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The impact of land-use change on the quality of groundwater in the Xiaotjiang watershed, China was assessed for the period 1982–2004. Groundwater samples were collected from 30 monitoring points across the watershed, and were representative of the various changes, determined by remote sensing and geographical information systems. The results indicate that 610 km2 (60% of the total watershed area) were subject to land-use change during the period. The most important changes were the conversion of 135 km2 of forested land to cultivated land, and 211 km2 of unused land to cultivated land. The main impact was ascribed to diffuse pollution from fertilizers applied to newly cultivated land, and from building development. Overall the groundwater pH value was significantly increased, as were the concentrations of ions , , , , and Cl in groundwater whilst the concentrations of Ca2+ and declined. More precisely, in the regions where forested land and unused land were converted into cultivated land, the pH value and the concentrations of Mg2+, , , , , Cl increased whilst the concentrations of Ca2+ and declined. However in the region where cultivated land was converted into construction land, the pH value and the concentrations of Ca2+, Mg2+, , , , , , Cl increased.
Résumé  L’impact des changements de l’utilisation du territoire sur la qualité de l’eau souterraine dans le bassin versant de Xiaojiang, en Chine, a été évalué de 1982 à 2004. Des échantillons d’eau souterraine ont été récoltés à partir de 30 points d’observation éparpillés sur le bassin, représentant les divers changements déterminés par télédétection et système d’information géographique. Les résultats indiquent que 610 km2 (soit 60% de la surface du bassin) ont été sujets à des modifications de l’utilisation du territoire sur cette période. Les changements les plus importants furent la conversion de 135 km2 de forêt et 211 km2 de terres inutilisées en terres cultivées. Le principal impact est attribué à la pollution diffuse des engrais utilisés en agriculture et pour les batiments. De manière générale le pH de l’eau souterraine a augmenté significativement, ainsi que les concentrations des ions , , , , et Cl, tandis que les concentration en Ca2+ et ont diminué. Plus précisément dans les régions transformées en terres cultivées, la valeur du pH et les concentrations en Mg2+, , , , , Cl ont augmenté tandis que les concentrations en Ca2+ et ont diminué. Toutefois dans les régions cultivées converties en zones de construction, le pH et les concentrations en Ca2+, Mg2+, , , , , , Cl ont augmenté.

Resumen  El impacto del cambio en uso de la tierra en la calidad del agua en la cuenca Xiaojiang, China fue evaluado para el periodo 1982–2004. Muestras de agua subterránea fueron tomadas de 30 puntos de monitoreo a través de la cuenca, y fueron representativas de los múltiples cambios, determinados por sensores remotos y sistemas de información geográfica. Los resultados indican que 610 km2 (60% del área total de la cuenca) estaban sujetos a cambios de uso de la tierra durante el periodo estudiado. Los cambios más importantes fueron la conversión de 135 km2 de bosques a tierra cultivada, y 211 km2 de tierra sin uso (ociosa) a tierra cultivada. El impacto principal fue causado por contaminación difusa de fertilizantes aplicados a la tierra recientemente cultivada, y a desarrollo de construcciones. En general el pH en agua subterránea creció significantemente, al igual que las concentraciones de los iones , , , , y Cl en agua subterránea mientras que las concentraciones de Ca2+ y decrecieron. Mas precisamente, en las regiones donde bosque y tierra ociosa fueron convertidas en tierra cultivada, el valor de pH y las concentraciones de Mg2+, , , , , Cl crecieron mientras las concentraciones de Ca2+ y decrecieron. Sin embargo en la región donde tierra cultivada fue convertida en construcciones, el valor de pH y las concentraciones de Ca2+, Mg2+, , , , , , Cl crecieron.
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3.
The thermodynamic stability constants for the hydrolysis and formation of mercury (Hg2+) chloride complexes
have been used to calculate the activity coefficients for Hg(OH) n (2–n)+ and HgCl n (2–n)+ complexes using the Pitzer specific interaction model. These values have been used to determine the Pitzer parameters for the hydroxide and chloro complexes and C ML). The values of and have been determined for the neutral complexes (Hg(OH)2 and HgCl2). The resultant parameters yield calculated values for the measured values of log to  ±0.01 from I  =  0.1 to 3 m at 25°C. Since the activity coefficients of and are in reasonable agreement with the values for Pb(II), we have estimated the effect of temperature on the chloride constants for Hg(II) from 0 to 300°C and I = 0–6 m using the Pitzer parameters for complexes. The resulting parameters can be used to examine the speciation of Hg(II) with Cl in natural waters over a wide range of conditions.  相似文献   

