The formation of crystalline rare earth element (REE) (e.g. La, Ce, Pr, Nd) carbonates from aqueous solutions was examined at ambient temperature using UV-Vis spectrophotometry, combined with X-ray diffraction, high-resolution microscopy and infrared spectroscopy. In all experiments REE-lanthanites (REE2(CO3)3·8H2O) formed via a highly hydrated, nanoparticulate and poorlyordered REE-carbonate precursor. The lifetime of this precursor as well as the kinetics of crystallization of the various REE-lanthanites were dependent on the specific REE3+ ion involved in the reaction. The induction time and the time needed to fully form the crystalline REE-lanthanite end products increase linearly with the ionic potential. The authors show here that the differences in ion size and ionic potential as well as differences in dehydration energy of the REE3+ ions control the lifetime of the poorly ordered precursor and thus also the crystallization kinetics of the REE-lanthanites; furthermore, they also affect the structural characteristics (e.g. unit-cell dimensions and idiomorphism) of the final crystalline lanthanites.

Cadmium sulfide mineralization occurs in grey-black shales of the late Mesoproterozoic Stoer Group, Torridonian Supergroup, northwest Scotland. Cadmium is strongly redox-controlled, and normally concentrated in anoxic marine sediments or epigenetic mineralization involving organic matter. However the Stoer Group was deposited in a terrestrial environment, including lacustrine deposits of shale. At the limited levels of atmospheric oxygenation in the Mesoproterozoic (∼10% of present), the near-surface environment could have fluctuated between oxic and anoxic, allowing fractionation of Cd from Zn, and the formation of Cd sulfide rather than Cd-bearing sphalerite. This occurrence emphasizes the importance of the Stoer Group as a record of the Mesoproterozoic terrestrial environment.

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.

A review is presented here of the crystal chemistry of natural silicates of alkaline elements, mainly Na, with a focus on reporting recent data on the structural mineralogy of the new members of this chemical family and their crystal structures. The majority of the natural hydrous silicates of alkaline elements studied are characterized by a specific crystal-chemical feature − the presence of silanol groups Si−OH. The discovery of the two new minerals, chesnokovite and yegorovite, means that all the main topological types of the [SixOy] complexes are represented in the crystal structures for this family.

Precipitation of amorphous silica (SiO2) in geothermal power plants, although a common factor limiting the efficiency of geothermal energy production, is poorly understood and no universally applicable mitigation strategy to prevent or reduce precipitation is available. This is primarily due to the lack of understanding of the precipitation mechanism of amorphous silica in geothermal systems.

In the present study data are presented about microstructures and compositions of precipitates formed on scaling plates inserted at five different locations in the pipelines at the Hellisheiði power station (SW-Iceland). Precipitates on these plates formed over 6 to 8 weeks of immersion in hot (120 or 60ºC), fast-flowing and silica-supersaturated geothermal fluids (~800 ppm of SiO2). Although the composition of the precipitates is fairly homogeneous, with silica being the dominant component and Fe sulfides as a less common phase, the microstructures of the precipitates are highly variable and dependent on the location within the geothermal pipelines. The silica precipitates have grown through aggregation and precipitation of silica particles that precipitated homogeneously in the geothermal fluid. Five main factors were identified that may control the precipitation of silica: (1) temperature, (2) fluid composition, (3) fluid-flow regime, (4) distance along the flow path, and (5) immersion time.

On all scaling plates, a corrosion layer was found underlying the silica precipitates indicating that, once formed, the presence of a silica layer probably protects the steel pipe surface against further corrosion. Yet silica precipitates influence the flow of the geothermal fluids and therefore can limit the efficiency of geothermal power stations.

