A TEM study of samples from acid mine drainage systems: metal-mineral association with implications for transport

Transmission electron microscopy (TEM), with energy dispersive X-ray (EDX) analysis and energy filtered transmission electron microscopy/electron energy loss spectroscopy (EFTEM/EELS), as well as powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), have been used to study bed sediments from two acid mine drainage (AMD) sites in western Montana, USA. TEM and associated techniques, including sample preparation via epoxy impregnation and ultramicrotome sectioning, afford the opportunity to better interpret and understand complex water-rock interactions in these types of samples. For the sample taken from the first site (Mike Horse mine), ferrihydrite is the dominant phase, Si and Zn are the most abundant elements sorbed to ferrihydrite surfaces, and Pb is notably absent from ferrihydrite association. Three additional important metal-containing phases (gahnite, hydrohetaerolite, and plumbojarosite), that were not apparent in the powder XRD pattern because of their relatively low concentration, were identified in the TEM. The presence of these phases is important, because, for example, gahnite and plumbojarosite act as sinks for Zn and Pb, respectively. Therefore, the mobility of Pb from this part of the drainage system depends on the stability of plumbojarosite and the ability of ferrihydrite to sorb the released Pb. From thermodynamic data in the literature, we predict that Pb will be released by the dissolution of plumbojarosite above a pH of 4 to 5, but it will then be recaptured by ferrihydrite if the pH continues to rise to 5.5 and higher, irrespective of competition effects from other metals. Therefore, only a relatively narrow pH window exists in which Pb can escape this portion of the system as an aqueous species. For the sample taken from the other site included in this study (the Carbonate mine), jarosite and quartz are the dominant phases. Interestingly, however, the jarosites are both Pb-poor and Pb-enriched. In addition, TEM reveals the presence of microcrystalline hematite with Si, S, and P sorbed to its surfaces, a nearly pure amorphous Si, Al oxyhydroxide, and an amorphous silica phase containing minor amounts of Al, Ca, and Fe. Pb will probably be released from these mixed K-Pb jarosites above pH 4 to 5, but the Pb may be retarded by the strongly adsorbing microcrystalline hematite in this pH range. The sink for Al in this system is the amorphous Si, Al oxyhydroxide, not Al(OH)₃ which is typically used in AMD modeling schemes.     

Mineralogical and chemical evolution of ochreous precipitates from the Libiola Fe–Cu-sulfide mine (Eastern Liguria,Italy)

The mineralogical and chemical evolution of ochreous precipitates forming from acid mine drainage (AMD) from the abandoned Libiola Fe–Cu-sulfide mine (Eastern Liguria, Italy) was followed through a multianalytical approach (XRD, TEM, XRF, ICP) applied to surface precipitates and associated waters collected from several mine adits. The mineralogy of the precipitates changed significantly as a consequence of the variations of the chemical parameters of the circulating solutions (mainly pH, Eh, and sulfate concentrations) which, in turn, were mainly controlled by mixing with unpolluted stream and rill waters of the mining area. A progressive transition from jarosite-, to schwertmannite-, to goethite-, to ferrihydrite-, to amorphous-dominated precipitates was observed, mainly as a consequence of an increase in the pH of the associated solutions. This mineralogical evolution agrees well with the aqueous speciation and Eh–pH stability calculations performed on the waters associated with the different precipitate types. Furthermore, TEM analysis indicated that metastable pristine phases (schwertmannite) tend to transform progressively to well-crystallized more stable species, here represented by goethite. The comparison of the water chemistry and the crystal chemistry of the different precipitates showed a significant decrease in the Zn, Cu, Ni, Co contents in waters where the coexisting precipitates were almost exclusively composed of goethite. The distribution of V, Sr, As concentrations within the different precipitates showed that the most efficient scavenging phase for these elements was jarosite, whereas ferrihydrite efficiently took up Pb ions, and schwermannite acted as a natural sink for Cr.     

Reductive dissolution of arsenical ferrihydrite by bacteria

Mining and metallurgical processing of gold and base metal ores can lead to the release of arsenic into the aqueous environment as a result of the weathering and leaching of As-bearing minerals during processing and following disposal. Arsenic in process solutions and mine drainage can be effectively stabilized through the precipitation of ferrihydrite. However, under anaerobic conditions imposed by burial and waste cover systems, ferrihydrite is susceptible to microbial reduction. This research, stimulated by the paucity of information and limited understanding of the microbial reduction of arsenical ferrihydrite, was conducted on synthetic adsorbed and co-precipitated arsenical 6-line ferrihydrite (Fe/As molar ratio of 10/1) using Shewanella sp. ANA-3 and Shewanella putrefaciens CN32 in a chemically defined medium containing 0.045 mM phosphate concentration. Both bacteria were equally effective in their reducing abilities around pH 7, resulting in initial rates of formation of dissolved As(III) of 0.10 μM/h for the adsorbed, and 0.08 μM/h for the co-precipitated arsenical 6-line ferrihydrite samples. The solid phases in the post-reduction samples were characterized by powder X-ray diffraction (XRD), micro-XRD, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron microprobe and X-ray absorption spectroscopy (XAS) techniques. The results indicate the formation of secondary phases such as a biogenic Fe(II)–As(III) compound, akaganeite, goethite, hematite and possibly magnetite during bacterial reduction experiments. Holes and bacterial imprints measuring about 1–2 μm were observed on the surfaces of the secondary phases formed after 1200 h of reduction. This study demonstrates the influence of Fe and As reducing bacteria on the release of significant concentrations of more mobile and toxic As(III) species from arsenical 6-line ferrihydrite, more readily from the adsorbed than from the co-precipitated ferrihydrite.     

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。     

Removal of trace metals by coprecipitation with Fe,Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District,Tennessee

This study examined the sorption of trace metals to precipitates formed by neutralization of 3 natural waters contaminated with acid mine drainage (AMD) in the former Ducktown Mining District, Tennessee. The 3 water samples were strongly acidic (pH 2.2 to 3.4) but had distinctively different chemical signatures based on the mole fractions of dissolved Fe, Al and Mn. One sample was Fe-rich (Fe=87.5%, Al=11.3%, and Mn=1.3%), another was Al-rich (Al=79.4%, Mn=18.0%, and Fe=2.5%), and the other was Mn-rich (Mn=51.4%, Al=25.7%, and Fe=22.9%). In addition, these waters had high concentrations of trace metals including Zn (37,700 to 17,400 μg/l), Cu (13,000 to 270 μg/l), Co (1,500 to 520 μg/l), Ni (360 to 75 μg/l), Pb (30 to 8 μg/l), and Cd (30 to 6 μg/l). Neutralization of the AMD-contaminated waters in the laboratory caused the formation of either schwertmannite at pH<4 or ferrihydrite at pH>4. Both phases were identified by XRD analyses of precipitates from the most Fe-rich water. At higher pH values (∼5) Al-rich precipitates were formed. Manganese compounds were precipitated at pH∼8. The removal of trace metals depended on the precipitation of these compounds, which acted as sorbents. Accordingly, the pH for 50% sorption (pH₅₀) ranged from 5.6 to 7.5 for Zn, 4.6 to 6.1 for Cu, 5.4 to 7.7 for Ni, 5.9 to 7.9 for Co, 3.1 to 4.3 for Pb, and 5.5 to 7.7 for Cd. The pH dependence of sorption arose not only because of changes in the sorption coefficients of the trace metals but also because the formation and composition of the sorbent was controlled by the pH, the chemical composition of the water, and the solubilities of the oxyhydroxide-sulfate complexes of Fe, Al, and Mn.     

Model biomimetic studies of templated growth and assembly of nanocrystalline FeOOH

We studied biomimetic mineralization of self-assembling polymer matrices in order to develop a model for biomineralization of iron oxides in nature. High-resolution transmission electron microscopy (HRTEM), rheology, and fluorescence probe analyses show self-assembly of acidic polysaccharide alginic acid (Alg) to form fibrils in dilute solutions. The resulting Alg fibrils are subsequently mineralized by FeOOH in a biomimetically controlled process. Experiments were conducted in pH 9.2 solutions containing millimolar concentrations of iron at 38°C. The unperturbed state of the hybrid mineral-organic structures was studied by characterization of samples of interfacial films collected from an inorganic-organic interface. Progress of mineralization over a 4-week period was followed by HRTEM, energy-dispersive X-ray analysis, and selected area electron diffraction. Morphologies of hybrid structures determined by HRTEM, X-ray powder diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, and selected area electron diffraction suggest formation of iron (III) oxyhydroxide phases and their assembly through a variety of mechanisms, possibly occurring simultaneously. An initial step involves precipitation of nanometer-scale amorphous particles and two-line ferrihydrite in bulk solution. Some nanoparticles assemble into chains that recrystallize to form akaganeite (β-FeOOH), presumably via a solid-state transformation pathway. Small organic molecules may mediate this process by stabilizing the akaganeite structure and controlling particle assembly. Ferrihydrite particles also bind to acidic polysaccharide fibrils and are transformed to ordered arrays of akaganeite. The parallel orientation of adjacent akaganeite nanocrystals may be inherited from the orientation of precursor ferrihydrite, possibly conferred during attachment of ferrihydrite to the polyacid fibrils. Alternatively, particle-particle interactions may induce orientation, leading to recrystallization. Subsequently, akaganeite is transformed to goethite that is characterized by nanoscale porosity and fine-scale twinning on {021}. Dislocation, twin, and nanopore microstructures are consistent with coarsening by nanoparticle assembly, possibly templated by the substrate. Nanoparticle assembly to generate biomimetic hybrid materials may be relevant to formation of complex natural biominerals in natural systems where mineral nanoparticles, small organic molecules, and more complex polymers coexist.     

