Inquiry into the dissolution kinetics of naturally occurring geologic materials, rather than individual mineral species, has been relatively neglected. This is especially true of surface processes, the realm of surface water hydrology and geomorphology. This paper focuses attention at a laboratory study of the rate of such complex reactions. Functions defining the dissolution rates of saline (0.1–20 per cent salt content) Mancos Shale-associated alluvium in distilled water follow varying patterns. Dissolution is characterized by an initial (<5 min) high rate constant, by a following phase (20 min-57 h) where rates are reduced drastically, and by a final period of encroachment to equilibrium. Initial dissolution rates increase with increase in salt content and sediment: water ratio. The time necessary to approach equilibrium is, however, found to be directly proportional to the sediment; water ratio. The concentration of Na+, Mg2+, Ca2+, SC2?4 and HCO?3, and the relative abundance of Ca2+ and HCO?3 increase continuously with contact time, indicating that the hydrated sodium and magnesium sulphate minerals provide most of the initial solutes, though not necessarily most of the total solute bulk. The results obtained in this study indicate that the high initial dissolution rate of soluble minerals from alluvium, and particularly from shales in contact with aqueous solutions, is too short-lived to account for most of the solutes occurring in heavily sediment-laden surface flow. Excluding input from slower, usually supersaturated subsurface flow, dissolution from sediment in transport should be a major source of solutes in originally undersaturated and kinetically unequilibrated surface water in semiarid and arid regions. 相似文献
Discrepancies between predicted and observed interstitial water profiles for sites 322 and 323, Leg 35, Bellingshausen Abyssal Plain, were used to identify sites of reaction for further mineralogical and chemical investigations. Two major reaction sites were identified at site 323:(1) In the silicification zone between 410 and 505 m depth, where dissolution of biogenic (opaline) silica, plagioclase and a few coccoliths and the formation of opal-CT, Mg-rich smectite and K-feldspar are responsible for the observed silica, Ca2+, Mg2+, and K+ interstitial water gradients. Dissolution of biogenic silica provided most of the silica for the porcelanites.(2) In the basalt, weathering of pyroxene and plagioclase and the formation of celadonite, smectite, calcite, and goethite are probably responsible for the observed Ca2+, Mg2+, and K+ interstitial water gradients below the silicification zone.The chemistry of authigenic smectites reflects the composition of their precursor(s). 相似文献
Four pyroxenes with compositions En48Fs48Wo4, En47·5Fs47·5Wo5, En45Fs45Wo10 and En40Fs40Wo20, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe2+ and Mg2+ without unmixing. The Fe2+-Mg2+ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca2+ at the M2 site. The preference of Fe2+ for the M2 site increases with decreasing temperature and increasing Ca2+. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact. 相似文献
Strong isotopic fractionation between234U and238U has been noted in deep oil-well brines. The waters are stratigraphically and structurally isolated from fresh-water inflow and have remained stagnant for more than five half-lifes of234U. Excess234U is explained by the234Th alpha-recoil nucleus event. 相似文献
Nearly 200 analyses of meltwaters, ice and snow from three alpine glacial sites in carbonate terrain are summarized and discussed in terms of sources of solutes and kinetic controls on the progress of weathering reactions. Most data derive from the Swiss Glacier de Tsanfleuron which is based on Cretaceous and Tertiary pure and impure limestones. Two other sites (Marmolada, Italian Dolomites and the Saskatchewan Glacier, Alberta) are based on a mixed calcitic-dolomitic substrate. Most solutes originate from carbonate dissolution; moreover, where pyrite is present its oxidation supplies significant sulphate and forces more dissolution of carbonate. The ratios Sr2+/Ca2+ and Mg2+/Ca2+ are much higher in Tsanfleuron melt-waters than local bedrock, a phenomenon that can be reproduced in the laboratory at small percentages of dissolution. These anomalous ratios are attributed to incongruent dissolution of traces of the metastable carbonates Mg-calcite and aragonite. These phases also provide Na+ to solution. K+ is argued to originate mainly by ion-exchange on clays with solute Ca2+. Quartz and very minor feldspar dissolution are also inferred. Locally enhanced input from atmospheric sources is recognized by high Cl? and associated Na+. The progress of weathering reactions has been evaluated by the trends in the data, computer modelling and some simple laboratory experiments. The most dilute samples show a trend towards removal of CO2 to low partial pressures (c. 10?5.5 atmospheres), reflecting initially rapid carbonate dissolution and relatively slow dissolution of gaseous CO2. Later addition of atmospheric CO2 or acid from pyrite oxidation allows further carbonate dissolution, but solutions show a wide range of saturations, and CO2 pressures as high as 10?2.2 where pyrite oxidation is important. In a carbonate terrain, measurement of electroconductivity (corrected to 25°C) and alkalinity in the field allows the following preliminary deductions (where meq stands for milliequivalents): where S is the minimum meq(Ca2+ + Mg2+) produced by simple dissolution of carbonate unconnected with pyrite oxidation. As with any proxy method, these deductions do not remove the need for chemical analysis of waters in a given study area. 相似文献
