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1.
To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K d) values were K d single (Pb) > K d binary (Pb) > K d single (Cd) > K d binary (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b 1), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d Cd*) was much greater than Pb (d Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.  相似文献   

2.
The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.  相似文献   

3.
The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.  相似文献   

4.
对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。  相似文献   

5.
Sorption of the 14 rare earth elements (REE) by basaltic rock is investigated as a function of pH, ionic strength and aqueous REE concentrations. The rock sample, originating from a terrestrial basalt flow (Rio Grande do Sul State, Brazil), is composed of plagioclase, pyroxene and cryptocrystalline phases. Small amounts of clay minerals are present, due to rock weathering. Batch sorption experiments are carried out under controlled temperature conditions of 20 °C with the <125 μm fraction of the ground rock in solutions of 0.025 M and 0.5 M NaCl and at pH ranging from 2.7 to 8. All 14 REEs are investigated simultaneously with initial concentrations varying from 10−7 to 10−4 mol/L. Some experiments are repeated with only europium present to evaluate possible competitive effects between REE. Experimental results show the preferential retention of the heavy REEs at high ionic strength and circumneutral pH conditions. Moreover, results show that REE sorption increases strongly with decreasing ionic strength, indicating two types of sorption sites: exchange and specific sites. Sorption data are described by a Generalised Composite (GC) non-electrostatic model: two kinds of surface reactions are treated, i.e. cation exchange at >XNa sites, and surface complexation at >SOH sites. Total site density (>XNa + >SOH) is determined by measuring the cation exchange capacity (CEC = 52 μmol/m2). Specific concentrations of exchange sites and complexation sites are determined by fitting the Langmuir equation to sorption isotherms of REE and phosphate ions. Site densities of 22 ± 5 and 30 ± 5 μmol/m2 are obtained for [>XNa] and [>SOH], respectively. The entire set of REE experimental data is modeled using a single exchange constant (log Kex = 9.7) and a surface complexation constant that progressively increases from log K = −1.15 for La(III) to −0.4 for Lu(III).The model proves to be fairly robust in describing other aluminosilicate systems. Maintaining the same set of sorption constants and only adjusting the site densities, we obtain good agreement with the literature data on REE/kaolinite and REE/smectite sorption. The Generalised Composite non-electrostatic model appears as an easy and efficient tool for describing sorption by complex aluminosilicate mineral assemblages.  相似文献   

6.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.  相似文献   

7.
对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。  相似文献   

8.
矿物材料与环境污染治理—以粘土矿物和沸石为例   总被引:9,自引:0,他引:9  
矿物的性能,矿区地质测试和吸附能力实验表明,粘土矿物和沸石等矿物材料对于Cr,Cd,Pb,Hg,As等有害元素具有很强的吸附能力,是理想的低成本吸附剂,在废水处理中可用来取代活性炭或离子交换树脂来去除重金属等有害元素。  相似文献   

9.
10.
针铁矿/水界面反应性的实验研究   总被引:1,自引:0,他引:1  
选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+>Pb2+>Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1~0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实.  相似文献   

11.
The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.  相似文献   

12.
Recent studies suggest that siderophores form stable complexes with divalent metals and affect their mobility. In this work, effects of trihydroxamate microbial siderophores and desferrioxamine-B (DFOB) on Pb(II), Zn(II), and Cd(II) sorption by two kinds of synthesized zeolites (13X and Na?CY) as a function of pH were investigated. Results showed that 13X zeolite has a higher sorption affinity for studied metals than Na?CY. DFOB strongly affected metal sorption on both zeolites. Under slightly acidic to neutral condition, DFOB increased the metal sorption on zeolites due to the sorption of positively charged heavy metal?CDFOB complexes. Whereas by increasing pH (>7), the mobilizing effect of DFOB was observed for Pb, Zn, and Cd. DFOB drastically decreased (80?%) Zn sorption in alkaline condition. As a result, siderophores can weaken the treatment efficiency of zeolites and increase the bioavailability of metals in soils. Surface complexation modeling revealed that the effects of DFOB on metal sorption by 13X and Na?CY zeolites can be explained by the differences in their surface charge. In general, the result shows the influence of DFOB on metal sorption by zeolites over the pH range 4?C9 and decreasing in the sequence Zn?>?Pb?>?Cd.  相似文献   

