Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.     

The rheology of crystal-bearing basaltic magmas from Stromboli and Etna

Our ability to forecast volcanic hazards at active volcanoes stems from our knowledge of parameters affecting eruption dynamics. Persistent activity displayed by basaltic volcanic systems, such as Etna and Stromboli, is governed mainly by the textural evolution and rheological properties of eruptive products. Here, we investigate the high temperature (1131 °C < T < 1187 °C) rheological behavior and textural evolution of remelted natural basaltic magmas from Stromboli and Etna volcanic systems upon cooling and crystallization at atmospheric conditions. The pure liquid and subliquidus isothermal viscosities are investigated using a concentric cylinder apparatus by varying strain rate applied to the investigated materials. Detailed textural analysis has been performed in order to evaluate the effect of crystal distribution on the rheological evolution of magmas. At subliquidus conditions, the mineralogical assemblage is dominated by the presence of spinel and plagioclase with the occurrence of stable clinopyroxene only at the lowest temperatures (1157 and 1131 °C for the Stromboli and the Etna samples, respectively). The overall crystal fraction (?) varies between 0.06 and 0.27. In the high T regime the viscous response to applied stress and strain rate is strongly affected by the presence of even small amounts of crystals. Large discrepancies between measured and predicted viscosities obtained using the Einstein-Roscoe (ER) equation are also found at low crystal fractions. We find here that, at the investigated conditions, the physical effect caused by the presence of elongated crystals is orders of magnitude higher than that predicted by existing models which only account for spherical particles. It also appears that a weak shear thinning behavior occurs at the lowest temperatures investigated. Crystal shape and, with it, the strain-rate dependence of the rheological properties appear to play primary roles in influencing the transport properties of these basaltic magmas.     

Review of geology, alteration and origin of iron oxide–apatite deposits in the Cretaceous Ningwu basin, Lower Yangtze River Valley, eastern China: Implications for ore genesis and geodynamic setting

In the Cretaceous Ningwu volcano-sedimentary basin in the Yangtze River Valley metallogenic belt, eastern China, there are three areas with a dense distribution of magnetite or hematite deposits: the Meishan deposit in the north; Washan, Nanshan and Taocun deposits in the center; and the Zhongjiu and Gushan deposits in the south. The mineralization in the Ningwu basin is associated mainly with subvolcanic intrusions, consisting of gabbro–diorite porphyry and/or gabbro–diorite. Alteration zoning of these deposits is pronounced, and includes: (1) an upper light colored zone of argillic, kaolinite, silica, carbonate and pyritic alteration (2) a middle dark colored zone of diopside, fluorapatite–magnetite, phlogopite, and garnet with fluorapatite–magnetite; (3) a lower light colored zone of extensive albitic alteration. However, at the Gushan iron deposit, the lower light colored zone and the middle dark colored zone are absent, whereas the principal alteration is represented by silicification, kaolinization, and carbonatization.The iron oxide–apatite deposits in the Ningwu basin are typically magmatic–metasomatic origin and are similar to the Kiruna-type deposits in Scandinavia, particularly with respect to mineral assemblages, fabric and structure of the iron ores, occurrence of the orebodies and wall rock alteration. The iron oxide–apatite deposits of the Ningwu basin contain magnetite and/or hematite, with diopside or actinolite and apatite gangue. They were formed in a rift or extensional environment and the mineralization is associated with alkaline magmatism. The time interval between magmatism and related mineralization is very short.     

Porphyry Cu–Au–Mo–epithermal Ag–Pb–Zn–distal hydrothermal Au deposits in the Dexing area, Jiangxi province, East China—A linked ore system