4.
Spherical geometry of quaternions is employed to characterize the Bingham distribution on the 3-dimensional sphere as being uniquely composed of a bipolar, a circular and a spherical component. A new parametrization of its dispersion parameters provides a classification of patterns of crystallographic preferred orientations (CPO, or textures). It is shown that the Bingham distribution can represent most types of ideal CPO patterns; in particular single component, fiber and surface textures are represented by rotationally invariant bipolar, circular and spherical distributions, respectively. Pole figures of given crystal directions are derived by the spherical Radon transform of the Bingham probability density function of rotations, which are displayed for general and special cases.  相似文献   

5.
Multivariate statistical analyses have been extensively applied to geochemical measurements to analyze and aid interpretation of the data. Estimation of the covariance matrix of multivariate observations is the first task in multivariate analysis. However, geochemical data for the rare elements, especially Ag, Au, and platinum-group elements, usually contain observations the below detection limits. In particular, Instrumental Neutron Activation Analysis (INAA) for the rare elements produces multilevel and possibly extremely high detection limits depending on the sample weight. Traditionally, in applying multivariate analysis to such incomplete data, the observations below detection limits are first substituted, for example, each observation below the detection limit is replaced by a certain percentage of that limit, and then the standard statistical computer packages or techniques are used to obtain the analysis of the data. If a number of samples with observations below detection limits is small, or the detection limits are relatively near zero, the results may be reasonable and most geological interpretations or conclusions are probably valid. In this paper, a new method is proposed to estimate the covariance matrix from a dataset containing observations below multilevel detection limits by using the marginal maximum likelihood estimation (MMLE) method. For each pair of variables, sayY andZ whose observations containing below detection limits, the proposed method consists of three steps: (i) for each variable separately obtaining the marginal MLE for the means and the variances, , , , and forY andZ: (ii) defining new variables by and and lettingA=C+D andB=CD, and obtaining MLE for variances, and forA andB; (iii) estimating the correlation coefficient YZ by and the covariance YZ by . The procedure is illustrated by using a precious metal geochemical data set from the Fox River Sill, Manitoba, Canada.  相似文献   

6.
Solubility experiments were conducted for the dissolution reaction of brucite, Mg(OH)2 (cr): Experiments were conducted from undersaturation in deionized (DI) water and 0.010–4.4 m NaCl solutions at 22.5°C. In addition, brucite solubility was measured from supersaturation in an experiment in which brucite was precipitated via dropwise addition of 0.10 m NaOH into a 0.10 m MgCl2 solution also at 22.5°C. The attainment of the reversal in equilibrium was demonstrated in this study. The solubility constant at 22.5°C at infinite dilution calculated from the experimental results from the direction of supersaturation by using the specific interaction theory (SIT) is: with a corresponding value of 17.0 ± 0.2 (2σ) when extrapolated to 25°C. The dimensionless standard chemical potential (μ°/RT) of brucite derived from the solubility data in 0.010 m to 4.4 m NaCl solutions from undersaturation extrapolated to 25°C is −335.76 ± 0.45 (2σ), with the corresponding Gibbs free energy of formation of brucite, , being −832.3 ± 1.1 (2σ) kJ mol−1. In combination with the auxiliary thermodynamic data, the is calculated to be 17.1 ± 0.2 (2σ), based on the above Gibbs free energy of formation for brucite. This study recommends an average value of 17.05 ± 0.2 in logarithmic unit as solubility constant of brucite at 25°C, according to the values from both supersaturation and undersaturation. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.  相似文献   

