Application of coal fly ash to circumneutral mine waters for the removal of sulphates as gypsum and ettringite

South African power stations generate large amounts of highly alkaline fly ash (FA). This waste product has a serious impact on the environment. Acid mine drainage (AMD) is another environmental problem associated with mining. AMD has high heavy metal content in addition to high sulphate concentrations. Several studies have shown that 80–90% of sulphates can be removed when FA is co-disposed with AMD rich in Fe and Al. In South Africa, sources of contaminated mine waters, unlike AMD have circumneutral pH and much lower concentrations of Fe and Al, but rich in Ca and Mg. Treatment of such waters with FA resulted in no significant removal of sulphates when treated to pH less than 10. Subsequent treatment of circumneutral mine water to pH greater than 11 resulted in more than 60% sulphate removal. Treatment of circumneutral mine water to pH greater than 11 with FA followed by seeding with gypsum crystals and the addition of amorphous Al(OH)₃ resulted in removal of sulphate to levels below the Department of Water Affairs and Forestry (DWAF) water quality effluent limit (500 ppm).     

Chemometrics in Ascertaining Hydrogeochemical Characteristics of Coal Mine Discharge vis-à-vis Behaviour of Surface and Groundwater Resources of the Mahan River Catchment Area,Central India

We investigated the hydrogeochemical regime of an AMD-affected coal mining province. 98 water samples were collected over two seasons and analysed for 14 parameters. We attempted to discriminate the sources of variation of water quality using select multivariate techniques: display methods (principal component analysis) and unsupervised pattern recognition (cluster analysis). Most of the groundwater and river water were characterised by shallow freshwater facies (Ca–Mg–HCO₃ type), whereas the samples representative of mine water were of the Ca–Mg–SO₄ type. The mines of the area annually discharge 2901 t of solute loads, ranging from 91 to 1030 t/year. Various molar ratios suggest that dissolution of the silicates associated with the mixing process is the predominant solute acquisition processes that govern the water chemistry of the region besides AMD. The chemometric results indicated that only a few groundwater and river water samples had low pH and elevated total dissolved solids, and these were near the three mines that were affected by AMD. These results substantiate the effectiveness of the mine water treatment measures implemented at the mine sites.

     

Adaptation of a Rare Earth Element Pre-concentration Method for Water Enriched in Al,Ca, Fe,and Mg

The use of rare earth elements (REE) as process indicators in water-rock interactions can be hampered by the fact that samples with high concentrations of total dissolved solids require dilution before ICP-MS analysis, which can lower REE concentrations close to or below detection limits. A pre-concentration method originally developed for chloride-dominated water with very low REE concentrations was tested for and adapted to sulfate-rich water from a mining-affected area with a pH of 6 and high concentrations of Ca, Fe, Mg, and sometimes Al. The adapted approach proved easy to implement in the field and produced very good recoveries and reliable REE patterns. Two factors, sample volume and ionic strength, were tested. Pre-concentration with high sample volumes (1000 mL) resulted in poor recoveries (1.8?±?0.3?% for La up to 17.8?±?0.6?% for Yb). When the sample volume was reduced to 25 mL, much better recoveries were achieved. Reducing the ionic strength by diluting the sample 1:100 or 1:1000 resulted in comparable recoveries than the approach with reduced sample volume, indicating that sample volume was more important than ionic strength. Among the tested competing elements, high concentrations of Ca, Fe, and Mg resulted in loss of light REE (La-Nd), while Al was found to reduce the recovery of all REE. Also for water with high concentrations of Ca and Fe and very low REE concentrations (ppt-range), especially La results should be considered with care after pre-concentration, and be neglected in REE patterns if necessary.     