Based on previous studies and detailed field investigations of the Dexing porphyry copper deposit, the Yinshan Ag-Pb-Zn deposit and the Jinshan shear zone – hosted gold deposit in the Dele Jurassic volcanic basin, in the northeastern Jiangxi province, East China, we propose that the three deposits share spatial, temporal and genetic relationships and belong to the same metallogenic system. Dexing is a typical porphyry Cu–Au–Mo deposit in which both ore-forming fluid and metals are derived from the granite porphyry. The Yinshan deposit consists of a porphyry copper ore located in the cupola of a quartz porphyry stock, in the lower part, and Ag–Pb–Zn ore veins in the upper part. The hydrothermal fluids were mainly derived from the magma in the early stages of the mineralizing event and became mixed with meteoric waters in the late stages. Its ore metals are magma-derived. Both the Jinshan base metal veins and the Hamashi, Dongjie and Naikeng quartz vein-type gold deposit are hosted by brittle–ductile structures, which are distal in relation to the porphyry intrusions and were formed by mixed magmatic fluids and meteoric water, whereas the gold was mainly leached from the country rocks (Mesoproterozoic Shuangqiaoshan Group phyllite and schist). The deposits show a distinct spatial arrangement from porphyry Cu, to epithermal Ag–Pb–Zn and distal Au. We suggest a porphyry–epithermal–distal vein ore system model for this group of genetically related mineral deposits. They were formed in a back-arc setting in a Middle Jurassic active continental margin, with magmas derived from the subducted slab.     

Mesozoic metallogeny in East China and corresponding geodynamic settings — An introduction to the special issue

The giant East China Mesozoic metallogenic province hosts some of the World’s largest resources of tungsten, tin, molybdenum, antimony and bismuth. Ores of gold, silver, mercury, lead, zinc, copper, uranium and iron are also of major importance. The province and its constituent metallogenic belts or regions (South China; Middle–Lower Yangtze River Valley; East Qinling–Dabie; Interior of North China Craton; Yan-Liao and North-east China) are the products of several pulses of igneous activity and mineralisation between ~240 and ~80 Ma. Each successive stage has produced a distinctive suite of deposits that can be readily related to the geodynamic evolution of the region during the Mesozoic. This geodynamic evolution is linked to a complex series of tectonic events, involving far-field-subduction, plate collisions, crustal thickening, post-collision collapse and rifting.     

A model of boiling for fluid inclusion studies: Application to the Bolaños Ag–Au–Pb–Zn epithermal deposit,Western Mexico

Boiling can be inferred from fluid inclusion microthermometry studies when a progressive increase in apparent salinity is observed along with a decrease of homogenization temperature (T_H) and depth, thus reflecting the partitioning of non-volatile solutes into the liquid phase during steam loss. We propose a model for fluid evolution during boiling based on mass and heat balance equations, which establishes paths in the T_H-salinity space that can be compared with fluid inclusion data to confirm or discard boiling. Additionally, the model allows calculating paleo-depths, for which the effect of steam bubbles lowering the hydrostatic pressure is taken into account.     

Karst springs as “natural” pluviometers: Constraints on the isotopic composition of rainfall in the Apennines of central Italy

This paper describes an indirect method to calculate the isotopic composition of rainfall by using the isotopic composition of karst springs fed by waters circulating in the most important regional aquifer of central Italy, i.e. the Mesozoic limestone sequence that forms the backbone of the Apennines. By using δ¹⁸O and δD data and the δ¹⁸O (and/or δD) average gradient for elevation, evaluated through the use of literature rainfall data and new measurements from a typical Alpine valley in northern Italy, the altitude of precipitation of their parent water has been re-calculated. Vertical descents of more than 2000 m, from recharge to discharge, have been assessed in some high flow-rate cold springs in the morphologically steep Adriatic sector of central Italy. A clear correlation between the vertical descents and more negative isotopic compositions at their relative emergence elevations is highlighted. In contrast, in the Tyrrhenian sector lower karstic drops (generally lower than 500 m) correlate with less negative isotopic composition of recharge areas.The δ¹⁸O iso-contour map of the “recalculated” parent rainfall in central Italy is more detailed than any possible isotopic map of rainfall made using pluviometers, unless large number of rainfall collectors were deployed on mountaintops. The data also show that the isotopic composition of rainfall depends on the source of the storm water. In particular, precipitation is isotopically heavier when originating in the Mediterranean Sea, and lighter when formed in the Atlantic Ocean. Consequently, the collision between air masses with such a different isotopic signature results in a relatively small latitudinal fractionation effect. The peninsular part of central Italy is very narrow, with several mountains and massifs more that 2000 m high, and any latitudinal variation in the isotopic composition between rainfall sourced in the Atlantic Ocean and in the Mediterranean Sea is much lower than that due to the isotopic fractionation due to elevation.     

