200 years of mining activities at La Paz/San Luis Potosí/Mexico - Consequences for environment and geochemical exploration

The Ag---Pb---Zn---Cu---Au mining district of Santa María de La Paz has been extensively exploited for approximately 200 years. Consequences of these activities are several deposits of tailings with high As and heavy metal concentrations, which are completely unstable. The climate is semiarid and as the dumps have no protective cover, material from the dumps is dispersed by strong winds. It is also washed out during seasonally heavy rainfalls. By these processes approximately 100 km² of surrounding have been contaminated by dump material. The As and heavy metal content of the soils was determined as well as their level in crops (Zea Maize) from agricultural lands in the vicinity of the dumps. In the direction of prevailing winds concentrations up to 1000 ppm Zn, 400 ppm Pb, 16 ppm Cd, 550 ppm Cu and 300 As have been detected in top soils. Using fuzzy cluster analysis the different contamination sources could be identified. Grains of corn from contaminated sites showed no critical concentrations, but leaves which are also used tor fodder, have As-concentrations up to 20 ppm.     

砷的仪器分析方法新进展

砷是自然界中广泛存在的一种物质在工业，农业，医药等方面应用很广。笔者着重介绍了近几个来砷的仪器分析方法新进展，主要有光度法，电化学法，原子吸收法等。     

Integration of aquifer geology,groundwater flow and arsenic distribution in deltaic aquifers – A unifying concept

Groundwater arsenic (As) presents a public health risk of great magnitude in densely populated Asian delta regions, most acutely in the Bengal Basin (West Bengal, India and Bangladesh). Research has focused on the sources, mobilisation, and heterogeneity of groundwater As, but a consistent explanation of As distribution from local to basin scale remains elusive. We show for the Bengal Aquifer System that the numerous, discontinuous silt‐clay layers together with surface topography impose a hierarchical pattern of groundwater flow, which constrains As penetration into the aquifer and controls its redistribution towards discharge zones, where it is re‐sequestered to solid phases. This is particularly so for the discrete periods of As release to groundwater in the shallow subsurface associated with sea level high‐stand conditions of Quaternary inter‐glacial periods. We propose a hypothesis concerning groundwater flow ( S ilt‐clay layers I mpose H ierarchical groundwater flow patterns constraining A rsenic progression [SIHA]), which links consensus views on the As source and history of sedimentation in the basin to the variety of spatial and depth distributions of groundwater As reported in the literature. SIHA reconciles apparent inconsistencies between independent, in some cases contrasting, field observations. We infer that lithological and topographic controls on groundwater flow, inherent to SIHA, apply more generally to deltaic aquifers elsewhere. The analysis suggests that groundwater As may persist in the aquifers of Asian deltas over thousands of years, but in certain regions, particularly at deeper levels, As will not exceed low background concentrations unless groundwater flow systems are short‐circuited by excessive pumping.     

陕西略阳张家山金矿成矿作用及Au-Se矿物形成物理化学条件研究

陕西略阳煎茶岭金矿矿集区中的张家山金矿主要由破碎蚀变岩型、角砾岩型和含金石英黄铁矿脉型矿石组成。含金石英-黄铁矿脉型矿石产于断层下盘的石英菱镁岩中。黄铁矿发育富As黄铁矿边,环边受As含量的变化呈现一定的韵律变化,自然金赋存在富As黄铁矿中。在断裂发育形成断层角砾岩的过程中,流体充填破碎石英菱镁岩的裂隙中形成热液矿物,包括硫化物、硒化物以及自然金。石英菱镁岩发生破碎形成的网状裂隙被含金石英-方解石-黄铁矿脉充填。破碎蚀变岩型矿石中,自然金主要分布在含金石英-黄铁矿脉的石英之中或靠近热液脉的菱镁矿或石英间隙。随着大量方解石脉沿裂隙贯入,进一步促进石英菱镁岩的破碎及岩石角砾的分离,形成由石英菱镁岩碎屑、石英和褐铁矿组成的复成分角砾岩,自然金和硒化物呈浸染状分布在角砾岩中。笔者在角砾岩型矿石中发现了灰硒汞矿、直硒镍矿、硒铅矿等硒化物,这些硒化物往往与自然金密切共生。结合矿物组合以及相关化学反应关系,通过热力学计算,构建了该矿床在不同温度条件下的热力学相平衡关系图,限定了硒化物与其他相关矿物稳定存在的物理化学条件。硒化物一般与自然金和石英共生,高的f(Se2)值和f(Se2)/f(S2)比值是控制硒化物形成的关键因素。     