Environmental Geochemistry and a Quality Assessment of Mine Water of the West Bokaro Coalfield,India

Mine water from the West Bokaro coalfield was qualitatively assessed with respect to domestic and irrigation criteria. Thirty water samples from different mines were collected and analyzed for pH, electrical conductivity, total dissolved solids (TDS), total hardness, major cations, anions, and dissolved silica. The pH of the samples ranged from 6.6 to 8.3 in the post-monsoon season and 6.7–8.4 in the pre-monsoon season, indicating its near-neutral to slightly alkaline nature. TDS ranged from 349 to 1029 mg L^?1 in the post-monsoon season and 499–1458 mg L^?1 in the pre-monsoon season. The spatial differences in TDS reflect the local lithology, surface activities, and hydrology. Ca–Mg–SO₄ and Ca–Mg–HCO₃ were the dominant hydrogeochemical facies; SO₄ ^2? and HCO₃ ^? were the dominant anions and Ca²⁺ and Mg²⁺ were the dominant cations during both seasons. High SO₄ ^2? concentrations are attributed to oxidative weathering of pyrite and gypsum dissolution. Computed supersaturation with respect to dolomite and calcite for most samples may result from the dissolution of gypsum after the water is saturated with respect to the carbonate minerals. Despite moderate to high TDS, total hardness, and SO₄ ^2? concentrations, most of the sampled mine water was of good to permissible quality for irrigation; however, locally higher salinity and Mg restrict its suitability for irrigation at some sites.     

Treatment of Acid Mine Drainage Using a Fly Ash Zeolite Column

Acid mine drainage (AMD) and fly ash from thermal power plants both pose substantial environmental problems in India. Fly ash from the Talcher super thermal power plant was converted into zeolite and used in a column to treat AMD from the abandoned Gorbi opencast mines (Singrauli coalfields, NCL). The pH of the mine water increased, and 100 % of the total hardness, Ca hardness, Mg hardness, Mn, Zn, Pb, Cd, Ni, and acidity were removed, along with 99 % of the Fe and 90 % of the Cu.     

The Potential Use of Phosphatic Limestone Wastes in the Passive Treatment of AMD: A Laboratory Study

In Morocco, there are many sedimentary phosphate mines that produce large quantities of phosphatic limestone wastes (PLW) that contain calcite (46 wt%) and dolomite (16 wt%). These mines are located near contaminated sites, such as the abandoned Kettara pyrrhotite mine. The surface drainage water at the Kettara mine site has a pH of 2.9–4.2 and elevated concentrations of SO₄ (from 47 to 5,000 mg/L) and Fe (from 1 to 1,200 mg/L). The efficiency of PLW was assessed in the laboratory as an alternative alkaline material for passive acidic mine drainage (AMD) treatment. A series of experiments were carried out using a synthetic AMD (pH 3) containing Fe (500 mg/L), SO₄ (3.4 g/L), Ca (220 mg/L), Al (160 mg/L), Mn (20 mg/L), Zn (15 mg/L), Cu (23 mg/L), and trace amounts of Co, Cr, and Ni. Experiments were done in both anoxic and oxic conditions, in batch and column tests, with hydraulic retention times of 24 and 15 h, respectively. The PLW efficiently increased the alkalinity and pH, inducing precipitation of most metals. The neutralizing capacity of PLW prepared at different particle sizes (0.8 mm–0.5 cm, 0.5–1, 1–2, and 2–3 cm) was found to be similar in batch tests. The initial AMD value increased from 3 to 5–6.5 during the batch tests and 6.5–8 in the columns. In batch tests under anoxic and oxic conditions, there was a significant decrease in concentrations of Fe (500–120 mg/L), Al (160–1.7 mg/L), and Cu (23–0.002 mg/L). In the column tests, Al and Cu decreased (177–2.5 and 26–0.002 mg/L, respectively), while Fe decreased less significantly (618–300 mg/L). The availability and low cost of the PLW make its use in passive AMD treatment potentially feasible.     

