Inverse models to analyze the spatiotemporal variations of chemical weathering fluxes in a granito-gneissic watershed: Mule Hole, South India

Water-rock reactions are driven by the influx of water, which are out of equilibrium with the mineral assemblage in the rock. Here a mass balance approach is adopted to quantify these reactions. Based on field experiments carried out in a granito-gneissic small experimental watershed (SEW), Mule Hole SEW (similar to 4.5 km(2)), quartz, oligoclase, sericite, epidote and chlorite are identified as the basic primary minerals while kaolinite, goethite and smectite are identified as the secondary minerals. Observed groundwater chemistry is used to determine the weathering rates, in terms of `Mass Transfer Coefficients' (MTCs), of both primary and secondary minerals. Weathering rates for primary and secondary minerals are quantified in two steps. In the first step, top red soil is analyzed considering precipitation chemistry as initial phase and water chemistry of seepage flow as final phase. In the second step, minerals present in the saprolite layer are analyzed considering groundwater chemistry as the output phase. Weathering rates thus obtained are converted into weathering fluxes (Q(weathering)) using the recharge quantity. Spatial variability in the mineralogy observed among the thirteen wells of Mule Hole SEW is observed to be reflected in the MTC results and thus in the weathering fluxes. Weathering rates of the minerals in this silicate system varied from few 10 mu mol/L (in case of biotite) to 1000 s of micromoles per liter (calcite). Similarly, fluxes of biotite are observed to be least (7 +/- 5 mol/ha/yr) while those of calcite are highest (1265 791 mol/ha/yr). Further, the fluxes determined annually for all the minerals are observed to be within the bandwidth of the standard deviation of these fluxes. Variations in these annual fluxes are indicating the variations in the precipitation. Hence, the standard deviation indicated the temporal variations in the fluxes, which might be due to the variations in the annual rainfall. Thus, the methodology adopted defines an inverse way of determining weathering fluxes, which mainly contribute to the groundwater concentration. (C) 2011 Elsevier B.V. All rights reserved.

Novel procedure for the estimation of swelling pressures of compacted bentonites based on diffuse double layer theory

Bentonite clays are proven to be attractive as buffer and backfill material in high-level nuclear waste repositories around the world. A quick estimation of swelling pressures of the compacted bentonites for different clay-water-electrolyte interactions is essential in the design of buffer and backfill materials. The theoretical studies on the swelling behavior of bentonites are based on diffuse double layer (DDL) theory. To establish theoretical relationship between void ratio and swelling pressure (e versus P), evaluation of elliptic integral and inverse analysis are unavoidable. In this paper, a novel procedure is presented to establish theoretical relationship of e versus P based on the Gouy-Chapman method. The proposed procedure establishes a unique relationship between electric potentials of interacting and non-interacting diffuse clay-water-electrolyte systems. A procedure is, thus, proposed to deduce the relation between swelling pressures and void ratio from the established relation between electric potentials. This approach is simple and alleviates the need for elliptic integral evaluation and also the inverse analysis. Further, application of the proposed approach to estimate swelling pressures of four compacted bentonites, for example, MX 80, Febex, Montigel and Kunigel V1, at different dry densities, shows that the method is very simple and predicts solutions with very good accuracy. Moreover, the proposed procedure provides continuous distributions of e versus P and thus it is computationally efficient when compared with the existing techniques.

