Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

污染土壤中镉、铅的活化及植物有效性研究

以草甸棕壤作为供试土壤，通过盆栽实验、模拟实验及吸附-解吸实验对影响镉、铅活化和植物有效性的主要因素，如施肥、老化、淹水、有机酸、无机阴离子与土壤污染负荷等因素进行系统的研究，得出以下结论： 肥料的种类、施用水平不同对小麦生长及镉、铅的植物有效性的影响亦不相同。增施氮肥提高了镉、铅的植物有效性；磷肥和钾肥可缓解镉、铅对小麦的毒害作用，并能显著抑制小麦对铅的吸收。低磷时降低了小麦对镉的吸收，而高磷时提高镉的植物有效性。钾肥可降低镉的植物有效性。 随老化时间的增长，镉存在着由交换态SE，铁锰氧化物结合态OX向碳酸盐结合态WSA，有机结合态OM，残渣态RES转化的趋势；而SE，OX，OM态铅有向WSA，RES转化的趋势。淹水处理引起土壤Eh值下降、pH值上升；降低镉、铅的迁移性，在持续淹水过程中，土壤中SE镉（铅）占总量的百分比明显下降，而其他四种形态的比例上升。 土壤中镉、铅的解吸率与有机酸和无机阴离子的类型、浓度密切相关。柠檬酸、草酸、组氨酸对Cd、Pb的浸提能力为：柠檬酸﹥草酸﹥组氨酸。C1- 、SO42- 、F- 对解吸土壤中镉、铅的影响力顺序分别是：C1- > SO42- > F-；SO42- > C1- > F-。 不同污染负荷的土壤Cd2+ 和Pb2+吸附动力学行为以及解吸动力学过程的最优拟合模型均为双常数方程，其次为Elovich方程，最差模型是一级动力学方程。

地下咸水的化学特征及其在水产养殖中的应用

地下咸水的化学成分与现代海水基本相同，它本身不带病毒，与海水也没有连接的渠道，故海水中的病毒宿主难以侵入，因此，它可以做为海水养殖的一种替代水体，在水产养殖方面有非常广阔的应用前景。本论文首次对用于养殖的胶州地区的地下咸水的形成原因和化学组分特征作了系统阐述。主要的研究内容和研究结果包括：1．咸水入侵和稀释作用是形成该地区地下咸水的主要原因。现代海水和卤水入侵及临近河口区淡水对地下卤水的稀释作用是形成该地区地下咸水的两种主要原因。地质调查结果表明，胶州地区属于地下卤水远景分布区，该地区有不边疆分布的斑块状的地下卤水存在，对地下水的超采造成地下水水位的下降，从而引起咸水入侵。在大沽河河口地区，河流淡水对地下卤水的稀释也是是该区地下咸水形成的一个原因。2．地下咸水的主要化学组分特征 在地下咸水的常量元素分布中，由于地下水流沉积物表面时产生的溶滤作用、离子交换吸附及还原环境下脱硫酸菌的作用使Ca~(2+)/Cl~-、Mg~(2+)/Cl~－、Na~+/Cl~-值与海水中的相应组分的比值相比，有不同程度的升高，SO_4~(2-)/Cl~-明显降低，K~+/Cl~-的值在不同的地区差异较大。通过对几个地区地下水中铁、锰的含量对比，发现其值远高于海水中的含量，可高达每升几毫克，这主要是由于在地下水的还原环境和较低的pH条件下，铁、锰的氧化物较易还原溶出，并讨论了不同地区的Mn/Fe值由于受Fe~(2+)、Mn~(2+)这两种还原产物稳定性的没和铁锰氧化物易被还原的程度不同这两个因素的影响，分别呈现出大于1和小于1的情形。对地下水中微量元素铜、铅、锌、镉的分析表明，这些元素在地下水中的含量与海水中的含量在同一个数量级，差异不显著。以Cl~-为参比因子，从所求得的相关关系来看，锌和铜在地下水中呈较好的保宋性分布，即没有显著的添加或去除行为，铅和镉的保守性较差。地下水中的营养盐分布与海水也有着显著不同，在地下咸水的Eh和pH分布范围内，NH_4~+态氮是地下水中无机氮分布的主要形式，并且由于吸附在粘土中的硅酸盐矿物的转出，地下咸水中的SiO_3~(2-)含量显著偏高。3．Ca~(2+)、Mg~(2+)对对虾生长的影响 利用正交实验证实了Ca~(2+)/Mg~(2+)比值、Ca~(2+)+Mg~(2+)总量以及二者之间的交互作用对对是生长都有显著性影响。对虾生长适宜的Ca~(2+)/Mg~(2+)比值范围是1:1～1:3，对是能在Ca~(2+)/Mg~(2+)比值为1：10的水环境中正常生长，只要有一定的Ca~(2+)+Mg~(2+)总量。较低的Ca~(2+)浓度可能会成为导致对虾存活率降低的原因。

