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1.
Kinetics of arsenopyrite oxidative dissolution by oxygen 总被引：1，自引：0，他引：1
We used a mixed flow reactor system to determine the rate and infer a mechanism for arsenopyrite (FeAsS) oxidation by dissolved oxygen (DO) at 25 °C and circumneutral pH. Results indicate that under circumneutral pH (6.3-6.7), the rate of arsenopyrite oxidation, 10−10.14±0.03 mol m−2 s−1, is essentially independent of DO over the geologically significant range of 0.3-17 mg L−1. Arsenic and sulfur are released from arsenopyrite in an approximate 1:1 molar ratio, suggesting that oxidative dissolution by oxygen under circumneutral pH is congruent. Slower rates of iron release from the reactor indicate that some of the iron is lost from the effluent by oxidation to Fe(III) which subsequently hydrolyzes and precipitates. Using the electrochemical cell model for understanding sulfide oxidation, our results suggest that the rate-determining step in arsenopyrite oxidation is the reduction of water at the anodic site rather than the transfer of electrons from the cathodic site to oxygen as has been suggested for other sulfide minerals such as pyrite. 相似文献
2.
Low grade submarine exhalative gold mineralization occurs at the London-Virginia deposit in central Virginia Piedmont. The deposit consists of a series of localized but conformable units — basal garnetiferous-chlorite schist, magnetite schist, quartz-muscovite schist, ferruginous quartzite, and chlorite-biotite schist — which represent a mixture of submarine epiclastic volcanic debris and exhalative chemical sediments. Finely disseminated gold occurs dispersed with minor amounts of pyrite, sphalerite, chalcopyrite, galena, and tennantite in the ferruginous quartzite and quartz-muscovite schist. The deposit is believed to have formed by processes analogous to those currently active in the Atlantis II Deep of the Red Sea. Silicarich, hypersaline brines discharged through fractures in the sea floor and ponded in a local basin. Epiosodic influx of clastic debris and extensive deposition of hydrothermal silica diluted the concentration of sulfides and gold to produce a low-grade, siliceous mineralized zone. Emanation from the exhalative vent was terminated when the basin was capped by a lava flow. Subsequent regional greenschist grade metamorphism has recrystallized the silica into a granular quartzite and produced minor remobilization of the gold and sulfides. 相似文献
3.
We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartzwhere 10−5.13 < aHF < 101.60, −0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silicawhere 10−2.37 < aHF < 101.61, −0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e.g. + H+, F− + H+, HF + , HF + F−, or + F−, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si–O bond to form a O–H group and a Si–FH group. 相似文献
4.
Samples taken from a shooting range near Blacksburg, VA, USA provide information about the reservoirs and pathways of lead
at shooting ranges in an upland setting and humid environment. The metallic lead shot corrodes rapidly and develops a coating
of hydrocerussite (Pb3(CO3)2(OH)2). Hydrocerussite dissolution releases soluble lead at concentrations ranging from 2 ppb to 2 ppm depending the soil pH values
at this site. This soluble lead is captured by the Fe and Mn oxides and carbonates soil fractions. The highest concentration
of extractable lead contained in the soil was directly correlated with the highest concentration of lead shot and bullets
measured on the shotgun range surface. Eh-pH and hydrolysis diagrams provide a useful geochemical framework for understanding
the corrosion process, recognizing the corrosion product(s), understanding their solubility, and identifying the geochemical
barriers to lead migration that provides a basis for selecting best management practices for this and other shooting range. 相似文献
5.
Juan Liu Deborah M. Aruguete J. Donald Rimstidt 《Geochimica et cosmochimica acta》2008,72(24):5984-5996
The acidic, non-oxidative dissolution of galena (PbS) nanocrystals has been studied in detail using transmission electron microscopy (TEM) to follow the evolution of the size and shape of the nanocrystals before and after dissolution experiments, X-ray photoelectron spectroscopy (XPS) to follow particle chemistry, and dissolution rate analysis to compare dissolution rates between nanocrystalline and bulk galena. Dissolution characteristics were also studied as a function of nanocrystal access to bulk vs. confined solution due to the degree of proximity of next-nearest grains. Nearly monodisperse galena nanocyrstals with an average diameter of 14.4 nm were synthesized for this study, and samples were exposed to pH 3, deoxygenated HCl solutions for up to 3 h at 25 °C. Detailed XPS analysis showed the nanocrystals to be free of unwanted contamination, surface complexes, and oxidative artifacts, except for small amounts of lead-containing oxidation species in both pre- and post-dissolution samples which have been observed in fresh, natural bulk galena. Depending on the calculation methods used, galena nanocrystals, under the conditions of our experiments, dissolve at a surface area normalized rate of one to two orders of magnitude faster than bulk galena under similar conditions. We believe that this reflects the higher percentage of reactive surface area on nanocrystalline surfaces vs. surfaces on larger crystals. In addition, it was shown that {1 1 1} and {1 1 0} faces dissolve faster than {1 0 0} faces on nanocrystals, rationalized by the average coordination number of ions on each of these faces. Finally, dissolution was greatly inhibited for galena nanocrystal surfaces that were closely adjacent (1-2 nm, or less) to other nanocyrstals, a direct indication of the properties of aqueous solutions and ion transport in extremely confined spaces and relevant to dissolution variations that have been suspected within aggregates. 相似文献
6.
