Characterization of limestone reacted with acid-mine drainage in a pulsed limestone bed treatment system at the Friendship Hill National Historical Site,Pennsylvania, USA

Armoring of limestone is a common cause of failure in limestone-based acid-mine drainage (AMD) treatment systems. Limestone is the least expensive material available for acid neutralization, but is not typically recommended for highly acidic, Fe-rich waters due to armoring with Fe(III) oxyhydroxide coatings. A new AMD treatment technology that uses CO₂ in a pulsed limestone bed reactor minimizes armor formation and enhances limestone reaction with AMD. Limestone was characterized before and after treatment with constant flow and with the new pulsed limestone bed process using AMD from an inactive coal mine in Pennsylvania (pH=2.9, Fe =150 mg/l, acidity =1000 mg/l CaCO₃). In constant flow experiments, limestone is completely armored with reddish-colored ochre within 48 h of contact in a fluidized bed reactor. Effluent pH initially increased from the inflow pH of 2.9 to over 7, but then decreased to <4 during the 48 h of contact. Limestone grains developed a rind of gypsum encapsulated by a 10- to 30-μm thick, Fe-Al hydroxysulfate coating. Armoring slowed the reaction and prevented the limestone from generating any additional alkalinity in the system. With the pulsed flow limestone bed process, armor formation is largely suppressed and most limestone grains completely dissolve resulting in an effluent pH of >6 during operation. Limestone removed from a pulsed bed pilot plant is a mixture of unarmored, rounded and etched limestone grains and partially armored limestone and refractory mineral grains (dolomite, pyrite). The ∼30% of the residual grains in the pulsed flow reactor that are armored have thicker (50- to 100-μm), more aluminous coatings and lack the gypsum rind that develops in the constant flow experiment. Aluminium-rich zones developed in the interior parts of armor rims in both the constant flow and pulsed limestone bed experiments in response to pH changes at the solid/solution interface.     

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations

Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m³ filled with limestone sand and wood shavings, and one tank of 1 m³ with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m³/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO₃ equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)₃ and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.     

Long-term interaction of wollastonite with acid mine water and effects on arsenic and metal removal

This paper reports the results of a laboratory experiment conducted to investigate the effects of wollastonite dissolution on removal of potentially toxic trace elements from stream waters affected by acid mine drainage (AMD). Nearly pure wollastonite was treated with natural acid mine water (pH 2.1) for different lengths of time (15, 30, 50 and 80 days). The compositional and textural characterization of the solid reaction products suggests that wollastonite was incongruently dissolved leaving a residual amorphous silica-rich phase that preserved the prismatic morphology of the parent wollastonite. The release of Ca into solution resulted in a pH increase from 2.1 to 3.5, and subsequent precipitation of gypsum as well as poorly crystallized Fe–Al oxy-hydroxides and oxy-hydroxysulfates whose components derived from the AMD solution. A geochemical modeling approach of the wollastonite–AMD interaction using the PHREEQC code indicated supersaturation with respect to schwertmannite (saturation index = 10.7–15.7), jarosite (SI = 8.7–10.2), alunite (SI = 5.1), goethite (SI = 4.7) and jurbanite (SI = 2.2). These secondary phases developed a thin coating on the reacted wollastonite surface, readily cracked and flaked off upon drying, that acted as a sink for trace elements, especially As, Cu and Zn, as indicated by their enrichment relative to the starting wollastonite. At such low pH values, adsorption of As oxyanions on the positively charged solid particles and coprecipitation of metals (mainly Cu and Zn) with the newly formed Fe oxy-hydroxides and oxy-hydroxysulfates seem to be the dominant processes controlling the removal of trace elements.     

Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn–Pb(–Ag–Bi–Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of ∼1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO₃, 4330 mg/L Fe and 29,250 mg/L SO₄. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO₄). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI ∼ 0.25) and anglesite (SI ∼ 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI ∼ 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI ∼ −0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (∼90 wt.% water) of pH ∼1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3–7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb ≈ Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu, and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn; all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks.     

