Cathodoluminescence imaging and titanium thermometry in metamorphic quartz

Cathodoluminescence (CL) of quartz from metamorphic rocks representing a range of conditions from the garnet grade to the migmatite grade reveals a variety of textures, that is, a function of metamorphic grade and deformation history. Ti concentrations, determined by electron microprobe and ion microprobe, generally correlate with CL intensity (blue wavelengths), and application of the Ti‐in‐quartz thermometer (TitaniQ) reflects the temperature of quartz growth or recrystallization, and, in some settings, modification by diffusion. Quartz from garnet grade samples is not visibly zoned, records temperatures of 425–475 °C, and is interpreted to have recrystallized during fabric formation. Quartz grains from staurolite grade samples are zoned in CL with markedly darker cores and brighter rims, some of which are interpreted to have been produced by the dominant staurolite‐producing reaction, whereas others are interpreted as having formed by diffusion of Ti into quartz rims. Quartz from the matrix of kyanite and sillimanite grade samples are generally unzoned, although locally displays slightly brighter rims (higher Ti); quartz inclusions within garnet and staurolite have distinctly brighter rims, which are interpreted as having been produced by diffusive exchange with the host mineral. Quartz from migmatite grade samples displays highly variable CL intensity, which is dependent on the location of the grain. Matrix grains in melanosomes are largely unzoned or rarely zoned with darker cores. Leucosome quartz is strongly zoned with bright cores and dark rims and is interpreted as having formed during crystallization of the melt. Locally within the leucosome is observed oscillatory‐zoned quartz, which is interpreted as a subsolidus recrystallization to achieve strain relaxation. Quartz inclusions within garnet or plagioclase crystals often show bright domains separated by zones of dark CL. These enigmatic textures possibly reflect local melting fluxed by fluid inclusions. Temperatures calculated from the Ti–in–quartz thermometer are a function of the metamorphic grade of the sample, the textural setting of the quartz, the reaction history and the deformation history of the rock. The TitaniQ temperatures can be used to constrain the conditions at which various metamorphic processes have occurred.     

The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Trace Element Partitioning and Accessory Phase Saturation during H2O-Saturated Melting of Basalt with Implications for Subduction Zone Chemical Fluxes

Experimental phase equilibrium and trace element partitioningdata are reported for H₂O-saturated mid-ocean ridge basalt at2·5 GPa, 750–900°C and oxygen fugacities atthe nickel–nickel oxide buffer. Garnet, omphacite andrutile are present at all temperatures. Amphibole and epidotedisappear as residual phases above 800°C; allanite appearsabove 750°C. The Na–Al-rich silicate glass presentin all run products is likely to have quenched from a supercriticalliquid. Trace element analyses of glasses demonstrate the importantcontrol exerted by residual minerals on liquid chemistry. Inaddition to garnet, which controls heavy rare earth elements(HREE) and Sc, and rutile, which controls Ti, Nb and Ta, allanitebuffers the light REE (LREE; La–Sm) contents of liquidsto relatively low levels and preferentially holds back Th relativeto U. In agreement with previous experimental and metamorphicstudies we propose that residual allanite plays a key role inselectively retaining trace elements in the slab during subduction.Experimental data and analyses of allanite-bearing volcanicrocks are used to derive a model for allanite solubility inliquids as a function of pressure, temperature, anhydrous liquidcomposition and LREE content. The large temperature dependenceof allanite solubility is very similar to that previously determinedfor monazite. Our model, fitted to 48 datapoints, retrievesLREE solubility (in ppm) to within a factor of 1· 40over a pressure range of 0–4 GPa, temperature range of700–1200°C and for liquids with anhydrous SiO₂ contentsof 50–84 wt %. This uncertainty in LREE content is equivalentto a temperature uncertainty of only ± 27°C at 1000K, indicating the potential of allanite as a geothermometer.Silicic liquids from either basaltic or sedimentary protolithswill be saturated in allanite except for Ca-poor protolithsor at very high temperatures. For conventional subduction geothermsthe low solubility of LREE (+ Th) in liquids raises questionsabout the mechanism of LREE + Th transport from slab to wedge.It is suggested either that, locally, temperatures experiencedby the slab are high enough to eliminate allanite in the residueor that substantial volumes of H₂O-rich fluids must pass throughthe mantle wedge prior to melting. The solubility of accessoryphases in fluids derived from subducted rocks can provide importantconstraints on subduction zone thermal structure. KEY WORDS: subduction; experimental petrology; allanite; solubility; supercritical liquid; eclogite     

