H,O,S and Pb isotope studies of uranium ore deposits in granitoid rocks of South China

Most altered clay minerals in uranium ore deposits in granites in the selected provinces of South China haveδ ¹⁸O _m values ranging from 6.22 to 7.24,δD_m from −60 to −70,δ ¹⁸O from +3.05 to −3.07, and from −20.2 to −37.5‰. Relative enrichment of³²S in the uranium ore deposits and greater variations in Pb isotopic composition of galenas from them show that uranium ores in the granites were formed in such a way that uranium in shallow-source granites had been mobilized by heated meteoric waters and then migrated to local favourable locations along great faults to form uranium ore deposits. Zhang Shaoli, Yang Wenjin, Tang Chunjing and Xu Wenxin did part of this work.     

Genesis and Geological—Geochemical Characters of the ushan Gold Deposit,Shandong,China

The Rushan gold deposit, explored in recent years in the Jiaodong area, Shandong Province, is a quartz vein-type gold deposit hosted in granite. The temperature of its major mineralization episode is between 220°C and 280°C. The salinity of the ore-forming fluid is 5 % to 9% NaCl equivalent, with H₂O and CO₂ as the dominant gas constituents. The fluid is rich in Na⁺, Ca²⁺ and Cl⁻, but relatively impoverished in K⁺ and F⁻, characterized by either Ca²⁺ > Na⁺ > K⁺ (in three samples) or Na⁺ > Ca²⁺ > K⁺ (in six samples). Hydrogen and oxygen isotopes in the ore-forming fluid are highly variable with δ¹⁸ ranging between − 7.70‰ and 5. 97‰ and between − 128‰ and − 71‰. The possibility of lamprophyre serving as the source of gold can be excluded in view of its low gold content on the order of 2.5 × 10⁻⁹. Rb-Sr isochron ages of the deposit and the host Kunyushan granite are ( 104.8 ± 1.5) Ma and 134.6 Ma respectively with the respective initial Sr ratios of 0. 71307 and 0.7096. It is considered that the emplacement of the lamprophyre under a tensile environment had provided sufficient heat energy to facilitate deep circulation of meteoric water by which ore metals were extracted from the Kunyushan granite through long-term water-rock reaction. This project was financially supported by the National Natural Science Foundation of China.     

Geochemistry and origin of gas pools in the Gaoqing-Pingnan fault zone,Jiyang Depression

In the surroundings of the Gaoqing-Pingnan fault zone are developed quite a number of gas reservoirs. Based on gas compositions, they can be divided into two groups, i.e., CO2 and CH4. Their composition and isotope geochemistry were dealt with in this study. The CO2 contents range from 60.72%–99.99%, the δ13CCO2 values from -3.41‰– -9.8‰, and the 3He/4He ratios from 4.35×10-6–6.35×10-6 (i.e. R/Ra=4.45–4.35). Based on the data on composition and isotope geochemistry, deep geological background, deep faults and volcanic rocks, it is shown that CO2 ,distributed in the Gaoqing area, mostly originated from mantle-source inorganic matter which is associated with magmatic rocks. The favorable tectonic environment for the formation of CO2 reservoirs is the rift, which is related to great fault-magmatic activity, the formation of CO2 gas pools and their space-time correlation to the most recent magmatic activities. Hydrocarbon gas pools occur in the Huagou area. The CH4 contents are within the range of 88.83%–99.12%, and the δ13CCH4 values, -44.7‰– -54.39‰. This indicates that the hydrocarbon gas resulted from the decomposition of oil-type gas at high temperatures. Volcanic rocks in the CO2 gas pool-and CH4 gas pool-distributed areas show significant differences in Fe2O3 and FeO contents. This has proven that the hydrocarbon gas may have resulted from various chemical reactions. Magmatic activities are the primary reason for the distribution of CO2 and CH4 gas pools in the Gaoqing-Pingnan fault zone.     

Oxygen isotope studies of wolframite in tungsten ore deposits of south China

Based on the oxygen isotopic compositions of 133 wolframite samples and 110 quartz samples collected from 30 tungsten ore deposits in south China, in conjunction withδD values and other data, these deposits can be divided into four types.

