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1.
The Rb–Sr and 147Sm–143Nd age data obtained for sheeted dolerite dykes and rocks of the Platinum Belt of the Urals within the Tagil segment of the paleoceanic spreading structure (Middle Urals) are discussed. The study of the Rb–Sr isotope systematics of gabbro allowed us to reveal errochronous dependencies, which yielded ages of 415 and 345 Ma at (87Sr/86Sr)0 = 0.70385 ± 0.00068 and 0.7029 ± 0.0010, correspondingly. The 147Sm–143Nd isotope age data demonstrate a specific coincidence of the chronometric ages of the sheeted dolerite dyke complex (426 ± 54, 426 ± 34, and 424 ± 19 Ma) and gabbro from the Revda gabbro–ultramafic massif (431 ± 27 Ma) and from screens between dolerite dykes in the sheeted dyke complex (427 ± 32 Ma, 429 ± 26 Ma). The proximity of the 147Sm–143Nd ages of gabbro and dolerite can be explained by the thermal effect of the basaltic melt, which is the protolith for the dyke complex, on the hosting gabbro. 相似文献
2.
A synthetic Topopah Spring Tuff water representative of one type of pore water at Yucca Mountain, NV was evaporated at 95°C
in a series of experiments to determine the geochemical controls for brines that may form on, and possibly impact upon the
long-term integrity of waste containers and drip shields at the designated high-level, nuclear-waste repository. Solution
chemistry, condensed vapor chemistry, and precipitate mineralogy were used to identify important chemical divides and to validate
geochemical calculations of evaporating water chemistry using a high temperature Pitzer thermodynamic database. The water
evolved toward a complex "sulfate type" brine that contained about 45 mol % Na, 40 mol % Cl, 9 mol % NO3, 5 mol % K, and less than 1 mol % each of SO4, Ca, Mg, ∑CO2(aq), F, and Si. All measured ions in the condensed vapor phase were below detection limits. The mineral precipitates identified
were halite, anhydrite, bassanite, niter, and nitratine. Trends in the solution composition and identification of CaSO4 solids suggest that fluorite, carbonate, sulfate, and magnesium-silicate precipitation control the aqueous solution composition
of sulfate type waters by removing fluoride, calcium, and magnesium during the early stages of evaporation. In most cases,
the high temperature Pitzer database, used by EQ3/6 geochemical code, sufficiently predicts water composition and mineral
precipitation during evaporation. Predicted solution compositions are generally within a factor of 2 of the experimental values.
The model predicts that sepiolite, bassanite, amorphous silica, calcite, halite, and brucite are the solubility controlling
mineral phases. 相似文献
3.
Reactions and partial melting of peraluminous rocks in the presence of H2O-CO2–salt fluids under parameters of granulite-facies metamorphism were modeled in experiments on interaction between orthopyroxene–cordierite–biotite–plagioclase–quartz metapelite with H2O, H2O-CO2, H2O-CO2-NaCl, and H2O-CO2-KCl fluids at 600 MPa and 850°C. Rock melting in the presence of H2O and equimolar H2O-CO2 fluids generates peraluminous (A/CNK1 > 1.1) melts whose composition corresponds to magnesian calcic or calc–alkaline S-type granitoids. The melts are associated with peritectic phases: magnesian spinel and orthopyroxene containing up to 9 wt % Al2O3. In the presence of H2O-CO2-NaCl fluid, cordierite and orthopyroxene are replaced by the association of K-Na biotite, Na-bearing gedrite, spinel, and albite. The Na2O concentrations in the biotite and gedrite are functions of the NaCl concentrations in the starting fluid. Fluids of the composition H2O-CO2-KCl induce cordierite replacement by biotite with corundum and spinel and by these phases in association with potassium feldspar at X KCl = 0.02 in the fluid. When replaced by these phases, cordierite is excluded from the melting reactions, and the overall melting of the metapelite is controlled by peritectic reactions of biotite and orthopyroxene with plagioclase and quartz. These reactions produce such minerals atypical of metapelites as Ca-Na amphibole and clinopyroxene. The compositions of melts derived in the presence of salt-bearing fluids are shifted toward the region with A/CNK < 1.1, as is typical of so-called peraluminous granites of type I. An increase in the concentrations of salts in the fluids leads to depletion of the melts in Al2O3 and CaO and enrichment in alkalis. These relations suggest that the protoliths of I-type peraluminous granites might have been metapelites that were melted when interacting with H2O-CO2-salt fluids. The compositions of the melts can evolve from those with A/CNK > 1.1 (typical of S-type granites) toward those with A/CNK = 1.0–1.1 in response to an increase in the concentrations of alkali salts in the fluids within a few mole percent. Our experiments demonstrate that the origin of new mineral assemblages in metapelite in equilibrium with H2O-CO2-salt fluids is controlled by the activities of alkaline components, while the H2O and CO2 activities play subordinate roles. This conclusion is consistent with the results obtained by simulating metapelite mineral assemblages by Gibbs free energy minimization (using the PERPE_X software), as shown in log(\({a_{{H_2}O}}\))–log(\({a_{N{a_2}O}}\)) and log(\({a_{{H_2}O}}\))–log(\({a_{{K_2}O}}\)) diagrams. 相似文献
