This special issue of the Mineralogical Magazine springs from the session we organized as part of the Goldschmidt 2013 conference in Florence. The title we proposed “GEOLIFE – Geomaterials for environment, technology and human activities” reflects our feeling that a wise use of the expertise gained by mineralogists while studying the crystal chemistry, as well as the chemical and physical properties of minerals in rocks and soils, still plays an important role in what is called “The cutting edge in Mineralogy and Mineral Physics”.

Indeed, the current expertise in the physical, chemical and structural characterization of geomaterials, i.e. minerals, rocks and their synthetic analogues, now allows us to design innovative applications both for technological and environmental purposes. During the meeting we discussed some frontier work on phases produced naturally by the Earth ‘laboratory’ or fabricated within academic laboratories, which have the potential to improve the quality of life for current and future generations.

Materials designed for nuclear waste disposal include a range of ceramics, glass ceramics and glass waste forms. Those with crystalline phases have provided the momentum for studies of minerals as a means to understand aspects of waste-form crystal chemistry, behaviour in aqueous systems and radiation damage over geological periods of time. Although the utility of natural analogue studies varies, depending upon the degree of analogy to the proposed geological repository and other factors such as chemical composition, the available data suggest that Th-U host phases such as brannerite, monazite, pyrochlore, zircon and zirconolite are resistant generally to dissolution in aqueous fluids at low temperatures. Geochemical durability may or may not extend to hydrothermal systems depending on the specifics of fluid composition, temperature and pressure. At elevated temperatures, for example, davidite may break down to new phase assemblages including titanite, ilmenite and rutile. Perovskite is generally less resistant to dissolution at low temperatures and breaks down to TiO2, releasing A-site cations to the aqueous fluid. Studies of radiation damage indicate that the oxide and silicate phases become amorphous as a result of the gradual accumulation of alpha-recoil collision cascades. Monazite tends to remain crystalline on geological time scales, a very attractive property that potentially eliminates major changes in physical properties such as density and volume, thereby reducing the potential for cracking, which is a major concern for zircon. In spite of recent success in describing the behaviour of Th-U minerals in geological systems, considerable work remains in order to understand the P-T-X conditions during alteration and T-t history of the host rocks.

Iron oxides resulting from the corrosion of large quantities of steel that are planned to be installed throughout a deep geological disposal facility (GDF) are expected to be one of the key surfaces of interest for controlling radionuclide behaviour under disposal conditions. Over the lengthy timescales associated with a GDF, the system is expected to become anoxic so that reduced Fe(II) phases will dominate. Batch experiments have therefore been completed in order to investigate how a model reduced Fe-oxide surface (wüstite, Fe1–xO) alters as a function of exposure to aqueous solutions with compositions representative of conditions expected within a GDF. Additional experiments were performed to constrain the effect that highly alkaline solutions (up to pH 13) have on the adsorption behaviour of the uranyl (UO22+) ion onto the surfaces of both wüstite and portlandite [Ca(OH)2; representative of the expected cementitious phases]. Surface co-ordination chemistry and speciation were determined by ex situ X-ray absorption spectroscopy measurements (both X-ray absorption near-edge structure analysis (XANES) and extended X-ray absorption fine structure analysis (EXAFS)). Diffraction, elemental analysis and XANES showed that the bulk solid composition and Fe oxidation state remained relatively unaltered over the time frame of these experiments (120 h), although under alkaline conditions possible surface hydroxylation is observed, due presumably to the formation of surface hydroxyl complexes. The surface morphology, however, is altered significantly with a large degree of roughening and an observed decrease in the average particle size. Reduction of U(VI) to U(IV) occurs during adsorption in almost all cases and this is interpreted to indicate that wüstite may be an effective reductant of U during surface adsorption. This work also shows that increasing the carbonate concentration in reactant solutions dramatically decreases the adsorption coefficients for U on both wüstite and portlandite, consistent with U speciation and surface reactivity determined in other studies. Finally, the EXAFS results include new details about exactly how U bonds to this metal oxide surface.

Several strategies are available to reduce or eliminate recalcitrant sulfonamide antibiotics (sulfa drugs) from aqueous media. These contaminants are bioactive and ubiquitous pollutants of soils and watercourses and are known to induce bacterial resistance. Here the biological, chemical and physical methods developed over the last 5 years to decontaminate waters polluted with sulfa drugs are reviewed with special attention to procedures that make use of porous adsorbent materials and their applicability to real waters.

