Arsenic mobility in alteration products of sulfide-rich, arsenopyrite-bearing mine wastes, Snow Lake, Manitoba, Canada

The Arsenopyrite Residue Stockpile (ARS) in Snow Lake, Manitoba contains approximately 250,000 tons of cyanide treated, refractory arsenopyrite ore concentrate. The residue was deposited between 1950 and 1959 in an open waste rock impoundment, and remained exposed until 2000, when the pile was capped with layers of waste rock and clay. During the time when the ARS was exposed to the atmosphere, arsenopyrite, pyrrhotite, pyrite and chalcopyrite were oxidized producing scorodite, jarosite and two generations of amorphous Fe sulfo-arsenates (AISA). These secondary phases attenuated some of the As released to pore water during oxidation in the upper layers of the ARS. The imposition of the cap prevented further oxidation. The secondary As minerals are not stable in the reduced environment that currently dominates the pile. Therefore, As currently is being released into the groundwater. Water in an adjacent monitoring well has concentrations of >20 mg/L total As with relative predominance of As(III).     

Arsenic and antimony contamination in the vicinity of Yata gold mine, Guizhou, China

The ores of the Yata gold mine in China are rich in arsenic and antimony, so the exploitation of this mine may also lead to the release of As and Sb to adjacent environments, such as stream water, stream sediment, soil, plants, and crops. To understand the environmental impact of mine tailings, samples of water, sediment, soil, plant and crop were collected and analyzed. In summer of 2005, the tailings dump was seriously flushed by a heavy flood, and the mine waste was transported far away. Samples were collected in December of 2004 and January of 2006, respectively, and the impact of the flood on the release of toxic elements was evaluated. The result shows that the Yata creek, which drains the mining area, was severely contaminated by As and Sb. The dissolved As and Sb in water are 86-1140 μg/L and 65-370 μg/L, the particulate As and Sb are 38-2100 μg/L and 25-420 μg/L, whereas As and Sb in the sediment are 190-760 μg/g and 69-210 μg/g, respectively. In water environment, As and Sb show a similar feature to SO4^2- since As and Sb exist dominantly as anions--H2AsO4^-, HAsO4^2- and SbO3^-. In contrast to Fe, Cu, Pb, Zn, which migrate mostly in particulate form, As and Sb tend to transport in dissolved form.     

Mercury mobility in unsaturated gold mine tailings,Murray Brook mine,New Brunswick,Canada

Elevated concentrations of Hg are present (averaging 36 μg/g), mainly as cinnabar, in the Murray Brook Au deposit, located in northern New Brunswick, Canada. After the mined ore was subjected to CN leaching, the tailings were deposited in an unsaturated pile, and 10 a after mine closure an estimated 4.7 × 10³ kg of CN and 1.1 × 10⁴ kg of Hg remain in the pile. Elevated Hg concentrations have been measured in the groundwater (up to 11,500 μg/L) and surface water (up to 32 μg/L) down-gradient of the tailings. To investigate the controls on Hg mobility and leaching persistence, laboratory experiments were conducted using unsaturated columns filled with tailings. Within the first 0.2 pore volumes (PV) eluted, the concentrations of Hg and CN increased to peak concentrations of 12,900 μg Hg/L and 16 mg CN/L, respectively. In the subsequent 0.9 PV, concentrations decreased to approximately 1300 μg Hg/L and 2.8 mg CN/L. Thermodynamic calculations demonstrate that >99.8% of the mobilized Hg in the tailings pore water is in the form of Hg–CN complexes, indicating that Hg mobility to the surrounding aquatic environment is directly dependent on the rate of CN leaching. One-dimensional transport simulations suggest that leached CN can be partitioned into conservative (24%) and non-conservative (76%) fractions. Extrapolation of simulation results to the field scale suggests that CN, and by extension Hg, will continue to elute from the tailings for at least an additional 130 a.     

