Arsenic and metal contamination of water resources from mining wastes in Korea

 Water resources near a gold-mine waste site were studied for the distribution and contents of contaminants, and their behavior in the surface and groundwater systems. Arsenic, cadmium, and manganese were identified with levels exceeding the drinking water guidelines of WHO (World Health Organization), and their distribution depended upon the differences in source materials and in spatial pH variations. Originating from arsenopyrite, concentrations of dissolved arsenic were controlled by sorption with amorphous iron (Fe(OH)₃) and carbonate minerals. Cadmium and manganese were derived from the mineral phase including sphalerite (ZnS), otavite (CdCO₃), and rhodochrosite (MnCO₃); their concentrations in water resources were limited by the solubility of mineral phases. All of these processes are significantly pH-dependent, implying that a small decline in pH could result in a drastic increase in contaminant concentrations and become a pollution threat to the water resources of the Gubong area. Received: 13 December 1999 · Accepted: 21 March 2000     

矿产品中污染物溶解释放研究进展

我国原矿、精矿消费量和尾矿产出量巨大,这些矿产品中有毒有害污染物的溶解释放(称为"溶出")已经成为一个普遍存在的环境问题。本文阐述了目前国内外矿产品污染物溶出的研究现状,总结了研究矿产品中污染物溶出最常用的四种模拟试验方法(湿度室试验、淋滤柱试验、静态浸泡试验、萃取试验)的应用进展。湿度室试验可模拟自然风化过程,确定污染物溶出速率和产物;淋滤柱试验可模拟降水和喷淋过程,提供污染物吸附和解吸附动力学依据;静态浸泡试验可模拟被水浸泡过程,探明溶出规律和产物;萃取试验可对污染物进行形态分析,评估介质中污染物的流动性、稳定性等。污染物溶出的各种影响因素由强到弱依次是pH值、淋溶浸泡时间、温度、固液比、矿石粒径,多数情况下pH值越大、浸泡时间越长、温度越高、固液比越小、粒径越小越有利于污染物的溶出。溶出是一个长期和具有潜伏性的过程,其内部发生一系列物理化学反应,显示出与扩散效应不同的规律。目前这方面的研究对象还主要集中于废弃的尾矿,对经运输、堆放并在人类生活区使用的原矿、精矿产品的污染物溶出有待进一步研究,需要对其溶出污染进行预测和评估,采取有效措施控制和治理矿产品的污染。     

银北平原浅层高砷地下水砷富集水化学特征研究

宁夏银川平原是继河套平原之后,在黄河流域发现的又一个高砷地下水分布区.为了总结其高砷地下水的水化学特征,并探索水化学因素对地下水砷释放和富集的影响机制,本文以银川平原北部（银北平原）作为典型研究区,采取野外水文地质调查、水样采集与测试、砷与水化学组分散点图相关分析及水文地球化学方法进行了综合研究.结果表明,银北平原地下水砷含量在0.2~177 μg/L之间;高砷地下水（大于50 μg/L） pH值多在7.5~8.5,水化学类型主要为HCO3-Na·Ca、Cl·HCO₃-Na及Cl·HCO₃-Na·Ca型,E_h多在-200~-100 mV.银北平原砷含量较高的地下水中COD、NH₄⁺、HCO3^-含量相应也较高,而NO3^-和SO₄^2-含量较低.高砷富有机质的冲-湖积含水层经过长期演化,形成偏碱性的中强还原性地下水环境和特殊的水化学特征,也具备极大的砷释放能力.较高的pH导致砷从铁锰氧化物或氢氧化物等水合物或黏土矿物表面解吸.其次部分铁锰氧化物在高pH、低E_h条件下可被还原为低价态可溶性铁锰,从而使与其结合的砷也得以释放进入地下水中.此外重碳酸根与砷酸根、亚砷酸根的竞争吸附行为促使含水层砷的解吸.     

