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1.
Drying induced pH changes were quantified on the surface of Na+, Ca2+, Mg2+ and Al3+ saturated smectite and kaolinite clays. This was achieved using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to measure real time changes to a pH indicator, sorbed to the clay mineral surface, during wetting and drying events. Using this technique it was possible to measure how low the pH of the surface drops during dehydration, the critical water content at which acidification of the surface begins and lastly how reversible the pH decrease is. The results show that only Al3+-smectite shows acidification below pH 4.8 with drying. The pH starts to decrease on the Al3+-smectite surface even when significantly hydrated (gravimetric water content ∼ 125 mg/m2), and falls to between 1.2 and 1.4 when completely air dry. The drying induced pH decrease is completely reversible on rewetting, suggesting large pH oscillations may occur on smectite surfaces with appreciable exchangeable Al3+. Aluminium saturated kaolinite did not show significant acidification in response to drying (pH > 3.5), however, a 0.1 M AlCl3 solution evaporated to a final pH of 2.8. The enhanced acidification observed on an Al-smectite clay compared to a solution containing free Al3+ ions highlights the role of highly charged surfaces in the hydrolysis reaction that occurs within the hydration shell of exchangeable Al3+ ions.  相似文献   

2.
The dissolution of well crystallized gibbsite far at from equilibrium was studied in batch and mixed flow through reactors. The dissolution experiments were carried out between pH 2 and 6 in the presence of 10 mmol L−1 citrate, at pH 2 and 3 in the presence of 10 mmol L−1 chloride, nitrate, and sulfate, and at pH 2 and 3 in the presence of 1.5 mmol L−1 silica at 20°C. The dissolution rate of gibbsite, RAl (mol m−2 s−1), increases in the order of chloride ≈ nitrate < silica < sulfate ≈ citrate. In presence of silica, sulphate, and citrate dissolution is catalysed by the formation of aluminium complexes at the gibbsite surface (pH 2 and 3). From pH 2 to 3 no effect of RAl on hydrogen activity is predicted as singly coordinated surface sites at the edges of the platy gibbsite crystals, [≡AlOH2+0.5] ≈ [≡AlOH], are almost saturated with protons. However at pH >3 dissolution is slowed by a decrease of [≡AlOH2+0.5].Gibbsite dissolution rates measured in closed and open systems were identical within the experimental and analytical uncertainty. This observation indicates that gibbsite dissolution is a surface controlled process. If dissolution of gibbsite occurs close to equilibrium RAl values may be predicted by an approximately linear function of ΔGr.  相似文献   

3.
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4.
Continuous core samples were taken through the unsaturated zone at three sites on the outcrop of Permo-Triassic sandstone in the British West Midlands. Sample sites were chosen for lack of recent, direct anthropogenic disturbance, and for differing vegetation: heathland, birch woodland and conifer forest. Interstitial water was extracted and analyzed for 32 major and trace elements. Solid phases were analyzed for exchangeable cations and mineralogy. The rate of recharge calculated using a Cl mass balance method was three times greater below heathland than below afforested sites owing to higher evapotranspiration rates in the woodlands.Carbonate minerals were absent from the unsaturated zone at each site. Soil solutions were acidic and soils at the woodland sites were more acidic (pH 4.0) than those at the heathland site (pH 4.5). Acidic interstitial water solutions were found to up to 5.0 m depth in the unsaturated zone and are partially neutralized by two aluminosilicate mineral reactions in the unsaturated zone: cation exchange and K-feldspar dissolution. The rate at which these acid neutralizing reactions act to neutralize acidity is revealed by the rate of depletion of base cations from the unsaturated zone in recharge solutions; K+ (dissolution), Ca+2 + Mg+2 (cation exchange). The total base cation depletion rate was greatest below heathland; this can be attributed mainly to the greater rate of SO4 assimilation by the woodland biome.  相似文献   

5.
Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO3 that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO3)3 solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al3+, AlOH2+, Al(OH)+2 and Al(OH)?4, and their ion activity products are 1K50 = 1.29 × 108, 1Ks1 = 1.33 × 103, 1Ks2 = 9.49 × 10?3 and 1Ks4 = 8.94 × 10?15. The calculated standard Gibbs free energies of formation (ΔG°f) for the synthetic gibbsite and the A1OH2+, Al(OH)+2 and Al(OH)?4 ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol?1, respectively. These ΔG°f values are based on the recently revised ΔG°f value for Al3+ (?117.0 ± 0.3 kcal mol?1) and carry the same uncertainty. The ΔG°f of the natural gibbsite is ?275.1 ± 0.4 kcal mol?, which suggests that a range of ΔG°f values can exist even for relatively simple natural minerals.  相似文献   