Arsenic contamination at the Mole River mine,northern New South Wales

Mining and processing of arsenopyrite ore at the Mole River mine in the 1920–1930s resulted in abandoned mine workings, waste dumps and an arsenic oxide treatment plant. Weathering of waste material (2.6–26.6 wt% As) leads to the formation of water soluble, As‐bearing mineral salts (pharmacolite, arsenolite, krautite) and sulfates which affect surface waters after rainfall events. Highly contaminated soils, covering about 12 ha at the mine, have extreme As (mean 0.93 wt%) and elevated Fe, Ag, Cu, Pb, Sb and Zn values compared with background soils (mean 8 ppm As). Regionally contaminated soils have a mean As content of 55 ppm and the contaminated area is estimated to be 60 km². The soils have acquired their metal enrichments by hydromorphic dispersion from the dissolution of As‐rich particulates, erosion of As‐rich particulates from the dumps, and atmospheric fall‐out from processing plant emissions. Stream sediments within a radius of 2 km of the mine display metal enrichments (62 ppm to 27.5 wt% As) compared with the mean background of 23 ppm As. This enrichment has been caused by erosion and collapse of waste‐dump material into local creeks, seepages and ephemeral surface runoff, and erosion and transportation of contaminated soil into the local drainage system. Water samples from a mine shaft and waste‐dump seepages have the lowest pH (4.1) and highest As values (up to 13.9 mg/L), and contain algal blooms of Klebsormidium sp. The variable flow regime of the Mole River causes dilution of As‐rich drainage waters to background values (mean 0.0086 mg/L As) within 2.5 km downstream. Bioaccumulation of As and phytotoxicity to lower plants has been observed in the mine area, but several metal‐tolerant plant species (Angophora floribunda, Cassinia laevis, Chrysocephalum apiculatum, Cymbopogon refractus, Cynodon dactylon, Juncus subsecundus and Poa sieberiana) colonise the periphery of the contaminated site.     

Arsenic mobility in mildly alkaline drainage from an orogenic lode gold deposit,Bralorne mine,British Columbia

The historical (1932–1971) Bralorne mine produced over 87 million grams of Au from an archetypal orogenic lode gold deposit in southwest British Columbia. High concentrations of As in mine drainage, however, represent an on-going environmental concern prompting a detailed study of effluent chemistry. The discharge rate at the mine portal was monitored continuously over a fourteen-month period during which effluent samples were collected on a quasi-weekly basis. Water samples were also collected on synoptic surveys of the adit between the portal and the main source of flow in the flooded workings. Total concentrations of As in the mildly alkaline (pH = 8.7) portal drainage average 3034 μg/L whereas at the source they average 5898 μg/L. As emergent waters from the flooded workings flow toward the portal, their dissolved oxygen content and pH increase from 0 to 10 mg/L and from 7.7 to 9, respectively. Near the emergence point, dissolved Fe precipitates rapidly, sorbing both As(III) and As(V). With increasing distance from the emergence point, dissolved As(III) concentrations drop to detection limits through sorption on hydrous ferric oxide and through oxidation to As(V). Concentrations of dissolved As(V), on the other hand, increase and stabilize, reflecting lower sorption at higher pH and the lack of available sorbent. Nonetheless, based on synoptic surveys, approximately 35% of the source As load is sequestered in the adit resulting in As sediment concentrations averaging 8.5 wt%. The remaining average As load of 1.34 kg/d is discharged from the portal. Partitioning of As(V) between dissolved and particulate phases in portal effluent is characterized by a sorption density of 0.37 mol As (mol Fe)⁻¹ and by a distribution coefficient (K_d) of 130 L/g HFO. The relatively high sorption density may reflect co-precipitation of As with Fe oxyhydroxides rather than a purely adsorption-controlled process. Results of this study show that the As self-mitigating capacity of drainage from orogenic lode gold deposits may be poor in high-pH and Fe-limited settings.     

Chemical weathering in soils from the glacial Lake Agassiz region of Manitoba, Canada

 Recently, there has been considerable interest in categorizing the availability of plant essential nutrients and selected transition metals in the soil environment so as to predict their effects on ecosystem health and the efficacy of potential management practices. Researchers desire to isolate important soil properties, determinant biotic activities and fundamental pedogenic processes that control biogeochemical cycling and are potentially modifiable for the goal of ecosystem sustainability. In a relative sense, a significant portion of this scientific effort has been directed towards temperate and tropical forest ecosystems, with relatively less attention given towards understanding the boreal forest ecosystem. Consequently, an investigation was undertaken near Thompson, Manitoba, to: (1) determine the extent of weathering of the principal soils, (2) employ a selective-sequential chemical extraction method to categorize the soil-chemical fractions responsible for nutrient availability, and (3) infer the importance of selected soil forming processes responsible for soil genesis and nutrient availability. Preliminary findings suggest that nutrient availability is related to the nutrient concentration in the cation exchange fraction and/or to nutrients sequestered by the organic fraction. The metals in the manganese, noncrystalline and crystalline iron oxide fractions may be bound so tightly to these oxides that they are largely unavailable to plants; however, they are largely responsible for buffering the more labile pools against gradually changing vegetational and climatic conditions. Received: 31 October 1996 · Accepted: 21 May 1997     

