国外尾矿酸性排水和重金属淋滤作用研究进展

尾矿引起的环境问题是水－气－矿物在地表条件下发生复杂反应的综合结果。近年来，国外学者研究显示，发生在尾矿中的风化作用不仅仅有硫化物的氧化作用，而且还伴随有机物氧化作用，碳酸盐等矿物中和作用，次生矿物沉淀作用、结晶作用、胶结作用，矿物交代蚀变作用、吸附作用、离子交换作用及生物作用。上述各种作用互相影响，互相制约。目前，最新研究表明，许多因素都会影响尾矿风化作用，这些因素主要包括：尾矿原生矿物组成、成回、化学成分、表面积和形态；尾矿酸中和潜力；溶液pH值；次生矿物形成及其吸附、离子交换、胶结作用；溶液中Fe^3 离子的浓度；有机物的种类和含量；尾矿粒度分布和空隙度；气候条件和尾矿的水文地质环境。     

不同来源溶解态腐殖酸与Cu2+作用的荧光特性

利用三维荧光等高线图以及其所确定的荧光峰荧光强度随溶液化学条件的变化,研究不同来源溶解态腐殖酸与Cu²⁺作用的荧光特性。研究结果表明：溶解态天然腐殖酸中主要存在二类发射荧光的有机物官能团能与Cu²⁺发生络合作用。位于激发波长和发射波长分别为271～281 nm和335～351 nm的荧光峰1所代表的有机物官能团是与Cu²⁺发生络合配位的主要点位;pH值为4～6时,其络合受pH值影响较显著;而受溶液离子强度影响较小。位于激发波长和发射波长分别为223～246 nm和335～371 nm的荧光峰2所代表的有机物官能团与Cu²⁺的络合作用受溶液pH值影响较小,受溶液离子强度影响较显著。溶解态商品腐殖酸荧光峰1′所代表的有机物官能团与Cu²⁺的络合作用荧光特性,与天然腐殖酸荧光峰1所代表的有机物官能团和Cu²⁺络合作用荧光特性相似,在pH值为3～7时,其络合受pH值影响较显著。     

U(Ⅵ)在石棉尾矿酸浸渣上的吸附

为了研究U(Ⅵ)在石棉尾矿酸浸渣上的吸附行为,利用红外光谱仪、X射线衍射仪和扫描电镜等手段分别对石棉尾矿和石棉尾矿酸浸渣进行详尽表征。采用静态实验法考察吸附剂浓度、时间、pH、离子强度和温度等因素对吸附的影响,并进一步分析了吸附动力学和热力学。在研究范围内,U(Ⅵ)在石棉尾矿酸浸渣上的吸附受pH值、离子强度和温度的影响明显。当pH6时,吸附率随pH的增大而增大,此时吸附作用主要是离子交换作用或表面络合;当pH6,随pH的增大吸附率会降低,且离子强度越大,吸附率越低,则表明静电吸附或表面络合是其主要的吸附机制。动力学符合准二级动力学方程,热力学符合Langmuir吸附等温线方程。     

催化氧化法处理难生化炼油污水研究

以三级生化处理后的炼油污水为研究对象,考察了催化氧化过程的氧化作用和混凝作用,结果表明,催化氧化法去除有机物主要通过将大分子有机物氧化分解为小分子有机物,从而提高污水的可生化性;催化氧化对有机物氧化具有选择性,对苯甲酸和苯胺等芳香类化合物去除效果好,去除率分别达到92.2%和84.8%;对草酸和乙酸等小分子有机酸去除效...     

硝酸根紫外光降解对硝基苯甲酸的研究

以硝酸铝做光氧化剂,研究了紫外光照射下,NO-3对PNB(对硝基苯甲酸)的光降解作用.探索了NO-3投加量、模拟废水初始浓度和pH值、光照时间、溶解氧浓度对处理效果的影响.结果表明,NO-3对PNB具有良好的光氧化作用,在最佳处理条件下,NO-3光降解PNB 4 h后降解率达90.8%.廉价硝酸盐对于有机物能起到显著光...     