The thermal regeneration of sulfamethoxazole (SMX)-loaded Y and ZSM-5 zeolites was studied using a combined in situ high-temperature synchrotron X-ray powder diffraction and thermal degradation study. The evolution of the structural features was monitored in real time in the 30–575°C temperature range by full-profile Rietveld analysis. SMX thermal degradation pathways into high-silica zeolite antibiotic adducts, as well as the release of evolved species are similar to those for pure SMX. The adsorption/desorption process occurs without any significant loss of zeolite crystallinity, though slight deformations to the channel apertures are observed. Regenerated zeolites regain almost perfectly ‘bare’ (i.e. unloaded) material unit-cell parameters and only a slight memory effect, in terms of structural deformations induced by the process, is registered in the channel geometry. Interestingly, these changes do not affect the adsorption properties of the regenerated samples, which are able to re-adsorb comparable amounts of antibiotic molecules as in the first adsorption cycle.

This study reports on experimental results concerning methyl-tert-butyl-ether (MTBE, C5H12O) adsorption from water into the pores of siliceous zeolite ferrierite (FER) by combining powder X-ray diffraction analyses and chromatography techniques. Rietveld structure refinement (Immm space group) highlighted the presence of two crystallographically independent MTBE sites located in the 10-ring channel parallel to the [001] direction (MTBE1) and in the ferrierite cage (MTBE2), respectively. On the whole, Rietveld refinement revealed clearly the incorporation of ~1.8 MTBE molecules per unit cell, in very good agreement with the weight loss given by thermogravimetric analyses, and saturation capacity as determined by adsorption isotherms. Rapid kinetics combined with good adsorption suggests that FER can be used beneficially as an adsorbent medium in removing this emerging organic contaminant from water.

Selected samples of asbestos-containing material (ACM) with different Ca/Si ratios have been treated thermally at 1200°C for 15 min to obtain an ‘end of waste geo-inspired material’. Before and after treatment, micro-Raman spectroscopy allowed the investigation of both powdered and massive samples by directing the laser beam onto crystals with elongated morphology, thin fibres and the matrix. In the raw samples, chrysotile and/or crocidolite were detected. After the thermal treatment, no asbestos phases were identified in the Raman spectra collected on fibrous or fibre-like morphologies. The scanning electron microscopy/energy dispersive spectroscopy investigations confirmed the onset of a pseudomorphic process during annealing, leading to the complete transformation of asbestos minerals into non-hazardous magnesium or calcium magnesium silicates such as forsterite, monticellite, a˚kermanite and merwinite.

The identification of such mineral assemblages was inspired by the close inspection of a natural counterpart, the high-temperature contact metamorphic imprint due to the intrusion of a sill into carbonate rocks. The process turned out to occur largely at the solid state and involved substantial mobilization of Ca and Mg to form a spinel phase (namely MgFe2O4) which was recognized in the matrix and within, or close to elongated morphologies.

The high-pressure behaviour of the thaumasite structure was investigated using synchrotron powder X-ray diffraction, up to 19.5 GPa. Based on Rietveld refinements, thaumasite retained the roompressure P63 space group throughout the whole investigated pressure range while the pressure dependence of the refined unit-cell parameters can be cast into three different compression regimes, each corresponding to a different thaumasite phase (th-I, th-II and th-III) related by isosymmetric phase transitions. In particular, the phase transition in the 7.40–15.02 GPa P-range (i.e. from th-II to th-III) is associated with an inversion of the axial bulk moduli which, by analogy with ettringite, can be rationalized as due to a change in the relative strengths of the iono-covalent bonds along the [Ca3Si(OH)6(H2O)12]4+ columns parallel to the c axis vs. the O–H bonds linking the columns within the ab plane. The linear inverse relationship between the low- and high-temperature data from the literature with those collected under high-pressure conditions reveals that the same bonding regime governs the anisotropic expansion and contraction of thaumasite up to ~1.4 GPa and 400 K (HP-HT stability limits of th-I phase).

Zeolites K-F and W (EDI and MER types) were synthesized hydrothermally using a natural rock as raw material. Chemical treatments were carried out on a diatomitic rock (containing opaline silica) from Crotone (Calabria, Italy) in order to separate/obtain potassium silicate, a reagent necessary for synthesizing zeolites. Synthesis experiments were performed by mixing the obtained siliceous solution with potassium hydroxide and alumina in varying proportions at 150°C and room pressure. Four synthesis series were performed to form zeolite K-F (EDI) and zeolite W (MER).

