Sorption behavior of selenium and antimony in soils as a function of phosphate ion concentration

Abstract

Both selenium (Se) and antimony (Sb) are major soil and water pollutants. Their sorption behavior in a soil–plant system was studied. Soil–soil solution distribution coefficients (K _ds) for Se and Sb were measured, using a radiotracer, as an indicator of their sorption levels. Both Se and Sb behave as oxoanions (SeO^2? ₄, H₂PO^? ₄ and SO^2? ₄) in soil; thus, the effects of concentrations of two major oxoanions (SeO^2? ₄ and SeO^2? ₃) on Se and Sb sorption were also examined. The K _d values for Se for Japanese soils significantly correlated with the K _d values for Sb (n = 141). The K _ds of both Se and Sb similarly decreased with increasing SbO^? ₃ concentration. These results indicated that the sorption of Se and Sb was similarly controlled by a ligand-exchange mechanism such as phosphate sorption in soil. However, an increase in the concentration of SeO^2? ₃ did not decrease the K _ds of Se and Sb. Furthermore, the ligand-exchangeable fractions of stable Se and Sb in major Japanese soils were determined by extraction with 0.1 mol L^?1 Na₂HPO₄ solution. For both Se and Sb, the phosphate-extractable fractions were 10-fold higher for Se and fivefold higher for Sb than their water-soluble fractions. Although the total Se and Sb amounts in soils were the same, their ligand-exchangeable fractions were different. Approximately 0.9–12% of total Se and 0.2–1.3% of total Sb were extracted by the phosphate solution. These findings suggested that Se was more likely to be mobilized by the addition of phosphate than Sb. The effect of plant-available phosphate in the soil and the phosphate sorption capacity of soil on Se and Sb availabilities for plants were also examined using a pot experiment with soybean plants. The experimental results suggested that a high content of available phosphate and/or low phosphate sorption capacity of soil increased both Se and Sb availabilities to the plant. However, the results also suggested that the soil Se availability to the plant was higher than that of Sb even though the soil total Se and Sb amounts were the same.     

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter (SOM) is considered the most important process affecting the bioavailability of hydrophobic organic chemicals (HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient (K_OC) of six selected polycyclic aromatic hydrocar...     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

2,4‐D Movement in Allophanic Soils from Two Contrasting Climatic Regions

Abstract

Allophanic top‐ and subsoils from the Mexican and Newzealand Central Volcanic Plateau, as well as a nonallophanic sandy loam soil, were sampled to study the impact of organic matter and allophane content on 2,4‐D fate. High sorption rates were found, especially in the two topsoils from Mexico and New Zealand, with distribution coefficient (K _d ) obtained from displacement experiments in packed columns equal to 7.61 and 8.43 L kg^?1 respectively. 2,4‐Dichlorophenoxyacetic acid transfer through the soil columns was found to be in chemical nonequilibrium and was well predicted using a two‐site sorption model. For the two allophanic top soils, K _d obtained from batch was very different to the K _d obtained from column experiments. Either the equilibrium could not be reached in batch or the two‐site model was not able to describe the wide range of sorption sites present in the highly reactive organic matter and allophane components.     

Organic matter effects on phosphorus sorption in sandy soils

Phosphorus (P) sorption processes in soils contribute to important problems in agriculture: a deficiency of this plant nutrient and eutrophication in aquatic systems. Soil organic matter (SOM) plays a major role in sorption processes, but its influence on P sorption remains unclear and needs to be elucidated to improve the ability to effectively manage soil P. The aim of this research was to investigate the influence of SOM on P sorption. The study was conducted in sandy soil profiles and in topsoils before and after removal of SOM with H₂O₂. The results were interpreted with the Langmuir and Freundlich isotherms. Our results indicated that SOM affected P sorption in sandy soils, but that P sorption also depended on specific soil properties (e.g. values of the degree of P saturation (DPS), P sorption capacity (PSC) and pH) often related to land use. Removal of SOM decreased PSC in most of the topsoils tested; other soil properties became important in controlling P sorption. An increase in P desorption observed after SOM removal indicated that SOM was potentially that soil constituent which increased P binding and limited P leaching from these sandy soils.     