离子型稀土尾矿除铵效果对比

离子型稀土尾矿存在氨氮残留污染问题,分析尾矿中氨氮的赋存形式能更有效地处理尾矿中的氨氮。通过室内柱浸实验、浸泡除铵实验和淋洗除铵实验,分析稀土尾矿中氨氮残留的赋存形式,并根据色层塔板理论计算和比较2种除铵方式下的除铵效率。结果表明,尾矿中氨氮残留赋存形式包括离子交换态氨氮、不可流动溶液残留氨氮、物理吸附氨氮和化学吸附氨氮。其中主要以化学吸附氨氮为主,占尾矿氨氮残留量的30.47%～40.73%;物理吸附氨氮含量最少,占尾矿氨氮残留量的4.86%～5.34%。3种硫酸铵单耗下淋洗方式的单位体积清水除铵效率为53.84%、54.05%和75.77%;浸泡方式的单位体积清水除铵效率为14.4%、20.66%和23.10%;淋洗方式效率相比浸泡方式更有效。在处理尾矿氨氮中使用淋洗方式能有效地解决尾矿残留氨氮污染。     

基于响应曲面法的聚合氯化铝对矿井废水中氟离子混凝去除工艺优化

为有效去除矿井废水中氟离子,利用聚合氯化铝(PAC)对某矿井含氟废水进行混凝效果研究,设计单因素实验,研究了铝氟摩尔比(r)、pH和凝聚时间等因素对PAC混凝去除氟离子的影响,依据响应曲面法的Box-Behnken Design(BBD)实验设计原理,探究了r、pH和凝聚时间对混凝效果的影响,并优化工艺参数。结果表明：各因素对混凝效果的影响顺序为r> pH>凝聚时间;在r=19.04、pH=6.5、凝聚时间为2.9 min的最佳条件下,氟离子的去除率为56.4%,与预测值(56.46%)基本吻合;去除氟离子的机理包括PAC对氟离子絮凝沉淀、离子交换和络合沉降等;pH影响PAC在溶液中的存在状态,凝聚时间则影响矾花在溶液中形成的速度以及密集程度,进而影响混凝沉淀效果。由此可以看出,BBD优化模型预测与实际处理效果基本一致,铝氟摩尔比和pH是去除氟离子的主要控制因素。本研究使用的实验方法具有处理工艺简单、效果稳定、成本低等优点,可为实际矿井废水中氟离子的去除提供参考。     

低电压条件下水体中诺氟沙星的去除效果及机理

研究低电压条件下诺氟沙星(NOR)的电化学降解去除效果。结果表明:在1.3 V外加电压条件下,NOR具有较好的去除效果,在初始浓度c_0=0.09 mmol·L~(-1)时,反应70 h后,NOR去除率为90%以上;NOR的去除过程符合伪一级动力学模型。溶液pH值、腐殖酸浓度、水质条件等因素均影响NOR的电化学降解效果。中性及弱碱性条件有利于NOR的电化学去除,腐殖酸及天然水体中的有机物会抑制NOR的去除效果。在低电压条件下,NOR的矿化作用不明显,NOR的电化学降解过程中伴随着大量有机中间产物生成。     

新型钝化剂与秸秆对黄铁矿的氧化抑制效果

尾矿中硫化矿物氧化产生的酸性矿山废水(AMD),因pH低和富含重金属离子而对周边生态环境造成巨大危害。黄铁矿作为尾矿中分布最广、含量最高的常见硫化矿物之一,其氧化是酸性矿山废水产生的一个重要因素。因此如何有效的从源头控制黄铁矿的氧化是治理AMD的根本途径。实验以黄铁矿为研究对象,合成了一种新型的钝化剂——二硫代胺基甲酸钠(DTC-TETA),并将该钝化剂与芦苇秸秆结合,分别考察了钝化剂和钝化剂-秸秆混合物抑制黄铁矿在酸性溶液中氧化的效果。结果显示:氧化24 h后,单纯的秸秆粉末覆盖对黄铁矿氧化抑制效果并不理想;0.5%(V/V)DTC-TETA对黄铁矿氧化抑制率为59.5%,0.5%(V/V)DTC-TET和秸秆混合物可以使黄铁矿氧化抑制率增加至76.9%。可见在减少钝化剂浓度的情况下,合理的添加秸秆物质,不仅能有效的抑制黄铁矿的氧化,而且从源头上减少了化学物质的使用量,同时还充分利用了农业废弃物,从而降低钝化成本和可能的环境风险。     