Numerical Modelling of Dissolving and Driving Exploitation of Potash Salt in the Qarhan Playa——A Coupled Model of Reactive olute Transport and Chemical Equilibrium in a Multi-component Underground Brine System

Firstly, the macroscopic chemical equilibrium state of a series of chemical reactions between intercrystal brine and its media salt layer (salt deposit) in Qarhan Salt Lake was studied by using the Pitzer theory. The concept of macroscopic solubility product and its relation with accumulated ore dissolving ratio were presented, which are used in the numerical model of dissolving and driving exploitation of potassium salt in Qarhan Salt Lake. And secondly, with a model forming idea oftransport model for reacting solutes in the multi-component fresh groundwater system in porous media being a reference, a two-dimensional transport model coupled with a series of chemical reactions in a multi-component brine porous system (salt deposits) was developed by using the Pitzer theory.Meanwhile, the model was applied to model potassium/magnesium transport in Qarhan Salt Lake in order to study the transfer law of solid and liquid phases in the dissolving and driving process and to design the optimal injection/abstraction strategy for dissolving and capturing maximum Potassium/Magnesium in the mining of salt deposits in Qarhan Salt Lake.     

Numerical Modelling of Dissolving and Driving Exploitation of Potash Salt in the Qarhan Piaya——A Coupled Model of Reactive Solute Transport and Chemical Equilibrium in a Multi-component Underground Brine System

Firstly,the macroscopic chemical equilibrium state of a series of chemical reactions between intercrystal brine and its media salt layer (salt deposit) in Qarhan Salt Lake was studied by using the Pitzer theory.The concept of macroscopic solubility product and its relation with accumulated ore dissolving ratio were presented,which are used in the numerical model of dissolving and driving exploitation of potassium salt in Qarhan Salt Lake.And secondly,with a model forming idea of transport model for reacting solutes in the multi-component fresh groundwater system in porous media being a reference,a two-dimensional transport model coupled with a series of chemical reactions in a multi-component brine porous system (salt deposits) was developed by using the Pitzer theory. Meanwhile,the model was applied to model potassium/magnesium transport in Qarban Salt Lake in order to study the transfer law of solid and liquid phases in the dissolving and driving process and to design the optimal injection/abstraction strategy for dissolving and capturing maximum Potassium/ Magnesium in the mining of salt deposits in Qarban Salt Lake.     

Vertical distribution and water solubility of phosphorus and heavy metals in sediments of the St. Lucie Estuary, South Florida, USA

Accumulation and distribution of heavy metals and phosphorus in sediments impact water quality. There has been an increasing concern regarding fish health in the St. Lucie Estuary, which is related to increased inputs of nutrients and metals in recent decades. To investigate vertical changes of contaminants (P, Cd, Cr, Co, Cu, Ni, Pb, Zn, and Mn) in sediments of the St. Lucie Estuary in South Florida, 117 layer samples from six of the 210 to 420 cm depth cores were analyzed for their total and water-soluble P and heavy metals, clay, total Fe, Al, K, Ca, Mg, Na, and pH. Principal component analysis (PCA) was used in two sets of analytical data (total and water-soluble contaminant concentrations) to document changes of contaminants in each core of sediments. The PCA of total contaminants and minerals resulted in two factors (principal components). The first and second factors accounted for 61.7 and 17.2 % of the total variation in all variables, and contrast indicators associated with contaminants of P, Cd, Co, Cr, Ni, Pb, Zn, and Mn and accumulation of Fe and Al oxides, respectively. The first factor could be used for overall assessment of P and heavy metal contamination, and was higher in the upper 45–90 cm than the lower depths of each core. The concentrations of P and heavy metals in the surface layers of sediments significantly increased, as compared with those in the sediments deeper than 45–90 cm. The PCA of water-soluble contaminants developed two factors. The second factor (Cu–P) was higher in the upper than the lower depths of the sediment, whereas the highest score of the first factor (Cd–Co–Cr–Ni–Pb–Zn–Mn) occurred below 100 cm. The water-soluble Cu and P concentrations were mainly dependent on their total concentrations in the sediments, whereas the water-soluble Cd, Co, Cr, Ni, Pb, Zn, and Mn concentrations were mainly controlled by pH.     