pH对土壤重金属吸附动力学的影响

The pH effect on the sorption kinetics of heavy metals in soils was studied using a constant flow leaching method. The soil samples were red soil collected from Yingtan, Jiangxi, and yellow-brown soil from Nanjing, Jiangsu. The heavy metals tested were zinc and cadmium. Assuming that the experimental data fitted to the following kinetic rate equation: 1/c·dx/dt = kx_∞-kx, the rate constant k of sorption could be determined from the slope of the straight line by plotting of 1/c·dx/dt vs. x. The results showed that the pH effect on the rate constants of heavy mental sorption in soils was very significant. The values of k decreased with increasing pH. The sorptions were more sensitive to pH in red soil than in yellow-brown soil.     

Predicting potassium fertilizer requirement using exchange isotherm approach in relation to soil characteristics

Determining potassium (K) fertilizer requirement using sorption isotherms is considered more accurate than conventional soil K tests. A total of 59 surface soil samples were used to establish K exchange isotherm. To evaluate K requirement sorption test, a glasshouse experiment using perennial ryegrass (Lolium perenne, cv. Roper) was carried out on 10 soil samples. The experiment was laid out as a completely randomized design with four replications and four K levels (K₀, K₂₀, K₄₀, K₈₀). Concentrations of K in solution established by adding K in the pots estimated from the sorption curve ranged from 20 to 80 mg K l^?1 including check treatment (no K). Dry matter yield of ryegrass in most soils approached maximum as adjusted K levels were increased to 20 mg K l^?1. The amounts of K required to bring the soils to 20 mg l^?1 in soil solution varied among soils and ranged from 99 to 399 mg kg^?1, on average 205 mg kg^?1 soil. It was found that a useful regression model for the prediction of standard K requirement (K₂₀) included the combination of plant available K extracted by NH₄OAc (Av-K) and clay content: K₂₀ = ?41 ? 0.63 Av-K + 9.0 Clay (R² = 0.61, p < 0.001, n = 59).     

The molecular composition of soil organic matter as determined by 13C NMR and elemental analyses and correlation with pesticide sorption

Although the chemical composition of soil organic matter (SOM) is known to significantly influence sorption of pesticides and other pollutants, it has been difficult to determine the molecular nature of SOM in situ. Here, using ¹³C nuclear magnetic resonance (NMR) data and elemental composition in a molecular mixing model, we estimated the molecular components of SOM in 24 soils from various agro‐ecological regions. Substantial variations were revealed in the molecular nature of SOM. As a proportion of soil carbon the proportion of the carbonyl component ranged from 0.006 to 0.05, charcoal from 0 to 0.15, protein from 0.09 to 0.29, aliphatic from 0.14 to 0.30, carbohydrate from 0.21 to 0.31, and lignin from 0.05 to 0.42. The relationships between K_oc (sorption per unit mass of organic carbon) of carbaryl (1‐naphthyl methylcarbamate) and phosalone (S‐6‐chloro‐2,3‐dihydro‐2‐oxobenzoxazol‐3‐ylmethyl O,O‐diethyl phosphorodithioate) and the molecular nature of organic matter in the soils were significant. Of the molecular components estimated, lignin and charcoal contents correlated best with sorption of carbaryl and phosalone. Aliphatic, carbohydrate and protein contents were found to be negatively correlated with the K_oc of both pesticides. The study highlights the importance of the molecular nature of SOM in determining sorption affinities of non‐ionic pesticides and presents an indirect method for sorption estimation of pesticides.     

Fast abiotic sorption of selenates (SeO42-) in soils: pitfalls of batch sorption data acquired by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS)