海相碳酸盐－稀土元素共沉淀过程中的分异作用研究

本文主要运用稳定加液－反应系统对海水中方解石和文石形成时稀土元素的共沉淀现象进行了分析，研究了稀土元素在固-液体系中的迁移、转化和分配。进而在对其定量描述的前提下，研究了稀土元素共沉淀对各种反应条件的响应，并对共沉淀行为的机制进行了探讨。 本实验首先运用pH测试、高精度滴定分析等手段测定了实验中的一些基本参数，如[H+]、碱度和[Ca2+]，根据计算结果获得了各碳酸体系要素，并以此为基础建立了5℃、15℃和25℃及pCO2=0.003atm下海水中方解石或文石的沉淀动力学方程。实验结果表明： 1）在各条件下，方解石或文石的沉淀速率（R）和其在海水中过饱和度（Ω）存在很好的线性相关性，即海相碳酸盐的沉淀动力学方程可以通过下面的基本表达式来表示：LogR=k*Log(Ω-1)+b ； 2）过高的稀土元素浓度会对文石或方解石的沉淀产生抑制作用，进而对共沉淀过程中YREEs的分异和分馏产生一定的影响。相比方解石而言，文石的沉淀动力学过程承受稀土元素的干扰能力更强； 3）不同温度下得到的方解石或文石各自的沉淀动力学方程存在明显的差异，表明这一过程受热力学因素控制。相对于方解石而言，温度对文石的沉淀动力学的影响更为显著。 与前人研究不同的是，本实验中YREEs的浓度设定在非常低的范围内，从而避免了过高浓度YREEs对方解石或文石沉淀动力学过程的干扰。在最终的反应液中，各种实验条件非常接近自然环境。有关稀土元素的共沉淀行为主要得出以下定性或定量化结论： 1）YREEs在随方解石或文石的共沉淀过程中，均发生了强烈的分异作用。在方解石实验中，稀土元素的分异系数分布曲线呈凸状分布；而在文石实验中，稀土元素的分异系数随原子序数的增加逐渐减小，遵循镧系收缩的规律。总的来说，稀土元素，尤其轻稀土元素在文石中的分异作用要强于方解石。 2）无论是方解石还是文石，沉淀速率对YREEs的分异作用都有着明显的影响。在方解石中，YREEs的分异系数随沉淀速率的增加呈一致性递减趋势；而在文石中，其分异系数对文石沉淀速率有着截然不同的响应：轻稀土元素（La, Ce, Nd, Sm, Eu, Gd）的分异系数随文石沉淀速率的增加而下降，而重稀土元素（Ho, Y, Tm, Yb , Lu）的分异系数则随文石沉淀速率的增加呈上升趋势。 3）在方解石中YREEs的分异系数之间存在非常好的相互关系，表明这些元素是以成比例的方式参与共沉淀。整个谱系呈现中等强度的分馏，MREE相对于LREE和HREE要更为富集；在文石中由于沉淀速率的作用不同，只有Y、Ho、Yb、Lu等元素的分异系数之间有较好的相互关系。YREEs出现了差异性的强烈分馏，在新生成沉淀中轻稀土元素相对于重稀土元素强烈富集。 4）YREEs在溶液中和碳酸盐晶体表面的碳酸根配位形式对YREEs在共沉淀过程中的分异作用极为重要，YREEs在碳酸盐晶体表面的吸附是整个谱系发生分馏效应的关键环节。对于文石来讲，晶体中有效YREE离子和Ca离子半价大小之间的相近程度是其分馏效应的关键因素；而对于方解石来说，YREEs在方解石晶格中的安置就是其分馏效应的关键控制因子，但在晶格安置中起到关键作用的是YREEs和方解石中O原子之间离子键M-O的键长，而非离子半径。 5）综合YREEs在方解石中的分异作用和分馏效应，我们认为M2(CO3)3-CaCO3和MNa(CO3)2-CaCO3是最为可能的两种固体溶液形成模式。 最为重要的是，对比我们的实验结果与前人在灰岩、叠层石、微生物成因碳酸盐等方解石质载体中的研究成果，两者之间出现了非常好的一致性。我们认为方解石质载体将是重建古海水中稀土元素相关信息的重要工具。相比之下，文石质载体不适合作为类似的载体。

