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1.
In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl−, Ca/(Ca + Mg)/SO4/(SO4 + HCO3), and environmental isotopes (δ18O, δ2H, 87Sr/86Sr, δ34S and δ13C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater.  相似文献   

2.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

3.
The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial 176Hf/177Hf(34 Ma) = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (176Hf/177Hf(34 Ma) = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (DZr = 0.220 ± 0.007 and DHf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (DNb = 0.0007 ± 0.0001 and DTa = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating DNb/DTa by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet DHf/DW = 17 and DNb/DZr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived 182Hf-182W and 92Nb-92Zr isotopic systems in Hadean time.  相似文献   

4.
Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO42−) to thiomolybdate (MoS42−) in overlying bottom waters. The average δ97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H2S]aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H2S]aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ97/95Mo signature in those shales. However, the heaviest δ97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ97/95Mo at 1.73 Ga.  相似文献   

5.
Raman spectroscopy is a powerful method for the determination of CO2 densities in fluid inclusions, especially for those with small size and/or low fluid density. The relationship between CO2 Fermi diad split (Δ, cm−1) and CO2 density (ρ, g/cm3) has been documented by several previous studies. However, significant discrepancies exist among these studies mainly because of inconsistent calibration procedures and lack of measurements for CO2 fluids having densities between 0.21 and 0.75 g/cm3, where liquid and vapor phases coexist near room temperature.In this study, a high-pressure optical cell and fused silica capillary capsules were used to prepare pure CO2 samples with densities between 0.0472 and 1.0060 g/cm3. The measured CO2 Fermi diad splits were calibrated with two well established Raman bands of benzonitrile at 1192.6 and 1598.9 cm−1. The relationship between the CO2 Fermi diad split and density can be represented by: ρ = 47513.64243 − 1374.824414 × Δ + 13.25586152 × Δ2 − 0.04258891551 × Δ3 (r2 = 0.99835, σ = 0.0253 g/cm3), and this relationship was tested by synthetic fluid inclusions and natural CO2-rich fluid inclusions. The effects of temperature and the presence of H2O and CH4 on this relationship were also examined.  相似文献   

6.
Fossils of megaherbivores from eight late Pleistocene 14C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ13C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C3 plant-dominated environment. Enamel δ18OPO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ18OPO4–δ18OH2O-calibrations for modern mammals and a present-day precipitation δ18OH2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.  相似文献   

7.
Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO4Al12(OH)24(H2O)127+ (Al13) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using 1H NMR at pH ∼ 5 in both aqueous and mixed solvents. The 1H NMR peak for protons on bound waters (η-H2O) lies near 8 ppm in a 2.5:1 mixture of H2O/acetone-d6 and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H2O is τ298 ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H2O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H2O)63+). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al13 molecule in addition to the fully protonated Al13 at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ2-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H2O/dmso-d6 over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ2-OH was also measured in D2O. The τ298 values are ∼0.013 and ∼0.2 s in the H2O/dmso-d6 solution and the τ298 value for the μ2-OH detectable in D2O is τ298 ∼ 0.013 s. The 1H NMR peak for the more reactive μ2-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.  相似文献   

8.
Evaporite outcrops are rare in the Basque Cantabrian basin due to a rainy climate, but saline springs with total dissolved solids ranging from 0.8 to 260 g/L are common and have long been used to supply spas and salterns. New and existing hydrochemistry of saline springs are used to provide additional insight on the origin and underground extent of their poorly known source evaporites. Saline water hydrochemistry is related to dissolution of halite and gypsum from two evaporitic successions (Triassic “Keuper” and Lower Cretaceous “Wealden”), as supported by rock samples from outcrops and oil exploration drill cuttings. The δ34S value of gypsum in the Keuper evaporites and sulfate in the springs is δ34SSO4 = 14.06 ± 1.07‰ and δ18OSO4 = 13.41 ± 1.44‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 124 and 288 ppm. The δ34S value of gypsum in the Wealden evaporites and sulfate in the springs is δ34SSO4 = 19.66 ± 1.76‰, δ18OSO4 = 14.93 ± 2.35‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 15 and 160 ppm. Wealden evaporites formed in a continental setting after the dissolution of Keuper salt. Gypsum δ34SSO4 and δ18OSO4 modification from Keuper to Wealden evaporites was due mainly to bacterial SO4 reduction in an anoxic, organic matter-rich environment. Saline springs with Wealden δ34SSO4 values are present in a 70 × 20 km wide area. Saline water temperatures, their δ2HH2O and δ18OH2O values, and the geological structure defines a hydrogeological model, where meteoric water recharges at heights up to 620 m above spring levels and circulates down to 720 m below them, thereby constraining the height range of evaporite dissolution. Groundwater flow towards saline springs is driven by gravity and buoyancy forces constrained by a thrust and fault network.  相似文献   