Low selenium (Se) dietary intake has encouraged the development of fortification strategies such as SeO₄^2- application to arable land. Selenate is highly mobile in soil systems, but it is not known whether fast abiotic retention could reduce Se loss from topsoil after SeO₄^2- fertilisation. This work explicitly aims at fast abiotic SeO₄^2- sorption in three soils exposed to 20–1250 µg L^?1 Se in a 24-h batch experiment. This study demonstrated the susceptibility of Se sorption data to distortion when inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) measurements suffered from non-spectral interferences induced by concomitant elements in an aqueous soil-derived matrix. The distribution coefficient (K_d), not exceeding 2 L kg^?1 at any Se level, was shown to be a useful indicator for the extent of ion competition for sorption sites depending on the SeO₄^2- concentration employed. Sorption experiments conducted in the presence or absence of nitrate (10 mM), sulphate (0.52 mM) and phosphate (0.21 mM) allowed three phenomena explaining different SeO₄^2- retention behaviours found even between similar Cambisols to be proposed. Finally, we showed that the co-application of sulphate or phosphate with SeO₄^2- might decrease Se sorption from 150–170 µg kg^?1 to a net release from native Se pool.

Abbreviations: 1^st IP: first ionisation potential; RSD: relative standard deviation     

Influence of organic matter on selenite sorption by Andosols

Abstract

The influence of soil organic matter on selenite sorption was investigated in the selenite adsorption capacity and the surface particle charge change by ligand exchange reaction using the hydrogen peroxide (H₂O₂) treatment and the ignition treatment of two Andosols. The removal of organic carbon (C) in soils accelerated selenite sorption, implying that organic matter of soils had negative influence on the selenite adsorption on the soils. Positive charge decrease on soil particles, concomitant proton consumption, and release of silicon (Si), sulfate (SO₄ ^2‐), and organic C were observed in selenite sorption by the soils. The development of surface particle negative charge with selenite sorption was smaller in the H₂O₂‐treated soil than in the original soils and was scarcely observed in the ignition‐treated soil. It can be assumed that the increase of negative charge by selenite sorption was attributed to new negative sites borne by released insoluble organic matter and negative charge development directly by selenite sorption was small.     

Low-molecular weight organic acids improve plant availability of phosphorus in different textured calcareous soils

Understanding the role of organic acids on phosphorus (P) sorption capacity of soils is very important for its economic and friendly management. Combining P application with low-molecular weight organic acids could result in its higher plant availability for prolonged time. Therefore, citric and oxalic acid (at the rate of 1.0 mM kg^?1 soil) were evaluated for their effect on P sorption capacity and its plant availability in two different textured calcareous soils. Organic acids decreased P sorption capacity and organic carbon partition coefficient (K_oc) whereas increased Gibbs free energy (ΔG) of P. Organic-acid-treated soils required lesser quantity of P fertilizer to produce soil solution P concentration optimum for plant growth (external P requirement [EPR_0.2]), that is, 0.2 mg L^?1. Citric acid was efficient than oxalic acid in the above effects. P sorption parameters of Freundlich model were negatively correlated with lime potential and ΔG whereas had positive correlation (P < 0.05) with EPR_0.2 and K_oc. Incubation with oxalic acid increased available P in loamy sand and loam soil by 20% and 30%, respectively. Thus, organic acids could help reduce application rate of P fertilizer through lowering its adsorption in highly P-fixing soils without compromise on yield.     

Adsorption isotherms of copper and zinc in clay minerals of calcareous soils and their effects on X-ray diffraction

Reactions of elements with the water mineral interface are important and affect their bioavailability and transportation within soil. Effects of metal sorption on X-ray-diffraction (XRD-photographs) of clay minerals have been not studied. Therefore, sorption experiments were done on clay fractions of two calcareous soils using 12 concentrations of 0–2000 mg L^?1 Zn(NO₃)₂ and Cu(NO₃)₂. Langmuir and Freundlich isotherms’ coefficients were determined. After sorption, XRD-diffraction were prepared and compared with those of initial samples. Langmuir (R² = 0.996–0.999 and SE = 0.001–0.002) and Freundlich equation were the best-model for Zn and Cu-sorption, respectively. Sorption energy was higher for Zn than Cu, whereas the maximum concentration of sorbed-Cu was higher than that of Zn. Distribution coefficient (K_d) of Cu were more (threefold) than that of Zn. The K_d values representing the slope of Freundlich isotherms decreased according to linear regression equations (R² = 0.72–0.91) as the equilibrium concentrations of metals increased. No significant differences were observed among XRD-photographs of applied concentrations (some negligible differences were found in position/sharpness of peaks). Dry-XRD-method resulted in omission of intensity peaks at 2θ which may interfere in recognition of clays that show a maximum intensity >1.4 nm in the mentioned 2θ. Zinc can become more leachable especially in Shekarbani-soil-series, whereas, Cu highly adsorb on clay minerals and can show less tendency to transportation.     