Source, attenuation and potential mobility of arsenic at New Britannia Mine, Snow Lake, Manitoba

This study was to investigate the source, mobility and attenuation of As at the New Britannia Mine, Snow Lake, Manitoba. One major source of As contamination was determined to be an arsenopyrite residue stockpile (ARS) containing refractory Au in a waste rock impoundment. It appears that As is still moving through glacial clay at the base of the ARS into a confined aquifer even though the pile was capped in the year 2000. Arsenic is also being mobilized from a deposit of tailings, which formed following spills by previous owners, Nor Acme. Arsenic from the tailings is being mobilized by oxidation of arsenopyrite and reduction of arsenate to the more mobile arsenite by arsenate-reducing bacteria. This contamination is affecting a shallow unconfined aquifer and surface water flowing from the tailings through wetlands towards Snow Lake. Arsenic is being attenuated by adsorption to hydrated ferric oxides (HFO) in the tailings, wetland soils and aquatic plants. Although As in surface water, soils and plants along the flow path from the mine to Snow Lake are above Canadian drinking water guidelines, efficient natural attenuation by HFO in soils and plants of the wetlands have limited the concentration in Snow Lake to below drinking water standards.     

High-pressure thermo-elastic properties of beryl (Al<Subscript>4</Subscript>Be<Subscript>6</Subscript>Si<Subscript>12</Subscript>O<Subscript>36</Subscript>) from ab initio calculations,and observations about the source of thermal expansion

Ab initio calculations of thermo-elastic properties of beryl (Al₄Be₆Si₁₂O₃₆) have been carried out at the hybrid HF/DFT level by using the B3LYP and WC1LYP Hamiltonians. Static geometries and vibrational frequencies were calculated at different values of the unit cell volume to get static pressure and mode-γ Grüneisen’s parameters. Zero point and thermal pressures were calculated by following a standard statistical-thermodynamics approach, within the limit of the quasi-harmonic approximation, and added to the static pressure at each volume, to get the total pressure (P) as a function of both temperature (T) and cell volume (V). The resulting P(V, T) curves were fitted by appropriate EoS’, to get bulk modulus (K ₀) and its derivative (K′), at different temperatures. The calculation successfully reproduced the available experimental data concerning compressibility at room temperature (the WC1LYP Hamiltonian provided K ₀ and K′ values of 180.2 Gpa and 4.0, respectively) and the low values observed for the thermal expansion coefficient. A zone-centre soft mode \( P6/mcc \to P\bar{1} \) phase transition was predicted to occur at a pressure of about 14 GPa; the reduction of the frequency of the soft vibrational mode, as the pressure is increased, and the similar behaviour of the majority of the low-frequency modes, provided an explanation of the thermal behaviour of the crystal, which is consistent with the RUM model (Rigid Unit Model; Dove et al. in Miner Mag 59:629–639, 1995), where the negative contribution to thermal expansion is ascribed to a geometric effect connected to the tilting of rigid polyhedra in framework silicates.     

Topological changes of the photospheric magnetic field inside active regions: A prelude to flares?

The detection of magnetic field variations as a signature of flaring activity is one of the main goals in solar physics. Past efforts gave apparently no unambiguous observations of systematic changes. In the present study, we discuss recent results from observations that scaling laws of turbulent current helicity inside a given flaring active region change in response to large flares in that active region. Such changes can be related to the evolution of current structures by a simple geometrical argument, which has been tested using high Reynolds number direct numerical simulations of the MHD equations. Interpretation of the observed data within this picture indicates that the change in scaling behavior of the current helicity seems to be associated with a topological reorganization of the footpoint of the magnetic field loops, namely with the dissipation of small scales structures in turbulent media.