An ochreous precipitate isolated from a stream receiving acid-sulfate mine drainage was found to consist primarily of goethite and lesser amounts of ferrihydrite-like materials. The Fe-oxide fraction, including goethite, was almost totally soluble in acid ammonium oxalate. Similar materials were produced in the laboratory by hydrolysis of ferric nitrate solutions containing 250 to 2000 μg/ml sulfate as Na2SO4. Initial precipitates of natrojarosite transformed to Fe-oxides upon aging for 30 days at pH 6.0. The proportion of goethite in the final products decreased with increasing sulfate (SO4/Fe = 0.2 to 1.8) in the initial hydrolysis solutions; only ferrihydrite-like materials were produced at SO4/Fe ratios > 1.5. Variations in SO4/Fe solution ratios also produced systematic changes in the color (10R to 7.5YR) and surface areas (49 to 310 m2/g) of the dried precipitates, even though total S contents were relatively constant at 2.5 to 4.0%.

This study characterizes various chemical and mineralogical properties of goethite and jarosite from a mine drainage environment using chemical extraction techniques, X-ray diffractometry (XRD), 57Fe Mössbauer spectroscopy and scanning electron microscopy (SEM). Goethite and jarosite precipitates were collected from leachate-contaminated soils and from groundwater samples that were stored for up to 3 y. The results indicate that the soil goethites have primarily microcrystalline morphologies with moderately large mean crystallite dimensions (MCD110 ∼ 40 nm), and are superparamagnetic at room temperature and magnetically ordered at 77 K. The substitution of Al for Fe in the goethites is less than 0.03 mol/mol, and there is consequently no measured contraction in the goethite unit cell volume. The jarosite unit cell dimensions, Mössbauer parameters and chemical compositions indicate that the precipitates are primarily well-crystallized K-Na-H3O solid solutions, although the presence of poorly crystalline H3O-rich jarosite is also identified in one sample.

Mine-drainage waters and associated precipitates from several active and abandoned lignite mines and mine dumps in the Sokolov Basin, northwestern Czech Republic, were sampled and analysed. The data showed considerable variations of effluent composition and pH that can generally be related to differences in the local microenvironments. Temporal changes such as seasonal fluctuations of precipitation, leading to variations of water infiltration through and runoff over mines and mine dumps, were also observed to noticeably affect effluent composition. These variations have led to a wide range of precipitates, the principal constituents of which are generally one or several of the ferric minerals jarosite, schwertmannite, goethite, ferrihydrite and lepidocrocite.

The present paper consists of two parts: a short review of the genesis and properties of the named minerals, and a study of mine-drainage precipitates formed under different local conditions in various lignite mines and mine dumps of the Sokolov mining district. We show that variations in mine-drainage precipitate mineralogy, such as the presence or absence of specific ‘key’ minerals, can serve as indicators for factors such as the pH and sulphate concentration, and thus — with certain limitations — for the genetic environment during precipitate formation. Such variations in composition are reflected, among other properties, in the precipitate colour, which can therefore be used for a rapid identification and classification — both in the field and by remote sensing — of regions that are potentially prone to acid mine drainage.

The influence of hydrological conditions and the pH of the environment on chlorite and mica transformations in the acidic weathering zone of pyrite-bearing schists was studied. Phyllosilicate transformations were investigated in the area of the abandoned pyrite open-pit mine in Wieściszowice (Lower Silesia, SW Poland) using X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy and chemical methods. (Mg, Fe)-chlorite, micas (muscovite and paragonite), quartz, feldspars and pyrite were reported to be the most abundant minerals occurring in pyrite-bearing schists. Phyllosilicate transformations were significantly stronger in dry conditions than in wet ones. This conclusion was supported by the fact that the inherited phyllosilicates predominated in the clay mineral fraction of waterlogged saprolites, whereas the secondary swelling minerals were minor components. In dry and extremely acidic saprolites (pH < 3), trioctahedral chlorite was dissolved and transformed into clay minerals (e.g. smectite and kaolinite), whereas swelling clays (smectite mainly) were formed at the expense of dioctahedral micas. The pH of water is an important factor influencing phyllosilicate transformations in waterlogged conditions. The phyllosilicate alterations under the influence of extremely acidic waters (pH < 3) were more advanced than in moderately acidic ones (pH of 4.6), as the secondary clay minerals seemed to be represented exclusively by smectite in the former, whereas HIMs and mixed-layer minerals such as R0 I-S-Ch, R0 I-S, as well as R1 Ch-V and/or R1 Ch-S occurred in the latter.

The S. Domingos abandoned mine is a major source of pollutant-metals contamination. Slags from the 19th-20th century contain the most hazardous material. However, the release of pollutant metals depends on the metal-retention capability of weathering products. This work shows that Zn is not effectively retained by these weathering products while As and Pb are partially stored in sulphates. Copper, on the other hand, has a different behaviour and is the most leachable of the elements studied.