Mobility of mercury in soil as affected by soil physicochemical properties

Purpose

The interaction of mercury with organic matter was studied on three soils with distinct physical-chemical compositions (Fluvisol, Luvisol, and Chernozem) and three vermicomposts based on various bio-waste materials (digestate, kitchen waste with woodchips, and garden bio-waste).

Materials and methods

Laboratory batch experiments, in which organic matter composition was modeled by adding graded doses of vermicompost to individual soils, were carried out. The composition of organic matter in these vermicomposts was assessed via fractionation of humic acids, fulvic acids, hydrophilic compounds, and possible hydrophobic neutral organic matter. Furthermore, the samples were artificially contaminated with inorganic and organic mercury. Prepared samples were stored under constant temperature of 25 °C. The incubation experiments lasted for 56 days, in which the samples were taken ten times. During the experiments, the changes in mercury mobile phase amount were observed, and the influence of the source of contamination was evaluated.

Results and discussion

The amount of mobile mercury increased and then decreased during the time. In most of the soils and vermicompost combinations, the content of mercury bound to the soil was stable after 21 days. The effects of the mercury source on the exchangeable portion of Hg in the soils were most obvious in samples without added vermicompost. Nevertheless, differences between mobile inorganic and organic forms of Hg were lower in the case of Fluvisol compared to other soils. Moreover, in this soil, the content of available mercury was higher than from others.

Conclusions

In general, the smallest differences between mobile inorganic and organic forms of Hg were observed in the case of soil with the highest content of organic matter. Also higher doses of vermicomposts decreased the amount of mercury mobile phase available. Additionally, the largest positive influence of vermicompost dose on Hg mobility was measured in soils combined with vermicompost with the highest portion of humic acids.

     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Influence of submergence and subsequent drainage on the partitioning and lability of added selenium fertilizers in a sulphur‐containing Fluvisol

We used an isotope dilution method to examine the time‐dependent changes in the partitioning and lability of selenium (Se) in a Sri Lankan rice soil after adding fertilizer with selenite (Se(IV)) and selenate (Se(VI)) (1 mg kg^?1) and incubation under anaerobic (submerged) (30 days) and subsequent aerobic (drained) conditions (7 days) in controlled reaction vessels mimicking rice paddy water management practices. The K_d (the ratio of sorbed ion to that in solution) values for Se(IV) were significantly (P≤ 0.001) larger than those for Se(VI) in all treatments and at all sampling times. The K_d values for Se(IV) and Se(VI) decreased significantly (P≤ 0.001) with time during the anaerobic and subsequent aerobic phases. Applied Se(IV) fertilizer was rapidly removed into non‐labile pools during the anaerobic phase (day 0 = 60% labile and day 14 = no labile Se), with no significant increase in the labile pool following short‐term aeration. The results suggest that the rapid decrease in Se(IV) lability may be caused by the strong non‐reversible (at least for 7 days) sorption of Se (IV). In contrast, applied Se(VI) fertilizer was 90% labile at 0 day and decreased during the anaerobic phase to 30% after 30 days. There was no significant change in the lability of Se(VI) following the short‐term aerobic phase following anaerobic conditions. These results indicate that Se(IV) would not be an effective pre‐planting fertilizer for rice production. Selenate is likely to be more effective, but losses to non‐labile forms during the submerged phase of rice production may mean that efficiency of pre‐planting Se(VI) fertilizer is also compromised.     

