Selenium adsorption in soils as influenced by different anions

Studies on selenium adsorption were conducted on seleniferous and non‐seleniferous soils of north‐west India. Soils were equilibrated with graded levels of Se ranging from 1 to 100 μg ml^—1 tagged with ⁷⁵Se in the presence of sulphate, nitrate and phosphate ions, generally being applied to soils as inorganic fertilizers. The adsorption of Se on different soils, both in the presence and absence of competing anions, increased with increase in the level of Se added. Adsorption of Se conformed to Langmuir equation. In the absence of any competing anions, adsorption maxima of Se for different soils ranged from 270 to 461 μg g^—1. The corresponding values decreased appreciably in the presence of competing anions; per cent decrease ranged from 3 to 21 at 10 μg SO₄‐S ml^—1, from 8 to 40 at 60 μg NO₃‐N ml^—1 and 32 to 56 at 15 μg H₂PO₄‐P ml^—1. The bonding energy of Se in different soils decreased by 33 to 66 per cent in the presence of only phosphate ions. The changes in bonding energy were inconsistent in the case of nitrate and sulphate ions. At equal concentration of added P and Se, the amount of P adsorbed was 2 to 3 times the amount of Se adsorbed. With increasing concentration of Se, greater amounts of S were released in the equilibrium solution. The distribution coefficients (K_d) decreased significantly in the presence of different anions; the effect was conspicuous in the case of phosphate ions.     

Adsorption-desorption of atrazine on four soils of Hyderabad

The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC^1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl₂. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g^?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.     

Adsorption und Desorption von Methabenzthiazuron in verschiedenen Böden

Adsorption and desorption of methabenzthiazuron in various soils A method investigating adsorption and desorption of pesticides using radioactive tracers and a computer programme is described. The adsorption and desorption of the herbicidal substance methabenzthiazuron in 7 soil samples is investigated. The adsorption of methabenzthiazuron decreases from the A_p- to the C-horizons. A good correlation exists between the adsorbed amount of the herbicidal substance and the C- and N-content of the soils. The relatively highest desorption was found with nearly humusfree soils. The amount of adsorbed herbicide residues, not desorbable by water in 5 desorption cycles, is much higher in the humic soils than in the nearly humusfree soils. From the relationship found between adsorption and corresponding herbicide concentrations proper adsorption values can be predicted for any herbicide concentration within the investigated concentration range by using one single adsorption measurement as a basis of calculation.     

Adsorption of sulphate and fluoride by variable charge soils

The adsorption of sulphate and fluoride by three variable charge soils was studied. Adsorption increased with increase in the amount of sulphate added at constant _pH, and decreased with increase of _pH.
The ratios of the amount of released OH⁻to that of the adsorbed SO^2-₄ at pH 5–0 were 0.12, 0.14 and 0.20 for the three soils, respectively, much lower than the corresponding OH⁻/F⁻ ratios which ranged from 0.3 to 1.0. For a ferric acrisol the OH⁻ released accounted, on average, for only 15% of the SO^2-₄ adsorbed, leaving more than 60% to be explained by the decrease in positive charge and the increase in negative charge carried by the soil.     

Adsorption and desorption of Cd on humic acid fraction of soils

The adsorption of ionic Cd has been investigated on three humic acids isolated from podzol, rendzina and brown Mediterranean soils of Tuscany. The adsorption isotherms have been determined at 5 and 25°C. Cadmium adsorption was described by the Langmuir adsorption equation. Langmuir parameters were related to the functional groups content of humic acids and decreased in the following order: rendzina>brown Mediterranean soil>podzol. Adsorption was independent on temperature and increased with pH. Desorption experiments with 0.1 N NH₄OAc and 0.25 M Cu (OAc)₂ proved that Cd is adsorbed on humic acid about 50% in an exchangeable form and 50% in coordination complexes.     