硫化物矿山尾矿生物氧化作用的抑制研究

硫化物矿山尾矿的风化、氧化会对周围环境产生危害,研究表明,以氧化亚铁硫杆菌为代表的嗜酸氧化菌起了非常重要的作用。本研究以从广东韶关大宝山尾矿分离得到的一株氧化亚铁硫杆菌作为实验菌株,添加不同剂量的杀菌剂,分析了杀菌剂对溶液pH、Eh值的影响,及杀菌剂的Fe2+氧化抑制率和最佳使用浓度。结果显示:实验用杀菌剂SDS和CTAB能有效地抑制金属硫化物尾矿的生物氧化和酸化:ρ(SDS)为30 mg/L时Fe2+的氧化抑制率达到82.83%;ρ(CTAB)为5 mg/L时Fe2+的氧化抑制率达到80.84%,添加了杀菌剂的溶液pH、Eh基本保持初始值不变,表明杀菌剂的使用可以控制金属硫化物尾矿的酸化污染。     

Distribution of inorganic arsenic species in mine tailings of abandoned mines from Korea

The main objective of the present study is to determine arsenic species in mine tailings by applying an ion exchange method. Three abandoned mines, Jingok, Cheonbo and Sino mines in Korea, which had produced mainly gold, were selected for the collection and analysis of the tailings. It was found that the arsenic speciation using an ion exchange method was effective to separate As(III) and As(V) in leachate of mine tailings. The concentration of As(V) was found to be 63-99% in the leachate, indicating that As(V) would be the major arsenic species in the mine tailings and the tailings were under oxic conditions. The total concentrations of arsenic and metal elements in the mine tailings were up to 62,350 mg/kg As, 40 wt.% Fe, 21,400 mg/kg Mn, and 7,850 mg/kg Al. Sulfate was the dominant anion throughout the leachate, reaching a maximum dissolved concentration of 734 mg/l. The results of XRD and SEM in the mine tailings showed that main arsenic-containing minerals were pyrite (FeS2) and arsenopyrite (FeAsS) which would be the source of arsenic contamination in the study area.     

Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Rapid oxidation of sulfide mine tailings by reaction with potassium ferrate

The chemistry of sulfide mine tailings treated with potassium ferrate (K2FeO4) in aqueous slurry has been investigated. The reaction system is believed to parallel a geochemical oxidation in which ferrate ion replaces oxygen. This chemical system utilized in a pipeline (as a plug flow reactor) may have application eliminating the potential for tailings to leach acid while recovering the metal from the tailings. Elemental analyses were performed using an ICP spectrometer for the aqueous phase extract of the treated tailings; and an SEM-EDX for the tailing solids. Solids were analyzed before and after treatments were applied. ICP shows that as the mass ratio of ferrate ion to tailings increases, the concentration of metals in the extract solution increases; while EDX indicates a corresponding decrease in sulfur content of the tailing solids. The extraction of metal and reduction in sulfide content is significant. The kinetic timeframe is on the order of minutes.     

