Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

The formation of metastable aluminosilicates in the Al-Si-H2O system: Results from solution chemistry and solid-state NMR spectroscopy

We present the results of a series of experiments designed to probe the interactions between Al and the amorphous silica surface as a function of thermodynamic driving forces. The results from ²⁷Al single pulse magic angle spinning (SP/MAS) and ²⁷Al{¹H} rotational echo double resonance (REDOR) allow us to identify the reaction products and constrain their structure. In all cases, despite low Al and Si concentrations we observe the formation of metastable aluminosilicates. Results from low temperature experiments indicate that despite thermodynamic driving forces for the formation of gibbsite we observe the precipitation of separate octahedrally coordinated Al (Al^[6]) and tetrahedrally coordinated Al (Al^[4]) silicate phases. At higher temperatures the Al^[4] silicate phase dominates the speciation. Structural models derived from the NMR data are also proposed, and the results are discussed as they relate to previous work on Al/Si cycling.     

The role of granites in volcanic-hosted massive sulphide ore-forming systems: an assessment of magmatic�Chydrothermal contributions

Assessment of geological, geochemical and isotopic data indicates that a significant subgroup of volcanic-hosted massive sulphide (VHMS) deposits has a major or dominant magmatic?Chydrothermal source of ore fluids and metals. This group, which is typically characterised by high Cu and Au grades, includes deposits such as those in the Neoarchean Doyon-Bousquet-LaRonde and Cambrian Mount Lyell districts. These deposits are distinguished by aluminous advanced argillic alteration assemblages or metamorphosed equivalents intimately associated with ore zones. In many of these deposits, ??³⁴S_sulphide is low, with a major population below ?3??; ??³⁴S_sulphate differs from coexisting seawater and ??³⁴S_{sulphate?Csulphide}????20?C30??. These characteristics are interpreted as the consequence of disproportionation of magmatic SO₂ as magmatic?Chydrothermal fluids ascended and cooled and as a definitive evidence for a significant magmatic?Chydrothermal contribution. Other characteristics that we consider diagnostic of significant magmatic?Chydrothermal input into VHMS ore fluids include uniformly high (>3 times modern seawater values) salinities or very ¹⁸O-enriched (??¹⁸O?>?5??) ore fluids. We do not consider other criteria [e.g. variable salinity, moderately high ??¹⁸O_fluid (2?C5??), ??³⁴S_sulphide near 0??, metal assemblages or a spatial association with porphyry Cu or other clearly magmatic-hydrothermal deposits] that have been used previously to advocate significant magmatic?Chydrothermal contributions to be diagnostic as they can be produced by non-magmatic processes known to occur in VHMS mineral systems. However, in general, a small magmatic?Chydrothermal contribution cannot be excluded in most VHMS systems considered. Conclusive data that imply minimal magmatic?Chydrothermal contributions are only available in the Paleoarchean Panorama district where coeval seawater-dominated and magmatic?Chydrothermal systems appear to have been physically separated. This district, which is characterised by chloritic and sericitic alteration assemblages and lacks aluminous advanced argillic alteration assemblages, is typical of many VHMS deposits around the world, suggesting that for ??garden variety?? VHMS deposits, a significant magmatic?Chydrothermal contribution is not required. Other than deposits associated with advanced argillic alteration assemblages, the only deposit for which we ascribe a major magmatic?Chydrothermal contribution is the Devonian Neves Corvo deposit. This deposit differs from other deposits in the Iberian Pyrite Belt and around the world in being extremely Sn-rich, with the Sn closely associated with Cu and in having formed from high ¹⁸O-rich fluids (??¹⁸O_fluid ??8.5??). We consider these characteristics, particularly the last, as diagnostic of a significant magmatic hydrothermal contribution. Our analysis indicates that two subgroups of VHMS deposits have a major magmatic?Chydrothermal contribution: Cu/Au-rich deposits with aluminous alteration assemblages and reduced, very Sn-rich deposits in which Sn was introduced in a high-temperature ore assemblage. Comparison with ??normal?? VHMS deposits suggests that these subgroups of VHMS deposits may form in specialised tectonic environments. The Cu/Au-rich deposits appear to form adjacent to magmatic arcs, an environment conducive to the generation of hydrous, oxidised melts by melting metasomatised mantle in the wedge above the subducting slab. This contrasts with the back-arc setting of ??normal?? VHMS deposits in which relatively dry granites (In this contribution, we use the term granite sensu latto) formed by decompression melting drive seawater-dominated hydrothermal circulation. The tectonic setting of highly Sn-rich VHMS deposits such as Neves Corvo is less clear; however, thick continental crust below the ore-hosting basin may be critical, as it is in other Sn deposits.     