Thermodynamic analysis of ore-forming conditions and sulfur isotopic systematics of Dachang ore field

On the basis of ore-forming periods and stages of the Dachang ore field, the pH and conditions and the S isotopic systematics during ore formation have been thcrmodynamically treated in this paper. Calculations show a progressively decreased pH, an increased oxidation regime and an intensified activity of sulfur from the early to the late stage. Owing to the unreliability of inferring the S source from δ³⁴S_min, has been calculated using the Ohmoto’s model. Results indicate that the δ³⁴ _min frequency distribution is more concentrated than that of δ³⁴S_min and the peak value shifts to negative region by 2.5%. The sulfur in the whole ore field seems to be of multiple source, i.e., different deposits have their own S sources. But the S isotopic composition pertaining to each stage is nearly constant, suggesting that the ore-forming system be open to sulfur and the supply of sulfur be sufficient. The conclusions deduced from calculations are supported by many lines of geological evidence.     

Genesis and geological and geochemical characteristics of Qixia gold deposit, Shandong, China

The Qixia gold deposit is one of the important quartz vein-type deposits hosted in metamorphic rocks in the east of Shandong, China. Compositionally the wolframite which is associated with gold mineralization in the deposit is rich in iron, but poor in manganese, showing that this mineral crystallized from hydrothermal solution at low temperature. The temperatures at the main metallogenic stage of the Qixia gold deposit are within the range of 160–270°C. The gaseous phases in fluid inclusions are dominated by H₂O and CO₂, while Na⁺, Ca²⁺ and Cl⁻ are the major species in the fluid phase with K⁺ and F⁻ present in relatively small amounts. The salinities of fluids are 4.2 wt% –8.0 wt% NaCl equiv. Meanwhile, the fluid is characterized by either Ca²⁺ < Na⁺ < K⁺ (in five samples) or Na⁺ < Ca²⁺ < K⁺ (in two samples), quite similar to the composition of ore-forming fluid derived from meteoric water. Primary data on the hydrogen and oxygen isotopic compositions of the ore-forming fluid fall within a wide range: = − 56‱ − 95‱. and = − 3. 6‱ − 4. 5‱ relative to SMOW. These isotopic values fully reflect the distribution features of meteoric water which has exchanged with the metamorphic rocks of the Jiaodong Group at different temperatures and W/ R ratios, and the metallogenic process is characterized by low W/R ratios. The Rb-Sr isochron age of the Qixia gold deposit is 125.8 ± 1.7 Ma, with (⁸⁷Sr/⁸⁶Sr)_i being 0.7168, and the time interval between the gold deposit and its country rocks (granite or metamoprhic rocks) is very large. The formation of the Qiaxia gold deposit is directly related to the evolution of geological history in eastern Shandong, and a genetic model in which the deep convective circulating meteoric water reacts with the country rocks can be used to explain the metallogenic mechanism of the deposit. This project was financially supported by the National Natural Science Foundation of China (No. 49000020).     

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

Mechanisms of hydrogen incorporation and diffusion in iron-bearing olivine

The incorporation and diffusion of hydrogen in San Carlos olivine (Fo₉₀) single crystals were studied by performing experiments under hydrothermal conditions. The experiments were carried out either at 1.5 GPa, 1,000°C for 1.5 h in a piston cylinder apparatus or at 0.2 GPa, 900°C for 1 or 20 h in a cold-seal vessel. The oxygen fugacity was buffered using Ni–NiO, and the silica activity was buffered by adding San Carlos orthopyroxene powders. Polarized Fourier transform infrared (FTIR) spectroscopy was utilized to quantify the hydroxyl distributions in the samples after the experiments. The resulting infrared spectra reproduce the features of FTIR spectra that are observed in olivine from common mantle peridotite xenoliths. The hydrogen concentration at the edges of the hydrogenated olivine crystals corresponds to concentration levels calculated from published water solubility laws. Hydrogen diffusivities were determined for the three crystallographic axes from profiles of water content as a function of position. The chemical diffusion coefficients are comparable to those previously reported for natural iron-bearing olivine. At high temperature, hydrogenation is dominated by coupled diffusion of protons and octahedrally coordinated metal vacancies where the vacancy diffusion rate limits the process. From the experimental data, we determined the following diffusion laws (diffusivity in m² s⁻¹, activation energies in kJ mol⁻¹): for diffusion along [100] and [010]; for diffusion along [001]. These diffusion rates are fast enough to modify significantly water contents within olivine grains in xenoliths ascending from the mantle.     

