Tertiary weathered sediments located immediately to the west of the harbor at Newhaven, Sussex, UK, were investigated by examination of major and trace elements by scanning electron microscope (SEM), microprobe, and inductively coupled plasma mass spectrometer (ICP-MS), and the mineralogy was studied by optical petrography, X-ray diffraction (XRD), transmission electron microscope (TEM), selective leaching, and thermodynamic modeling. Studied outcrops experienced acid leaching by sulfuric acid percolating downward through Tertiary sediments overlying Cretaceous chalk. The progressive neutralization of the percolating acid fluids resulted in “sequentially” layered neoformation of minerals: jarosite, iron oxides, aluminous minerals (sulfates, oxyhydroxides), gypsum, and Fe-Mn oxides. Substantial agreement was found between field observations and mineral assemblages obtained by modeling with the program CHILLER. These results suggest that the initial assumptions on the weathering process and mechanisms are correct. The relevance and implications of this study in the modeling of future denudation and weathering processes of radioactive waste-disposal sites (both deeply buried sites for high-leveI waste and surface sites for low-level waste) are discussed. Neoformed phases, such as jarosite, aluminous minerals, and silico-aluminous gels may play a significant role in the efficient trapping of mobilized pollutant radionuclides.

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.

Altered basaltic tephra from Haleakala, Maui, are characterized using multiple techniques in order to identify the minerals formed under a variety of conditions and to understand the soil formation processes here. We collected samples that are representative of typical bulk weathered material in the crater, as well as solfataric alteration in a hydrothermal environment. For this study X-ray diffraction, electron probe microanalysis, scanning electron microscopy and transmission electron microscopy are coupled with spectroscopic techniques including Mössbauer, visible-infrared reflectance, transmission infrared, and thermal infrared emission spectroscopies to analyze these samples. The unaltered tephra are composed of feldspar, glass, pyroxene and olivine. Observed alteration products include Fe oxides, phyllosilicates and sulfates, as well as SAED amorphous Al-Si-bearing material. These samples are potential analogs for altered volcanic material on Mars as the pedogenic influences and contact with plants and animals are minimal. Results from this study may help to determine spectral signatures of these samples that could be used for identification on Mars of the minerals observed here.

Secondary Fe(III) oxyhydroxides play a key role in controlling the mobility and bioavailability of trace metals in acidic, sulfate-rich soils, such as mining and smelter sites. Schwertmannite, jarosite, goethite, and ferrihydrite are the most common mineral phases identified in such soils. A good understanding of the precipitation and transformation of these minerals in soils is very important for predicting the mobility and long-term stability of trace metals associated with them. In the present study, bulk powder X-ray diffraction (XRD), scanning electron microscopy (SEM), synchrotron based micro- X-ray diffraction (µ-XRD), and micro X-ray fluorescence (µ-SXRF) spectroscopy were used to investigate precipitates fromthe surface horizon of an organic soil (Histosol) at a site that once contained a lead smelter. Soil samples were collected from 0 to ≈10 cm depth during both wet and dry seasons. Goethite and akaganeite were identified as the major mineral phases in this soil. Schwertmannite and jarosite were also occasionally identified, particularly in the soil samples from dry periods. The peaks in the akaganeite XRD pattern were significantly broadened and the relative intensities of some major peaks were distinctly different compared with the diffraction pattern of synthetic akaganeite, possibly due to the effects of pH and the incorporation of sulfate. The SEM and µ-XRD data support the hypothesis that the goethite in the precipitates is not the product of direct precipitation froms olution but the transformation of previously precipitated schwertmannite or akaganeite.

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.

A single crystal of natrojarosite, NaFe3(SO4)2(OH)6, was investigated by single-crystal X-ray diffraction at high-pressure conditions (up to 8.8 GPa) using a diamond-anvil cell. The unit-cell parameters were determined at 11 different pressures and no indications of a phase transition were found up to the maximum pressure reached. The volume and axial moduli were fitted to a third-order Birch–Murnaghan equation-of-state which gave the following values: V0 = 769.6(2) Å3, KT0 = 50.6(9) GPa, K' = 9.9(4); a = 7.3172(6) Å, KT0 = 104(2), K' = 7.6(9); c = 16.5965(20) Å, KT0 = 24.6(4) and K' = 7.1(2). The crystal structure of natrojarosite was refined at seven different pressures up to 8.779(11) GPa [a = 7.3170(4), c = 16.5955(5) Å and V = 769.46(9) Å3 in Rm at 0.00010(1) GPa and a = 7.1594(8), c = 15.6003(17) Å and V = 692.49(8) Å3 at 8.779(11) GPa]. The structural analysis shows that the 12-fold Na polyhedron accommodates most of the deformation by a large volume decrease (14%) and strong polyhedral distortion (63%). Our results indicate that natrojarosite has the most compressible structure of the supergroup studied so far, and has a very strong axial anisotropy.