The hydrochemical analyses of twenty-three springs were used to determine the properties and types of groundwater of the Tertiary-Quaternary Aquifer of northern Jordan. The result shows that the geological formation influences the quality of the investigated groundwater more than the anthropogenic factors. The water of the Quaternary-Tertiary aquifer is enriched in Ca++ due to the dissolution of the nearby carbonate rocks. The investigated water has a low EC values with Ca(Na)-HCO3 water type. Most springs belong to this hydrochemical facies except Malka. Groundwater in the Malka wells has high salinity with NaCl waters and a strong Ca(Mg)-HCO3 facies (900 to 1000 mg/l TDS). The area long-term hydrochemical data have been also evaluated; general trend of increase of the analyzed ion was observed. Bicarbonate represents the most abundant anion in the studied water, which exceeds the permissible limits. Nitrates (NO3?) also exceed the permissible limit and are the most common contaminant in the investigated water. Data on dissolved major and trace elements (K+, Na+, Mg2+, Ca2+, Cl?, SO42?, Fe, Zn, Cu and Pb) in the investigated water revealed that the concentrations lie within the natural background range. The positive correlation values between various ions indicate that most of ions come from same lithological sources. According to the residual sodium carbonate, and EC values, the studied springs are suitable for agricultural purposes. 相似文献
Gypsum and halite crystals, together with saponite and phillipsite, were found in a vein in a basalt sill 625 m below the sea floor at DSDP Site 395A, located 190 km west of the crest of the Mid-Atlantic Ridge. The δ34S value of the gypsum (+19.4‰) indicates a seawater source for the sulfate. The δ18O values of the saponite (+19.9‰) and phillipsite (+18.1‰) indicate either formation from normal seawater at about 55°C or formation from18O-depleted seawater at a lower temperature.The gypsum (which could be secondary after anhydrite) was formed by reaction between Ca2+ released from basalt and SO42? in circulating seawater. The halite could have formed when water was consumed by hydration of basalt under conditions of extremely restricted circulation. A more probable mechanism is that the gypsum was originally precipitated as anhydrite at temperatures above 60°C. As the temperature dropped the anhydrite converted to gypsum. The conversion would consume water, which could cause halite precipitation, and would cause an increase in the volume of solids, which would plug the vein and prevent subsequent dissolution of the halite. 相似文献
Oxygen and hydrogen isotopic compositions were measured on 12 serpentine and 2 actinolite samples from the Troodos ophiolite complex, Cyprus. The single analyzed antigorite(δD= ?60, δ18O= 7.1) is isotopically similar to all previously analyzed antigorites from ultramafic bodies. However, although their D/H ratios are relatively “normal”(δD= ?70to?92), the δ18O values of most of the Troodos lizardite-chrysotile serpentines (+12.6 to +14.1) are much higher than the 2.0–9.3‰ range typically found in such serpentines. Such high δ18O values have previously been found only in the serpentine-like mineraloids termed “deweylites”, which apparently formed at Earth-surface temperatures, and in a single sample from Vourinos, Greece that is in contact with high-18O limestone. The Troodos lizardite-chrysotile samplescannot have formed by reaction with heated ocean waters, but instead must have formed in contact with large amounts of some type of meteoric, metamorphic, or formation water, either (1) at very low temperatures in a near-surface environment, or (2) at about 100°C from waters that were abnormally enriched in18O(δ18O ≈ +4 to +8). The latter possibility seems most plausible inasmuch as extensive evaporites were deposited throughout the Mediterranean Sea during the late Miocene, and this would have been accompanied by strong18O enrichments of the local meteoric waters. Heated ocean waters, however, probably were responsible for the formation of the actinolitic amphiboles(δ18O= 4.6 to 5.5; δD= ?51to?46) from the gabbro and ultramafic zones in the Troodos complex. The amphiboles must have formed at considerably higher temperatures and at an earlier stage than the lizardite-chrysotile serpentinization. 相似文献
