Comparison of Five Adsorption Isotherms for Prediction of Zinc Retention in Calcareous Soils and the Relationship of their Coefficients with Soil Characteristics

Abstract

Zinc (Zn) deficiency is believed to be a consequence of reactions taking place between soluble Zn and the soil solid phase. This study was carried out to obtain quantitative relationships between Zn in equilibrium solution and that retained by the soil solids in calcareous soils. Twenty calcareous soils (saturated paste pH 6.9–7.9; calcium carbonate equivalent 4.64–22.80%) from Tehran province, Iran, were equilibrated with varying solution concentrations of Zn, and the amounts removed from the solution were used to check the fit to five adsorption isotherms, namely, Freundlich, Langmuir, Temkin, Gunary, and two‐surface Langmuir. Adsorption data of all soils showed statistically significant fit to the first four adsorption isotherms, but only 7 of the 20 soils tested showed fit to the two‐surface Langmuir. Coefficients of the adsorption isotherms showed statistically significant relationship with soil characteristics. Clay percentage, calcium carbonate equivalent percentage, and cation exchange capacity appeared to be the most influential soil characteristics with regard to Zn adsorption, whereas soil organic matter seemed to be of no importance under the conditions of this study.     

Zinc Adsorption by Mineral Soils of Finland

Abstract

Zinc adsorption by 10 (pH 4.0–6.5) cultivated mineral soils from Finland was studied in batch experiments. Additions of Zn ranged up to 600 mg kg^?1 of soil and the corresponding equilibrium concentrations were 0.1–13 mg 1^?1. In each soil, Zn adsorption conformed to the Freundlich isotherm. Despite a relatively low initial Zn adsorption by the acidic soils, each of the soils proved to have a high potential to adsorb Zn, but the capacity was highly pH dependent. In addition to the conventional Freundlich adsorption isotherms, calculated separately for each soil, extended Freundlich-type isotherms that also incorporate soil pH and other soil characteristics were used to describe Zn adsorption of several soils simultaneously in one equation. The pH-dependent Freundlich adsorption isotherm proved to serve as a practical tool to assess Zn adsorption by soils varying in pH and other characteristics.     

Manganese retention by selected calcareous soils as related to soil properties

Abstract

Calcareous soils often need supplemental manganese (Mn) to support optimum plant growth, but some reports show that the apparent recovery of applied Mn is very low in such soils, i.e., nearly all of the applied Mn is retained in the soil. This experiment was conducted to find the relationship between the retained Mn and selected properties of calcareous soils. Eleven surface (0–20 cm) soil samples with pH ranging from 7.7 to 8.1 and calcium carbonate equivalent (CCE) ranging from 20 to 50% were used in the Mn adsorption study. Two‐gram subsamples of each soil were equilibrated with 20 mL of 0.01M CaCl₂ solutions initially containing 10 to 200 mg Mn L^‐1. The Mn that disappeared from solution (after 6 h shaking at 25°C) was considered as adsorbed (retained) Mn. The adsorption data showed a highly significant fit to Freundlich and also to the two‐surface Langmuir adsorption isotherms. The coefficients of both isotherms showed significant positive correlations with cation exchange capacity (CEC), organic matter (OM), and CCE of the soils indicating that OM and calcium carbonate are the sites of Mn retention in calcareous soils. Comparison of the adsorption data of this experiment with those of plant Mn uptake of the same soils (published earlier) shows that as the Langmuir second surface adsorption maxima (maximum retention capacity) of the soils increase the plant Mn concentration and uptake decrease.     

