New constraints on the thermodynamic equation of state of water and the predicted water fugacity dependence of OH-solubility at elevated P-T conditions along with its influence on dislocation dynamics in olivine are reviewed. Water is shown to control the style of tectonics of a planetary lithosphere by switching on highly localized weak faulting instead of a broad, slow creeping flow. The transition occurs above a water concentration of 200 ppm H/Si. We argue that this changeover in style of tectonics has important implications for the mechanics of subduction and for plate tectonics in general. Efficient recycling of water is only given if the top strong part of the lithosphere can fail and be dragged down into the mantle in a steady way. Due to different starting conditions and differences in accretion through planetismals, Venus may have never have reached a water content above 200 ppm H/Si in the upper mantle while Mars would have now left the plate tectonic regime due to fast cooling.

Transmission electron microscope samples were prepared of ALH 78045 and ALH 88045, two clay-and phyllosilicate-bearing Antarctic meteorites, using argon ion milling and focused ion beam (FIB) techniques. ALH 78045 contains clay- and phyllosilicate-filled veins that have formed by terrestrial weathering of olivine, orthopyroxene and metal. Very narrow (∼10 nm) intragranular clay-filled veins could be observed in the TEM samples prepared by argon ion milling, whereas differential thinning and lack of precision in the location of the electron-transparent areas hindered the study of wider (5 — 15 μm) phyllosilicate-filled intergranular veins. Using the FIB instrument, electron-transparent slices were cut from specific parts of the wider veins and lifted out for TEM study. Results show that these veins are occluded by cronstedtite, a mixed-valence Fe-rich phyllosilicate. This discovery shows that silicates can be both dissolved and precipitated during terrestrial weathering within the Antarctic ice. ALH 88045 is one of a small number of known CM1 carbonaceous chondrites. This meteorite is largely composed of flattened ellipsoidal aggregates of serpentine-group phyllosilicates. To determine the mineralogy and texture of phyllosilicates within specific aggregates, TEM samples were prepared by trenching into the cut edge of a sample using the FIB instrument. Results show that Mg-rich aggregates are composed of lath-shaped serpentine crystals with a ∼0.73 nm basal spacing, which is typical of the products of low temperature aqueous alteration within asteroidal parent bodies. Results of this work demonstrate that the FIB has enormous potential in a number of areas of Earth and planetary science.

Soil profiles developed in different climates and physical settings are highly variable in structure, in mineralogy, in the local biosphere and in the compositions of the soil gas and water phases. Discussion of metals in ‘the weathering environment’ needs to acknowledge and address this diversity.

The thermochemical methods developed by Pourbaix (1949) and Garrels and Christ (1965) remain useful predictors of metal speciation and solubility but the approach is valid only for processes involving carbonates, sulphides, hydroxides and similar minerals in soils and sediments. Almost no primary silicates are thermodynamically stable: they spontaneously decompose to non-equilibrium solid products with metal release determined by kinetics.

Hydrolysis constants for aquo-complexes are useful indicators of metal speciation, mobility and availability. Recent work on soluble soil organic matter confirms that the active ligands are overwhelmingly oxygen based: phenols, carboxylic acids, alcohols. Many of these molecules compete very effectively with aquo-complexes to form strong metal chelates and appear to be responsible for substantial Al and Fe mobilization within and translocation down soil profiles.

It is important to note also that strong clay mineral/organic matter associations (clay-organic complex) will fix metals as a consequence of the same chelation reactions (in this case removing them from solution - retardation).