Contrasting water–rock interaction behaviors of antimony and arsenic in contaminated rivers around an antimony mine,Hunan Province,China

Although antimony (Sb) and arsenic (As) exhibit similar geochemical behavior and toxicity in the environment, growing evidence suggests that their water–rock interaction behavior in contaminated rivers is quite different. Twenty-nine river water samples were collected between September and November 2018 from contaminated rivers around an antimony mine in Hunan Province, China. The concentrations of As and Sb were inversely proportional to the water flow distance. The rates and magnitudes of Sb decrease were more prominent than those of As. Silicate mineral dissolution from rocks such as silicified limestone increased the As and Sb concentration of in-mine-district (IMD) water. Dissolution of carbonate minerals, ion exchange, and competitive adsorption were the major water–rock interactions, resulting in rapidly decreasing As and Sb concentration in IMD direct impacted water and IMD indirect impacted water. The behaviors of As and Sb during water–rock interaction were dissimilar for areas dominated by carbonate and silicate minerals.     

2010—2020年黄河下游河南典型灌区浅层地下水中砷和氟的演化特征及变化机制

黄河下游典型灌区河南段是豫北平原重要的农业种植区。该地区浅层水质整体较差,因常用于作物灌溉或家畜饮用,会对人体健康产生风险,因此对该地区地下水中砷与氟浓度变化特征和机制的研究将有助于提高对该地区地下水污染的认识水平。本文基于2010年和2020年在灌区范围内采集的327组浅层地下水样品,研究区内地下水砷和氟分布情况,并在此基础上对比研究十年间灌区浅层地下水中砷、氟的演化特征,探索分析砷与氟浓度及空间变化机制。研究结果表明：该地区浅层地下水中存在砷与氟超标问题,2020年浅层地下水中高砷（砷浓度大于10μg/L）和高氟（氟浓度大于1mg/L）的样品数量分别占总数的26.1%和26.06%。高砷水分布在太行山前洼地与黄河冲积平原等泥沙互层结构的沉积环境中,还原性较强,同时地下水径流不畅,较强的阳离子交换作用使得其所处环境中Ca²⁺浓度较高。近十年间砷浓度增加的水样占总数31.8%,砷浓度减少的水样占36.7%。砷浓度的增长（减少）是地下水还原性增强（减弱）使得锰氧化物溶解释放（吸附）导致。近十年间不同地区农业灌溉和水源置换等用水方式导致水位变化是引起砷浓度变化的潜在因素。高氟水主要分布在河南新乡与濮阳的黄河沿线,氟离子浓度受到沉积物中萤石等钙质矿物溶解影响,使得高氟地下水出现在低钙环境中。近十年间研究区中氟离子浓度减少的占总数60.2%,氟离子浓度增加的占32.1%,整体变化趋势向好,但是高氟区中氟离子浓度继续增加。氟浓度的变化同样受到Ca²⁺变化影响,在Ca²⁺浓度降低（升高）时氟浓度进一步升高（降低）。地下水中氟升高地区分布在黄河沿线,因此受到黄河水补给影响较大,地下水径流条件较好,阳离子交换作用减弱,使得Ca²⁺浓度降低,此时地下水中砷浓度受到环境影响而降低,因此研究区氟增加地区中砷与氟的分布和演化呈现反向关系。     