磷酸盐吸附对可变电荷土壤正负电荷的影响

本文研究了华南地区不同类型的可变电荷土壤，并对磷酸盐的吸附量和吸附磷后土壤的正、负电荷的变化，以及ｐＨ和游离氧化铁对这种变化的影响进行了研究。结果表明，土壤吸磷量与土壤游离氧化铁含量成良好的正相关。土壤吸磷后正电荷减少，负电荷增加，土壤电荷量与吸磷量之间呈抛物线状相关。吸附１摩尔磷酸盐对土壤净负电荷的贡献在０．３－１．０摩尔之间。土壤中的游离氧化铁使吸附的磷对土壤负电荷的贡献减少。     

Extractability and adsorption of sulphate in soils

Virtually all of the indigenous sulphate (SO₄) in a range of UK soils with moderately high pH values (> 6) was found to be present in the soil solution and, as a consequence, was highly susceptible to leaching. For acid soils containing adsorbed SO₄, the extractability of SO₄ in NaCl and CaCl₂ solutions was dependent on both the ionic strength and cation species. Addition of small amounts (<～ 10^?2M) of either NaCl or CaCl₂ actually decreased the amount of SO₄ extracted, but SO₄ extractability increased sharply with concentrations of NaCl or CaCl₂ higher than about 0.1 M. At a similar ionic strength, more SO₄ was extracted by NaCl than CaCl₂. Sequential extraction with 1 M NaCl removed essentially all of the absorbed SO₄. The release characteristics of SO₄ were very different to those of phosphate and this difference in behaviour is not easily reconciled with the view that SO₄ is chemisorbed, as is phosphate. Except for a few acid soils with high oxide contents, the capacity of the soils to adsorb added SO₄ was quite small. None of the soils with pH values higher than 6 adsorbed a significant amount SO₄. The results raise questions regarding the efficiency of SO₄-containing fertilizers in correcting and preventing S deficiency in situations where leaching is important.     

Ionic-strength and pH effects on the sorption of cadmium and the surface charge of soils

Two Oxisols (Mena and Malanda), a Xeralf and a Xerert from Australia and an Andept (Patua) and a Fragiaqualf (Tokomaru) from New Zealand were used to examine the effect of pH and ionic strength on the surface charge of soil and sorption of cadmium. Adsorption of Cd was measured using water, 0.01 mol dmp^?3 Ca(NO₃)₂, and various concentrations of NaNO₃ (0.01–1.5 mol dm^?3) as background solutions at a range of pH values (3–8). In all soils, the net surface charge decreased with an increase in pH. The pH at which the net surface charge was zero (point of net zero charge, PZC) differed between the soils. The PZC was higher for soils dominated by variable-charge components (Oxisols and Andept) than soils dominated by permanent charge (Xeralf, Xerert and Fragiaqualf). For all soils, the adsorption of Cd increased with an increase in pH and most of the variation in adsorption with pH was explained by the variation in negative surface charge. The effect of ionic strength on Cd adsorption varied between the soils and with the pH. In Oxisols, which are dominated by variable-charge components, there was a characteristic pH below which increasing ionic strength of NaNO₃ increased Cd adsorption and above which the reverse occurred. In all the soils in the normal pH range (i.e. pH>PZC), the adsorption of Cd always decreased with an increase in ionic strength irrespective of pH. If increasing ionic strength decreases cation adsorption, then the potential in the plane of adsorption is negative. Also, if increasing ionic strength increases adsorption below the PZC, then the potential in the plane of adsorption must be positive. These observations suggest that, depending upon the pH and PZC, Cd is adsorbed when potential in the plane of adsorption is either positive or negative providing evidence for both specific and non-specific adsorption of Cd. Adsorption of Cd was approximately doubled when Na rather than Ca was used as the index cation.     

Kinetics and adsorption of metolachlor and atrazine and the conversion products (deethylatrazine, deisopropylatrazine, hydroxyatrazine) in the soil profile of a river basin

