Silicon control of strontium and cesium partitioning in hydroxide-weathered sediments     

Jon Chorover  Sunkyung Choi  R. Jeff Serne  Caleb Strepka  Karl T. Mueller 《Geochimica et cosmochimica acta》2008,72(8):2024-2047

Cation partitioning and speciation in an aqueous soil suspension may depend on the coupling of reaction time, sorbate amount and mineral weathering reactions. These factors were varied in sediment suspension experiments to identify geochemical processes that affect migration of Sr²⁺ and Cs⁺ introduced to the subsurface by caustic high level radioactive waste (HLRW). Three glacio-fluvial and lacustrine sediments from the Hanford Site (WA, USA) were subjected to hyperalkaline (pH > 13), Na-Al-NO₃-OH solution conditions within a gradient field of (i) sorptive concentration (10⁻⁵-10⁻³ m) and (ii) reaction time (0-365 d). Strontium uptake (q_Sr) exceeded that of cesium at nearly all reaction times. Sorbent affinity for both Cs⁺ and Sr²⁺ increased with clay plus silt content at early times, but a prolonged slow uptake process was observed over the course of sediment weathering that erased the texture effect for Sr²⁺; all sediments showed similar mass normalized uptake after several months of reaction time. Strontium became progressively recalcitrant to desorption after 92 d, with accumulation and aging of neoformed aluminosilicates. Formation of Cs⁺ and Sr²⁺-containing cancrinite and sodalite was observed after 183 d by SEM and synchrotron μ-XRF and μ-XRD. EXAFS data for q_Sr ≈ 40 mmol kg⁻¹ showed incorporation of Sr²⁺ into both feldspathoid and SrCO₃(s) coordination environments after one year. Adsorption was predominant at early times and low sorbate amount, whereas precipitation, controlled largely by sediment Si release, became increasingly important at longer times and higher sorbate amount. Kinetics of contaminant desorption at pH 8 from one year-weathered sediments showed significant dependence on background cation (Ca²⁺ versus K⁺) composition. Results of this study indicate that co-precipitation and ion exchange in neoformed aluminosilicates may be an important mechanism controlling Sr²⁺ and Cs⁺ mobility in siliceous sediments impacted by hyperalkaline HLRW.  相似文献   

Geochemical controls on lead concentrations in stream water and sediments     

John D. Hem 《Geochimica et cosmochimica acta》1976,40(6):599-609

The equilibrium distribution of lead in solution and adsorbed on cation exchange sites in sediment theoretically may be calculated from equations representing selectivities of substrate for lead over H⁺, Ca²⁺ and Na⁺, and the stabilities of lead solute species. Such calculations include consideration of total concentrations of major ions, cation exchange capacity (CEC) of substrate, and pH, at values expected in various natural systems. Measurements of CEC and selectivity coefficients were made for synthetic halloysite, a finely divided amorphous 1:1 clay prepared by precipitation from a mixture of solutions of aluminum and silica. Where suspended sediment having the same properties is present in concentrations of 10-1,000 mg/1 at pH 6–8, more than 90% of the lead present can be adsorbed on sediment surfaces. The cation exchange behavior of lead and other minor cationic species in natural systems could be predicted by this type of model if enough other supporting information were available. Information of the type needed describing natural stream sediments, however, is presently inadequate for accurate predictions.  相似文献   

Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA   总被引：1，自引：0，他引：1  

John M Zachara  Steven C SmithChongxuan Liu  James P McKinleyR.Jeffrey Serne  Paul L Gassman 《Geochimica et cosmochimica acta》2002,66(2):193-211

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 NaNO_3(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   

Interstitial solutions and diagenesis in deeply buried marine sediments: results from the Deep Sea Drilling Project     

Frederick L Sayles  Frank T Manheim 《Geochimica et cosmochimica acta》1975,39(2):103-127

