Mackinawite, tetragonal FeS, has been synthesised by reacting iron with Na2S solutions. A Rietveld structure refinement of X-ray powder diffraction data, recorded using X-rays monochromated from synchrotron radiation with a wavelength of 0.6023 Å, has been performed. The structure has been refined in the tetragonal space group, P4/nmm, and has the following cell parameters: a = 3.6735(4), c = 5.0328(7) Å, V = 67.914(24) Å3. Our refinement shows that the FeS4 tetrahedron in mackinawite is almost perfectly regular, with a much smaller distortion than has been previously reported. An improved X-ray diffraction data set is provided.

Structural complexity of minerals is characterized using information contents of their crystal structures calculated according to the modified Shannon formula. The crystal structure is considered as a message consisting of atoms classified into equivalence classes according to their distribution over crystallographic orbits (Wyckoff sites). The proposed complexity measures combine both size- and symmetry-sensitive aspects of crystal structures. Information-based complexity parameters have been calculated for 3949 structure reports on minerals extracted from the Inorganic Crystal Structure Database. According to the total structural information content, IG, total, mineral structures can be classified into very simple (0–20 bits), simple (20–100 bits), intermediate (100–500 bits), complex (500–1000 bits), and very complex (> 1000 bits). The average information content for mineral structures is calculated as 228(6) bits per structure and 3.23(2) bits per atom. Twenty most complex mineral structures are (IG, total in bits): paulingite (6766.998), fantappieite (5948.330), sacrofanite (5317.353), mendeleevite-(Ce) (3398.878), bouazzerite (3035.201), megacyclite (2950.928), vandendriesscheite (2835.307), giuseppetite (2723.097), stilpnomelane (2483.819), stavelotite-(La) (2411.498), rogermitchellite (2320.653), parsettensite (2309.820), apjohnite (2305.361), antigorite (m = 17 polysome) (2250.397), tounkite (2187.799), tschoertnerite (2132.228), farneseite (2094.012), kircherite (2052.539), bannisterite (2031.017), and mutinaite (2025.067). The following complexity-generating mechanisms have been recognized: modularity, misfit relationships between structure elements, and presence of nanoscale units (clusters or tubules). Structural complexity should be distiguished from topological complexity. Structural complexity increases with decreasing temperature and increasing pressure, though at ultra-high pressures, the situation may be different. Quantitative complexity measures can be used to investigate evolution of information in the course of global and local geological processes involving formation and transformation of crystalline phases. The information-based complexity measures can also be used to estimate the 'ease of crystallization' from the viewpoint of simplexity principle proposed by J.R. Goldsmith (1953) for understanding of formation of simple and complex mineral phases under both natural and laboratory conditions. According to the proposed quantitative approach, the crystal structure can be viewed as a reservoir of information encoded in its complexity. Complex structures store more information than simple ones. As erasure of information is always associated with dissipation of energy, information stored in crystal structures of minerals must have an important influence upon natural processes. As every process can be viewed as a communication channel, the mineralogical history of our planet on any scale is a story of accumulation, storage, transmission and processing of structural information.

The problems of characterizing inter-granular regions and of estimating rates of intergranular diffusion in metamorphic rocks are discussed. Inter-granular regions can be anhydrous, hydrated but under-saturated with H2O, or saturated with H2O, but only in the latter case can a free aqueous fluid phase be present. Estimates of intergranular diffusion coefficients (DIGR) at 550°C derived from a variety of published experimental work, vary from ∼ 10−8 m2 s−1 for diffusion of species through an intergranular fluid film to ⩽ 4 × 10−24 m2 s−1 for diffusion of SiO2 or O in anhydrous grain boundaries in quartzite. Estimates of DIGR for hydrated grain boundaries vary from ∼ 10−13 m2 s−1 to ∼ 10−21 m2 s−1; the concentration of H2O in the grain boundaries and the identity of the diffusing species (generally unknown) may be important controlling factors, and there exists the possibility of a spectrum of values between these two extremes.