13.
《Applied Geochemistry》2003,18(11):1723-1731
The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (KD) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l−1) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller KD values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher KD values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low KD values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.  相似文献   

14.
The adsorption of thirteen trace metals from seawater was studied on interfacial sediment from MANOP site H. The adsorption data indicate a long (~20 day) equilibration time for most metals, an increase in adsorption with an increase in pH and particle concentration, a dependence of adsorption on total metal concentration at high adsorption densities, and a lack of correlation between metal binding ability and metal hydrolysis in solution.Apparent equilibrium binding constants normalized to the total number of available sites on the solid were determined for metal binding with the interfacial sediment. The binding constants indicate that the affinity sequence for metal interactions with the interfacial sediment is: Pb > Fe > Sn ? Co≈ Mn > Cu > Be > Sc ? Zn > Ni > Cd ? Ba > Cs at pH 7.82 in seawater.A comparison of the binding constants for suspended particles, interfacial sediment, and surface sediment indicate that the composition of particles influences the binding ability of the particles. Biogenic particles tend to bind most metals more strongly than lithogenic or authigenic particles.Based on limited data, there is a strong positive correlation between the measured binding constants and the observed partitioning of metals between sediment and seawater.  相似文献   

15.
Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K dmedium) for each metal and soil were calculated. The highest K dmedium value was found for Pb and followed by Cu. However, low K dmedium values were shown for Zn and Cd. On the basis of the K dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q m) of soils ranged from 32.57 to 90.09 mmol kg−1. Highly significant positive correlations were found between the K dΣmedium and Q m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.  相似文献   

16.
The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E1) with a kinetic rate constant k1 having values around 1 min−1 and a much slower exchangeable pool (E2) with k2 ranging from 0.0001 min−1 to 0.001 min−1. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k1 values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k2 values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.  相似文献   

17.
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   

18.
Conditional surface binding constants and complexation capacities for Zn, Pb, Cd, and Cu were determined from surface titration experiments of heterogeneous natural aquatic particulate matter of different origin and composition. Metals and particles were evaluated in naturally occurring concentration ranges in river water.The adsorption of trace metals can be adequately described with a single conditional binding constant over a wide range of metal : particle ratios. Binding constants for aquatic particles at pH 8.0 are remarkably independent from particle composition and are specific for each metal: log Kads Zn = 8.39, log Kads Pb = 9.67, log Kads Cd = 8.61, log ads Cu = 9.84. From competition experiments with Ca and Pb we extracted a sorption coefficient for Ca of log Kads Ca = 2.5 (pH 8.0). Maximum surface binding capacities for all metal ions were found for particles containing high fractions of Mn-oxides which are associated with large specific surface areas. Generally, we found sorption capacities to decrease in the sequence Cu Pb, Zn > Cd.The experiments suggest that the conditional surface binding constants and complexation capacities are applicable to model trace metal adsorption in the concentration ranges of natural waters under conditions similar to the experiments. Results also imply that the chemical nature of particle surface sites is rather uniform in the intermediate concentration range or that the array of binding sites averages out differences in sorption strength over the prevailing concentration range of metal ions, respectively.  相似文献   

19.
The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO22+) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10−3 M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)6] octahedral sites over [Al(O,OH)6] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO2. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO2.  相似文献   

20.
The sorption capacity of five clay soils from South Wales in the United Kingdom was investigated using two main tests; physico-chemical and batch equilibrium (BET). The physico-chemical property results show that soil weathered mudrocks (MR1), glacial till (GT1), and estuarine alluviums (NEA4, PEA3 and CEA3) are capable of being used as landfill liners and are chosen for further sorption tests. The batch tests (i.e. sorption tests) on soil suspension produce adsorption-pH curves, showing increasing adsorption at higher pH levels. The sorption data are also presented using adsorption isotherm curves and are best fitted using the Langmuir adsorption equation that yields the maximum adsorption capacity of the soils. The sorption capacity of soils are ranked as estuarine alluvium soils>glacial till>weathered mudrocks. Estuarine alluvium soils show a good buffering capacity and high sorption capability compared to glacial till and weathered mudrocks. The study also discovers that the maximum sorption capacities are highly influenced by the chemical properties of the soils.  相似文献   

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