Recent advances in offshore geotechnics for deep water oil and gas developments

The paper presents an overview of recent developments in geotechnical analysis and design associated with oil and gas developments in deep water. Typically the seabed in deep water comprises soft, lightly overconsolidated, fine grained sediments, which must support a variety of infrastructure placed on the seabed or anchored to it. A particular challenge is often the mobility of the infrastructure either during installation or during operation, and the consequent disturbance and healing of the seabed soil, leading to changes in seabed topography and strength. Novel aspects of geotechnical engineering for offshore facilities in these conditions are reviewed, including: new equipment and techniques to characterise the seabed; yield function approaches to evaluate the capacity of shallow skirted foundations; novel anchoring systems for moored floating facilities; pipeline and steel catenary riser interaction with the seabed; and submarine slides and their impact on infrastructure. Example results from sophisticated physical and numerical modelling are presented.     

Projecting uncertainty onto marine megafauna trajectories

In this study, a method is proposed for estimating the uncertainty of a Lagrangian pathway calculated from an undersampled ocean surface velocity field. The primary motivation and application for this method is the differentiation between active and passive movements for sea turtles whose trajectories are observed with satellite telemetry. Synthetic trajectories are launched within a reconstructed surface velocity field and integrated forward in time to produce likely trajectories of an actual turtle or drifter. Uncertainties in both the initial conditions at launch and the velocity field along the trajectory are used to yield an envelope of possible synthetic trajectories for each actual trajectory. The juxtaposition of the actual trajectory with the resulting cloud of synthetic trajectories provides a means to distinguish between active and passive movements of the turtle. The uncertainty estimates provided by this model may lead to improvements in our understanding of where and when turtles are engaged in specific behaviors (i.e. migration vs. foraging)—for which potential management efforts may vary accordingly.     

Comprehensive Utilization of Vanadium–Titanium Magnetite Deposits in China Has Come to a New Level

There are two production areas for vanadium-titanium magnetite deposits in China:the Panzhihua area in Sichuan Province and the Chengde area in Hebei Province. The Panzhihua vanadium titanomagnetite iron ore deposits are hosted by a mafic-ultramafic intrusive complex,and belong to late magmatic differentiation condensation of crystalline iron deposits.The rock mass is characterized by good differentiation,clear and differentiated facies zones and rhythm.The rock assemblage can be divided into the following rock facies combination:gabbro,gabbro-norite,gabbro troctolite,gabbro-plagioclase,gabbro-eclogite-olivine pyroxenite,and diabase types.The orebodies occur mostly as close-bedded,distributed in the dark facies zone in the bottom layers of the middle or lower part of the stratiform rock mass.The main ore minerals are granular ilmenite,magnetite,ilmenite spar,and magnesium aluminum spinel,with small amounts of pyrrhotite,pyrite and cobalt,nickel and copper sulfide.The ores have siderite and mosaic textures and occur as compact massive,banded and disseminated structures;they consist of TFeO 20％-45％,TiO2 3％-16％,V2O50.15％-0.5％,Cr2O30.1％-0.38％,associated with trace amounts of Cu,Co,Ni,Ga,Mn,P,Se,Te,Sc and Pt group elements.     

Aftershock of the Wenchuan Earthquake in Sichuan Triggers Large Earthquake in Minxian County, Gansu

Because of the confining compression of the Pacific,Eurasian and Indian plates,the Chinese mainland is frequently stricken with earthquakes,especially in the Qinghai-Tibet Plateau and surrounding areas and along the NS-trending tectonic zone from Yinchuan to Lanzhou,Chengdu,and finally to the Kunming tectonic belt (Fig.1).Historical records show that there are 14 earthquakes of＞Ms 8 occurring in the two regions,eight of which occurred along the latter tectonic belt.The 2008 Wenchuan earthquake located on both the NS tectonic zone and the Longmenshan fault zone along the eastern margin of the Qinghai-Tibet Plateau.     