9.
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 (ΔHo = −44.0 kJ mol−1, ΔSo = −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.  相似文献   

10.
New He and C relative abundance, isotope and concentration results from nine geothermal locations situated along an 800-km transect of the North Anatolian Fault Zone (NAFZ), Turkey, that were monitored during the period November 2001–November 2004, are reported. The geothermal waters were collected every 3–6 months to study possible links between temporal geochemical variations and seismic activity along the NAFZ. At the nine sample locations, the He isotope ratios range from 0.24 to 2.3RA, δ13C values range from −4.5 to +5.8‰, and CO2/3He ratios range from 5 × 109 to 5 × 1014. The following geochemical observations are noted: (1) the highest 3He/4He ratios are found near the Galatean volcanic region, in the central section of the NAFZ, (2) at each of the nine sample locations, the 3He/4He ratios are generally constant; however, CO2/3He ratios and He contents both show one order of magnitude variability, and δ13C values show up to ∼4‰ variability, and (3) at all locations (except Re?adiye), δ13C values show positive correlations with CO2 contents. The results indicate that at least three processes are necessary to account for the geochemical variations: (1) binary mixing between crustal and mantle-derived volatiles can explain the general characteristics of 3He/4He ratios, δ13C values, and CO2/3He ratios at the nine sample locations; (2) preferential degassing of He from the geothermal waters is responsible for variations in CO2/3He values and He contents at each sample location; and (3) CO2 dissolution followed by calcite precipitation is responsible for variations in CO2 contents and δ13C values at most locations. For each of the geochemical parameters, anomalies are defined in the temporal record by values that fall outside two standard deviations of average values at each specific location. Geochemical anomalies that may be related to seismic activity are recorded on June 28, 2004 at Yalova, where a M = 4.2 earthquake occurred 43 days earlier at 15 km distance from the sample location, and on April 7, 2003 at Efteni, where a M = 4.0 earthquake occurred 44 days later at a distance of 12 km. At both locations, the sampling periods containing geochemical anomalies were preceded by an increase in M ? 3 earthquakes occurring within 60 days and less than 40 km distance.  相似文献   

11.
Diffuse CO2 efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO2 efflux, in many places exceeding 1000 g m−2 d−1, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m2 in area. Total diffuse CO2 emission was estimated at 21–44 t d−1. Gas vents 3-km away at The Gas Rocks produce 0.5 t d−1 of CO2 that probably derives from the Ukinrek Maars basalt based on similar δ13C values (∼−6‰), 3He/4He ratios (5.9–7.2 RA), and CO2/3He ratios (1–2 × 109) in the two areas. A lower 3He/4He ratio (2.7 RA) and much higher CO2/3He ratio (9 × 1010) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO2 emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.  相似文献   

12.
Dissolution rates of limestone covered by a water film open to a CO2-containing atmosphere are controlled by the chemical composition of the CaCO3-H2O-CO2 solution at the water-mineral interface. This composition is determined by the Ca2+-concentration at this boundary, conversion of CO2 into H+ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca2+, , and CO2 is derived. The Ca2+ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO2 across the air-water interface. In the solution, CO2 is converted into H+ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = αi(miceq − c), where c is the calcium concentration in the water film, ceq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α0 = 3 × 10−6 m s−1 and m0 = 0.3. For c > m0ceq, a slow rate law is valid with α1 = 3 × 10−7 m  s−1 and m1 = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.  相似文献   