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/10³yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/10³ yr the changes chiefly involve gains of Ca²⁺ and Sr²⁺ and losses of Mg²⁺ which balance the Ca²⁺ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr²⁺ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg²⁺ for Ca²⁺ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca²⁺ and Sr²⁺ enrichment is again characteristic, but Mg²⁺ losses exceed Ca²⁺ gains with the excess being balanced by SO₄^{post staggered2?} losses. The data indicate that the reactions are similar to those noted above, except that the Ca²⁺ released is not kept in solution but is precipitated by the HCO₃^{post staggered?} produced in SO₄^{post staggered2?} reduction. In both these types of pore waters Na⁺ is usually conservative, but K⁺ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na⁺, Si and CO₂, and slight enhancement in Cl^?. The changes are attributed to exchange of Na⁺ for Ca²⁺ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO₄^{post staggered2?}, strong HCO₃^{post staggered?} enrichment, formation of NH₄^{post staggered+}, and methane synthesis from H₂ and CO₂ once SO₄^{post staggered2?} is eliminated. K⁺ and often Na⁺ (slightly) are depleted in the interstitial waters. Ca²⁺ depletion may occur owing to precipitation of CaCO₃. In most cases interstitial Cl^? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl^? are observed in some sediments adjacent to continents.  相似文献   

Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA     

Chongxuan Liu  John M. Zachara  James P. McKinley 《Geochimica et cosmochimica acta》2003,67(16):2893-2912

The desorption of ¹³⁷Cs⁺ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline ¹³⁷Cs⁺-containing high level nuclear wastes (HLW, 2 × 10⁶ to 6 × 10⁷ pCi ¹³⁷Cs⁺/g) were studied. The desorption of ¹³⁷Cs⁺ was measured in Na⁺, K⁺, Rb⁺, and NH₄⁺electrolytes of variable concentration and pH, and in presence of a strong Cs⁺-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). ¹³⁷Cs⁺ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of ¹³⁷Cs⁺ desorption increased with increasing electrolyte concentration and followed a trend of Rb⁺ ≥ K⁺ > Na⁺ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of ¹³⁷Cs⁺ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K⁺, Rb⁺, or NH₄⁺. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs⁺ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs⁺-sorbed micas showed that the ¹³⁷Cs⁺ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of ¹³⁷Cs⁺. Controlled desorption experiments using Cs⁺-spiked pristine sediment indicated that the ¹³⁷Cs⁺ diffusion rate was fast in Na⁺-electrolyte, but much slower in the presence of K⁺ or Rb⁺, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed ¹³⁷Cs⁺ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60-80%. The remainder of the sorbed ¹³⁷Cs⁺ was fixed or desorbed at much slower rate than our experiments could detect.  相似文献   

Ion exchange properties of oceanic ferromanganese nodules and enclosing pelagic sediments     

G. V. Novikov  I. O. Murdmaa 《Lithology and Mineral Resources》2007,42(2):137-167

Results of the experimental study of ion exchange properties of deep-sea pelagic sediments and related ferromanganese nodules (FMN) are considered. The exchange complex of sediments and nodules includes Na⁺, K⁺, Ca²⁺, and Mg²⁺ cations. The FMNs also include Mn²⁺ cations. Series of reactivity of metal cations during exchange reactions in different types of pelagic clayey sediments and diagenetic-sedimentary FMN are compiled. Series of exchange capacity of the sediments and FMN for alkali and heavy metal cations are also presented. The exchange capacity of FMN is always higher than that of enclosing sediments. Sediments are characterized by reversible equivalent sorption of cations of both alkali and heavy metals. Irrespective of the mineral composition, the FMNs are characterized by the reversible equivalent sorption of alkali metal cations, whereas sorption of heavy metal cations is only partly reversible. More over, alkali metal cations do not replace heavy metal cations. The results obtained refine the role of ion exchange processes in the redistribution of heavy metal cations at the water-bottom sediment interface during the diagenetic-sedimentary formation of ferromanganese nodules.  相似文献   