Zinc adsorption characteristics of selected calcareous soils of Iran and their relationship with soil properties

Abstract

The apparent recovery of applied zinc (Zn) by plants is very low in calcareous soils of Iran because most of it is retained by the soil solids. Subsamples of 24 surface soil (clay 130–530 g kg^‐1; pH 7.7–8.4; electrical conductivity 0.63–3.10 dS m^‐1; organic matter 6.0–22.0 g kg^‐1; cation exchange capacity 8–20 cmol kg^‐1; calcium carbonate (CaCO₃) equivalent 180–460 g kg^‐1) representing 13 soil series in three taxonomic orders were equilibrated with zinc sulphate (ZnSO₄) solutions and the amount of Zn disappeared from solution after a 24‐h shaking period was taken as that adsorbed (retained) by the soil solids. The adsorption data were fitted to Freundlich (X=AC^B) and Langmuir [X=(K‐bC)/(1+K#lbC)] adsorption isotherms. Backward stepwiseprocedure was used to obtain regression equations with isotherms coefficients as dependent and soil properties as independent variables. Freundlich A and Langmuir K were found to be highly significantly related to pH and clay and increasing as these soil properties increased. But Langmuir b was related only to clay and Freundlich B showed no significant relationship with any of the properties studied. The distribution coefficient (also called maximum buffering capacity), calculated as the product of Langmuir K and b, was also found to be highly significantly related to pH and clay. It is concluded that pH and clay content of calcareous soils are the most influential soil properties in retention of Zn.     

Zinc desorption kinetics from some calcareous soils of orange (Citrus sinensis L.) orchards,southern Iran

Zinc (Zn) desorption is an important process to determine Zn bioavailability in calcareous soils. An experiment was performed to assess the pattern of Zn release from 10 calcareous soils of orange orchards, southern Iran and the soil properties influencing it. For Zn desorption studies, soil samples were extracted with diethylene triamine penta-acetic acid solution at pH 7.3 for periods of 0.083–48 h. Suitability of seven kinetic models was also investigated to describe Zn release from soils. Generally, Zn desorption pattern was characterized by a rapid initial desorption up to 2 h of equilibration, followed by a slower release rate. The simple Elovich and two-constant rate kinetic models described Zn release the best, so it seems that Zn desorption is probably controlled by diffusion phenomena. The values of the rate constants for the superior models were significantly correlated with some soil properties such as soil organic matter (SOM) content, cation exchange capacity (CEC), and soil pH, whereas carbonate calcium equivalent and clay content had no significant influence on Zn desorption from soils. SOM had a positive effect on the magnitude of Zn release from soils, while soil pH showed a negative effect on Zn desorption. Furthermore, the initial release rate of soil Zn is probably controlled by CEC in the studied soils. Finally, it could be concluded that SOM, CEC, and soil pH are the most important factors controlling Zn desorption from calcareous soils of orange orchards, southern Iran.

Abbreviations: Soil organic matter (SOM); Cation exchange capacity (CEC); Calcium carbonate equivalent (CCE); Zinc (Zn).     

Effect of pH on Zinc Sorption–Desorption by Soils

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.     

Zinc ion adsorption on montmorillonite–Al hydroxide polymer systems

Clay–Al hydroxide polymers (CAlHO) can bind heavy metals effectively and may play an important role in the adsorption behaviour and metal binding capacity of soils. We studied the dependence of Al loading and pH on the adsorption of Zn on Na-saturated montmorillonite–Al hydroxide polymer systems. The available binding sites on Al hydroxide polymers (AlHO) had a very strong affinity for Zn ions. Zinc binding on the clay surface became important when the binding sites on the AlHO were nearly all occupied. The pH had a very strong effect on the Zn binding. At pH 6.6 much more Zn could be adsorbed to the AlHO than at pH 5.0. The effect of the Al:clay ratio on Zn binding was influenced by pH. At pH 6.6, Zn binding to the AlHO, expressed per mole AlHO, was independent of the Al:clay ratio, whereas at pH 5.0 this relation was dependent. This is related to the constant charge of the AlHO at pH 6.6, whereas at pH 5.0 the charge decreases with increasing Al:clay ratio. If clay–Al hydroxide polymers are present in the soil their Zn binding to the AlHO will strongly influence the availability of the Zn.     