Formation of iron-containing colloids by the weathering of phyllite

The formation of colloids during the weathering of phyllite was investigated by exposing ground phyllite to Milli-Q water. Secondary mineral colloids of 10¹–10² nm were detected in significant concentrations. At pH of about 8.5, the solution concentration of these colloids reached up to 10 mg/L (however, acidification to pH 4.0 prevented the formation of the colloids). The mineralogical composition of the secondary mineral colloids is assumed to be a mixture of ferrihydrite, manganese oxyhydroxides, aluminosilicates, amorphous Al(OH)₃ and gibbsite with possible additions of iron silicates and␣iron-alumino silicates. The colloids were stable over longer periods of time (at least several weeks), even in the presence of suspended ground rock. Direct formation of iron-containing secondary mineral colloids at the rock–water interface by the weathering of rock material is an alternative to the well-known mechanism of iron colloid formation in the bulk of water bodies by mixing of different waters or by aeration of anoxic waters. This direct mechanism is of relevance for colloid production during the weathering of freshly crushed rock in the unsaturated zone as for instance crushed rock in mine waste rock piles. Colloids produced by this mechanism, too, can influence the transport of contaminants such as actinides because these colloids have a large specific surface area and a high sorption affinity.     

Encapsulation of limestone waste in concrete after arsenic removal from drinking water

Arsenic is one of the many naturally occurring contaminants in drinking water. Although various treatment technologies can remove arsenic, most suffer from a common problem of disposal of arsenic-enriched waste after treatment. This project focused on improving a limestone-based disposal technique by encapsulating the arsenic-enriched limestone waste in concrete. The research work determined the compressive strengths of the concrete cubes prepared using treated limestone after arsenic removal and determined the amount of leaching from the arsenic-encapsulated concrete. The removal of arsenic was done with batch experiments using 0.5–1 mm sized Minnekahta Limestone. The efficiency of the limestone in removing arsenic ranged from 85.9 to 95.5%. The amount of arsenic adsorbed onto the surface of each gram of limestone ranged from 0.8 to 3.9 μg. Compressive strength results of concrete cubes prepared by incorporating arsenic-enriched limestone showed typical strength curves at 1, 3, 7 and 28 days. Leaching of arsenic was less than 0.05 mg/L, which is 1/100 of the US Environmental Protection Agency’s standard for disposal of arsenic in a landfill. Hence, encapsulating the arsenic-enriched limestone in concrete has potential for recycling the waste material, thereby reducing disposal costs of the limestone-based removal method.     

The attenuation of chemical elements in acidic leachates from coal mineral wastes by soils

The chemical attenuation of acidity and selected elements (aluminum, arsenic, cadmium, cobalt, chromium, copper, fluorine, iron, manganese, nickel, and zinc) in acidic leachates from coal mineral wastes by four natural subsurface soils has been investigated using laboratory column methods Leachate solutions were allowed to percolate through the soils under simulated natural flow conditions, and the elemental concentrations in the influents and effluents were measured periodically Elemental retentions were substantial for all species except managanese, which was eluted in excess from all soils except the most calcareous Two processes appeared to operate in decreasing influent concentrations: (1) precipitation of solid phases caused by increased pH of the leachate as it percolated through the soil, and (2) adsorption of elements onto exchange and sorption sites naturally present in the soil and on iron and aluminum oxide precipitates formed in situ from leachate components because of the increased pH The soil property most important in retention was its alkalinity Thus, carbonaceous soils provide the best control material for acidic leachates from coal mineral wastes. Results show that natural soils can substantially reduce pollutant fluxes to the environment from acidic coal waste dumps and should be considered when selecting waste disposal sites Performed under the auspices of the U.S. Department of Energy     

Arsenic fixation on iron-hydroxide-rich and plant litter-containing sediments in natural environments

Iron-hydroxide-rich and plant litter-containing sediments from natural sites contaminated with uranium mine tailing leachates were examined for their ability to adsorb arsenic. The samples with high contents of iron hydroxides (Fe_total concentration, >300 g kg⁻¹) exhibited remarkable fixation of arsenic (up to 40 g As kg⁻¹). This value corresponded approximately to the supersaturation point for natural iron hydroxides under the present conditions, and it was significantly lower than the value found for synthetic iron hydroxides. There was a strong correlation (R=0.8999) between the concentration of iron and that of arsenic at low arsenic contents, indicating adsorption on strong binding sites. Although all the samples had noticeable contents of organic carbon (plant litter), calcium, and manganese, no obvious effect of these elements on arsenic fixation could be detected. The amount of iron hydroxides was found the only fixation-controlling parameter immediately below a leaching water source.     