7.
Interaction of freshly precipitated silica gel with aqueous solutions was studied at laboratory batch experiments under ambient and near neutral pH-conditions. The overall process showed excellent reversibility: gel growth could be considered as an opposite process to dissolution and a linear rate law could be applied to experimental data. Depending on the used rate law form, the resulting rate constants were sensitive to errors in parameters/variables such as gel surface area, equilibrium constants, Si-fluxes, and reaction quotients. The application of an Integrated Exponential Model appeared to be the best approach for dissolution data evaluation. It yielded the rate constants k dissol ∼ (4.50 ± 0.68) × 10−12 and k growth ∼ (2.58 ± 0.39) × 10−9 mol m−2 s−1 for zero ionic strength. In contrast, a Differential Model gave best results for growth data modeling. It yielded the rate constants k dissol ∼ (1.14 ± 0.44) × 10−11 and k growth ∼ (6.08 ± 2.37) × 10−9 mol m−2 s−1 for higher ionic strength (I ∼ 0.04 to 0.11 mol L−1). The found silica gel solubility at zero ionic strength was somewhat lower than the generally accepted value. Based on the and standard Gibbs free energy of silica gel formation was calculated as and −850,318 ± 20 J mol−1, respectively. Activation energies for silica gel dissolution and growth were determined as and respectively. An universal value for growth of any silica polymorph, is not consistent with the value for silica gel growth, which questions the hypothesis about one unique activated complex controlling the silica polymorph growth.  相似文献   

8.
本研究分别利用顶空平衡法与qPCR技术测定了2018年春季黄、渤海5个典型站位柱状沉积物中甲烷(CH4)和氧化亚氮(N2O)浓度及产甲烷菌与硫酸盐还原菌功能基因拷贝数,并分析了其与间隙水中相关环境因子的关系。沉积物上方水文条件的差异以及其中复杂的碳氮生物地球化学过程使得CH4和N2O浓度呈现出明显的空间和垂直变化。结果显示,沉积物中CH4浓度为0.23~0.92 μmol·kg-1,N2O浓度为18.90~104.96 nmol·kg-1。总体来说,渤海沉积物中CH4和N2O平均浓度高于黄海。垂向分布上,CH4浓度均随深度增加逐渐升高, $\text{SO}_{4}^{2-}$浓度随深度增加逐渐降低,并与CH4浓度呈镜像关系,产甲烷菌与硫酸盐还原菌的丰度也遵循着同样规律,这表明沉积物中产甲烷作用受$\text{SO}_{4}^{2-}$浓度的抑制。 mcrA基因拷贝数平均值为渤海低于黄海。除3500-7站外,沉积物中mcrA基因拷贝数随深度增加而升高。各站位mcrA 基因丰度与CH4浓度均无显著相关性,且mcrA丰度与$\text{SO}_{4}^{2-}$浓度之间也未检测到显著相关性。dsrB基因拷贝数远高于mcrA基因拷贝数,且两者相差至少两个数量级。 dsrB基因拷贝数随深度逐渐增加,直至10 cm左右,随后至沉积物底部逐渐减少。各站位dsrB基因拷贝数与CH4浓度剖面略有镜像关系,但均未检测到显著负相关性。以上结果均表明沉积物中存在着同时消耗沉积物中$\text{SO}_{4}^{2-}$与CH4的其他作用。N2O浓度随深度增加先降低,在深度30 cm以下逐渐升高。间隙水中$\text{NO}_{3}^{-}$和$\text{NO}_{2}^{-}$浓度均随深度减小,同时$\text{NH}_{4}^{+}$浓度与其呈相反趋势。沉积物中N2O与$\text{NO}_{2}^{-}$及$\text{NO}_{3}^{-}$浓度均呈正相关,且前者相关性较高,说明反硝化作用是沉积物中N2O产生的主要过程。这些结果为进一步了解近岸陆架海域沉积物中CH4和N2O的来源、分布及碳氮生物地球化学循环提供了参考资料。  相似文献   

9.
A nonuniform glacio-isostatic uplift results in differential uplift for different parts of a lake. If the lake outlet is situated in the area with the greatest rate of uplift, then the lake will be continuously transgressed. Ancient lake levels can be estimated by dating transgressed peat at different depths in such a lake. Two lakes in southwestern Sweden have been investigated by this method and the course of glacio-isostatic uplift has been determined empirically. The uplift can be expressed by an exponential function through the following formula
  相似文献   

10.
This paper presents a design approach for strip footings upon glacier ice. Safety against ultimate limit state is proved by the geotechnical slip-line field solution by Prandtl. Glacier ice at 0°C can be modelled as purely cohesive material. Statistical evaluation of uniaxial compression tests with high strain rate revealed a mean value of the cohesion of 600 kPa and a characteristic value c k = 355 kPa (5% fractile). With a coefficient of variation V c = 0.3, the partial safety factor turns out to be γ c = 1.9. An approximate solution for estimating the creep settlement rate is presented to check the serviceability limit state: with the width b of the strip foundation, p the foundation pressure and for ice at 0°C. Experiences on Stubai glacier with grate shaped footings showed that creep settlements occurring per year due to maximum foundation pressures 250 kPa did not influence the operation and the maintenance of the cable cars.  相似文献   