13.
The hexa-aqua complexes [Fe(H2O)6−m−n(OH)n](2−n)+n = 0 → 3, m = 0 → 6 − n; [Fe(H2O)6−m−n(OH)n](3−n)+n = 0 → 4, m = 0 → 6 − n were investigated by ab-initio methods with the aim of determining their ground-state geometries, total energies and vibrational properties by treating their inner solvation shell as part of their gaseous precursor1 (or “hybrid approach”). After a gas-phase energy optimization within the Density Functional Theory (DFT), the molecules were surrounded by a dielectric representing the Reaction Field through an implicit Polarized Continuum Model (PCM). The exploration of several structural ligand arrangements allowed us to quantify the relative stabilities of the various ionic species and the role of the various forms of energy (solute-solvent electronic interaction, cavitation, dispersion, repulsion, liberation free energy) that contribute to stabilize the aqueous complexes. A comparison with experimental thermochemistries showed that ab-initio gas-phase + solvation energies are quite consistent with experimental evidence and allow the depiction of the most stable form in solution and the eventual configurational disorder of water/hydroxyl species around central cations. A vibrational analysis performed on the 54Fe, 56Fe, 57Fe and 58Fe isotopomers indicated important separative effects systematically affected by the extent of deprotonation. The role of the system’s redox state (fO2) and acidity (pH) on the isotopic imprinting of the aqueous species in solution was investigated by coupling the separative effects with speciation calculations. The observed systematics provided a tool of general utility in the interpretation of the iron isotopic signature of natural waters. Applications to the interpretation of isotopic fractionation in solution dictated by redox equilibria and to the significance of the Fe-isotopic imprinting of Banded Iron Formations are given.  相似文献   

14.
The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H2O melts. These methods allowed viscosity determinations between 102 and 107 Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H2O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature Tg, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X(H2O). The fitted expressions do not account for composition-dependent parameters other than X(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H2O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm3/mol) and increase strongly with H2O-content. Variations in melt structure that may account for the observed property variations are discussed.  相似文献   

15.
Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of δ18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in δ18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that δ18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ18O values of CO2 were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using 18O enriched water for the experiments it was demonstrated that changes in the δ18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in δ18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the δ18O values of CO2 and water are sufficiently distinct.  相似文献   

16.
To understand possible volcanogenic fluxes of CO2 to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO2 solubility. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe3+/FeT was measured by Mössbauer spectroscopy. The CO2 contents of glasses show no dependence on Fe3+/FeT and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO2 contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol−1 cm−2 for the integrated area under the carbonate doublet at 1430 and 1520 cm−1. The experimentally determined CO2 solubilities allow calibration of the thermodynamic parameters governing dissolution of CO2 vapor as carbonate in silicate melt, KII, (Stolper and Holloway, 1988) as follows: , ΔV0 = 20.85 ± 0.91 cm3 mol−1, and ΔH0 = −17.96 ± 10.2 kJ mol−1. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO2 dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and fO2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO2 contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO2 at IW and 0.24 wt.% of CO2 at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO2 to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO2 to an early Martian greenhouse is plausible.  相似文献   

17.
The solubility of baddeleyite (ZrO2) and the speciation of zirconium have been investigated in HF-bearing aqueous solutions at temperatures up to 400 °C and pressures up to 700 bar. The data obtained suggest that in HF-bearing solutions zirconium is transported mainly in the form of the hydroxyfluoride species ZrF(OH)3° and ZrF2(OH)2°. Formation constants determined for these species (Zr4+ + nF− + mOH− = ZrFn(OH)m°) range from 43.7 at 100 °C to 46.41 at 400 °C for ZrF(OH)3°, and from 37.25 at 100 °C to 43.88 at 400 °C for ZrF2(OH)2°.Although the solubility of ZrO2 is retrograde with respect to temperature, the measured concentrations of Zr are orders of magnitude higher than those predicted from theoretical extrapolations based on simple fluoride species (ZrF3+-ZrF62−). Model calculations performed for zircon show that zirconium can be transported by aqueous fluids in concentrations sufficient to account for the concentration of this metal at conditions commonly encountered in fluoride-rich natural hydrothermal systems.  相似文献   

18.
Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe3+ and Fe2+ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H2O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi2O6, Ca0.5AlSi2O6, and Mg0.5AlSi2O6. Iron oxide was added in the form of Fe2O3, NaFeO2, CaFe2O4, and MgFe2O4 with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe2O3. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe2+ and one of Fe3+. From the area ratios of the Fe2+ and Fe3+ absorption doublets, with corrections for differences in recoil-fractions of Fe3+ and Fe2+, the Fe3+/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe3+, δFe3+, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, ΔFe3+, ranging from ∼1.2 to ∼1.6 mm/s. Both δFe3+ and δFe2+ are negatively correlated with total iron oxide content and Fe3+/ΣFe. The dominant oxygen coordination number Fe3+ changes from 4 to 6 with decreasing Fe3+/ΣFe. The distortion of the Fe3+-O polyhedra of the quenched melts (glasses) decreases as the Fe3+/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δFe2+ and ΔFe2+ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe3+/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe2+ in a range of coordination states from 4- to 6-fold. The lower δFe2+-values for the most oxidized melts are consistent with a larger proportion of Fe2+ in 4-fold coordination compared with more reduced glasses and melts.  相似文献   