This study investigates the influence of Ca2+ and Mg2+ on the removal of F? by magnesium potassium phosphate (MPP) from water. The kinetic experiments reveal that the F? concentration decreased from 3.5 to 3.31 mg L?1 in a single (F?) system and to 1.45 mg L?1 in a ternary system (F?, Ca2+, and Mg2+) after 1 min, respectively. Thus, the F? removal efficiencies are found to increase by about 53% with the co‐active effect of Ca2+ and Mg2+ in the solution. Moreover, Ca2+ and Mg2+ are almost completely removed in the F?, Ca2+, and Mg2+ system. According to the pseudo‐first‐order modeling, the rate constants k for F?, Ca2+, and Mg2+ are 0.00348, 0.0106, and 0.0159 min?1 respectively; thus, Mg2+ > Ca2+ > F?. In the ternary system, the removal efficiencies are 53.29–66.03% for F?, 99.99–100% for Ca2+, and 87.21–95.19% for Mg2+ with initial pH 5–10. The removal efficiencies of F? increases with increases in initial concentrations of F?, Ca2+, and Mg2+. The removal of F? is governed by two routes: 1) adsorption by electrostatic interactions and outer sphere surface complexation; 2) co‐precipitation with Ca3(PO4)2, CaHPO4, Mg3(PO4)2, and Mg(OH)2. 相似文献
Concentrations of major ions in surface waters of the rivers of Khara-Murin and Snezhnaya are compared based on data of many-year observations carried out in the 1950s and 2000s. The concentrations of HCO3?, Cl?, Ca2+, Mg2+, Na+ + K+ are shown to be stable. A considerable increase in SO4?2 concentration was revealed. 相似文献
An experimental investigation is presented on the batch foam fractionation of the heavy metal cations Pb2+, Cd2+, Cu2+, Sb3+ and As5+ from diluted aqueous solutions with hexamethylenedithiocarbamate (HMDC) as complexing agent and sodiumdodecylsulfate (SDS) as surfactant. Among the considered pH-values of 2,4 and 7 the pH 2 experiments allow a direct application of foam fractionation on acidic extracts from heavy metal contaminated soil. The experiments at pH 2 and pH 4 show better results than those at neutral pH. Although a simple device was used, a maximum enrichment factor of 13.8 and a minimum removal factor of 0.01 have been measured. The flotation with weak organic acids like citric acid (CA) and acetic acid (AA) show about 50–70% smaller enrichment factors than those acidified with hydrochloric acid. The dissolution and mixing of the reacting components as well as the concentration of the detergent and the gaseous volume flow can be regarded as basic parameters of foam fractionation. 相似文献
Hydrogeochemical evolution of interactions between surface water and groundwater is crucial for guaranteeing water supply quality in a riverside water source area. This study focuses on the seasonal and spatial characteristics of hydrogeochemical evolution affected by groundwater exploitation in the Hulan water source area using hydrochemical analyses and stable isotope tracers. Results show that the concentrations of major ions and total dissolved solids (TDS) increase considerably during the dry season. A bicarbonate water type is primarily produced by the dissolution of calcite, dolomite and gypsum, as well as the cation exchange and human activities. Along the typical infiltration path, the proportions of surface water increase with proximity to the river from 8%-63% during the wet season to 11%-84% during the dry season, which are attributed to an increased hydraulic gradient by exploitation. The typical path is classified into two zones. The first is the intensive mixing zone (within 1 km) with increasing concentrations of major ions and TDS due to mixing effect. The second is the exploitation influence zone (1-3.3 km) with increased concentrations of Ca2+, Mg2+, SO42−, and HCO3− during the dry season due to two reasons of seasonal variations in evaporation, stronger water-rock interactions and mixing effects with increased surface water by exploitation. 相似文献
The anionic structure of magmatic liquids has been estimated at 1 atm and at pressures corresponding to those of the upper mantle. These estimates are based predominantly on spectroscopic data on binary metal oxide-silica and ternary metal oxide-silica-alumina melts. Structural information on melt compositions in aluminate-silica joins has been used to provide detailed information on the role of Al3+ in natural magma at atmospheric and high pressure.Regardless of pressure, andesitic melts may be described as combinations of chain, sheet, and three-dimensional network units. Nearly all Al3+ in the magmatic liquid resides in the three-dimensional network units. This Al3+ is locally charge-balanced with Na+, K+, Ca2+, and Mg2+. In the latter two cases, Al3+ and Si4+ are ordered, whereas for Na+ and K+, Si4+ and Al3+ are randomly mixed. Solution of water in natural magma results in the formation of new nonbridging oxygens in addition to OH groups attached to Si4+ and metal cations.On the basis of determined solution mechanisms of CO2 and H2O in silicate melts, thermodynamic properties of HO+CO2, fluids and hydrous silicate melts and melting phase relations in peridotite-H2O-CO2, systems, it is found that natural andesitic magma in equilibrium with spinel Iherzolite in the upper mantle (10–20 kbar) must contain at least 5–7 wt.% H2O. Andesitic magma with 5–7 wt.% H2O in solution may be described as a mixture of Al-free three-dimensional units, sheets, and chains with a small proportion (less than 10%) of monomers. 相似文献
Porewater profiles often are used to identify and quantify important biogeochemical processes occurring in lake sediments.