The chemical-physical and morphological characterization of the zeolite phases were carried out. Cell parameters were calculated using the Rietveld method. Infrared, thermal and nuclear magnetic resonance (29Si) experiments confirmed the high quality of the zeolite products. The amorphous phase in the synthesis powders was estimated with quantitative phase analysis using the combined Rietveld and reference intensity ratio methods.

Clay/polymer nanocomposites (CPN) exhibit improved technical properties compared to their microand macro-counterparts. Nevertheless, thermal degradation of CPN may limit the applicability of these hybrid materials. In this paper accelerated ageing (110°C and 150°C) was performed in injection moulded pure polyamide 66 (PA66-S-0 samples) and polyamide 66 reinforced with 5 wt.% sepiolite (PA66-S-5 samples) CPN. Polymer degradation was monitored by the amount of newly formed carbonyl bonds. The carbonyl indices obtained indicate that degradation occurs to a greater extent as the temperature of the ageing process increases. Moreover, the degradation increases with time at the highest treatment temperature (150°C). On the other hand, the occurrence of carbonaceous silicates in the nanocomposite samples at high temperatures yields greater thermal stability of sepiolite/PA66 nanocomposites compared to pure PA66. Furthermore, the sepiolite nanofibres maintain their position in the reticulated semicrystalline structure. In agreement with those results, differential scanning calorimetry and X-ray diffraction analyses show that the motion of the amide groups in the polymer chains are constrained by the well dispersed sepiolite.

The crystal structure of rabejacite from Jáchymov, ideally Ca2[(UO2)4O4(SO4)2](H2O)8, was solved by charge flipping from single-crystal data and refined to R1 = 11.94% for 1422 unique observed reflections [I > 3σ(I)]. According to single-crystal X-ray data, rabejacite is triclinic, space group P, with a = 8.7434(11), b = 8.309(3), c = 8.8693(10) Å , a = 77.86(2), b = 104.635(11), g = 82.935(18)°, V = 598.8(3) A˚ 3 and Z = 1, with Dcalc = 4.325 g cm–3. The structure refinement proved that rabejacite is related to the zippeite group of minerals, as it is based upon the structural sheets of the zippeite topology of composition [(UO2)4O4(SO4)2]4–. Located in the interlayer between the sheets, which are stacked perpendicular to [010], are Ca2+ cations and H2O groups. Ca2+ ions are [7]-coordinated, by three uranyl O atoms from adjacent sheets and four H2O groups. An additional H2O group, which is not bonded directly to any cation, is located in the interlayer. Along with rabejacite, its Cu-rich variety was found in the specimens examined and characterized structurally. Its crystal structure (R1 = 10.15% for 1049 reflections with I > 3s(I)) is practically the same as that of rabejacite, but there is an additional Cu2+ site located in between pairs of Ca polyhedra. The structural formula is (Ca1.56Cu0.40)Σ1.90[(UO2)4O4(SO4)2](H2O)8, Z = 1. Its existence suggests a greater diversity in zippeite crystal chemistry than was thought previously and also the possibility of a new Cu2+-dominant zippeite mineral besides pseudojohannite.

This study describes the occurrences of sulfate minerals in mines of the Czech part of the Upper Silesian Basin. This mineralization originates from the oxidation of Fe disulfides contained in the coal matrix and enclosing sediments. The oxidation occurs in the presence of formational brines and chemotrophic bacteria. The brines have a pH between 6.3 and 8.5 and total solute content of up to 300 g/l. They are rich in Na, Ca, K, Mg, Ba and Sr and Cl– is the major anion. The minerals of the pickeringite–halotrichite series with coexisting magnesiocopiapite are formed primarily in drier places and areas where the water is only slightly mineralized. In more humid places where the brines are more concentrated, a diverse assemblage of up to 20 different sulfates are found (e.g. natrojarosite, sideronatrite, metasideronatrite, tamarugite, magnesiocopiapite, bílinite, starkeyite, blödite, rozenite and siderotil). These sulfates are accompanied by halite, sulfur, goethite and a number of phases of uncertain identity, such as sulfates containing Sr and REE. This is an example of mineral paragenesis formed by weathering in a saline evaporite environment, which is extremely rare in Europe but is found in arid regions elsewhere (e.g. in the Atacama Desert in Chile).

