Solvation processes in steam: Ab initio calculations of ion-solvent structures and clustering equilibria

Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H₃O⁺·(H₂O)_m and the more weakly bound water oligomers (H₂O)_m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H₃S⁺·(H₂O)_m(H₂S)_n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H₂O and H₂S onto H₃O⁺, and H₃S⁺ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H₂S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H₂O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔH^o = −44.0 kJ mol⁻¹, ΔS^o = −118.8 J K mol⁻¹). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H₃O⁺, and H₃S⁺ ions exists as solvated moieties.     

The hydrolysis and precipitation of Pd(II) in 0.6 mol kg NaCl: A potentiometric, spectrophotometric, and EXAFS study

The soluble and insoluble hydrolysis products of palladium were investigated in aqueous solutions of 0.6 mol kg⁻¹ NaCl at 298.2 K. Potentiometric titrations of millimolal palladium(II) solutions were used to monitor hydrolysis reactions of the mononuclear PdCl₃OH²⁻ and species. Spectrophotometric titrations were also used to corroborate the speciation change and to extract the correlative molar absorption coefficients for the PdCl₃OH²⁻ species in the 210-320 nm range. Longer-term potentiometric titrations systematically yielded precipitates which matured over a period of 6 weeks and resulted in a more extensive release of protons to the solution. Precipitation experiments in the 3-11 pH range showed the dominant precipitating phase to be Pd(OH)_1.72Cl_0.28. EXAFS measurements yielded an average of 3.50 O and 0.50 Cl atoms per Pd atom with a Pd-O distance of 2.012 Å and a Pd-Cl distance of 2.185 Å. Speciation modeling of proton and palladium mass balance data of experiments for palladium concentrations ranging from 0.047 to 10.0  mmol kg⁻¹ required the presence of polynuclear complexes containing 3-9 palladium atoms. The existence of such complexes is moreover supported by previous investigations of palladium hydroxide chains of the type [Pd(OH)_1.72Cl_0.28]_n, that are coiled and/or aggregated into nanometer-sized (15-40 Å) spheroids.     

Dating of young (<1 Ma) tephras: Using U‐Pb (zircon) and (U‐Th[‐Sm])/He (zircon,apatite, magnetite) chronometers to unravel the eruption age of a tephra in the Woodlark Rift of Papua New Guinea

The dating of volcanic tephras forms a critical cornerstone of chronostratigraphy and is paramount for the resolution of the geological timescale. (U‐Th[‐Sm])/He dating is an emerging tool in Quaternary tephrochronology and ideally suited to date tephras <1 Ma. We present zircon, magnetite and apatite (U‐Th[‐Sm])/He combined with zircon U‐Pb data for a Pleistocene tephra in syn‐rift strata of the Woodlark Rift in Papua New Guinea. The results reveal a young He age mode (~0.5 to 0.8 Ma), consistent with an autocrystic zircon U‐Pb crystallisation age of 0.8 ± 0.1 Ma, as well as a broad range of older (U‐Th[‐Sm])/He (~1.6 to 10.2 Ma) and U‐Pb (~4.4 to 107 Ma) ages. These data demonstrate the potential of integrated U‐Pb and (U‐Th[‐Sm])/He multi‐method chronometry for dating the youngest coherent age mode, detecting contaminant grains and evaluating the isotopic systematics of these techniques.     

The Punjab foreland basin of Pakistan: a reinterpretation of zircon fission‐track data in the light of Miocene hinterland dynamics

Sedimentary basins represent an archive of tectonic events of the hinterland source regions. By determining the variation in sediment lagtime over time, events can be distinguished which may no longer be available as the source has been eroded. In regions characterized by rapid exhumation this is most often the case but the erosion products form a record of these events. Detrital zircon fission‐track ages from sediments of the Siwalik basin, Pakistan, originally presented by Cerveny et al. (New Perspectives in Basin Analysis, Springer‐Verlag, New York, 1988, p. 43), have been reinvestigated and reinterpreted using a revised methodological approach. Detrital age populations were determined from different stratigraphic levels and were correlated through time in order to assess the change in lag time over the stratigraphic section. This information was combined with the many new ages from the hinterland to further interpret events in the source region. The new investigation suggests that steady‐state evolution has not always existed. An overall trend of exhumation increasing by 0.1 mm Myr^?1 (from 0.9 to 2.65 mm yr^?1) from 18 Ma to the present is evident with a major exception of a net pulse between 11.7 and 10.9 Ma associated with an increase in sedimentation increasingly rich in hornblende. Earlier studies suggested that at this time the source of the sediments was the presently outcropping Kohistan Arc. We are able to demonstrate that this cannot be so but was rather the rapidly exhuming Nanga‐Parbat Haramosh syntaxis (> 2 mm yr^?1) coevally with transpressional displacement along the Main Karakorum Thrust, whereby the overlying Kohistan Arc sequences were removed. Furthermore, comparison of our detrital thermochronological data set with another one from the same basin and one from another foreland basin to the east, in NW India suggest that the Himalayan orogenesis was probably not synchronous for the late Early–Middle Miocene. Overall, regions that undergoes today's rapid uplift may be useless to reconstruct earlier phases of exhumation as the levels that may have yielded such info were eroded and deposited into the adjacent basin(s). Such scenario is reproducible in most orogens as in the Himalaya in NW Pakistan stressing the high potential of detrital thermochronological studies to trace hinterland dynamics. Terra Nova, 18, 248–256, 2006     

