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1.
Any oxide and silicate mineral which is nominally anhydrous but crystallized in the presence of H2O incorporates traces of H2O in solid solution. In the case of MgO it can be shown that OH? pairs convert into H2+O 2 2? . If the H2 molecules are lost, the O 2 2? remain in the lattice as excess oxygen stabilized by excess cation vacancies. When the O 2 2? anions decay either thermally or by decompression unbound O? states (positive holes) are generated which lead to surface charges and subsurface space charge layers. Calculated space charge profiles are presented. O? concentrations as small as 10–20 ppm suffice to create electric surface fields of the order of 4·107 V·m?1. The diffusion mechanism which derives from these premises incorporates novel features: the cation diffusion is coupled to the counterdiffusion of unbound and vacancy-bound O? states. The cation diffusion is predicted to be very fast because first, it is field-enhanced (electrochemically driven) and second, it is not rate-limited by the intrinsic cation vacancy concentration nor by the counter-diffusion of other cations. The model may apply to cases of inverse zoning and diffusion rim formation in minerals under certain P-T conditions.  相似文献   

2.
In this paper we discuss the main petrogenetic models for granitic pegmatites and how these models have evolved over time. We suggest that the present state of knowledge requires that some aspects of these models to be modified, or absorbed into newer ones. Pegmatite formation and internal evolution have long supposed the need for highly water- and flux-enriched magmas to explain the differences between pegmatites and other intrusives of similar major element composition. Compositions and textural characteristics of fluid and melt inclusions in pegmatite minerals provide strong evidence for such magmas. Furthermore, we show that melt inclusion research has increased the number of potential flux components, which may include H2O, OH?, CO2, HCO 3 ? , CO 3 2? , SO 4 2? , PO 4 3? , H3BO3, F , and Cl, as well as the elements Li, Na, K, Rb, Cs, and Be, herein described as melt structure modifiers. In this paper we emphasize that the combined effect which these components have on the properties of pegmatite melts is difficult to deduce from experimental studies using only a limited number of these components. The combination and the amount of the different magmatic species, together with differences in the source region, and variations in pressure and temperature cause the great diversity of the pegmatites observed. Some volatile species, such as CO 3 2? and alkalis, have the capacity to increase the solubility of H2O in silicate melt to an extraordinary degree, to the extent that melt-melt-fluid immiscibility becomes inevitable. It is our view that the formation of pegmatites is connected with the complex interplay of many factors.  相似文献   

3.
Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO 3 3? , CO 3 2? , NO 3 ? series and for NO 2 ? and LiNO3(g). Calculated trends in average polarizability and polarizability anisotropy in the BO 3 3? -NO 3 ? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a1′, a2″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO 3 2? ion in a D3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO3 molecule and on the free NO 3 ? ion in the distorted geometry found in LiNO3(g) allow us to separate polarizability contributions internal to the NO 3 ? and Li+ ions from those which arise from the Li+-NO 3 ? interaction. The Li+-NO 3 ? interaction term so obtained is much smaller than the NO 3 ? contribution but is in turn larger than the Li+ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO 3 ? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for 14N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO 3 3? -NO 3 ? series are properly reproduced.  相似文献   

4.
An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO4) · 2H2O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K+, Na+, NH 4 + , Mg2+, SO 4 2? , CO 3 2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg2+ and SO 4 2? concentrations. The enrichment in K+, Na+, and NH 4 + does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.  相似文献   

5.
Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO 4 2? /CO 3 2? ratios. Chemical determination of CO 3 2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO 4 2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO 4 2? /CO 3 2? ratio. Then, the stoichiometry of the anionic interlayers, X s , X c , and X OH were determined, and the influence of X s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X s =0 and X s =1) was characterized. In addition, a partitioning curve of SO 4 2? and CO 3 2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO 4 2? /CO 3 2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO 3 2? -rich solid solutions.  相似文献   