Surface coatings on quartz grains in bentonites and their relevance to human health

The cytotoxicity of quartz in the human lung is recognized to be dependent on both the inherent properties of the silica dust and external factors related to the history of the dust and including the presence of surface contamination. In this study, the physical and chemical surface properties of quartz grains in commercial bentonite deposits from the western (South Dakota) and southern (Alabama) USA were investigated. Measured quartz contents of bentonites range from 1.9 to 8.5 wt% with the <10 μm size fraction comprising 6–45% of this total. Trace element contents (Fe–Ti–Al) of quartz grains from any given bentonite are similar, indicating a single origin for the quartz with little if any contamination from other sources. Surface coatings are pervasive on all quartz grains and resist removal by repeated vigorous washings and reaction with HCl. Textural attributes and XPS and EDS analyses of these coatings are consistent with most being montmorillonite and, less frequently, mixtures of montmorillonite and opaline silica. Opaline silica (opal-A and opal-CT) occurs in two texturally distinct generations: an early massive grain-coating event and as later lepispheres. Montmorillonite coating thicknesses range from <1 μm to more than 10 μm thick. Surfaces of plagioclase, K-feldspar, and biotite grains are conspicuously devoid of montmorillonite coatings, but may show sparse distributions of opal-CT lepispheres. HRTEM has not confirmed a topotactic relationship or atomic structural concordance between montmorillonite coatings and underlying quartz grains. Alternatively, a precursor volcanic glass phase that coats the quartz surfaces during volcanic eruption and/or preferential early precipitation of opaline silica on quartz may provide substrates for development of montmorillonite coatings. Estimations of montmorillonite biodurability under pulmonary pH conditions suggest possible prolonged sequestration of respired bentonite quartz grains from contact with lung materials and modified cytotoxic reactivity.     

Geochemical changes during neutralisation of acid mine drainage in a dynamic mountain stream, New Zealand

The Mangatini Stream drains a coal mining area in the mountains of northwestern South Island of New Zealand. Abundant rainfall on pyritic rocks yields acid mine drainage (AMD) to the stream, which flows through a steep gorge at discharges that rapidly increase from <1 to >100 m³/s during frequent rain events. The AMD is treated with finely ground limestone, which is discharged as a slurry at a point in the middle of the gorge. The limestone slurry mixes and reacts with the AMD during flow ∼4 km downstream over ∼12 h. Neutralisation reactions increase stream pH from near 3 (untreated Mangatini Stream water impacted by AMD) to 5–6 in the first 250 m downstream, although mixing is commonly incomplete in this zone. Large stream discharge volumes in rain events dilute the neutralising material input, thus driving the pH back towards 4 downstream of treatment. More complete neutralisation is achieved 4 km downstream, even in major rain events, and pH can rise to >7. Partial neutralisation is sufficient to remove most of the dissolved Fe(III) (typically ∼30 mg/L) from the Mangatini Stream in the first 10 m, and remaining dissolved Fe is essentially all Fe(II), which decreases over time as it oxidises and precipitates. Dissolved Al in the Mangatini Stream (typically ∼50 mg/L) decreases steadily downstream over ∼100 m in the limestone mixing zone. Precipitated Fe and Al form amorphous oxyhydroxides that are transported as suspended solids and deposited on the stream bed with excess limestone in zones of low flow velocity. Dissolved Zn is removed from solution by adsorption to Fe oxyhydroxide when pH reaches ∼5, but dissolved Ni remains in solution despite the neutralisation process. Gypsum precipitation occurs throughout the limestone mixing zone, resulting in at least 30% decrease in dissolved . Minor ettringite forms in the first 100 m, but then probably redissolves. The limestone dosing system is an effective method of neutralising the effects of AMD and removing most dissolved metals in a steep mountain stream with frequent rain events where this dynamic environment places many constraints on treatment options.     

