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1.
Abstract

Time dependent zinc (Zn) desorption in eight benchmark soils of India was studied in relation to various pH values and ionic strengths. Soil samples were equilibrated in solutions containing 10 μg Zn g‐1 soil at pH 5.5,6.5, and 7.5 for 48 h at 25±2°C, and adsorbed Zn extracted with calcium chloride (CaCl2) for various periods of time. Desorption of Zn decreased with increasing pH, and the desorption rate decreased abruptly at pH 7.5. In contrast, an increase in the equilibration period and ionic strength of the background electrolyte increased Zn desorption. Four rival kinetic models were fitted and evaluated for their suitability for describing the Zn desorption process. Reaction rate constant (ß) calculated from the Elovich model for the different soils ranged from 9.99 to 25 (mg Zn kg‐1)‐1. The different kinetic models tested indicated that Zn desorption in soils was a diffusion controlled process. The desorption was rapid in the first 4 h, followed by slower phase in the rest of the time at all the pH values indicating a biphasic desorption, characteristic of a diffusion controlled process. The ß value for the Elovich equation showed a strong association with soil clay content and cation exchange capacity (CEC). Further, the best prediction of Zn desorption reaction rate constant could be made using multiple‐regression equation with soil clay content and CEC as variables.  相似文献   

2.
《Geoderma》2005,124(3-4):335-348
In order to gain understanding of the movement of pollutant metals in soil, the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmolc kg−1, 5.6 and 8.4 pore volumes of 10 mM CaCl2, respectively, were required to displace a pulse of ZnCl2 . A simple Burns-type model (Wineglass) using an adsorption coefficient (Kd) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (Kd=0.73 and 1.29 ml g−1, respectively).Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%, cation exchange capacity (CEC) 11.8 and 6.1 cmolc kg−1, respectively) were leached with 10 mM calcium chloride, nitrate and perchlorate. With chloride, the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The Kd values were 6.1 and 2.0 ml g−1, but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus, a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and Kd values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher Kd values when the isotherms were measured using this anion (7.7 and 2.8 ml g−1, respectively). Although pH values were a little higher with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn2+ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate.Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard.  相似文献   

3.
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4.
Abstract

To investigate the activity of free cadmium (Cd2+), copper (Cu2+), lead (Pb2+), and zinc (Zn2+) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (CdT, CuT, PbT, and ZnT, respectively), 0.43 MHNO3‐extractable Cd, Cu, Pb, and Zn (CdN, CuN, PbN, and ZnN, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca2+]. The activity of free Pb2+, Cd2+, Cu2+, and Zn2+ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L‐1, Cu from 3.43 to 7.42 μg L‐1, Pb from 1.23 to 5.8 μg L‐1, and Zn from 24.5 to 34.3 μg L‐. In saturation soil extracts, the activity of free Cd2+ ions constituted 42 to 82% of the dissolved fraction, for Cu2+the range was 0.1 to 7.8%, for Pb2+ 0.1 to 5.1% and for Zn2+2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd2+, Cu2t, Pb2+, and Zn2+ ions.  相似文献   

5.
The adsorption of Zn by soils which are different in their major cation-exchange materials was measured at equilibrium Zn concentrations up to 10?2 M in 10?2 to 10?3 M CaCl2. The results are interpreted on KZnCa[Zn]soil plots, where KZnCa is the selectivity coefficient defined by the equation All natural samples except those containing halloysite exhibited no or very small specific Zn adsorption. All Ca-saturated samples exhibited specific Zn adsorption dependent on cation-exchange materials. The cation-exchange sites with high selectivities for Zn (KZnCa > 10) constitute more than 40 per cent of the total exchange sites in soils containing allophane, imogolite, and halloysite, whereas those with moderate to low selectivities for Zn (KZaCa < 10) predominate in montmorillonitic, vermiculitic, and humic soils. Differences in the contribution of the respective cation-exchange materials to specific Zn adsorption are discussed relating to differences in the origin of their negative charge.  相似文献   

6.
Experiments on Zn2+ sorption-desorption by Ca-kaolinite using a wide range of Zn2+ concentrations and two acid pH values allowed us to reach the following conclusions: (1) For Zn2+ surface coverages below the kaolinite C.E.C., Zn2+ was sorbed mainly via ion exchange; (2) At Zn2? sorption values above the C.E.C., Zn2+ was sorbed with higher affinity by a mechanism stronger than ion exchange, involving a strong association of Zn ions with silicate solid phases; and (3) Use of C.E.C. values and/or Langmuir's calculated maxima would greatly underestimate Zn2+ sorption capacity by kaolinite, even at acid pH values.  相似文献   

