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).     

Manganese‐Release Characteristics of Highly Calcareous Soils

Manganese (Mn) deficiency is common in calcareous soils of southern Iran. The ability of these soils to replenish the soil solution Mn depends highly on their Mn‐release characteristics. Kinetics of native Mn release by ammonium bicarbonate diethylenetriaminepentaacetic acid (AB‐DTPA) from 10 highly calcareous soils were studied for the periods of 1 to 1440 min. Results showed that Mn‐release rates were initially fast, followed by a much slower rate. Among seven kinetic models tested, two constant‐rate, simple Elovich, and parabolic diffusion models best predicted the pattern of time‐dependent Mn release well, much better than zero‐, first‐, second‐, and third‐order models. Significant correlations were observed between constant values of parabolic diffusion with those of simple Elovich model (Kp and Q₀ with β _s and α _s, respectively), which demonstrated that Mn release from calcareous soils of southern Iran is probably a diffusion‐controlled process. Results of stepwise regression analysis between constant values of the best‐fitted models and selected soil properties showed that the content of easily reducible Mn oxides (ERMn) was the only soil property capable of predicting some constant values of the best‐fitted models. According to the equations, Mn‐release rates increased as the amount of ERMn increased. It is therefore concluded that ERMn is probably the main source of Mn release in these calcareous soils. Further research to assess the relationships of constant values of the best‐fitted models with plant growth parameters in calcareous soils is warranted.     

Copper Release Behavior in Two Calcareous Soils Amended with Three Organic Materials

Understanding time-dependent copper (Cu) desorption behavior is critical for improving the prediction of Cu availability in soils. This study was conducted to evaluate the influence of municipal waste compost, sheep manure, and wheat straw on desorption characteristics of Cu and to evaluate the suitability of different kinetic models to describe the Cu release pattern in two calcareous soils. Diethylenetriaminepentaacetic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA) were employed to extract Cu from soils. Best-fitted kinetic models including Elovich, simple Elovich, two-constant rate, and parabolic diffusion were selected based on their low standard error and high coefficient of determination. Extractable copper significantly decreased with increasing rates of sheep manure and wheat straw but increased with increasing rates of municipal waste compost amendment. Results revealed that copper was more readily desorbed from clay soil compared to silt loam soil. The copper desorption patterns were almost similar for both extractants; however, EDTA extracted more Cu from soils.     

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.     

Extractability of previously‐applied zinc as influenced by properties of calcareous soils

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.     

Zinc Desorption of Calcareous Soils as Influenced by Applied Zinc and Phosphorus and Described by Eight Kinetic Models

The activity of zinc (Zn) ions in the soil solution bathing plant roots is controlled by the simultaneous equilibrium of several competing reactions, such as surface exchange, specific bonding, lattice penetration, precipitation reactions, and the processes leading to the desorption of surface and lattice-bound ions. Desorption of Zn in 15 calcareous soils from southern Iran, treated with 10 mg Zn kg^?1 soil as zinc sulfate (ZnSO₄·7H₂O) and 100 mg phosphorus (P) kg^?1 soil as calcium phosphate [Ca(H₂PO₄)₂H₂O] and then equilibrated and extracted with diethylentriaminepentaacetic acid (DTPA), was studied in this experiment. The results were fitted to zero-order, first-order, second-order, third-order, parabolic diffusion, two-constant rate, Elovich, and simple Elovich kinetic models. Two-constant rate, simple Elovich, and parabolic diffusion models were determined to best describe Zn-desorption kinetics. Zinc desorption increased as Zn was applied but decreased with applied P.     