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Phase equilibria in the system CaO–MgO–SiO2–CO2–H2O–NaCl are calculated to illustrate phase relations in metacarbonates over a wide-range of P–T–X[H2O–CO2–NaCl] conditions. Calculations are performed using the equation of state of Duan et al. (Geochim Cosmochim Acta 59:2869–2882, 1995) for H2O–CO2–NaCl fluids and the internally consistent data set of Gottschalk (Eur J Mineral 9:175–223, 1997) for thermodynamic properties of solids. Results are presented in isothermal-isobarical plots showing stable mineral assemblages as a function of fluid composition. It is shown that in contact-metamorphic P–T regimes the presence of very small concentrations of NaCl in the fluid causes almost all decarbonation reactions to proceed within the two fluid solvus of the H2O–CO2–NaCl system. Substantial flow of magma-derived fluids into marbles has been documented for many contact aureoles by shifts in stable isotope geochemistry of the host rocks and by the progress of volatile-producing mineral reactions controlled by fluid compositions. Time-integrated fluid fluxes have been estimated by combining fluid advection/dispersion models with the spatial arrangement of mineral reactions and isotopic resetting. All existing models assume that minerals react in the presence of a single phase H2O–CO2 fluid and do not allow for the effect that fluid immiscibility has on the flow patterns. It is shown that fluids emanating from calc-alkaline melts that crystallize at shallow depths are brines. Their salinity may vary depending mainly on pressure and fraction of crystallized melt. Infiltration-driven decarbonation reactions in the host rocks inevitably proceed at the boundaries of the two fluid solvus where the produced CO2 is immiscible and may separate from the brine as a low salinity, low density H2O–CO2 fluid. Most parameters of fluid–rock interaction in contact aureoles that are derived from progress of mineral reactions and stable isotope resetting are probably incorrect because fluid phase separation is disregarded. 相似文献
7.
Applying Fe2+–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe3+ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO2 buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe3+/Fe2+ ratios were generated. The Fe3+ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fetotal = Fe2+, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe2+–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe3+ in garnet (i.e. using only measured Fe2+) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe3+ whilst direct accounting of Fe3+ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers. 相似文献
8.
The phase state of the fluid in the H2O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H2O content of the glassy phase. 相似文献
9.
M. Shamim K. Dana 《International Journal of Environmental Science and Technology》2018,15(6):1275-1284
Evans blue (EB) dye has been successfully removed from aqueous solution through chemisorption process with synthetic layered double hydroxides (LDH) [Zn1?x Al x (OH)2NO3·nH2O, x = 0.2–0.33]. Detailed evaluation of dye adsorption characteristics in aqueous medium has been studied for different layer charged hydroxides. The objective of the study was efficient removal of a dye by LDH and understanding the structure–property relationship of the LDH on its adsorption behaviour. Highest Langmuir monolayer adsorption capacity (Qt) of 113.64 mg g?1 was observed for highest layer charge x = 0.33, and it is higher than previously reported values for the LDH-EB dye system. Under optimized condition, 99% of EB dye is removed from aqueous solution within 60 min at 313 K. The monotonous increase in Qt value with increasing layer charge is correlated with layer charge density (LCD) and lower particle size of the synthetic LDH. The variation in Qt among different layer charged materials is marginal (3.46–4.17%) with respect to the respective anion exchange capacity (AEC) of LDH NO3. The limited contribution of AEC surmises the occurrence of surface-only adsorption and absence of intercalation as validated by the XRD analysis. The spontaneity of the EB dye removal increases with increasing temperature and LCD. The chemisorption nature of the adsorption reaction is well supported by the thermodynamics values. 相似文献
10.