11.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H2O t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O t ) and water-rich (~2 wt% H2O t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
where is the water diffusivity at 1 wt% H2O t in m2/s, T is the temperature in K and P is the pressure in MPa. The above equation reproduces the experimental data (14 runs in total) with a standard fit error of 0.15 log units. It can be employed to model degassing of peralkaline melts at water contents up to 2 wt%.  相似文献   

12.
The thermodynamic calculation of dehydration reacton suggests very low activity of H2O during metamorphic peak of the Archaean granulite complex in the region studied.The αH2O values for Al-rich gneiss and hypersthene biotite gneiss-granulite in the Taipingzhai region are usually between 0.10 and 0.20,and those in the Louzishan region are 0.15-0.25.The fugacity of O2 in terms of lgf O2 in whole region ranges form-8to-14.The average coefficients of (δμH2O/δHMg^Bt)and(δμO2/δXMg^Bt)in the Taipingzhai region are-0.293 and-1.60 respectively,and those in the Louzishan region are-0.364and-1.420.The activity of H2O is very low in the whole region,but its values and other data mentioned above are considerably constant from place to place within a given region,even in rocks of dirrerent lithological characters.However,they show a certain gradient between different regions.Such characteristics are compatible with the genetic mechanism known as“carbonic metamorphism” put forward by Newton et al.,i.e.,the α H2O during the peak stage is controlled by permeation of pervasive CO2 influx of the mantle source,and shows features of external buffering.  相似文献   

13.
Stochastic modeling of gold mineralization in the Champion lode of Kolar gold fields was carried out using assay data taken from developmental headings. After dividing the lode into 71 horizontal and 18 vertical strata, autoregressive (AR), moving average (MA), and autoregressive and moving average (ARMA) models were developed and applied. The model selection with the acf and pacf for the various strata showed that in most of the cases, ARMA modeling of first-order would forecast gold headings with a reasonable degree of confidence. This was substantiated by comparing the coefficients of variation. From a parsimony point of view, AR (1) model may also be considered valid. The best overall models are: ARMA (1, 1), ; AR (1), , where at is N (0, a 2 ), x is in logarithms of in-dwt, and t is in block units of 100 ft. The applications of these models to a specific stratum are given. These models would also be helpful to describe the characteristics of the gold mineralization process of this lode.  相似文献   

14.
This systematic study was carried out with objective to delineate the various sources responsible for \(\hbox {NO}_{3}^{-}\) contamination and \(\hbox {F}^{-}\) enrichment by utilizing statistical and graphical methods. Since Central Ground Water Board, India, indicated susceptibility of \(\hbox {NO}_{3}^{-}\) contamination and \(\hbox {F}^{-}\) enrichment, in most of the groundwater, \(\hbox {NO}_{3}^{-}\) and \(\hbox {F}^{-}\) concentration primarily observed \({>}45\) and \({>}1.5~\hbox {mg/L}\), respectively, i.e., higher than the permissible limit for drinking water. Water Quality Index (WQI) indicates \({\sim }22.81\%\) groundwater are good-water, \({\sim }71.14\%\) groundwater poor-water, \({\sim }5.37\%\) very poor-water and 0.67% unsuitable for drinking purpose. Piper diagram indicates \({\sim }59.73\%\) groundwater hydrogeochemical facies are Ca–Mg–\(\hbox {HCO}_{3 }\) water-types, \({\sim }28.19\%\) Ca–Mg–\(\hbox {SO}_{4}\)–Cl water-types, \({\sim }8.72\%\) Na–K–\(\hbox {SO}_{4}\)–Cl water-types and 3.36% Na–K–\(\hbox {HCO}_{3 }\) water-types. This classification indicates dissolution and mixing are mainly controlling groundwater chemistry. Salinity diagram indicate \({\sim }44.30\%\) groundwater under in low sodium and medium salinity hazard, \({\sim }49.66\%\) groundwater fall under low sodium and high salinity hazard, \({\sim }3.36\%\) groundwater fall under very-high salinity hazard. Sodium adsorption ratio indicates \({\sim }97\%\) groundwater are in excellent condition for irrigation. The spatial distribution of \(\hbox {NO}_{3}^{-}\) indicates significant contribution of fertilizer from agriculture lands. Fluoride enrichment occurs in groundwater through the dissolution of fluoride-rich minerals. By reducing the consumption of fertilizer and stress over groundwater, the water quality can be improved.  相似文献   