红十字湖地区锂云母-透锂长石伟晶岩脉中锡锰钽矿的发现

锡锰钽矿(wodginite)理想式为MnSnTa2O8,Z=4,其结构为锡铁钽矿(ixiolite)结构的有序化形式。它是钽的主要工业矿物,是高度分异演化伟晶岩的标志矿物之一。在加拿大红十字湖地区锂云母-透锂长石伟晶岩脉中发现了这一钽矿物。矿物为黑褐色,呈半自形,颗粒达0.2mm,分布于由锂云母钠长石构成的条带中,与之共生的是一套典型的、高演化的花岗伟晶岩矿物组合。锡锰钽矿具有Mn/Fe、Sn/Ti、Ta/Nb比值高,杂质少的特点。矿物平均分子式为:Mn1.00(Sn0.64Ta0.24Ti0.04Mn0.04Zn0.02Fe0.01)0.99(Ta1.69Nb0.31)2.00O8;晶胞参数a=0.9534nm,b=1.1482nm,c=0.5123nm,β=91°07',V=0.5607nm3。依据矿物β>91°、V>0.560nm3、对偶面网221与221具强分裂衍射双峰、I021/I220为0.19和Mn/(Fe+Mn)≈1等特征,在锡锰钽矿与锡铁钽矿所构成的同质多像、有序-部分有序-无序这样一个连续系列中,本区所产锡锰钽矿属有序端员矿物,其阳离子在八面体中分布的有序度约为95%。在钽资源的寻找和开发利用中,应重视含锡锰钽矿的锂云母-透锂长石伟晶岩脉。     

Colloidal arsenic composition from abandoned gold mine tailing leachates in Nova Scotia,Canada

Asymmetric-Flow Field-Flow Fractionation (AsFlFFF) coupled to an inductively coupled plasma-mass spectrometer (ICP-MS) was used to determine whether colloidal As exists in mine tailings from abandoned Au mine sites in Nova Scotia. Using this technique, the chemical composition and the size of the colloidal material was determined. Tailings samples were collected from the sites and leachates were analyzed. The resulting fractograms showed the presence of colloidal As. Arsenic co-elutes with Fe and Al suggesting that the As is associated with colloids containing these elements. The colloidal material present in the samples has a calculated median size of 7 nm. The leachates were also analyzed for totalAs, Fe and Al using ICP-MS. The colloidal fraction was determined to account for approximately 20% of the total dissolved As present in these samples. Dissolved As concentrations at the selected mine sites are very high and the arbitrary cutoff for dissolved still incorporates colloidal material. Therefore. it is important to distinguish between truly dissolved and colloidal As as the speciation will affect the toxicity and mobility of As at these locations.     

贵州苗龙金矿床毒砂中金的赋存状态研究

苗龙矿区赋矿地层为寒武系上统三都组灰岩和泥灰岩,矿体严格受断裂构造控制,矿体主要赋存于东西向Fm₁、Fm₁₄断裂中。矿床成矿作用可划分为3个期次,即沉积成岩期、热液成矿期和表生氧化期。毒砂为热液成矿期主阶段重要产物之一,主要呈菱形体、针状、柱状及放射柱状集合体产出。通过对毒砂进行电子探针分析及面扫描分析,结果表明毒砂中主成分稳定,w(Fe)为32.47%~35.71%,平均34.05%;w(S)为21.01%~26.38%,平均为23.13%;w(As)为38.50%~44.73%,平均为41.86%。其成分(FeAs_0.80S_1.17~FeAs_1.02S_1.21)明显偏离理论毒砂的成分(FeAs_1.12S_1-x≤|0.13|),具有富硫亏砷等低温热液特征。毒砂含金性较好,w(Au)为0.05%~0.14%,平均为0.06%。面扫描图像中,Au元素分布均匀,说明Au主要以晶格金(固溶体金)形式存在于毒砂中。     

Water quality impacts from waste rock at a Carlin-type gold mine,Elko County,Nevada

Changes in water quality in the North Fork of the Humboldt River, Nevada are caused by weathering of waste rock from an inactive Carlin-type gold mine. Review of historical water-quality data, monthly water sampling, and continuous monitoring of water-quality parameters were used to quantify these impacts. River water pH, which ranged between 7 and 8, did not show statistically significant variation from upstream of the mine to downstream. Several constituents, most notably sulfate, calcium, and magnesium, showed statistically significant increases in dissolved-ion concentrations. These data, along with geochemical modeling, suggest that oxidation of sulfide minerals and in situ acid neutralization by carbonate host rocks are occurring. Large increases in dissolved-ion concentrations were observed twice a year—during spring snow melt and the onset of the winter precipitation season. These spikes are likely caused by flushing of pore waters that have reacted with waste rock during months-long periods when shallow groundwater recharge is not occurring.     