Reworking of Earth's first crust: Constraints from Hf isotopes in Archean zircons from Mt. Narryer,Australia

Discoveries of >4 Ga old zircon grains in the northwest Yilgarn of Western Australia led to the conclusion that evolved crust formed on the Earth within the first few 100 Ma after accretion. Little is known, however, about the fate of the first crust that shaped early Earth's surface. Here we report combined solution and laser-ablation Lu–Hf–U–Pb isotope analyses of early Archean and Hadean detrital zircon grains from different rocks of the Narryer Gneiss Complex (NGC), Yilgarn Craton, Western Australia. The zircons show two distinct groups with separate evolutionary trends in their Hf isotopes. The majority of the zircon grains point to separation from a depleted mantle reservoir at ∼3.8–3.9 Ga. The second Hf isotope trend implies reworking of older Hadean zircon grains. The major trend starting at 3.8–3.9 Ga defined by the Hf isotopes corresponds to a Lu/Hf that is characteristic for felsic crust and consequently, the primary sources for these zircons presumably had a chemical composition characteristic of continental crust. Reworked Hadean crust appears to have evolved with a similar low Lu/Hf, such that the early crust was probably evolved with respect to Lu–Hf distributions. The co-variation of Hf isotopes vs. age in zircon grains from Mt. Narryer and Jack Hills zircon grains implies a similar crustal source for both sediments in a single, major crustal domain. Age spectra and associated Hf isotopes in the zircon grains strongly argue for ongoing magmatic reworking over hundreds of millions of years of the felsic crustal domain in which the zircon grains formed. Late-stage metamorphic zircon grains from the Meeberrie Gneiss unit yield a mean U–Pb age of 3294.5 ± 3.2 Ma with initial Hf isotopes that correspond to the evolutionary trend defined by older NGC zircon grains and overlap with other detrital zircon grains, proving their genetic relationship. This ‘Meeberrie event’ is interpret here as the last reworking event in the precursor domain before final deposition. The continuous magmatic activity in one crustal domain during the Archean is recorded by the U–Pb ages and Hf isotope systematics of zircon grains and implies reworking of existing crust. We suspect that the most likely driving force for such reworking of crustal material is ongoing crustal collision and subduction. A comparison of Hf isotope signatures of zircon grains from other Archean terranes shows that similar trends are recognised within all sampled Archean domains. This implies either a global trend in crustal growth and reworking, or a genetic connection of Archean terranes in close paleo-proximity to each other. Notably, the Archean Acasta gneiss (Canada) shows a similar reworking patterns to the Yilgarn Craton of Hadean samples implying either a common Hadean source or amalgamation at the Hadean–Archean transition.     

Experimental study on prevention of acid mine drainage by silica coating of pyrite waste rocks with amorphous silica solution

Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)₃ on the surface of pyrite, reaction between Fe(OH)₃ and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.     

The effect of Ca–Fe–As coatings on microbial leaching of metals in arsenic bearing mine waste

Globally arsenic (As) is a ubiquitous trace element derived from the natural weathering of As-bearing rock. With the onset of reducing conditions, the prevalence of aqueous As(III) may be intensified through biotic and abiotic processes. Here we evaluate the stability of arsenic bearing Ca–Fe hydroxide phases collected from exposed tailings at Ketza River mine, Yukon, Canada, during the reductive dissolution of both acid treated and untreated samples by Shewanella putrefaciens 200R and Shewanella sp. ANA-3. Samples were acid treated in order to remove Ca–Fe oxide coatings and evaluate the influence of these coatings on the rates of microbial Fe(III) and As(V) reduction. Environmental scanning electron microscope (ESEM) micrographs of the solid phase show significant differences in the chemistry and physical morphology of the material by the bacteria over time and are especially evident in the acid treated samples. Moreover, while solution chemistry showed similar As(III) respiration rates of the inoculated acid treated samples for both ANA3 and 200R at ~ 1.1 × 10⁻⁶ μM·s^− 1·m^− 2, the Fe(II) respiration rates differed at 1.4 × 10^− 7 and 9.5 × 10^− 8 μM·s^− 1·m⁻² respectively, thus suggesting strain specific metal reduction metabolic pathways Additionally, the enhanced metal reduction observed in the acid treated inoculated samples suggests that the presence of the Ca–Fe hydroxide phase in the untreated samples acted as a barrier, inhibiting the bacteria from accessing the metals. This has implications for increased mobilization of metals by metal reducing bacteria within areas of increased acidity, such as acid mine drainage sites and industrial tailings ponds that can come into contact with surface and ground water sources.     

