Experimental Study of Gold and Platinum Solubility in a Complex Fluid under Hydrothermal Conditions

Abstract: The solubility of gold was studied in water and aqueous NaCl (1– 5 m) solutions under oxygen and sulfur buffered conditions between 300–500C at a constant pressure 1 kb. Two buffer assemblages HMP and PPM were used. Analysis of the scatter in measured values in log m_Au–m_NaCl–T frame fixed linear dependence between log m_Au and T at any studied iso‐pleth (m_NaCl) in the form of log m_Au = a. T(C) + b. Coefficients of the equation were calculated for water and NaCl (1, 3, 5 m) solutions. The maximum solubility characterizes the NaCl‐free system in the presence of HMP. In the case, Au solubility increases from (log m_Au) –6. 72 to –5. 04 at 300 and 500C, respectively. In the presence of PPM, maximum of Au solubility was obtained for the 5 mNaCl solution. In a similar manner solubility rises from –6. 54 to –5. 77 at 300 and 500C, accordingly. In studied f_O2/f_S2 area the behavior of Au solubility testified that: (i) – a composite interaction between chloride and hydrosulfide speciation of gold affects its total solubility; (ii) – in addition of NaCl up to about 1. 5 m the solubility decreases, more pronounced in the presence of HMP; (iii) – the contribution of chloride in total Au solubility is more for PPM despite of lower f_O2value, than for HMP. The solubility of platinum was studied in the Pt–Cl–S–H₂O system between 300 and 500C, 1 kb. PPM solid buffer controlled oxidation state, pH and sulfur activity of solutions (H₂O, 1 mNaCl and 0. 1 mHCl). Under the conditions, PtS precipitated from the solutions with increasing temperature and acidity. The PtS solubility in the 0. 1 m_HCl solutions lowers slightly in the range of 300–500C from –5. 30 to –5. 60 (in log m_Pt) that is typical to the hydrosulfide species. It was deduced that reducing media, regulated by the PPM assemblage, suppress activity of chloride species of Pt. More oxidizing conditions were modeled in runs using mixtures of Mn(II), Mn(III) and Mn(IV) oxides to buffer the aqueous‐chloride solutions between 300 and 500C, 1 kb. It was found that MnO tends to oxidize at T below 400C forming intermediate Mn‐hydroxides (β–MnOOH, Mn (OH)₂ and Mn₂(OH)₃Cl). These phases are metastable and transfer to Mn₃O₄ with increasing duration. Generation of the Mn‐hydroxides leads to a change of physical‐chemical parameters of the solutions, such as water activity, pH and Eh. The last results in abrupt increase in the noble metals dissolution. At stable existence of only Mn₃O₄, the solubility of both Pt and Au lowers to equilibrium values. Essential catalysis effect of Pt on intensity and rate of Mn(II) oxidation was found. The dominant role of chloride of Pt and Au was defined under most oxidized conditions, specified by Mn₂O₃–MnO₂ buffer. So at 400C, dissolved Au (log m_Au) increases from –4. 40 in water to –1. 00 in 0. 1 m_HCl, and ones of Pt (log m_Pt) from –4. 80 to –2. 90 accordingly. Thus, mixing of hydrosulfide and chloride solutions, as well as transformation of the systems to the stable state act upon total solubility of the noble metals.     

Experimental simulation of degrading structures through active control

In experimental studies of structural behaviour, it is often desirable, even necessary, to perform tests on a test structure from its undamaged state, through its damaged states, and finally to failure. The fact that experiments of this type are not often done primarily because of its prohibitive cost. In this paper, a testing procedure is proposed in which a test structure is allowed to undergo its degradation in real time yet it is not physically damaged, thus allowing it to be reused. The underlying concept is that of active structural control. Considerable research and development of active structural control in civil engineering has taken place relative to responsive control of structures against damaging environmental loads. While the use of active control systems to simulate damage in an experimental setting as proposed in this paper appears to be new, much of the existing knowledge base in active structural control is directly applicable. © 1998 John Wiley & Sons, Ltd.     