Using available kinetic data it is shown that a free aqueous fluid could never have been present in parts of the basement terrane of the Sesia Zone (Western Alps) during uplift from the eclogite facies, except possibly late in the cooling history. The breakdown of sodic pyroxene + quartz occurred in response to the localized infiltration of catalytic aqueous fluid, possibly over a time interval as short as 6–6000 a, and possibly under conditions remote from equilibrium. H2O-present conditions during a dehydration reaction in metapelites of the Adula nappe (central Alps) could also have been of short duration. These examples are consistent with a model in which basement rocks at deep crustal levels are dry for long periods of time and in which the development of equilibrium mineral assemblages and microstructures generally occurs over relatively short periods of time under transitory fluid-present conditions (caused by devolatilization and/or infiltration).

The system Na2O-CaO-MgO Al2O3-SiO2-H2O is proposed to model phase equilibria and mineral parageneses for low-temperature metamorphism of basaltic rocks. Univariant reactions marking the transitions between various sub-greenschist facies are identified and some have been experimentally determined. The introduction of Fe2O3 into the model system at fixed FeO/MgO ratio creates continuous reactions for facies boundaries and discontinuous reactions for invariant points of the model system. Both qualitative and quantitative effects on P-T displacement and phase compositions are discussed. The XFe3+ isopleths for epidote were plotted to exemplify the transition from the zeolite through prehnite-pumpellyite to prehnite-actinolite facies. T-XFe3+ relations were established for continuous and discontinuous reactions relating such facies transitions. Because of the common occurrence of two or three Ca-Al hydrosilicates in low-grade metabasites, an isobaric Al-Ca-Fe3+ projection from chlorite may be used to illustrate mineral assemblages and compositions of the coexisting Ca-Al silicates in the presence of quartz, albite, and chlorite. Reported occurrences in several classic burial metamorphic terrains and ocean-floor metabasites in ophiolites are described. Only the composition of a mineral from a buffered assemblage can constrain the intensive properties for metamorphism; previously reported compositional trends for pumpellyite and epidote with increasing metamorphic grade are oversimplified.

The chemical and structural alteration of metamict zircon crystals from a 619 ±17 (2σ) Ma old, posttectonic granite in the southern part of the Eastern Desert, Egypt was studied. The crystals show simple oscillatory growth zones with metamictization–induced fractures, which provided pathways for fluid infiltration. Electron and ion microprobe analyses reveal that metamict, i.e. U and Th–rich, areas are heavily enriched in Ca, Al, Fe, Mn, LREE, and a water species, and have lost Zr and Si as well as radiogenic Pb. These chemical changes are the result of an intensive reaction with a low–temperature (120—200°C) aqueous solution. The chemical reactions probably occurred within the amorphous regions of the metamict network. During the zircon–fluid interactions the metamict structure was partially recovered, as demonstrated by micro-Raman and -infrared measurements. A threshold degree of metamictization, as defined empirically by an α–decay dose, Dc, was necessary for zircons to undergo hydrothermal alteration. It is proposed that Dc marks the first percolation point, where the amorphous domains start to form percolating clusters in the metamict network and where bulk chemical diffusion is believed to increase dramatically. The time of the hydrothermal alteration is determined by a lower intercept age of a U-Pb SHRIMP discordia of 17.9 (2σ) Ma, which is in good agreement with an apatite fission track age of 22.2 (2σ) Ma. The hydrothermal alteration event occurred contemporaneously with the main rifting phase of the Red Sea and widespread low- temperature mineralizations along the Red Sea coast.