Arsenopyrite (FeAsS), gudmundite (FeSbS) and the rarer Fe sulfosalts berthierite (FeSb2S4) and garavellite (FeSbBiS4), were investigated by Raman spectroscopy. Whereas (Sb,Bi)S3 pyramids are responsible for the Raman spectra of berthierite and garavellite, the spectra of gudmundite and arsenopyrite arise from the stretching and bending modes of (Sb,As)S units. Internal vibrations for berthierite and garavellite occur between 400 and 50 cm–1, and those of the gudmundite and arsenopyrite between 500 and 100 cm–1. The longer bond distances of the SbS3 groups readily explain the lower frequencies for berthierite in comparison with garavellite. Similarly, the greater mass and the longer bond distances of the Sb–S units also explain the lower frequencies observed for gudmundite relative to arsenopyrite.

A suite of sheared syenites occurring along the western margin of the Eastern Ghats Belt, India have developed extensive flame perthite in K-feldspar. Albite flames show large variation in size, shape and abundance. Field, petrographic and chemical evidence suggests complex interplay between differential stress, recycling of K-Na-Ca and supply of Na by infiltration for the development of flame perthite. Partial replacement of pyroxenes, plagioclase and alkali feldspar by amphibole, biotite, nepheline and calcite causes internal recycling of Na-Ca-K in a closed system. Representative compositions of the minerals are used to constrain the model dissolution–reprecipitation ion-exchange reactions involving Na and K either as reactants and/or as products. A substantial proportion of Na+ required for the development of the albite flames, originates from Na metasomatism accompanied by ductile shearing in the feldspathic rocks, providing an ideal open system wherein both the differential stress and Na+ are made available for the development of the flame perthites. This process probably augmented the replacement of K-feldspar grains by flame albite and the K+ released was carried away by the fluid or, possibly, augmented the biotite-forming reactions in the associated quartz-poor syenites and, hence, trigger the Na-K cycle in these rocks.

Bluebellite, Cu6[I5+O3(OH)3](OH)7Cl and mojaveite, Cu6[Te6+O4(OH)2](OH)7Cl, are new secondary copper minerals from the Mojave Desert. The type locality for bluebellite is the D shaft, Blue Bell claims, near Baker, San Bernardino County, California, while cotype localities for mojaveite are the E pit at Blue Bell claims and also the Bird Nest drift, Otto Mountain, also near Baker. The two minerals are very similar in their properties. Bluebellite is associated particularly with murdochite, but also with calcite, fluorite, hemimorphite and rarely dioptase in a highly siliceous hornfels. It forms bright bluishgreen plates or flakes up to ~20 mm 620 mm 65 mm in size that are usually curved. The streak is pale bluish green and the lustre is adamantine, but often appears dull because of surface roughness. It is non-fluorescent. Bluebellite is very soft (Mohs hardness ~1), sectile, has perfect cleavage on {001} and an irregular fracture. The calculated density based on the empirical formula is 4.746 g cm–3. Bluebellite is uniaxial (–), with mean refractive index estimated as 1.96 from the Gladstone-Dale relationship. It is pleochroic O (bluish green) >> E (nearly colourless). Electron microprobe analyses gave the empirical formula Cu5.82I0.99Al0.02Si0.12O3.11(OH)9.80Cl1.09 based on 14 (O+Cl) a.p.f.u. The Raman spectrum shows strong iodate-related bands at 680, 611 and 254 cm–1. Bluebellite is trigonal, space group R3, with the unit-cell parameters: a = 8.3017(5), c = 13.259(1) Å , V = 791.4(1) Å 3 and Z = 3. The eight strongest lines in the powder X-ray diffraction (XRD) pattern are [dobs/Å (I) (hkl)]: 4.427(99)(003), 2.664(35)(211), 2.516(100)(21), 2.213(9)(006), 2.103(29)(033,214), 1.899(47)(312,21), 1.566(48)(140,217) and 1.479(29)(045,14,324).