Field application of calcite Dispersed Alkaline Substrate (calcite-DAS) for passive treatment of acid mine drainage with high Al and metal concentrations

Passive treatment systems are widely used for remediation of acid mine drainage (AMD), but existing designs are prone to clogging or loss of reactivity due to Al- and Fe-precipitates when treating water with high Al and heavy metal concentrations. Dispersed alkaline substrate (DAS) mixed from a fine-grained alkaline reagent (e.g. calcite sand) and a coarse inert matrix (e.g. wood chips) had shown high reactivity and good hydraulic properties in previous laboratory column tests. In the present study, DAS was tested at pilot field scale in the Iberian Pyrite Belt (SW Spain) on metal mine drainage with pH near 3.3, net acidity 1400–1650 mg/L as CaCO₃, and mean concentrations of 317 mg/L Fe (95% Fe(II)), 311 mg/L Zn, 74 mg/L Al, 20 mg/L Mn, and 1.5–0.1 mg/L Cu, Co, Ni, Cd, As and Pb. The DAS-tank removed an average of 870 mg/L net acidity as CaCO₃ (56% of inflow), 25% Fe, 93% Al, 5% Zn, 95% Cu, 99% As, 98% Pb, and 14% Cd, but no Mn, Ni or Co. Average gross drain pipe alkalinity was 181 mg/L as CaCO₃, which increased total Fe removal to 153 mg/L (48%) in subsequent sedimentation ponds. Unfortunately, the tank suffered clogging problems due to the formation of a hardpan of Al-rich precipitates. DAS lifetime could probably be increased by lowering Al-loads.     

Removal of arsenic from aqueous solution by natural siderite and hematite

Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.     

Limestone drains to increase pH and remove dissolved metals from acidic mine drainage

Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO₃) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO₃ dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L⁻¹ of O₂, Fe³⁺, Al³⁺ and Mn²⁺. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O₂>1 mg·L⁻¹) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)₃ and Al(OH)₃, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)₃ and Al(OH)₃ particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO₃ dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO₃ dissolution and Fe(OH₃) precipitation were associated with the relatively low pH and high Fe³⁺ concentration near the inflow. The rate of CaCO₃ dissolution decreased with increased pH and concentrations of Ca²⁺ and HCO₃⁻ and decreased Pco₂. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.     

Iron oxyhydroxide coating of pyrite for acid mine drainage control

When pyrite oxidizes at near neutral pH in the presence of sufficient alkalinity, Fe oxyhydroxide coatings develop on the surface. As these coatings grow thicker and denser they block oxidant transport from the solution to the pyrite surface and reduce the rate of pyrite oxidation. The authors’ measurements of pyrite oxidation rates in a NaHCO₃ solution show that the coating grows in two stages. In the first stage Fe oxyhydroxide colloids form and then attach to the pyrite surface to produce a slight reduction in oxidant transport. In the second stage interstitial precipitation of Fe oxyhydroxide material between the colloidal particles reduces the oxidant’s diffusion coefficient by more than five orders of magnitude. This causes the pyrite oxidation rate to decline as the square root of time. The kinetic predominance diagram, which compares the rates of Fe transformation reactions, shows that when pyrite oxidation releases Fe quickly enough for the total Fe concentration to rise to about 10⁻⁸ m, ferrihydrite forms but lower rates of Fe release will not produce coatings. Extrapolation of the results to longer times predicts that pyrite-bearing materials need to be treated with an extra source of alkalinity for several decades to produce coatings that are thick enough to be sustained by alkalinity levels typical of groundwater. However, once the coatings develop no additional treatment is needed and further pyrite oxidation simply causes the coating to grow thicker and denser until the entire pyrite grain is pseudomorphically replaced by goethite.     