Magnitudes, spatial scales and processes of environmental antimony mobility from orogenic gold–antimony mineral deposits, Australasia

Antimony (Sb) is strongly concentrated into hydrothermal mineral deposits, commonly with gold, in metasedimentary sequences around the Pacific Rim. These deposits represent potential point sources for Sb in the downstream environment, particularly when mines are developed. This study documents the magnitude and scale of Sb mobility near some mineral deposits in Australia and New Zealand. Two examples of New Zealand historic mining areas demonstrate that natural groundwater dissolution of Sb from mineral deposits dominates the Sb load in drainage waters, with Sb concentrations between 3 and 24 μg/L in major streams. Mine-related discharges can exceed 200 μg/L Sb, but volumes are small. Sb flux in principal stream waters is ca 1–14 mg/s, compared to mine tunnel fluxes of ca 0.001 mg/s. Dissolved Sb is strongly attenuated near some mine tunnels by adsorption on to iron oxyhydroxide precipitates. Similar Sb mobilisation and attenuation processes are occurring downstream of the historic/active Hillgrove antimony–gold mine of New South Wales, Australia, but historic discharges of Sb-bearing debris has resulted in elevated Sb levels in stream sediments (ca 10–100⁺ mg/kg) and riparian plants (up to 100 mg/kg) for ca 300 km downstream. Dissolution of Sb from these sediments ensures that river waters have elevated Sb (ca 10–1,000 μg/L) over that distance. Total Sb flux reaching the Pacific Ocean from the Hillgrove area is ca 8 tonnes/year, of which 7 tonnes/year is particulate and 1 tonne/year is dissolved.     

Arsenic distribution and hydrochemical factors in urban groundwater,Foshan City,South China

The distribution of arsenic （As） in shallow groundwater of eastern Chancheng District in Foshan City as a function of season and water table was investigated, and the influence of hydrochemical factors on the As distribution was discussed. The groundwater samples were collected from 20 sites in dry season and 9 sites in wet season. As concentrations in 20% groundwater samples exceeded value of the WHO guideline （10 μg/L）, and the highest As concentration of 23.5 μg/L occurred in dry season. It is observed that groundwater As concentration decreased with the increase of depth of water table in dry season, and were generally higher in wet season than that in dry season, indicating that ground surface As might be one of the main sources for shallow groundwater As in study area, especially in wet season. Groundwater As concentration in study area had significantly positive correlation with the concentration of Fe, Mn, NH4, F, and COD, and was positively correlated to pH, but negatively correlated to Eh and K, indicating that reductive dissolution of Fe and Mn （oxy）hydroxides might be one of the main control mechanisms for groundwater As mobilization, while pH and F also played an important role in controlling the groundwater As mobilization in study area.     

Mercury mobility in mine waste from Hg-mining areas in Almería,Andalusia (Se Spain)

Mining wastes and calcines from two abandoned mining areas (Valle del Azogue and Bayarque in Almería) have been characterized. In the mining wastes, the dominant mercury phases are cinnabar and elemental mercury in the matrix. In the calcines, however, the dominant mercury phase is elemental mercury bounded to the matrix. Water-leaching experiments were conducted on low-grade stockpiles and calcines in order to simulate the mobilization of mercury by runoff under environmental conditions. The laboratory column-leaching experiments show a possible mobilization of mercury from Hg⁰ dissolution, colloid transport and a possible dissolution of calomel and other soluble phases in the mine wastes from the Valle del Azogue and Bayarque mines. Equilibrium speciation modeling of Hg, conducted using the numerical code MINTEQ, showed that the theoretical dominant mercury species in the calcine and mining wastes samples are Hg(OH)₂, HgCl₂, HgClOH and Hg⁰. In some leachates obtained from the Valle del Azogue mining wastes (sample A06), the high Hg concentrations may indicate the possible dissolution of mineral phases such as calomel and other soluble phases, which are subsaturated. The environmental results indicate a great environmental mobility of mercury, especially during wet episodes associated with intense precipitation events, when there are significative amounts of secondary soluble minerals.     

