Geochemical modeling approach to predicting arsenic concentrations in a mine pit lake

Between 1968 and 1983, the North pit at the Getchell Mine, Humboldt County, NV, filled with water to form a lake. In 1983, water quality data were collected with the following results: As concentrations of 0.29 to 0.59 mg/L, pH of 7.1 to 7.9, SO₄ concentrations of 1490 to 1640 mg/L, and TDS of 2394 to 2500 mg/L. Using geochemical modeling techniques presented here, pit lake waters have been theoretically allowed to react for 8.5 a, the approximate time that the North pit had been completely full by 1983. Modeling results predict pH of 7.9 to 8.2, SO₄ concentrations of 1503 to 1644 mg/L, TDS of 2054 to 2366 mg/L, and As concentrations ranging from 0.57 in the hypolimnion to 96 mg/L in the epilimnion. In the epilimnion, model results do not match observed As concentrations, suggesting that mechanisms, such as precipitation of arsenate salts or adsorption to mineral surfaces, may control As levels in an actual pit lake system. Adsorption to Fe oxyhydroxide surfaces is questioned by the authors because of the low Fe content in the Getchell system, but adsorption to Al(OH)₃ (gibbsite) and clay mineral surfaces may be important in controlling natural As concentrations.     

Sulfide oxidation in brown coal overburden and chemical modeling of reactions in aquifers influenced by sulfide oxidation

With a mean annual flow of 5.9×10¹¹m³yr^–1 and sediment load of 1600x10¹²gyr^–1 the Ganges river ranks second and third, respectively, in terms of water flow and sediment load among the world's rivers. Considering the enormous sediment transport by Ganges to the Bay of Bengal, a study was conducted on the size distribution and mineral characteristics of the suspended sediments of the Ganges river and is reported here. Most of the sediment load has a size range between <4–5.75 ). The sediments are mostly medium to coarse silt and are poorly sorted. Mica dominates among the clay minerals, followed by chlorite, vermiculite, kaolinite, and smectite. Due to differences in geology, smectite becomes a major clay mineral in downstream rivers. At Calcutta, the clay mineral transport in millions of tons per year is 18,464, 8000, and 2147, for mica, smectite, and chlorite, respectively.     

Heavy metal and arsenic dispersion in a copper-skarn mining district in a Mexican semi-arid environment: sources, pathways and fate

The Cu–Au rich ores of the Concepción del Oro mining district, located on the semi-arid Mexican Altiplano, have been mined for over 400 years. The residues of these activities were piled on the banks of the main stream that drains the area. The tailings piles are neither treated nor protected, so the waste material has been dispersed over the surroundings by seasonally occurring heavy rains and winds. A small town with 5,000 inhabitants has grown up around the mining operations. Mineralogical observations indicate that sulphates are the first products of alteration of the primary sulphides and that Fe hydroxides are the stable minerals that are formed after longer periods of time. At the present time, an area of about 40 km² along both sides of the stream has being severely contaminated with Cu–As–Zn-rich tailings, indicating that the seasonal heavy rains are indeed the main dispersion factor. Contaminated soils reach Cu-concentrations of up to 100 times, and As-concentrations of up to 20 times the local natural values. Factor analysis and geostatistical methods helped to identify pollutant origins and sources. Extraction tests on polluted agricultural soils using acetic acid mobilized 5–10 % of the total As content, 0.5–2.75 and 1–4.5 % of Cu and Zn, respectively, indicating the potential of the biological activity of the soil to enhance the mobility of the elements mentioned, and, in this way, to get into the food chain and/or groundwater. Stabilization measures of the tailings heaps must be urgently undertaken in order to minimize the risk for the inhabitants of the region and to stop the pollution of a broader area.     

Influence of arsenic on iron sulfide transformations

The association of arsenate, As(V), and arsenite, As(III), with disordered mackinawite, FeS, was studied in sulfide-limited (Fe:S = 1:1) and excess-sulfide (Fe:S = 1:2) batch experiments. In the absence of arsenic, the sulfide-limited experiments produce disordered mackinawite while the excess-sulfide experiments yield pyrite with trace amounts of mackinawite. With increasing initially added As(V) concentrations the transformation of FeS to mackinawite and pyrite is retarded. At S:As = 1:1 and 2:1, elemental sulfur and green rust are the end products. As(V) oxidizes S(-II) in FeS and (or) in solution to S(0), and Fe(II) in the solid phase to Fe(III). Increasing initially added As(III) concentrations inhibit the transformation of FeS to mackinawite and pyrite and no oxidation products of FeS or sulfide, other than pyrite, were observed. At low arsenic concentrations, sorption onto the FeS surface may be the reaction controlling the uptake of arsenic into the solid phase. Inhibition of iron(II) sulfide transformations due to arsenic sorption suggests that the sorption sites are crucial not only as sorption sites, but also in iron(II) sulfide transformation mechanisms.     