15.
Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)2L-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$ The formation constant for this reaction at 25 °C and 0.7 molkg-1 ionic strength is $K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)2 $CO_3^ - $ concentration inseawater at 25 °C is on the order of 2 μmol kg-1. Dueto the presence of B(OH)2 $CO_3^ - $ , theboric acid dissociation constant ( $K\prime _B $ ) in natural seawaterdiffers from $K\prime _B $ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO2 fugacity, pH, totalcarbon and alkalinity in seawater.  相似文献   

16.
Shallow aquifer vulnerability has been assessed using GIS-based DRASTIC model by incorporating the major geological and hydrogeological factors that affect and control the groundwater contamination in a granitic terrain. It provides a relative indication of aquifer vulnerability to the contamination. Further, it has been cross-verified with hydrochemical signatures such as total dissolved solids (TDS), \(\hbox {Cl}^{-},\, \hbox {HCO}_{3}^{-},\, \hbox {SO}_{4}^{2-}\) and \(\hbox {Cl}^{-}/\hbox {HCO}_{3}^{-}\) molar ratios. The results show four zones of aquifer vulnerability (i.e., negligible, low, moderate and high) based on the variation of DRASTIC Vulnerability Index (DVI) between 39 and 132. About 57% area in the central part is found moderately and highly contaminated due to the 80 functional tannery disposals and is more prone to groundwater aquifer vulnerability. The high range values of TDS (2304–39,100 mg/l); \(\hbox {Na}^{+}\)(239– 6,046 mg/l) and \(\hbox {Cl}^{-}\) (532–13,652 mg/l) are well correlated with the observed high vulnerable zones. The values of \(\hbox {Cl}^{-}/\hbox {HCO}_{3}^{-}\) (molar ratios: 1.4–106.8) in the high vulnerable zone obviously indicate deterioration of the aquifer due to contamination. Further cumulative probability distributions of these parameters indicate several threshold values which are able to demarcate the diverse vulnerability zones in granitic terrain.  相似文献   

17.
High-precision WBVR photoelectric observations of the eclipsing binary GG Ori (B9.5V+B9.5V), which has an eccentric orbit (e=0.22), were carried out in 1988–2001 at the Moscow and high-altitude Tian-Shan Observatories of the Sternberg Astronomical Institute. The aim of these observations was investigation of the apsidal motion of the system. Analysis of the resulting 12-year series of observations enabled us for the first time to accurately (to within 11%) measure the rate of rotation of the orbit $\dot \omega _{obs} = 0.046 \pm 0.005^\circ /yr$ and to appreciably improve estimates of the photometric and absolute parameters. The observed value of $\dot \omega _{obs}$ is 28% higher than the theoretical prediction of $\dot \omega _{th} = \dot \omega _{cl} + \dot \omega _{rel} = 0.036 \pm 0.001^\circ /yr$ . The relativistic part of the apsidal motion in this system $\dot \omega _{rel}$ is a factor of 2.5 greater than the classical term $\dot \omega _{cl}$ due to the tidal and rotational deformations of the components. The interstellar extinction in the direction of the star (at a distance of r=425 pc) is very large (A v =1.75 m ). A number of recently published results (in particular, the conclusion that the components of this eclipsing binary are young) are confirmed.  相似文献   

18.
Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.  相似文献   

19.
In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO2 and ZrO2; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO2 contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO2 contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO2 concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO2 in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.  相似文献   