A Modified DMT-HFO Technique for Investigating the Kinetics of Phosphorus Desorption from Calcareous Soils and its Relationship with Maize Growth

In this research, phosphorus (P) desorption was investigated using DMT-HFO as an “infinite” sink for 10 calcareous soils over a period of 1–35 days and the kinetic data was related to soil properties and P uptake by maize (Zea mays L.). First- and second-order, and simple Elovich equations adequately described P desorption kinetics, however parabolic, exponential and zero order equations provided the best fits to the data. A systematic relationship exists between the second order rate parameter (k₂) and the clay content of the soils. There are positive relationships between P desorption rate constants (for zero order, Elovich and parabolic equations), and both dry matter and P content of maize shoots and also for roots. These relationships indicate that P desorption rate may be a limiting factor for maize growth in these soils. The DMT-HFO technique may be used to assess the long-term availability of P to plants.     

Comparison of Four Equations to Describe the Kinetics of Lead Desorption from Soils

The rate of Pb desorption was investigated from clay (Silty clay, Torrifluvent), CaCO₃-rich (Sandy clay, Calciorthid), and sandy (Sandy loam, Quartzipsamment) soils at two different temperatures. Lead has not been released from CaCO₃-rich soils which suggests irreversible Pb sorption by the soil. The desorption was quite hysteretic from sand and clay soils. The total amount of Pb released from the clay soil exceeded that released from the sandy soil. The lower Pb desorption associated with the sandy soil is probably due to its higher calcium carbonate content relative to the clay soil. The kinetics of Pb desorption were evaluated using the Elovich, modified Freundlich, parabolic diffusion, and first order equations. The first order and parabolic diffusion equations adequately described the kinetics of Pb desorption from clay and sandy soils under isothermal conditions. The choice of first order and parabolic equations among others investigated was based on the goodness of fit and the more scientific theoretical assumptions of the equations. The apparent Pb diffusion rate coefficient (D_d) and desorption rate coefficient (k_d) values from the clay and sandy soils increased with increasing temperature.     

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.     

Effects of soil properties on the kinetics of desorption of phosphate from Alfisols by anion‐exchange resins

Phosphorus‐desorption rates by anion‐exchange resins were best described by three empirical kinetic models: Elovich equation, the parabolic diffusion equation, and the fractional power equation in that order. The objective of this study was to determine the relationship between kinetic rate constants from Elovich, fractional power, and parabolic rate equations and soil physical and chemical properties from soils of different lithogenic origins from the Nigerian savanna. Phosphorus‐desorption patterns included an initial fast reaction, followed by a slow release that continued up to 20 h. Particle diffusion was observed to be the rate‐limiting step in the kinetic desorption of native P in the soils studied as opposed to ligand exchange or surface reaction. The influence of parent material is not prominent due to long history of pedogenesis over the soils. The rate coefficients from the Elovich equation, parabolic diffusion equation, and the fractional power model were best predicted from clay, pH, and extractable Al and Fe oxides and therefore exert a profound influence on the rate of P release from the soils. These soil properties together explained between 93% and 99% of the variance in the rate coefficients of P desorption from the soils.     

Time‐dependent zinc desorption in soils

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.     

Evaluation of copper desorption characteristics using DTPA and citric acid for wheat (Triticum aestivum L.) rhizosphere of soils amended with sewage sludge

A greenhouse experiment was carried out to determine copper (Cu) desorption characteristics in ten bulk and rhizosphere soils (Typic Calcixerepts) amended with sewage sludge (1% w/w) using rhizoboxes. The kinetics of Cu desorption in the bulk and the rhizosphere soils were determined after successive extraction with DTPA‐TEA and 10 mM citric acid in a period of 1 to 504 h at (25 ± 1)°C. The results show that Cu extracted after 504 h using DTPA‐TEA were significantly (P < 1%) lower in the rhizosphere than the bulk soils. However, Cu extracted after 504 h using citric was significantly (P < 1%) higher in the rhizosphere than in the bulk soils. The results illustrated that, on average, citric acid extracted 56% more Cu from the bulk soils than DTPA‐TEA, and citric acid extracted 85% more Cu from the rhizosphere soils than DTPA‐TEA. Desorption kinetics of Cu in the two extractants was well described by power‐function, parabolic diffusion, and first‐order equations. The results show that a 10 mM citric acid extractant may be recommended to determine the kinetics of Cu desorption in calcareous soils amended with sewage sludge.     