6.
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7.
The evaluation of soil quality is an important tool for degradation monitoring and sustainable management implementation. The objective of this study was to measure physical and chemical soil properties to set soil quality and validate a model of soil quality indicator in latosols (oxisols) under sugarcane cropping and native forest. The study was carried out in the cities of Araras, Santa Ernestina, and Guariba in São Paulo State, Brazil. We collected 24 samples of disturbed and undisturbed soil at 0.0–0.10 m layer from three areas grown with sugarcane and neighboring locations under native woodland. We assessed the following soil properties: (a) chemical—pH in CaCl2, organic matter (OM), phosphorus (P), potassium (K+), calcium (Ca2+), magnesium (Mg2+), potential acidity (H?+?Al), aluminum (Al3+), and sulfur (S); (b) physical—macro- and microporosity, soil bulk density (Ds), aggregate stability, mean weight diameter (MWD), rill (Kr) and interrill (Ki) global erodibility, shear stress (τc), and magnetic susceptibility (MS). Data underwent multivariate statistics to identify the properties that denote soil quality and to set their weights within the functions of soil quality indicator (SQI). This study showed that the multivariate analysis was efficient in determining which physical and chemical properties were most sensitive, of which we can mention total sand, MS, clay, microporosity, Mg, Ca, pH, and OM. We can therefore conclude that the quality indicators of soils grown with sugarcane were lower than those under forest were, showing the need for adoption of conservation management practices.  相似文献   

8.
Two springs (Cuihua Spring, Shuiqiuchi Spring) in Cuihua Mountain of the Qinling Mountains were observed and sampled monthly during 2004 and 2005 to trace their physical properties and chemical compositions with seasons. Although both pH values and cation (Ca2+, Mg2+, K+, and Na+) contents of Cuihua Spring are higher than those of Shuiqiuchi Spring, seasonal variations in both springs are obvious. The pH values of both spring waters are between 5.69 and 6.98, lower than that of rainwater during summer and autumn. From January to November, the pH values of both springs similarly vary from high to low and then to high again. Variations in electric conductivities of two spring waters are contrary, although their electric conductivities are positively correlative with the cation content respectively. This can be attributed to different water sources of the two springs or different acidic rocks they passed. The contents of HCO3 −, Ca2+, Mg2+, K+, and Na+ are low, indicating a low silicate weathering that the strata in this district are mainly composed of granite and schist of quartz and mica. Differing from change in spring water in karst regions of South China where abundant precipitation and dilution of rainwater cause low pH and electric conductivity in summer and autumn, the seasonal variations in the pH values and the electric conductivities of two springs in Qinling Mountains are attributed to seasonal changes in CO2 produced by microorganisms’ activity in soil within respective year, rather than rainfall. The microorganisms’ activity in soil produces more CO2 during summer and autumn. Therefore, the water nature of springs in silicate regions chiefly reflects the seasonal changes of CO2 produced by the microorganisms in soil.  相似文献   

