首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
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   

2.
The stoichiometries of activated complexes responsible for controlling the kinetics of mineral dissolution can be inferred from experimental rate data. Constraints are provided by adsorption equilibria, surface ion exchange reactions, and the pH-dependence of the steady-state rates of surface detachment. Adsorption equilibria may lead to accelerated or decelerated rates of hydrolysis due to formation of surface species. They may also result in pH-independent dissolution rates at low pH as a consequence of hydrogen ion surface saturation. Surface exchange reactions of H+ or H3O+ for M(2) site cations in pyroxenes, Ca2+ in wollastonite, and alkali cations in feldspars go essentially to completion for dissolution in solutions that are appreciably undersaturated with respect to the reactant mineral. The rate of surface exchange is proportional to the fraction of exchangeable cations on the reacting surface, which leads to an integrated exponential relation for mass transfer as a function of time. The independence of detachment rates on the degree of surface exchange indicates approximately equivalent formation of activated complexes at both exchanged and unexchanged sites. The degree of hydration or protonation of activated complexes formed from surface species at active sites can be inferred from the dependence of the steady-state hydrolysis rates on pH.  相似文献   

3.
The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al3+ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al3+ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al3+-exchanged montmorillonite, whereas the Na+- and K+-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg2+- and Li+-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al3+- and Mg2+-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H 0 ≤ ?3.0). Li+- and Na+-exchanged montmorillonites exhibited an acid strength distribution of ?3.0 < H 0 ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li+-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H 0 ≤ 4.8) were present in K+-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.  相似文献   

4.
The North Appalachian Experimental Watershed in Coshocton, Ohio, USA has recorded average pH of precipitation of 4.7 over a 30-year period. The area lies within the Pennsylvanian siltstones and shale, dominated by aluminosilicates and <5% calcite. A study was conducted to determine the evolution of acid deposition through an unsaturated to saturated zone composed of siltstone and shale in an isolated hill, precluding lateral flow and seepage. The results from water–rock chemical reactions modeled using PHREEQM demonstrate the percolating precipitation water is neutralized to pH 7.5 within the top 1.5 m. The model suggests that, along with calcite, dissolution of albite, illite, and kaolinite are the dominant mechanisms of neutralization. The cation exchange capacity of the siltstone and shale, in the range 54.6–386 meq/100 g, appears to be a function of high organic carbon content of 2.0–3.2%. While cation exchange is responsible for some of the Na+ in solution, it is not the primary source of Ca2+, Mg2+, or K+ ions. Exchange onto clays is occurring, but is secondary to exchange on organic matter. Chemical composition of groundwater perched within a coal seam is controlled by oxidation and dissolution of pyrite, returning pH to approximately 4.0.  相似文献   

5.
The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO3 type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ 2H and δ 18O values in groundwater downgradient. Values of δ 13C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ 13C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ 13C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication  相似文献   

6.
《Applied Geochemistry》1994,9(2):161-173
Possible groundwater quality changes related to pyrite oxidation during artificial groundwater recharge and its storage in the Tertiary sands of the London Basin are investigated. Pyrite textures in the Tertiary sands are examined by scanning electron microscopy while an experimental approach is used to study mechanisms of pyrite oxidation and of some associated chemical reactions. In the Tertiary sands of the London Basin aquifer, pyrite occurs as aggregates made of discrete individual crystals 0.5–5 μm in size or, in a cryptocrystalline form, often as pseudomorphs of biogenic debris. It can expose a very large specific surface area to porefluids. Although ferric iron, which can be an oxidising agent of pyrite, is abundant in the solid phase of the Tertiary sands, it does not appear to take a significant part in this case. Pyrite oxidation seems to rely on a supply of oxygen. Leaching experiments using a 0.001 M H2SO4 solution were carried out to examine interactions between mildly acidic groundwater resulting from pyrite oxidation at a moderate rate and the host-sediment. In the presence of CaCO3 in the solid phase, H+ is rapidly buffered by CaCO3 dissolution. Oscillations of this reaction around equilibrium appear to trigger cation-exchange reactions on clay mineral surfaces, resulting in the release of major cations (e.g. K and Mg) into solution. In the absence of CaCO3 in the solid phase, H+ buffering occurs less efficiently solely through exchange of cations for H+ on clay minerals surfaces. If the rate of pyrite oxidation in the Tertiary sands becomes high enough for the buffering capacity of the system to be exceeded, the groundwater pH begins to fall. Interactions between low pH (2) groundwaters and the host sediments were examined by leaching solid material in 0.01 M and 0.1 M H2SO4 solutions. Concentrations of Fe, Mg and K increase in solution throughout the experiment, indicating partial dissolution of clay minerals. The composition of the porefluid thus depends on the geochemical composition and surface area of the different clay minerals present.  相似文献   