Water plays an important role in most processes within the Earth's mantle, e.g. transport phenomena, differentiation and seismic properties. This paper reviews the various aspects of water in the mantle, with a special emphasis on the water content in nominally anhydrous minerals, especially lower-mantle minerals. The saturation of the upper mantle with respect to water is calculated as a function of pressure, based on available water-solubility data obtained for upper-mantle minerals. The result indicates that the upper mantle is saturated at pressures between 2 and 4 GPa for bulk water contents of 250 to 700 ppm wt., as retrieved from measurements on mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs). Whereas up to 4000 ppm wt. of H2O could be dissolved in the upper mantle at pressures corresponding to 410 km depth, such a value is less than the 1.5–2.5 wt.% solubility stored in the hydrous phases of the transition zone. Water solubility in mantle perovskite is still controversial, because of the difficulty of synthesizing samples free of impurities. Reported data indicate that water solubility in perovskite decreases with increasing temperature and Al content. Water partitions preferentially into ferropericlase rather than into perovskite, and its water solubility increases with the incorporation of trivalent cations.

Studies of the inclusions contained in natural diamonds have shown the occurrence of minerals which must have formed at depths below the lithosphere and which may be closely matched with the silicate mineral assemblages determined by high pressure and temperature experimental studies for depths of 300 to 800 km in the Earth's mantle. The inclusions come principally from two main depth zones: (1) the lower asthenosphere and upper transition zone; (2) the Upper Mantle/Lower Mantle (UM/LM) boundary region and the uppermost LM. The inclusions from zone 1 are very largely majoritic garnets (with or without clinopyroxene) which indicate bulk compositions of eclogitic/metabasic affinity. The minerals from zone 2 include Ca-Si and Mg-Si perovskites and ferropericlase and are dominantly of metaperidotitic bulk composition, but include some possible metabasite assemblages. In many of these natural assemblages, the tetragonal almandine pyrope phase occurs rather than the garnet found in experiments.

As natural diamonds are believed to crystallize in fluids/melts, the hypothesis is developed that the restriction of diamonds and inclusions of particular compositions to the above two depth intervals is because they are controlled by loci of fluid/melt occurrence. Attention is focused on subduction zones because both suites of inclusions show some evidence of subducted protoliths. The lower zone (600–800 km) coincides with the region where dehydration may be expected for hydrous ringwoodite and dense hydrous Mg-silicates formed in subducted peridotites. The dehydration of lawsonite in subducted metabasites provides a particular location for melt formation and the inclusion of the shallower (~ 300 km) majoritic inclusions. For the deeper majoritic inclusions in the region of the upper transition zone, melt development may occur as a consequence of the hydrous wadsleyite-to-olivine transformation, and such melt may then interact with the upper crustal portion of a subducting slab. These suggestions offer an explanation of the depth restrictions and the compositional restrictions of the inclusions. The differences in δ13C values in the host diamonds for the two suites of inclusions may also be explained on this basis.

A specimen from Långban, Sweden, was found to consist largely of sjögrenite in which segregation and ordering of the metal cations had occurred, yielding an intergrowth of regions of two main types with compositions probably of or near Mg2/3Fe1/3(OH)2(CO3)1/6(H2O)0·4 and Mg12/13Fe1/13(OH)2(CO3)1/26(H2O)0·8. To a smaller extent segregation had proceeded further, giving regions probably approximating to the end-member Mg(OH)2.H2O. It is suggested that the names sjögrenite and pyroaurite be used for the 2H- and 3R- polytypes of this structure irrespective of Mg:Fe ratio, segregation, or cation ordering.

The molecular structure of the three vivianite-structure, compositionally related phosphate minerals vivianite, baricite and bobierrite of formula M32+(PO4)2.8H2O where M is Fe or Mg, has been assessed using a combination of Raman and infrared (IR) spectroscopy. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 3460, 3281, 3104 and 3012 cm−1 for vivianite. The high wavenumber band is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH-bending modes where a strong IR band centred around 1660 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH-bending bands fromstrongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. The Raman phosphate PO-stretching region shows strong similarity between the three minerals. In the IR spectra, complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong IR bands around 800 cm−1 are attributed to water librational modes. The spectra of the three minerals display similarities due to their compositions and crystal structures, but sufficient subtle differences exist for the spectra to be useful in distinguishing the species.