6.
The borate polyhedra BO 3 3? , B(OH)3, BO 4 5? , and B(OH) 4 ? are studied using the ab initio and multiple scattering Xα quantum mechanical methods. The ab initio self-consistent-field (SCF) molecular orbital (MO) method, at the minimum basis set level, predicts equilibrium B-O distances within 0.04 Å of their average values in solids so long as the polyhedron charge is small. Orbital energies from double zeta basis set ab initio calculations and analogies with isoelectric compounds are used to assign the X-ray spectra of BO 3 3? and to predict the valence region spectra of BO 4 5? . Contour maps of the difference between molecular and superimposed free atom electron densities show charge buildup along the B-O bond which is only slightly smaller than that observed in CO 3 2? .  相似文献   

7.
A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O2, Cl?, NO 3 ? , SO 4 2? , dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ15NNO3 and δ18ONO3 composition. Samples in which NO 3 ? was too low for stable isotope analysis were analyzed for excess dissolved N2. Groundwater NO 3 ? concentrations declined between the agricultural field and the discharge point. Chloride and δ15NNO318ONO3 data indicated that the drop in NO 3 ? was caused primarily by dilution of shallow NO 3 ? -rich water with deeper, NO 3 ? -depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ15NNO3 and δ18ONO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N2. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO 3 ? is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.  相似文献   

8.
Ionic conductivity of polycrystalline calcite containing varying amounts of PO 4 3? ions was measured in the pressure range of 1–6 GPa and at room temperature. Electrical conductivity increased with pressure corresponding to the phase transition of calcite I to calcite II. The conductivity in calcite III decreased exponentially with pressure. Calculated activation volumes of the conductivity varied with PO 4 3? content in the range of 0.94–5.34 cm3/mol. This variation corresponded to the lattice parameter change of calcite I due to PO 4 3? incorporation and indicated the contribution of CO 3 2? -vacancies associated with PO 4 3? ions to the conductivity.  相似文献   

9.
Submarine groundwater discharge (SGD) was quantified at select sites in San Francisco Bay (SFB) from radium (223Ra and 224Ra) and radon (222Rn) activities measured in groundwater and surface water using simple mass balance box models. Based on these models, discharge rates in South and Central Bays were 0.3?C7.4?m3?day?1?m?1. Although SGD fluxes at the two regions (Central and South Bays) of SFB were of the same order of magnitude, the dissolved inorganic nitrogen (DIN) species associated with SGD were different. In the South Bay, ammonium (NH 4 + ) concentrations in groundwater were three-fold higher than in open bay waters, and NH 4 + was the primary DIN form discharged by SGD. At the Central Bay site, the primary DIN form in groundwater and associated discharge was nitrate (NO 3 ? ). The stable isotope signatures (??15NNO3 and ??18ONO3) of NO 3 ? in the South Bay groundwater and surface waters were both consistent with NO 3 ? derived from NH 4 + that was isotopically enriched in 15N by NH 4 + volatilization. Based on the calculated SGD fluxes and groundwater nutrient concentrations, nutrient fluxes associated with SGD can account for up to 16?% of DIN and 22?% of DIP in South and Central Bays. The form of DIN contributed to surface waters from SGD may impact the ratio of NO 3 ? to NH 4 + available to phytoplankton with implications to bay productivity, phytoplankton species distribution, and nutrient uptake rates. This assessment of nutrient delivery via groundwater discharge in SFB may provide vital information for future bay ecological wellbeing and sensitivity to future environmental stressors.  相似文献   

10.
Experiments carried out in the system granite-H2O-HF at 0.1 GPa show that the crystal-liquid equilibrium temperature of quartz rises and that of alkali-feldspar goes down with increasing F content. The calculated results of quartz and alkali feldspar crystal-liquid equilibrium show that the activity of SiO2 in melt increases and the activities of NaAlSi3O8(Ab) and KAlSi3O8(Or) decrease, with a greater decreasing extent for a Ab L than a Or L . These systematic changes are believed to be caused by F complexing with Al, Na, K, but not Si in the melt, and are consistent with F decomposing AlO 2 ? tetrahedra and more preferentially forming complexes with Na than K. The comparison between effects of F and H2O on phase equilibrium suggests that the maximum difference affecting melt structure between F and OH is F complexing without Si and OH complexing with Si in granitic melt.  相似文献   

11.
Irrigation in semi-arid agricultural regions can have profound effects on recharge rates and the quality of shallow groundwater. This study coupled stable isotopes (2??, 18O), age-tracers (3H, CFCs, 14C), 87Sr/86Sr ratios, and elemental chemistry to determine the sources, residence times, and flowpaths of groundwater and agricultural contaminants (e.g. NO 3 ?C ) in the Saddle Mountains Basalt Aquifer in central Washington, USA, where over 80% of the population depend on groundwater for domestic use. Results demonstrate the presence of two distinct types of water: contaminated irrigation water and pristine regional groundwater. Contaminated irrigation water has high NO 3 ?C concentrations (11?C116? mg/l), 87Sr/86Sr ratios (0.70659?C0.71078) within range of nitrogen-based fertilizers, detectable tritium (2.8?C13.4 TU), CFC ages 20?C40?years, high ??18O values (?16.9 to ?13.5??), and ??100 percent modern 14C. Pristine regional groundwater has low NO 3 ?C concentrations (1?C5? mg/l), no detectable tritium (??0.8 TU), low ??18O values (?18.9 to ?17.3??) and 14C ages from ??15 to 33?ky BP. Nitrogen and oxygen isotopes of NO 3 ?C , combined with high dissolved oxygen values, show that denitrification is not an important process in the organic-poor basalt aquifers resulting in transport of high NO 3 ?C irrigation water to depths greater than 40?m in less than 30? years.  相似文献   

12.
A number of experimental CO2 solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO2 in the melt by polymer condensation reactions such as SiO 4(m 4? +CO2(v)+Si n O 3n+1(m) (2n+1) ?Si n+1O 3n+4(m) (2n+4)? +CO 3(m )2? . For various metalsilicate systems the relative solubility of CO2 should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li2O-SiO2, Na2O-SiO2, K2O-SiO2, CaO-SiO2, MgO-SiO2 and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO2 solubility data for a number of mineral and natural melts suggests that for the reaction CO2(m) ? CO2(v)
  1. CO2-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
  2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO2 in the melt, is approximately equal to 30 cm3 mole?1 and independent of P and T;
  3. Δ C p 0 is approximately equal to zero in the T range 1,400° to 1,650 °C and
  4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO2 content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form
$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO2 isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.  相似文献   

13.
Hydrogeochemical studies have been carried out in a coastal region, using multivariate statistical model, for better understanding the controlling processes that influence the aquifer chemistry. Two principal components (PC1 and PC2) are extracted from the data set of chemical variables (pH, TDS, Ca2+, Mg2+, Na+, K+, HCO 3 ? , Cl?, SO 4 2? , NO 3 ? and F?), which account for 79% of the total variation in the quality of groundwater. The PC1 (salinity controlled process) includes the concentrations of TDS, Mg2+, Na+, K+, Cl?, SO 4 2? and NO 3 ? , while the PC2 (alkalinity controlled process) comprises the concentrations of pH, HCO 3 ? and F?. The spatial distribution of PC scores identifies the locations of high salinity and alkalinity processes. The first process corresponds to the influences of geogenic, anthropogenic and marine sources, and the second one to the influence of water-soil-rock interaction. Thus, the present study shows the usefulness of multivariate statistical model as an effective means of interpretation of spatial controlling processes of groundwater chemistry.  相似文献   

14.
According to Koopmans' theorem, only the electrons associated with molecular levels of negative energy are stable. Many ions which cannot exist in the isolated state because certain occupied levels are positive, become stable in crystals under the stabilization effect arising from the crystal field. As examples, we have studied CO 3 2? in calcite, NO 3 ? in NaNO3, and several natural limpurities: O 3 ? in fluorite, [(OH)4]4?, [(OH)3F]4? and [(OH)2F2]4? in zircon and thorite, by means of the molecular self-consistent field, the crystal field being simulated by point charges. As expected, all the energies corresponding to the occupied levels are negative within the crystal field, contrary to what occurs in the isolated state. Informations concerning the structure and the size of the critical germ are obtained for CaCO3 and NaNO3.  相似文献   

15.
The carbonate (CO 3 ?2 ) produced by Sporosarcina pasteurii was injected electrokinetically to enhance the mechanical properties of soft clay soils. In this method the Ca2+ was injected into the anode chamber and moved towards the cathode by electromigration and electroosmotic flow. Then the released CO 3 ?2 from a blend of bacteria and urea was injected into the cathode chamber. The CO 3 ?2 ions were moved from the cathode to the anode under electromigration mechanism. The CaCO3 was precipitated in the presence of calcium in porous medium of the soil, and consequently increased the shear strength of the soil. The polarity reversal was applied to have a homogeneous distribution of CaCO3.  相似文献   