Meta-analysis of 173 rate measurements from 21 publications was used to develop rate laws for chalcopyrite dissolution under environmentally relevant conditions. Multiple linear regression analysis of 28 data for nonoxidative chalcopyrite dissolution in the presence of O2 and Cl− produced the following rate law: 相似文献
7.
Gold has played an important role in the settlement and economics of the United States. Commercial production from 24 states totaled more than 420 million troy ounces (13,000 metric tons) from 1804 through 1995. There were, no doubt, early undocumented discoveries by Native Americans, but the first records are those from the mid-1600's in the east and from the 1770's in the west. Commercial production began in 1804 in North Carolina and spread among several Appalachian states in the 1820's and 1830's as placer deposits were discovered and exploited. After peaking in the 1830's and 1840's, Appalachian production began to decline as deposits were worked out and as miners moved westward in response to the news of the discoveries in California in 1848. Appalachian production virtually ceased with the Civil War while production from California and adjacent states remained at several millions of ounces per year. As the California Gold Rush waned, new discoveries brought the Rocky Mountain states, South Dakota, and Alaska into prominence. Local, state and total production responded to time of discovery, extent of placers, labor availability, technology, government mandates and, of course, the price of gold. By 1900, the major gold rushes had occurred and most of the major producing districts were defined; however, the fixed price of gold (since 1837) provided a decreasingly attractive incentive for more exploration and exploitation. The rise in the price of gold, during the Depression provided a powerful incentive to increase gold production, but one that was cut short by War Production Board Order L-208 which closed the gold mines in 1942. In the post-war period, the fixed price, combined with the prohibition of American gold ownership, again proved to be a disincentive and gold production dropped. The era of free gold price that began in 1968, followed by the permission for Americans to again own gold, brought new interest in gold with prices rising briefly in 1980 to US$850 per ounce and remaining above US$350 per ounce through 1995. This higher price, combined with the technology for bulk mining and processing of low grade ores, provided incentive for new exploration and exploitation. Consequently, gold production soared above 10 million ounces per year in the early 1990's with 65% coming from Nevada. There has been a general decrease in the grade of gold ores since the early 1900's and significant changes in the methods of recovery. Despite the decreasing grade, the reserves of recoverable gold have more than doubled since the early 1970's. 相似文献
8.
A numerical compaction model of overpressuring in shales 总被引：1，自引：0，他引：1
A one-dimensional model of sediment compaction is presented to relate pressure, porosity, permeability, and fluid and solid-particle velocities in an evolving sedimentary basin. The burial history of a sedimentary package is followed and incorporated into rate models for diagenetic reactions to predict clay compositions with depth. The governing set of nonlinear, partial differential equations constitutes a moving boundary problem and is solved by a finite difference scheme. Sedimentation rates and a permeability-porosity function for shales are required to implement the model. Additional factors are incorporated to mimic the effect of increased fluid volume generated by dehydration from clay mineral transformations and by thermal expansion. We demonstrate that the major cause of overpressuring in sediments accumulating along passive margins is nonequilibrium compaction. Sedimentation rates and strata permeability are the most important geologic factors in the formation of overpressured zones. Smectite dehydration and aquathermal pressuring play secondary roles in the development and sustenance of overpressures. 相似文献
9.
Matthew Steele-MacInnis Liang Han Robert P. Lowell J. Donald Rimstidt Robert J. Bodnar 《Central European Journal of Geosciences》2012,4(2):275-286
Results of a numerical modeling study of quartz dissolution and precipitation in a sub-seafloor hydrothermal system have been used to predict where in the system quartz could be deposited and potentially trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the fact that quartz solubility depends on many inter-related factors, including temperature, fluid salinity and fluid immiscibility, and is further complicated by the fact that quartz exhibits both prograde and retrograde solubility behavior, depending on the fluid temperature and salinity. Using the PVTX properties of H2O-NaCl, the petrographic and microthermometric properties of fluid inclusions trapped at various locations within the hydrothermal system have been predicted. Vapor-rich inclusions are trapped as a result of the retrograde temperature-dependence of quartz solubility as the convecting fluid is heated in the vicinity of the magmatic heat source. Coexisting liquid-rich and vapor-rich inclusions are also trapped in this region when quartz precipitates as a result of fluid immiscibility that lowers the overall bulk quartz solubility in the system. Fluid inclusions trapped in the shallow subsurface near the seafloor vents and in the underlying stockwork are liquid-rich with homogenization temperatures of 200?C400°C and salinities close to that of seawater. Volcanogenic massive sulfide (VMS) deposits represent the uplifted and partially eroded remnants of fossil submarine hydrothermal systems, and the relationship between fluid-inclusion properties and location within the hydrothermal system described here can be used in exploration for VMS deposits to infer the direction towards potential massive sulfide ore. 相似文献
10.
A differential rate equation for silica-water reactions from 0–300°C has been derived based on stoichiometry and activities of the reactants in the reaction SiO2(s) + 2H2O(l) = H4SiO4(aq) where () = (the relative interfacial area between the solid and aqueous phases/the relative mass of water in the system), and k+ and k? are the rate constants for, respectively, dissolution and precipitation. The rate constant for precipitation of all silica phases is and Eact for this reaction is 49.8 kJ mol?1. Corresponding equilibrium constants for this reaction with quartz, cristobalite, or amorphous silica were expressed as . Using , k was expressed as and a corresponding activation energy calculated: