Pathfinder applications of arsenic, antimony and bismuth in geochemical exploration

The potential applications of As, Sb and Bi as pathfinder elements in geochemical exploration have been researched using a new, rapid technique for the simultaneous determination of the three elements. Following a warm hydrochloric acid sample leach, the volatile hydrides of the elements are generated and flushed into an inductively-coupled plasma linked to an emission spectrometer. The technique offers a combination of good analytical precision and detection limits of 100 ppb for each of the elements.The principal sulphide ore minerals commonly contain traces of As, Sb and Bi, and concentrations of more than 1% of any one of these have been found in some sulphide specimens. During sub-aerial oxidation of sulphides, any As, Sb and Bi present is released and forms dispersion patterns in the surficial environment. Geochemical surveys of localities in the United Kingdom have demonstrated that anomalous dispersion trains of these elements can be detected in the sediments of streams draining the mineralized localities. In a geochemical mapping programme covering 16,000 km² of central Nepal, over 3500 stream sediment samples were analyzed for As, Sb and Bi, and many known occurrences of Cu, Pb and Zn mineralization are reflected by As, Sb and Bi anomalies. However, bedrock lithology appears to be an important factor influencing Sb and Bi dispersion patterns.In the areas studied, some or all of the elements As, Sb and Bi produce stream sediment anomalies that compare favourably in terms of contrast and extent with the heavy metal expressions, even though none of the three elements have been reported as important constituents of the mineralization with which they occur.     

Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah

Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O₂ (DO), and water temperature (T_w) whereas As varied opposite to Se, pH, DO and T_w. Changes in pH, DO and T_w showed a direct linear correlation (r = 0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and T_w were inversely correlated to filtered As concentration (r = −0.88, −0.87, and −0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn.     

Mercury, arsenic, antimony, bismuth and boron as geochemical indicators for geothermal areas

From 1982 to 1983, 131 soil samples were collected within an area of 60 km² in known geothermal field and their vicinities in Tengchong, Yunnan Province. Distinct anomalies of Hg, As, Sb and Bi were found on the known geothermal fields. The contour of the multiplicative anomaly of Hg × As × Sb encircled the two known geothermal fields, Reshuitang and Rehai, within its extent, disclosing the interrelation between these two fields, and enlarging their future prospects. The B anomaly is related to structural features. Significant correlations among Hg, As and Sb are shown by correlation analysis. It was concluded that a geochemical survey with a density of two samples per km² could be carried out effectively to delineate promising targets of geothermal resources.     

Identifying environmental and geochemical variables governing metal concentrations in a stream draining headwaters in NW Spain

Headwater stream, draining from a rural catchment in NW Spain, was sampled during baseflow and storm-event conditions to investigate the temporal variability in dissolved and particulate Al, Fe, Mn, Cu and Zn concentrations and the role of discharge (Q), pH, dissolved organic carbon (DOC) and suspended sediment (SS) in the transport of dissolved and particulate metals. Under baseflow and storm-event conditions, concentrations of the five metals were highly variable. The results of this study reveal that all metal concentrations are correlated with SS. DOC and SS appeared to influence both the metal concentrations and the partitioning of metals between dissolved and particulate. The SS was a good predictor of particulate metal levels. Distribution coefficients (K_D) were similar between metals (4.72–6.55) and did not change significantly as a function of discharge regime. Stepwise multiple linear regression analysis reveals that the most important variable to explain storm-event K_D for Al and Fe is DOC. The positive relationships found between metals, in each fraction, indicate that these elements mainly come from the same source. Metal concentrations in the stream were relatively low.     

微波消解-原子荧光光谱法测定化探样品中的砷和锑

准确测定砷和锑的含量是化探样品测定中的重要内容.本文介绍了测定这两种元素的一种新方法,笔者基于原子荧光光谱仪,试样经氢氟酸-盐酸-硝酸混酸微波消解,高氯酸-硫酸混酸蒸发除去氢氟酸,由盐酸-酒石酸混合溶液定容,从而得到样品中准确的砷、锑含量.本方法砷、锑校准曲线的线性相关系数均大于0.999;检出限分别为砷0.039μg/L、锑0.0058μg/L.按照实验方法测定水系沉积物、土壤标准物质中砷、锑,结果的相对误差砷为1.52%~6.77%,锑为1.25%~7.17%;相对标准偏差(RSD,n=6)砷为2.27%~5.15%、锑为1.88%~5.81%.本方法适用于化探样品中砷含量在0.05~500μg/g、锑含量在0.05~300μg/g之间的样品测定.     