Small domestic cooking furnaces are widely used in China. These cooking furnaces release SO2 gas and dust into the atmosphere and cause serious air pollution. Experiments were conducted to investigate the effects of vermiculite, limestone or CaCO3, and combustion temperature and time on desulphurization and dust removal during briquette combustion in small domestic cooking furnaces. Additives used in the coal are vermiculite, CaCO3 and bentonite. Vermiculite is used for its expansion property to improve the contact between CaCO3 and SO2 and to convey O2 into the interior of briquette; CaCO3 is used as a chemical reactant to react with SO2 to form CaSO4; and bentonite is used to develop briquette strength. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside the briquette, and thus brings enough oxygen for combustion and sulphation reaction. Effective combustion of the original carbon reduces amounts of dust in the fly ash. X-ray diffraction, optical microscopy, and scanning electron microscopy with energy dispersive X-ray analysis show that S exists in the ash only as anhydrite CaSO4, a product of SO2 reacting with CaCO3 and O2. The formation of CaSO4 effectively reduces or eliminates SO2 emission from coal combustion. The major factors controlling S retention are vermiculite, CaCO3 and combustion temperature. The S retention ratio increases with increasing vermiculite amount at 950°C. The S retention ratio also increases with increasing Ca/S molar ratio, and the best Ca/S ratio is 2-3 for most combustion. With 12 g of the original coal, 1 to 2 g of vermiculite, a molar Ca/S ratio of 2.55 by adding CaCO3, and some bentonite, a S retention ratio >65% can be readily achieved. The highest S retention ratio of 97.9% is achieved at 950°C with addition of 2 g of vermiculite, a Ca/S ratio of 2.55 and bentonite.

We report in this paper the first occurrence of the rare assemblage corundum + quartz in the high-grade metamorphic zone in the core of the Namaqualand Metamorphic Complex (NMC) (South Africa). The magnetite-bearing rocks hosting the corundum-quartz assemblage are very rare, and occur discontinuous bands a few cm wide, associated with diorite, tonalite and anorthosite within quartzfeldspar ± sillimanite ± biotite ± spinel supracrustal rocks extensively intruded by a foliated granite gneiss. The magnetite-bearing rocks are characterized by the presence of abundant crystals of magnetite together with ilmenite, spinel and large (∽1 cm in diameter) euhedral crystals of corundum both displaying a sharp contact with magnetite and quartz. However, in some micro-domains, spinel and quartz, as well as corundum and quartz, are separated by a thin corona of sillimanite with or without magnetite. These textural features suggest that the following reactions have taken place: quartz + corundum → sillimanite, and quartz + spinel + O2 → sillimanite + magnetite. These reactions are interpreted as occurring at higher, as yet unknown, P-T conditions than previously estimated for the NMC. Whether corundum and quartz were once in equilibrium is worth investigating, as it could constitute a geothermobarometric assemblage for ultra-high T granulites.

We summarize the main ideas used to determine the thermodynamic properties of pure systems and binary alloys from first principles calculations. These are based on the ab initio calculations of free energies. As an application we present the study of iron and iron alloys under Earth,s core conditions. In particular, we report the whole melting curve of iron under these conditions, and we put constraints on the composition of the core. We found that iron melts at 6350士600 K at the pressure corresponding to the boundary between the solid inner core and the liquid outer core (ICB). We show that the core could not have been formed from a binary mixture of Fe with S, Si or O and we propose a ternary or quaternary mixture with 8—10% of S/Si in both liquid and solid and an additional ~8% of oxygen in the liquid. Based on this proposed composition we calculate the shift of melting temperature with respect to the melting temperature of pure Fe of ~—700 K, so that our best estimate for the temperature of the Earth's core at ICB is 5650±600 K.

Alluvial rubies and sapphires are found in palaeodrainage deposits along the Cudgegong-Macquarie River system, central eastern New South Wales, Australia. A pink to red suite contains Cr (up to 0.6 wt.% Cr2O3) as the main chromophore, exceeding Fe (up to 0.5 wt.%Fe2O3). Corrosive etching suggests a prior xenocrystic Mesozoic-Cenozoic basaltic transport, while Cr2O3/Ga2O3 to Fe2O3/TiO2 ratios indicate an original metamorphic source. Syngenetic mineral inclusions include Al-rich diopside, meionite and anatase. The Al-rich diopside (‘fassaite’) contains extremely high Al2O3 (20–21 wt.%). A blue-green suite contains Fe (up to 0.8 wt.% Fe2O3) as a dominant chromophore, while a rare nepheline-anorthoclase composite inclusion supports a magmatic phonolitic origin. The Cudgegong- Macquarie ruby formation is compared with a garnet granulite origin proposed for Thailand rubies and a xenolith of corundum-bearing garnet granulite from Ruby Hill, Bingara, Australia. Clinopyroxenecorundum thermometry suggests the Cudgegong-Macquarie rubies formed at T >1000–1300ºC, a high equilibration T for proposed lithospheric granulites. These rubies form a distinctive suite compared to other rubies from Australian and SE Asian basalt fields, but have some similarities with eastern Thailand rubies.