In this study, multiple porewater profiles were obtained from two eutrophic Swiss lakes using porewater equilibrators (peepers)
in order to examine spatial and seasonal trends in biogeochemical processes. Variability in profile shapes and concentrations
was small on spatial scales of a few meters, but the uncertainty in calculated diffusive fluxes across the sediment surface
was, on average, 35%. Focusing of Fe and Mn oxides toward the lake center resulted in systematic increases in porewater concentrations
and diffusive fluxes of Fe2+ and Mn2+ with increasing water depth; these fluxes are postulated to be regulated by the pH-dependent dissolution of reduced-metal
phases. Despite higher concentrations of inorganic carbon, NH
4+
, Si and P in pelagic compared to littoral sites, diffusive fluxes of these substances across the sediment surface increased
only slightly or not at all with increasing water depth. Porewater profiles did reveal temporal changes in Fe2+, Mn2+, Ca2+ and Mg2+ that were an indirect result of the large, seasonal changes in seston deposition, but no clear seasonal variations were found
in diffusive fluxes of nutrients across the sediment surface. The intense mineralization occurring at the sediment surface
was not reflected in the porewater profiles nor in the calculated diffusive fluxes. Calculated diffusive fluxes across the
sediment surface resulted from decomposition occurring primarily in the top 5–7 cm of sediment. Diffusive fluxes from this
subsurface mineralization were equal to the solute release from mineralization occurring at the sediment-water interface.
Buried organic matter acts as a memory of previous lake conditons; it will require at least a decade before reductions in
nutrient inputs to lakes fully reduce the diffusive fluxes into the lake from the buried reservoir of organic matter. 相似文献
Snowmelt‐fed springs and small (0.5 km2) upland catchments in alpine areas of the western United States contribute significantly to the quantity and inorganic chemistry of water delivered to downstream basins but have not been studied extensively. Mineral weathering, transit time, and hydrologic mixing control the solute chemistry of waters that drain the upland zone of Niwot Ridge, Colorado Front Range, and adjacent areas in the granitic core of the Southern Rocky Mountains. Water in 37 springs sampled in this study flows in generally short steep paths (~0.3 km) through shallow regolith with mean transit times (MTT) of weeks to months, producing solutions dominated by Si, Ca2+, Na+, and HCO3?, locally SO42?. Rock type is a significant control on spring, surface, and shallow groundwater chemistry, and plagioclase (oligoclase) is the major source of dissolved Na+ and Si. Concentrations of Ca2+ exceed stoichiometric predictions of oligoclase weathering by ~3.5×; excess Ca2+ likely represents weathering of aeolian material, vein calcite, or trace minerals. Concentrations of base cations and Si increase slowly with estimated MTT of 0.2 years for Niwot Ridge spring waters, and several years for shallow groundwater sampled by wells. Chemical weathering of silicate minerals is slow with estimated rates of ~2.0 and 0.2 pmol·m?2·s?1 for oligoclase and microcline, respectively; the most mineralized spring waters are saturated only with respect to kaolinite and montmorillonite. More than 50% of the dissolved base cations + Si measured in Boulder Creek at Orodell (~25 km downstream) accumulate before water emerges from alpine springs on Niwot Ridge. Warming global temperatures are shifting more high‐elevation precipitation to rain, potentially changing run‐off patterns, transit time, and solute loads. Acquisition of solutes by alpine waters thus has implications far beyond small upland catchments. 相似文献
下载免费PDF全文