7.
The objective of this study was to examine the effect of soil pH on zinc (Zn) sorption and desorption for four surface soils from the Canterbury Plains region of New Zealand. Zinc sorption by the soils, adjusted to different pH values, was measured from various initial solution Zn concentrations in the presence of 0.01 M calcium nitrate [Ca(NO3)2]. Zinc desorption isotherms were derived from the cumulative Zn desorbed (µg g?1 soil) after each of 10 desorption periods by sequentially suspending the same soil samples in fresh Zn‐free 0.01 M Ca(NO3)2. Zinc sorption and desorption varied widely with soil pH. Desorption of both native and added Zn decreased continuously with rising pH and became very low at pH values greater than 6.5. The proportion of sorbed Zn that could be desorbed back into solution decreased substantially as pH increased to more than 5.5. However, there were differences between soils regarding the extent of the hysteresis effect.  相似文献   

8.
Assessment of zinc (Zn) phytoavailability by the newly developed technique of diffusive gradients in thin films (DGT) has started gaining more importance because of some advantages over routine soil extractants. A greenhouse study was conducted to determine Zn phytotoxicity thresholds and the phytoavailability of Zn to sorghum sudan (Sorghum vulgare var. sudanese) grass by DGT, compared with calcium chloride (CaCl2) extraction. Treatments were five Zn levels and two soil pH (6.5 and 6). To obtain various amounts of Zn phytoavailability, soils having two different pH values were amended with zinc sulfate (ZnSO4) at rates of 0, 150, 300, 600, and 1200 mg Zn kg?1. Control soil (pH = 6.5) was treated with predetermined elemental sulfur to create different soil pH values (6). Shoot and root Zn concentrations ranged from 27 to 827 mg kg?1 and 101 to 2858 mg kg?1, respectively. In general, the Zn concentrations in shoots and roots were increased by increasing Zn concentrations and soil pH. Increasing applied Zn to soil decreased the plant biomass yield and increased adsorption of Zn by DGT. Calcium (Ca) to Zn ratios for all treatments except controls were <26 for shoots and <13 for roots. The CaCl2‐extractable Zn and effective concentration (CE) correlated well with plant Zn concentration. A critical shoot Zn concentration for 90% of the control yield was chosen as an indicator of Zn toxicity. The performance of DGT, CaCl2 extraction, Ca/Zn ratio and plant Zn concentrations were similar for assessing Zn phytoavailability.  相似文献   

9.
In industrial areas, heavy metals may accumulate in forest soil organic horizons, affecting soil microorganisms and causing changes in the chemical composition of the accumulated organic matter. The objectives of this study were to test the ability of near-infrared spectroscopy (NIRS) to detect heavy metal effects on the chemical composition of forest soil O horizons and to test whether NIRS may be used to quantitatively determine total and exchangeable concentrations of Zn and Pb (Znt, Pbt, Znex, Pbex) and other chemical and microbial properties in forest soil O horizons polluted with heavy metals. The samples of O horizons (n = 79) were analyzed for organic C (Corg), total N and S (Nt, St), Znt, Pbt, Znex, Pbex, basal respiration (BR), microbial biomass (Cmic) and Cmic-to-Corg ratio. Spectra of the samples were recorded in the Vis-NIR range (400–2,500 nm). To detect heavy-metal-induced changes in the chemical composition of O horizons principal components (PC1–PC7) based on the spectral data were regressed against Znt + Pbt values. A modified partial least squares method was used to develop calibration models for prediction of various chemical and microbial properties of the samples from their spectra. Regression analysis revealed a significant relationship between PC3 and PC5 (r = −0.27 and −0.34, respectively) and Znt + Pbt values, indicating an effect of heavy metal pollution on the spectral properties of the O horizons and thus on their chemical composition. For quantitative estimations, the best calibration model was obtained for Corg-to-Nt ratio (r = 0.98). The models for Corg, Nt, and microbial properties were satisfactory but less accurate. NIRS failed to accurately predict St, Corg-to-St, Znt, Pbt, Znex, and Pbex.  相似文献   