Potential environmental impact at São Domingos mining district (Iberian Pyrite Belt,SW Iberian Peninsula): evidence from a chemical and mineralogical characterization

São Domingos like other long-term activity mines of the Iberian Pyrite Belt (IPB) dating back to pre-Roman times, is supposed to produce considerable amounts of mining wastes which cause significant downstream negative environment impact related to the acid mine drainage (AMD) production and high content of potentially toxic metals and metalloids in Chanza and Guadiana Rivers. The AMD production of a given mining waste depends on the ratio of its acid production to neutralizing phases. In this work, a chemical and mineralogical characterization of the sulphide-rich wastes from São Domingos has been developed to discriminate which residues are the main sources of AMD generation. A total of 47 representative samples of the different residue types were collected to estimate their possible contamination hazards through detailed studies of (1) for a mineralogical characterization: reflected-light optical microscope, scanning electron microscope (SEM) and XRD analysis; and (2) for a chemical characterization: bulk-rock analysis. AMD prediction by the standard acid-base accounting method (ABA) was used in order to determine the acidification potential of each residue type. This study also offers an estimation of the contribution of toxic elements to the environment, being thus, a base for future remediation actions at São Domingos and other abandoned massive sulphide mines within the IPB.     

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10⁻⁶ mol m⁻² h⁻¹. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H₂S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.     

Removal of antimony and arsenic from circum-neutral mine drainage in Poproč, Slovakia: a field treatment system using low-cost iron-based material

The main aim of this paper was to investigate the removal efficiency of antimony (Sb) and arsenic (As) from circum-neutral mine drainage in the former Sb mine in Popro? (Slovakia) using a simple field treatment system based on the adsorption onto iron fillings. The treatment system consisted of two batch reactors with a volume of 1 m³: the first was used for settling of spontaneously precipitated ochreous sediments and the second, filled with reactive iron material, was designed to remove Sb and As from mine water. This passively operated treatment system contained 150 kg of low-cost iron fillings and was able to treat approximately 360 l of mine drainage per hour. The average removal efficiency of Sb and As reached 84 and 89% during a period of 2.3 years of the system operation, respectively. On average, dissolved Sb and As concentrations in mine drainage decreased from 175 to 24.3 µg/l and from 452 to 50.6 µg/l, respectively. Based on the electron microprobe (EMP) analyses of corrosion products developed on the surfaces of iron fillings, average Sb and As contents were 0.28 and 0.73 wt%, respectively. The chemical analyses of precipitated HFOs in the settling reactor showed that these ochreous precipitates contained up to 19.3 g/kg Sb and 65.8 g/kg As, indicating their natural role in the removal of the two metalloids from circum-neutral mine drainage. The results of transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses confirmed the presence of ferrihydrite and goethite in ochreous sediments.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.     

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.     

Microbial sulfidogenesis in ferrihydrite-rich environments: Effects on iron mineralogy and arsenic mobility

Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28 days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe²⁺ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe²⁺ was transported with advecting groundwater, facilitating the downstream Fe²⁺-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe²⁺-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings show that microbial sulfidogenesis can trigger significant As mobilization in subsurface environments with advective groundwater flow. The results also demonstrate that formation of mackinawite by sulfidization of ferric (hydr)oxides is not effective for the immobilization of As, whereas the Fe²⁺-catalyzed transformation of ferrihydrite to goethite under mildly acidic conditions may mitigate As mobility.     

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.     

