Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。     

微生物絮凝剂投加方式对好氧颗粒污泥性能的影响

为提高好氧污泥颗粒化速度, 采用微生物絮凝剂, 探讨在好氧颗粒污泥培养过程中微生物絮凝剂的投加方式对颗粒污泥理化性能及生物降解效能的影响。结果表明:微生物絮凝剂每隔2、3、5、7 d投加一次时, 均可培养出成熟的好氧颗粒污泥, 微生物絮凝剂的投加方式对好氧污泥颗粒化的影响较显著;微生物絮凝剂最佳投加方式为每5天投加一次, 此时颗粒化速度快, 颗粒形成时间由未投加的60 d缩短为42 d, 好氧颗粒污泥疏水性好, 污泥体积指数稳定在40 mL/g左右, 沉降速度达35.06 m/h, COD、氨氮和总磷的去除率分别为96.55%、93.29%和87.29%。     

酸性矿坑废水对流域酸化的影响——以贵州兴仁县典型废弃煤矿区小流域为例

人们在开采使用矿产资源的同时,堆弃大量含有硫化物的废弃矿石和废渣于周围环境中。矿山环境中因硫化矿物氧化,导致采矿产生大量的酸性矿坑排水。这种水体具有低pH值,高电导率,高硫酸根和高重金属含量的特征。酸性矿坑排水对下游水生生物及植物等具有很强的毒性,大量排放引起的环境问题受到广泛关注。为了了解酸性矿山排水对流域水体和土壤的影响,本文选择位于贵州省西南部兴仁的一个典型废弃煤矿区进行研究,通过测定矿坑排水、水库水、河水的pH值和EC,以及土壤的pH值,分析矿坑排水、地表水以及土壤pH值的空间变化情况,在此基础上对矿坑排水对流域酸化的影响进行了综合评价。调查结果表明,酸性矿坑排水和受其影响的水库水体的电导率很高,且pH值均小于3。研究区域地表水（水库水、河水）本底水化学类型为Ca2+-HCO3-型,其pH值在7左右,反映了流域内有碳酸盐岩广泛分布的自然环境特征。当受到酸性矿坑排水影响后,水化学类型转变为Ca2+-SO42-型,pH值则低于4.0。通常,酸性矿坑排水在流动过程中与河床的碳酸盐岩发生中和反应,促使水体的pH升高。野外考察发现,研究区河道中碳酸盐岩中空易碎,其CaCO3成分因长期与酸性矿山排水发生反应而被耗尽。同时,在氧化条件下,酸性矿坑排水中的铁在流动过程中生成大量的氢氧化物覆盖了沿程的河床。这种覆盖作用抑制了酸性矿山排水进一步与碳酸盐岩发生中和反应。因此,在研究区分布有广泛的碳酸盐岩情况下,受酸性矿坑排水影响的河水到下游5 km处仍保持较低的pH值。研究区的主要农作物是水稻,其灌溉水源主要是水库水。为了了解酸性矿坑排水对土壤的影响,对水库下游流域土壤pH值的空间分布进行普查,统计其出现的频率。结果表明,以受酸性矿坑排水影响的水库水作为灌溉水源的土壤,其表土的pH值较低,平均值在5.0左右。反之,土壤表土的pH值平均值在6.5左右。此外,通过对受到酸性矿坑排水影响显著的土壤进行剖面调查,发现从地表到深度90 cm的土壤的pH值均小于4.0。结合受酸性矿坑排水影响的河水pH值普遍偏低的情况可以推测流域酸化与酸性矿坑排水有密切关系。      

Treatment of Acid Mine Drainage (AMD) in South Brazil: Comparative active processes and water reuse