9.
Plant-available reserves of major base cations, Ca2+ and Mg2+, decreased markedly in soils over the past century, thus posing a potential threat to forest ecosystem health. Trees are thought to obtain dissolved Ca2+ ions mainly from an easily accessible soil-water reservoir also termed the ‘exchangeable cation pool’. The status of Ca reserves in this soil pool is sensitive to anthropogenic perturbations such as soil acidification induced by acid rain and/or excessive timber harvesting. Here we show that in a base-poor forest of the northeastern USA (i.e. Wachusett Mountain, Massachusetts) the ‘exchangeable Ca pool’ of deeper mineral soils has a unique isotope signature that is significantly enriched in the radiogenic 40Ca, due to the dissolution of K-rich silicate minerals such as biotite. Using a simple isotope mass balance, and assuming that the input of Ca from biotite has a εCa signature of ∼16, the results of our calculation indicate that the weathering of biotite may supply a sizeable fraction, up to 25%, of Ca2+ ions into the ‘exchangeable cation pool’ of deeper mineral soils. Importantly, samples of local vegetation (i.e. woody tissues of red oak) show no detectable excess of the radiogenic 40Ca, and based on our model the upper limit of a possible biotite-derived Ca contribution in vegetation is estimated at ∼5%. We also found no evidence of the radiogenic 40Ca signal in the samples of forest floor and the uppermost organic-rich soils (0-15 cm depth), which in turn suggest that over the long-term development of the forest and its organic matter accumulation, the vegetation growth must have also relied primarily on the non-radiogenic Ca sources. Based on our experimental data, such sources may include (i) wet atmospheric deposition, (ii) the organically-complexed Ca in topsoil horizons, and (iii) chemical weathering and/or fungal-mediated dissolution of apatite and Ca-rich plagioclase. Hence, our stable and radiogenic Ca isotope data indicate that the studied base-poor forest is able to bypass the ‘exchangeable cation pool’ of deeper (i.e. below 15 cm) mineral soils, and still manages to meet its nutritional requirements with respect to Ca. Another important implication of this study is that the organically-complexed Ca in the topsoil horizon (0-15 cm depth) has to be tightly bound to the ion exchange sites, otherwise the large radiogenic 40Ca signatures present in the ‘exchangeable cation pool’ of deep mineral soils would be swamped by the downward gravitational flux of non-radiogenic Ca from the decaying organic matter and litterfall. Hence, the limited mobility of the organically-complexed Ca in soils and its tight biological cycling could explain the lack of a significant impact of vegetation on the Ca isotope systematics observed in large rivers.  相似文献   

10.
在中国东部皖北地区分布着新元古代镁铁质岩,其中一些碱性基性岩为金刚石的赋矿岩石。为了确定安徽栏杆金刚石矿区的石榴子石种类,对矿区内不同类型的石榴子石进行系统采样,测定了62件石榴子石微区化学成分。结果显示,安徽栏杆石榴子石矿物化学式A_3~(2+)B_2~(3+)(SiO_4)_3中的A组阳离子由Mg~(2+)、Fe~(2+)和Ca~(2+)离子占位,B主要由Al~(3+)、Fe~(3+)、Mn~(3+)和Cr~(3+)离子占位,三价阳离子主要为Al~(3+),二价阳离子主要为Ca~(2+),表明研究区石榴子石主要为钙铝-钙铁-镁铝石榴子石系列。在62个样品中,发现了超硅石榴子石。经过计算其形成的压力范围为12.1～12.8GPa,深度可达300km。  相似文献   

11.
Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al3+ by Mg2+ or Fe3+, tetrahedral substitution of Si4+ by Al3+, and different interlayer cations (IC) (Na+, K+, Ca2+, and Mg2+). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe3+ and dispersion tendency of Mg2+ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.  相似文献   

12.
The mechanism for reclaiming sodic soils using calcium sulfate (CaSO4) could provide a theoretical basis for the field application of CaSO4 substitutes, including the by-products of flue gas desulfurization (BFGD), fly ash, and phosphorus gypsum. In this study, Ca2+ application experiment was conducted to analyze the dynamic changes of the cations in the reclamation of sodic soils with CaSO4. A multicomponent solute transport model (UNSATCHEM) that considers ion adsorption exchange and dynamic changes in the soil’s hydraulic conductivity was subsequently used to simulate and predict the movement of ions. The Ca2+ application experiment consisted of four treatments with four CaSO4 concentrations (0.5, 1, 1.5, and 2 g L?1). When the Ca2+ concentrations in the supplied water were 14.71, 22.06, and 29.41 mmol L?1, Ca2+ achieved penetration, and this process was faster when the Ca2+ concentration in the supplied water was higher. Ca2+ did not achieve penetration when the Ca2+ concentration was 7.35 mmol L?1. UNSATCHEM was able to simulate the transportation mechanism of Ca2+ and Na+ in the soil solution in the Ca2+ application experiment, the adsorption and exchange between the Na+ in the soil colloid and Ca2+ in the soil solution, and the precipitation and dissolution of CaSO4 with a high degree of accuracy. Sodic soil reclamation with CaSO4 was not a short-term process. Compared with applying CaSO4 only once, applying CaSO4 in batches decreased the accumulation of soil salts and promoted its dissolution.  相似文献   