Influential factors on the levels of cation exchange capacity in sediment at Langat river     

Nur Aliaa Shafie  Ahmad Zaharin Aris  Nadzhratul Husna Ahmad Puad 《Arabian Journal of Geosciences》2013,6(8):3049-3058

An exploratory study was carried out at 22 sampling stations along the Langat River, Selangor in order to investigate on the vitality of cation exchange capacity (CEC) in sediment (0–5 cm). Parameters such as pH, Eh, salinity, and electrical conductivity (EC) were determined. The CEC in sediment has been calculated by the determination of Ca²⁺, Na⁺, Mg²⁺, and K⁺ using the flame atomic absorption spectrophotometer, while the organic matter content in sediment was ascertained using the loss on ignition method. The characteristic of the sediment shows that pH (3.09–7.46), salinity (0.02–10.71 ppt), EC (3.39–517 μS/cm) and Eh (?16.20–253.10 mV) were substantially high in variation. This study also revealed that exchangeable Ca²⁺ and Mg²⁺ were controlled by organic matter contents, while exchangeable Na⁺ and K⁺ were influenced by salinity. Salinity was observed to play a major part in controlling all the exchangeable cations, as it gives strong significant correlations with Na⁺, K⁺, Mg²⁺, CEC, and organic matter at p?<?0.01. The presence of seawater, clay mineralogy, and organic matter proves that it does play an important role in determining the CEC and soon relates to the pollution magnitude in the sediment.  相似文献   

Cation-exchange characteristics of Amazon River suspended sediment and its reaction with seawater     

Frederick L Sayles  Paul C Mangelsdorf 《Geochimica et cosmochimica acta》1979,43(5):767-779

The cation-exchange characteristics of Amazon River suspended sediment have been studied in order to determine the contribution of exchangeable cations to the geochemical fluxes from the river. Sediment samples were obtained throughout most of the Amazon Basin. The range of exchangeable cation compositions is very narrow in the river and in seawater as well. In river water, the exchangeable cation complement (equivalent basis, exclusive of H⁺) is 80% Ca²⁺, 17% Mg²⁺, 3% Na⁺ plus K⁺. In seawater Na⁺ and Mg²⁺ are about equal (38%) while Ca²⁺ ~ 15% and K⁺ ~ 9%.On reaction with seawater, river suspended sediment took up an amount of Na⁺ equal to nearly one-third of the dissolved river load, as well as amounts corresponding to 15–20% of the dissolved fluvial K⁺ and Mg²⁺. These estimates reflect an unusually high suspended-sediment:dissolved-solids ratio of 6.4 at the time of sampling. At a more representative world average ratio of four, the uptake of Na⁺ would be 20% of the dissolved fluvial load, and that for K⁺ and Mg²⁺ about 10%. Over the annual cycle of the Amazon, it is estimated that ion exchange has a still smaller effect, as a consequence of the low average suspended-solids:dissolved-solids ratio of 1.7.Variations in the ratio $\text{X}{}_{\mathrm{Ca}}\text{X}{}_{\mathrm{Mg}}$, the equivalent fraction of exchangeable Ca²⁺ and Mg²⁺, throughout the river, can be described by a single isotherm. This same isotherm accurately describes the distribution of exchangeable Ca²⁺ and Mg²⁺ on sediment equilibrated with seawater, despite that a high proportion of exchange sites is occupied by Na⁺ and K⁺.  相似文献   

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites     

Sarah H. Wallace  Samuel Shaw  Katherine Morris  Joe S. Small  Adam J. Fuller  Ian T. Burke 《Applied Geochemistry》2012

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.  相似文献   

Modelling Zn(II) sorption onto clayey sediments using a multi-site ion-exchange model     