The publication of the British Geological Survey memoir on Rum and the Small Isles in 1997 was followed by a period of intense petrological and mineralogical research, leading to some 40 papers, books and other publications. The research progress since then is reviewed here and integrated with the information previously available to provide an overview of the current status of understanding of the centre. New data on the acidic and mixed acid/basic magmas of the early Rum caldera demonstrate that frequent mafic replenishments were the main driver for magmatic activity at Rum right from its initial stages. The caldera is bound by the Main Ring Fault, a structure which probably also exercised an influence on the emplacement of the subsequent basic and ultrabasic intrusions. The later emplacement of gabbros and ultrabasic rocks caused only limited thermal metamorphism of the surrounding Torridonian sandstones, contrasting markedly with the crustal isotope signatures of the early intracaldera ignimbrite magmas and the intense alteration of uplifted masses of Lewisian gneiss within the ring fault. Rare picritic dykes provide an indication of the possible parent magma for the mafic and ultrabasic rocks, but these, as with most other magmatic rocks on Rum, have undergone varying degrees of crustal contamination, involving both Lewisian granulite and amphibolite-type crust but, notably, no Moine metasedimentary compositions as is the case at the nearby Ardnamurchan centre. Detailed textural studies on the gabbroic and ultrabasic rocks allow a distinction between intrusive peridotites and peridotite that forms part of the classic layered cumulate units of Rum and, furthermore, this work and that on the chromite seams and veins in these rocks shows that movement of trapped magma and magma derived from later intrusions, may produce textures regarded previously as of primary cumulate origin. Sulfides in the chromitite seams and ultrabasic rocks, in turn, show possible influences from assimilated Mesozoic sediments. Igneous activity on Rum was short-lived, possibly only between 0.5 and 1 m.y. in duration and commenced at ∼60.5 Ma. The Rum Central Complex was extinct by the time the main activity at the nearby Skye Central Complex commenced (∼59 Ma). From recent apatite fission-track studies it seems probable that Rum, in common with other Palaeogene centres, underwent a brief, but significantly later heating event (∼45 Ma).

The natural hydroniumjarosite sample from Cerros Pintados (Chile) was investigated by electron microprobe, single-crystal X-ray diffraction and vibrational spectroscopy (Infrared and Raman). The chemical composition of studied specimens (wt.%, mean of seven analyses) obtained from electron microprobe (in wt.%): Na2O 1.30, K2O 0.23, CaO 0.04, Fe2O3 50.49, Al2O3 0.37, SiO2 0.33, SO3 33.88, H2O (calculated on the basis of Σ(OH–+H3O+) deduced from the charge balance) 13.32, total 99.98, corresponds to the empirical formula (H3O)0.77+(Na0.20K0.02)∑0.22(Fe2.95Al0.03)∑2.98 (OH)6.12[(SO4)1.97(SiO4)0.03]∑2.00 (calculated on the basis of S + Si = 2 a.p.f.u. (atoms per formula unit)). The studied hydroniumjarosite is trigonal, with space group Rm, with a = 7.3408(2), c = 17.0451(6) Å and V = 795.46(4) Å3. The refined structure architecture is consistent with known jarosite-series minerals, including synthetic hydroniumjarosite. However, in the current study the presence of H3O+ is well documented in difference Fourier maps, where characteristic positive difference Fourier maxima, with apparent trigonal symmetry, were localized in the vicinity of the O4 atom in the channel-voids of the structure. The structure of natural hydroniumjarosite, including the H atoms, was refined to R1 = 0.0166 for 2113 unique observed reflections, with Iobs>3σ(I). The present structure model, which includes the position of the H atom within the hydronium ion, is discussed with regard to the vibration spectroscopy results and earlier published density-functional theory (DFT) calculations for the alunite-like structure containing H3O+.

New fluid inclusion analyses using a range of analytical techniques including quadropole mass spectrometric analyses coupled with gemmological investigations were conducted on rough and gemquality faceted emeralds from the Piteiras Mine, Minas Gerais, Brazil. These data complement those of Rondeau et al. (2003) who also presented analyses of the Piteiras emeralds. Emeralds are found typically as euhedral-to-anhedral crystals disseminated in biotite-phlogopite schist and range from 0.5 to 50 mm long. Emerald mineralization is associated closely with alkaline metasomatized pegmatite bodies, quartz boudin and veins, and talc-chlorite bands. Four types of fluid inclusions are recognized in the emeralds. These include aqueous brine and aqueous carbonic varieties containing one or two liquid phases, along with gas bubbles and/or solid crystals (e.g. carbonates). Primary fluid inclusions in emeralds record salinities of ~4–24 eq. wt.% NaCl and minimum trapping temperatures from ~350 to 480ºC. Combined microthermometry, Raman spectroscopy and crush-leach gas analyses indicate that the mineralizing fluid was an aqueous carbonic brine enriched in reduced volatile species such as CH4, N2, H2S and alkanes. With respect to their optical properties (RI ε = 1.573–1.580; RI ω = 1.580–1.588; birefringence = 0.006–0.008) and specific gravity (2.65–2.78), the Piteiras emeralds fall within the expected range for metasomatic, schist-hosted emeralds.