This work describes AMD techniques of neutralization, with lime, flocculation of the precipitates and comparative flocs/liquid separation by flotation with microbubbles or by lamellar settling (LS). The AMD treated water was characterized by its quality for recycling in terms of inorganic or organic elements, suspended or dissolved solids, among others. Two types of flocs were formed, “aerated” or not, in a special flocculation reactor, patented by this research group (RGF^®). Aerated flocs formed (within seconds) entered into contact with microbubbles under high shearing and raised-up at rates > 120 mh^− 1 allowing a rapid solid–liquid separation by flotation (HR-high rate), at about 13–15 m³m^− 2 h^− 1 loading capacity. Conversely, the non-aerated flocs settled at about 5–6 m h^− 1 in a lamella settler. Both AMD treatment techniques showed similar efficiencies (removal of ions > 90%) but the separation by lamella settling presented advantages, namely less reagents (no flotation collector required), lower power requirements and easier to operate. The operating costs (approximate values) of the AMD treatment by LS at pH 9 reaches about 0.3 US$ m^− 3 against 0.6 US$ m^− 3 for the HR-flotation process. Results found were proved to be similar to those found in recent ADM treatment installations in South Brazil. The quality of the treated water is fairly good, nearly free of heavy metals ion, low BOD (biological oxygen demand) and TOC (total organic content), low solids content and may be readily reused for irrigation, industrial processes and as wash water (among others, streets, vehicles, dust control). However, there is a need to extend the use of this treated water resource, but this, at least in Brazil, has not been legislated properly. It is concluded that this research will contribute in the discussion of this old and complex problem in acid mining effluents worldwide.     

Feasibility and cost of creating an iron-phosphate coating on pyrrhotite to prevent oxidation

 Acid mine drainage (AMD) occurs when sulfide minerals are exposed to an oxidizing environment. Most of the methods for preventing AMD are either short-term or high cost solutions. Coating with iron phosphate is a new technology for the abatement of AMD. It involves treating the sulfide with a coating solution composed of H₂O₂, KH₂PO₄, and sodium acetate as a buffer agent. The H₂O₂ oxidizes the sulfide surface and produces Fe³⁺ so that iron phosphate precipitates as a coating on the sulfide surface. Experiments performed under laboratory conditions prove that an iron phosphate coating can be established on pyrrhotite surfaces with optimal concentrations of the coating solution in the range of: 0.2M/0.01M H₂O₂, 0.2M KH₂PO₄, and 0.2M sodium acetate NaAc, depending on the experimental scale. Iron phosphate coating may be a long-term solution to the problem of AMD. The method would be easy to implement; the reagent cost, however, is not low enough, although it is lower than the conventional treatment with lime. Received: 30 March 1995 · Accepted: 6 September 1995     

Systematic assessment of electrocoagulation for the treatment of marble processing wastewater

In this study, the treatability of marble processing wastewater by electrocoagulation using aluminum and iron electrodes was investigated. The sample used was from the marble-processing plant in Sivas and its turbidity, suspended solids, chemical oxygen demand and total solids concentrations were about 1,914?NTU, 2,904, 150 and 4,750?mg/L, respectively. The effects of various operating parameters such as initial pH, current density and electrolysis time on turbidity, suspended solids, chemical oxygen demand and total solids removal efficiencies were investigated. The settling characteristics of waste sludge produced and energy and electrode consumption were also determined. The optimum values of initial pH, current density and electrolysis time in electrocoagulation studies carried out using aluminum electrode were found to be 7.8, 30?A/m² and 5?min, respectively. Under these conditions, the removal efficiencies obtained for turbidity, suspended solids, chemical oxygen demand and total solids were 98.5, 99.2, 55.2 and 92.4?%, respectively. Corresponding energy and electrode consumptions were 0.143?kWh/kg SS and 0.010?kg Al/kg SS. For iron electrode, the optimum parameter values were found to be 7.8 pH, 20?A/m² and 5?min, respectively. Under these conditions, removal efficiencies for turbidity, suspended solids, chemical oxygen demand and total solids were determined as 94.3, 99.1, 54.2, and 96.1?%, respectively. Energy and electrode consumptions were 0.0571?kWh/kg SS and 0.0206?kg Fe/kg SS, respectively. Settling characteristics of sludge produced during experiments carried out using both aluminum and iron electrodes were fairly good. The results showed that electrocoagulation method can be used efficiently for the treatment of marble processing wastewater under proper operating conditions.     