E. Tertre  C. Beaucaire  N. Coreau  A. Juery 《Applied Geochemistry》2009

In environmental studies, it is necessary to be able to predict the behaviour of contaminants in more or less complex physico-chemical contexts. The improvement of this prediction partly depends on establishing thermodynamic models that can describe the behaviour of these contaminants and, in particular, the sorption reactions on mineral surfaces. In this way, based on the mass action law, it is possible to use surface complexation models and ion exchange models. Therefore, the aim of this study is (i) to develop an ion-exchange model able to describe the sorption of transition metal onto pure clay minerals and (ii) to test the ability of this approach to predict the sorption of these elements onto natural materials containing clay minerals (i.e. soils/sediments) under various chemical conditions. This study is focused on the behaviour of Zn(II) in the presence of clayey sediments. Considering that clay minerals are cation exchangers containing multiple sorption sites, it is possible to interpret the sorption of Zn(II), as well as competitor cations, by ion-exchange equilibria with the clay minerals. This approach is applied with success to interpret the experimental data obtained previously in the Zn(II)–H⁺–Na⁺–montmorillonite system. The authors’ research team has already studied the behaviour of Na⁺, K⁺, Ca²⁺ and Mg²⁺ versus pH in terms of ion exchange onto pure montmorillonite, leading to the development of a thermodynamic database including the exchange site concentrations associated with montmorillonite and the selectivity coefficients of Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺ versus H⁺.  相似文献   

Diagenetic processes in Holocene carbonate sediments: Florida Bay mudbanks and islands     

STEPHEN J. BURNS  PETER K. SWART 《Sedimentology》1992,39(2):285-304

The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions. In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca²⁺, Mg²⁺ and Sr²⁺ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition. Stratigraphic analysis and δ¹³C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr^?1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.  相似文献   

Cancrinite and sodalite formation in the presence of cesium, potassium, magnesium, calcium and strontium in Hanford tank waste simulants   总被引：1，自引：0，他引：1  

Youjun Deng  Markus Flury  James B. Harsh  Andrew R. Felmy  Odeta Qafoku 《Applied Geochemistry》2006,21(12):2049-2063

  相似文献   

Geochemical evolution of highly alkaline and saline tank waste plumes during seepage through vadose zone sediments     

Jiamin Wan  Tetsu K Tokunaga  R.Jeff Serne 《Geochimica et cosmochimica acta》2004,68(3):491-502

Leakage of highly saline and alkaline radioactive waste from storage tanks into underlying sediments is a serious environmental problem at the Hanford Site in Washington State. This study focuses on geochemical evolution of tank waste plumes resulting from interactions between the waste solution and sediment. A synthetic tank waste solution was infused into unsaturated Hanford sediment columns (0.2, 0.6, and 2 m) maintained at 70°C to simulate the field contamination process. Spatially and temporally resolved geochemical profiles of the waste plume were obtained. Thorough OH⁻ neutralization (from an initial pH 14 down to 6.3) was observed. Three broad zones of pore solutions were identified to categorize the dominant geochemical reactions: the silicate dissolution zone (pH > 10), pH-neutralized zone (pH 10 to 6.5), and displaced native sediment pore water (pH 6.5 to 8). Elevated concentrations of Si, Fe, and K in plume fluids and their depleted concentrations in plume sediments reflected dissolution of primary minerals within the silicate dissolution zone. The very high Na concentrations in the waste solution resulted in rapid and complete cation exchange, reflected in high concentrations of Ca and Mg at the plume front. The plume-sediment profiles also showed deposition of hydrated solids and carbonates. Fair correspondence was obtained between these results and analyses of field borehole samples from a waste plume at the Hanford Site. Results of this study provide a well-defined framework for understanding waste plumes in the more complex field setting and for understanding geochemical factors controlling transport of contaminant species carried in waste solutions that leaked from single-shell storage tanks in the past.  相似文献   

Cation exchange processes and human activities in unconfined aquifers   总被引：1，自引：0，他引：1  

G.?PanagopoulosEmail author  N.?Lambrakis  P.?Tsolis-Katagas  D.?Papoulis 《Environmental Geology》2004,46(5):542-552