Hydrochemical characteristics of mine waters from abandoned mining sites in Serbia and their impact on surface water quality

Upon completion of exploration and extraction of mineral resources, many mining sites have been abandoned without previously putting environmental protection measures in place. As a consequence, mine waters originating from such sites are discharged freely into surface water. Regional scale analyses were conducted to determine the hydrochemical characteristics of mine waters from abandoned sites featuring metal (Cu, Pb–Zn, Au, Fe, Sb, Mo, Bi, Hg) deposits, non-metallic minerals (coal, Mg, F, B) and uranium. The study included 80 mine water samples from 59 abandoned mining sites. Their cation composition was dominated by Ca²⁺, while the most common anions were found to be SO₄ ^2? and HCO₃ ^?. Strong correlations were established between the pH level and metal (Fe, Mn, Zn, Cu) concentrations in the mine waters. Hierarchical cluster analysis was applied to parameters generally indicative of pollution, such as pH, TDS, SO₄ ^2?, Fe total, and As total. Following this approach, mine water samples were grouped into three main clusters and six subclusters, depending on their potential environmental impact. Principal component analysis was used to group together variables that share the same variance. The extracted principal components indicated that sulfide oxidation and weathering of silicate and carbonate rocks were the primary processes, while pH buffering, adsorption and ion exchange were secondary drivers of the chemical composition of the analyzed mine waters. Surface waters, which received the mine waters, were examined. Analysis showed increases of sulfate and metal concentrations and general degradation of surface water quality.     

改性油页岩灰渣对水中镉离子的吸附性能

采用酸碱化改性方法对油页岩灰渣进行改性,确定最佳酸碱化方案,并研究了环境因素对改性油页岩灰渣吸附镉离子的影响。实验研究结果表明,油页岩灰渣经50%的HNO3和20%的NaOH处理时,对镉离子的吸附能力最强。在吸附温度为30℃,初始溶液pH为6～7条件下,0.6 g的改性油页岩灰渣对50 mg/L Cd2+溶液50 mL,吸附150 min时,其吸附率达到86%以上。在实验条件下,改性油页岩灰渣对Cd2+的吸附符合Langmuir和Freundlich等温吸附方程,相关系数分别为0.9626和0.9944,其对Cd2+的理论饱和吸附量达到7.91 mg/g。改性油页岩灰渣对Cd2+的吸附主要归因于离子交换和表面吸附作用。     

The solid-phase controls on the mobility of heavy metals at the Copper Cliff tailings area, Sudbury, Ontario, Canada

The Copper Cliff Tailings Disposal Area, located near Sudbury, Ontario, covers an area of approximately 2200 ha and constitutes more than 10% of the total area of all mine tailings in Canada. The area has been utilized since 1936, receiving sulphide-containing tailings from the Inco Sudbury operations. Field measurements of pore-gas oxygen and carbon dioxide in the vadose zone indicate that sulphide oxidation has progressed to depths of 1.6 m to 1.7 m within the tailings. The oxidation of sulphide minerals within the vadose zone, and the accompanying dissolution of carbonate and aluminosilicate minerals within these tailings releases SO₄, Fe(II) and other metals to the pore water. In the vadose and saturated zones, concentrations of Fe and Ni exceed 10100 mg/l and 2210 mg/l, respectively. These high concentrations of dissolved metals are attenuated by a series of precipitation, coprecipitation and adsorption reactions. The precipitation of secondary sulphate and hydroxide phases also create hardpan layers at or near the oxidation front. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary-phase precipitation is occurring at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of jarosite, gypsum and goethite within the shallow tailings, suggesting that these phases are controlling the dissolved concentrations of Fe, SO₄ and Ca. Extraction experiments conducted on the tailings solids indicate that the constituents contained in the water-soluble fraction of the shallow, weathered tailings are derived from the original pore water and the dissolution of highly soluble phases such as gypsum. The acid-leachable fraction of the weathered tailings accounts for up to 25% of the heavy metals, and the reducible fraction may contain up to 100% of the heavy metals within the shallow, weathered tailings. Based on the pore water profiles and the geochemistry of the tailings solids, a relative mobility scale of Fe=Mn=Ni=Co>Cd Zn>Cr=Pb>Cu can be determined.     