7.
Nuclear waste that bore 90Sr2+ was accidentally leaked into the vadose zone at the Hanford site, and was immobilized at relatively shallow depths in sediments containing little apparent clay or silt-sized components. Sr2+, 90Sr2+, Mg2+, and Ca2+ was desorbed and total inorganic carbon concentration was monitored during the equilibration of this sediment with varying concentrations of Na+, Ca2+. A cation exchange model previously developed for similar sediments was applied to these results as a predictor of final solution compositions. The model included binary exchange reactions for the four operant cations and an equilibrium dissolution/precipitation reaction for calcite. The model successfully predicted the desorption data. The contaminated sediment was also examined using digital autoradiography, a sensitive tool for imaging the distribution of radioactivity. The exchanger phase containing 90Sr was found to consist of smectite formed from weathering of mesostasis glass in basaltic lithic fragments. These clasts are a significant component of Hanford formation sands. The relatively small but significant cation exchange capacity of these sediments was thus a consequence of reaction with physically sequestered clays in sediment that contained essentially no fine-grained material. The nature of this exchange component explained the relatively slow (scale of days) evolution of desorption solutions. The experimental and model results indicated that there is little risk of migration of 90Sr2+ to the water table.  相似文献   

8.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

9.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   

10.
Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA   总被引：1，自引：0，他引：1  
The sorption of Cs+ was investigated over a large concentration range (10−9−10−2 mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO3 brine) is the carrier. Cs+ sorption was measured on homoionic sediments (Na+, K+, Ca2+) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na+ electrolyte, concentrations were extended to near saturation with NaNO3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs+ for both high- and low-affinity sites according to the trend K+ >> Na+ ≥ Ca2+. At high salt concentration, Cs+ adsorption occurred only on high-affinity sites. Na+ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs+(aq), and analyzed by electron microprobe to identify phases and features important to Cs+ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na+ in HLW and indigenous K+ displaced from the sediments may act to expedite the migration of strongly sorbing Cs+ in subsurface environments.  相似文献   

11.
In order to determine whether Li+ cations penetrate into the octahedral layers of montmorillonites upon mild heating (Hofmann-Klemen effect) 57Fe Mössbauer spectra of Na+ and Li+ exchanged montmorillonite were obtained before and after treatment at 220 ° C. The 57Fe nucleus was used as a remote probe to detect electronic perturbations which would occur if a Li cation was to move into the octahedral layer from the interlayer after heating. The ambient Mössbauer spectra showed that a high charge density interlayer cation such as Li+ is effective in reducing the phonon energy of VIFe2+. In addition the EFG at octahedral sites can be significantly modified by interlayer cations as evidenced by the larger quadrupole splitting value measured for the Li+-exchanged sample with respect to the Na+-sample. Interlayer collapse and migration of exchange cations into the montmorillonite lattice after heating to 220 ° C resulted in the oxidation of the VIFe2+ and a decrease in site distortion for IVFe3+. Similar spectral parameters for the Fe3+ resonances of both Na+ — and Li+-heated samples suggested the interlayer cations do not penetrate as far as the octahedral layers. In order to utilize the enhanced sensitivity of VIFe2+ Δ values to changes in EFG the Fe3+ in the heated montmorillonites was reduced to Fe2+ with hydrazine. Similar spectral parameters for both the Na+ — and Li+-exchanged montmorillonite were observed giving further evidence that Li cations do not migrate into vacant octahedral sites.  相似文献   