The application of wood ash as a reagent in acid mine drainage treatment

The paper deals with a possible utilisation of wood ash as a reagent in treating acid mine drainage (AMD) from opencast mining of brown coal. Wood ash samples were obtained having combusted deciduous and coniferous tree wood in a household furnace. The dominant mineral phases in wood ash are calcite, quartz, lime and periclase. The used AMD is characteristic of high contents of sulphates, iron, manganese, heavy metals and low pH. The AMD treatment process included dosing of wood ash to adjust pH values about 8.3 (a dose of 0.5 g l⁻¹) or calcium hydroxide (a dose of 0.2 g l⁻¹) for comparison. The reaction time was 20 min. Dosing of wood ash in AMD resulted in an increase of pH in solution from 3.5 to 8.3, which caused the removal of metal ions mainly by precipitation, co-precipitation and adsorption. Comparing the application of Ca(OH)₂ in AMD treatment, at an almost identical pH value the concentrations fell in both cases for Fe, Mn, As, Co, Cu, Ni, Zn, Mg, Al and Mo. Applying wood ash the drop was even more distinct in Mn, Zn and Mg. The results of sedimentation tests in an Imhoff cone confirm that the settling capacities of sludge using wood ash are significantly better than when using calcium hydroxide in acid mine drainage treatment.     

The Geochemical Behaviour of Mine Tailings from the Touiref Pb–Zn District in Tunisia in Weathering Cells Leaching Tests

Flotation tailings associated with the extraction of Pb and Zn in the Touiref mining district, Tunisia, contain galena, sphalerite, pyrite, and marcasite in a carbonate gangue. The geochemical behaviour of oxidized and unoxidised tailings were consistent with their mineralogical and chemical characteristics. The leaching proceeded under neutral to slightly alkaline condition (pH 7.3–8.5), and positive Eh (250–470 mV). The concentrations of sulfate and Ca released during the leaching tests were associated with the neutralization of acidity by carbonates and the dissolution of gypsum initially present in the tailings. The iron precipitated, but significant amounts of Zn (5–3,300 μg/L), Cd (3–18 μg/L), and Pb (28–83 μg/L) were released during leaching, with the latter two exceeding international environmental norms (5 μg/L for Cd and 10 μg/L for Pb).     

高碱煤燃烧过程细颗粒物排放特性

准东煤储量巨大,但由于其碱金属和碱土金属含量较高,准东煤燃烧时会生成更多的细颗粒物。在一维沉降炉上对新疆准东地区高碱煤、准南低碱煤及混煤燃烧过程细颗粒物的排放特性进行了研究,对其燃烧生成的颗粒物粒径分布、生成浓度、元素组成进行了分析,获得了高碱煤中Na,K,Mg,Ca,Fe在细颗粒物中的分布及对细颗粒物生成特性的影响。结果显示:高碱煤燃烧生成的细颗粒物主要由Na,K,Mg,Ca的硫酸盐和氧化物组成;低碱煤燃烧产生的细颗粒物量明显减少;同时发现了低碱煤的掺烧有明显降低细颗粒物生成量的协同效应,Ca,Fe在混烧降低PM_(10)过程中起到了重要作用。     

ICP-AES法同时测定锂离子正极材料钴酸锂的杂质元素

研究了电感耦合等离子发射光谱法(ICP-AES)测定钴酸锂的杂质元素Cu, Ni, Fe, Mg, Mn, Ca, Na的分析方法。优化了仪器的工作条件, 选择了各元素合适的分析线, 考察了样品的溶解方法, 实验采用内标法消除干扰, 选择钇作为内标元素, 考察了内标元素的加入量、酸度等对测定的影响。结果表明该方法简便、快捷, 有很好的分析精密度和准确度, 各元素的相对标准偏差为0.75%～2.96%, 各元素的回收率在94.3%～108.3%, 完全能满足日常分析的需要。     

Fate of sulphate removed during the treatment of circumneutral mine water and acid mine drainage with coal fly ash: Modelling and experimental approach