Sulfur Isotope Fractionation in Magmatic Systems：Models of Rayleigh Distillation and Selective Flux

The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ^34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ^34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ^34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ^34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ^34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ^34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.     

Study on the origin of the Hongshan brecciated copper deposit in Huichang County,Jiangxi Province,China

The Hongshan copper deposit is a typical cryptoexplosive breccia-type deposit, which occurs in a metamorphic rock series of the Mesoproterozoic Taoxiyuan Formation. Orebodies are distributed inside and outside porphyry-cryptoexplosive breccia pipes. The isotope geochemistry of the deposit is consistent with the origin of porphyry breccia: the δ18OH2O values ranging from 1.2‰ to 6.1‰ and the δ34S values varying from 0 to 2.5‰. 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of pyrite, which coexists with ore minerals, indicate it was derived from the orogenic belt. Thermodynamic analysis indicates that the main metals were deposited largely as a result of the decreasing of proton concentrations associated with H2S and CO2 exsolution during explosion and temperature dropping. Based on K-Ar dating of quartz coexisting with ore minerals, the age of mineralization was estimated to be 97.1–98.8 Ma, which suggests that mineralization occurred between the Early and Late Cretaceous. According to the relevant information obtained, a diagenetic and metallogenic pattern in the area has been presented in this paper.     

Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

Stable isotope study of the mineralization and alteration in the Madjarovo Pb–Zn district,south-east Bulgaria

The Madjarovo ore district is centred on the exposed section of a Lower Oligocene volcano and consists of radially disposed Pb–Zn-precious metal veins and attendant intermediate sulfidation wallrock alteration. Earlier high sulfidation and potassic porphyry style alterations are found in the centre of the district spatially associated with monzonitic intrusions. The total duration of all mineralization and alteration was ca. 300 ka. Stable isotope analyses (S, O, H) have been carried out on a suite of sulfides, sulfates and silicates from the mineralization, high and intermediate sulfidation alterations and a suite of basement rocks. These data range between the following limits: . We also analysed δD of fluid inclusions in quartz and barite for which we obtained, respectively, the ranges of −43.6 to −78.6 and −58.4 to −67.1‰. The data show that high sulfidation alteration was dominated by magmatic fluids with minor meteoric water, whereas the fluids responsible for the intermediate sulfidation alteration were essentially magmatic. The fluids responsible for the intermediate sulfidation Pb–Zn mineralization were mixed magmatic–meteoric and certainly contained a significant meteoric component. Sulphur is likely derived from basement and/or igneous sources. The evolution of alteration and mineralization styles from potassic, porphyry copper style to high sulfidation to intermediate sulfidation can be understood in terms of changing ore fluid composition resulting from an increasing permeability of the system and an increasingly remote source of magmatic fluid with time. These changes link directly to the geological evolution of this volcanic centre.     

Mineralogical and stable isotope studies of gold–arsenic mineralisation in the Sams Creek peralkaline porphyritic granite, South Island, New Zealand

At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ¹⁸O_magma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO₂) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO₂) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO₂-CH₄ + liquid H₂O ± CO₂ vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ¹⁸O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ¹⁸O (+12 to +16‰) and δ¹³C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ¹³C_{bulk carbon} values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ¹⁸O = +25‰ and δ¹³C = 0‰). Calculated δ¹⁸O_water (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ³⁴S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ³⁴S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.     