水-岩土反应的力学与环境效应研究

The research on mechanical effects of water-rock and soil interaction on deformation and failure of rocks and soils involves three aspects of mechanics, physics and chemistry. It is the cross between geochemistry and rock mechanics and soil mechanics. To sum up, the mechanical effects of water-rock and soil interaction is related to many complex processes. Research in this respect has been being an important forward field and has broad prospects. In connection with the mechanism of the effects of the chemical action of water-rock on deformation and failure of rocks and soils, the research significance, the present state, the developments in this research domain are summarized. Author prospects the future of this research. The research of the subject should be possessed of important position in studying engineering geology and will lead directly to a new understand on geological hazard and control research. In order to investigation the macroscopic mechanics effects of chemical kinetics of water-rock interaction on the deformation and failure, calcic rock, red sandstone and grey granite reacting chemically with different aqueous solution at atmospheric temperature and atmospheric pressure are uniaxially compressed. The quantitative results concerning the changes of uniaxially compressive strength and elastic modulus under different conditions are obtained. It is found that the mechanical effects of water on rock is closely related to the chemical action of water-rock or the chemical damage in rock, and the intensity of chemical damage is direct ratio to the intensity of chemical action in water-rock system. It is also found that the hydrochemical action on rock is time-dependent through the test. The mechanism of permeation and hydrochemical action resulting in failure of loaded rock mass or propagation of fractures in rocks would be a key question in rock fracture mechanics. In this paper, the fracture mechanical effects of chemical action of water-rock and their time- and chemical environment-dependent behavior in grey granite, green granite, grey sandstone and red sandstone are analyzed by testing K_(IC) and COD of rock under different conditions. It is found that: ①the fracture mechanical effect of chemical action of water-rock is outstanding and time-dependent, and high differences exist in the influence of different aqueous solution, different rocks, different immersion ways and different velocity of cycle flow on the fracture mechanical effects in rock. ②the mechanical effects of water-rock interaction on propagation of fractures is consistent with the mechanical effects on the peak strength of rock. ③the intensity of the mechanical fracture effects increases as the intensity of chemical action of water-rock increases. ④iron and calcium ion bearing mineral or cement in rock are some key ion or chemical composition, and especially iron ion-bearing mineral resulting in chemical action of water-rock to be provided with both positive and negative mechanical effects on rock. Through the above two tests, we suggest that primary factors influencing chemical damage in rock consist of the chemical property of rock and aqueous solution, the structure or homogeneity of rocks, the flow velocity of aqueous solution passing through rock, and cause of formation or evolution of rock. The paper explores the mechanism on the mechanical effects of water-rock interaction on rock by using the theory of chemistry and rock fracture mechanics with chemical damage proposed by author, the modeling method and the energy point of view. In this paper, the concept of absorbed suction between soil grains caused by capillary response is given and expounded, and the relation and basic distinction among this absorbed suction, surface tension and capillary pressure of the soil are analyzed and established. The law of absorbed suction change and the primary factors affecting it are approached. We hold that the structure suction are changeable along with the change of the saturation state in unsaturated soils. In view of this, the concept of intrinsic structure suction and variable structure suction are given and expounded, and this paper points out: What we should study is variable structure suction when studying the effective stress. By IIIy κHH's theory of structure strength of soils, the computer method for variable structure suction is analyzed, the measure method for variable structure suction is discussed, and it reach the conclusions: ①Besides saturation state, variable structure suction is affected by grain composition and packing patter of grains. ②The internal relations are present between structure parameter N in computing structure suction and structure parameter D in computing absorbed suction. We think that some problems exit in available principle of effective stress and shear strength theory for unsaturated soil. Based on the variable structure suction and absorbed suction, the classification of saturation in soil and a principle of narrow sense effective stress are proposed for unsaturated soils. Based on generalized suction, the generalized effective stress formula and a principle of generalized effective stress are proposed for unsaturated soils. The experience parameter χ in Bishop's effective stress formula is defined, and the principal factors influencing effective stress or χ. The primary factor affecting the effective stress in unsaturated soils, and the principle classifying unsaturated soils and its mechanics methods analyzing unsaturated soils are discussed, and this paper points out: The theory on studying unsaturated soil mechanics should adopt the micromechanics method, then raise it to macromechanics and to applying. Researching the mechanical effects of chemical action of water-soil on soil is of great importance to geoenvironmental hazard control. The texture of soil and the fabric of soil mass are set forth. The tests on physical and mechanical property are performed to investigate the mechanism of the positive and negative mechanical effects of different chemical property of aqueous solution. The test results make clear that the plastic limit, liquid limit and plasticity index are changed, and there exists both positive and negative effects on specimens in this test. Based on analyzing the mechanism of the mechanical effects of water-soil interaction on soil, author thinks that hydrochemical actions being provided with mechanical effects on soil comprise three kinds of dissolution, sedimentation or crystallization. The significance of these tests lie in which it is recognized for us that we may improve, adjust and control the quality of soils, and may achieve the goal geological hazard control and prevention.The present and the significance of the research on environmental effects of water-rock and soil interaction. Various living example on geoenvironmental hazard in this field are enumerated. Following above thinking, we have approached such ideals that: ①changing the intensity and distribution of source and sink in groundwater flow system can be used to control the water-rock and soil interaction. ②the chemical action of water-rock and soil can be used to ameliorate the physical and mechanical property of rocks and soils. Lastly, the research thinking and the research methods on mechanical effects and environmental effects of water-rock and soil interaction are put forward and detailed.