20.
Crystallochemical data on metamict davidite from albitites and albitised rocks from the Bichun area (Jaipur district, Rajasthan, India) of Banded Gneissic Complex (BGC) are provided. Davidite occurs as euhedral, subhedral to anhedral crystals in the form of disseminated grains and also as fracture filled veins. The crystals of davidite are up to 8 cm in length and 6 cm in width. The powder X-ray diffraction (XRD) pattern of the heat-treated davidite (at \(900{^{\circ }}\hbox {C}\)) reveals well-defined reflections of crystallographic planes. The calculated unit-cell parameters of the heat treated davidite are: \(\hbox {a}_{0} = \hbox {b}_{0} = 10.3556 \, \text {\AA }\) and \(\hbox {c}_{0} = 20.9067 \, \text {\AA }\), with unit-cell volume \(\hbox {(V)} = 1941.6385 \, \text {\AA }^{3}\); and \({\upalpha }={\upbeta }= 90^{\circ }\) and \({\upgamma }= 120^{\circ }\), which are in agreement with the values of davidite standard. Geochemical data reveals that the investigated davidite contains 51.5–52.6% \(\hbox {TiO}_{2}\), 14.8–15.1% \(\hbox {Fe}_{2} \hbox {O}_{3}\), 9.8–10.2% FeO, 6.97–7.12% \(\hbox {U}_{3} \hbox {O}_{8}\), 6.72–6.92% \(\hbox {RE}_{2} \hbox {O}_{3}\), 3.85–3.61% \(\hbox {K}_{2}\hbox {O}\), 0.9–1.4% \(\hbox {Al}_{2} \hbox {O}_{3}\), and 0.8–1.2% \(\hbox {SiO}_{2}\). The calculated structural formulae of the two davidite crystals are: D-1: \(\hbox {K}_{0.0044/0.004} \hbox {Ba}_{0.0044/0.005} \hbox {Ca}_{0.20/0.20} \hbox {Na}_{0.012/0.012} \hbox {Mn}_{0.053/0.053} \hbox {Mg}_{0.14/0.14} \hbox {Pb}_{0.0076/0.008} \hbox {Fe}_{2.675/2.675} \hbox {Fe}_{1.59/1.59} \hbox {Y}_{0.1175/0.118} \hbox {P}_{0.053/0.053} \hbox {Nb}_{0.008/0.008} \hbox {Sn}_{0.001/0.001} \hbox {Zr}_{0.033/0.033} \hbox {U}_{0.468/0.468} \hbox {Th}_{0.009/0.009} \,\,\hbox {REE}_{0.6829/0.683})_{6.05/6.05} (\hbox {Ti}_{12.15/12.15}\,\, \hbox {Fe}_{1.9022/1.903} \hbox {Si}_{0.372/0.372}\,\, \hbox {Al}_{0.517/0.517}\,\, \hbox {Cr}_{0.018/0.018} \hbox {Co}_{0.009/0.009} \hbox {Ni}_{0.027/0.027})_{15/15} \hbox {O}_{36/36} (\hbox {OH}_{0.319/0.319[]1.681/1.681})_{2/2}\) and D-2: \((\hbox {K}_{0.004/0.004} \hbox {Ba}_{0.005/0.005} \hbox {Ca}_{0.20/0.20} \hbox {Na}_{0.012/0.012} \hbox {Mn}_{0.05/0.05} \hbox {Mg}_{0.094/0.094} \hbox {Pb}_{0.007/0.007} \hbox {Fe}_{2.58/2.58} \hbox {Fe}_{1.71/1.71} \hbox {Y}_{0.112/0.112} \hbox {P}_{0.106/0.106} \hbox {Nb}_{0.006/0.006} \hbox {Sn}_{0.001/0.001} \hbox {Zr}_{0.03/0.03} \hbox {U}_{0.48/0.48} \hbox {Th}_{0.009/0.009} \hbox {REE}_{0.665/0.665})_{6.088/6.088} (\hbox {Ti}_{12.48/12.48} \hbox {Fe}_{1.87/1.87} \hbox {Si}_{0.249/0.249} \hbox {Al}_{0.334/0.334} \hbox {Cr}_{0.019/0.019} \hbox {Co}_{0.008/0.008} \hbox {Ni}_{0.04/0.04})_{15/15} \hbox {O}_{36/36} (\hbox {OH}_{0.098/0.098[]1.90/1.90})_{2/2}\). The calculated structural formulae are not fully stoichiometric, which could be due to metamict nature of davidite. The characteristic feature of distribution pattern of REE in davidite is unusually high concentration of LREE and HREE and substantially low content of MREE. It may be due to the occupation of REEs in two distinct crystallographic sites in davidite structure, i.e., M(1) and M(O) sites. Chondrite-normalised plot of davidite reveals a pronounced negative Eu-anomaly (\(\hbox {Eu}/\hbox {Eu}^{*} = 0.30{-}0.39\)), which suggests extremely fractionated nature of the metasomatising fluids from which davidite had crystallized. Metamict davidite-bearing U ores not only from Rajasthan, but also from other parts of India are likely to yield very high U leachability, thereby making them attractive sources of U, which otherwise are ignored by mineral engineers as uneconomic U ores.  相似文献   

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