10.
The effectiveness of lime-ammonium-nitrate (LAN) as a nitrogen (N) fertilizer in weathered soils depends on the respective selectivity for ammonium (NH4) and calcium (Ca) by the soils. The study assessed Ca2+/NH4+ exchange selectivity of two benchmark soils from Botswana and examined the soil fertility management implications. Surface horizons (0–20 cm) of Pellustert and Haplustalf were equilibrated with 50 ml stock solution containing variable concentrations of Ca2+ and NH4+. The Ca2+/NH4+ exchange data were fitted into the Vanselow (KV), Gaines and Thomas (KGT), Davies (KD), and the regular solution (KRS) equations. The selectivity coefficients for the Ca2+/NH4+ exchange reactions varied widely with the soil exchanger composition except for the relatively stable KRS. The selectivity coefficients indicated strong preference for NH4+ to Ca2+. The thermodynamic exchange constant, Kex, was 5.75 ± 1.24 in the Pellustert, indicating preferential adsorption of NH4+, but not in the Haplustalf with Kex = 0.92 ± 0.27. The free energy for Ca2+/NH4+ exchange (ΔG°ex) was negative (?4.26 ± 0.59 kJ mol?1) in the Pellustert but slightly positive in the Haplustalf (0.34 ± 0.87 kJ mol?1). In conclusion, the soil-NH4 complex was more stable than soil-Ca complex in the Pellustert, indicating LAN as a N fertilizer would have greater potential effectiveness in the Pellustert than in the Haplustalf.  相似文献   

11.
A soil's cation exchange capacity (CEC) is expected to be relatively inert against changes in cation loading. In this study, we treated a soil sample originating from the organic layer of a forest soil with various bivalent cations after removing the native cations. Sorption isotherms and cation exchange capacity were determined, the latter using the BaCl2 method. Sorption showed Langmuir characteristics, with the maximum coverage (Qmax) increasing in the order Ba2+ < Ca2+ < Mg2+, but being clearly smaller than the initial load of native exchangeable cations. The Langmuir coefficient, kMe, depended oppositely to the order obtained for Qmax. CEC increased upon cation treatment and it varied by a factor of almost two. The unexpected variation of CEC was explained by the low cation exchange capacity of the organic matter such that not all functional groups are close enough to be bridged and the second charge of a bivalent cation is not neutralized by the organic functional group. The Langmuir sorption type, and Qmax being smaller than the content of sorption sites and being largest for Mg, suggested that only a part of the sites can be cross‐linked and at least part of the cross‐links are formed by hydrated cations. Thermodynamic considerations allowed reconstruction of two contrasting processes during CEC determination by Ba2+: Case A: the disruption of cross‐links, which increases with the cationic strength and the cation load before CEC determination, but does not require structural re‐orientation in the SOM matrix, and Case B: the formation of new cross‐links during CEC determination, depending only on the content of unoccupied sites before CEC determination and requiring structural re‐organization of the matrix and thus a minimum matrix flexibility. The use of bivalent cations for CEC determination may thus result in an overestimation of CEC for organic matter with low CEC. This has, however, promising potential when comparing CEC determined with monovalent cations and bivalent cations. Using a set of bivalent cations, may allow probing distribution of distances between functional groups in the organic matter and even characterize the matrix rigidity of the cation‐cross‐linked network.  相似文献   

12.
Abstract

Zinc solubility in soils can be affected by both pH and pyrophosphate (PP), yet the reaction of PP is influenced by pH, thus there is a need to evaluate pH effect on Zn transformation in soils treated with PP. Samples of three autoclaved soils, a Dalhousie (DT) clay, a St. Bernard (ST) loam, and an Uplands (UT) sand were equilibrated first with PP (0.0 and 9.0 P mM), then with Zn (0.0, 0.5, 1.0 Zn mM) and followed by 0.03 M KC104 solutions at the initial pH of 4.5, 6.0, and 7.5 with constant ionic strength. The first equilibration was for PP sorption, the second for Zn sorption and PP desorption, and the third for Zn desorption and further PP desorption. And finally, Zn of selected samples were extracted with 0.5 M KNO3 (exchangeable Zn, ZnKNO3), 0.5 M NaOH (organic and Fe oxides associated Zn, ZnNaOH) solutions, and concentrated HNO3+H2O2 (residual Zn, ZnHNO3).