Sustaining Earth, in the face of both technology thrusts and population dynamics, depends on our ability to maintain a delicate balance between human-promoted planetary modification and decline thresholds for land (soils), water, atmosphere, and biological systems. Mineralogy, as much as any other single science, will be central to this process. A set of links between Earth sustainability issues and the science of mineralogy are formulated and discussed in this discourse. The strongest ties exist in the areas of mineral-water and mineral-atmosphere interactions. Minerals are also particularly important in human disease generation. In addition, due to the role of minerals as invaluable economic resources, the environmental consequences of mining also come into play. New subdisciplines have recently emerged to bring mineralogy even closer to Earth sustainability issues, particularly mineral-microbe interaction science and nanomineralogy

Schwertmannite is a new oxyhydroxysulphate of iron from the Pyhäisalmi sulphide mine, Province of Oulu, Finland. It occurs there, and elsewhere, as an ochreous precipitate from acid, sulphate-rich waters. Associated minerals at other localities may include jarosite, natrojarosite, goethite and ferrihydrite. Schwertmannite is a poorly crystalline, yellowish brown mineral with a fibrous morphology under the electron microscope. A high specific surface area in the range of 100 to 200 m2/g, rapid dissolution in cold, 5 M HCl or in ammonium oxalate at pH 3, and pronounced X-ray diffraction line broadening are consistent with its poorly crystalline character.

Colour parameters for the type specimen as related to CIE illuminant C are L* = 53.85, a* = + 15.93, and b* = +47.96. Chemical analysis gives Fe2O3, 62.6; SO3, 12.7; CO2, 1.5; H2O−, 10.2; H2O+, 12.9; total 99.9 wt.%. These data yield an empirical unit cell formula of Fe16O16(OH)9.6(SO4)3.2·10H2O after exclusion of CO2 and H2O−. The most general simplified formula is Fe16O16(OH)y(SO4)z·nH2O, where 16 − y = 2z and 2.0 ⩽ z ⩽ 3.5. Schwertmannite has a structure akin to that of akaganéite (nominally β-FeOOH) with a doubled c dimension. Its X-ray powder diffraction pattern consists of eight broad peaks [dobs in (Iobs) (hkl)] 4.86(37)(200,111); 3.39(46)(310); 2.55(100)(212); 2.28(23)(302); 1.95(12)(412); 1.66(21)(522); 1.51(24)(004); and 1.46(18)(204,542), giving a = 10.66(4), c = 6.04(1) Å, and V = 686(6) Å3 for a primitive, tetragonal unit cell. The probable space group is P4/m. Upon heating, schwertmannite transforms to hematite with Fe2(SO4)3 occurring as an intermediate phase. Bidentate bridging complexes between Fe and SO4 are apparent in infrared spectra. Mössbauer data show the Fe in schwertmannite to be exclusively trivalent and in octahedral coordination; it has a Néel temperature of 75 ± 5 K and a saturation magnetic hyperfine field of about 45.6 T. Pronounced asymmetry of the Mössbauer spectra indicates different locations for Fe atoms relative to SO4 groups in the structure. The name is for Udo Schwertmann, professor of soil science at the Technical University of Munich.

Ferric precipitates in the water column at the San Telmo acidic mine pit lake in the Iberian Pyrite Belt, southwest Spain, have been studied by scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, X-ray fluorescence, inductively coupled plasma massspectrometry and other complementary techniques. These Fe(III) precipitates were recovered from sediment traps which were left at different depths (25, 35, 40 and 100 m) in the lake for several months. Seasonal variations in the water chemistry were recorded to link the mineralogical findingsto vertical and temporal changes in aqueous composition. The results indicate that schwertmannite is the first Fe(III) mineral to crystallize after the oxidation of Fe(II), in agreement with previous studies. Schwertmannite is kinetically favoured in comparison to other Fe(III) minerals, andit buffers the pH at 2.6–3.0. It is metastable, and alters to a (H3O+)- and (K+)-bearing jarosite (containing 58 mol.% H3O+ and 42 mol.% K+ on average) at lower pH (e.g. at pH 2.2–2.5 in the summer season), eitherin the water column (during settling) and/or in the benthic sediments, in a time period of weeks to months. The extent of hydronium substitution at the alkali site in the jarosite reflects the higher activity of free aqueous protons in solution (10–2.2 to 10–3.0)in comparison to the activities of K+ (10–4.5) and Na+ (10–3.2). Microscopic examination of mixed schwertmannite–jarosite precipitates found in the water column suggest that some textural and compositional features of metastableschwertmannite (e.g. the internal 'pincushion' arrangement and incorporation of trace amounts of Mg, Al, As and Pb) are conserved in the jarosite during the early stages of the mineralogical transformation, but many of these relics are lost in the later stages of crystal growth. Despite thehydronium-rich nature of the jarosite solid solution, this material is also an important sink for K+, which decreases in concentration with decreasing pH unlike most of the other major cations in the water column (notably Na+, Mg2+, Ca2+, Al3+,Fe3+, Cu2+, Zn2+). In addition to the release of Fe3+ to the aqueous solution, the conversion of schwertmannite to (H3O+, K+)-bearing jarosite consumes protons and thus may represent an additional pH control at SanTelmo and other acidic mine pit lakes of the area.