During the 1999–2002 water years, a hydrogeological research project was carried out on the unconfined aquifer of Trifilia in the Peloponnese. Seawater intrusion due to overpumping, and intensive use of fertilizers caused the groundwater quality degradation that is a typical case for the coastal aquifers in Greece. Isopiezometric maps along with ion distribution balances, ion distribution maps and factor analysis indicate the existence of three zones of groundwater quality. In the first zone of saline water, a cation exchange process between the Ca²⁺ of sediments and the Na⁺ of groundwater contribute to the formation of the water type Na⁺-Ca²⁺-Cl^–. In the second zone, which is considered as a transition zone, dominate the Ca²⁺-Na⁺-HCO₃^–-Cl^– water type. In the third zone of Ca²⁺-HCO₃^–-SO₄^2– water type, relationships among Ca²⁺, SO₄^2–, NO₃^– and NH₄ can be attributed to the dissociation of ammonium nitrate and sulfate fertilizers on one hand, and Ca²⁺ derivation from cation exchange processes between water, rocks and clay minerals, such as smectite and illite, on the other.  相似文献   

Ion exchange properties of manganese and iron minerals in oceanic micronodules     

G. V. Novikov  V. N. Sval’nov  O. Yu. Bogdanova  A. V. Sivtsov 《Lithology and Mineral Resources》2010,45(5):410-424

The results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules (MN) from diverse bioproductive zones of the World Ocean are considered. It was found that the sorption behavior of these minerals is similar to that of ore minerals from ferromanganese nodules (FMN) and low-temperature hydrothermal crusts. The exchange complex of minerals in the MN includes the major (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Mn²⁺) and the subordinate (Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, and others) cations. Reactivity of theses cations increases from Pb²⁺ and Co²⁺ to Na⁺ and Ca²⁺. Exchange capacity of MN minerals increases from the alkali to heavy metal cations. Capacity of iron and manganese minerals in the oceanic MN increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite Fe-vernadite + Mn-feroxyhyte. The data obtained supplement the available information on the ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in the redistribution of metal cations at the bottom (ooze) water-sediment interface during the MN formation and growth.  相似文献   

The morphology of calcite crystals grown in a porous medium doped with divalent cations     

《Chemical Geology》2006,225(3-4):314-321

Calcite crystals were grown in the presence of small concentrations (50, 200, and 600 ppm) of divalent cations (Ba²⁺, Sr²⁺, Co²⁺ and Mn²⁺) in a silica hydrogel medium. The calcite crystals grown in the presence of cations larger than Ca²⁺ (Ba²⁺ or Sr²⁺) developed rhombohedral habits defined by {101¯4} form, similar to the morphology of calcite grown in a pure gel. SEM images show that growth on {101¯4} occurs by lateral advancement of layers bounded by macroscopic dendritic or jagged steps. In the case of calcite crystals grown in a gel doped with cations smaller than Ca²⁺ (Co²⁺ or Mn²⁺), a variety of morphologies was obtained, ranging from blocky crystals (at lower concentrations: 50 and 200 ppm) to peanut-like aggregates, spheres and spherulites (at 600 ppm). The macroscopic morphological characteristics of such doped calcite crystals reflect closely the growth behaviour of calcite {101¯4} surface at a nanoscale, reported by previous AFM studies. Morphological features have been interpreted on the basis of the modification of growing steps characteristics as a consequence of asymmetrical cation incorporation. The use of such morphologies as a criterion of biological activity is, therefore, unreliable.  相似文献   

Modeling alternative paths of chemical evolution of Na-HCO3-type groundwater near Oak Ridge, Tennessee, USA   总被引：2，自引：0，他引：2  