山东莱芜中生代高镁侵入岩及其超镁铁质岩捕掳体的成因研究

In order to know better about the Phanerozoic lithosphere thinning process of Sino-Korea Plate, four Cretaceous intrusion complexes and their ultramafic xenoliths are investigated by this thesis, which are located in Laiwu, Shandong Province, Eastern China, a region far away from plate margin. The four complexes, Kuanshan, Jiaoyu, Jingniushan and Tietonggou, intruded into Archaeozoic granite gneiss and Paleozoic carbonate rocks with scam iron ore at their contact zone. The four complexes can be divided into two magma series, abyssal rocks for the early and hypabyssal rocks for the later. K-Ar dating show that the abyssal rocks intrusion began with 120 ±2 Ma and the hypabyssal rocks intruded about 113 Ma. Abyssal rocks, mainly made up of augite diorites, amphibole diorites and gabbros for the lesser, are chemically characterized with high-Mg (Mg#>0.5) high-K calcalklic rock, which are depleted with Nb, Ta and Ti related to LILE and extremely enriched with Sr and Pb. Comparatively, augite diorites are the most LREE enriched in abyssal rocks, and they show no Eu abnorrnity or weak positive Eu abnormity. Gabbros show the least LREE enrichment with a strong Eu abnormity relatively. In (~(87)Sr/~(86)Sr)_1 -ε Nd(T) diagram, the abyssal rocks show a mixing trend , a rapid change in ε Nd(T) with a relatively small change in (~(87)Sr/~(86)Sr)_1. Low radiogenic Sr and Pb composition with high radiogeic Nd composition indicate that the mixing processes happened in lower crust Melt-rock interactions in lower crust might be the most possible processes to produce these high-Mg and high-K calcalklic magmas. Hypabyssal rocks, mainly made up of granite porphyry and dioritic porphrite, show much higher ε Nd(T) than abyssal rocks. Granite porphyry are distinct with an adakite geochemical characteristics, high (La/Yb)_N, Sr/Y and low Rb/Sr ratio. The adakitic granite porphyry indicates a new lower crust produced by underplating within plate. Ultramafic xenoliths had been found only in augite diorites and amphibole diorites. Field investigations show that ultramafic xenoliths in augite diorites had been inherited from amphibole diorites, so ultramafic xenoliths had been only entrained by hydrous dioritic magma. Ultramafic xenoliths are mainly made up of dunite and harzburgite, orthopyroxenite and bistangite are the lessor. Coarse olivines in dunite often show many chromite exsolution lamellae. Opx in orthopyroxenite often show dense chromite exsolution lamellae. The presence of exsolution minerals indicates that ultramafic xenoliths had cooled before entraining. Metasomatism phenomenons are popular in dunite and harzburgite xenoliths, including two kinds of assemblage, cpx+phlogapite and opx+pl. The first metasomatism assemblage indicates an ancient enrichment. Rb-Sr dating of xenoliths shows that the ancient enrichment happened in 223 ± 7Ma. The second metasomatism assemblage indicates a recent, relatively not deep melt-rock interaction, which might be related with the genesis of the high-Mg high-K calcalklic rocks. Mineralogy and geochemistry indicate that these ultramafic xenoliths might sample the crust-mante transition zone (or the base of lower crust, moho). Investigation of high-Mg intrusions and their ultramafic xenoliths in Laiwu indicate that the thinning processes of Sino-Korea Plate can be divided into two stages. The first stage is lithosphere mantle thinning with crust thickening by underplating in lower crust. The second stage is that the thickened lower crust delaminated into the underlying mantle.