The treatment of acid mine drainage (AMD) and circumneutral mine water (CMW) with South African coal fly ash (FA) provides a low cost and alternative technique for treating mine wastes waters. The sulphate concentration in AMD can be reduced significantly when AMD was treated with the FA to pH 9. On the other hand an insignificant amount of sulphate was removed when CMW (containing a very low concentration of Fe and Al) was treated using FA to pH 9. The levels of Fe and Al, and the final solution pH in the AMD–fly ash mixture played a significant role on the level of sulphate removal in contrast to CMW–fly ash mixtures. In this study, a modelling approach using PHREEQC geochemical modelling software was combined with AMD–fly ash and/or CMW–fly ash neutralization experiments in order to predict the mineral phases involved in sulphate removal. The effects of solution pH and Fe and Al concentration in mine water on sulphate were also investigated. The results obtained showed that sulphate, Fe, Al, Mg and Mn removal from AMD and/or CMW with fly ash is a function of solution pH. The presence of Fe and Al in AMD exhibited buffering characteristic leading to more lime leaching from FA into mine water, hence increasing the concentration of Ca²⁺. This resulted in increased removal of sulphate as CaSO₄·2H₂O. In addition the sulphate removal was enhanced through the precipitation as Fe and Al oxyhydroxysulphates (as shown by geochemical modelling) in AMD–fly ash system. The low concentration of Fe and Al in CMW resulted in sulphate removal depending mainly on CaSO₄·2H₂O. The results of this study would have implications on the design of treatment methods relevant for different mine waters.     

Performance of Semi-passive Systems for the Biological Treatment of High-As Acid Mine Drainage: Results from a Year of Monitoring at the Carnoulès Mine (Southern France)

Two semi-passive treatment systems for iron (Fe) and arsenic (As) removal in AMD were installed and monitored in-situ for more than a year. These technologies were designed to treat the As-enriched AMD (≈ 1 g/L Fe(II) and 100 mg/L As(III)) of the ancient Carnoulès mine. The treatment was based on biological Fe and As oxidation by indigenous bacteria, and subsequent immobilization of As by ferric hydroxysulfates. Forced aeration and wood/pozzolana or plastic support were used for biofilm attachment. The system performance ranged from 86 to 98% for Fe oxidation, 30 to 60% for Fe removal, and 50 to 80% for As removal at a hydraulic retention time of 9 h. No significant difference were measured between the two biofilm supports. The wood/pozzolana support had a shorter delay for performance recovery after interruptions. Iron oxidation rates were similar to those obtained in the Carnoulès AMD stream and laboratory bioreactor, while As oxidation seemed to be enhanced. The sludge accumulated between 39 and 91 mg/g of As, mainly in the As(V) oxidation state; jarosite and amorphous ferric hydroxysulfate phases were the main Fe and As scavengers. Challenging environmental conditions during the long monitoring period confirm the robustness of the treatment units. The data will be useful in designing future full-scale treatment systems adapted to As-rich AMD.

     

Removal of Metals and Acidity from Acid Mine Drainage Using Municipal Wastewater and Activated Sludge

Co-treatment of acid mine drainage (AMD) and municipal wastewater (MWW) using the activated sludge process is an innovative approach to AMD remediation that utilizes the alkalinity of MWW and the adsorptive properties of the wastewater particulates and activated sludge biomass to buffer acidity and remove metals. The capacity of these materials to treat AMD was investigated in batch mode metal removal tests using high-strength synthetic AMD (pH 2.8, Al 120–200 mg/L, Cu 18–30 mg/L, Fe 324–540 mg/L, Mn 18–30 mg/L, and Zn 36–60 mg/L). Using material from a range of MWW treatment plants, the performance of screened and settled MWW, activated sludges with mixed liquor suspended solids (MLSS) concentrations of 2.0 and 4.0 g/L, and return activated sludges with 6.0 and 7.4 g/L MLSS were compared. Similar trends were observed for the MWW and activated sludges, with removal efficiency generally decreasing in the order Al = Cu > Mn > Zn > Fe. Trends in Fe removal using settled MWW and activated sludges were highly variable, with removal <30 %. Using activated sludges, average removal efficiencies for Al, Cu, Mn, and Zn were 10–65 %, 20–60 %, 10–25 %, and 0–20 %, respectively. Sludge solids concentration was an important controlling factor in metal removal, with removal of Al, Cu, Mn, and Zn increasing significantly with solids concentration. Municipal wastewaters had greater neutralization capacities than activated sludges at high AMD loading ratios. Mixing AMD with screened MWW gave the highest removal efficiency for all metals, achieving average removal of 90–100 % for Al, Cu, and Fe, 65–100 % for Zn, and 60–75 % for Mn. These empirical findings are useful for developing process design parameters in co-treatment systems. Utilizing MWW and activated sludge to remediate AMD can potentially reduce materials and energy requirements and associated costs.     