X-ray absorption spectroscopy study on the effect of hydroxybenzoic acids on the formation and structure of ferrihydrite

Organic ligands are known to interfere with the polymerization of Fe(III), but the extent of interference has not been systematically studied as a function of structural ligand properties. This study examines how the number and position of phenol groups in hydroxybenzoic acids affect both ferrihydrite formation and its local (<5 Å) Fe coordination. To this end, acid Fe(III) nitrate solutions were neutralized up to pH 6.0 in the presence of 4-hydroxybenzoic acid (4HB), 2,4-dihydroxybenzoic acid (2,4DHB), and the hydroquinone 3,4-dihydroxybenzoic acid (3,4DHB). The initial molar ligand/Fe ratios ranged from 0 to 0.6. The precipitates were dialyzed, lyophilized, and subsequently studied by X-ray absorption spectroscopy and synchrotron X-ray diffraction. The solids contained up to 32 wt.% organic C (4HB ∼ 2,4DHB < 3,4DHB). Only precipitates formed in 3,4DHB solutions comprised considerable amounts of Fe(II) (Fe(II)/Fe_tot ≤ 6 mol%), implying the abiotic mineralization of the catechol-group bearing ligand during Fe(III) hydrolysis under oxic conditions. Hydroxybenzoic acids decreased ferrihydrite formation in the order 4HB ∼ 2,4DHB ? 3,4DHB, which documents that phenol group position rather than the number of phenol groups controls the ligand’s interaction with Fe(III). The coordination numbers of edge- and double corner-sharing Fe in the precipitates decreased by up to 100%. Linear combination fitting (LCF) of Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed that this decrease was due to increasing amounts of organic Fe(III) complexes in the precipitates. Although EXAFS derived coordination numbers of Fe in ferrihydrite remained constant within error, all organic ligands decreased the coherently scattering domain (CSD) size of ferrihydrite as indicated by synchrotron X-ray diffraction analysis (4HB < 2,4DHB ? 3,4DHB). With decreasing particle size of ferrihydrite its Fe(O,OH)₆ octahedra became progressively distorted as evidenced by an increasing loss of centrosymmetry of the Fe sites. Pre-edge peak analysis of the Fe K-edge XANES spectra in conjunction with LCF results implied that ferrihydrite contains on an average 13 ± 3% tetrahedral Fe(III), which is in very good agreement with the revised single-phase structural model of ferrihydrite (Michel, F. M., Barron, V., Torrent, J., Morales, M. P. et al. (2010) Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism. Proc. Natl. Acad. Sci. USA107, 2787-2792). The results suggest that hydroxybenzoic acid moieties of natural organic matter (NOM) effectively suppress ferrihydrite precipitation as they kinetically control the availability of inorganic Fe(III) species for nucleation and/or polymerization reactions. As a consequence, NOM can trigger the formation of small ferrihydrite nanoparticles with increased structural strain. These factors may eventually enhance the biogeochemical reactivity of ferrihydrite formed in NOM-rich environments. This study highlights the role of hydroquinone structures of NOM for Fe complexation, polymerization, and redox speciation.     

乳腺纤维腺瘤病灶中钙化的矿物学研究

选取8例乳腺纤维腺瘤的钙化样品,利用光学显微镜（OM）、环境扫描电镜（ESEM）、高分辨透射电镜（HR-TEM）、显微红外光谱仪（FTIR）、微区X射线衍射等矿物学方法对样品进行了原位和分离后形貌、结构及成分的测试分析,探讨了病灶中钙化的矿物学特征,初步探讨了钙化的组成及形成机理。研究结果表明,乳腺纤维腺瘤中的钙化是由病变后期玻璃样变性胶原中的羟基和羧基为钙化提供了成核位点,伴随病情发展最后形成OM下可见的以羟磷灰石为主要成分的坏死钙化。     

A quantitative estimation of the factors affecting pH changes using simple geochemical data from acid mine drainage

The behavior of heavy metals in acid mine drainage (AMD) is mainly controlled by pH values. Therefore, a quantitative estimation of factors affecting pH values in AMD is very important in predicting the behavior of those metals. Many different factors cause pH changes in streams affected by AMD and we quantitatively estimated those factors by making simple equations from geochemical data collected from the Dalsung mine. In a stream from that mine, the pH values decrease as the stream flows downstream from the AMD source, which is different from normal streams affected by AMD. The stream shows low pH ranges (4.04–5.96), high electrical conductivity (1,407–1,664 μS/cm), and sulfate concentration (680–854 ppm). Most ion concentrations decrease or do not show noticeable changes mainly due to dilution. The change of the iron content is most significant, even though the concentration of iron is relatively low compared with other ions. The iron concentration (13.4 ppm) becomes almost 0 ppm due to precipitation. Schwertmannite is the dominant precipitated phase downstream and whitish basaluminite is observed in the upstream. From our pH estimation, precipitation is the most important process lowering pH values from 5.96 to 4.04. The dilution factor was calculated by the concentration changes in sulfate ions. Dilution increases pH values, but compared with the precipitation factor, the contribution of the dilution factor to pH is relatively small. Alkalinity is the main factor that buffers hydrogen, which is released by precipitation. The redox changes, which were calculated from the pH and Eh values, also affect pH at each sampling site. The trend of estimated pH changes is almost identical to the observed ones, but the values are slightly different. Some errors are expected mainly due to the uncertainty in the observed Eh values and the chemistry of the added water for dilution.     