河南商城汤家坪钼矿地球化学异常特征及找矿标志

商城汤家坪钼矿是近年在大别山地区探明的一处大型钼矿床。该矿区地球化学异常特征研究表明，成矿元素含量变化与花岗斑岩体空间位置、岩石类型、蚀变特征密切相关；在三度空间内，地球化学异常的分布严格受斑岩体控制；Mo异常浓度分带清晰，其内带指示了钼工业矿体位置，中带反映了边界矿体和强矿化范围，外带反映了弱矿化和矿化蚀变范围。在对成矿地质背景、指示元素地球化学参数和地球化学异常特征分析研究的基础上，建立了地质、地球化学找矿标志。     

Antimony and arsenic mobility in a creek draining an antimony mine abandoned 85 years ago (upper Orb basin,France)

Mining residues from the Sb mine of Bournac in the upper Orb River valley (Southern France), constitute an important source of As and Sb pollution. Arsenic concentrations are as high as 78 μg/L and Sb reaches 32 μg/L in the small creek draining the tailings impoundment. Although both metalloids occur mainly in oxidized form in the creek water, their behaviour differs significantly. Iron oxides are the main carrier phases for both elements in the suspended particulate matter. In oxic conditions the two elements are mainly present in water in oxidised form As(V) and Sb(V) and both field studies and laboratory experiments indicate a higher affinity of As(V) than Sb(V) for the solid phase. In the pool, which receives the water from Bournac Creek, the reductive dissolution of Fe-oxides is linked to the oxidation of small pyrite grains transported from the tailings dump. In oxic conditions Sb is released to solution more efficiently than As. Conversely, in anoxic conditions, mobilisation of As is greater than that of Sb. This is attributed to the reduction of As, which favours its mobility. Whatever the conditions, the activity of bacteria naturally present in the sediments enhances the remobilization of Sb in oxidizing conditions and that of As in reducing conditions.     

物化探方法在黑龙江古金厂地区水系沉积物异常查证中的应用

利用1∶2万土壤测量、地面高精度磁法测量及激电中梯测量等方法对黑龙江黑河市古金厂地区1∶5万水系沉积物异常进行查证,发现Au等11种单元素土壤异常75处、组合异常6处、高磁异常5处和激电异常2处。在综合分析其地质背景基础上,对物化探异常套合处进行了槽探工程揭露,发现681.5高地金矿体。     

甘蒙北山四道梁南钼矿土壤地球化学异常特征及找矿潜力分析

甘蒙北山四道梁南地处东天山-北山中亚增生造山带南缘,早二叠世-三叠纪早期完成了俯冲增生体制到伸展构造体制动力转换过程,伸展背景下多期次的酸性岩浆活动为斑岩型和浅成低温热液型铜、金、银、钼矿床的形成提供了良好的地质条件。本文通过对区内土壤地球化学测量数据的多元统计分析,探讨了成矿元素及伴生元素异常组合、分布特征,结合成矿地质背景评价了找矿潜力。研究发现区内Bi、Mo、As等元素高强度数据占比大、分异程度高,是主要的成矿元素,异常主要分布在印支期中细粒二长花岗岩与早二叠世双堡塘组英安岩的接触带附近;成矿元素组合与矿化蚀变分带具有从高温W、Mo、Bi→中高温Pb、Zn、Ag→中低温Hg、Sb、Cu→低温As、Au演化的规律;结合矿床地质特征,认为其具有与斑岩型成矿系统相似的成矿元素组合和矿物分带特征,属于斑岩型钼矿床且具有较好的找矿前景。同时确定W-Mo-Bi元素组合异常是区内寻找Mo（W）矿床的有利指示元素或找矿标志,可有效地确定成矿部位并指导勘查工程布置     

Behavior of arsenic and geochemical modeling of arsenic enrichment in aqueous environments