新疆萨吾尔金矿带构造-流体地球化学及成矿作用

The Sawuer gold belt is located in the transition belt between Siberian plate and Kazakhstan-Junggar plate. Based on the geological and geochemical studies on the Kuoerzhenkuola and Buerkesidai gold deposits, in Sawuer gold mineralization belt, the time-space structure of mineralization and mineralizing factor are studied, the metallogenic regularity is concluded in thistheses. The ore bodies have the regularity that orebody are of the extensive and compressive in the sallow and depth of volcanic apparatue, respectively, and the vertical extension of orebody is more intensive than the horizontal extension. The gold deposits were controlled by the fractures of volcanic apparatus and regional faults, and featured by the hydrothermal alteration and metasomatism type disseminated mineralization and filling type vein mineralization. By virtue of the geological and geochemical studies on the two deposits that the formation of the two deposits are significantly related to the volcanic activity, we propose new ideas about their origin: (1) the two deposits are located in the same strata, and share the same genesis. (2) both of two deposits are volcanogenic late-stage hydrothermal gold deposits. Based on mapping of volcanic lithofacies and structure for the first time, it is discovered that a volcanic apparatus existed in the study area. Volcanic-intrusive activity can be divided into three cycles and nine lithofacies. where the two deposits are hosted in the same volcanic cycle, in this case, the wall-rock should belong to the same strata. The 40Ar-39Ar age method is employed in this work to analyze the fluid inclusions of quartz in the ore bodies from Kuoerzhenkuola and Buerkesidai gold deposits. The results show that the main mineralization occurred in 332.05 + 2.02-332.59 + 0.5IMa and 335.53 + 0.32Ma~336.78 + 0.50Ma for Kuoerzhenkuola and Buerkesidai gold deposits respectively, indicating that the two deposits are formed almost at the same time, and the metallogenic epoch of the tow deposits are close to those of the hosting rocks formed by volcanic activity of Sawuer gold belt. This geochronological study supplies new evidence for determining the timing of gold mineralization, the geneses of gold deposits? and identifies that in Hercynian period, the Altai developed tectonic-magmatic-hydrothermal mineralization of Early Carboniferous period, except known two metallogenic mineralization periods including tectonic-magmatic-hydrothermal mineralization of Devonian period and Late Carboniferous-Permian period respectively. The study of fluid inclusions indicates that the ore-forming fluid is a type of NaCl-HbO fluid with medium-low temperature and low salinity, Au is transported by the type of auric-sulfur complex (Au (HS)2-), the ore is formed in reduction condition. Hydrogen and oxygen isotopes of fluid inclusions in the major mineralizating stage show that the solutions mainly originated from magmatic water and meteoric water. The fluid mixing and water-rock reaction cause the deposition of Au. The helium and argon isotope compositions of fluid inclusions hosted in pyrite have been measured from Kuoerzhenkuola and Buerkesidai gold deposits in Sawuer gold belt. The results show that the ore-forming fluids of two deposits possessed the same source and is a mixture of mantle- and partial meteoric water-derived fluid, and the reliability of He and Ar isotopic compositions in Hercynian period is discussed. Isotopic studies including H, O, He, C, S, Pb and Sr reveal the same result that the ore-forming fluids of two deposits possessed the same source: the water derived mainly from magmatic water, partially from meteoric water; the mineralizers and ore materials derived mainly from mantle beneath the island arc, and partially from crust. The ore-forming fluids of two deposits are a mixture of mantle-derived fluids being incorporated by crust-derived fluid, and shallow partial meteoric water. Based on these results, it is proposed that the geneses of the two gold deposits are the same, being volcanogenic late-stage hydrothermal gold deposits that the ore-forming fluids filled in fractures of volcanic apparatus and metasomatized the host rocks in the volcanic apparatus. It is the first time we carried out the geophysical exploration, that is, the EH-4 continuous electrical conductivity image system measurement, the results show that relative large-size mineralizing anomalies in underground have been discovered.lt can confirm the law and genesis of the deposits mentioned above, and change the two abandoned mines to current large-size potenial exploration target.