Zinc Uptake by Spinach (Spinacia oleracea L.) as Affected by Zn Application Rate,Zeolite, and Vermicompost

Zinc deficiency in calcareous soils is a serious problem, which may be ameliorated by the application of some soil amendments. A completely randomized factorial experiment was done to investigate the effect of zeolite, vermicompost, zeolite + vermicompost, and Zn application to a calcareous soil on Zn availability, dry weight of spinach (Spinacia oleracea L.), and Zn concen-tration in spinach. Results indicated that zeolite had no effect on soil Zn availability, dry weight, and Zn concentration in spinach. Vermicompost significantly increased dry weight (1.33 g pot^?1) and decreased Zn concentration in spinach (16 mg kg^?1). Application of zeolite + vermicompost significantly increased dry weight (by 2.8 times) and Zn uptake in spinach and it also decreased Zn concentration in spinach less than vermicompost. Zinc application increased Zn concentration in spinach (up to 496 mg kg^?1), but did not affect dry weight except in soils treated with zeolite + vermicompost. Generally, application of zeolite + vermicompost is recommended instead of separate zeolite or vermicompost application for improvement of soil Zn fertility and Zn uptake by spinach.     

Influence of applied zinc and organic matter on zinc desorption kinetics in calcareous soils

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 (β_s) 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.     

Zinc Sorption in Sandy Soils from Central Vietnam as a Function of Soil Characteristics

Zinc (Zn) sorption curves were established for 11 cultivated sandy soils from central Vietnam. Soil samples (10 g) were equilibrated with 5 mM calcium chloride (CaCl₂) solutions (50 mL) at five zinc chloride (ZnCl₂) concentrations (0 to 80 mg Zn L^–1). The experimental sorption data were fitted with the Freundlich equation. The amounts of Zn sorbed by soil (Q_Zn) at different Zn concentrations in the equilibrium solution (C_Zn) were closely related to cation exchange capacity (CEC) and pH, that is, to the available exchange sites at given pH values. More specifically, an excellent correlation was found between Zn sorption and exchangeable calcium (Ca_ex), which evidently also depends on CEC and pH. A unique equation was proposed to predict Q_Zn from C_Zn and Ca_ex in the range of Zn loading covered in our research, that is, from traces to Q_Zn ≈ 60 mg Zn kg^–1.     

Effect of Calcium on the Soil Adsorption of Cadmium and Zinc in Some Spanish Sandy Soils

Castellón Plain is a natural area with an extension of 464 km², situated in Castellón (eastern coast of Spain), with an important number of ceramic industries which generate waste waters containing cadmium and zinc. In this paper, equilibrium adsorption isotherms have been obtained to examine the behaviour of cadmium and zinc in three selected soils of Castellón Plain (Spain) by means of batch experiments. Both metals exhibit non-linear adsorption isotherms with adsorption maximum beyond the dissolved concentration range considered in this study. Statistical analysis showed that data fit slighty better to Freundlich linearization than that of Langmuir. Adsorption coefficients obtained from Freundlich approximation were calculated to evaluate the relative cadmium and zinc distribution between solution and studied soils obtaining coefficients ranging from 5200 to 5900 μg kg^-1μg l^{-1 -n} for cadmium and from 3500 to 43200 μg kg^-1μg l^{-1 -n} for zinc. The effects of salt concentration and calcium competition for adsorption sites were investigated providing different concentrations of CaCl₂ in background solutions. Adsorption capacities of cadmium and zinc in the studied soils decreased when the salt concentration increased. A tenfold increase in calcium concentration reduced the cadmium adsorption capacity approximately by one third whereas the Ca²⁺ ion does not seem a significant competitor with Zn²⁺ for adsorption sites in soils with high organic matter content, where precipitation of zinc can be expected.     

Zinc Fertilization Impact on Irrigated Cotton Grown in an Aridisol: Growth,Productivity, Fiber Quality,and Oil Quality

Zinc (Zn) deficiency is widespread in calcareous soils. Therefore, we conducted a 2-year field experiment to investigate the impact of graded Zn levels on growth, yield, and fiber and oil quality of cotton (Gossypium hirsutum L., cv. CIM-473) grown in a calcareous Aridisol having 0.54 mg diethylenetriaminepentaacetic acid (DTPA)-extractable Zn kg^?1 soil. Zinc use increased boll bearing, boll weight, seed index, and seed cotton yield (P ≤ 0.05). Maximum yield increase was 15%, with 7.5 kg Zn ha^?1; however, greater Zn levels depressed yield. Leaf chlorophyll, membrane permeability, seed protein, and oil content and quality improved (P ≤ 0.05), and fiber quality remained unaffected with Zn use. Critical Zn concentration in cotton leaves was 36 mg kg^?1. Positive relationships of leaf Zn concentration were observed with boll weight, protein content, total unsaturated fatty acids, and fiber characteristics. Thus, Zn fertilization of low-Zn Aridisols is suggested for improving cotton productivity and seed quality.     

Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

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.     

Comparison of Prewashing Procedures for the Assessment of Phosphate Rock Dissolution in Soils

When evaluating phosphate rock (PR) dissolution, previous to the extraction with sodium hydroxide (NaOH), dry soil samples with PR were extracted with three solutions to remove exchangeable and solution calcium (Ca) [sodium chloride (NaCl) 1 M, buffered NaCl with ethylenediaminetetraacetic acid (EDTA) (NaCl–EDTA), and NaCl buffered at pH 7 with triethanolamine (TEA) (NaCl–TEA)] for comparison with the extraction of soil samples without any prewash. In acidic soils, up to 51% of applied P was recovered during the NaCl extraction because of the high exchangeable acidity released during the extraction. In soils with exchangeable Ca>2 cmol₍₊₎kg^?1, high EDTA quantities also promoted PR dissolution. The NaCl–TEA solution efficiently removed Ca, avoiding PR dissolution and P retention by calcium hydroxide [Ca(OH)₂] during the NaOH extraction. Thus, when evaluating PR dissolution we recommend the use of NaCl–TEA to remove Ca. We also recommend the same procedure when applying the Chang and Jackson fractionation to calcareous soils and soils submitted to PR application.     

Calcium‐ and iron‐related phosphorus in calcareous and calcareous marsh soils: Sequential chemical fractionation and 31p nuclear magnetic resonance study

Abstract

Phosphorus (P) forms in soils determine the amount of P available for crops and the potential for this element to be released to water. Sequential chemical fractionation can provide some information about major P forms in soils, and allow one to distinguish iron (Fe)‐related phosphorus from calcium (Ca)‐bound P. The ³¹P nuclear magnetic resonance (NMR) spectroscopy has been used in the identification of organic P, precipitated Ca‐phosphates, and aluminum (Al)‐related P in acid soils. Three calcareous soils and four calcareous marsh soils were used in this study. These two types of soils differ in the nature of iron oxides, which are the main P sorbent surfaces. The ratio of low crystalline to high crystalline iron oxides is higher in marsh soils than in calcareous soils as a consequence of the special genesis and conditions of the soil (reduction‐oxidation cycles). Such a ratio is related to the proportion of occluded P in low crystalline oxides relative to that of high crystalline oxides. Citrate‐bicarbonate extractable P (CB‐P) in the fractionation schemes can be ascribed to adsorbed P and high soluble calcium phosphates. CB‐P is correlated with the sum of P fractions in all the soils, thus indicating that the amount of the P that can be easily released is related to the rate of P enrichment of the soil. The ³¹P NMR spectral data reveal that hydroxyapatite is the dominant P form in the soils studied. This is consistent with the fractionation data, where acid‐extractable P is the main P fraction. The spectra also provide some information about the amount of total inorganic P and Ca‐phosphates in calcareous soils.     

Reactions of zinc with iron-oxide coated calcite surfaces at alkaline pH

Both iron oxides and carbonate minerals, such as calcite, can sorb zinc (Zn), and therefore are important in controlling the solution concentration and availability of Zn to plants growing in calcareous soil. When present together, interactions between these components affect their sorption behaviour. We investigated changes in the reactions of Zn with calcite at alkaline pH, as the calcite surface was progressively coated by iron oxide. Coated calcite surfaces were prepared that had from 0.05 to 1.45% iron oxide. The initial concentration of Zn and the amount of iron oxide on the calcite were the most critical factors affecting adsorption, precipitation of solid phases, and the desorbability of sorbed Zn. For pure calcite at small initial Zn concentrations (< 2.5 × 10^?5 m ) adsorption was dominant; with increasing concentration, precipitation of hydrozincite (ZHC) became more important. With increasing amounts of iron oxide the amount of Zn adsorbed increased, the desorbability of the Zn decreased, and precipitation became progressively less evident, and at 1.45% iron oxide content there was no evidence of any precipitation of ZHC. The calculated maximum adsorption attributable to the iron oxide coating was inversely proportional to the thickness of the oxides on the calcite, and greatly exceeded that of iron oxide as a separate phase. The common occurrence of iron‐coated carbonates in calcareous soils and their capacity to adsorb Zn contributes to the problems of Zn deficiency, for which these soils are noted.     