Arsenic is present in aqueous environments in +III and +V oxidation states. In oxidizing environments, the principle attenuation mechanism of As migration is its adsorption on Fe(III) oxide and hydroxides. The adsorption affinity is higher for As(V) under lower pH conditions and for As(III) under higher pH conditions. Ferric oxide and hydroxides can dissolve under low Eh and pH conditions releasing adsorbed As. Oxidation-reduction processes often involve high organic matter content in sediments and also contamination by organics such as BTEX. Arsenic may desorb under high pH conditions. Changes of pH can be related to some redox reactions, cation exchange reactions driving dissolution of carbonates, and dissolution of silicates. In very reducing environments, where SO₄ reduction takes place, secondary sulfide minerals like As-bearing pyrite and orpiment, As₂S₃, can incorporate As. Geochemical modeling can be divided into two principal categories: (a) forward modeling and (b) inverse modeling. Forward modeling is used to predict water chemistry after completion of predetermined reactions. Inverse modeling is used to suggest which processes take place along a flowpath. Complex coupled transport and geochemistry programs, which allow for simulation of As adsorption, are becoming available. A common modeling approach is based on forward modeling with surface complexation modeling (SCM) of As adsorption, which can incorporate the effect of different adsorbent/As ratios, adsorption sites density, area available for adsorption, pH changes and competition of As for adsorption sites with other dissolved species such as phosphate. The adsorption modeling can be performed in both batch and transport modes in codes such as PHREEQC. Inverse modeling is generally used to verify hypotheses on the origin of As. Basic prerequisites of inverse modeling are the knowledge of flow pattern (sampling points used in model have to be hydraulically connected) and information about mineralogy including As mineral phases. Case studies of geochemical modeling including modeling of As adsorption are presented.     

Precipitation of iron,manganese, zinc,and copper on clean,ceramic surfaces in a stream draining a polymetallic sulfide deposit

Acid-cleaned ceramic plates placed upstream and downstream from a Cu-Zn-Pb sulfide deposit (Magruder mine) developed a precipitate of Fe-Mn oxides in a 36-day period. Copper and Zn concentrations on the coated surface, normalized to surface area and ratios with Fe and/or Mn, are distinctly anomalous for a distance of 2 km downstream from the mine.The major source of metals in the coatings is interpreted to be groundwater percolating into the stream bed. Anomalous concentrations of Cu and Zn in groundwater from the Magruder mine area, due to oxidation of sulfide minerals, probably accounts for the anomaly identified on the ceramic plates.     

Partitioning geochemistry of arsenic and antimony,El Tatio Geyser Field,Chile

The abundance of As and Sb in aqueous, mineral and biological reservoirs was examined at El Tatio Geyser Field, a unique hydrothermal basin located in the Atacama Desert region of Chile. Here the concentration of total As and Sb in hydrothermal springs and discharge streams are the highest reported for a natural surface water, and the geyser basin represents a significant source of toxic elements for downstream users across Region II, Chile. The geyser waters are near neutral Na:Cl type with ∼0.45 and 0.021 mmol L⁻¹ total As and Sb, respectively, primarily in the reduced (III) redox state at the discharge with progressive oxidation downstream. The ferric oxyhydroxides associated with the microbial mats and some mineral precipitates accumulate substantial As that was identified as arsenate by XAS analysis (>10 wt% in the mats). This As is easily mobilized by anion exchange or mild dissolution of the HFO, and the ubiquitous microbial mats represent a significant reservoir of As in this system. Antimony, in contrast, is not associated with the mineral ferric oxides or the biomats, but is substantially enriched in the silica matrix of the geyserite precipitates, up to 2 wt% as Sb₂O₃. Understanding the mobility and partitioning behavior of these metalloids is critical for understanding their eventual impact on regional water management.     

Mapping geochemical singularity using multifractal analysis: Application to anomaly definition on stream sediments data from Funin Sheet,Yunnan, China

Most conventional statistical methods aiming at defining geochemical concentration thresholds for separating anomalies from background have limited effectiveness in areas with complex geological settings. This paper uses multifractal analysis to combine the characteristics of geochemical frequency distribution and spatial dispersion in order to map geochemical singularities instead of using conventional statistically derived concentration thresholds. The model, termed radius–areal Productivity (r–P) model, employs a stable measure and a scale-increasing method to estimate geochemical singularities spatially on geochemical landscape for delineating potential anomalies. The model is applied to geochemical data of regional stream sediments from the Funin Sheet, Yunnan, China.     

Colorimetric determination of arsenic in geochemical samples

A colorimetric method and apparatus for the determination of arsenic in batches of geochemical survey samples is described. The powdered material can be digested with a perchloric/nitric acid mixture, or most conveniently by an HF/aqua regia attack utilizing aliquots from the same acid solution as used for routine multi-element atomic absorption analyses. Aliquots are treated with potassium iodide and stannous chloride to reduce arsenic to the trivalent state, and arsine is liberated by the action of zinc pellets. The arsine is absorbed in a solution of silver diethyldithiocarbamate in chloroform-quinoline, the reaction being carried out in batches using very simple, inexpensive apparatus which is easily constructed. Detection limits are variable according to aliquot quantities taken, but in routine use working ranges of 1–800 ppm As are readily achieved. Coefficient of variation is 6.6% at the 5 μg As level. The method is shown to be virtually free from matrix interferences commonly encountered in gossans, soils, rocks and many ores. At least 100 powdered samples can be analyzed per man-day.     