Assessment of hazardous mine waste transport in west central Sinai,using remote sensing and GIS approaches: a case study of Um Bogma area,Egypt

Um Bogma area is the most famous mineralized locality in Sinai, Egypt. It is characterized by the presence of manganese, iron, and copper deposits. Apart from the mill tailings and spoil heaps, the results indicated the decrease of soil contamination downstream. As a result of random manganese mining activity in Um Bogma area, many hazardous elements such as iron, copper, manganese, lead, and zinc as well as many others associating heavy metals such as arsenic, selenium, and sulfur are dispersed in the environment. This study assesses and monitors the environmental impacts of such mining activities in the west central Sinai, using multitemporal spectral remote-sensing sensors (MSS 1972, TM 1986, and ETM+7 2000). The results have shown the very high potential of temporal imagery in mining-related contamination either directly through mineral and rock mapping of the mining waste and residues and related contaminated areas.     

Implications of rock mineralogy and texture on the feasibility of in situ leach mining of Mn-bearing iron formations of central Minnesota,U.S.A.

The U.S. Bureau of Mines is investigating the feasibility of extracting Mn using in situ leach mining methods. Among the deposits being examined are the iron formations of the Cuyuna range, Minnesota, which contain high-tonnage, low grade deposits of manganese oxides. Manganese minerals identified include pyrolusite, cryptomelane-hollandite, manganite, braunite and lithiophorite. Ore reactivities, as measured by batch leaching tests using aqueous SO₂, are compared to theoretical estimates of the leaching behavior of individual manganese minerals based on kinetic and thermodynamic evaluations. Experimental results in some cases show opposite trends to those predicted by theoretical estimates. In batch leaching tests of Cuyuna Range ores, texture was shown to be of greater importance, than thermodynamic reactivity in determining amenability to leaching. Predicting the practical potential for recovery of Mn by in situ leaching must involve identification of the effects of texture (massive, fractured-host, or interstitial) in addition to ore mineral reactivity.     

Co-management of landfill leachate concentrate with brick waste by solidification/stabilization treatment

The treatment of landfill leachate by reverse osmosis (RO) generates huge volumes of heavily polluted concentrate that has to be properly treated before its discharge into the environment. The aim of this work was to assess the solidification/stabilization (S/S) treatment of the leachate concentrate (LC) for chemical/physical immobilization of contaminants and for obtaining durable monolithic matrix suitable for storage, landfilling, or use. In addition, the possible use of brick waste as a partial replacement of natural aggregates used for S/S process was investigated. Concrete mixtures were prepared using local PC, sand, gravel, and tap water/LC. The substitution of coarse aggregate material by brick waste was examined for the replacement ratios 25, 50, and 75%. Hardened concrete specimens were subject to compressive test as well as flexural strength test at 7 and 28 days. Besides, a leaching test was performed, and the collected eluates were analyzed for pH, total dissolved solids, chemical oxygen demand, chlorides, sulfates, phosphorus, and heavy metals. The aggregate replacement with brick waste showed various trends according to the substituted fraction size and ratio. A 28-day compressive strength of more than 25 MPa was obtained even at 50% simultaneous substitution of PC, gravel, and sand. Leaching test analysis confirmed that S/S could be a successful treatment for RO LC decreasing most of the pollutants to comply with landfilling criteria, except for chromium known to be mobile at high pH. Furthermore, the substitution of natural aggregates with brick waste revealed the possibility to cast valuable masonry units. However, a long-term assessment is still needed to ensure the mechanical and chemical stability/durability of concrete.     

Using CaO to stabilize arsenic sulfide slag by moderate temperature calcination

This study was conducted to investigate the stabilization of arsenic sulfide slag (ASS) with CaO calcinations at moderate temperature, including the effects of calcination temperature and different As/Ca molar ratios on arsenic leaching concentration. In the process of calcination for arsenic-contained waste, 90.95–97.23% of arsenic was reserved and the original waste was transformed into a dense and liquation state, which could physically wrap arsenic and reduce its leaching concentration. Meanwhile, the decrease in the As/Ca molar ratios was conducive to the formation of Ca₅(AsO₄)₃(OH). When As/Ca molar ratio was less than 1:8, there was excessive CaO and the ASS samples stopped reacting with CaO. The results showed that the leaching concentration of arsenic was 4.08 mg/L when As/Ca molar ratio was 1:8 and the ASS sample was calcined for 2 h at temperature of 550 °C. In the process, arsenic’s chemical reaction and physical wrapping resulted in a remarkable decrease in its leaching concentration.     