Homogeneous single crystals of synthetic monticellite with the composition \({\text{Ca}}_{0.88}{\text{Mg}}_{1.12}{\text{SiO}}_4\) (Mtc I) were annealed in a piston-cylinder apparatus at temperatures between 1000 and \(1200\,^{\circ }\hbox {C}\), pressures of 1.0–1.4 GPa, for run durations from 10 min to 24 h and applying bulk water contents ranging from 0.0 to 0.5 wt% of the total charge. At these conditions, Mtc I breaks down to a fine-grained, symplectic intergrowth. Thereby, two types of symplectites are produced: a first symplectite type (Sy I) is represented by an aggregate of rod-shaped forsterite immersed in a matrix of monticellite with end-member composition (Mtc II), and a second symplectite type (Sy II) takes the form of a lamellar merwinite–forsterite intergrowth. Both symplectites may form simultaneously, where the formation of Sy I is favoured by the presence of water. Sy I is metastable with respect to Sy II and is successively replaced by the latter. For both symplectite types, the characteristic spacing of the symplectite phases is independent of run duration and is only weeakly influenced by the water content, but it is strongly temperature dependent. It varies from about 400 nm at \(1000\,^{\circ }\hbox {C}\) to 1200 nm at \(1100\,^{\circ }\hbox {C}\) in Sy I, and from 300 nm at \(1000\,^{\circ }\hbox {C}\) to 700 nm at \(1200\,^{\circ }\hbox {C}\) in Sy II. A thermodynamic analysis reveals that the temperature dependence of the characteristic spacing of the symplectite phases is due to a relatively high activation energy for chemical segregation by diffusion within the reaction front as compared to the activation energy for interface reactions at the reaction front. The temperature dependence of the characteristic lamellar spacing and the temperature-time dependence of overall reaction progress have potential for applications in geo-thermometry and geo-speedometry. 相似文献
11.
《Comptes Rendus Geoscience》2018,350(5):195-201
To protect their steel structures from corrosion by cathodic protection, many harbours use aluminium sacrificial anodes, which induces aluminium release and potential contamination of the surrounding waters and sediments. To study the impact on Al mobility, a natural marine sediment was artificially contaminated with aluminium from different sources: sulphate or chloride salts, or sacrificial anodes. To estimate Al mobility in sediments, single (HCl) and sequential (F6) extractions were performed; they highlighted that aluminium is poorly mobile in natural sediment (HCl-leachable: 2% and F6-leachable: 9%). Contamination by aluminium salts inhibits HCl-leachability (≤ 2%), whereas the Al F6-leachability is intensified up to 18%, suggesting that the additional aluminium is scavenged in a mobile fraction that HCl is not able to solubilise. In case of aluminium anode contamination, sediments present surging Al HCl-leachable (15%) and F6-leachable (32%) fractions, which are related to aluminium mineralogical speciation. Indeed, contrary to the Al naturally present or introduced by salts, Al released by anodes is partly bound to the acid-soluble fraction, probably because of the integration of the released Al into the calcareous deposit produced at the anodes surfaces that finally comes away and gets mixed up with the sediment. The presence of aluminium in the acid-soluble fraction of sediments could have an important environmental impact as this fraction is easily available. Indeed, Al scavenged in the acid-soluble fraction of sediments participates in enhancing Al lability near the sacrificial anodes and may affect the surrounding ecosystems. 相似文献
12.
We determined the forward rate constant (K+) for the Fe2+–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The
rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron
and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while
at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2)
n
with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition
is given by
where C
o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals
around the closure temperature (T
c) of Fe–Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe–Mg ordering states of several
OPx crystals (∼ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T
c ∼290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model
yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11–17°C/Myr
below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints. 相似文献
13.