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.     

京西潭柘寺东山红庙岭组硬绿泥石矿物学研究

利用偏光显微镜、X射线衍射（XRD）、拉曼光谱分析（Raman）、扫描电镜和能谱分析（SEM and EDS）等,从矿物学角度对潭柘寺东山红庙岭组中硬绿泥石特征进行了研究。结果表明,该区硬绿泥石属单斜晶系,发育接触双晶,呈玫瑰花状或束状集合体。硬绿泥石中有部分Fe2＋被氧化为Fe3＋,并替换了Al3＋,其化学式可写为（Fe2＋,Mg）（Al,Fe3＋）2SiO5（OH）2。该区硬绿泥石与钠云母共存,形成温度为350～500℃,呈定向排列,为受构造应力影响而形成的应力矿物,其形成还可能与受构造控制的深部热液活动有关。     

Hydrogeochemical characteristics of acid mine drainage and water pollution at Makum Coalfield,India

Acid mine drainage (AMD) is one of the severe environmental problems that coal mines are facing. Generation of AMD in the northeastern part of India due to the coal mining activities has long been reported. However detailed geochemical characterization of AMD and its impact on water quality of various creeks, river and groundwater in the area has never been reported. Coal and coal measure rocks in the study area show finely disseminated pyrite crystals. Secondary solid phases, resulted due to oxidation of pyrite, occur on the surface of coal, and are mainly consisting of hydrated sulphate complexes of Fe and Mg (copiapite group of minerals). The direct mine discharges are highly acidic (up to pH 2.3) to alkaline (up to pH 7.6) in nature with high concentration of SO₄²⁻. Acidic discharges are highly enriched with Fe, Al, Mn, Ni, Pb and Cd, while Cr, Cu, Zn and Co are below their maximum permissible limit in most mine discharges. Creeks that carrying the direct mine discharges are highly contaminated; whereas major rivers are not much impacted by AMD. Ground water close to the collieries and AMD affected creeks are highly contaminated by Mn, Fe and Pb. Through geochemical modeling, it is inferred that jarosite is stable at pH less than 2.5, schwertmannite at pH less than 4.5, ferrihydrite above 5.8 and goethite is stable over wide range of pH, from highly acidic to alkaline condition.     

Spatial variability of arsenic in some iron-rich deposits generated by acid mine drainage

Potential contamination of rivers by trace elements can be controlled, among others, by the precipitation of oxyhydroxides. The streambed of the studied area, located in “La Châtaigneraie” district (Lot River Basin, France), is characterised by iron-rich ochreous deposits, acidic pH (2.7–4.8) and SO₄–Mg waters. Beyond the acid mine drainage, the presence of As both in the dissolved fraction and in the deposits is also a problem. Upstream, at the gallery outlet, As concentrations are high (As_max = 2.6 μmol/l and up to 5 wt% locally, respectively, in the dissolved and in the solid fractions). Downstream, As concentrations decrease below 0.1 μmol/l in the dissolved fraction and to 1327 mg/kg in the solid fraction. This natural attenuation is related to the As retention within ochreous precipitates (amorphous to poorly crystalline Fe oxyhydroxides, schwertmannite and goethite), which have great affinities for this metalloid. Upstream, schwertmannite is dominant while downstream, goethite becomes the main mineral. The transformation of schwertmannite into goethite is observed in the upstream deposits as schwertmannite is unstable relative to goethite. Furthermore, thermodynamic calculations indicate that the downstream goethite is not able to precipitate in situ according to the water chemistry. Goethite mainly results from the transformation of schwertmannite and its solid transport downstream.Moreover, as highlighted by leaching experiments carried out on the ochreous precipitates, this transformation does not seem to affect the As-retention in solids as no release of As was observed in the solution. Arsenic may either be strongly trapped by co-precipitation in the present minerals or it may be quickly released and re-adsorbed on the precipitate surface.