硫介导细菌还原载砷铁矿对砷迁移转化的影响

硫在铁和砷的生物地球化学循环中发挥着重要作用,但地下水系统中硫循环的中间产物S(0)对细菌转化铁和砷的影响尚不清楚.采用室内模拟实验,研究硫参与下细菌D2201对液相和载砷针铁矿中Fe(III)和As(V)的还原作用.结果表明:细菌D2201具有很强的铁还原能力,可以将液相中74%的Fe(III)还原;加入硫后,细菌还原S(0)产生的S(-II)使铁还原率提高到94%.但是,硫没有明显影响细菌对砷的还原.在实验初期,细菌明显加速了载砷针铁矿的还原,最终还原释放到液相中的Fe(II)浓度为32.12 μmol/L;硫的加入增强了细菌对载砷针铁矿的还原,还原溶解的Fe(II)增加至284.13 μmol/L,同时,砷的释放量也增加了1.6倍.这些结果表明硫显著促进了细菌对针铁矿的还原溶解并加速砷的释放.XRD和SEM-EDS结果显示,细菌还原针铁矿但不改变其矿相,而硫的加入也仅使矿物发生一定程度的团聚,并没有使其转变为其他矿物,也未导致砷的再吸附.      

北京市蔬菜和菜地土壤砷含量及其健康风险分析

通过对北京市蔬菜和菜地土壤砷含量状况进行大规模调查,研究了蔬菜和土壤砷含量及其健康风险,并筛选出抗砷污染能力强的蔬菜品种。根据蔬菜的消费量并兼顾品种多样性的原则,在北京市规模化蔬菜栽培基地 (采集蔬菜及土壤样品) 和蔬菜批发市场 (蔬菜样品) 共采集93种蔬菜400多份蔬菜样品和39个土壤样品系统地分析其砷含量。研究发现：北京市菜地土壤砷含量范围和平均含量分别为4.44~25.3和9.40 mg/kg,明显超过北京市土壤砷背景值;北京市蔬菜砷含量最高达0.479 mg/kg,平均含量为0.028 mg/kg,均未超过《食品中砷限量卫生标准》(GB4810-94) 的限量值,但其中有2个蔬菜样品 (萝卜和大蒜) 砷含量超过WHO/FAO制订的限量标准。北京市蔬菜砷含量在东偏北方向 (偏转11^o-30^o) 存在明显的"U"型趋势分布。裸露地蔬菜砷含量显著高于设施蔬菜。油菜、萝卜、小白菜、大葱、芥菜、黄瓜、大白菜和甘蓝抗砷污染能力较弱,而辣椒、云架豆、冬瓜、茄子、菠菜、西红柿、芹菜等抗砷污染能力则较强。北京市居民从蔬菜中摄入砷平均值为0.016 mg/(人·d),蔬菜砷对北京市部分人群存在一定的健康风险。     

Mineralogical and Geochemical Constraints on Arsenic Mobility in a Philippine Geothermal Field

Arsenic is usually associated with sulphide minerals formed in the geothermal environment. However, sulphide minerals are prone to dissolution after contact with meteoric water under surface oxidizing conditions. Secondary precipitates that form from the dissolution of the primary sulfides exert a greater influence on arsenic mobility in the geothermal environment. Fe-hydroxides have very good affinity with dissolved arsenate and are stable under most surface oxidizing conditions. Both amorphous silica directly precipitated from geothermal fluids and possibly a kaolinite alteration can host a small significant amount of arsenic. These silicates are also more stable under a wide range of pH and redox conditions.     

Inorganic arsenic speciation in the waters of the Penzé estuary (NW France): Seasonal variations and fluxes to the coastal area

Over this one-year study, the variations of inorganic As species were examined monthly along the salinity gradient of the Penzé estuary (NW France) in relation with different biogeochemical parameters. In most cases, dissolved As exhibited a non-conservative behaviour which resulted from the competition between two major processes. In the upstream section of the estuary, a strong input of both total inorganic As and As(III) occurred. Then, the removal of the same species, under precipitation of iron oxides/oxyhydroxides, was observed in the low-salinity range (S < 10). Using our experimental data, the fluxes of the various As species were estimated for the first time in estuarine waters. Inputs from the river were mainly constituted of particulate As (∼70%). Conversely, dissolved species were predominant in the net fluxes (∼65%) and As(III) accounted for ∼15% of the dissolved net flux.