河北邯邢铁矿区矿山环境生态地球化学评价

在河北邯邢西石门及周边铁矿区系统地采集了各类生态环境地球化学样品,包括土壤（n=242）、玉米（n=110）、地表水（n=37）、地下水（n=31）和水系沉积物（n=81）。通过对矿区各样品元素含量特征和元素富集程度的研究,利用区域地球化学基准值和地质累积指数定量评价了矿山污染扰动程度。研究表明,矿区土壤、玉米、地表水、地下水、水系沉积物中相对富集较高的与成矿作用有关的元素及主要的伴生元素,部分重金属元素超标,土壤和水系沉积物中Se、As、Cd、Cu、As、Cd、Cu、Co元素超标,玉米中F、Cr、Cd元素接近食品卫生限值,地表水和地下水部分指标浓度接近三类水质限值。研究表明,造成污染的主要来源是铁矿尾矿沙和煤矸石中的硫化物发生氧化作用,导致重金属淋滤转移,另一来源是燃煤降尘的积聚。     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.     

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.     

Geochemical controls on arsenic distribution in the Baccu Locci stream catchment (Sardinia,Italy) affected by past mining

The Baccu Locci stream catchment (Sardinia, Italy) is affected by serious As contamination as a consequence of past mining. The presence of both point and widespread sources of contamination (waste-rock dumps and flotation tailings, respectively) strongly affects surface water chemistry, and produces high As concentrations (hundreds of μg l⁻¹) in stream waters. Water chemistry of the Baccu Locci stream changes considerably over a distance of about 10 km as a consequence of various, locally concomitant, processes acting along the stream course: (1) mixing with metal-rich SO₄ waters; (2) dissolution/precipitation of metal-bearing phases; (3) mixing with HCO₃-dominated lake waters; (4) gypsum dissolution coupled with calcite precipitation; (5) mixing with dilute surface and/or ground waters. In contrast to metals (e.g. Pb, Cu, Zn and Cd), whose dissolved concentrations rapidly decrease downstream of the mined area through (co-)precipitation/adsorption mechanisms, As concentrations tend to gradually increase (up to 0.9 mg l⁻¹) along the stream course as far as the alluvial plain, though significant variations are locally observed. This behaviour is mainly due to the higher mobility of As than metals under the near neutral-oxidative conditions occurring in the Baccu Locci stream waters. Results of a leaching test indicate that part of the As contained in the flotation tailings occurs as As(III), which is more mobile and less strongly sorbed than As(V). The As released to the waters by various mechanisms (i.e. release/desorption from the Fe(III)-hydroxides coatings of silicate grains, oxidation of residual arsenopyrite, decomposition of scorodite) tends to remain in solution and to be transported long distances. As a consequence of the widespread presence of highly As-contaminated flotation tailings all over the medium-lower Baccu Locci stream catchment, long-term As contamination is expected.     

Geochemical mobility of arsenic in the surficial waters from Argentina

The presence of arsenic (As) in surface water constitutes an important environmental risk, where mobility and adsorption processes are responsible for its behavior in the sediment–water interface. Therefore, the assessment of adsorption, mobility and water availability of arsenic in freshwater sediments, with agricultural, livestock and urban soil uses was performed. Arsenic concentrations in sediments ranged from 5.4 to 15.9 mg kg^?1 (total) and 2.8 to 6.5 mg kg^?1 (labile), and those of iron and manganese were 11,563–23,500 and 140.6–662.1 mg kg^?1, respectively. The As levels in water were significantly lower than those of sediments. Results would suggest that As co-precipitation and adsorption on Fe oxides are probably the major route of immobilization, determining its low lability. Manganese did not present an outstanding contribution to the retention, and cation-exchange capacity, pH and organic matter of sediments did not show an influence on the mobility of As.     