地表水体中微量金属元素分布的水/胶体作用控制机理的实验研究

水体中轻重稀土元素之间的分异，特别是一些具有相同电价而又具有近似相同离子半径的元素对（如Y3＋/Ho3＋、Zr4+/Hf4+、Nb5+/Ta5+）之间的分异，Ce异常和REE四重效应存在及产生原因和不同因素的控制机理构成了水体稀土元素及其它微量金属元素地球化学研究的核心科学问题，是我们合理解释地表水体中REE及其它微量金属元素组成变化的重要理论基础。目前研究水I微粒界面作用的工作不少，但至今进行的胶体或其它微粒对REE和高价阳离子（如Zr、Hf、Nb和Ta）的吸附实验研究不多，已有的实验也未能对不同控制因素（如pH、溶液介质类型、无机和有机配位体等）的控制机理进行系统研究。本文通过系列批次实验，定量研究了水合氧化铁（日FO）在不同溶液介质条件下对二价（Cu2+）、三价（Ln3＋）、四价（Zr4+、Hf4+）以及五价（Nb5+、Ta5+）阳离子的吸附／去除作用，重点讨论了溶解配位体和pH影响下水l胶体作用对轻重稀土以及Y-Ho、Zr-Hf和Nb-Ta元素对之间分异行为的影响，并模拟了稀土元素在溶液中的形态分布。研究结果表明：微量金属元素在HFO上吸附的动力学特征受控于HFO生成的动力学，溶液介质条件（包括pH、电解质、溶解配位体、吸附剂及吸附质的浓度以及吸附质的形态分布等）是影响微量金属元素水l胶体作用的主要因素；稀土元素的分配系数在水胶体作用过程中受不同因素的影响而呈现不同的分布模式，但都存在丫的负异常和较低pH下Ce的正异常现象，在CO32-、腐殖酸和SO42-、PO43-的影响下，稀土元素的分配系数分别呈现轻稀土富集和重稀土富集的分布模式，REE在HFO上的作用机制是离子交换和特性吸附综合作用的结果；在天然水体p日范围内，Zr、Hf和Nb、Ta在吸附／共沉淀过程中发生了分异，但均显示相对惰性的行为并表现出较好的一致性，指示了其地球化学孪生对的行为。上述研究结果为合理解释地表水体中稀土和其它微量金属元素分布变化的多样性提供了实验依据。

Geochemical and isotopic evidence for seawater contamination of the hydrothermal system of Taal volcano, Luzon, the Philippines

The hydrologic structure of Taal Volcano has favored development of an extensive hydrothermal system whose prominent feature is the acidic Main Crater Lake (pH<3) lying in the center of an active vent complex, which is surrounded by a slightly alkaline caldera lake (Lake Taal). This peculiar situation makes Taal prone to frequent, and sometimes catastrophic, hydrovolcanic eruptions. Fumaroles, hot springs, and lake waters were sampled in 1991, 1992, and 1995 in order to develop a geochemical model for the hydrothermal system. The low-temperature fumarole compositions indicate strong interaction of magmatic vapors with the hydrothermal system under relatively oxidizing conditions. The thermal waters consist of highly, moderately, and weakly mineralized solutions, but none of them corresponds to either water-rock equilibrium or rock dissolution. The concentrated discharges have high Na contents (>3500 mg/kg) and low SO4/Cl ratios (<0.3). The Br/Cl ratio of most samples suggests incorporation of seawater into the hydrothermal system. Water and dissolved sulfate isotopic compositions reveal that the Main Crater Lake and spring discharges are derived from a deep parent fluid (T≃300°C), which is a mixture of seawater, volcanic water, and Lake Taal water. The volcanic end member is probably produced in the magmatic-hydrothermal environment during absorption of high-temperature gases into groundwater. Boiling and mixing of the parent water give rise to the range of chemical and isotopic characteristics observed in the thermal discharges. Incursion of seawater from the coastal region to the central part of the volcano is supported by the low water levels of the lakes and by the fact that Lake Taal was directly connected to the China sea until the sixteenth century. The depth to the seawater-meteoric water interface is calculated to be 80 and 160 m for the Main Crater Lake and Lake Taal, respectively. Additional data are required to infer the hydrologic structure of Taal. Geochemical surveillance of the Main Crater Lake using the SO4/Cl, Na/K, or Mg/Cl ratio cannot be applied straightforwardly due to the presence of seawater in the hydrothermal system.