Laura E. Toran  James A. Saunders 《Hydrogeology Journal》1999,7(4):355-364

 This paper demonstrates that both cation exchange, a commonly invoked mechanism, and silicate hydrolysis, which is less commonly considered, can produce Na-HCO₃-type water in sedimentary rocks. Evolution of Na-HCO₃ groundwater beneath the Oak Ridge Reservation, Tennessee, USA, was studied by comparing observed end-member groundwater composition from multiport samplers to compositions generated by reaction-path geochemical models. Observed groundwater compositions could be reproduced by either the silicate-hydrolysis model or the cation-exchange model. Secondary minerals precipitated in the silicate-hydrolysis model are similar to those present along fractures in the shale and carbonate host rocks, and observed molar Sr²⁺/Ca²⁺ ratios more closely resemble evolution from shale weathering. Both mechanisms should be considered to understand the evolution of Na-HCO₃ groundwater. Received, April 1998 · Revised, January 1999 · Accepted, March 1999  相似文献   

The composition and diagenesis of interstitial solutions—I. Fluxes across the seawater-sediment interface in the Atlantic Ocean     

F.L. Sayles 《Geochimica et cosmochimica acta》1979,43(4):527-545

Studies of the composition of interstitial solutions of marine sediments have been carried out utilizing in situ sampling techniques. Samples were obtained from the Caribbean, North Atlantic and South Atlantic. In virtually all cases, diagenesis has led to the uptake of Mg²⁺ and K⁺ and the release of Ca²⁺, HCO^?₃ and Na⁺ by the solid phases. SO^2?₄ is slightly enriched at nearly all stations, reduction being observed only at continental margin stations. Cl^? is conservative within experimental precision.The reactions controlling the fluxes of most components across the water-sediment interface occur almost entirely in the upper 100 cm of sediment. Contributions of Mg ²⁺, Ca ²⁺, K⁺ and HCO^?₃ from below 100 cm amount to less than 15% of the calculated fluxes across the interface. Reactions in the upper 30 cm account for 70–90% of the fluxes of these components across the interface. Only Na⁺ has a deep source, gradients often being linear in the upper 2m of sediment.Calculated fluxes across the sediment-water interface are of the same order of magnitude as river inputs for the components studied. In the case of Mg²⁺ and K ⁺, 60–100% of the river input can be balanced by diagenetic uptake in the sediment. For Ca²⁺ and HCO^?₃ additions to seawater augment the river supply by 25–50%. When the uptake of Mg²⁺ and K⁺ by the sediment is calculated by integrating the fluxes across the interface, calculated concentrations of both of these elements are inconsistent with published average concentrations for the types of sediment studied.  相似文献   

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results   总被引：1，自引：0，他引：1  

Richard A. Jahnke  Deborah B. Jahnke 《Geochimica et cosmochimica acta》2004,68(1):47-59

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.  相似文献   

Deciphering the interaction between quaternary and continental Sabkhas aquifers in Central Tunisia using hydrochemical and isotopic tools   总被引：1，自引：0，他引：1  

Intissar Farid  Rim Trabelsi  Kamel Zouari  Kamel Abid  Mohamed Ayachi 《Environmental Earth Sciences》2013,70(7):3289-3309

Climate aridity and intensive exploitation due to uncontrolled pumping for irrigation have caused a drastic decrease in the piezometric level of the shallow aquifer of Chougafiya plain, central Tunisia, and have seriously degraded groundwater quality. According to the hydrochemical data (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Br^?, Na⁺, Mg²⁺, K⁺, Ca²⁺, Sr²⁺) and the stable isotopes (¹⁸O and ²H content), groundwater salinization in the investigated aquifer is caused by four main processes: (1) evaporite dissolution (2) cation exchange reactions (3) evaporation processes and (4) mixing with Sabkhas salt water causing salinity to increase in the central and southern parts of the basin. The radiogenic (³H) isotope data provided insight into the presence of significant contemporaneous recharge waters in the western part of the shallow aquifer. The movement of the tritiated water may have occurred according to the general flow path (NW–SE). When tritium was used in conjunction with the stable isotopes and chloride, the mixing process could be clearly identified, especially in the central part of the study area.  相似文献