and Fe²⁺ are concentrated and the M1 site. The eight-coordinated sites contain Ca and Na with negligible amounts of Fe and/or Mg. Ordering of Ca and Na takes place in the P2/n samples in such a way that in the most ordered crystal the M2 site contains almost exactly 0.75 Na+0.25 Ca and the M21 site 0.25 Na+0.75 Ca.Some geometrical features of the tetrahedra as well as of the octahedra (e.g. tetrahedral quadratic elongation and TILT angle) are not a simple linear function of composition, even when no change in space group occurs. The crystals evidently do not behave like a binary system of the two components, Di and Jd, but behave rather as if the composition Di_0.50 Jd_0.50 was a distinct end member.The boundaries between disordered and ordered phases in the Nybö pyroxenes fall at about 0.35 and 0.65 Jd/(Di+ Jd), in close agreement with the previous TEM investigations.The degree of order varies with composition following a bell-shaped curve: different coaxial bell-shaped curves can be drawn for crystals which have similar compositions but come from different metamorphic environments. The order vs composition diagrams may be useful for the interpretation of the P-T-t histories of the host rocks.     

Determination of melt influence on divalent element partitioning between anorthite and CMAS melts

We propose a theory for crystal-melt trace element partitioning that considers the energetic consequences of crystal-lattice strain, of multi-component major-element silicate liquid mixing, and of trace-element activity coefficients in melts. We demonstrate application of the theory using newly determined partition coefficients for Ca, Mg, Sr, and Ba between pure anorthite and seven CMAS liquid compositions at 1330 °C and 1 atm. By selecting a range of melt compositions in equilibrium with a common crystal composition at equal liquidus temperature and pressure, we have isolated the contribution of melt composition to divalent trace element partitioning in this simple system. The partitioning data are fit to Onuma curves with parameterizations that can be thermodynamically rationalized in terms of the melt major element activity product (a_Al2O3)(a_SiO2)² and lattice strain theory modeling. Residuals between observed partition coefficients and the lattice strain plus major oxide melt activity model are then attributed to non-ideality of trace constituents in the liquids. The activity coefficients of the trace species in the melt are found to vary systematically with composition. Accounting for the major and trace element thermodynamics in the melt allows a good fit in which the parameters of the crystal-lattice strain model are independent of melt composition.     

Chemical composition of river particulates in eastern China

A total of 42 aquatic particulate sample:, (suspended matter and < 63 m surficial sediments) was collected from 11 large rivers in eastern China. Contents of both major elements (Al, Si, Ca, Mg, K, Na, Ti, Fe, Mn) and trace elements (Cu, Pb, Zn, Cd, Cr, Co, Ni, V) in the particulate samples were analyzed. The geographic variations of river particulate compositions were studied. The results showed that the Yellow River particulates contained a notably high content of Ca and a low content of Al. Except for the Yellow River, A1 contents in particulates increased from the northern rivers to the southern rivers, while K and Na decreased. Trace elements were relatively enriched in the southern river particulates. The geographic variations seemed to be related to the weathering types and geological background within the river basins. The average composition of river particulates in China was then estimated. Based on the Chinese river data from this paper, as well as on the literature data for other main world rivers, a new estimation of the global average particulate composition was reported. Since the earlier estimations in the literature were not concerned with or at best concerned only with few of the Chinese rivers which contribute a major proportion to the global load of river particulates, this new estimation may be more reasonable.     

Spatial geochemical variation of major and trace elements in the marine sediments of Mumbai Harbor Bay

The resulting concentration data sets of major (Na, K, Mg, Ca and Fe) and trace elements (Cu, Ni, Co and Mn) in bed and suspended sediments were used to evaluate the enrichment factor for anthropogenic influences and principal component analysis for identifying the origin of source contributions in the studied area. Normalization of metals to Fe indicated that high enrichment factors in the bed sediment were in the order of Co > Cu > Na > Ca > Ni except Mg, K and Mn while for suspended sediments, only Co has a high enrichment factor. High enrichment of Co and Cu reflected the contamination of sediments from anthropogenic sources. The high influence of Na and Ca in sediments may be caused for seawater salinization factor. A significant positive correlation among enrichment factors of various elements of interest suggests a common origin/identical behavior during transport in the sediment system.