Geotechnical properties of municipal sewage sludge

The geotechnical properties of municipal sewage sludge, in particular those pertinent to the handling and landfilling of the material, are presented. Index, drying, compaction, shear strength and consolidation tests were conducted on the material at different states of biodegradation. The organic content and specific gravity of solids were found to be inversely related, with typical organic contents of 50–70% and specific gravity of solids values of 1.55–1.80. The density of the compacted material was low in comparison with mineral soils. Standard Proctor compaction yielded a maximum dry density of 0.56 tonne/m³ at 85% water content. Laboratory vane-shear and triaxial compression tests indicated that, below about 180% water content, the shear strength of the sludge material increased exponentially with reducing water content. Consolidated-undrained triaxial compression tests on the pasteurised sludge material indicated an effective angle of shearing resistance of 32° for the moderately degraded material and 37° for the strongly degraded material. Biogas was produced at rates of up to 0.33 L/day/kg slurry due to ongoing biodegradation and the resulting pore pressure response must be taken into account in any stress analysis. Consolidation tests using the hydraulic consolidation cell, oedometer and triaxial apparatus indicated that the sludge material was highly compressible although practically impermeable, for example the coefficient of permeability for the moderately degraded slurry was of the order of 10⁻⁹m/s. However, creep deformation was significant with typical coefficient of secondary compression values of 0.02–0.08 for the compacted material. A more free-draining material was produced at higher states of biodegradation.     

As(Ⅴ)对嗜酸性氧化亚铁硫杆菌混合培养物氧化性能的影响

通过对pH、Eh、溶液中Fe2+浓度的定期监测以及对实验结束时生成沉淀的XRD、SEM和元素能谱扫描等手段,对比研究了不同初始浓度的As(Ⅴ)对Fe2+的化学氧化和嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)氧化的影响, 同时就As(Ⅴ)在实验体系中固液相之间的分配行为进行了分析.结果表明,Fe2+的化学氧化速率极低,最终氧化率低于8%,As(Ⅴ)的浓度对Fe2+的化学氧化没有影响.有A. ferrooxidans的实验体系,100 mg/L As(Ⅴ)对Fe2+的氧化具有一定的促进作用.当As(Ⅴ)浓度为500 mg～1 g/L时,Fe2+的氧化率在约60 h左右即可达到100%;但4g/L的As(Ⅴ)则会明显抑制Fe2+的氧化,Fe2+的完全氧化大约需要106 h.体系中初始的100 As/(As+S)(摩尔比)会对沉淀物的物相及结晶程度造成一定影响.As(Ⅴ)浓度为0 g/L时,微生物体系中生成的固体沉淀物黄钾铁矾的特征峰明显,随着As(Ⅴ)浓度的提高,沉淀物的结晶程度逐步下降,至4 g/L时沉淀物全部为无定形.元素能谱扫描检测到有大量的As(Ⅴ)存在于固体沉淀物中,表明在Fe2+的氧化过程中,As(Ⅴ)可能会以吸附或共沉淀的形式被固定在固相沉淀物中,这为酸性矿坑水(AMD)地区As(Ⅴ)污染的治理提供了重要的参考.     