Sorption and desorption of diuron and norflurazon in Florida citrus soils

The potential for surface and groundwater contamination of soil applied herbicides is partly dependent on soil properties. Sorption and desorption of diuron and norflurazon were studied in seven soils representative of the southern citrus-belt of Florida using the batch-equilibrium technique. Sorption of herbicides was influenced by soil properties. Sorption coefficients (K _d) ranged from 0.84 to 3.26 mL g^?1 for diuron and 0.63 to 2.20 mL g^?1 for norflurazon indicating weak to moderate binding of herbicides to soil. For norflurazon, K _dwas significantly related to organic C content, soil pH, and cation exchange capacity. For diuron, absence of a significant relationship between K _dand selected soil properties suggests that the soil properties other than those studied may play a role in determining sorption on these soils. Desorption studies showed that higher amounts of diuron and norflurazon was desorbed by water than by 0.5 M CaCl₂. An inverse relationship was apparent between herbicides sorbed and that which was desorbed among the soils studied. The soil which exhibited higher sorption had lower desorption and the soil which exhibited lower sorption had higher desorption.     

Differential Sorption Behavior of Cadmium,Lead, Zinc,and Copper in Some Tropical Soils and Their Environmental Implications

This study evaluated cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) sorption characteristics of three tropical soils. Data obtained conformed to Freundlich sorption model and the S-shaped isotherm curve. Sorption efficiency of Zn and Pb were highest in alkaline soil while slightly acid soil had the highest Cd and Cu sorption efficiency for monometal sorption. In competitive sorption, metals were more sorbed in slightly acid soil while the least efficiency was recorded in acid soil. Distribution coefficient; K_d (average across soil types) in monometal sorption followed the order: Pb > Zn > Cd > Cu. For competitive sorption, the order was Zn > Pb > Cu > Cd. When in competition, Cd was preferentially sorbed in slightly acid and alkaline soils and Zn for acid soil. Conclusively, lead is more in equilibrium solution when in competition with Cd, Zn and Cu making it potential agent of soil and groundwater pollution.     

Assessment of three vermicomposts as organic amendments used to enhance diuron sorption in soils with low organic carbon content

Vermicomposts from the wine and distillery industry containing spent grape marc (V1), biosolid vinasse (V2) and alperujo (V3) from the olive‐oil industry were investigated as organic amendments to a sandy and a clay soil with low organic carbon (OC) contents (≤1%). The sorption‐desorption process was studied in batch experiments using diuron as a non‐ionic herbicide model. The effect of soil and vermicompost characteristics, the solution's ionic strength and incubation time of amended soils on the sorption process was studied. The addition of vermicompost changed soil properties and enhanced sorption capacity by two‐ to four‐fold. The K_oc variability showed that exogenous OC composition influenced diuron sorption. Vermicompost V1, which had the largest OC and lignin content, recorded the largest sorption increment. Vermicompost V3, which had the greatest dissolved organic carbon content and a high degree of humification, made the smallest contribution to sorption. Sorption was also dependent on extraneous calcium in the solution. The incubation of amended soils reduced diuron sorption efficiency except with V3. Pyrolysis‐gas chromatography (Py‐GC) analysis was a useful tool to characterize the vermicomposts and to understand the variation of diuron sorption constants after vermicompost incubation. This research encourages the use of vermicompost from agro‐industrial wastes as a sustainable means to minimize the side effects of neutral herbicides.     

How Can Organic Amendments Help to Bind Sulfadiazine in the Soil? – An Iranian Soil Study

ABSTRACT

Veterinary antibiotics can enter the environment especially agricultural soils via animal manure application in which Sulfadiazine (SDZ) is considered as one of the most used antibiotic. After soil application, it may be transported into subsurface water. The sorption behavior of SDZ is not only influenced by the soil type but also by soil organic matters as well. Hence, an experiment was executed aimed to study sorption/desorption processes of SDZ under experimental conditions in three various soils treated by different bio fertilizers including rice husk compost (RHC), rice husk biochar (RHB) and Micrococcus yunnanensis (My) bacterium. Sorption/desorption data of soils with and without bio-fertilizers were well fitted with Freundlich model (R² = 0.97). Results showed that bio-amended soils had higher values of k_d sorption ranged from 1.16 to 52.4 without and with bio-fertilizers application respectively, proposing low sorption of SDZ with substantial risk of leaching without bio-fertilizers application. Also for the desorption cycle values of K_d increased from 1.03 to 39.1 without and with bio-fertilizers application, respectively. Furthermore, there was a hysteresis effect using organic matter. As a result of bio-fertilizers application, a significant value of SDZ was strongly adsorbed on the soil particles which was not desorb through desorption process.