Influence of pH and temperature on the early stage of mica alteration

Mineral dissolution and precipitation reactions actively participate in controlling fluid chemistry during water–rock interaction. In this study, the changes in the biotite and muscovite basal surface nano-morphology were evaluated during interaction with fluids of different pH (pH = 1.1, 3.3 and 5.7) at different temperatures (T = 25°, 120°, and 200 °C). Results show that at the nanometre scale resolution of the atomic force microscope (AFM), dissolution generates etch pits with a stair-shaped pattern over the (0 0 1) surface. The flux of dissolved elements decreases when pH increases. However, at pH 5.7, a change was found in the flux after 42 h of reaction when abundant gibbsite and kaolinite coat the dissolving mineral surface. This phenomenon was widely observed at edges of the etch pits by AFM. It was also found that an increase in temperature produces an enhancement in the elemental flux in both micas. Dissolution regime changes after less than one day of interaction at high temperature because of abundant coating formation over the etch pits and edges. The results demonstrate the key role of nanometre size neogenic phases in the control of elemental flux from mica surfaces to solution. The formation of nanometre size coatings, blocking the sites active for dissolution, appears to control the alteration of phyllosilicates even at the early stage of the interaction.     

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。      

Influence of waterfall aeration and seasonal temperature variation on the iron and arsenic attenuation rates in an acid mine drainage system

Dramatic seasonal changes in water chemistry and precipitate mineralogy associated with acid-mine drainage (AMD) in the waterfall and creek sections of the Chinkuashih area, northern Taiwan were investigated. Special attention has been paid to the kinetic effects of seasonal temperature variation and waterfall aeration. Precipitation of schwertmannite associated with removal of metals and As are indicated by delicate growth microstructures on precipitate surfaces, X-ray diffraction data, and downstream reductions of metal and As concentrations. Geochemical modeling suggested a downstream increase of the degree of saturation/supersaturation with respect to schwertmannite in the waterfall section, which can be attributed to high Fe²⁺ oxidation rates. The waterfall section was characterized by high rates and model rate constants of Fe²⁺ oxidation (6.1–6.7 × 10⁻⁶ mol L⁻¹ s⁻¹ and 2.7–2.9 × 10⁻² s⁻¹) and Fe (schwertmannite) precipitation (1.7–2.1 × 10⁻⁶ mol L⁻¹ s⁻¹ and 3.5–4.1 × 10⁻⁷ mol L⁻¹ s⁻¹). A high As sorption rate (4.7–6.3 × 10⁻⁹ mol L⁻¹ s⁻¹) and low As distribution coefficient (7.9–11.8 × 10⁻⁹ mol⁻¹ L) were observed. The creek section showed up to 1–2 orders of magnitude slower rates and lower rate constants than the waterfall section and had seasonal variations comparable to those in areas polluted by AMD elsewhere. The summer rates were 4–5 times higher than the winter rates in the creek section, and are largely attributed to a temperature effect. In contrast, the seasonal differences in rate and rate constant were small in the waterfall section. Several factors associated with the waterfall aeration in addition to elevated temperature and As concentration enhanced Fe and As attenuation in the waterfall section. The waterfall effects on Fe precipitation rate were enhanced when the flow rate was large in the winter. Despite the remarkable removal of metals and As by the rapid precipitation of As-bearing schwertmannite, large effluent loads of potentially hazardous contaminants including As, Cu and Zn discharged to the sea in the Chinkuashih area.     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments,Prince William Sound,Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ? sphalerite < chalcopyrite ? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe–Al sulfate. The oxi dation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (∼3) and highest concentrations of base metals (to ∼25,000 μg/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO₄ are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe²⁺ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach–seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7–7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.     

