Hydrolysis and soil sorption of insecticide pyraclofos

The hydrolysis of the insecticide pyraclofos in buffered solutions at pH 5.0, 7.0 and 9.0, and its sorption on four soils of different physicochemical properties were investigated. The results showed that the degradation of pyraclofos in buffered solutions followed pseudo-first-order kinetics. At 40°C, the rate constants for the hydrolysis of pyraclofos at pH 5.0, 7.0 and 9.0 were 0.0214, 0.1293, and 2.1656 d^?1, respectively. Pyraclofos was relatively stable under both acidic and neutral conditions, while it was readily hydrolyzed under basic conditions. The sorption of pyraclofos on four soils was well described by the Freundlich equation. The sorption constant, K _f, increased with an increase in soil organic carbon content, suggesting that organic carbon content was an important factor affecting sorption. The K _oc values for Xiaoshan clay loam soil, Hangzhou I clay loam soil, Hangzhou II soil, and Fuyang silt loam soil were 30.4, 6.7, 5.3, and 7.1, respectively. These results suggest that the sorption of pyraclofos on the tested soils was relatively weak.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48-72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K(d)) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48–72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K _d) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Sorption and leaching of flucetosulfuron in soil

Abstract

The adsorption–desorption and leaching of flucetosulfuron, a sulfonylurea herbicide, was investigated in three Indian soils. Freundlich adsorption isotherm described the sorption mechanism of herbicide with adsorption coefficients (K_f) ranging from 17.13 to 27.99 and followed the order: Clayey loam?>?Loam?>?Sandy loam. The K_f showed positive correlation with organic carbon (OC) (r?=?0.910) and clay content (r?=?0.746); but, negative correlation with soil pH (r = ?0.635). The adsorption isotherms were S-type suggesting that herbicide adsorption was concentration dependent and increased with increase in concentration. Desorption followed the sequence: sandy loam?>?clayey loam?>?loam . Hysteresis (H) was observed in all the three soils with H?<?1. Leaching of flucetosulfuron correlated positively with the soil pH; but, negatively with the OC content. Sandy loam soil (OC- 0.40%, pH ?7.25) registered lowest adsorption and highest leaching of flucetosulfuron while lowest leaching was found in the loam soil (pH ? 7.89, OC ? 0.65%). The leaching losses of herbicide increased with increase in the rainfall intensity. This study suggested that the soil OC content, pH and clay content played important roles in deciding the adsorption–desorption and leaching behavior of flucetosulfuron in soils.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

表面活性剂在北京碱性土壤中的吸附行为研究

通过静态吸附实验,研究了北京碱性土壤对阴离子表面活性剂SDS、阳离子表面活性剂CTAB和非离子表面活性剂Tween80的吸附行为,考察了温度对表面活性剂吸附的影响.结果表明:7种不同土样对SDS、CTAB和Tween80的吸附等温线均较好地符合Langmuir吸附模式,其吸附能力的大小顺序为2号轻壤土》轻粘土》中壤土》砂壤土》5号轻壤土》重壤土》紧砂土,这主要是由于7种土样的pH、有机质含量和机械组成不同的缘故;同一土壤中,CTAB的吸附量》Tween80的吸附量》SDS的吸附量;温度的升高,不利于SDS和CTAB在土壤中的吸附,而有利于Tween80的吸附.     

Tylosin sorption to silty clay loam soils, swine manure, and sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 micro mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K(f)) or K(d) values, were calculated. K(f) values for the silty clay loams were similar, not influenced by landscape position, and averaged 1,350 with isotherm slopes ranging from 0.85 to 0.93. K(f) values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K(d) values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K(f) values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.     