水-岩反应与稀土元素行为

大量研究表明，水-岩反应过程中REE均表现为不同程度的活动性。富含各种络合剂的流体与岩石反应时可活化REE；水-岩反应过程中既可出现HREE优先活化，亦可出现LREE优先活化, 这取决于流体的化学成分、Eh、pH以及REE的寄主相及其赋存状态；水-岩反应过程中的可出现Eu的正异常、负异常或无异常，其主要影响因素是流体的氧化-还原状态；单矿物组合的REE行为受制于矿物的晶体化学性质，而多矿物组合则取决于体系的Eh、pH、水/岩值和络合剂浓度等，目前亟待开展实验工作有：：①流体的化学组成及其性质，尤其是各种络合剂的活度及其对REE的活动性的影响；② REE在热液矿物与流体相之间的分异机制及控制因素；③T、P、pH、Eh和水/岩比如何影响REE的活动性和分异行为。

八方山大型多金属矿床热水沉积岩相特征与矿化剂组分关系

陕西八方山大型(金)多金属矿床赋存在于中泥盆统吉维特晚期的热水沉积岩相中。富SiO2酸酐型热水同生—交代沉积作用形成热水同生沉积微相(层状硅质岩)、热水同生交代微相(微晶石英岩及硅化灰岩)；富Fe^2+ - Mg^2+碳酸盐型热水同生沉积作用形成层状含铜硅质铁白云岩；在同生断裂附近，因热水液压致裂-隐爆作用形达含铜黄铁矿硅质铁白云石角砾岩；富Na^+铝硅酸盐型／富Fe^2+、Mg^2+碳酸盐型热流体在同生断裂中形成热水充填微相(穿层脉状钠长石碳酸岩)；低温热卤水(富F、Ba、B、As、Sb)形成热卤水同生沉积微相。矿质大规模沉淀的地球化学动力学因素为：在热水沉积成矿盆地中，在单一成分热水体系的温度、压力改变而发生快速化学沉淀；不同成分、性态的热水混合后，强烈的酸—碱作用及Eh-pH剧变等，触发热水体系失稳，引起矿质大规模沉积。[SiO2]和F可能是重要的矿化剂。