Arsenoflorencite-(La), ideally LaAl3(AsO4)2(OH)6, was studied at high pressure by single-crystal X-ray diffractometry. The unit cell was determined at nine pressures up to 7.471(8) GPa; no evidence of a phase transformation was found in this range. The pressure volume data (refined simultaneously) were fitted to a third-order Birch Murnaghan equation of state which gave V0 = 710.71(8) Å3, KT0 = 106(2) GPa and K' = 9.2(9). These values were confirmed independently from an FE–fE plot. The crystal structure was refined at 1.596, 3.622, 5.749 and 7.471 GPa, the first time this has been done for a member the alunite supergroup. The compressibility of arsenoflorencite-(La) is strongly anisotropic, with βc > βa. The main compression mechanism was found to be governed by the internal angle O3 La O2 of the La polyhedron, where the O2 and O3 atoms move toward the c axis during compression.

W-bearing rutile formed during alteration of jarosite by resurgent hydrothermal fluids in the oxide zone of the Kori Kollo gold deposit. The rutile shows sector zoning in basal sections and well developed multiple growth zones, both defined in backscatter electron images by variations in the W content. The maximum WO3 content is 5.3 wt.% and W substitutes for Ti with double substitution of Fe to maintain charge balance. The causes of multiple growth bands are considered to be changes in externally controlled variables occurring in a shallow hydrothermal system. Whereas Ti is probably leached from biotite in dacitic rocks, the W is introduced by hydrothermal fluids.

Jarosite, a hydrous potassium iron sulphate mineral, has been found as the product of weathering in a silicic chalk building stone of a 13th century abbey at Fontevrault (Maine-et-Loire, France). Destabilization of pyrite and glauconite dispersed in the calcareous stone results in the formation of jarosite. The alteration process is probably of very local origin, within the zone in the building stone at its surface where oxidation occurs during wetting and drying on a cyclical basis. The problem of the incompatibility of highly acidic solutions needed to stabilise jarosite (2.5 < pH) within the highly porous, calcareous silicate rock is not explained at present.

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.

An assemblage of alunite-supergroup minerals (ASM), rhabdophane-group minerals (RGM), goethite and associated clay minerals occurs in Permian A-type porphyritic microgranite in the eastern part of the Velence Hills, Hungary. The secondary sulfates/phosphates include jarosite, Pb-rich jarosite and alunite, corkite, hinsdalite and rhabdophane-(Ce), -(La) and -(Nd). Detailed electron probe microanalysis and Raman spectroscopy reveal a wide miscibility among RGM end-members and show a rhabdophane–tristramite–brockite solid solution with extensive compositional variation. Moreover, ASM show heterogeneous composition and complex substitution mechanisms within the alunite, beudantite and plumbogummite groups. The formation of this rare mineral assemblage reveals extensive remobilization of rare-earth elements (REE), Th, U, P, S, Fe and Pb under supergene conditions. Compositional variations and substitution trends of the RGM investigated indicate that Th, U, Ca and Pb are incorporated into the rhabdophane structure by a (Ca, Pb)2+ + (Th, U)4+ ↔ 2REE3+ substitution mechanism. Consequently, we suggest the following end-member formulae for RGM containing divalent and tetravalent cations: (Ca0.5Th0.5)PO4·H2O for brockite, (Pb0.5Th0.5)PO4·H2O for grayite and (Ca0.5U0.5)PO4·2H2O for tristramite. The ASM and RGM originated from total leaching of the primary magmatic REE, Th, U and P minerals in the microgranite [most probably allanite-(Ce), fluorapatite and possibly also xenotime-(Y)], together with input of Pb and S in low-temperature, acid sulfate solutions, connected with an adjacent Palaeogene andesite–diorite intrusion and the accompanying hydrothermal sulfide mineralization.

Rietveld-based quantitative X-ray diffraction (QXRD) has been extensively used for mineralogical characterization in order to understand the reaction chemistry, and kinetics of minerals leaching and formation. This work presents examples where QXRD has been applied to understanding fundamental aspects of these two processes. Firstly, the co-processing of nickel laterites and sulphidic materials has the potential to offer several advantages that include the use of lower grade (including non-smeltable) concentrates, improvement in the rheological behaviour of the blends, and reduction in the use of sulphuric acid. The leaching kinetics and chemistry of mixed nickel laterite ore and sulphide concentrate were explored by the QXRD analysis of feed materials and, intermediates and final leach residues produced using controlled oxidation rates. Under high temperature (250 °C) and pressure oxidation (~40 to 45 atm.) conditions, sulphide minerals in the nickel concentrate underwent several oxidative hydrothermal transformations, and ferrous iron was oxidized and precipitated primarily as hematite. High recovery of nickel can be achieved with low acid consumption under these conditions. Secondly, iron precipitation/removal is an important down-stream process in hydrometallurgy. Moderate concentrations of ferrous iron can be oxidized using micro-organisms with oxidation rates several orders of magnitude faster compared with abiotic oxidation at ambient temperature and pressure. QXRD and chemical analysis have indicated that after oxidation, iron at pH ~2 mostly precipitates as jarosite with various amounts of K+, Na+, NH4+, and H3O+ incorporated into the structure. Bio-catalysed iron removal can be achieved with minimum copper and nickel losses at relatively low pH conditions.