我国生物气藏碳、氢同位素特征、形成途径及意义

生物气碳、氢同位素组成是探讨其形成途径和成藏特征的基本手段,研究基于我国10个生物气气藏31个气样的碳、氢同位素组成资料探讨了这些气藏的形成途径和成藏特征。研究表明:这些气藏的氢同位素组成可以分为三个区间,即δDCH4>-200‰;δDCH4值在-250‰～-200‰之间和δDCH4<-250‰。前人认为在陆相淡水条件下生物气的形成途径主要是乙酸发酵作用,我国10个气藏31个气样碳、氢同位素研究表明,海相及盐湖相条件下生物气形成途径为典型的CO2还原途径,具有重的氢同位素组成,其δDCH4>-200‰,而陆相条件下成藏的生物气也主要为CO2还原途径,但氢同位素组成较典型海相成因生物气轻,其δDCH4值在-250‰～-200‰之间。其值可能与古湖泊水介质的咸化程度有关。从柴达木的资料来看,随水介质咸度增大,生物甲烷氢同位素组成也具有相应增大趋势。陆相条件下有处于CO2还原和乙酸发酵两种作用过渡区形成的生物气气藏,其形成可能与古水介质无咸化过程和地温梯度较高有关,如保山盆地。该区形成的生物气具有轻的氢同位素组成,δDCH4<-250‰,碳同位素组成则相对较重,其碳、氢同位素组成之间具有较好的负相关。生物气碳、氢同位素组成的成气机理及途径有可能成为判识自然界采集的生物气气样是否具有工业意义,一般而言,乙酸发酵途径形成的生物气不利于成藏。     

Impact of land use change on groundwater quality in a typical karst watershed of southwest China: a case study of the Xiaojiang watershed,Yunnan Province

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.

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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.

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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.

     

Interaction of Freshly Precipitated Silica Gel with Aqueous Silicic Acid Solutions under Ambient and Near Neutral pH-conditions: A Detailed Analysis of Linear Rate Law

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.     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.     

Britvinite, Pb15Mg9(Si10O28)(BO3)4(CO3)2(OH)12O2, a new mineral species from Långban, Sweden