Arsénio em águas subterrâneas em Portugal

Da totalidade da água existente na Terra, somente 1% diz respeito à água subterrânea, recurso finito e essencial para a sobrevivência do Homem. A composição química das águas subterrâneas é influência não só pela actividade humana, mas também pelas características químicas do substrato geológico. As rochas e os sedimentos funcionam como meio de transporte e armazém desse tipo de águas e a presença de certos minerais pode originar a contaminação natural das águas subterrâneas em elementos prejudiciais para o Homem. Um desses elementos é o arsénio. Uma vez que a concentração máxima admitida de arsénio para água consumo humano diminuiu dos anteriores 50 mg.l-1 para os actuais 10 mg.l-1,a probabilidade de encontrar concentrações naturais em arsénio em águas subterrâneas acima desse limite aumentou. Este trabalho visa estudar e compreender, através de ensaios laboratoriais, a interacção água/rocha em termos químicos e a mobilidade/comportamento do arsénio em seis zonas de Portugal Continental com contextos geológicos diferentes (Vila Flor – Formação Filito-Quartzítica, Baião – granitos, Cacia – sedimentos do Cretácico, Mamodeiro – sedimentos do Neogénico, Escusa – calcários dolomíticos e Beja - gabros). Para o efeito, nas zonas de estudo mencionadas foram colhidas amostras de rocha ou sedimento e de água subterrânea que foram analisadas para 36 e 76 elementos, respectivamente. A componente mineralógica e as fases suporte do As foram estudadas recorrendo à análise por difracção de raios X, microssonda electrónica e à aplicação da extracção química selectiva sequencial. A mobilização do As foi avaliada através da realização de ensaios de coluna e de agitação com hidrocarbonetos derivados do petróleo. No primeiro ensaio, a circulação de diferentes soluções com diferentes velocidades lineares no interior de colunas de vidro cheias de rocha moída, avaliou a presença de As associado a fases hidrossolúveis e biodisponíveis. No segundo, a agitação de rocha moída com água e hidrocarbonetos derivados do petróleo pretendeu avaliar o comportamento do As quando um aquífero apresenta uma contaminação com aquele tipo de hidrocarbonetos.

Stable hydrogen and oxygen isotope composition of waters from mine tailings in different climatic environments

The stable isotope composition of waters (delta H-2, delta O-18) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta H-2 and delta O-18 values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Caren at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta O-18 values (by similar to +2% delta O-18 relative to delta H-2) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of H-2 and O-18 in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in H-2 and O-18. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.

Stable isotope composition of smectite in suevites at the Ries crater, Germany: Implications for hydrous alteration of impactites