Focused subaerial erosion during ridge subduction: impact on the geomorphology in south‐central Peru

Data obtained from low‐temperature thermochronometers such as apatite fission‐track and (U‐Th)/He are combined with morphometric information extracted from digital elevation models. This combination shows several geomorphological effects that are caused by the migration of the Nazca Ridge along the Peruvian Coastal margin. Offshore, the depth of the deep‐sea trench decreases by ～1500 m where the Nazca Ridge collides with the continental South American Plate. Onshore the ridge causes an uplift of at least 800 m in the Coastal Cordillera. This uplift results in a westward shift of the coastline thereby focusing and increasing erosion in the uplifted areas. At the trailing edge, the shelf subsides and the coastline retreats eastwards, producing at least part of the indentation observed between Paita and Pisco. The Ridge acts therefore like a wave uplifting the Andean margin as it traverses inland and southwards leaving a clear fingerprint on the topographic evolution of the Peruvian coastal margin.     

Hydrosulfide/sulfide complexes of copper(I): Experimental confirmation of the stoichiometry and stability of Cu(HS)2− to elevated temperatures

The solubility of chalcocite has been measured over the temperature range 35-95°C at pH 6.5-7.5 in aqueous hydrosulfide solutions in order to determine the stability constants of the Cu(HS)₂⁻ complex. A heated flow-through system was used in which solutions are collected at temperature to avoid the problem of copper precipitation due to quenching. The quality of the data was sufficient to resolve a 0.1 log unit increase of the dissolution/complexation equilibrium constant with each 10°C increase in temperature. The equilibrium constants were fit using previously published methods to obtain the values of thermodynamic parameters for the Cu(HS)₂⁻ complexation reaction. To compare results with predictive techniques, one-term and two-term isocoulombic extrapolation methods were applied to the stability constants measured below 100°C. The two-term extrapolation to 350°C showed excellent agreement with the derived constants proving its applicability to soft metal-soft ligand interactions. The one-term method gave a reasonable agreement but deviated about one logarithmic unit at 350°C. This is attributed to differences in energetic, volumetric, and structural properties of the reactants and products. Speciation calculations show that at low temperatures (<150°C), the hydrosulfide complexes of copper will dominate over chloride complexes at low salinites (<0.1 mol kg⁻¹) while at higher temperatures, chloride complexes will be dominant under most geological conditions. Only in solutions with high reduced sulfur content and alkaline pH values will hydrosulfide complexes predominate and may play a role in the generation of economic copper mineralization.     

Determination of the first ionization constant of silicic acid from quartz solubility in borate buffer solutions to 350°C

The solubility of quartz has been determined in borax buffer solutions having total boron concentrations of 0.10, 0.20, 0.40 and 0.60 mol kg^?1 and over the temperature range 130–350°C at the saturated vapour pressure of the system. The first ionization constant of silicic acid was calculated from the solubility data and varied from ?logK₁ = 8.88 (± 0.15) at 130°C to ?logK₁ = 10.06 (± 0.20) at 350°C. The solubility of quartz in these solutions was due to the presence of the three species, H₄SiO₄, H₃SiO₄^? and NaH₃SiO₄°. The equilibrium constant for the reaction, Na⁺ + H₃SiO₄^? = NaH₃SiO₄° extended from log K_as = 1.18?1.40 (± 0.20) over the temperature interval 135–301°C. The formation of NaH₃SiO₄° ion pairs was concluded to contribute significantly to the solubility of quartz in alkaline hydrothermal solutions when pH > 8 and sodium concentration exceeds 0.10 mol kg^?1.     

Thermotectonic evolution of an extensional dome: the Cenozoic Osogovo–Lisets core complex (Kraishte zone,western Bulgaria)

The Kraishte region of Bulgaria is located at the junction of the Balkanides and Hellenides-Dinarides tectonic belts. Fission-track analysis on both apatites and zircons documents the Cenozoic exhumation of a Precambrian basement bounded by low-angle detachments. Late Eocene–Oligocene extension began prior to 47 Ma and was dominantly in a top-to-the-southwest direction, confirmed by the sense of younging of apatite and zircon ages. This crustal extension controlled the formation of half-graben sedimentary basins on the hanging walls of the detachments. Thermal modelling of these hanging wall units provides evidence for heat transfer across the detachments from a relatively warm rising footwall. From 32 to 29 Ma, pervasive magmatic activity resulted in the emplacement of rhyolitic to dacitic subvolcanic bodies and dykes, along with intrusion of the Osogovo granite. The results give evidence for extension in the southern Balkan older than, and separated from, the Miocene to Quaternary Aegean extension. This might reflect transtension during northeastward extrusion and rotation of continental fragments around the western boundary of Moesia. Eocene–Oligocene extension seems to have been controlled by the distribution of earlier thickening all around the Carpatho-Balkanic orocline, which is reflected by the Cretaceous emplacement of the Morava Nappe in the Kraishte.