Application of waterworks sludge in wastewater treatment plants

The potential for reuse of iron-rich sludge from waterworks as a replacement for commercial iron salts in wastewater treatment was investigated using acidic and anaerobic dissolution. The acidic dissolution of waterworks sludge both in sulphuric acid and acidic products such as flue gas washing water and commercial iron solution was successful in dissolving the iron from waterworks sludge. The anaerobic dissolution of waterworks sludge due to co-digestion with biological sludge (primary and biological activated sludge) resulted in reduction of iron, increase in dissolved iron(II), increase in pH due to the produced alkalinity from dissolution of iron(III)hydroxides from waterworks sludge, lower internal recirculation of phosphate concentration in the reject water and reduced sulphide in the digested liquid. However, recirculation of the produced soluble iron(II) as an iron source for removal of phosphate in the wastewater treatment was limited, because the dissolved iron in the digester liquid was limited by siderite (FeCO₃) precipitation. It is concluded that both acidic and anaerobic dissolution of iron-rich waterworks sludge can be achieved at the wastewater treatment plant, and are economically and environmentally more favourable compared to deposition of the waterworks sludge in controlled landfills.     

Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.     

Predicting arsenic concentrations in the porewaters of buried uranium mill tailings

The proposed JEB Tailings Management Facility (TMF) to be emplaced below the groundwater table in northern Saskatchewan, Canada, will contain uranium mill tailings from McClean Lake, Midwest and Cigar Lake ore bodies, which are high in arsenic (up to 10%) and nickel (up to 5%). A serious concern is the possibility that high arsenic and nickel concentrations may be released from the buried tailings, contaminating adjacent groundwaters and a nearby lake. Laboratory tests and geochemical modeling were performed to examine ways to reduce the arsenic and nickel concentrations in TMF porewaters so as to minimize such contamination from tailings buried for 50 years and longer. The tests were designed to mimic conditions in the mill neutralization circuit (3 hr tests at 25°C), and in the TMF after burial (5–49 day aging tests). The aging tests were run at, 50, 25 and 4°C (the temperature in the TMF). In order to optimize the removal of arsenic by adsorption and precipitation, ferric sulfate was added to tailings raffinates¹ having Fe/As ratios of less that 3–5. The acid raffinates were then neutralized by addition of slaked lime to nominal pH values of 7, 8, or 9.Analysis and modeling of the test results showed that with slaked lime addition to acid tailings raffinates, relatively amorphous scorodite (ferric arsenate) precipitates near pH 1, and is the dominant form of arsenate in slake limed tailings solids except those high in Ni and As and low in Fe, in which cabrerite-annabergite (Ni, Mg, Fe(II) arsenate) may also precipitate near pH 5–6. In addition to the arsenate precipitates, smaller amounts of arsenate are also adsorbed onto tailings solids.The aging tests showed that after burial of the tailings, arsenic concentrations may increase with time from the breakdown of the arsenate phases (chiefly scorodite). However, the tests indicate that the rate of change decreases and approaches zero after 72 hrs at 25°C, and may equal zero at all times in the TMF at 4°C. Consistent with a kinetic model that describes the rate of breakdown of scorodite to form hydrous ferric oxide, the rate of release of dissolved arsenate to tailings porewaters from slake limed tailings: (1) is proportional to pH above pH 6–7; (2) decreases exponentially as the total molar Fe/As ratio of tailings raffinates is increased from 1/1 to greater than 5/1; and (3) is proportional to temperature with an average Arrhenius activation energy of 13.4 ± 4.2 kcal/mol.Study results suggest that if ferric sulfate and slaked lime are added in the tailings neutralization circuit to give a raffinate Fe/As molar ratio of at least 3–5 and a nominal (initial) pH of 8 (final pH of 7–8), arsenic and nickel concentrations of 2 mg/L or less, are probable in porewaters of individual tailings in the TMF for 50 to 10,000 yrs after tailings disposal. However, the tailings will be mixed in the TMF, which will contain about 35% tailings with Fe/As = 3.0, and 65% tailings with Fe/As = 5.0–7.7. Thus, it seems likely that average arsenic pore water concentrations in the TMF may not exceed 1 mg/L.     