Geochemistry of molybdenum in some stream sediments and waters

Elevated concentrations of Mo are present in both the waters and sediments of Tenmile Creek, downstream from the large Mo deposit at Climax. Colorado. Concentrations of Mo reach a maximum of 10mg/1 in the water and 384μ/g in the (?) 80 mesh fraction of the sediment. The Mo anomaly extends for more than 80 km downstream from Climax, and results from the mining and milling at Climax. Background Mo concentrations in the nearby mountainous area are < 10μg/l (water) and < 5μg/g (sediment). Immediately below three small unmined Mo-rich orebodies elsewhere in Colorado < 3μg/l Mo are present in the waters and 20–30μg/g Mo in the fine fraction of the sediments.The Mo in the sediment of Tenmile Creek is chiefly adsorbed on coatings of amorphous Fe oxyhydroxide. and is similar to its form below two small, unmined Mo deposits. Mining has not changed the character of the chemical processes responsible for Mo dispersion from the Climax site.A modified version of the WATEQF computer program (Plummeret al., 1976) predicts that Tenmile Creek is undersaturated with respect to ferrimolybdite. molybdenite, powellite, and ilsemannite. The Mo in the stream water occurs as the molybdate ion which can be adsorbed on amorphous Fe oxyhydroxides. These predictions are supported by the absence of Mo minerals in the sediment of Tenmile Creek.     

Arsenic and antimony contamination of waters,stream sediments and soils in the vicinity of abandoned antimony mines in the Western Carpathians,Slovakia

Environmental contamination with As and Sb caused by past mining activities at Sb mines is a significant problem in Slovakia. This study is focused on the environmental effects of the 5 abandoned Sb mines on water, stream sediment and soil since the mines are situated in the close vicinity of residential areas. Samples of mine wastes, various types of waters, stream sediments, soils, and leachates of the mine wastes, stream sediments and selected soils were analyzed for As and Sb to evaluate their geochemical dispersion from the mines. Mine wastes collected at the mine sites contained up to 5166 mg/kg As and 9861 mg/kg Sb. Arsenic in mine wastes was associated mostly with Fe oxides, whereas Sb was present frequently in the form of individual Sb, Sb(Fe) and Fe(Sb) oxides. Waters of different types such as groundwater, surface waters and mine waters, all contained elevated concentrations of As and Sb, reaching up to 2150 μg/L As and 9300 μg/L Sb, and had circum-neutral pH values because of the buffering capacity of abundant Ca- and Mg-carbonates. The concentrations of Sb in several household wells are a cause for concern, exceeding the Sb drinking water limit of 5 μg/L by as much as 25 times. Some attenuation of the As and Sb concentrations in mine and impoundment waters was expected because of the deposition of metalloids onto hydrous ferric oxides built up below adit entrances and impoundment discharges. These HFOs contained >20 wt.% As and 1.5 wt.% Sb. Stream sediments and soils have also been contaminated by As and Sb with the peak concentrations generally found near open adits and mine wastes. In addition to the discharged waters from open adits, the significant source of As and Sb contamination are waste-rock dumps and tailings impoundments. Leachates from mine wastes contained as much as 8400 μg/L As and 4060 μg/L Sb, suggesting that the mine wastes would have a great potential to contaminate the downstream environment. Moreover, the results of water leaching tests showed that Sb was released from the solids more efficiently than As under oxidizing conditions. This might partly explain the predominance of Sb over As in most water samples.     

陕西商洛马角寺钼矿区土壤地球化学特征及找矿前景——地球化学找矿的典型实例

陕西商洛马角寺钼矿位于小秦岭多金属成矿带西部,矿区出露元古界至新生界地层,区内褶皱和断裂较为发育。1∶50 000水系沉积物测量在本区圈出Mo、Pb、Zn等元素异常,指示有多金属找矿前景。在区内开展1∶10 000土壤测量工作,并对取得的大量数据进行统计分析,研究总结矿区土壤地球化学特征,显示本区Mo、(Au)为成矿元素,Ag、Pb、Zn等为指示元素;同时,在区内再次圈出Mo、Ag、Pb、Zn等元素异常,异常再现性较好。运用1∶2 000地球化学剖面对土壤异常进行查证,发现一条含钼矿化构造带(Q1),从中圈出Mo矿体多条。综合研究1∶10 000地球化学特征显示,本区仍有Mo、(Au)矿床的找矿前景。