Migration of acidic groundwater seepage from uranium-tailings impoundments, 1. Field study and conceptual hydrogeochemical model

In this first paper of a series, the results of a study at a non-operational tailings site are presented and are used to construct a general conceptual model for seepage migration from uranium-tailings impoundments. Many parts of the model are applicable to other types of tailings and to acid drainage in general.At the field site, the impoundment lies over a portion of a glaciofluvial sand aquifer. Tailings seepage drains downward into the aquifer and then migrates laterally away. Results of the field study indicate the seepage can be divided into three geochemical zones: (1) the inner core, which is essentially unaltered, acidic seepage from the tailings; (2) the neutralization zone, in which inner-core water is neutralized and aqueous concentrations decrease significantly; and (3) the outer zone, which contains both neutralized water from the neutralization zone and pH-neutral process water from the uranium milling operation. Yearly comparisons from 1979 to 1984 indicate the neutralization zone and inner core are migrating downgradient at a rate of about 1 meter/year, which is about 1/440 of the groundwater velocity. The mechanisms that produce the retardation and the decreases in aqueous concentrations are part of the conceptual model.The main features of the conceptual model are solid-liquid interactions, particularly mineral precipitation-dissolution, and buffering effects of dominant aqueous species. The important minerals undergoing precipitation-dissolution are the calcite-siderite solid solution, gypsum, Al-OH minerals, and Fe-OH minerals. “Cell and streamtube” calculations are used to evaluate the general trends in aqueous concentrations and to assist in explaining observed migration rates. Co-precipitation with the above minerals apparently accounts for decreases in other major, minor, and metal solutes. Because of the large amount of mineral precipitation and co-precipitation, variations in ²H and ¹⁸O were observed over a flow distance of several meters, while ¹³C remained essentially constant.     

Assessment of 222Rn emanation from ore body and backfill tailings in low-grade underground uranium mine

This paper presents a comparative study of ²²²Rn emanation from the ore and backfill tailings in an underground uranium mine located at Jaduguda, India. The effects of surface area, porosity, ²²⁶Ra and moisture contents on ²²²Rn emanation rate were examined. The study revealed that the bulk porosity of backfill tailings is more than two orders of magnitude than that of the ore. The geometric mean radon emanation rates from the ore body and backfill tailings were found to be 10.01?×?10^?3 and 1.03 Bq m^?2 s^?1, respectively. Significant positive linear correlations between ²²²Rn emanation rate and the ²²⁶Ra content of ore and tailings were observed. For normalised ²²⁶Ra content, the ²²²Rn emanation rate from tailings was found to be 283 times higher than the ore due to higher bulk porosity and surface area. The relative radon emanation from the tailings with moisture fraction of 0.14 was found to be 2.4 times higher than the oven-dried tailings. The study suggested that the mill tailings used as a backfill material significantly contributes to radon emanation as compared to the ore body itself and the ²²⁶Ra content and bulk porosity are the dominant factors for radon emanation into the mine atmosphere.     

Stream water chemistry in the arsenic-contaminated Baccu Locci mine watershed (Sardinia, Italy) after remediation

The abandoned Pb–As Baccu Locci mine represents the first and only case of mine site remediation in Sardinia, Italy. Arsenic is the most relevant environmental concern in the Baccu Locci stream watershed, with concentrations in surface waters up to and sometimes over 1 mg/L. The main remediation action consisted in creation of a “storage site”, for the collection of contaminated materials from different waste-rock dumps and most of tailings piles occurring along the Baccu Locci stream. This paper reports preliminary results on the level of contamination in the Baccu Locci stream after the completion of remediation measures. Post-remediation stream water chemistry has not substantially changed compared to the pre-remediation situation. In particular, dissolved As maintains an increasing trend along the Baccu Locci stream, with a concentration of about 400 μg/L measured at a distance of 7 km from the storage site. Future monitoring will provide fundamental information on the effectiveness of remediation actions conducted and their applicability to other mine sites in Sardinia. At the stage of mine site characterisation of future remediation plans, it is recommended to pay more attention to the understanding of mineralogical and geochemical processes responsible for pollution. Moreover, mixing of materials with different composition and reactivity in a storage site should require careful consideration and long-term leaching tests.