Subsurface thermal and hydrothermal characterization based on geothermal resources map, drill hole thermal gradients, Curie point depths and hypocenter distribution — Examples of Tohoku district, Japan

Subsurface thermal structure in Tohoku district are characterized by existing data such as geothermal resources maps, drill hole thermal gradients, Curie point depths and hypocenters distribution maps. The collected data are registered in a database system, then, compared in plan view, cross-section and bird's-eye pictures. The comparison indicates that subsurface temperatures extrapolated from drill hole thermal gradients are generally concordant to the Curie point depth, assumed to be 650 °C. Tohoku district is generally divided into 5 type areas; fore arc lowland, fore arc mountain country, Quaternary volcanic terrain, back arc lowland and back arc mountain country. The surface thermal manifestations in Quaternary volcanic terrain are mainly controlled by the magma chambers as heat sources, while, surface thermal features such as hot springs in non-volcanic areas are controlled by degrees of heat flows, and hydrothermal flows in permeable Cenozoic formations and along permeable fault zones.     

Ion microprobe baddeleyite and zircon ages for Late Archaean mafic dykes of the Pilbara Craton,Western Australia

Ion microprobe U–Th–Pb analyses of baddeleyite and zircon yield precise ages for several mafic intrusions in the Pilbara Craton of Western Australia. Baddeleyite was dated from four dolerite dykes of the north‐northeast‐trending Black Range swarm intruded into granitoid‐greenstone basement in the northern part of the craton. The mean ²⁰⁷Pb*/²⁰⁶Pb* age of 2772 ± 2 Ma, interpreted as an unambiguous age of emplacement for the dykes, is within error of previous ion microprobe U–Pb zircon ages for the Mt Roe flood basalts and confirms that the dykes acted as feeders to the volcanic rocks. The Sylvania Inlier, in the southeastern Pilbara Craton, also contains north‐northeast‐trending dykes that were correlated previously with the Black Range swarm. Based on concordant and discordant zircon analyses from samples of two dykes, the best estimate of the age of the Sylvania dykes is 2747 ± 4 Ma. The Sylvania dykes thus appear to be significantly younger than, and hence unrelated to, the Black Range swarm, but may have acted as feeders to younger volcanic units in the Fortescue Group such as the Kylena Formation.     

Formation by silicate–fluoride + phosphate melt immiscibility of REE-rich globular segregations within aplite dikes

Aplite dikes intruding the Proterozoic 1.42(±?3) Ga Longs Peak-St. Vrain Silver Plume-type peraluminous granite near Jamestown, Colorado, contain F, P, and rare earth element (REE)-rich globular segregations, with 40–46% REE, 3.7–4.8 wt% P₂O₅, and 5–8 wt% F. A combination of textural features and geochemical data suggest that the aplite and REE-rich globular segregations co-existed as two co-genetic liquids prior to their crystallization, and we propose that they are formed by silicate–fluoride?+?phosphate (+?S?+?CO₂) melt immiscibility following ascent, cooling, and decompression of what was initially a single homogeneous magma that intruded the granite. The REE distribution coefficients between the silica-rich aplites and REE-rich segregations are in good agreement with experimentally determined distribution coefficients for immiscible silicate–fluoride?+?phosphate melts. Although monazite-(Ce) and uraninite U–Th–Pb microprobe ages for the segregations yield 1.420(±?25) and 1.442(±?8) Ga, respectively, thus suggesting a co-genetic relationship with their host granite, ε_Nd1.42Ga values for the granites and related granitic pegmatites range from ??3.3 to ??4.7 (average ??3.9), and differ from the values for both the aplites and REE-rich segregations, which range from ??1.0 to ??2.2 (average ??1.6). Furthermore, the granites and pegmatites have (La/Yb)_N <50 with significant negative Eu anomalies, which contrast with higher (La/Yb)_N >100 and absence of an Eu anomaly in both the aplites and segregations. These data are consistent with the aplite dikes and the REE-rich segregations they contain being co-genetic, but derived from a source different from that of the granite. The higher ε_Nd1.42Ga values for the aplites and REE-rich segregations suggest that the magma from which they separated had a more mafic and deeper, dryer and hotter source in the lower crust or upper mantle compared to the quartzo-feldspathic upper crustal source proposed for the Longs Peak-St. Vrain granite.     