Bioavailability of jarosite for stimulating acid mine drainage attenuation

Biological reduction of iron-sulfate minerals, such as jarosite, has the potential to contribute to the natural attenuation of acid mine drainage (AMD) sites. Previous studies of AMD attenuation at Davis Mine, an abandoned pyrite mine in Rowe Massachusetts, provided evidence of iron and sulfate reduction by indigenous bacteria. Jarosite is a large component of the sediment at Davis Mine and may play a role in AMD attenuation. In this study, microcosms were constructed with groundwater and sediment from Davis Mine and amended with glycerol, nitrogen and phosphorus (GNP) and naturally formed natrojarosite. Over time, higher total iron, sulfate, pH and sodium concentrations and lower oxidation–reduction potentials were observed in microcosms amended with GNP and jarosite, compared with unamended microcosms and killed controls. Geochemical modeling predicted jarosite precipitation under microcosm conditions, suggesting that abiotic processes were unlikely contributors to jarosite dissolution. SEM imaging at the jarosite surface showed microbial attachment. Microbial community composition analysis revealed a shift to higher populations of Clostridia, which are known to reduce both iron and sulfate. The results show that jarosite may be utilized as an electron acceptor by iron and/or sulfate reducing bacteria at Davis Mine and its presence may aid in the attenuation of AMD.     

A mass balance approach to estimate the dilution and removal of the pollutants in stream water polluted by acid mine drainage

 A few simple mass balance equations were developed to simultaneously estimate how much the pollutants from acid mine drainage (AMD) in stream water are diluted and removed during their migration. The application of the equations requires knowledge of the variations in the concentrations of the dissolved pollutants and the stoichiometry of the precipitation reaction of the pollutants when none of the pollutant shows a conservative behavior along the stream path. The calculation should be restricted to the pollutants showing much higher concentrations in the polluted main stream water than in the combining or diluting water of the same target area. The mass balance equations were applied to estimate the dilution factor and precipitation fractions of pollutants in Imgok Creek such as Fe, SO₄ and Al from the AMD of Yeongdong mine. The results show that the estimation, especially for SO₄ and Al, significantly depends on the kinds of the precipitates. When FeOHSO₄ and AlOHSO₄ are assumed to precipitate, the maximum removal fractions of SO₄ and Al by precipitation are respectively 34% and 46% of the original input, which is much higher than the values estimated when SO₄ is considered to be perfectly conservative. It indicates that the stoichiometry of precipitation reaction is very important in the interpretation of the pollutant dilution and migration and assessment of environmental impacts of AMD. The applicability of the mass balance equations may still need to be verified. However, examining the calculated dilution factor and precipitation fractions with the equations can provide invaluable information on not only the behavior but also unexpected input of the pollutants in the stream water polluted by AMD and other point sources. Received: 12 November 1997 · Accepted: 30 March 1998     

Coupled physicochemical and bacterial reduction mechanisms for passive remediation of sulfate- and metal-rich acid mine drainage

Treatment of acid mine drainage (AMD) highly rich in sulfate and multiple metal elements has been investigated in a continuous flow column experiment using organic and inorganic reactive media. Treatment substrates that composed of spent mushroom compost (SMC), limestone, activated sludge and woodchips were incorporated into bacterial sulfate reduction (BSR) treatment for AMD. SMC greatly assisted the removals of sulfate and metals and acted as essential carbon source for sulfate-reducing bacteria (SRB). Alkalinity produced by dissolution of limestone and metabolism of SRB has provided acidity neutralization capacity for AMD where pH was maintained at neutral state, thus aiding the removal of sulfate. Fe, Pb, Cu, Zn and Al were effectively removed (87–100%); however, Mn was not successfully removed despite initial Mn reduction during early phase due to interference with Fe. The first half of the treatment was an essential phase for removal of most metals where contaminants were primarily removed by the BSR in addition to carbonate dissolution function. The importance of BSR in the presence of organic materials was also supported by metal fraction analysis that primary metal accumulation occurs mainly through metal adsorption onto the organic matter, e.g., as sulfides and onto Fe/Mn oxides surfaces.     