G. S. Nikolaev A. A. Ariskin G. S. Barmina M. A. Nazarov R. R. Almeev 《Geochemistry International》2016,54(4):301-320
Testing the Ballhaus–Berry–Green Ol–Opx–Sp oxybarometer (BBG) on independent experimental data indicates that it overestimates the oxygen fugacity by 0.6–1.3 log units under mildly reduced conditions (near the C–CO buffer) and by as much as 2–3 log units under reduced conditions (at the IW buffer and below it). A newly developed oxibarometer is suggested to minimize this effect and enhance the capabilities of redoxometry of low-pressure mineral associations, including magmatic melts undersaturated with respect to orthopyroxene (Opx). The new empirical equation of the oxybarometer is applicable to a wide range of mafic–ultramafic magmas of normal alkalinity, including terrestrial, lunar, and meteoritic systems under pressures of 0.001–25 kbar and oxygen fugacity ranging from IW–3 to NNO + 1. The derived regression fits the ΔQFM values of the calibration dataset (154 experiments) accurate to ~0.5 log units. The new oxybarometer eliminates systematic errors when redox parameters are evaluated for the reduced region (from IW–3 to C–CO) and for crystallization of magmas without Opx on the liquidus. The efficiency of the suggested model is demonstrated by its application to natural rocks: (1) low-Ti lunar basalts, (2) tholeiites from the Shatsky Rise, (3) Siberian flood basalts, (4) rocks of the layered series of the Yoko-Dovyren intrusion, and (5) mantle xenoliths collected in southern Siberia, Mongolia, China, and the southern Russian Far East. The values yielded by such oxybarometers for intrusive rocks, which underwent long-lasting cooling and postcumulus reequilibration, should be regarded with reserve. 相似文献
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The dissolution rate of minerals in silicate melts is generally assumed to be a function of the rate of mass transport of the released cations in the solvent. While this appears to be the case in moderately to highly viscous solvents, there is some evidence that the rate-controlling step may be different in very fluid, highly silica undersaturated melts such as basanites. In this study, convection-free experiments using solvent melts with silica activity from 0.185–0.56 and viscosity from 0.03–4.6 Pa s show that the dissolution rate is strongly dependent on the degree of superheating, silica activity and the viscosity of the solvent. Dissolution rates increase with increasing melt temperature and decreasing silica activity and viscosity. Quartz dissolution in melts with viscosity <0.59–1.9 Pa s and silica activity <0.47 is controlled by the rate of interface reaction as shown by the absence of steady state composition and silica saturation in the interface melts. Only in the most viscous melt with the highest silica activity is quartz dissolution controlled by the rate of diffusion in the melt and only after a long initiation time. The results of this study indicate that although a diffusion-based model may be applicable to dissolution in viscous magmas, a different approach that combines the interplay between the degree of undersaturation of the melt and its viscosity is required in very fluid melts.This revised version was published online September 2004 with a correction to Figure 8. 相似文献
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Experimental investigations in the system rare-metal granite–Na2O–SiO2–H2O with the addition of aqueous solutions containing Rb, Cs, Sn, W, Mo, and Zn at 600°C and 1.5 kbar showed that the typical elements of rare-metal granites (Li, Rb, Cs, Be, Nb, and Ta) are preferentially concentrated in hydrosilicate liquids coexisting with aqueous fluid. The same behavior is characteristic of Zn and Sn, the minerals of which are usually formed under hydrothermal conditions. In contrast, Mo and W are weakly extracted by hydrosilicate liquids and almost equally distributed between them and aqueous fluids. Liquids similar to those described in this paper are formed during the final stages of magmatic crystallization in granite and granitepegmatite systems. The formation of hydrosilicate liquids in late magmatic and postmagmatic processes will be an important factor controlling the redistribution of metal components between residual magmatic melts, minerals, and aqueous fluids and, consequently, the mobility of these components in fluid-saturated magmatic systems enriched in rare metals. 相似文献
19.
Georgios Papastergios Jose-Luis Fernandez-Turiel Anestis Filippidis Domingo Gimeno 《Environmental Earth Sciences》2011,64(3):743-751
The procedure proposed in this study is based on the extraction of elements in soils by analytical grade HNO3, the distribution of the elemental data displayed on probability graphs (Q–Q plots) and the visualization of the results
spatially by GIS software. The applicability of the procedure is demonstrated in an urban area and its surroundings (Kavala,
northern Greece). A major (Ca) and a trace (Ag) element are used as examples in order to demonstrate the applicability of
the proposed procedure. Normal probability and lognormal probability plots of Ca and Ag show that their concentrations are
lognormally distributed and that their geochemical baseline and anomaly threshold values can be calculated with the aid of
their geometric mean and geometric deviation. The advantages of the proposed procedure are simplicity, comprehensiveness,
and low cost. It can be applied to environmental geochemical studies of soils in a variety of areas. 相似文献
20.
We conducted reversed deliquescence experiments in saturated NaCl–NaNO3–H2O, KNO3–NaNO3–H2O, and NaCl–KNO3–H2O systems from 90 to 120°C as a function of relative humidity and solution composition. NaCl, NaNO3, and KNO3 represent members of dust salt assemblages that are likely to deliquesce and form concentrated brines on high-level radioactive
waste package surfaces in a repository environment at Yucca Mountain, NV. Discrepancy between model prediction and experiment
can be as high as 8% for relative humidity and 50% for dissolved ion concentration. The discrepancy is attributed primarily
to the use of 25°C models for Cl–NO3 and K–NO3 ion interactions in the current Yucca Mountain Project high-temperature Pitzer model to describe the nonideal behavior of
these highly concentrated solutions. 相似文献