13.
The present study deals with the hydrogeochemistry and water quality of shallow aquifers in two important river basins—the Ithikkara and Kallada river basins—draining the south western flanks of Western Ghats in Kerala, South West India. Well water samples were collected from 20 dug wells with a depth range of 1 m below ground level (mbgl) to 18.2 mbgl during pre-monsoon, monsoon, and post-monsoon seasons of the year 2011–2012. These samples were analyzed for various physico-chemical parameters following standard methods and were evaluated for their interrelations and drinking water suitability. The pH of the water samples shows wide variation from highly acidic to highly alkaline water. About 80% of pre-monsoon samples recorded Fe2+ concentration above the permissible limit of drinking water standard. Water Quality Index (WQI) shows that majority of the well water samples fall in the category of excellent–good for drinking purpose. The results of the irrigation suitability assessment using the procedures like Percent Sodium, Sodium Absorption Ratio, Residual Sodium Carbonate, Kelly Index, Permeability Index, and Magnesium Hazard reveal that the well waters of the study area are fit for irrigation purpose. Na+/Cl? ratio reflects the release of sodium to water due to silicate weathering. The samples have a Ca2+/Mg2+ ratio equal or greater than 2 indicating the effect of silicate minerals in contributing Ca2+ and Mg2+ ions to the well water. The saturation indices reveal that groundwater is supersaturated with SiO2. Among the causative factors that determine the hydrochemical quality of well water samples, silicate weathering plays a pivotal role with significant input of ions from anthropogenic sources.  相似文献   

14.
Rock–water interaction along with mineral dissolution/ precipitation plays a profound role in the control of fluoride ion concentration within the alluvial groundwater in a part of semi-arid northern India. In the premonsoon season, the alluvial region experiences evaporative processes leading to increase in Na+ ions which through reverse ion exchange processes are adsorbed onto suitable sites within the aquifer matrix in exchange for Ca2+ ion in solution. Increase in Ca2+ ions in solution inhibits fluorite mineral dissolution, thereby controlling premonsoon fluoride ion concentration within alluvial groundwaters (1.40?±?0.5 mg/l). In the postmonsoon season, however, higher average fluoride ion concentration within the alluvial aquifer samples (2.33?±?0.80 mg/l) is observed mainly due to increase in silicate weathering of fluoride-bearing rocks and direct ion exchange processes enabling Ca2+ ion uptake from solution accompanied with the release of fluoride ions. Combined effect of these processes results in average fluoride ion concentration falling above the WHO drinking water permissible limit (1.5 mg/l). Alternatively, the hard rock aquifer samples within the study area have an average fluoride ion concentration falling below the permissible limit in both the seasons.  相似文献   

15.
South China is one of the regions severely suffering from acid rain in the world.However,few systematic studies of rural precipitation chemistry have been performed in comparison with the extensive studies on their urban counterparts of this region.In order to characterize the current acid rain status and identify its possible sources in the rural area of South China,we analyzed precipitation collected event by event from a rural forested watershed in southern Anhui Province between March 2007 and February 2010.The results showed that the concentrations of major ions within precipitation in the studied rural area were significantly lower than those reported for the urban areas of the same latitude in China.Nevertheless,the precipitation acidity(with an average pH value of 4.49) and the frequency of acid rain(95%) were considerably high.The relatively high ratio of(SO42+ NO 3)/(Ca2+ +NH4+) was the main cause of acid rain in this rural area,as SO 2 and NO x were the main precursors of acid rain,while Ca2+ and NH4+acted as the dominant neutralizers to the acidity.Source identification indicated that Ca2+ and Mg2+ mainly were derived from alkaline dust,SO42,NO 3 and NH4+originated mainly from anthropogenic sources such as industrial and agricultural activities,most Na +,Cl,K + and some of Mg2+ were derived from the sea.The results suggested that the major ions within precipitation in the rural area of South China were related to the meso-scale and long-range transport of particles and aerosols in the air.  相似文献   

16.
Geometrical changes induced by cation substitutions {Si4+/Al3+}[Mg2+/Al3+], {2Si4+/2Al3+} [2Mg2+/2Al3+], {Si4+/Fe3+} [Mg2+/Al3+] or [Mg2+/Fe3+], where {} and [] indicate tetrahedral and octahedral sheet in lizardite 1T, are studied by ab-initio quantum chemistry calculations. The majority of the models are based on the chemical compositions reported for various lizardite polytypes with the amount of Al in the tetrahedral sheets reported to vary from 3.5% to 8% in the 1T and 2H 1, up to ~30% in the 2H 2 polytype. Si4+ by Fe3+ substitution in the tetrahedral sheet with an Al3+ (Fe3+) in the role of a charge compensating cation in the octahedral sheet is also examined. The cation substitutions result in the geometrical changes in the tetrahedral sheets, while the octahedral sheets remain almost untouched. Substituted tetrahedra are tilted and their basal oxygens pushed down from the plane of basal oxygens. Ditrigonal deformation of tetrahedral sheets depends on the substituting cation and the degree of substitution.  相似文献   