Geochemical assessement of actinide isolation in a German salt repository environment

A significant criterion in evaluating disposal strategies for high-level nuclear waste is the assessment of the isolation capacity for the most radiotoxic radionuclides, the actinides. Important processes pertinent to potential mobilization from the waste forms, retention in secondary phases and migration of actinides in the geochemical environment of the near field of disposal locations are summarized. Criteria are formulated for assessing engineered barrier performance as a geochemical barrier for actinide long-term retention.     

Geochemical study of different-aged mining dump materials in the Freiberg mining district, Germany

Historical mining dumps are useful archives for the investigation of weathering processes. The objective of this study was to investigate the weathering behavior of waste-rock material derived from the 800-year-old silver ore mining in Freiberg, Germany. For identifying time-dependent weathering indices, dumped material of four dumps of different ages and corresponding rock was examined regarding the geochemical composition. The dumped material is characterized by high contents of heavy metal containing sulfidic ores, such as pyrite, arsenopyrite, sphalerite and galena. Acid mine drainage is produced by the oxidative weathering of the sulfide minerals and causes the increased dissolving of soluble metals with increasing age of dumps. As a result of these weathering processes, a clear depletion of chalcophile elements in the older dump material (800 years) compared to the youngest dump (100 years) was observed. In the soil horizons downstream the dumps, high quantities of heavy metals (e.g., up to 12,000 ppm As, 3,300 ppm Pb, 640 ppm Zn), mainly adsorbed on organic matter, were determined and indicate a time-dependent element transfer from the dumps into their surrounding soils.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

耕作土壤中砷的物质平衡模拟

本文描述了砷在耕作土壤中的作用过程中，有关砷的物质平衡的数学表述形式。需要用许多模型参数定义所涉及砷的物质平衡的数学表述形式，即使是简化的数学形式。根据参数值的范围和源于出版的文献的初始条件进行实例模拟。研究结果表明，由于对耕作土壤施肥和灌溉水，植被对砷的摄入量引起根部区总砷含量逐渐增加。搞清楚植物对砷的吸收和析出与弄清楚对增加砷的去除途径同等重要。反过来，矿物相的溶解动力学和吸附相的分布系数影响植物吸收和浸出的可用性。根据实验室砷矿相的分解、As（III）的矿化和氧化推导出参数，而砷植物的吸收似乎对砷在土壤中的传输估计过高。数学模型的研究是一个简明的过程，而用自信度定义的模型参数值的不同阻碍了它在实际情况中的应用。目前对土壤一一植被系统中砷的传输过程和作用的了解是不充分的，所以要校准或者验证模型。研究必须了解土壤中砷矿物分解和沉淀的动力学原理和土壤中根部生长以及植被砷吸收的动力学原理。     

Rejection of arsenic minerals in sulfide flotation — A literature review

Arsenic is one of the most dangerous inorganic pollutants and thus a penalty element in many base metal concentrates. Arsenic removal in sulphide flotation has been studied extensively with various approaches, including pre-oxidation of flotation pulp, E_h control during flotation and the use of selective depressants/collectors. Pre-oxidation of flotation pulp using oxidizing agents or aeration conditioning represents a simple approach in arsenic removal and was found effective in many cases. Selective flotation of arsenic minerals through E_h control has made significant advances in recent years with promising results achieved. In addition, various depressants and collectors have also been studied in arsenic removal. In this communication, the various approaches used in selective flotation of arsenic minerals are reviewed with emphasis on the development in recent years.     

高砷地下水的反向地球化学模拟:以中国吉林砷中毒病区为例

饮水型砷中毒分布在中国台湾、新疆、内蒙、山西、吉林等地。笔者采用GIS的空间数据叠加技术、化验测试与环境模拟技术,进行了地下水砷的反向地球化学模拟研究。研究表明,受构造运动控制,低洼地带堆积了巨厚的粉砂淤泥质沉积物和富含有机质的湖积物,为砷的赋存提供了空间。地下水砷的富集受水中Fe、Mn、pH、Cl-、PO34-、HCO3-、SO24-、Se的影响,其中,重碳酸钙型水中砷含量最低,氯化物重碳酸钠型水砷含量最高。臭葱石(FeAsO4:2H2O)等含铁、含锰矿物在进入地下水的溶解过程中,形成铁(锰)氧化物和砷化合物(砷酸盐或亚砷酸盐)。随着Eh降低,氧化物被还原形成更为活泼的离子组分,吸附在氧化物表面的砷化合物随之解吸,还原环境有利于砷从沉积物中向水中溶解、迁移。研究结果为实施安全供水提供了重要依据。