The adsorption kinetics and adsorption parameters of metolachlor, atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (HA) were investigated in a soil profile in a maize field formed from recent alluvial deposits in a river basin in Greece. We used the batch equilibrium method modified to simulate field conditions as closely as possible for the use and practices related to soil applied pre‐emergence herbicides. Pseudo‐equilibrium times, determined by kinetic studies, were achieved after 16, 16, 24, 24 and 48 hours for metolachlor, DIA, DEA, HA and atrazine, respectively. At pseudo‐equilibrium the percentage of the adsorbed amount increased in the order of DEA (10%) < DIA (14%) < atrazine (27%) < metolachlor (43%) ≪ HA (94%) which indicates that more than 57% of all compounds except for HA are in solution and available for transport to deeper soil layers when conditions similar to those simulated in the laboratory exist in the field. Adsorption isotherms of all compounds and in most of the cases correlated well with the Freundlich model and adsorption coefficients (K_f) decreased with increased soil depth. Principal component and multiple regression analyses confirmed the importance of the soil organic carbon content on the adsorption capacity of soils for all compounds except HA in the plough layers (0–40 cm). In the subsurface soils (40–110 cm) variables such as clay content and pH were more important. For HA, the K_f values determined for the plough and subsurface soil layers were better correlated with clay content and pH. Also in the subsurface soils, the variation in organic carbon content was not correlated with the variation of K_f values. Thus calculated K_oc‐f‐values misrepresent the adsorptive capacity of these soils towards the compounds studied.     

Phosphate sorption in allophanic soils and release of sulphate, silicate and hydroxyl

Phosphate (P) sorption and the concomitant release of sulphate (SO,), silicate (Si) and hydroxyl ion (OH) were determined on three allophanic soils from Spain, at different P concentrations. P effectively replaced SO₄, Si and OH. However, at every stage of P sorption, the molar ratios of the total amounts of anions released (SO₄+ Si + OH) to that of the sorbed P were low. The amount of added P affected the relative proportions of SO₄, Si and OH exchanged. At low concentrations of P, phosphate sorption was accompanied mostly by release of the adsorbed SO₄ with some Si. As more P was sorbed an increasing displacement of OH was also observed.     

Cadmium Sorption and Desorption Characteristics of Tropical Alfisols from Different Land Uses

Cadmium (Cd) sorption and desorption characteristics by Alfisols from different land uses were examined, and the relationships between soil and sorption/desorption characteristics were investigated. Adsorption studies were done using Cd concentrations (0–100 mg Cd kg^?1) in 0.01 M CaCl₂. The Cd sorbed by the soils was then subjected to two desorption runs. The soils' adsorption conformed to Freundlich and Langmuir equations. The amount of Cd sorbed by the soils varied. Two desorption runs detached more than 95% of sorbed Cd, but the first accounted for more than 80% of the total. Desorption of Cd in degraded soils was more than in soils from other land uses. The amount of Cd desorbed correlated with amount applied (r = 0.90??), solution concentration (r = 0.83??), and amount sorbed (r = 0.70??). A positive relationship exists between the adsorption maxima of the soils and soil organic matter (r = 0.13, p = 0.87). The relationship between amount of Cd desorbed and sorbed is quadratic for all the soil.     

Adsorption of Cry1Ab protein isolated from Bt transgenic rice on bentone, kaolin, humic acids, and soils

Adsorption on a soil matrix of the insecticidal protein from Bacillus thuringiensis ( Bt) transgenic plants affects their accumulation and release and, hence, bioavailability in soil. Cry1Ab protein isolated from Bt transgenic rice was used to evaluate the adsorption and desorption on bentone, kaolin, and humic acids (HAs). The adsorption equilibrium of Cry1Ab protein was reached within 1-2 h for bentone and kaolin and within 4-8 h for HAs. The adsorption isotherms were better described by linear expressions ( R (2) >/= 0.973) rather than by the Freundlich model. No saturation was observed, even at the maximum concentration used (3.71 microg mL (-1)). The adsorbed protein was not easily desorbed at the used protein concentrations (0.18-3.71 microg mL (-1)); more than 50-70%, 70-80%, and 90% of the adsorbed protein remained on HAs, kaolin, and bentone, respectively, after washing with water. Adsorption and desorption of the Cry1Ab protein were further studied using five soils, and the isotherms were also well-described by linear equations ( p < 0.05). Adsorption of the Cry1Ab protein on soils was positively related to the soil organic matter content.     