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.

The crystal chemistry of a meso-octahedral Li,Be-bearing mica from the Harding pegmatite (Dixon, Taos County, New Mexico, USA) has been investigated by constant-wavelength single-crystal neutron diffraction at 20 K, single-crystal X-ray diffraction at 100 K and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The chemical composition based on ICP-AES analysis leads to the following chemical formula (calculated on the basis of 12 oxygen atoms): Ca(Na0.26K0.04Ca0.69)∑0.99M(Li0.29Mg0.03Fe0.023+Al1.78)∑2.12T(Al1.73Be0.16Si2.11)S4.00O12H2.53. The apparent excess of H is probably due to the fact that the fraction of H2O was assumed by difference to 100 wt.%, and slightly overestimated. On the basis of the previous experimental findings on Li,Be-bearing mica, X-ray (at 100 K) and neutron (at 20 K) structure refinements were performed in the space groups Cc and C2/c. The neutron structure refinement in the space group Cc offers a view about the (Al,Be,Si)-tetrahedral ordering: the best fit of the refinement was reached with the T1 and T4 sites occupied by (Be + Al) and T2 and T3 fully occupied by Si. This leads to a final population of T(Al1.88Be0.12Si2.00)∑4.00 p.f.u., in reasonable agreement with the chemical analysis. The neutron refinement provides unambigous evidence of the occurrence of Li at the M1 site. The refined fraction of Li at the M1 site ranges between 0.27 and 0.29 a.p.f.u., in excellent agreement with the chemical analysis. The presence of Li, at least at a significant level, at the M2 (and M3) site can be ruled out, as a full site occupancy with the scattering length of Al was obtained. The location of the H sites and the complex hydrogen-bonding scheme are described. A comparison between the structure features of this Li,Be-mica and other brittle micas is carried out.

The crystal structure and the chemical composition of a paravauxite from the Siglo Veinte Mine, Llallagua, Bustillo Province, Potosi Department, Bolivia [Fe (Fe0.916 2+Mn0.016 2+Mg0.064Ca0.002)∑0.998Al(1)Al(2)Al2.005P (P1.998Si0.002)∑2O8(OH)2·8H2O, a = 5.242(1) Å, b = 10.569(2) Å, c = 6.970(2) Å, α = 106.78(3)°, β = 110.81(2)° and γ = 72.29(2)°, space group P ], was investigated by single-crystal neutron diffraction and electron microprobe analysis in wavelength-dispersive mode. Neutron-intensity data were collected at 293 K and anisotropic structure refinement was performed. At the end of the refinement no peak larger than ±1.3 fm/Å3 was present in the final difference-Fourier map of the nuclear density. The final statistical index was R 1 = 0.0495 for 194 refined parameters and 1678 unique reflections with F o > 4σ(F o). Eleven independent H sites (i.e. H(1), H(2), H(3), H(4A), H(4B), H(5), H(6), H(7), H(8), H(9A) and H(9B)), all at ∼1 Å from the respective O sites, were located successfully. H(4A) and H(4B) and H(9A) and H(9B) are two mutually exclusive subsite couples only 0.4−0.6 Å apart. The complex H-bonding scheme in the paravauxite structure is now well defined and 12 independent H bonds, with an energetically favourable bonding configuration, are described. A comparison between the previous experimental findings based on Raman and infrared spectroscopy and those obtained in this present study is carried out. Paravauxite provides the rare opportunity to investigate the H-bond configuration of coexisting hydroxyl groups and H2O molecules in minerals by single-crystal neutron diffraction. H2O is present as zeolitic (i.e. lying in the cavities) and non-zeolitic H2O (i.e. bonded to Al or Fe to form Al or Fe octahedra).