Comparative study of metal micronutrients release from two calcareous soils

Adsorption and release are the most influential reactions controlling zinc (Zn), manganese (Mn) and copper (Cu) availability in soils. Characteristics of native Zn, Mn and Cu release by ethylenediaminetetraacetic acid (EDTA) in two calcareous soils for periods from 1 min to 24 h were studied. The pattern of Zn, Mn and Cu release from both soils fitted well with power function, Elovich and parabolic diffusion models. The magnitude and rate of release was greatest for Mn, followed by Zn and Cu, respectively. This trend suggests a higher ability of the studied soils to replenish soil solution Mn, compared with Zn and Cu. The results showed that higher Mn release in clay soil compared with sandy loam soil was considerably related to higher initial Mn release rates in the former compared with the latter. However, Cu release rates of the two soils at initial times were not significantly different. Higher Cu release in clay soil was, therefore, attributed tohigher Cu release rates at subsequent time intervals. It is assumed that the different Zn release rates of these soils were due to consistent differences in Zn release rates throughout the release periods.     

Growth and manganese uptake by soybean in highly calcareous soils as affected by native and applied manganese and predicted by nine different extractants

Abstract

Manganese (Mn) becomes a limiting factor of plant growth under some soil conditions. High pH and abundance of free calcium carbonate in calcareous soils are conducive to Mn‐deficient plants. The Mn status of highly calcareous soils in Iran has not been studied in detail. This experiment was conducted to obtain such information. Twenty‐three surface (0–20 cm) soil samples with pHs from 7.7 to 8.2 and calcium carbonate equivalent (CCE) from 19 to 46% were used in a 7‐week greenhouse study with soybean [Glycine max (L.) Merr.]. The experiment was a 23 × 3 factorial with three replicates, i.e., 23 soils and 3 Mn levels (0, 15, and 30 mg/kg soil as manganese sulfate). Extractable Mn of the untreated soils were determined before planting by nine different procedures. Dry matter yield, Mn concentration of soybean tops, and Mn uptake were used as the measure of plant response. Multiple regression equations showed that the most influencial soil properties in extractability of Mn in highly calcareous soils are cation exchange capacity (CEC) and calcium carbonate equivalent (CCE). Application of Mn increased dry matter, Mn concentration and Mn uptake of soybean plants in most soils. The Mn concentration of plants on some of the soils, however, decreased following the application of Mn. This was attributed to dilution effect caused by enhanced growth. The recovery of applied Mn in all soils was low, persumably due to conversion of the applied Mn to unavailable forms. Regression equations were developed to predict dry matter, Mn concentration, and Mn uptake by plants from soil Mn extracted by water, hydrochloric acid, disodium‐EDTA, and EDTA‐ammonium acetate.     

Pollution and Desorption Kinetics of Heavy Metals at Agricultural Soils in Southeastern Iran

Desorption of heavy metals is an important factor in determining heavy-metal availability in soils. The objective of this research was to determine the applicability of kinetic equations to describe the kinetics of copper (Cu) and cadmium (Cd) desorption at two agricultural soils of Kerman Province in Iran. For Cd and Cu desorption studies, 5 g of the air-dried <2-mm soil fraction was extracted with 25 ml of 0.01 M ethylenediamenetetraacetic acid (EDTA) at pH 7.0 with a shaker for periods of 5 to 2880 min. The desorption patterns of Cu and Cd were generally characterized by an initial fast reaction, followed by a slower continuing reaction. Desorption of Cu and Cd from the two soils was equally well described by the two-constant rate and simple Elovich equations. The results of this study can be used to make better prediction about the mobility and bioavailability of the Cu and Cd in soil.     