Controls on sediment evacuation from glacially modified and unmodified catchments in the eastern Sierra Nevada,California

The degree of glacial modification in small catchments along the eastern Sierra Nevada, California, controls the timing and pattern of sediment flux to the adjacent fans. There is a close relationship between the depth of fan‐head incision and the pattern and degree of Late Pleistocene catchment erosion by valley glaciers; catchments with significant glacial activity are associated with deeply incised fan heads, whereas fans emerging from glacially unmodified catchments are unincised. We suggest that the depth of fan‐head incision is controlled by the potential for sediment storage during relatively dry ice‐free periods, which in turn is related to the downstream length of the glacially modified valley and creation of accommodation through valley floor slope lowering and glacial valley overdeepening and widening. Significant storage in glacially modified basins during ice‐free periods leads to sediment supply‐limited conditions at the fan head and causes deep incision. In contrast, a lack of sediment trapping allows quasi‐continuous sediment supply to the fan and prevents incision of the fan head. Sediment evacuation rates should thus show large variations in glacially modified basins, with major peaks during glacial and lows during interglacial or ice‐free periods, respectively. In contrast, sediment removal from glacially unmodified catchments in this type of setting should be free of this effect, and will be dominated instead by short‐term variations, modulated for example by changes in vegetation cover or storm frequency. This distinction may help improve our understanding of long‐term sediment yields as a measure of erosional efficiency. Copyright © 2008 John Wiley & Sons, Ltd.     

Numbers,types, and compositions of an unbiased collection of cosmic spherules

Abstract— Micrometeorites collected from the bottom of the South Pole water well (SPWW) may represent a complete, well‐preserved sample of the cosmic dust that accreted on Earth from 1100–1500 A.D. We classified 1588 cosmic spherules in the size range 50–800 μm. The collection has 41% barred olivine spherules, 17% glass spheres, 12% cryptocrystalline spherules, 11% porphyritic olivine spherules, 12% relicgrain‐bearing spherules, 3% scoriaceous spherules, 2% I‐type spherules, 1% Ca‐AI‐Ti‐rich (CAT) spherules, and 1% G‐type spherules. We also found bubbly glass spherules, spherules with glass caps, and ones with sulfide coatings—particles that are absent from other collections. A classification sequence of the stony spherules (scoriaceous, relic‐grain‐bearing, porphyritic, barred olivine, cryptocrystalline, glass, and CAT) is consistent with progressive heating and evaporation of Fe from chondritic materials. The modern‐day accretion rate and size distribution measured at the SPWW can account for the stony spherules present in deep‐sea collection through preferential dissolution of glass and small stony spherules. However, weathering alone cannot account for the high accretion rate of I‐type spherules determined for two deep‐sea collections. The SPWW collection provides data to constrain models of atmospheric‐entry heating and to assess the effects of terrestrial weathering.     

Strain localization as a key to reconciling experimentally derived flow-law data with dynamic models of continental collision

Published strength profiles predict strength discontinuities within and/or at the base of continental crust during compression. We use finite element models to investigate the effect of strength discontinuities on continental collision dynamics. The style of deformation in model crust during continued subduction of underlying mantle lithosphere is controlled by: (1) experimental flow-law data; (2) the crustal geotherm; (3) strain localization by erosion; (4) strain-softening and other localization effects. In the absence of erosion and other factors causing strain localization, numerical models with typical geothermal gradients and frictional/ductile rheologies predict diffuse crustal deformation with whole-scale detachment of crust from mantle lithosphere. This prediction is at odds with earlier model studies that only considered frictional crustal rheologies and showed asymmetric, focused crustal deformation. Without localization, model deformation is not consistent with that observed in small collisional orogens such as the Swiss Alps. This suggests that strain localization by a combination of erosion and rheological effects such as strain softening must play a major role in focusing deformation, and that strength profiles derived under constant strain rates and uniform material properties cannot be used to infer crustal strength during collision dynamics.