12.
Chemical analyses were performed on soil water extracted from two cores taken from a sandy calcareous soil near Delhi, Ontario. Calcite saturation is attained within the unsaturated zone over short distances and short periods of time, whereas dolomite undersaturation persists to the groundwater table. The progressive dissolution of dolomite by soil water, within the unsaturated zone, after calcite saturation is reached results in calcite supersaturation.Deposition of iron and manganese oxyhydroxide phases occurs at the carbonate leached/unleached zone boundary. This is a result of soil water neutralization due to carbonate dissolution during infiltration but may also reflect the increased rate of oxidation of dissolved ferrous and manganous ions at higher pH's. The role of bacteria in this process has not been investigated.The depth of the carbonate leached/unleached zone boundary in a calcareous soil has important implications for 14C groundwater dating. The depth of this interface at the study site (?2 m) does not appear to limit 14C diffusion from the root zone to the depth at which carbonate dissolution occurs. Thus, soil water achieves open system isotopic equilibrium with the soil CO2 gas phase. It is calculated that in soils with similar physical properties to the study soil but with depths of leaching of 5 m or more, complete 14C isotopic equilibration of soil water with soil gas would not occur. Soil water, under these conditions would recharge to the groundwater exhibiting some degree of closed system 14C isotopic evolution.  相似文献   

13.
Groundwater and surface water samples were collected to improve understanding of the Senegal River Lower Valley and Delta system, which is prone to salinization. Inorganic ion concentrations and environmental isotopes (18O, 2H and 3H) in groundwater, river, lake and precipitation were investigated to gain insight into the functioning of the system with regard to recharge sources and process, groundwater renewability, hydraulic interconnection and geochemical evolution. The geochemical characteristics of the system display mainly cation (Ca2+ and/or Na+) bicarbonated waters, which evolve to chloride water type; this occurs during groundwater flow in the less mineralized part of the aquifer. In contrast, saline intrusion and secondary brines together with halite dissolution are likely to contaminate the groundwater to Na–Cl type. Halite, gypsum and calcite dissolution determine the major ion (Na+, Cl−, Ca2+, Mg2+, SO4 2− and HCO3 −) chemistry, but other processes such as evaporation, salt deposition, ion exchange and reverse exchange reactions also control the groundwater chemistry. Both surface water and groundwater in the system show an evaporation effect, but high evaporated signatures in the groundwater may be due to direct evaporation from the ground, infiltration of evaporated water or enriched rainwater in this region. The stable isotopes also reveal two types of groundwater in this system, which geomorphologically are distributed in the sand dunes (depleted isotopes) and in the flood plain (enriched isotopes). Consideration of the 3H content reinforces this grouping and suggests two mechanisms of recharge: contribution of enriched surface water in recharging the flood plain groundwater and, in the sand dunes area where water table is at depth between 8 and 13 m, slow recharge process characterized the submodern to mixed water.  相似文献   

14.
This paper presents the results of a new investigation of the Guarani Aquifer System (SAG) in São Paulo state. New data were acquired about sedimentary framework, flow pattern, and hydrogeochemistry. The flow direction in the north of the state is towards the southwest and not towards the west as expected previously. This is linked to the absence of SAG outcrop in the northeast of São Paulo state. Both the underlying Pirambóia Formation and the overlying Botucatu Formation possess high porosity (18.9% and 19.5%, respectively), which was not modified significantly by diagenetic changes. Investigation of sediments confirmed a zone of chalcedony cement close to the SAG outcrop and a zone of calcite cement in the deep confined zone. The main events in the SAG post-sedimentary history were: (1) adhesion of ferrugineous coatings on grains, (2) infiltration of clays in eodiagenetic stage, (3) regeneration of coatings with formation of smectites, (4) authigenic overgrowth of quartz and K-feldspar in advanced eodiagenetic stage, (5) bitumen cementation of Pirambóia Formation in mesodiagenetic stage, (6) cementation by calcite in mesodiagenetic and telodiagenetic stages in Pirambóia Formation, (7) formation of secondary porosity by dissolution of unstable minerals after appearance of hydraulic gradient and penetration of the meteoric water caused by the uplift of the Serra do Mar coastal range in the Late Cretaceous, (8) authigenesis of kaolinite and amorphous silica in unconfined zone of the SAG and cation exchange coupled with the dissolution of calcite at the transition between unconfined and confined zone, and (9) authigenesis of analcime in the confined SAG zone. The last two processes are still under operation. The deep zone of the SAG comprises an alkaline pH, Na–HCO3 groundwater type with old water and enriched δ13C values (<?3.9), which evolved from a neutral pH, Ca–HCO3 groundwater type with young water and depleted δ13C values (>?18.8) close to the SAG outcrop. This is consistent with a conceptual geochemical model of the SAG, suggesting dissolution of calcite driven by cation exchange, which occurs at a relatively narrow front recently moving downgradient at much slower rate compared to groundwater flow. More depleted values of δ18O in the deep confined zone close to the Paraná River compared to values of relative recent recharged water indicate recharge occur during a period of cold climate. The SAG is a “storage-dominated” type of aquifer which has to be managed properly to avoid its overexploitation.  相似文献   