The crystallization of hexagonal NdCO3OH through hydrothermal synthesis carried out at slow (reaching the desired temperature within 100 min) and quick (50 min) rates of heating but at variable temperatures (165–220ºC) are reported here. The formation of NdCO3OH occurs via the crystallization of an amorphous precursor. Both the precursor and the crystalline NdCO3OH were characterized by X-ray diffraction, infrared spectroscopy and high-resolution electron microscopy. The mechanism of crystallization is very dependent on the experimental conditions (rate of heating and temperature treatment). With increasing temperature, the habit of NdCO3OH crystals changes progressively to more complex spherulitic or dendritic morphologies. The development of these crystal morphologies is suggested here to be controlled by the level at which supersaturation was reached in the aqueous solution during the breakdown of the amorphous precursor. At the highest temperature (220ºC) and during rapid heating (50 min) the amorphous precursor breaks down rapidly and the fast supersaturation promotes spherulitic growth. At the lowest temperature (165ºC) and slow heating (100 min), however, the supersaturation levels are approached more slowly than required for spherulitic growth, and thus more regular, previously unseen, triangular pyramidal shapes form.

This is a review of the elastic behaviour and pressure (P)-induced structural evolution of zeolites and presents a comparative analysis of the deformation mechanisms of the Si/Al-framework and the rearrangement of the extra-framework species in response to applied pressure. The interaction between P-transmitting fluids and zeolites, which can lead to phenomena such as ‘P-induced over-hydration’, is described. The comparative elastic analysis and the high-P structural data of zeolites reported so far allow us to make some generalizations: (1) The range of compressibility among this class of openframework silicates is large, with bulk moduli ranging between 15 and 70 GPa; (2) Microporosity does not necessarily imply high compressibility, as several zeolites are less compressible than other nonzeolitic rock-forming minerals; (3) Compressibilities of zeolites do not seem to be directly related to microporosity, at least if we model microporosity with the ‘framework density’; (4) The flexibility observed in zeolites under hydrostatic compression is mainly governed by tilting of rigid tetrahedra around O atoms that behave as hinges within the framework. Pressure-induced tilting commonly leads to continuous rearrangement of the framework without any phase transition. More rarely, tilting induces displacive phase transitions and isothermal P-induced reconstructive phase transitions (i.e. with change in framework topology), have not been reported in this class of materials; (5) Deformation mechanisms in response to applied pressure are generally dictated by the topological configuration of the framework rather than the Si/Al-distribution or the extra-framework content. The channel content governs the compressibility of the cavities, leading to different unit-cell-volume compressibilities in isotypic structures.

The crystal structure of synthetic BaMg(CO3)2 whose mineral name is norsethite was re-investigated by single-crystal X-ray diffraction. Complementary in situ high- and low-temperature studies by means of vibrational spectroscopy (Raman, IR), powder X-ray diffraction techniques and thermal analyses were performed. Diffraction images (298 K) revealed weak superstructure reflections caused by the displacement of the O atoms in the earlier considered Rm structure model (a = 5.0212(9), cnew = 2 cold = 33.581(6) Å , Rc, Z = 6, R1 = 0.011, sinθ/λ < 0.99 Å –1). Thermal analyses reveal decarbonatization in two decomposition steps above 750 K, and the heat-flow curves (difference scanning calorimetry) give clear evidence of a weak and reversible endothermal change at 343±1 K. This agrees with a discontinuity in the IR and single-crystal Raman spectra. The changing trend of the c/a ratio supports this discontinuity indicating a temperature-induced structural transition in the range between 343 and 373 K. As the change of the unit-cell volume is almost linear, the character of the transition is apparently second order and matches the mechanism of a subtle displacement of the oxygen atom position. The apparent instability of the Rc structure is also evidenced by the remarkably larger anisotropic displacement of the oxygen atom.

