The measurement of sulfate mineral solubilities in the Na-K-Ca-Cl-SO4-H2O system at temperatures of 100, 150 and 200°C

At T > 100°C development of thermodynamic models suffers from missing experimental data, particularly for solubilities of sulfate minerals in mixed solutions. Solubilities in Na⁺-K⁺-Ca²⁺-Cl⁻-SO₄²⁻/H₂O subsystems were investigated at 150, 200°C and at selected compositions at 100°C. The apparatus used to examine solid-liquid phase equilibria under hydrothermal conditions has been described.In the system NaCl-CaSO₄-H₂O the missing anhydrite (CaSO₄) solubilities at high NaCl concentrations up to halite saturation have been determined. In the system Na₂SO₄-CaSO₄-H₂O the observed glauberite (Na₂SO₄ · CaSO₄) solubility is higher than that predicted by the high temperature model of Greenberg and Møller (1989), especially at 200°C. At high salt concentrations, solubilities of both anhydrite and glauberite increase with increasing temperature. Stability fields of the minerals syngenite (K₂SO₄ · CaSO₄ · H₂O) and goergeyite (K₂SO₄ · 5 CaSO₄ · H₂O) were determined, and a new phase was found at 200°C in the K₂SO₄-CaSO₄-H₂O system. Chemical and single crystal structure analysis give the formula K₂SO₄ · CaSO₄. The structure is isostructural with palmierite (K₂SO₄ · PbSO₄). The glaserite (“3 K₂SO₄ · Na₂SO₄”) appears as solid solution in the system Na₂SO₄-K₂SO₄-H₂O. Its solubility and stoichiometry was determined as a function of solution composition.     

The impact of hydrological changes on travertine deposits related to thermal springs in the Pamukkale area (SW Turkey)

Pamukkale thermal waters (35 °C), exhibiting calcium-bicarbonate-sulfate composition and high carbon dioxide concentration, are of a predominantly meteoric origin. The meteoric fluid, circulating through faults and fractures, is heated by magmatic intrusions at great depth, and ascends from deep reservoirs to the surface. Mixing with relatively cold groundwater in the near surface zone promotes different saturation conditions with respect to calcium carbonate that later precipitates at depth and/or the surface. Dissolution-deposition processes of calcium carbonate both at surface and depth environments may help to reconstruct past climate direction in the field. During wet climate conditions a high-rate of calcium carbonate accumulation would be expected to occur at the surface because thermal fluid would be under-saturated with respect to calcium carbonate at depth because of a relatively higher mixing ratio with cold groundwater. During dry climate conditions the thermal fluid would be super-saturated at depth because of the highly acidic environment. Hydrometeorological studies reveal that the annual precipitation at the Pamukkale hydrothermal field tends to decrease with time. This climatic change in the area was also detected from geological records. While humid climate conditions prevailed during the late Quaternary, the area has recently been affected by arid/semi-arid climate conditions, followed by some episodic transitions. This study has shown how the system has possibly reacted to different climate conditions since antiquity.     

Influences of wastewater discharges on the water quality of Mamasın dam watershed in Aksaray, Central Anatolian part of Turkey

Sustaining the human ecological benefits of surface water requires carefully planned strategies for reducing the cumulative risks posed by diverse human activities. Municipal governments in Aksaray City play a key role in developing solutions to surface water management and protection problems. The responsibility to provide drinking water and sewage works, regulate the use of private land, and protect public health provides the mandate and authority to take action. A large part of Aksaray City uses Mamasın dam water as its primary source for drinking water. Several point sources of contamination may result from direct wastewater discharges from Melendiz and Karasu rivers, which recharge the Mamasın dam watershed. Relevant studies were carried out for monitoring the eutrophication process, which usually occurs in the static water mass of the Mamasın dam lake. This process may be caused by the continual increase in nutrients and decrease of O₂ levels, causing anaerobic conditions. Stimulated algae growth in these water bodies consequently reduces water quality. Hydrochemical parameters were evaluated to estimate the types of pollution sources, the level of pollution, and its environmental impacts on the Mamasın dam drinking water reservoir.     

Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.