黄土性土壤在连续液流条件下吸附、解吸磷酸根的动力学研究

采用连续液流法研究了黄土性土壤吸附,解吸磷酸根的动力学性质。结果表明：（１）供试土壤对磷酸根的吸附,解吸扫速率可分为快,中,慢三种反应类型;（２）描述吸附,解吸反应的最优模型均为Ｅｌｏｖｉｃｈ方程,最差模型分别为一级反应方程及双常数方程,拟合差的模型对反应速率变化“敏感”,可用于反应类型划分和机理研究;（３）粘粒含量及代换量对吸附速率有著影响,游离铁对吸附速率,ＣａＣＯ３对较低温度下的吸附及较高温     

Impact of Organic-Matter Application on Phosphorus-Desorption Kinetics in Two Agricultural Soils in Southeastern Iran

Phosphorus (P) desorption from soil is one process that governs P uptake by roots and its subsequent utilization in plant growth. The objective of this research was to study the kinetics of P desorption in agricultural soils of Kerman in the unamended and amended soils. For this purpose, 4% of organic manure was added to each soil. The soils were incubated for 90 days. Afterward, the desorption of P was studied by the successive extraction with 0.5 M sodium bicarbonate (NaHCO₃). The results of this research indicated that the P-desorption rate was initially rapid and then became slower until equilibrium was approached. The addition of the organic matter increased P desorption in the soils studied. The kinetic data were best described by power function and simple Elovich equations. The parabolic diffusion equation was also well fitted to the time-dependent P-desorption data.     

土壤钾解吸的动力学方程和大麦反应的关系

本文应用Ｅｌｏｖｉｃｈ、抛物线扩散、权函数和指数方程研究电超滤恒电场下１２种土壤钾解吸的动力学。Ｅｌｏｖｉｃｈ、抛物线扩散和权函数方程具有高的相关系数和小的标准差，可以很好地描述土壤钾解吸的动力学，而指数方程的相关系数低和标准差大而不适宜应用。本文成功地建立了动力学方程与大麦多点田间试验钾肥反应和土壤钾素状况之间的相关关系，Ｅｌｏｖｉｃｈ、抛物线扩散和权函数方程的常数（斜率或截距）与土壤速效钾、大     

钾解吸动力学方程及方程常数的应用

Elovich,parabolic diffusion,power function and exponential equations were used to describe K desorption kinetics of 12 soils in a constant electric field of electro-ultrafiltration(EUF),Results showed that the Elovich,parabolic diffusion and power function equations could describe K desorption kinetics well owing to their high correlation coefficients and low standard errors;but the exponential equation was not suitable to be used in this study due to its relatively low correlation coefficients and relatively high standard errors.This work established successfully the relationships between the constants(slope or intercept)of kinetic equations and the barley responses to K fertilizer in the multiple-site field experiments and K-supplying status of soilsk,the constants of Elovich,parabolic diffusion and power function equations were very significantly or significantly correlated to the soil available K,relative yield of barley and K uptake of barley in NP plot.It was suggested that the kinetic equation constants could be used to estimate K-supplying power of soils.     

Mathematical models to study the kinetics of potassium release from swell-shrink soils of Central India in relation to their mineralogy

Employing four mathematical models (first-order, parabolic-diffusion, Elovich and zero-order), kinetics of potassium desorption from eight soils with and without cropping were studied to evaluate their ability in explaining K release from soils. The decline in the soil test K in cropped soils over original soils was drastic in easily desorbable forms compared to that of strongly held forms like 3 M H₂SO₄ K. Results showed that parabolic diffusion as well as first-order kinetic equation explained the K release data well for both original and K depleted (cropped) soils. Elovich and zero-order equations were not suitable to describe the kinetic data. However, zero-order equation explained K release data better in case of K-depleted soils as compared to original soils. Soils with higher initial K contents registered higher release rate constants. Over the entire period of cropping the range of release rate (b) decreased from 1.26 to 1.53 × 10^?2 to values ranging from 1.12 to 1.30 × 10^?2 h^?1. In contrast, the first-order equation, parabolic diffusion showed higher b values for cropped soils as they represent the diffusion gradient. Mica and its biotite content in both silt and clay fractions showed significant correlation (r) with b values. Similarly with the rate of K release, clay content of soils maintained significant r whereas the silt content did not.