Our recent discovery of hazardous concentrations of arsenic in shallow sedimentary aquifers in Cambodia raises the spectre of future deleterious health impacts on a population that, particularly in non-urban areas, extensively use untreated groundwater as a source of drinking water and, in some instances, as irrigation water. We present here small-scale hazard maps for arsenic in shallow Cambodian groundwaters based on >1000 groundwater samples analysed in the Manchester Analytical Geochemistry Unit and elsewhere. Key indicators for hazardous concentrations of arsenic in Cambodian groundwaters include: (1) well depths greater than 16 m; (2) Holocene host sediments; and (3) proximity to major modern channels of the Mekong (and its distributary the Bassac). However, high-arsenic well waters are also commonly found in wells not exhibiting these key characteristics, notably in some shallower Holocene wells, and in wells drilled into older Quaternary and Neogene sediments.

It is emphasized that the maps and tables presented are most useful for identifying current regional trends in groundwater arsenic hazard and that their use for predicting arsenic concentrations in individual wells, for example for the purposes of well switching, is not recommended, particularly because of the lack of sufficient data (especially at depths >80 m) and because, as in Bangladesh and West Bengal, there is considerable heterogeneity of groundwater arsenic concentrations on a scale of metres to hundreds of metres. We have insufficient data at this time to determine unequivocally whether or not arsenic concentrations are increasing in shallow Cambodian groundwaters as a result of groundwater-abstraction activities.

A method for the preparation of chemically homogeneous powders by a weighing and gelling technique is described in detail. Stress is placed on the importance of the weight yield as an indication of the bulk chemical composition and on the chemical analysis of several portions to test the homogeneity. A list of recommended chemicals is included in an appendix.

Pyrite, the most widespread and abundant of sulphide minerals in the Earth's surficial rocks, commonly constitutes the primary opaque phase in ore deposits. Consequently, an understanding of the behaviour of pyrite and its relationships with coexisting phases during the metamorphism of pyritebearing rocks is vital to the interpretation of their genesis and post-depositional history. Metamorphism is commonly responsible for the obliteration of primary textures but recent studies have shown that the refractory nature of pyrite allows it to preserve some pre-metamorphic textures. Pyrrhotite in pyritic ores has often been attributed to the breakdown of pyrite during metamorphism. It is now clear that pyrrhotite can be primary and that the presence of pyrrhotite with the pyrite provides a buffer that constrains sulphur activity during metamorphism. Pyrite-pyrrhotite ratios change during metamorphism as prograde heating results in sulphur release from pyrite to form pyrrhotite and as retrograde cooling permits re-growth of pyrite as the pyrrhotite releases sulphur. Retrograde growth of pyrite may encapsulate textures developed during earlier stages as well as preserve evidence of retrograde events. Sulphur isotope exchange of pyrite with pyrrhotite tends to homogenise phases during prograde periods but leaves signatures of increasingly heavy sulphur in the pyrite during retrograde periods.

Microprobe analyses of Ca-rich pyroxenes crystallized in the melting ranges of a magnesian alkali basalt, a transitional basalt, an olivine tholeiite, a tholeiitic andesite, and an augite leucitite at pressures between 8 and 45 kb show complex variation. Ca-poor pyroxene precipitated only from the alkali basalt at pressures between 14 and 18 kb. Pyroxene falling near the Di-Hed join in the pyroxene quadilateral formed at all pressures and temperatures from the leucitite, whereas ‘Ca-rich’ pyroxene crystallizing from the other four compositions was Ca-poor augite to sub-calcic augite. The liquidus Ca-rich pyroxenes all show rising Al and Na and falling Ti with increasing pressure and temperature. Other elements show complex behaviour; all but the leucitite pyroxenes tend to make temporary excursions of solid solution towards Ca-poor pyroxene at intermediate pressures, returning to more Ca-rich compositions at high pressures. At sub-liquidus temperatures Na and Ti consistently rise with falling T at constant P and also with rising P at constant T in these pyroxenes. The behaviour of the other elements in these circumstances depends on the nature of the coexisting phases.