韩城矿区象山矿井奥灰水化学特征

以水质分析、岩石化学组成检测资料为基础,分析了韩城矿区象山矿井奥灰水质的赋存与分布等水文地质背景,重点研究了水化学组分特征。结果表明:对水质类型划分、TDS含量变化贡献最大的为SO42-,Cl-,Na+,Ca2+,Mg2+,其绝对含量随含水层段的埋深而增加。水化学组分垂向上差异,由介质石膏含量及其溶解作用决定。在象山矿井深部奥灰水水动力条件较浅部活跃。     

Acid Mine Drainage Flowing from Abandoned Gas Wells

Abstract  In northwestern Pennsylvania (USA), numerous abandoned natural gas wells are producing artesian flows of Fe-contaminated water. The origin of the polluted water has been generally assumed to be brines from the gas-producing sands. We sampled 20 artesian discharges where iron staining was conspicuous. The waters were not brines, but were more characteristic of acid mine drainage (AMD). The dominant cations were Fe, Ca, and Mg, while the dominant anion was sulfate. The study area has a long history of coal mining in the lower Allegheny formation; however, the coal beds are generally at higher elevations than the discharges. We propose that AMD formed in the coal mines is infiltrating into lower aquifers, moving outside the lateral limits of mining, and using abandoned gas wells as conduits to the surface. While flowing through the underlying sandstones, the AMD chemistry is modified by contact with siderite, the dominant carbonate mineral in this stratigraphy. This would suggest that current remediation strategies that emphasize plugging the pollution-producing gas wells may be ill-advised because the source of the polluted water is more shallow than currently assumed.     

皖北任楼煤矿深层地下水稀土元素地球化学特征

为深入理解深层地下水稀土元素特征及水岩相互作用机制,对皖北任楼煤矿深部3个含水层（四含、煤系和太灰水）的稀土元素组成进行了测试,结果表明:任楼煤矿3个含水层均以轻稀土亏损、重稀土富集为特征,且均具有明显的Eu正异常以及普遍的负Ce异常,但三者在稀土分异、Eu和Ce异常程度上存在区别。其中,Ce异常主要与氧化还原程度有关,正Eu异常除与测试中BaO的干扰有关外,还原环境下Eu2+和Sr2+之间的交换、氧化状态下Eu3+的存在形态可能分别对太灰水和四含水存在影响,但煤系水中最高的正Eu异常可能主要与斜长石的溶解有关。除围岩成分、温度及酸碱度之外,稀土元素无机形态可能对地下水稀土分异程度存在重要影响。含水层之间稀土元素特征的差异为水源识别提供了可行性,但仍需进一步的研究以待证实。     

Geophysical Diagnosis of Diversion Channel Infiltration in a Uranium Waste Rock Pile

The Osamu Utsumi mine was the first to economically mine uranium ore in Brazil. During its operation, a river valley was buried for the construction of the waste rock pile. The original stream was diverted to the northwest side of the pile and has since flowed into a diversion channel devoid of basal waterproofing, while an acid mine drainage (AMD) source flows at the base of this waste rock pile. This research aims to evaluate the possible relationship between water infiltration of the diversion channel and the AMD resurgence at the base of the pile using electrical resistivity tomography and induced polarization. 2D inversion models and pseudo-3D maps allowed the recognition of low resistivity zones (<?100 Ω·m) with high chargeability areas (10 mV/V). Some of these low-resistivity areas have been interpreted as infiltration zones in segments of the diversion channel into the pile, and in one of them, the flow intercepts a high chargeability area interpreted as a sulfide-rich zone that is expected to contribute to AMD at the base of the pile. Understanding the hydrogeochemical process will help select effective actions to mitigate the generation of AMD at the mine, which is currently in the decommissioning phase.