Mojaveite occurs at the Blue Bell claims in direct association with cerussite, chlorargyrite, chrysocolla, hemimorphite, kettnerite, perite, quartz and wulfenite, while at the Bird Nest drift, it is associated with andradite, chrysocolla, cerussite, burckhardtite, galena, goethite, khinite, mcalpineite, thorneite, timroseite, paratimroseite, quartz and wulfenite. It has also been found at the Aga mine, Otto Mountain, with cerussite, chrysocolla, khinite, perite and quartz. Mojaveite occurs as irregular aggregates of greenish-blue plates flattened on {001} and often curved, which rarely show a hexagonal outline, and also occurs as compact balls, from sky blue to medium greenish blue in colour. Aggregates and balls are up to 0.5 mm in size. The streak of mojaveite is pale greenish blue, while the lustre may be adamantine, pearly or dull, and it is non-fluorescent. The Mohs hardness is ~1. It is sectile, with perfect cleavage on {001} and an irregular fracture. The calculated density is 4.886 g cm–3, based on the empirical formulae and unit-cell dimensions. Mojaveite is uniaxial (–), with mean refractive index estimated as 1.95 from the Gladstone-Dale relationship. It is pleochroic O (greenish blue) >> E (light greenish blue). The empirical formula for mojaveite, based on 14 (O+Cl) a.p.f.u., is Cu5.92Te1.00Pb0.08Bi0.01O4(OH)8.94Cl1.06. The most intense Raman bands occur at 694, 654 (poorly resolved), 624, 611 and 254 cm–1. Mojaveite is trigonal, space group R3, with the unit-cell parameters: a = 8.316(2), c = 13.202(6) Å and V = 790.7(1) Å 3. The eight strongest lines in the powder XRD pattern are [dobs/Å (I) (hkl)]: 4.403(91)(003), 2.672(28)(211), 2.512(100)(21), 2.110(27)(033,214), 1.889(34)(312,21,22), 1.570(39)(404,140,217), 1.481(34)(045,14,324) and 1.338(14)(422). Diffraction data could not be refined, but stoichiometries and unit-cell parameters imply that bluebellite and mojaveite are very similar in crystal structure. Structure models that satisfy bondvalence requirements are presented that are based on stackings of brucite-like Cu6MX14 layers, where M = (I or Te) and X = (O, OH and Cl). Bluebellite and mojaveite provide a rare instance of isotypy between an iodate containing I5+ with a stereoactive lone electron pair and a tellurate containing Te6+ with no lone pair.

Hloušekite, (Ni,Co)Cu4(AsO4)2(AsO3OH)2(H2O)9, is a new supergene arsenate mineral from the Geister vein (Rovnost mine), Jáchymov (St Joachimsthal), Western Bohemia, Czech Republic. It was found along with veselovský ite, pradetite, lavendulan, arsenolite, babánekite and gypsum on the surface of strongly altered ore fragments containing dominant tennantite and chalcopyrite. Hloušekite forms thin, lath-like crystals, locally elongated reaching up to 3 mm across. It is transparent, has a pale green colour with vitreous lustre, has a greyish-white streak and it is very brittle with an uneven fracture. It does not fluoresce under shortwave or longwave ultraviolet radiation. Cleavage on {010} is perfect; the Mohs hardness is 2–3. The calculated density is 3.295 g cm–3. Hloušekite is optically biaxial with α’ = 1.653(2) and γ’ = 1.73. The estimated optical orientation is γ’ vs. elongation (c) = 14(1)°. In larger grains it is weakly to moderately pleochroic (α = colourless, γ = pale green to green). Hloušekite is triclinic, space group P, a = 6.4010(6), b = 8.0041(6), c = 10.3969(14) Å , α = 85.824(8), β = 79.873(9), γ = 84.655(7)° and V = 521.23(10) Å3, with Z = 1, a:b:c = 0.800:1:1.299. The eight strongest lines in the powder X-ray diffraction (XRD) pattern [d in Å (I)(hkl)] are 10.211(100)(001), 7.974(9)(010), 3.984(6)(020), 3.656(5)(12), 3.631(5)(01), 3.241(5)(022), 3.145(5)(200) and 3.006(5)(210). Chemical analysis by electron microprobe yielded MgO0.20, FeO0.10, NiO 5.79, CoO1.80, CuO29.53, ZnO 0.66, Al2O3 0.14, P2O5 0.11, As2O5 45.01, H2O 17.71 (calc.), for a total of 101.05 wt.%. The resulting empirical formula, calculated by stoichiometry (9H2O + 2OH), obtained from the crystal structure, is (Ni0.79Co0.25)Σ1.04(Cu3.78Zn0.08Mg0.05Al0.03Fe0.01)Σ3.95 (AsO4 )1.98(PO4 )0.02(AsO3OH)2.00(H2O)9.00 . The ideal endmember formula , NiCu4(AsO4)2(AsO3OH)2(H2O)9.00, requires NiO7.23, CuO30.81, As2O5 44.51, H2O17.45, total 100.00 wt.%. The crystal structure of hloušekite was solved by charge flipping from single-crystal XRD data and refined to R1 = 0.0599 for 1441 reflections with [Iobs > 3σ(I)]. Hloušekite is a new member of the lindackerite group (also including lindackerite, pradetite and veselovský ite) of the lindackerite supergroup. The ondrušite group of the lindackerite supergroup includes ondrušite, chudobaite, geigerite and klajite. The establishment of these two groups reflects the difference between the crystal structures of their members, mainly in the coordination environment of the Me cations.