新疆萨瓦亚尔顿（穆龙套型）金矿床物质来源与成矿机制

萨瓦亚尔顿金矿床是我国90年代金矿地质工作者在新疆西南天山地区寻找穆龙套型金矿床的一个突破。本文通过对新疆萨瓦亚尔顿金矿床的矿石矿物组成、稀土元素地球化学、同位素地球化学以及流体包裹体特征等方面的研究，探讨了萨瓦亚尔顿金矿床地质地球化学特征、金的赋存状态及成矿流体特征、成矿流体来源，提出了该矿床的成矿机制，取得如下认识：1．流体包裹体岩相学研究表明，萨瓦亚尔顿金矿床的流体包裹体主要为V＋L相和富CO_2相包裹体，前者为NaCl-H_2O体系，后者主要有L_(CO2)、L_(CO2)+L、V_(CO2)+L、V_(CO2)＋L_(CO2)＋L相包裹体；并发现极少量含子晶流体包裹体。2．通过流体包裹体显微测温学研究，表明金矿床的均一温度成矿早阶段为270～320 ℃，成矿主阶段为170～250 ℃，成矿晚阶段为110-250 ℃，呈逐渐降低的趋势，低温成矿作用明显。3．单个流体包裹体的激光拉曼分析表明，流体包裹体中除含有CO2之外，还含有一定量的N_2和CH_4。4.成矿物质来源的复杂性。萨瓦亚尔顿金矿床矿石中微量元素组成、稀土配分模式大都反映了成矿金属物质主要来自赋矿地层本身。金属硫化物的6345：-3.4‰～+2.6‰，西南天山地区下古生界地层中广泛存在各类火山岩可能是该矿床的主要硫源，部分可能有深部物质的参与。矿石中主要脉石矿物石英和菱铁矿 中包裹体水的氢氧同位素组成为δD = -72％～-62‰，δ~(18)O ＝ -11.6‰～＋5.4‰。成矿流体主要为大气降水补给的地下卤水，并有少量岩浆水的混合。5．Ar-Ar同位素地球化学研究表明，萨瓦亚尔顿金矿床的主要成矿时代为印支晚期，210 Ma。6. 对矿石中的流体包裹体进行了温度、压力、成分、pH、含盐度等的分要的，并系统的进行了矿床形成时的物理化学条件的理论计算，基中包括EH、PH、f_(O_2)、f_(S_2)等及金在矿液运移中的搬运形式。指出减压过程或伴生沸腾的减压过程，是矿床形成过程中矿质卸载的基本机制，此外，酸蚀变过程（如绢云母化等）中由于H~+的消耗促进了溶液中pH值的升高；含高炭质的围岩，降低了矿液的氧逸度以及含矿热液与地表下渗冷水的混合等诸多因素，则是矿订形成的辅助机制。

The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.

Avaliação da contaminação das águas subterrâneas na área de influência da usina de tratamento de resíduos s.a. UTRESA, em Estância Velha (RS)

Este trabalho objetiva avaliar a contaminação das águas subterrâneas em uma área de disposição de resíduos, originados, principalmente, nas indústrias pertencentes ao ramo coureiro-calçadista, a partir da comparação dos resultados das análises físicas e químicas realizadas em amostras de água subterrânea do aquífero freático à jusante da área, com os padrões de potabilidade da água estabelecidos na legislação vigente e com as características das águas subterrâneas do aquífero à montante da área de disposição de resíduos, através da determinação dos seguintes parâmetros: condutividade, SDT, Eh, pH, OD, temperatura, DQO, alcalinidade, turbidez, SST, cloreto, sulfato, nitrato, ferro, manganês, cromo, sódio, magnésio, potássio, cálcio, cádmio, cobre, chumbo, zinco e níquel. Objetiva, também, quantificar os diferentes tipos de resíduos dispostos na área e fornecer subsídios técnicos para o Sistema de Gerenciamento de Resíduos Sólidos Industriais da FEPAM, no que tange ao monitoramento da qualidade das águas subterrâneas em áreas de disposição de resíduos sólidos. A área estudada é a UTRESA - Usina de Tratamento de Resíduos S/A, que abrange 29 ha e está localizada no extremo sudoeste do município de Estância Velha- RS. A metodologia utilizada consistiu das seguintes etapas: quantificação dos resíduos depositados na área, seleção e instalação de nove poços de monitoramento, realização de quatro amostragens das águas subterrâneas, no período compreendido entre junho de 1999 e março de 2000 e tratamento dos dados, com a determinação de índices de qualidade de água subterrânea para cada poço de monitoramento. O monitoramento demonstrou que alguns parâmetros amostrados nos diferentes poços de monitoramento não atenderam os valores recomendados para a potabilidade das águas pelo Ministério da Saúde e pela Organização Mundial da Saúde, bem como apresentaram valores superiores quando comparados ao ponto controle, localizado à montante da área, observando-se o pior índice de qualidade das águas subterrâneas no PM 05, devido a presença de cromo, nitrato, sulfato, cloreto, sódio e SDT.