The 24-km diameter Ries crater, Germany, exhibits well-preserved crater filling and surficial melt-rich breccia deposits that are believed to have been altered by post-impact hydrothermal fluids. The alteration mineralogy of the crater filling breccias is characterized by clay (smectite, chlorite) and a zeolite assemblage, and secondary clay phases (smectite, minor halloysite) in surficial melt-bearing breccia deposits. Using stable isotope analysis of secondary smectitic clay fractions, evidence of significant hydrous alteration of impactites at large water/rock ratios was found. The estimated fluid temperatures, using data derived by delta(18)O and delta D fractionation, suggest smectite precipitation in surficial breccias in equilibrium with meteoric fluids at temperatures 16 +/- 5 degrees C in agreement with the long-term variation of modern precipitation in the area. The stable isotope composition of smectite in crater-fill breccia, however, suggests a trend of monotonously increasing temperatures from 43 to 112 degrees C. with increasing depth through the breccia sequence. This demonstrates a different origin of alteration and temperature distribution for the surficial and crater filling melt-bearing impact breccias in the Ries crater. Our results suggest that the inverted structure of hydrothermal systems observed in some terrestrial impact craters, including the Ries crater, could indicate the initial configuration of a thermal anomaly in the crater filling sequence, but which is replaced with a normal hydrothermal convection in crater proper, during the course of post-impact cooling. (C) 2010 Elsevier B.V. All rights reserved.

Catchment-scale modelling of flow and nutrient transport in the Chalk unsaturated zone

The unsaturated zone exerts a major control on the delivery of nutrients to Chalk streams, yet flow and transport processes in this complex, dual-porosity medium have remained controversial. A major challenge arises in characterising these processes, both at the detailed mechanistic level and at an appropriate level for inclusion within catchment-scale models for nutrient management. The lowland catchment research (LOCAR) programme in the UK has provided a unique set of comprehensively instrumented groundwater-dominated catchments. Of these, the Pang and Lambourn, tributaries of the Thames near Reading, have been a particular focus for research into subsurface processes and surface water-groundwater interactions. Data from LOCAR and other sources, along with a new dual permeability numerical model of the Chalk, have been used to explore the relative roles of matrix and fracture flow within the unsaturated zone and resolve conflicting hypotheses of response. From the improved understanding gained through these explorations, a parsimonious conceptualisation of the general response of flow and transport within the Chalk unsaturated zone was formulated. This paper summarises the modelling and data findings of these explorations, and describes the integration of the new simplified unsaturated zone representation with a catchment-scale model of nutrients (INCA), resulting in a new model for catchment-scale flow and transport within Chalk systems: INCA-Chalk. This model is applied to the Lambourn, and results, including hindcast and forecast simulations, are presented. These clearly illustrate the decadal time-scales that need to be considered in the context of nutrient management and the EU Water Framework Directive. (C) 2007 Elsevier B.V. All rights reserved.

Laboratory simulation of terrestrial meteorite weathering using the Bensour (LL6) ordinary chondrite

Laboratory dissolution experiments using the LL6 ordinary chondrite Bensour demonstrate that meteoritic minerals readily react with distilled water at low temperatures, liberating ions into solution and forming reaction products. Three experiments were performed, all for 68 days and at atmospheric fO(2) but using a range of water/rock ratios and different ternperatures. Experiments I and 2 were batch experiments and undertaken at room temperature, whereas in experiment 3, condensed boiling water was dripped onto meteorite subsamples within a Soxhlet extractor. Solutions from experiment 1 were chemically analyzed at the end of the experiment, whereas aliquots were extracted from experiments 2 and 3 for analysis at regular intervals. In all three experiments, a very significant proportion of the Na, Cl, and K within the Bensour subsamples entered solution, demonstrating that chlorapatite and feldspar were especially susceptible to dissolution. Concentrations of Mg, Al, Si, Ca, and Fe in solution were strongly affected by the precipitation of reaction products and Mg and Ca may also have been removed by sorption. Calculations predict saturation of experimental solutions with respect to Al hydroxides, Fe oxides, and Fe (oxy)hydroxides, which would have frequently been accompanied by hydrous aluminosilicates. Some reaction products were identified and include silica, a Mg-rich silicate, Fe oxides, and Fe (oxy)hydroxides. The implications of these results are that even very short periods of subaerial exposure of ordinary chondrites will lead to dissolution of primary minerals and crystallization of weathering products that are likely to include aluminosilicates and silicates, Mg-Ca carbonates, and sulfates in addition to the ubiquitous Fe oxides and (oxy)hydroxides.