天然磁铁矿化学改性及其在水体除砷中的应用

铁氧化物及其复合氧化物(如菱铁矿、水铁矿)的表面电荷高、比表面积大,在特定条件下对亚砷酸盐和砷酸盐有较强的结合能力和亲和性,以铁氧化物作为吸附剂处理高砷水已经成为研究热点之一。天然磁铁矿的主要成分为Fe_3O_4,但其本身活性较弱,直接应用于处理高砷水的除砷率低。本文对天然磁铁矿采取酸化、碱化、不同温度灼烧、不同灼烧时间等简易的方法进行改性,达到有效去除水中砷的目的。实验结果表明:经0.5 mol/L盐酸浸泡、150℃灼烧10 min的改性磁铁矿分别处理As(Ⅲ)溶液和As(Ⅴ)溶液时,As(Ⅴ)去除率达98%,吸附能力显著增强,达到预期目标;溶液中As(Ⅲ)浓度从1000μg/L下降到250μg/L,去除率达75%,即As吸附能力明显优于未改性的天然磁铁矿,与其他改性铁矿除砷能力相近,而改性方法更加简便、易行。本文研究的改性天然磁铁矿吸附剂为控制高砷水的砷含量提供了一种切实可用的吸附材料。     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

广东河台金矿床矿物特征对成矿环境的制约

位于高要市境内的河台金矿床是目前广东省最大的金矿床,被普遍认为是韧性剪切带型金矿床。为了进一步认识金矿床的成矿环境,对采自河台矿区高村矿段的矿石进行了详细的研究,利用电子探针(EPMA)分析了矿石中毒砂、绿泥石和闪锌矿等矿物的成分。通过矿物温度计计算,毒砂的形成温度在330℃左右,绿泥石的形成温度集中在230~250℃之间,闪锌矿的形成温度在205~230℃之间,可能分别代表成矿早、中、晚期的温度;结合前人包裹体测试结果,推测河台金矿床成矿温度可能在205~250℃之间,属于中低温热液矿床。而糜棱岩的形成温度可能在300~500℃之间,明显高于金矿床的形成温度,因此,河台金矿床可能是动力变质期形成的糜棱岩带在热液期又发生脆性变形,并伴随含矿热液活动,最终导致成矿。在成矿过程中,绿泥石和闪锌矿是随着温度降低而相继连续产出的。在此过程中硫逸度也在不断降低,表现出比较宽泛的特征,lgf(S2)可能介于-20~-1,lgf(O2)可能介于-50~-30。     

Mechanisms of physico-chemical interaction of mercury with river sediments from a gold mining region in Brazil: Relative mobility of mercury species

Mercury accumulation in the food chain, as a consequence of gold recovery in Brazil, has been an issue of concern. Reactions of Hg in the environment are quite complex, and can involve various Hg chemical species. Laboratory experiments were carried out on Hg⁰ solubility, Hg complexation and sorption on river sediments from a gold mining region in Brazil. The reactivity and the mobility of Hg species were considered. Results indicate that methyl mercury is more mobile than ionic mercury, and that the presence of humic acid enhances drastically the solubility of Hg⁰. The soluble complex formed has a relatively lower interaction at the sediment/water interface and is more prone to spread through the aquatic environment.     

氧化还原动态变化对沉积物砷和氟释放的影响:以河北白洋淀平原为例

季风性波动引起的降雨、径流和排泄过程会引发浅层地下水系统周期性氧化还原动态变化,从而对地下水系统中有害组分的迁移转化产生影响。为探讨氧化还原动态过程对沉积物中砷(As)和氟(F)释放的影响,本研究选择河北白洋淀地区沉积物样品,利用发酵罐作为反应器,建立氧化还原动态实验体系,并监测动态变化过程中实验体系各组分含量的变化。结果表明,碱性和还原环境均有利于地下水中As、F的富集。还原阶段较高的pH条件有利于溶液中F^-的解吸,且体系中有机物降解会产生大量HC0₃^-和C0₃^2-,与F^-发生竞争吸附而有利于F^-的富集。对于溶液中As的富集,一方面是由于还原条件下体系中的As以As(III)为主,受沉积物的吸附作用较弱,从而有利于As被释放到溶液中;另一方面是因为还原阶段较高的pH也会使反应体系中As和沉积物间的吸附作用被减弱,造成As的解吸附。由于实验所用沉积物砷含量较低,不同S0₄^2-浓度条件对氧化还原动态过程中As、F迁移的影响不明显。总之,氧化还原动态变化过程会强烈影响地下水系统中砷、氟的富集。