Uranium speciation in groundwaters from Parana basin, Brazil

This paper describes the results of a regional study involving the sampling of 60 pumped tubular wells drilled at the Parana sedimentary basin, Brazil, which was carried out with the purpose of evaluating the U speciation in the Botucatu-Piramboia aquifer. Uranium proved to be intensively dissolved even under the enhanced reducing conditions occurring at the most confined zones of the aquifer, and Eh-pH diagrams were utilized to evaluate the influence of temperature and pressure on the migration of the U-species within the aquifer.

Vivianite and siderite in lateritic iron crust: an example of bioreduction

Lateritic iron crust (LIC) samples from Padauari (AM) were analysed by XRD, optical microscopy and SEM-EDS. The equilibrium of iron minerals (IM) was studied using Eh-pH diagram. It was shown that the minerals of the LIC are goethite (a-FeOOH), vivianite [Fe₃(PO₄)₂.8H₂O] and siderite (FeCO₃). Carbonate grains are a solid solution of FeCO₃-MnCO₃. The LIC presents textures and structures of dissolution of IM. The siderite and vivianite are stable from Eh =-0.3 to 0.0 V and pH=5.0-7.5. These results indicate that vivianite and siderite are products of bioreduction through biogenic dissolution of IM, the new conditions of ecosystems of the Amazon region.

Simulação de contaminação de sedimentos e águas subterrâneas por gasolina e álcool: um estudo de monitoramento de variações das propriedades físico-químicas

Geophysics studies in areas impacted by petroleum derivatives describe abnormalities of both low and high electrical resistivity (the opposite of electrical conductivity), confirmed as contaminant phase by chemical analysis: this contradiction can be explained by degrading processes that naturally occur and create sub products that can change the environment conductivity. Monitoring the variation of the parameters mentioned serves as a comparative basis to the variation in geoelectrical parameters, which identified the correlation between the same contaminant parameters and the difference between their behavior studied apart, as well as its relations with the biodegradation process. The results are applied to the fuel distribution and storage sectors, leading to the diagnosis and monitoring of possible groundwater contamination scenarios, and the knowledge of the area exposure time to the contaminant, besides the better remediation alternative and impacts control. Among some conclusions, the most significant are the decrease in conductivity over time, so as the increase in Eh value in the gasoline contaminated tank, as well as the decrease in the pH value in the second tank with ethanol, which can be attributed to its degradation. Comparing the variations in both tanks, it is evident that Eh, pH and electrical conductivity do not behave temporally in a similar way, although some correlations between Eh and pH can be related.

Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Voltammetric Investigation of Xanthate Chemisorption on a Chalcopyrite Surface

Cyclic Voltammetry experiments have been conducted on copper, iron, and chalcopyrite (CuFeS2) and compared to mass-balanced EH-pH Diagrams. Potassium ethyl xanthate (KEX) was added to solution and additional voltammetry experiments were performed to determine the surface chemistry reactions of flotation collector in solution with these minerals. The ultimate goal of this research was to investigate the possibility of xanthate chemisorption onto the chalcopyrite mineral surface. Results of the copper mineral testing confirm previous literature studies and corroborate published isotherm data. Results of the iron mineral testing showed changes in surface reactions with the addition of potassium ethyl xanthate to solution, however, these results were not attributed to the chemisorption of xanthate. Results of the chalcopyrite mineral testing indicate that the surface of the mineral oxidizes to chalcocite (Cu2S). In the presence of ethyl xanthate, small currents were observed and attributed to chemisorption of the potassium ethyl xanthate at the chalcocite surface, suggesting that the mineral's hydrophobicity is induced by more than dixanthogen. This phenomenon was found to be pH-dependent under a range of alkaline conditions (i.e., pH 7-12) at narrow potentials (i.e., 0 to -200mV).