Fe/Mg distribution between Ca-rich pyroxene and liquid, in the form

has a constant value of 0.29 for three separate bulk compositions at widely differing temperatures and pressures. Distribution coefficients for Mg and Fe between pyroxenes and coexisting garnets at high pressures are very similar to those found in garnet pyroxenite xenoliths from Oahu, Hawaii. Systematic shifts in the apparent stoichiometry (all Fe taken as Fe2+) of the augite leucitite pyroxenes are thought to indicate that they have considerable Fe3+ contents at low pressure, decreasing as P rises. If so, they show a strong negative correlation between Na and Fe3+, which negates the customary practice of forming acmite before jadeite component when recalculating the analyses of high-pressure pyroxenes.

The sets of pyroxenes crystallized from each composition show consistent trends when plotted on such diagrams as jadeite vs Ca-Tschermak's ‘molecule’, which have often been used in attempts to discriminate natural pyroxenes formed in differing P-T environments. However, these new data show clearly that the bulk chemistry of the magma has a predominating influence on the composition of the pyroxenes crystallizing from it. Unless it is certain that a suite of natural pyroxenes have all precipitated from the same magma, it is probably pointless to attempt to deduce the relative P-T conditions of their formation from their major element chemistry.

Coesite has been found as an inclusion in garnet from the Mengzhong eclogite in Donghai county, northeastern Jiangsu province, eastern China. The host eclogite occurs closely associated with regionally developed gneiss and was formed under P-T conditions of about 810°C and more than 28 kbar.

End-members and species defined with permissible ranges of composition are presented for the true micas, the brittle micas, and the interlayer-deficient micas. The determination of the crystallochemical formula for different available chemical data is outlined, and a system of modifiers and suffixes is given to allow the expression of unusual chemical substitutions or polytypic stacking arrangements. Tables of mica synonyms, varieties, ill-defined materials, and a list of names formerly or erroneously used for micas are presented. The Mica Subcommittee was appointed by the Commission on New Minerals and Mineral Names of the International Mineralogical Association. The definitions and recommendations presented were approved by the Commission.

The soluble metal sulphate salts melanterite, rozenite, rhomboclase, szomolnokite, copiapite, coquimbite, hexahydrite and halotrichite, together with gypsum, have been identified, some for the first time, on the banks of the Rio Tinto, SW Spain. Secondary Fe-sulphate minerals can form directly from evaporating, acid, sulphate-rich solutions as a result of pyrite oxidation. Chemical analyses of mixtures of these salt minerals indicate concentrations of Fe (up to 31 wt.%), Mg (up to 4 wt.%), Cu (up to 2 wt.%) and Zn (up to 1 wt.%). These minerals are shown to act as transient storage for metals and can store on average up to 10% (9.5 — 11%) and 22% (20—23%), Zn and Cu respectively, of the total discharge of the Rio Tinto during the summer period.

Melanterite and rozenite precipitates at Rio Tinto are only found in association with very acidic drainage waters (pH <1.0) draining directly from pyritic waste piles. Copiapite precipitates abundantly on the banks of the Rio Tinto by (1) direct evaporation of the river water; or (2) as part of a paragenetic sequence with the inclusion of minor halotrichite, indicating natural dehydration and decomposition. The natural occurrences are comparable with the process of paragenesis from the evaporation of Rio Tinto river water under laboratory experiments resulting in the formation of aluminocopiapite, halotrichite, coquimbite, voltaite and gypsum.

We have developed a system using ‘forescatter detectors’ for backscattered imaging of specimen surfaces inclined at 50–80° to the incident beam (inclined-scanning) in the SEM. These detectors comprise semiconductor chips placed below the tilted specimen. Forescatter detectors provide an orientation contrast (OC) image to complement quantitative crystallographic data from electron backscatter patterns (EBSP). Specimens were imaged using two detector geometries and these images were compared to those collected with the specimen surface normal to the incident beam (normal-scanning) using conventional backscattered electron detector geometries and also to an automated technique, orientation imaging microscopy (OIM). When normal-scanning, the component of the BSE signal relating to the mean atomic number (z) of the material is an order of magnitude greater than any OC component, making OC imaging in polyphase specimens almost impossible. Images formed in inclined-scanning, using forescatter detectors, have OC and z-contrast signals of similar magnitude, allowing OC imaging in polyphase specimens.