Adsorption and Desorption of Cry1Ab Proteins on Differently Textured Paddy Soils

In recent years, selected cry genes from Bacillus thuringiensis (Bt) encoding the production of Cry proteins (Bt toxins) have been engineered into crop plants (Bt-crops). Through the cultivation of Bt crops and the application of Bt pesticides, Cry proteins could be introduced into arable soils. The interaction between the proteins and soils was analyzed in this study to investigate the affinity of Cry proteins in paddy soil ecosystems. Four Paddy soils were selected to represent different soil textures. Cry proteins were spiked in soils, and the amount of protein adsorbed was measured over 24 h. Desorption of Cry1Ab proteins from paddy soils was performed by washing with sterile Milli-Q water (H₂O_MQ), and subsequently extracted with an extraction buffer. The paddy soils had a strong affinity for Cry1Ab proteins. Most of the Cry1Ab proteins added (> 98%) were rapidly adsorbed on the paddy soils tested. More Cry1Ab proteins were adsorbed on non-sterile soils than on sterile soils. Less than 2% of the adsorbed Cry1Ab proteins were desorbed using H₂O_MQ, while a considerable proportion of the adsorbed proteins could be desorbed with the buffer, ranging from 20% to 40%. The amount of proteins desorbed increased with the increases in the initial amount of Cry1Ab proteins added to the paddy soils. The concentration of Cry1Ab proteins desorbed from the paddy soils was higher for sterile soils than non-sterile ones. Our results indicate that Bt toxins released via the cultivation of Bt crops, the application of Bt pesticides can be adsorbed on paddy soils, and soil texture could impose an impact on the adsorption capability.     

锌在石灰性土壤中的吸附

本文用平衡法研究石灰性土壤对锌的吸附.供试土壤为徐州丰县的黄潮土表层(0-15厘米).结果表明:吸附要用两个Laagmuir方程来描述,可以假想成两个L型表面,采用平移坐标法求出最大吸附量与实验结果基本相符.pH对锌的吸附影响很大,高pH(7.5)时,CaCO₃组分对锌的吸附的贡献约占70%,低pH时,对吸附的贡献较小.     

Adsorption isotherms of some heavy metals under conditions of their competitive adsorption onto highly calcareous soils of southern Iran

Recently, application of sewage sludge or effluents resulted in raising the concentrations of some heavy metals in some agricultural soils of Iran. Experiments were conducted to evaluate the competitive adsorption of lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) on six calcareous soils. Adsorption characteristics were evaluated by equilibration of 1 g of each soil sample with 20 ml of 0, 10, 20, 30, 40, 50, 100, or 200 mg L^?1 of their nitrate solutions and 0.01 M NaNO₃ as background electrolyte. Furthermore, solid/liquid distribution coefficients (K_d) of studied metals, as an index of soil capacity to resist a change of the soil solution concentration, were calculated. Results indicated that amounts of adsorbed Pb, Cu, Zn, and Cd increased with increase in their concentrations in the contact solutions, but this trend was more pronounced for Pb and Cu than the others. For all studied soils and metals, Langmuir equation described the adsorption behavior fairly well. Furthermore, Langmuir and Freundlich equation parameters were positively correlated to cation exchange capacity (CEC) and smectite contents; whereas, they were negatively correlated to sand content. Considering K_d values, the selectivity sequence of the metal adsorption was Pb > Cu > Zn > Cd. Therefore, the risk of leaching and also plant uptake of Zn and Cd will be higher as compared to those of the other elements.     

Factors affecting the adsorption of micro‐amounts of tagged phosphorus by soils

Abstract

Adsorption of a small amount of P by soil from a solution, which delivers concentrations approximating the composition of soil solution systems, was measured for a heterogeneous group of 343 soils using ³²P‐labelled KH₂PO₄ solution. The method allowed accurate determination of small quantities of P and identified the P under consideration as that added from solution. Simple correlations and stepvise linear regression analyses indicated that soil pH, Ca, P, Al, Fe, organic matter and particle size significantly influenced the amount of P adsorbed by the soils.     