Approaches currently used for remediating acid mine drainage (chiefly active chemical treatment and passive bioremediation systems) have a number of major detractions, including their failure to recover potentially valuable metals from these waters. Bioremediation strategies that utilizereactor-housed microorganisms can circumvent this problem, but have tended not to be widely used due to their relatively high costs. We have devised innovative approaches for remediating mine waters that use acidophilic bacteria to remove metals either as oxidized or reduced phases, usingmodular bioreactors that are designed to operate at minimal cost and to generate products that have commercial value. A composite system is described that combines microbial oxidation of ferrous iron with abiotic precipitation of ferric iron as schwertmannite, a mineral that has commercialvalue as an absorbent of arsenate and other environmental pollutants, and as a pigment. Sulfidogenic bioreactors maintained at acidic pH values are used to selectively precipitate metal sulfides, such as CuS. Tests with synthetic mine drainage containing mixtures of soluble metals confirmedthat these systems can generate relatively pure mineral deposits from complex acid waters. The units are designed to be configured differently, according to the nature of the mine water requiring treatment.

Mineralogical, bulk and field leachate compositions are used to identify important processes governing the evolution of discharges from a coal spoil heap in County Durham. These processes are incorporated into a numerical one-dimensional advective-kinetic reactive transport model which reproduces field results, including gas compositions, to within an order of magnitude. Variation of input parameters allows the effects of incorrect initial assumptions on elemental profiles and discharge chemistry to be assessed. Analytical expressions for widths and speeds of kinetic reaction fronts are developed and used to predict long-term development of mineralogical distribution within the heap. Results are consistent with observations from the field site. Pyrite oxidation is expected to dominate O2 consumption in spoil heaps on the decadal timescale, although C oxidation may stabilize contaminants in effluents on the centennial scale.

The (110) surfaces of arsenopyrite (FeAsS) and enargite (Cu3AsS4) have been modelled using a Density Functional Theory (DFT) plane-wave pseudopotential method (CASTEP) in order to better understand aspects of the geometric and electronic structures of these minerals, which have important implications for the release of arsenic in acid mine drainage environments. In this study, bulk calculations of these minerals have been conducted to give consistent geometries for surface models and to establish reference states for changes at the surfaces in these models. Surface structure experimental data for enargite were collected using low-energy electron diffraction which confirmed an unreconstructed 161 (110) lattice, with a and b values of 6.38±0.3 Å and 9.92±0.5 Å, respectively. Surface calculations demonstrate geometric and electronic relaxation of both arsenopyrite and enargite (110) surfaces. Changes in atomic positions, interatomic distances, Mulliken charges and electronic configurations are reported. Enargite has a surface energy of ∼0.02 eV/Å2 compared with arsenopyrite which has a surface energy of ∼0.11 eV/Å2, indicating that the enargite (110) surface is more energetically stable than that of arsenopyrite. The most stable surfaces are those which relax to restore the surface coordination and partial charge balance. For both minerals this is achieved by the formation of covalent bonds. Arsenic has the most positive Mulliken charge of all the surface atoms and is, therefore, predicted to be the most reactive atom at the arsenopyrite and enargite (110) surfaces. This implies that, according to these calculations, arsenic is most likely to react with oxidative species such as O2 and H2O in environments such as those associated with acid mine drainage, potentially releasing oxides and acids of arsenic into the environment.

The sodium-magnesium hydrated double salt konyaite, Na2Mg(SO4)2·5H2O, has been studied by single-crystal X-ray diffraction and thermogravimetry on synthetic samples and by quantitative X-ray diffraction utilizing the Rietveld method on natural samples from the Mount Keith mine, Western Australia. Konyaite crystallizes in space group P21/c, with the cell parameters: a = 5.7594(10), b = 23.914(4), c = 8.0250(13) Å, β = 95.288(9)°, V = 1100.6(3) Å3 and Z = 4. The crystal structure has been refined to R1 = 3.41% for 2155 reflections [Fo>4σ(Fo)] and 6.44% for all 3061 reflections, with all atoms located.

Quantitative phase analysis utilizing the Rietveld method was undertaken on five samples of konyaite-bearing mine tailings from the Mount Keith Nickel Mine, Western Australia. Konyaite was found to decompose over time and after 22 months had transformed to other sulphate and amorphous phases. Blödite did not increase in any ofthe samples indicating that konyaite may not always transform to blödite. Over the same time frame, synthetic konyaite completely decomposed to a mixture of thenardite (Na2SO4), hexahydrite (MgSO4·6H2O), blödite (Na2Mg(SO4)2·4H2O) and löweite (Na12Mg7(SO4)13). Detection of konyaite and other Mg-rich sulphates is important in terms of CO2 fixation. Magnesium bound to sulphate mineral phases reduces the overall potential of tailings piles to lock up atmospheric carbon in Mg carbonates, such as hydromagnesite. Amorphous sulphates are also highly reactive and may contribute to acid mine drainage ifpresent in large quantities, and may dissolve carbonate phases which have already sequestered carbon.