Britvinite, a new mineral species, has been found in manganese ore at the Långban deposit, Bergslagen ore district, Filipstad, Värmland County, Sweden. Calcite, barytocalcite, brucite, cerussite, and hausmannite are associated minerals. Britvinite occurs as pale yellow to colorless transparent plates with a white streak up to 0.2 × 0.5 × 0.5 mm in size, which are flat parallel to {001}; the luster is adamantine. Thin lamellae are flexible, whereas thick ones are brittle; the Mohs hardness is 3. The cleavage is eminent parallel to {001}. The calculated density is 5.51 g/cm³. In the infrared spectrum of the new mineral, the bands of (OH)?, (CO₃)^2?, and (BO₃)^3? are recorded, whereas those corresponding to water molecules are absent. Britvinite is optically biaxial and negative, α = 1.896(2), β = 1.903(2), γ = 1.903(2), 2Vmeas = 20(10), Z≈c. Dispersion is strong, r<v. The chemical composition (electron microprobe; H₂O determined with the Alimarin method, CO₂, with selective sorption) is (wt %) 7.95 MgO, 71.92 PbO, 0.41 Al₂O₃, 12.77 SiO₂, 2.2 H₂O, 2.1 CO₂, 2.67 B₂O₃ (calculated on the basis of structural data); total 100.02. The empirical formula calculated on the basis of 59 anions (O + OH) (Z = 1) is as follows: Pb_14.75Mg_9.03Si_9.73Al_0.37O_30.76(BO₃)_3.51(CO₃)_2.18(OH)_11.7. The simplified formula (Z = 2) is Pb_{7 + x} Mg_4.5(Si₅O₁₄)(BO₃)₂(CO₃)(OH,O)₇ (x < 0.5). The crystal structure of britvinite has been studied on a single crystal at 173 K; R = 0.0547. The new mineral is triclinic, space group P $ \bar 1 Britvinite, a new mineral species, has been found in manganese ore at the L?ngban deposit, Bergslagen ore district, Filipstad, V?rmland County, Sweden. Calcite, barytocalcite, brucite, cerussite, and hausmannite are associated minerals. Britvinite occurs as pale yellow to colorless transparent plates with a white streak up to 0.2 × 0.5 × 0.5 mm in size, which are flat parallel to {001}; the luster is adamantine. Thin lamellae are flexible, whereas thick ones are brittle; the Mohs hardness is 3. The cleavage is eminent parallel to {001}. The calculated density is 5.51 g/cm³. In the infrared spectrum of the new mineral, the bands of (OH)−, (CO₃)²⁻, and (BO₃)³⁻ are recorded, whereas those corresponding to water molecules are absent. Britvinite is optically biaxial and negative, α = 1.896(2), β = 1.903(2), γ = 1.903(2), 2Vmeas = 20(10), Z≈c. Dispersion is strong, r<v. The chemical composition (electron microprobe; H₂O determined with the Alimarin method, CO₂, with selective sorption) is (wt %) 7.95 MgO, 71.92 PbO, 0.41 Al₂O₃, 12.77 SiO₂, 2.2 H₂O, 2.1 CO₂, 2.67 B₂O₃ (calculated on the basis of structural data); total 100.02. The empirical formula calculated on the basis of 59 anions (O + OH) (Z = 1) is as follows: Pb_14.75Mg_9.03Si_9.73Al_0.37O_30.76(BO₃)_3.51(CO₃)_2.18(OH)_11.7. The simplified formula (Z = 2) is Pb_{7 + x} Mg_4.5(Si₅O₁₄)(BO₃)₂(CO₃)(OH,O)₇ (x < 0.5). The crystal structure of britvinite has been studied on a single crystal at 173 K; R = 0.0547. The new mineral is triclinic, space group P ; the unit-cell dimensions are a = 9.3409(8), b = 9.3597(7), c = 18.8333(14) ?, α = 80.365(6)°, β = 75.816(6)°, γ = 59.870(5)°, V = 1378.74(19) ?³. The structure consists of alternating TOT stacks (containing octahedral brucite-like and discontinuous tetrahedral (Si₅O₁₄)_∞∞ layers) and multilayered [Pb_7.1(OH)_3.6(CO₃)(BO₃)_1.75(SiO₄)_0.25]_∞∞ blocks. The strongest reflections in the X-ray powder diffraction pattern [d, ? (I, %)(hkl)] are 18.1(100)(001), 3.39(30)(12, 14, 015), 3.02(90)(006, 130, 106, 20, 11), 2.698(70)(332, 134, 030, 1), 2.275(30)(008, 420, 424), 1.867(30)(446, 239, 2.1.10, 18), 1.766(40)(151, 31, 10, 453, 542, 512, 42), 1.519(40)(0.0.12). The mineral has been named in honor of Sergei Nikolaevich Britvin (b. 1965), a Russian mineralogist. The type material of britvinite is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. The registration number is 3458/1. Original Russian Text ? N.V. Chukanov, O.V. Yakubovich, I.V. Pekov, D.I. Belakovsky, W. Massa, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, Pt CXXXVI, No. 6, pp. 18–25. The new mineral britvinite and its name were accepted by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, June 7, 2006, and approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, October 17, 2006.     

Fluid regime and the behavior of ore, trace, and rare-earth elements during granitization of metagabbro-norites of the Belomorian Group (Gorelyi Island, Kandalaksha Bay)

The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the $ f_{H_2 O} The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the -f _HCl relations in fluid during its percolation through the rock. It was shown that biotite was formed at metamorphic peak in the presence of highly aggressive high-f _HCl fluids (log /f _HCl ≈ 0.8–1.2). Apatite was formed in the presence of less acid and more aqueous residual solutions (log /f _HCl ≈ 2.98−3.91), which presumably lost their salt components at metamorphic peak. The calculations showed that the flux of fluid that percolated through the rock during granitization accounted for q ≈ 4 × 10² to 2 × 10³ cm³/cm². Due to insignificant volume of the fluid, the transformations spanned only marginal part of the metagabbro-norites on Gorelyi Island. Original Russian Text ? L.I. Khodorevskaya, 2009, published in Petrologiya, 2009, Vol. 17, No. 4, pp. 397–414.