Increases in pH reduced PP sorption in the UT and the ST soils while high or low pH values tended to reduced it in the DT soil, indicating a competition between PP and OH ions for sorption sites. Zinc sorption was linearly related to solution pH, the slopes varied from 0.10 to 1.06, lower values were associated with PP addition, with low Zn rate, with finer textured soils, with high contents of Fe and Al materials, and with high pH buffer capacity. The values of Zn desorption and ZnKN03 were greater at low than high pH while the reverse was true for ZnNaOH. The pH effects on Zn sorption‐desorption and fraction distributions were less significant in soil with than without PP. The overall effect of high pH and the presence of the sorbed PP was the increased Zn specific sorption, compared to the pH or PP effect alone.  相似文献   

13.
Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO3 solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO3 content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO3 content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.  相似文献   

14.
The sorption and ion-exchange behavior of Co(II) and Zn in the soil-equilibrium solution system was studied for different types and varieties of native soils and their clay fractions before and after mild oxidation with H2O2 to remove the organic carbon. The parameters of the ion-exchange adsorption and the selectivity coefficients of the (Co(II), Zn)/Ca ion exchange were determined using different models for describing the relationship between the dissolved and sorbed forms of the metals. These were the empirical Langmuir and Freundlich adsorption isotherms and the model of the ion-exchange adsorption based on the acting mass law. It was found that the soil organic matter played an important role in the selectivity of the ion-exchange adsorption of Co(II) and Zn by the soils and their clay fractions. This was confirmed by an abrupt decrease (to almost 1) of the selectivity coefficients of the Co2+/Ca2+ and Zn2+/Ca2+ exchange after the treatment of the clay fraction with hydrogen peroxide.  相似文献   

15.
The sorption and desorption of phosphorus (P) from eroding soil particles in land runoff are important processes contributing to agriculturally‐driven eutrophication. We investigated the P‐exchange properties and related chemical characteristics of contrasting European agricultural soils and sediment material eroded from them under indoor (small‐scale) and outdoor (larger‐scale) rainfall simulations. Quantity‐intensity (Q/I) relationships revealed large variation in equilibrium P concentrations at zero net P sorption (EPC0) (0–10.3 mg l−1) and instantly labile P (−Q0, the amount of P to be desorbed to obtain a P equilibrium concentration of 0 mg l−1) (2–75 mg kg−1), both correlating closely with Al‐bound P and the P saturation degree of Al oxides (DPSAlox). Maximum P sorption (Qmax) (43–515 mg kg−1) also correlated most closely with Alox. The indoor and outdoor rainfall simulations produced sediments with different P sorption properties: in the indoor simulation (less kinetic energy, constant slope), the sediments had larger EPC0 values, and usually larger −Q0 values, than the sediments in the outdoor simulation (greater kinetic energy, variable slopes). Furthermore, the P exchange properties of the sediments differed from those of the bulk soil depending on the enrichment of soil P‐sorption components (Fe/Al oxides, clay). The outdoor simulation indicated that sites with gentle slopes produced sediments that were more enriched with Alox, Feox, Mnox and organic C than those with steeper slopes. In this study, when the bulk soil had an initial EPC0 greater than 1.3 mg l−1, the outdoor rainfall simulation produced sediment with smaller EPC0 and vice versa, indicating that, depending on the P status of the bulk soil, the sediment material was acting as source or sink for P during transport. However, on the basis of their EPC0 values, most eroding sediments might be expected to desorb, rather than adsorb, P when entering surface water.  相似文献   

16.
Assessing the accumulation and transport of trace metals in soils and the associated toxicological risks on a national scale requires generally applicable sorption equations. Therefore Freundlich equations were derived for Cd, Zn and Cu using multiple linear regression on batch sorption data from the literature with a wide variety of soil and experimental characteristics, and metal concentrations ranging over five orders of magnitude. Equations were derived based on both total dissolved metal concentrations and free metal activities in solution. Free metal activities were calculated from total metal concentrations taking into account ionic activity, and inorganic (all metals) and organic complexation (Cu only). Cadmium and Zn were present in solution predominantly as free ions, while Cu was present as organic complexes. Since actual dissolved organic carbon (DOC) concentrations were not available they were estimated using an empirical field relation between DOC and organic matter content. The logarithmic transformation of the Freundlich constant for Cd was regressed on the logarithmic transformations of cation exchange capacity (CEC) (H+) and dissolved Ca, and for Zn with CEC and (H+). For Cu the log–log regression model of the Freundlich constant included the solid:solution ratio of the batch to account for dilution of DOC in the batch as compared with the field. The explained variance for the fitted Freundlich equations was 79% for Cd, 65% for Cu and 83% for Zn, using log-transformed adsorbed concentrations and soil solution activities. The Freundlich adsorption models underestimated metal contents determined from 1 m HNO3 digestion on field samples, up to a factor of 6 (Cd and Cu) or 10 (Zn).  相似文献   