Generalized Born scattering of elastic waves in 3-D media

It is well known that when a seismic wave propagates through an elastic medium with gradients in the parameters which describe it (e.g. slowness and density), energy is scattered from the incident wave generating low-frequency partial reflections. Many approximate solutions to the wave equation, e.g. geometrical ray theory (GRT), Maslov theory and Gaussian beams, do not model these signals. The problem of describing partial reflections in 1-D media has been extensively studied in the seismic literature and considerable progress has been made using iterative techniques based on WKBJ, Airy or Langer type ansätze. In this paper we derive a first-order scattering formalism to describe partial reflections in 3-D media. The correction term describing the scattered energy is developed as a volume integral over terms dependent upon the first spatial derivatives (gradients) of the parameters describing the medium and the solution. The relationship we derive could, in principle, be used as the basis for an iterative scheme but the computational expense, particularly for elastic media, will usually prohibit this approach. The result we obtain is closely related to the usual Born approximation, but differs in that the scattering term is not derived from a perturbation to a background model, but rather from the error in an approximate Green's function. We examine analytically the relationship between the results produced by the new formalism and the usual Born approximation for a medium which has no long-wavelength heterogeneities. We show that in such a case the two methods agree approximately as expected, but that in a media with heterogeneities of all wavelengths the new gradient scattering formalism is superior. We establish analytically the connection between the formalism developed here and the iterative approach based on the WKBJ solution which has been used previously in 1-D media. Numerical examples are shown to illustrate the examples discussed.     

On the variability of the Charnock constant and the functional dependence of the drag coefficient on wind speed

A model for the air–sea interface, based on the coupled pair of similarity relations for “aerodynamically” rough flow in both fluids, is presented, which is applied to fetch-limited and high wind speed conditions which occur, for example, in hurricanes. It is shown that the specification of the maximum 10-m drag coefficient and the 10-m wind speed and the peak wave speed at which it occurs are sufficient to uniquely determine the drag law, which asymptotes at low wind speeds to a Charnock constant similar to that for the fully developed wind wave sea and is almost independent of the peak wave speed at the maximum in drag coefficient. A feature of the drag law is that it is of Charnock form, almost independent of the wave age, consistent with the transfer of momentum to the wave spectrum being due to the smaller rather than the dominant wavelengths. The analysis is also applied to a variable sea state in which either the surface wind or the surface Stokes drift vary, but the peak wave speed is kept constant. The corresponding variability in the Charnock constant is in general accord with observations.     

Gap Filling and Quality Assessment of CO2 and Water Vapour Fluxes above an Urban Area with Radial Basis Function Neural Networks

Vertical turbulent fluxes of water vapour, carbon dioxide, and sensible heat were measured from 16 August to the 28 September 2006 near the city centre of Münster in north-west Germany. In comparison to results of measurements above homogeneous ecosystem sites, the CO₂ fluxes above the urban investigation area showed more peaks and higher variances during the course of a day, probably caused by traffic and other varying, anthropogenic sources. The main goal of this study is the introduction and establishment of a new gap filling procedure using radial basis function (RBF) neural networks, which is also applicable under complex environmental conditions. We applied adapted RBF neural networks within a combined modular expert system of neural networks as an innovative approach to fill data gaps in micrometeorological flux time series. We found that RBF networks are superior to multi-layer perceptron (MLP) neural networks in the reproduction of the highly variable turbulent fluxes. In addition, we enhanced the methodology in the field of quality assessment for eddy covariance data. An RBF neural network mapping system was used to identify conditions of a turbulence regime that allows reliable quantification of turbulent fluxes through finding an acceptable minimum of the friction velocity. For the data analysed in this study, the minimum acceptable friction velocity was found to be 0.15 m s⁻¹. The obtained CO₂ fluxes, measured on a tower at 65 m a.g.l., reached average values of 12 μmol m⁻² s⁻¹ and fell to nighttime minimum values of 3 μmol m ⁻² s⁻¹. Mean daily CO₂ emissions of 21 g CO₂ m⁻²d ⁻¹ were obtained during our 6-week experiment. Hence, the city centre of Münster appeared to be a significant source of CO₂. The half-hourly average values of water vapour fluxes ranged between 0.062 and 0.989 mmol m⁻² s⁻¹and showed lower variances than the simultaneously measured fluxes of CO₂.