17.
The potential for metal release associated with CO2 leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO2 sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO2 and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO2 leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO2 leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO2 conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO2. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr2+, CO2+, Mn2+, Ni2+, Tl+, and Zn2+ increased when these dolomite rocks were exposed to elevated concentrations of CO2. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca2+ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO2 leakage conditions. Aqueous concentrations of Ca2+ and Mg2+ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.  相似文献   

18.
Analysis of soil, soil water and groundwater in the Mount William Creek catchment, southeastern Australia, shows that Mg2+ and Ca2+ within infiltrating rainfall are rapidly depleted by plant uptake and adsorption on clay minerals. Na+ and K+ may exhibit minor enrichment at shallow depths but are quickly readsorbed, so that cation/Cl– ratios typical of groundwater are observed in soil water within the upper 200 cm of the soil profile for all species. The concentrations of K+ and Ca2+ in soil and groundwater are more depleted than Na+ and Mg2+ due to preferential uptake by vegetation. Removal of organic matter results in a continuing, long-term export of all major cations from the soil profiles. The processes of biogeochemical fractionation within the unsaturated zone rapidly modify the cation/Cl– ratios of infiltrating rainfall to values characteristic of seawater. These mechanisms may have reached steady state, because groundwaters with seawater ion/Cl– ratios are thousands of years old; the exchange sites on the soil clays are probably saturated, so cations supplied in rainfall are exported in organic matter and incorporated into recharge infiltrating into the groundwater. Much of the chemical evolution of groundwater traditionally attributed to processes within the aquifer is complete by the time recharge occurs; this evolutionary model may have broad application.  相似文献   

19.
Electron paramagnetic resonance (EPR) measurements were made on Gd3+ and Eu2+ ions in polycrystalline samples to determine the nature of the sites occupied by those ions in mineral structures. Both Gd3+ and Eu2+ ions were incorporated at Ca2+ structural sites in β-Ca2SiO4, pseudo-CaSiO3, CaMgSiO4, CaMgSi2O6, hex-CaAl2Si2O8, CaAl2O4, and Ca3Al2O6. For tri-CaAl2Si2O8, Eu2+ was incorporated at a Ca2+ site and Gd3+ was incorporated at a site where the crystalline electric field was disordered. That difference in behavior may contribute to the anomalous behavior of Eu in plagioclase feldspar. Both Gd3+ and Eu2+ were incorporated as aggregates or clusters of those ions in Mg2SiO4 and clino-MgSiO3.  相似文献   

20.
《Geochimica et cosmochimica acta》1999,63(19-20):3087-3096
Calcium adsorption by rutile was studied potentiometrically from 25 to 250°C, at ionic strengths of 0.03 and 0.30 m in NaCl media, using two complementary experimental methodologies. In the first, net proton adsorption in the presence and absence of Ca2+ was monitored, and in the second, samples were periodically withdrawn during the course of a titration to determine Ca2+ adsorption directly. These experiments revealed that Ca2+adsorption systematically increased with temperature relative to the pH of zero net proton charge in NaCl media alone (pHznpc(NaCl) – pH). That is, as temperature increased, Ca2+ adsorption commenced at progressively more positive pHznpc(NaCl) – pH values. Increasing ionic strength from 0.03 to 0.30 m NaCl suppressed Ca2+ adsorption at all temperatures as a result of either increased competition from Na+ or greater complexation of Ca2+ by Cl−. Finally, there was no apparent trend in the proton stoichiometric ratios (moles H+ released / moles Ca2+ adsorbed) with increasing temperature. This suggests that the electrostatic and/or chemical processes involved in Ca2+ adsorption do not change greatly with increasing temperature. Favorable entropic effects, related to the increasing ease of releasing Ca2+ waters of hydration, are believed to be primarily responsible for the increase in adsorption with temperature.  相似文献   

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