刁江流域偏枯态水质安全风险分析

为实现刁江流域水质水量同步监测,收集了2018年非汛期至2019年汛期共14个地市的降水量、3个水文测站的逐时水位和流量、9个水质监测断面的实验检测成果等数据,借鉴美国环保署健康风险评价方法,对砷、镉、铅、铁、锰、铜、锌、汞共8种采、选、冶矿作业特征污染物的化学致癌风险指数和毒害风险指数等有关风险指标进行评价分析.结果...     

Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous–Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium–iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.     

Characterization of stabilized waste: Evaluation of pollution risk

This study relates to the characterization of stabilized waste. Various parameters such as granulometric distribution, percentage of mineral and organic matter were estimated to appreciate environmental hazard potential and possibility of metal leaching of the samples of waste from Grange site in France. From the results, it was shown that the granulometric distribution was variable. Therefore, a strong proportion of fines (44.6 %) and medium (45.9 %) was observed due to the age of waste that supports the degradation of a great quantity of organic matter. That was confirmed by the strong mineral matter rate (63.8 %) obtained to determine the organic percentage of matter (36.2 %). The amount of heavy metals such as iron, nickel, copper, zinc, cadmium and lead was also studied. The results obtained were in a good agreement with the ones of the literature. Indeed, it appeared that iron, lead, copper, nickel and zinc are in relative strong proportion while cadmium was not very present. Iron represents 78 % of the metals. From the leaching tests, it was shown that the heavy metals concentration were very weak. Moreover, the deposit of studied waste could be a potential source of organic pollution (COD = 150 Mg C/L on average) in the case of precipitation and flood.     

Effects of iron on arsenic speciation and redox chemistry in acid mine water

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes.     

Occurrence,distribution and source of arsenic in deep groundwater wells in Maydavood area,southwestern Iran

Groundwater in some deep wells of Maydavood aquifer, southwestern Iran, contains relatively high concentrations of arsenic. Detailed hydrochemical analysis of these groundwaters (with ICP-OES instrument) showed that concentrations of iron, manganese, nickel, and vanadium are also high in them and concentrations of total arsenic in 81% of deep wells are greater than World Health Organization’s permissible value (10 ppb). XRF analysis of surrounding geological formations and aquifer sediments proposed that original source of arsenic in aquifer material can be attributed to minerals from Asmari Formation. It appears that a key mechanism for arsenic mobilizing to deep wells is microbial biodegradation of petroleum related organic matters (PROMs), which exist in aquifer sediments and originates from the bedrock of the aquifer (Gachsaran Formation). This process is followed by microbially mediated reductive dissolution of arsenic-bearing iron/manganese oxyhydroxides/oxides and further by nickel and vanadium mobilizing to groundwater. According to hydrogeochemical conditions and cluster analysis, water wells in Maydavood aquifer are divided to four subgroups: the wells with mildly reducing condition (subgroup I), moderately reducing condition (subgroup II), reducing condition (subgroup III), and high reducing condition (subgroup IV). Affected wells to arsenic are belonged to subgroups III and IV.     

Remediation technologies for metal-contaminated soils and groundwater: an evaluation

Metals including lead, chromium, arsenic, zinc, cadmium, copper and mercury can cause significant damage to the environment and human health as a result of their mobilities and solubilities. The selection of the most appropriate soil and sediment remediation method depends on the site characteristics, concentration, types of pollutants to be removed, and the end use of the contaminated medium. The approaches include isolation, immobilization, toxicity reduction, physical separation and extraction. Many of these technologies have been used full-scale. This paper will review both the full-scale and developing technologies that are available. Contaminants can be isolated and contained to minimize further movement, to reduce the permeability of the waste to less than 1×10⁻⁷ m/s (according to U.S. guidelines) and to increase the strength or bearing capacity of the waste. Physical barriers made of steel, cement, bentonite and grout walls can be used for isolation and minimization of metal mobility. Another method is solidification /stabilization, which contains the contaminants in an area by mixing or injecting agents. Solidification encapsulates contaminants in a solid matrix while stabilization involves formation of chemical bonds to reduce contaminant mobility. Another approach is size selection processes for removal of the larger, cleaner particles from the smaller more polluted ones. To accomplish this, several processes are used. They include: hydrocyclones, fluidized bed separation and flotation. Addition of special chemicals and aeration in the latter case causes these contaminated particles to float. Electrokinetic processes involve passing a low intensity electric current between a cathode and an anode imbedded in the contaminated soil. Ions and small charged particles, in addition to water, are transported between the electrodes. This technology have been demonstrated in the U.S. full-scale, in a limited manner but in Europe, it is used for copper, zinc, lead, arsenic, cadmium, chromium and nickel. The duration of time that the electrode remains in the soil, and spacing is site-specific. Techniques for the extraction of metals by biological means have been not extensively applied up to this point. The main methods include bioleaching and phytoremediation. Bioleaching involves Thiobacillus sp. bacteria which can reduce sulphur compounds under aerobic and acidic conditions (pH 4) at temperatures between 15 and 55°C. Plants such as Thlaspi, Urtica, Chenopodium, Polygonum sachalase and Alyssim have the capability to accumulate cadmium, copper, lead, nickel and zinc and can therefore be considered as an indirect method of treating contaminated soils. This method is limited to shallow depths of contamination. Soil washing and in situ flushing involve the addition of water with or without additives including organic and inorganic acids, sodium hydroxide which can dissolve organic soil matter, water soluble solvents such as methanol, nontoxic cations, complexing agents such as ethylenediaminetetraacetic acid (EDTA), acids in combination with complexation agents or oxidizing/reducing agents. Our research has indicated that biosurfactants, biologically produced surfactants, may also be promising agents for enhancing removal of metals from contaminated soils and sediments.