Structural transformations between the different hydration states of three vermiculite samples from Sta. Olalla (Huelva, Spain), Paulistana (Piaui, Brasil) and West China, have been observed by X-ray diffraction at atmospheric pressure, P = 1.4 x 10–2 mbar and P = 2.4 x 10–4 mbar. The samples were studied in flake and powder forms. The effect of vacuum has been proven to be the same as that of temperature, i.e. it causes dehydration of vermiculite, but with a different evolution through the different hydration states. In fact, under vacuum, the process seems to be inhibited at a one-water layer hydration state (1-WLHS), without a further dehydration of samples to a zero-water layer hydration state (0-WLHS).

Furthermore, the dehydration process has been shown to occur through different interstratified states in each vermiculite. This result has been related to the interlayer Mg-cation content, due to its affinity to water molecules. The interstratified states have been analysed by the direct Fourier-transform method. The vermiculite from Sta. Olalla exhibits the most complex process, with formation of three different interstratified phases: two phases characterized by an interstratification of interplanar distances, d = 11.5 –13.8 Å and d = 9.6 –11.5 Å , respectively, and a practically segregated phase characterized by d = 13.8 Å . For the vermiculite from China, an interstratified phase not previously reported has been found, with an interplanar distance of 12.10 Å.

The inhibition of dehydration at 1-WLHS, as observed, could be used in applications such as adsorption and separation technology of gases and liquids, or in heterogeneous catalysis processes.

Fahlores [~(Cu,Ag)10(Zn,Fe)2Sb4S13] from the Keno Hill mining district, central Yukon, Canada record virtually the entire petrogenetic history of a Cretaceous hydrothermal system extending over 40 km outward from the Mayo Lake granitic pluton. These fahlores are an essential constituent of polymetallic sulphide veins developed in a graphitic Mississippian quartzite, where they occur in association with sphalerite, pyrargyrite, galena and siderite. Fahlores exhibit pronounced east-west zoning in average Ag/(Ag+Cu) and Zn/(Zn+Fe) values, with these simultaneously increasing and decreasing from east to west over 20 km of hydrothermal activity. These zonations are coupled with average Ag/(Ag+Cu) and Zn/(Zn+Fe) values in fahlore roughly paralleling the 300°C isotherm for fahlores in equilibrium with pyrargyrite, miargyrite and sphalerite in the simple system Ag2S-Cu2S-ZnS-FeS-Sb2S3. Early high-Ag, high-Zn fahlores from the eastern and western mines have Ag/(Ag+Cu) and Zn/(Zn+Fe) values requiring temperatures ≥400°C, in agreement with temperatures established from the As-content of arsenopyrite coexisting with pyrite, pyrrhotite and sphalerite. Ag/(Ag+Cu) and Zn/(Zn + Fe) values in later, main-stage fahlores are consistent with the 250–310°C range of temperatures established for boiling of Keno Hill fluids. Finally, Ag- and Fe-rich fahlores were produced by retrograde Fe-Zn exchange with sphalerite or crystallized from late-stage epithermal fluids which produced polybasite, stephanite, acanthite and wire silver. One such fahlore exhibits unmixing into high-Ag and low-Ag varieties. This is the first reported miscibility gap for freibergite fahlores and confirms the earlier prediction of such gaps.