16.
Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO4, celestite SrSO4 and barite BaSO4 have revealed the presence of PO 3 2? and SO 3 ? radicals. Hyperfine structure from33S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO 3 ? . The dynamics of one of the two SO 3 ? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.  相似文献   

17.
Assessment of groundwater quality is essential to ensure sustainable use of it for drinking, agricultural, and industrial purposes. The chemical quality of groundwater of Gaya region has been studied in detail in this work to delineate the potable groundwater zones. A total of 30 groundwater samples and 2 surface water samples were collected in and around Gaya district of Bihar. The major cations follow the trend: Ca2+?>?Mg2+?>?Na+?>?K+. The domination of calcium ions in the groundwater is due to weathering of rocks. The K+ ranged between 0.2 and 47.95 ppm, suggesting its abundance the below desired limit; but some samples were found to be above permissible limit. K+ weathering of potash silicate and the use of potash fertilizer could be the source. The major anions abundance followed the order HCO 3 ? ?>?Cl??>?SO 4 2? ?>?NO 3 ? ?>?PO 4 3? . Dissolution of carbonates and reaction of silicates with carbonic acid accounts for the addition of HCO 3 ? to the groundwater and oxidation of sulphite may be the source of SO 4 2? . Principal component analysis was utilized to reflect those chemical data with the greatest correlation and seven major principal components (PCs) representing >80 % of cumulative variance were able to interpret the most information contained in the data. PC1, PC2 and PC3 reflect the hydrogeochemical processes like mineral dissolution, weathering and anthropogenic sources. PC4, PC5, PC6 and PC7 show monotonic, random and independent relationships.  相似文献   

18.
Hydrogeochemical investigations were carried out around Fetzara Lake, Northeast Algeria, to assess the quality of groundwater for its suitability for drinking and irrigation purposes. The groundwater chemistry is mainly controlled by the water?Crock interactions, but also influenced by other processes such as evapotranspiration and ion exchange. Groundwater samples collected, during two periods (1993 and 2007) from wells in the area were analyzed for pH, EC, TDS, Ca2+, Mg2+, Na+, K+, CO 3 2? , HCO 3 ? , Cl?, SO 4 2? , and NO 3 ? . The chemical relationships in Piper??s diagram and Gibbs??s diagram suggest that groundwaters mainly belong to noncarbonate alkali type and Cl? group and are controlled by evaporation dominance, respectively, due to the sluggish drainage conditions, greater water?Crock interaction, and anthropogenic activities. A comparison of the groundwater quality in relation to drinking water quality standards proves that most of the water samples are not suitable for drinking. US Salinity Laboratory??s and Wilcox??s diagrams and %Na+ used for evaluating the water quality for irrigation suggest that the majority of the groundwater samples are not good for irrigation.  相似文献   

19.
Si, Al, Ca, Mg, Fe, Na, K, CO 3 ?2 , F, etc. are detected from the fluid inclusion leachates. Among these constituents, Si, Na, and CO 3 ?2 are predominant, amounting to more than 80 percent. This indicates that the ore-forming solution must be alkaline with Si, Na, and CO 3 ?2 as its dominant components. Homogenization temperatures for the solution range from 80 to 360°C. Although rock quartz can crystallize at the above temperature interval, perfect crystals of economic importance are largely formed below 260°C. The temperature of formation increases toward the granite intrusives at a rate of about one degree per meter. It is estimated from the lithostatic load that the salinity of rock quartz is 17–23 (NaCl wt%), while that of vein quartz is relatively high as compared with the former. There is a tendency for the salinity of the ore-forming solution to increase with depth.  相似文献   

20.
The electron paramagnetic resonance (EPR) spectra of Fe3+ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B 2 0 = 0.112 cm?1, B 2 2 = 0.0688 cm?1 for one and B 2 0 = 0.116 cm?1, B 2 2 = 0.0766 cm?1 for the second. These two spectra arise from Fe3+ substituted for Al3+ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.  相似文献   

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