     

常见金属阳离子对黑云母浮选行为影响研究

研究了在油酸钠捕收剂体系中金属阳离子Ca~(2+)、Mg~(2+)、Cu~(2+)、Fe~(3+)、Pb~(2+)、Al~(3+)对黑云母纯矿物可浮性的影响,并通过溶液化学计算探讨其作用机理。试验结果表明:1在油酸钠捕收体系中,6种金属阳离子在碱性条件下对黑云母都有活化作用,其中Cu~(2+)、Fe~(~(3+))、Al~(3+)的活化作用最强,Pb~(2+)次之,Ca~(2+)、Mg~(2+)的活化作用最弱.2Ca~(2+)对黑云母浮选起活化作用的主要组分是羟基络合物;Mg~(2+)、Cu~(2+)、Fe~(3+)和Al~(3+)对黑云母起活化作用的优势组分主要是氢氧化物沉淀;Pb~(2+)的羟基络合物和氢氧化物沉淀都是活化黑云母的优势组分。     

Downflow Limestone Beds for Treatment of Net-Acidic, Oxic, Iron-Laden Drainage from a Flooded Anthracite Mine, Pennsylvania, USA: 2. Laboratory Evaluation

Acidic mine drainage (AMD) containing elevated concentrations of dissolved iron and other metals can be neutralized to varying degrees by reactions with limestone in passive treatment systems. We evaluated the chemical and mineralogical characteristics and the effectiveness of calcitic and dolomitic limestone for the neutralization of net-acidic, oxic, iron-laden AMD from a flooded anthracite mine. The calcitic limestone, with CaCO₃ and MgCO₃ contents of 99.8 and <0.1 wt%, respectively, and the dolomitic limestone, with CaCO₃ and MgCO₃ contents of 60.3 and 40.2 wt%, were used to construct a downflow treatment system in 2003 at the Bell Mine, a large source of AMD and baseflow to the Schuylkill River in the Southern Anthracite Coalfield, in east-central Pennsylvania. In the winter of 2002–2003, laboratory neutralization-rate experiments evaluated the evolution of effluent quality during 2 weeks of continuous contact between AMD from the Bell Mine and the crushed calcitic or dolomitic limestone in closed, collapsible containers (cubitainers). The cubitainer tests showed that: (1) net-alkaline effluent could be achieved with detention times greater than 3 h, (2) effluent alkalinities and associated dissolution rates were equivalent for uncoated and Fe(OH)₃-coated calcitic limestone, and (3) effluent alkalinities and associated dissolution rates for dolomitic limestone were about half those for calcitic limestone. The dissolution rate data for the cubitainer tests were used with data on the volume of effuent and surface area of limestone in the treatment system at the Bell Mine to evaluate the water-quality data for the first 1.5 years of operation of the treatment system. These rate models supported the interpretation of field results and indicated that treatment benefits were derived mainly from the dissolution of calcitic limestone, despite a greater quantity of dolomitic limestone within the treatment system. The dissolution-rate models were extrapolated on a decadal scale to indicate the expected decreases in the mass of limestone and associated alkalinities resulting from the long-term reaction of AMD with the treatment substrate. The models indicated the calcitic limestone would need to be replenished approaching the 5-year anniversary of treatment operations to maintain net-alkaline effluent quality.     

Statistical Evaluation of Dependence Between pH,Metal Contaminants,and Flow Rate in the AMD-Affected Smolnik Creek

Acid mine drainage (AMD) with a pH of 3.7–4.1 seeps from an abandoned sulphide mine in Smolnik, Slovakia at a flow rate of 5–10 L/s. Metals precipitate as the AMD mixes with the higher pH Smolnik Creek, adversely affecting the stream’s water quality and ecology. Multivariate statistics were used to interpret surface water and sediment quality effects. Factor analysis generated three significant factors that explained 79.9 % of the variance in the data: the pH is indirectly proportional to the concentration of dissolved metals; Fe precipitation is associated with a decrease in Al in the sediment; and increased Cu concentrations are associated with more Zn in the sediment. High rainfall events increase the flow of Smolnik Creek, which ranges from 0.3 to 2.0 m³/s (monitored 2000–2012). Increased flow is associated with a pH increase and precipitation of metals (Fe, Al, Cu, and Zn). The dependence of pH on flow in Smolnik Creek was evaluated using regression analysis, which confirmed the significance of the exponential relationship between pH and flow rate.