15.
Fayalite, hypersthene, basalt, and obsidian were dissolved in buffered solutions (25°C; pH 4.5 and 5.5) under air, N2 or O2 atmospheres, in order to follow the kinetics of dissolution. Each dissolved more rapidly at lower pH values, dissolving most rapidly in the initial few days, followed by slower dissolution for periods up to six months. Dissolution was more rapid when air was excluded. In oxygen atmospheres an Fe(OH)3 precipitate armors mineral surfaces, thus inhibiting further dissolution, and further affects the solution by scavenging dissolved silica and cations. Dissolution reactions include initial exchange between cations and H+, incongruent dissolution of silicate structures, oxidation of Fe2+ in solution, precipitation of Fe(OH)3, and scavenging of dissolved silica and cations by Fe(OH)3. Dissolution kinetics may explain weathering of mafic rocks and minerals at the Earth's surface, the formation of Fe-oxide coatings on mineral grains, weathering of submarine mafic rocks and intrastratal solution of mafic minerals in buried sandstones. Early Precambrian weathering would have been more rapid before the appearance of large amounts of oxygen in the atmosphere, and continental denudation rates may have been higher than at present because of this effect and the predominance of mafic igneous rocks at an early stage of continent formation and growth.  相似文献   

16.
Exchange reactions between Ca2+, H+ and Al species and their effects on the aluminium mobility in two Chinese acidic forest soils were studied. The study was based on a batch experiment using extractant solutions with different base cation (calcium) concentrations and pH. The experimental data showed that increased Ca2+ concentrations increased the release of soil hydrogen—and aluminium ions, especially from the more acid soil. In agreement with a cation exchange process, the treatment with Ca2+ extracts gave significantly decreased soil aluminium saturation (AlS) and increased calcium saturation (CaS) on the ion exchanger. Geochemical calculation using AlCHEMI program showed that activities of Al3+ in the extracts were all strongly under-saturated with respect to any gibbsite mineral in the studied pH region (i.e. below 4.1). There were instead apparently two different mechanisms controlling the activities of Al3+ in extracts. At pH between about 4.1 and 3.7, the Al3+ activity did not change significantly with pH. This is especially the case in the more acid soil. Apparently there are no sizeable pools available to release Al in this pH region. At pH below 3.7 (induced by higher Ca2+concentration) the activity of Al3+ increased with H+ though not in a pattern that complies with a gibbsite solubility control. An increase of base cation deposition would therefore mainly enhance the release of hydrogen ions between pH 4.1 and 3.7 and aluminium ions below pH 3.7 from Chinese mature acidic soils. This will cause an increased acidity of soil water in the short term and a decrease in the soil acidity in the long term. More attention should be paid to this fact in Chinese acid rain studies and control options.  相似文献   