Impact of AMD on water quality in critical watershed in the Hudson River drainage basin: Phillips Mine,Hudson Highlands,New York

A sulfur and trace element enriched U–Th-laced tailings pile at the abandoned Phillips Mine in Garrison, New York, releases acid mine drainage (AMD, generally pH < 3, minimum pH 1.78) into the first-order Copper Mine Brook (CMB) that drains into the Hudson River. The pyrrhotite-rich Phillips Mine is located in the Highlands region, a critical water source for the New York metro area. A conceptual model for derivation/dissolution, sequestration, transport and dilution of contaminants is proposed. The acidic water interacts with the tailings, leaching and dissolving the trace metals. AMD evaporation during dry periods concentrates solid phase trace metals and sulfate, forming melanterite (FeSO₄·7H₂O) on sulfide-rich tailings surfaces. Wet periods dissolve these concentrates/precipitates, releasing stored acidity and trace metals into the CMB. Sediments along CMB are enriched in iron hydroxides which act as sinks for metals, indicating progressive sequestration that correlates with dilution and sharp rise in pH when mine water mixes with tributaries. Seasonal variations in metal concentrations were partly attributable to dissolution of the efflorescent salts with their sorbed metals and additional metals from surging acidic seepage induced by precipitation.     

The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O₂ partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × ⁻¹¹ mol m⁻² s⁻¹.In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at pH approx. 10.45. In this experiment, iron was depleted completely from the solution and attenuation of the sludge oxidation was produced in this conditions. The attenuation was likely promoted by precipitation of iron-bearing phases upon the pyritic surface forming Fe-coatings (of ferrihydrite and/or Fe(III) amorphous phases) that halted the pyrite oxidation (as in non-stirred flow-through experiments). Results suggest that buffering capacity of fly ash can be used to attenuate the pyrite-rich sludge oxidation.     

Identification of the uranium speciation in an underground acid mine drainage environment

The subsurface acid mine drainage (AMD) environment of an abandoned underground uranium mine in Königstein/Saxony/Germany, currently in the process of remediation, is characterized by low pH, high sulfate concentrations and elevated concentrations of heavy metals, in particular uranium. Acid streamers thrive in the mine drainage channels and are heavily coated with iron precipitates. These precipitates are biologically mediated iron precipitates and related to the presence of Fe-oxidizing microorganisms forming copious biofilms in and on the Fe-precipitates. Similar biomineralisations were also observed in stalactite-like dripstones, called snottites, growing on the gallery ceilings.The uranium speciation in these solutions of underground AMD waters flowing in mine galleries as well as dripping from the ceiling and forming stalactite-like dripstones were studied by time resolved laser-induced fluorescence spectroscopy (TRLFS). The fluorescence lifetime of uranium species in both AMD water environments were best described with a mono-exponential decay, indicating the presence of one major species. The detected positions of the emission bands and by comparing it in a fingerprinting procedure with spectra obtained for acid sulfate reference solutions, in particular Fe(III) - SO₄²⁻ - UO₂²⁺ reference solutions, indicated that the uranium speciation in the AMD environment of Königstein is dominated in the pH range of 2.5-3.0 by the highly mobile aquatic uranium sulfate species UO₂SO_4(aq) and formation of uranium precipitates is rather unlikely as is retardation by sorption processes. The presence of iron in the AMD reduces the fluorescence lifetime of the UO₂SO_4(aq) species from 4.3 μs, found in iron-free uranium sulfate reference solutions, to 0.7 μs observed in both AMD waters of Königstein and also in the iron containing uranium sulfate reference solutions.Colloids were not observed in both drainage water and dripping snottite water as photon correlation spectroscopy analyses and centrifugation experiments at different centrifugal accelerations between 500g and 46000g revealed. Thus transport and uranium speciation at the investigated AMD sites is neither influenced by U(IV) or U(VI) eigencolloids nor by uranium adsorbed on colloidal particles.This study shows that TRLFS is a suitable spectroscopic technique to identify the uranium speciation in bulk solutions of AMD environments.