In summary, the main techniques that have been used for metal removal are solidification/stabilization, electrokinetics, and in situ extraction. Site characteristics are of paramount importance in choosing the most appropriate remediation method. Phytoremediation and bioleaching can also be used but are not as well developed.     

Chromium,molybdenum, vanadium,and fluoride sorption from steelwork slag eluates by different mineral additives

Today, the environmental behavior of steelwork slags is very important for their application. When slags are used as building materials, they can interact with water and soil, with the possibility of leaching of harmful components, e.g., metals such as vanadium or anions such as fluoride. The leachable concentrations of various environmentally relevant parameters have to be below defined limit values, which are given by environmental authorities. In this study, different mineral additives have been investigated for their suitability to reduce chromium, molybdenum, vanadium, and fluoride concentrations in slag eluates, as a basis for planned investigations of the long-term leaching behavior of slag/additive mixtures. Seven mineral additives including iron oxide hydroxide, sludge from aluminum production, triple superphosphate, two water work sludges I and II, zeolite powder, and zeolite granules were tested for their efficiency to sorb trace elements and fluoride from four slag eluates comprising two basic oxygen furnace slags and two electric arc furnace slags. The limit values according to the German Alternative Construction Material Ordinance were used to verify which additives were able to minimize concentrations of trace elements and fluoride in slags eluates. Due to high eluate concentrations, the sludge from aluminum production and the triple superphosphate could be excluded from further investigations. The efficiency of the other additives follows the trend iron oxide hydroxide > water work sludges > zeolites. Particularly, the iron oxide hydroxide and the water work sludge I seem to be appropriate to enhance possible applications of slags with respect to the German regulation.     

砷的水地球化学及其环境效应

砷在水环境中的迁移和富集可以产生严重的砷污染，砷在自然水系中主要以无机砷酸盐（AsO4^3-）和亚砷酸盐（AsO3^3-）两种形式存在，而砷的有机化合物的含量一般都很低，砷酸盐在富氧化性的水体中占优势，而亚砷酸盐则富集于还原性水体中，水体中As3 和As5 的相对含量主要受氧化还原条件和一些吸附一解吸平衡过程控制，As3 类比As5 类的毒性强得多，而无机砷化合物比有机砷化合物的毒性大，在pH值为5－6时，As^5 不易被还原成气态AsH3，而s^3 却能定量地被还原出来，根据这一性质，可完成水体中As3 和As5 的测定，砷在饮用水中的安全阀值仅为10ug/L，水体中高砷的危害可以通过水质净化予在消除或降低，铁的化学沉淀和吸附法，石灰软化法，活性氧化铝净化法和逆流渗透法等都可以有效地去除或降低饮用水中砷的含量。     

煤矸石中潜在有害微量元素淋溶析出研究

在煤矸石淋溶实验的基础上，研究了有害微量元素从煤矸石中淋溶析出的浓度与其在煤矸石中的含量和赋存状态的关系。结果表明，溶出浓度受淋溶时间，淋溶液温度，酸碱度的影响。淋溶液温度越高，淋溶时间越长，则有害微量元素从煤矸石中析出的浓度越高；不同的有害微量元素受淋溶液pH值大小影响程度也不相同。