This study addresses the crystal chemistry of a set of five samples of F-rich amphiboles from the Franklin marble (USA), using a combination of microchemical (Electron microprobe analysis (EMPA)), single-crystal refinement (SREF) and Fourier transform infrared (FTIR) spectroscopy methods. The EMPA data show that three samples fall into the compositional field of fluoro-edenite (Hawthorne et al., 2012), whereas two samples are enriched in high-charged C cations and – although very close to the CR3+ boundary – must be classified as fluoro-pargasite. Magnesium is by far the dominant C cation, Ca is the dominant B cation (with BNa in the range 0.00−0.05 a.p.f.u., atoms per formula unit) and Na is the dominant A cation, with A☐ (vacancy) in the range 0.07−0.21 a.p.f.u.; WF is in the range 1.18−1.46 a.p.f.u. SREF data show that: TAl is completely ordered at the T(1) site; the M(1) site is occupied only by divalent cations (Mg and Fe2+); CAl is disordered between the M(2) and M(3) sites; ANa is ordered at the A(m) site, as expected in F-rich compositions. The FTIR spectra show a triplet of intense and sharp components at ~3690, 3675 and 3660 cm−1, which are assigned to the amphibole and the systematic presence of two very broad absorptions at 3560 and 3430 cm−1. These latter are assigned, on the basis of polarized measurements and FPA (focal plane array) imaging, to chlorite-type inclusions within the amphibole matrix. Up to eight components can be fitted to the spectra; band assignment based on previous literature on similar compositions shows that CAl is disordered over the M(2) and M(3) sites, thus supporting the SREF conclusions based on the <M−O> bond distance analysis. The measured frequencies of all components are typical of O−H groups pointing towards Si−O(7)−Al tetrahedral linkages, thus allowing characterization of the SRO (shortrange- order) of TAl in the double chain. Accordingly, the spectra show that in the fluoro-edenite/ pargasite structure, the T cations, Si and Al, are ordered in such a way that Si−O(7)−Si linkages regularly alternate with Si−O(7)−Al linkages along the double chain.

Pore-volume changes in porous media during water–rock interaction can be studied using hydrological tracers. The tracers used here were amino G acid, napthionic acid and fluorescein at pH 3 and 6.5 in contact with basaltic glass, quartz and rhyolite. The experimental setup mimicked that of a hydrological tracer test where a fixed volume of tracer was injected into a flow-through column and the breakthrough curve monitored. The measured breakthrough tracer curves were compared to theoretical 1-D reactive transport simulations calculated using the PHREEQC program. In some cases the tracers were observed to behave ideally, whereas in others they clearly reacted with the solid surfaces. This implies that some common hydrological tracers used in groundwater hydrology may not be suitable under all conditions as they may react with the surrounding rocks in the groundwater system.

A description of the new mineral innsbruckite, Mn33(Si2O5)14(OH)38, a hydrous manganese phyllosilicate found in Tyrol, Austria is given. The crystal structure was determined by singlecrystal synchrotron radiation diffraction experiments at the X06DA beamline at the Swiss Light Source (Paul Scherrer Institute, Villigen, Switzerland). The space group is Cm and lattice parameters are a = 17.2760(19), b = 35.957(5), c = 7.2560(8) Å , β = 91.359(7)º, V = 4506.1(10) Å3, Z = 2. Innsbruckite belongs to the group of modulated 1:1 layer silicates and is chemically and structurally quite closely related to bementite, Mn7(Si2O5)3(OH)8. The chemical analysis revealed a close to ideal composition with only minor amounts of Al, Fe and Mg. Using Liebau’s nomenclature for silicate classification the silicate anion can be described as an unbranched siebener single layer. Innsbruckite shows a complex topology of the silicate sheet, exhibiting 4-, 5-, 6- and 8-membered rings. The silicate sheet is fully characterized using vertex symbols, and its topology is compared to those in other complex sheet silicates. Furthermore, the structural investigation is complemented with Raman spectroscopic studies.

Bariopharmacoalumite-Q2a2b2c, Ba0.5(Cu,ZnO)0.1H0.6[Al4(OH)4(As0.9Al0.1O4)3]·5.5H2O, from the south mine of the old copper mine at Cap Garonne, France, has a 2 × 2 × 2 I-centred tetragonal superstructure of the basic pharmacosiderite-type structure. Cell parameters are a = 15.405(2) Å and c = 15.553(3) Å. The structure was determined and refined in I 2m to R 1= 0.057 for 2697 reflections with I > 2σ(I), using synchrotron X-ray data on a twinned crystal. The origin of the superlattice cell doubling was determined to be due predominantly to the ordering of Ba atoms in half of the [0 0 1] channels, centred at (0, 0, 0) and (½, ½, 0). The other channels, centred at (½, 0, 0) and (0, ½, 0), were found to be occupied by corner-connected chains of Cu/Zn-centred square planar units.

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.