Effect of organic matter on the parameters of the selective sorption of cobalt and zinc by soils and their clay fractions

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.     

Zinc sorption by acid tropical soils as affected by cultivation

The sorption of zinc (Zn) by two acid tropical soils, Mazowe clay loam (kaolinitic, coarse, Rhodic Kandiustalf) and Bulawayo clay loam (coarse, kaolinitic, Lithic Rodustalf), was studied over a wide range of Zn solution concentrations. Samples of the two soils used in the experiments were collected at both uncleared, uncultivated (virgin) sites and cultivated sites. The two virgin soils showed similar abilities to bind Zn. Mazowe soil (40 g organic matter kg^?1) presented the highest affinity for Zn. Yet, Bulawayo soil (23.5 g organic matter kg^?1) sorbed almost the same amount. Bulawayo soil had higher pH and Fe and Mn-oxide content than Mazowe soil. Once cultivated, the two soils behaved quite differently. After 50 years, Mazowe soil had lost 60% of its organic matter and effective cation exchange capacity (ECEC). In this soil, Zn sorption capacity had also been decreased by 60%. Clearing and 10 years under cultivation had affected neither the organic matter content nor the ECEC of Bulawayo soil. For this soil, Zn sorption was even higher in the cultivated soil, presumably due to an increase in the amount of Fe and Mn oxide from subsoiling. Zinc sorption was dependent upon pH, with retention dramatically increasing in the pH range 6–7. Sorption occurred at pH values below the point of zero charge (PZC), indicating that the sorption reaction can proceed even in the presence of electrostatic repulsion between the positively charged soil surface and the cation. In the two soils, the reversibility of the sorption reaction was very low. More than 90% of the sorbed Zn was apparently strongly bonded.     

Immobilization of Zinc Fertilizer in Flooded Soils Monitored by Adapted DTPA Soil Test

Zinc (Zn) deficiency is a persistent problem in flooded rice (Oryza sativa L.). Severe Zn deficiency causes loss of grain yield, and rice grains with low Zn content contribute to human nutritional Zn deficiencies. The objectives of this study were to evaluate the diethylenetriaminepentaacetic acid (DTPA) extraction method for use with reduced soils and to assess differences in plant availability of native and fertilizer Zn from oxidized and reduced soils. The DTPA‐extractable Zn decreased by 60% through time after flooding when the extraction was done on field‐moist soil but remained at original levels when air‐dried prior to extraction. In a pot experiment with one calcareous and one noncalcareous soil, moist‐soil DTPA‐extractable Zn and plant Zn uptake both decreased after flooding compared with the oxidized soil treatment for both soils. In the flooded treatment of the calcareous soil, both plant and soil Zn concentrations were equal to or less than critical deficiency levels even after fertilization with 50 kg Zn ha^?1. We concluded that Zn availability measurements for rice at low redox potentials should be made on reduced soil rather than air‐dry soil and that applied Zn fertilizer may become unavailable to plants after flooding.     

石灰性土壤与磷酸盐的反应及吸持态磷的同位素交换性

本文研究了种石灰性土壤（Ｌｏｕ土）与磷酸盐的反应动态过程，短期反应的等温吸附研究表明，在低磷浓度下，以吸附反应机制为主，吸持态磷的同位素交换性随着吸持量的增加而增加；在高磷浓度下，以形成磷酸盐的沉淀反应机制为主，吸持态磷的同位素交换性随着反应时间的延长和吸持量磷数量的增加而了降低。认为在低施磷水平下，土壤中铁，铝氧化物对磷的吸持起重要作用。本文还探讨了在长期（２６０天）恒温恒湿培养过程中，土壤可溶