19.
The solubility of neodymium (III) fluoride was investigated at temperatures of 150, 200 and 250 °C, saturated water vapor pressure, and a total fluoride concentration (HF°aq + F−) ranging from 2.0 × 10−3 to 0.23 mol/l. The results of the experiments show that Nd3+ and NdF2+ are the dominant species in solution at the temperatures investigated and were used to derive formation constants for NdF2+ and a solubility product for NdF3. The solubility product of NdF3(logKsp=logaNd3++3logaF-) is −24.4 ± 0.2, −22.8 ± 0.1, and −21.5 ± 0.2 at 250, 200 and 150 °C, respectively, and the formation constant of NdF2+(logβ=logaNdF2+-logaNd3+-logaF-) is 6.8 ± 0.1, 6.2 ± 0.1, and 5.5 ± 0.2 at 250, 200 and 150 °C, respectively. The results of this study show that published theoretical predictions significantly overestimate the stability of NdF2+ and the solubility of NdF3.The potential impact of the results on natural systems was evaluated for a hypothetical fluid with a composition similar to that responsible for REE mineralization in the Capitan pluton, New Mexico. In contrast to results obtained using the theoretical predictions of Haas [Haas J. R., Shock E. L., and Sassani D. C. (1995) Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim. Cosmochim. Acta59, 4329-4350.], which indicate that NdF2+ is the dominant species in solution, calculations employing the data presented in this paper and previously published experimental data for chloride and sulfate species [Migdisov A. A., and Williams-Jones A. E. (2002) A spectrophotometric study of neodymium(III) complexation in chloride solutions. Geochim. Cosmochim. Acta66, 4311-4323; Migdisov A. A., Reukov V. V., and Williams-Jones A. E. (2006) A spectrophotometric study of neodymium(III) complexation in sulfate solutions at elevated temperatures. Geochim. Cosmochim. Acta70, 983-992.] show that neodymium chloride species predominate and that neodymium fluoride species are relatively unimportant. This suggests that accepted models for REE deposits that invoke fluoride complexation as the method of hydrothermal REE transport may need to be re-evaluated.  相似文献   

20.
Published solubility data for amorphous ferric arsenate and scorodite have been reevaluated using the geochemical code PHREEQC with a modified thermodynamic database for the arsenic species. Solubility product calculations have emphasized measurements obtained under conditions of congruent dissolution of ferric arsenate (pH < 3), and have taken into account ion activity coefficients, and ferric hydroxide, ferric sulfate, and ferric arsenate complexes which have association constants of 104.04 (FeH2AsO42+), 109.86 (FeHAsO4+), and 1018.9 (FeAsO4). Derived solubility products of amorphous ferric arsenate and crystalline scorodite (as log Ksp) are −23.0 ± 0.3 and −25.83 ± 0.07, respectively, at 25 °C and 1 bar pressure. In an application of the solubility results, acid raffinate solutions (molar Fe/As = 3.6) from the JEB uranium mill at McClean Lake in northern Saskatchewan were neutralized with lime to pH 2-8. Poorly crystalline scorodite precipitated below pH 3, removing perhaps 98% of the As(V) from solution, with ferric oxyhydroxide (FO) phases precipitated starting between pH 2 and 3. Between pH 2.18 and 7.37, the apparent log Ksp of ferric arsenate decreased from −22.80 to −24.67, while that of FO (as Fe(OH)3) increased from −39.49 to −33.5. Adsorption of As(V) by FO can also explain the decrease in the small amounts of As(V)(aq) that remain in solution above pH 2-3. The same general As(V) behavior is observed in the pore waters of neutralized tailings buried for 5 yr at depths of up to 32 m in the JEB tailings management facility (TMF), where arsenic in the pore water decreases to 1-2 mg/L with increasing age and depth. In the TMF, average apparent log Ksp values for ferric arsenate and ferric hydroxide are −25.74 ± 0.88 and −37.03 ± 0.58, respectively. In the laboratory tests and in the TMF, the increasing crystallinity of scorodite and the amorphous character of the coexisting FO phase increases the stability field of scorodite relative to that of the FO to near-neutral pH values. The kinetic inability of amorphous FO to crystallize probably results from the presence of high concentrations of sulfate and arsenate.  相似文献   

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