Refining the estimation of metal loads dissolved in acid mine drainage by continuous monitoring of specific conductivity and water level

The accurate estimation of metal loads transported by streams is necessary to calculate reliable mass transfers of metals between compartments, both at local and global scales. This estimation is particularly relevant in the case of the Tinto and Odiel Rivers (SW Spain) due to their significant contribution to the total metal transfer from continents to the ocean. At a local scale, the metal load transported by streams plays a key role in predicting the biogeochemical evolution of water reservoirs affected by Acid Mine Drainage (AMD). This work uses the relationships between specific conductivity (SC) and dissolved elements to calculate the metal load of the River Meca, a tributary of the Odiel. The SC and the water level were continuously monitored from April 2009 to June 2010. Water samples were also collected and measurements of the discharge were carried out manually once a month. The relationships between the SC and the concentration of dissolved elements are, in general, very good (R² > 0.90). However, some key elements such as Fe show a very poor correlation. A simple methodology based on the MIX code (a maximum likelihood method to estimate mixing ratios) was used to elucidate their different behaviours. During the dry period (April–December, 2009) the Fe concentration was lower than that deduced from the SC recorded value due to the precipitation of Fe-oxihydroxides, which also reduced the concentrations of As, Cr, Pb and, to a lesser extent, Cu. At the same time Na, Sr, Ca and Li were enriched because of the higher interaction with the riverbed materials. Correlations between the SC and the metal concentration improved significantly when each period was considered separately. A second dry period (April–June 2010) shows high SC values, although no dissolution/precipitation of solid phases is evidenced. This indicates that SC alone is not enough to predict the dissolved metal loads in Mediterranean AMD streams. The metal load transported by the River Meca was determined for the hydrological year 2009/10 as 1933 ± 129 tonnes of Fe, 990 ± 155 of Al and 378 ± 41 of Zn.     

Hydrogeochemical patterns,processes and mass transfers during aquifer storage and recovery (ASR) in an anoxic sandy aquifer

The hydrogeochemical processes that took place during an aquifer storage and recovery (ASR) trial in a confined anoxic sandy aquifer (Herten, the Netherlands) were identified and quantified, using observation wells at 0.1, 8 and 25 m distance from the ASR well. Oxic drinking water was injected in 14 ASR cycles in the period 2000–2009. The main reactions consisted of the oxidation of pyrite, sedimentary organic matter, and (adsorbed) Fe(II) and Mn(II) in all aquifer layers (A–D), whereas the dissolution of carbonates (Mg-calcite and Mn-siderite) occurred mainly in aquifer layer D. Extinction of the mobilization of SO₄, Fe(II), Mn(II), As, Co, Ni, Ca and total inorganic C pointed at pyrite and calcite leaching in layer A, whereas reactions with Mn-siderite in layer D did not show a significant extinction over time. Iron(II) and Mn(II) removal during recovery was demonstrated by particle tracking and pointed at sorption to neoformed ferrihydrite. Part of the oxidants was removed by neoformed organic material in the ASR proximal zone (0 – ca. 5 m) where micro-organisms grow during injection and die away when storage exceeds about 1 month. Anoxic conditions during storage led to increased concentrations for a.o. Fe(II), Mn(II) and NH₄ as noted for the first 50–200 m³ of abstracted water during the recovery phase. With a mass balance approach the water–sediment reactions and leaching rate of the reactive solid phases were quantified. Leaching of pyrite and calcite reached completion at up to 8 m distance in layer A, but not in layer D. The mass balance approach moreover showed that Mn-siderite in layer D was probably responsible for the Mn(II) exceedances of the drinking water standard (0.9 μmol/L) in the recovered water. Leaching of the Mn-siderite up to 8 m from the ASR well would take 1600 more pore volumes of drinking water injection (on top of the realized 460).