Understanding the biogeochemical behaviour of arsenic in the weathering and shallow subsurface environment depends critically upon determining the nature and distribution of the chemical species present in natural waters. To this end, coupled ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) is widely used, though species fractionation during ultrasonic nebulization, and matrix-dependent ionization in the plasma are analytical issues that need to be addressed. Hexapole collision cell technology is shown to be effective in suppressing chloride-based polyatomic interferences. Irrespective of the analytical technique used, As(III)/As(V) ratios of natural waters may change substantially during storage due to (1) differential adsorption of arsenic species on hydrated ferric oxides (HFOs); and (2) microbial activity. A wide range of apparently contradictory speciation changes observed by various workers can be rationalized in terms of the differences of microbial consortia present in different water samples. Arsenic speciation in certain water types can be stabilized for days or even weeks by combined filtration, acidification and refrigeration whilst the addition of EDTA and the use of 0.1 mm filters is indicated for iron-rich waters and waters with high activities of redox-active bacteria, respectively. Although the use of hydrochloric acid has been reported elsewhere as resulting in the apparent oxidation of As(III), we show that for certain water types it acts as an extremely effective preservative of arsenic speciation.

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.

Lead, zinc and arsenic mobilization/attenuation processes during interactions between smelter slag and water show differences depending on the origin of the slag. The studied samples, waste from ore and car-battery processing, were submitted to long-term (365 days) batch leaching at two different initial pH values. The leachate analyses were input to the EQ3NR speciation-solubility code to speciate the solutions and determine the degree of saturation with respect to different phases, and a mineralogical investigation was made of the newly formed phases. An ‘oxidizing’ scenario can be proposed for slag waste disposal, considering that cerussite (PbCO3) at pH >6 becomes a major solubility-controlling phase for Pb, and newly formed hydrous ferric oxides (HFO – common secondary phases under oxidizing conditions) efficiently adsorb As. No efficient scavenging mechanism was found for Zn, which was progressively leached from the slag and in particular from the ore-processing slag. Quenched glass-rich slag from old car-battery processing was found to release significant amounts of Pb, especially in acidic environments. Neither slag would therefore be suitable for recycling for civil engineering purposes. Conversely, extremely low releases of Pb, Zn and As were observed for recent car-battery processing slag, which could therefore be considered for road construction.

Ilmenite concentrates obtained from heavy mineral deposits in the Murray Basin, southeastern Australia contain appreciable quantities (up to 10 wt.%) of an unusual hydrated Fe titanate mineral in the form of orange to red coloured translucent grains. The grains are weakly magnetic and have a low apparent density (<3.3 g cm–3) due to microprosity, which enables them to be easily concentrated in a pure state. Samples from different deposits have similar analyses of 67–69% TiO2, 8 –9% Fe2O3, 2–3% FeO, 11 –12% H2O and 8 –9% of intra-pore impurities, mainly SiO2 and Al2O3. The powder pattern for the mineral closely matches that for pseudorutile; having a hexagonal subcell with a = 2.844 (1) Å, c = 4.575 (1) Å. The idealized composition range of the Fe titanate, calculated from analyses and structure refinements, is [FeTi6O12(OH)3].3H2O to [FeTi6O11(OH)5].2H2O. The molecular water is nonstructural, probably adsorbed on the surfaces of nano-scale domains of the mineral. Electron microprobe and scanning electron microscopy studies provide evidence for formation of the mineral by replacement reactions acting on MgO-rich ferrian ilmenite grains. The mineral represents a distinct intermediate in the chemical weathering of ilmenite, having a pseudorutile-like structure but a leucoxene-like composition. It is unusual in not having undergone any recrystallization to phases such as rutile and anatase.