Mutual Influence of Cu and a Cationic Herbicide on Their Adsorption-Desorption Processes on Two Selected Soils

Adsorption of Cu and the cationic herbicide chlordimeformwas carried out on two acidic soils (S-48 and LM).Chlordimeform adsorption occurred by cationic exchange andwas higher on LM soil due to its higher CEC, partlyassociated to the presence of vermiculite. Cu adsorptionwas also higher on LM soil and was related to its higheriron and manganese oxides content. The presence of theherbicide in solution always decreased Cu adsorption on S-48 soil, but on LM soil the amount of Cu adsorbed onlydecreased at the highest concentrations used. This togetherwith the lower amounts of Cu desorbed from LM soil afterfive successive desorptions in comparison to S-48 soil,indicates that Cu was being mostly adsorbed on oxides whichexhibit a very high affinity for the heavy metal. Themaximal amount of Cu desorbed on both soils only reached upto 13% of the amount adsorbed. Chlordimeform adsorption decreased in the presence of Cu as aresult of its competition for the adsorption sites on bothsoils. Cu competition on LM soil was not so strong as on S-48 soil due to the higher adsorption of the heavy metal onoxides, for which the herbicide’s affinity is not so high. Thelower the amounts of chlordimeform adsorbed on both soilsthe higher its desorption percentage. This was attributedto steric impediment of chlordimeform molecule itself forthe desorption from lamellar silicates.     

SOLUBILITY AND SORPTION OF CADMIUM IN SOILS AMENDED WITH SEWAGE SLUDGE

The mechanisms governing the retention and release of Cd in two soils, a loam and a loamy sand, pretreated with anaerobically digested sewage sludges or with chemical fertilizers, were studied using batch equilibration in 0.05 m Ca(NO₃)₂ solution containing up to 6 μg Cd/ml. Adsorption rather than precipitation as Cd₃(PO₄)₂ limited solution Cd²⁺ concentration. With the addition of 50 μg Cd/g, however, precipitation as CdCO₃ was likely at pH 7.6. Cadmium adsorption increased with increasing soil pH. The differences in Cd adsorption between different soil treatments were attributed mainly to the soil pH (6.9 to 7.9) induced by sludge application. About 82 to 92 per cent of adsorbed Cd was retained by cation exchange and complexing sites. Soils treated with sludge increased the amount of exchangeable Cd but reduced the amount of complexed Cd compared with the fertilized soil. Cadmium retention by cation exchange became more dominant as the amount of Cd in the soil was increased.     

Relationship between Freundlich isotherm Coefficients,log K F and 1 / n for atrazine desorption from soils in Japan

Desorption experiments were conducted on 21 soils at 3 atrazine concentrations. The Freundlich isotherm was used to estimate atrazine desorption. For the relationship between Freundlich isotherm coefficients, log K _F and 1 / n, 1 / n was also represented by a linear regression of log K _F as in the case of atrazine adsorption. All the linear regression lines of desorption exhibited larger slopes and intercepts than those of adsorption. When the atrazine concentration was high, the slope and intercept values were smaller than those for the desorption regression lines. The results showed that the larger the capacity of a soil to adsorb atrazine, the lesser the amount of atrazine desorbed. For the cultivated soils except for Andisols, the percentages of atrazine taken from solutions using the sequential exchange method after the first adsorption experiments, were the same as those desorbed from soils in relation to the initial amount adsorbed. Thus, reversible adsorption occurred in the soils due to weak physical adsorption.     

电解质阴离子和pH对可变电荷土壤硫酸盐吸附的影响

The effects of three electrolyte anions, ionic strength and pH on the adsorption of sulfate by two variable charge soils, with different surface charge properties were studied. Under the conditions of the same pH and ionic strength the effect of electrolyte anions on the adsorption of sulfate was in the order of Cl^- > NO₃^- > ClO₄^-, indicating the difference of the nature among these three anions. For Ferralsol in the same concentration of chloride and perchloride solutions, the two sulfate adsorption-pH curves could intersect at certain pH value. When pH was higher than the intersecting point, more sulfate was adsorbed in the perchloride solution, while when it was lower than the intersecting point, more sulfate was adsorbed in the chloride solution. In different concentrations of electrolyte solution, the curves of the amount of oxy-acid anion adsorbed, which changed with pH, could intersect at a certain pH, which is termed point of zero salt effect (PZSE) on adsorption. The nature of electrolyte anions influenced obviously the appearance of PZSE for sulfate adsorption. For ferralsol the curves of adsorption converged to about pH 7 in NaCl solution seemed to intersect in NaNO₃ solution and to have a typical PZSE for sulfate adsorption in NaClO₄ solution. For Acrisol the three curves of adsorption were nearly parallel in NaCl and NaNO₃ solutions and converged to pH 6.5 in NaClO₄ solution.