17.
Abstract

The recovery of applied zinc (Zn) by plants is relatively small. Coupled with lack of leaching, this leads to accumulation of Zn in topsoil which may result in unfavorable growth conditions for the subsequent plants. Different extractants may be used for assessing the Zn status of soils previously treated with Zn sources. The extractability of retained Zn is influenced by soil properties. This experiment was conducted to study the influence of selected properties of calcareous soils on extractability of Zn by three popular Zn soil tests. Twenty samples from surface horizons (0–20 cm) of highly calcareous soils of southern Iran (pH 7.9 to 8.5; calcium carbonate equivalent 16 to 58%) previously treated with three levels of Zn (0, 10, and 20 mg Zn kg‐1 soil as ZnSO4#lb7H2O) in triplicate and under one crop of corn (Zea mays L.) were extracted with DTPA, EDTA‐(NH4)2CO3 and Na2‐EDTA. Extractability (EXT) in a particular extractant was defined as the slope of the regression line, relating extractable Zn of each soil to the rate of applied Zn, multiplied by 100. The EXT values of soils ranged from 24.9 to 73.0% for DTPA, 47.2 to 84.4% for EDTA‐(NH4)2CO3, and 28.2 to 56.7% for Na2‐EDTA. Stepwise regression equations showed that cation exchange capacity (CEC) and calcium carbonate equivalent (CCE) followed by clay content were the most influential soil properties in EXT of retained Zn of highly calcareous soils. The EXT values decreased with increase in CEC, and CCE but increased with increase in clay.  相似文献   

18.
Twenty-four surface soils (0–15 cm) were collected from Tal land soils (vertisols) in the southern part of Bihar state in India. Six extractants were used to predict the extractability and their suitability for measuring available zinc (Zn) in these soils. Pot experiment with chickpea (Cicer arietinum cv. C-235) as test crop was conducted with five levels of Zn (0, 2.5, 5.0, 7.5, and 10.0 mg kg?1) to determine critical levels of Zn in soils and chickpea. The efficiency rating of different extractants in extracting available Zn from soils followed the order ethylenediaminetetraacetic acid (EDTA)–ammonium carbonate [(NH4)2CO3] > diethylenetriaminepentaacetic acid (DTPA)–ammonium bicarbonate (NH4HCO3) > DTPA– calcium chloride (CaCl2) > DTPA–sodium bicarbonate (NaHCO3) > magnesium nitrate [Mg (NO3)2] > magnesium chloride (MgCl2). The DTPA-CaCl2-extractable Zn was significantly and positively correlated with clay, organic carbon, cation exchange capacity, dry-matter yield, and plant Zn concentration and uptake but significantly and negatively correlated with soil pH. These properties attributed 87% variability in DTPA-CaCl2-extractable Zn.  相似文献   

19.
Zinc (Zn) desorption from an exchange complex to solution, the release of Zn from organic matter (OM), crystalline minerals and other precipitates into the solution phase, is the process that controls Zn mobility in soils. An experiment was conducted to determine the pattern of Zn desorption and the soil characteristics affecting it. Desorption of Zn in 15 calcareous soils from southern Iran, treated with 10 mg Zn kg soil?1 as zinc sulfate (ZnSO4?7H2O) and 10 g organic matter (OM) kg?1 as feedlot cattle manure, equilibrated and extracted with diethylenetriamine pentaacetic acid (DTPA), was studied. Eight kinetic models were evaluated to describe the rate of Zn desorption of soil extracted with DTPA. There was a rapid rate of desorption during the first 4 h followed by a slower rate during the next 12 h. Two-constant rate and simple Elovich models were determined as the best models describing Zn desorption kinetics. Zinc desorption increased as Zn was applied, whereas it decreased with applied OM. The constants of the simple Elovich (βs) and two-constant rate equations (a and b) were closely correlated with cation-exchange capacity (CEC), OM and pH, which affect Zn solubility, sorption–desorption and diffusion in soils.  相似文献   

20.
Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl2 or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl2 than in NaCl of the same ionic strength. Apparently Ca2+ ions were more effective than Na+ ions in screening the negative charge on HA. In CaCl2 the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl2 sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca2+ or Na+) for charge balance. The Ca2+ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca2+ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.  相似文献   

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