17.
The groundwater extracted from the unconfined Quaternary aquifer is the main source of water supply in El-Tur area. The area is bounded from the east by the elevated basement complex of Southern Sinai and from the west by El-Qabaliyat Ridge. The wadis dissecting these highlands form effective watersheds of the Quaternary aquifer. These wadis form areas of focused recharge. Recharge also occurs directly via the Quaternary sediments covering El-Qaa Plain. Subsurface lateral groundwater flow from the fractured basement contributes significant recharge to the aquifer as well. The aquifer sediment facies affect the type and quality of groundwater. In the eastern part where the aquifer is composed mainly of gravel and coarse sand with fragments of weathered basement, the Na-Cl-SO4 water dominates. In the west where the facies change is rapid and complex, many water types arise. The base exchange index (BEX) is positive in this part reflecting the role of clay minerals in changing the water types via cation exchange. In the east where clays are insignificant in the aquifer, the BEX is negative. In the western part next to El-Qabaliyat Ridge, the wells discharging from the calcareous sand zone have low groundwater salinities compared to the wells discharging from the alluvium. In general, the groundwater salinity increases in the direction of groundwater flow from the northeast to the southwest which reflects the dissolution of aquifer sediments. The concentration relationships between the major ions on one hand and chloride on the other reflect the dissolution of calcium carbonates, precipitation of K- and Mg-bearing minerals, and cation exchange of Ca for Na on clay minerals. The hydrochemical models support these reactions. In addition, they show that the effect of evaporation on the recharge water in the western catchment is about four times its effect on the eastern recharge water which reflects the rapid recharge through the wadis draining the fractured basement. Moreover, the contribution from the eastern catchment in sample No. 23 is more than four-folds the contribution from the western recharge area. The stable isotopes (2H and 18O) show that the Quaternary aquifer is recharging from recent rainfall. However, upward leakage of Paleogene groundwater (depleted in 18O) also occurs. The groundwater level map shows strong overpumping impact especially in the areas close to El-Tur city.  相似文献   

18.
《Geochimica et cosmochimica acta》1999,63(19-20):3217-3227
A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO4 background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10−8 M and 7 × 10−5 M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO4 concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.  相似文献   

19.
Geochemical processes occurring at a seawater/freshwater interface were studied in a shallow coastal siliclastic aquifer containing minor amounts of calcite. Data were collected from 106 piezometers in a 120-m transect from the coastline and landward. In the first 40 m from the coastline, a wedge of saltwater is intruding below the freshwater aquifer. The aquifer is strongly reduced with mineralization of organic matter by methanogenesis in the freshwater aquifer, and sulfate reduction dominating in the most seaward part of the saline aquifer. The spatial separation of cations in the aquifer indicated a slow freshening process where Ca2+ from freshwater displaced the marine cations Na+ and Mg2+ from the exchanger complex. The resulting loss of Ca2+ from solution decreases the saturation state for calcite and possibly causes calcite dissolution. A storm-flooding event was recorded where pulses of dense seawater sank through the fresh aquifer. As a result, the terminal electron accepting process switched from methanogenesis to sulfate reduction. The pulses of sinking seawater also triggered cation exchange reactions where Ca2+ was expelled from the exchanger by seawater Na+ and Mg2+. The released Ca2+ is being flushed from the aquifer by groundwater flow, and this export of Ca2+ will, in the long term, cause decalcification of the sediment. The water composition in the aquifer is in a transient state as the result of various processes that operate on different timescales. Oxidation of organic matter occurs continuously but at a rate decreasing on a geological time scale. The freshening of the aquifer operates on the timescale of a few years. The episodic flooding and sinking of seawater through the aquifer proceeds in the course of days to weeks, but occurs irregularly with years in between.  相似文献   

20.
A study of environmental chloride, deuterium, oxygen-18, and tritium in deep sand profiles (35 m) has been carried out in order to estimate their relative value for measuring average groundwater recharge. The investigation was located at a 0.1-km2 site in Quaternary sands near the northwestern coast of Senegal in a zone of rainfed agriculture. By using a steady-state model for duplicate unsaturated zone chloride profiles, the long-term average recharge at the site was estimated to be 30 mm yr–1 or around 10% of the average precipitation (290 mm). The chloride concentration of adjacent shallow groundwater was relatively uniform and comparable to the unsaturated zone average, while the spatial variability in the depth distribution of Cl– in the unsaturated zone was considerable. Stable isotope (deuterium and oxygen-18) data show that there is some isotopic enrichment due to direct evaporation through the soil surface. The degree of heavy isotope enrichment is proportional to the extent of evaporative loss and there is good correspondance with the chloride enrichment. Nevertheless, stable isotopes cannot be used quantitatively to estimate the recharge. The excellent preservation of the peak in thermonuclear tritium in precipitation in the unsaturated zone at depths between 12 and 20 m enables an estimated annual recharge of 24 mm yr–1 in this area to be calculated, using the piston flow model. Agreement therefore between Cl and3H as tools for recharge measurement is reasonable over the site.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号