OC imaging is purely qualitative, and by repeatedly imaging the same area using different specimen-beam geometries, we found that a single image picks out less than 60% of the total microstructural information and as many as 6 combined images are required to give the full data set. The OIM technique is limited by the EBSP resolution (1–2°) and subsequently misses a lot of microstructural information. The use of forescatter detectors is the most practical means of imaging OC in tilted specimens, but it is also a powerful tool in its own right for imaging microstructures in polyphase specimens, an essential asset for geological work.

At time-scales of 102 to 105 years, erosion by rivers, landslides and glaciers can exceed 5 mm/y. Sustained denudation at these rates is sufficient to account for many of the rapid rates of unloading or cooling that are revealed by geobarometric or thermochronologic studies. Because feedbacks exist among many surface processes, determinations of erosion rates on a few geomorphic processes can be adequate to estimate mean rates across an entire landscape. Rates of fluvial and glacial incision exert a dominant control on landscape lowering, because these rates set the local base level and modulate the flux from adjacent hillslopes. When rates of deformation are sufficiently rapid and sustained, a collisional orogen approaches a dynamic equilibrium or topographic steady state. Due to variations in erosion rates as a function of Late Cenozoic climate changes, such a steady state should be defined at time-scales longer than one climate cycle. During dynamic equilibrium, the geomorphic system displays a predictable configuration of interacting rivers, hillslopes and glaciated process zones. A dynamic equilibrium appears to prevail near Nanga Parbat, Pakistan, and the Southern Alps of New Zealand, where spatial variations in geomorphic erosion rates mimic variations in bedrock cooling rates at time-scales of 106 y.

Diagenetic illitic clays from seven North American bentonites of Ordovician, Devonian, and Cretaceous ages and from three subsurface North Sea sandstones of Permian and Jurassic ages have been examined by X-ray diffraction (XRD) and transmission and scanning electron microscopy (TEM and SEM). XRD indicates that the clays from the bentonites are randomly and regularly interstratified illite/smectites (I/S) with 30–90% illite layers, whereas the clays from the Jurassic and Permian sandstones are regularly interstratified I/S, with 80–90% illite layers, and illite respectively. TEM of shadowed materials shows that randomly interstratified I/S consists primarily of mixtures of elementary smectite and ‘illite’ particles (10 and 20Å thick respectively) and that regularly interstratified I/S and illite consist mainly of ‘illite’ particles 20–50 Å thick and > 50 Å thick respectively. Regularly interstratified I/S from bentonites and sandstones are similar with regard to XRD character and particle thickness distribution. These observations can be rationalized if the interstratified XRD character arises from an interparticle diffraction effect, where the smectite interlayers perceived by XRD, result from adsorption of exchangeable cations and water or organic molecules at the interfaces of particles generally < 50Å thick. A neoformation mechanism is proposed by which smectite is converted to illite with increasing depth of burial in sedimentary rocks, based on dissolution of smectite particles and the precipitation/growth of ‘illite’ particles occurring within a population of thin phyllosilicate crystals.

The crystallographic properties of the hydrated iron oxide obtained by the hydrolysis of FeCl3 are described. The characterizing X-ray powder pattern can be indexed on a tetragonal unit cell with a 10·48 and c 3·023 Å. This cell is shown to contain eight formula units of FeOOH but Cl- or other anions are necessary for the crystallization of the material The structure is that of hollandite or α-MnO2. The unit cell has been confirmed by electron diffraction from single crystals having dimensions about 5000 × 500 × 500 Å. and twinning, which produces hexagonal stars, has been studied. On heating, the structure breaks down and recrystallizes as α-Fe2O2, probably with an intermediate stage involving a spinel phase.