Mechanisms of physico-chemical interaction of mercury with river sediments from a gold mining region in Brazil: Relative mobility of mercury species

Mercury accumulation in the food chain, as a consequence of gold recovery in Brazil, has been an issue of concern. Reactions of Hg in the environment are quite complex, and can involve various Hg chemical species. Laboratory experiments were carried out on Hg⁰ solubility, Hg complexation and sorption on river sediments from a gold mining region in Brazil. The reactivity and the mobility of Hg species were considered. Results indicate that methyl mercury is more mobile than ionic mercury, and that the presence of humic acid enhances drastically the solubility of Hg⁰. The soluble complex formed has a relatively lower interaction at the sediment/water interface and is more prone to spread through the aquatic environment.     

金伯利岩中新发现的两种Zr-Ti、REE-Ti氧化物矿物──上地幔含大阳离子Cr、Ti、Fe氧化物矿物研究之四

在研究沂蒙矿、蒙山矿等地幔矿物时，新发现了两种Zr－Ti、REE－Ti氧化物矿物。Zr－Ti氧化物新相6个样品点的探针成分分析（wt％）：TIO227.756～46.811，ZrO231.724～58.092，TFeo2.75～5．82，CrO31．728～4．765，Nb2O51．353～4．357，Ta2O50．155～2.814，SiO20．894～13．749，主次元素的成分变化幅度均较大，但以氧为4计算的阳离子总数均为2，因此分子式可简写为（Ti，Zr，Si，Fe）2O4或（Ti，Zr）2O4，与人工化合物ZrTiO4相似。REE－Ti氧化物矿物新相的成分也较复杂，主要元素为REE（Ce，Nd，La，Sm，Pr…）及Ti，次要元素有Nb，根据五个样点的探针分析结果，简化的分子式（Ce…）2（Ti…）3O9，与人工化合物Ce2Ti3O8.7类似，属等轴晶系。两个新矿物相均产于蒙山矿中的微裂隙和熔融交代海绵边中，呈斑点状、蠕虫状、微脉状，组成元素复杂，不同颗粒分析点成分有差异，且在同一微脉中成分也有变化，反映了这两种新矿物相是非平衡的交代一结晶产物。从矿物的产出关系和成分的特征来看，它们的形成与地幔流体交代作用有关。     

热液中二氧化硅与成矿元素锡络合作用的实验标定

热液中二氧化硅与成矿元素锡络合作用的实验标定＊樊文苓陈紫新王声远田弋夫（中国科学院矿床地球化学开放研究实验室，贵阳５５０００２）关键词锡石溶解度二氧化硅的络合作用迁移形式前人对锡在流体中迁移形式的实验研究和热力学计算表明，锡（Ⅱ）的多种氯络合物是高温...     

The Solubility of Sulphur in Hydrous Rhyolitic Melts

Experiments performed at 2 kbar, in the temperature range 800–1000°C,with fO₂ between NNO–2·3 and NNO+2·9 (whereNNO is the nickel–nickel oxide buffer), and varying amountsof sulphur added to hydrous metaluminous rhyolite bulk compositions,were used to constrain the solubility of sulphur in rhyolitemelts. The results show that fS₂ exerts a dominant control onthe sulphur solubility in hydrous silicate melts and that, dependingon fO₂, a rhyolitic melt can reach sulphur contents close to1000 ppm at high fS₂. At fO₂ below NNO+1, the addition of ironto a sulphur-bearing rhyolite magma produces massive crystallizationof pyrrhotite and does not enhance the sulphur solubility ofthe melt. For a given fO₂, the melt-sulphur-content increaseswith fS₂. For fixed fO₂ and fS₂, temperature exerts a positivecontrol on sulphur solubilities, at least for fO₂ below NNO+1.The mole fraction of dissolved sulphur exhibits essentiallylinear dependence on fH₂S at low fO₂ and, although the experimentalevidence is less clear, on fSO₂ at high fO₂. The minimum insulphur solubility corresponds to the redox range where bothfH₂S and fSO₂ are approximately equal. A thermodynamic modelof sulphur solubility in hydrous rhyolite melts is derived assumingthat total dissolved sulphur results from the additive effectsof H₂S and SO₂ dissolution reactions. The model reproduces wellthe minimum of sulphur solubility at around NNO+1, in additionto the variation of the sulphide to sulphate ratio with fO₂.A simple empirical model of sulphur solubility in rhyoliticmelts is derived, and shows good correspondence between modeland observations for high-silica rhyolites. KEY WORDS: sulphur; solubility; rhyolite; thermodynamics; fO₂; fS₂