Borehole samples of carbonatites and phlogopite-pyroxenites from the Angico dos Dias (AdD) intrusive alkaline complex, State of Bahia, Brazil, have been investigated in terms of mineralogy, geochemistry and C-O-Sr-Nd isotopes. The AdD complex, of Early Proterozoic age (2 Ga), intrudes the northern side of the São Francisco Craton. Mineralogy and petrography indicate that the studied rocks only partially preserved their magmatic textural features owing to their metamorphic re-equilibration (greenschist facies). The REE contents and LREE/HREE ratios of the AdD carbonatites are very high (mean 3979±718 ppm and La/Yb = 215±23, respectively), as for most Precambrian magmatic carbonatites. The AdD carbonatites are also enriched in 18O (δ18O = 11.9 to 15.8‰), possibly due to secondary processes (e.g. metamorphism, alteration) whereas carbon isotopes are in the range of ‘primary carbonatites’ (δ13C = –5.7 to –7.1‰). Most of the initial 87Sr/86Sr and 143Nd/144Nd values of the studied carbonatites were not appreciably modified by secondary processes. Their εtSr and εtNd values (20.0 to 25 and 0.7 to –4.5, respectively) indicate enriched mantle sources very different from the ‘depleted’ ones related to many Precambrian carbonatites from North America (0.6 –2.6 Ga) and Africa (0.5 –2.0 Ga). The Early Proterozoic Sr-Nd isotopic signatures of the AdD carbonatites are similar to those of the Early Cretaceous carbonatites from the Paraná basin. The latter carbonatites show a great isotopic variability ranging from Bulk Earth to the related potassic magmatism from Asunción-Sapucai graben in the Eastern Paraguay (K-ASU magmatism: εtSr = 35 to 50 and εtNd = –12 to –20). The very similar isotopic compositions of Precambrian and post-Palaeozoic carbonatites worldwide indicate that the subcontinental mantle variability lasted for long periods of time and indicate a large-scale mantle heterogeneity.

Weakly peralkaline syenite ejecta within the plinian fall deposits of Agua de Pau volcano (São Miguel, Azores Islands) are divisible into (1) silica-undersaturated and (2) silica-saturated/oversaturated groups. The first group occurs in the pre-Fogo-A pyroclastic falls (15.2 ka) whereas the second occurs in the Fogo-A pumices (5 ka). The petrography indicates that the syenites of both groups crystallized at shallow depths and whole-rock geochemistry shows that they have compositions reflecting those of the Agua de Pau trachyte magmas. The syenites are inferred to be derived from solidification zones around the margins of the parental magma chamber. Mineral parageneses in both syenite groups permit distinction of three magmatic stages of crystallization: (1) an early crystallization stage; (2) a main crystallization stage during which most of the feldspar growth occurred; and (3) a late interstitial stage. Crystallization of the trachytic magmas yielded peralkaline residuals, highly enriched in volatiles, alkalis, HFSE and REE. In the silica-undersaturated syenites, the complex Zr-Ti silicate minerals, eudialyte and a låvenite-like mineral, crystallized interstitially from the residual magmas. In contrast, the zircono-silicate dalyite, and REE-rich minerals (chevkinite-(Ce), britholite-(Ce) and pyrochlore), together with thorite, were late-stage interstitial products of the silica-saturated/oversaturated syenites.

Au-Cu mineralization at Palai-Islica occurs as disseminations in massive silicified volcanic rocks and, more abundantly, in sulphide-bearing quartz veins. The major ore minerals in the deposit are pyrite ± chalcopyrite, sphalerite and galena and there is a great variety of accessory minerals, including Au-Ag alloys and native gold. Pyrite, the most abundant sulphide, is closely associated with gold. Seven different types of pyrite have been distinguished with a variable concentration of different trace elements. Among these, the only one free of trace elements (type IV) is related to Au-Ag alloys. Pyrite associated with these Au-Ag alloys has cubic and pentagonal dodecahedral habits, whereas pyrite with pentagonal dodecahedral habit only is from barren zones. In addition, there is no significant invisible gold in the pyrite, but there is a relatively large amount of Ag in collomorphic pyrite (up to 0.20 wt.%) or type III pyrite (up to 1.47 wt.%). Arsenic is the most abundant trace element in pyrite (up to 6.11 wt.%), present as a metastable solid solution or as a non-stoichiometric element. A variety of marcasite related to the gold levels also has a considerable amount of trace elements (As up to 1.15 wt.%, Sb up to 0.40 wt.%).