Carbendazim sorption-desorption in Vietnamese soils

Four Vietnamese soils (denoted AG, CT, ST and TG) which differed with respect to pH (pH 2.9-5.4), clay (17-50%) and organic matter (0.3-9.8%) content, were selected for sorption and desorption studies of carbendazim using the batch equilibration technique. Sorption increased with increasing organic carbon (OC) and clay content. Kd values for carbendazim sorption on AG, CT, ST, TG soils at initial concentration of 20 microg/g were 12.5, 127, 8.1 and 9.6 ml/g, respectively. The OC partition coefficients (Koc) for AG, CT, ST and TG were 1140, 1300, 2700 and 960 ml/g, respectively. Carbendazim was strongly sorbed and the binding was less reversible in the acid sulfate soil (CT), than in the other soils. The CT soil had both the highest OC content (9.8%) and the highest clay content (49.8%). The influence of pH on carbendazim sorption was studied in the ST and CT soils. Sorption of carbendazim by the sandy ST soil (OC 0.3%; clay content 26.3%) increased as the pH decreased, while sorption of carbendazim by the CT soil decreased as pH decreased.     

Influence of pH on pesticide sorption by soil containing wheat residue-derived char

Field burning of crop residues incorporates resulting chars into soil and may thus influence the environmental fate of pesticides in the soil. This study evaluated the influence of pH on the sorption of diuron, bromoxynil, and ametryne by a soil in the presence and absence of a wheat residue-derived char. The sorption was measured at pHs approximately 3.0 and approximately 7.0. Wheat char was found to be a highly effective sorbent for the pesticides, and its presence (1% by weight) in soil contributed >70% to the pesticide sorption (with one exception). The sorption of diuron was not influenced by pH, due to its electroneutrality. Bromoxynil becomes dissociated at high pHs to form anionic species. Its sorption by soil and wheat char was lower at pH approximately 7.0 than at pH approximately 3.0, probably due to reduced partition of the anionic species of bromoxynil into soil organic matter and its weak interaction with the carbon surface of the char. Ametryne in its molecular form at pH approximately 7.0 was sorbed by char-amended soil via partitioning into soil organic matter and interaction with the carbon surface of the char. Protonated ametryne at pH approximately 3.0 was substantially sorbed by soil primarily via electrostatic forces. Sorption of protonated ametryne by wheat char was also significant, likely due not only to the interaction with the carbon surface but also to interactions with hydrated silica and surface functional groups of the char. Sorption of ametryne by char-amended soil at pH approximately 3.0 was thus influenced by both the soil and the char. Environmental conditions may thus significantly influence the sorption and behavior of pesticides in agricultural soils containing crop residue-derived chars.     

Factors influencing 2,4-D sorption and mineralization in soil

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2.4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 microg(1 - 1/n) g(-1) mL(1/n). First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Can we predict uranium bioavailability based on soil parameters? Part 1: effect of soil parameters on soil solution uranium concentration

Present study aims to quantify the influence of soil parameters on soil solution uranium concentration for (238)U spiked soils. Eighteen soils collected under pasture were selected such that they covered a wide range for those parameters hypothesised as being potentially important in determining U sorption. Maximum soil solution uranium concentrations were observed at alkaline pH, high inorganic carbon content and low cation exchange capacity, organic matter content, clay content, amorphous Fe and phosphate levels. Except for the significant correlation between the solid-liquid distribution coefficients (K(d), L kg(-1)) and the organic matter content (R(2)=0.70) and amorphous Fe content (R(2)=0.63), there was no single soil parameter significantly explaining the soil solution uranium concentration (which varied 100-fold). Above pH=6, log(K(d)) was linearly related with pH [log(K(d))=-1.18 pH+10.8, R(2)=0.65]. Multiple linear regression analysis did result in improved predictions of the soil solution uranium concentration but the model was complex.     

Sorption of ametryn and imazethapyr in twenty-five soils from Pakistan and Australia.

Sorption of ametryn and imazethapyr in 25 soils from Pakistan and Australia was investigated using the batch method. The soils varied widely in their intrinsic capacities to sorb these herbicides as shown by the sorption coefficients, Kd, which ranged from 0.59 to 47.6 for ametryn and 0.02 to 6.94 for imazethapyr. Generally the alkaline soils of Pakistan had much lower Kd values of both herbicides than the soils of Australia. Both soil pH and soil organic carbon (SOC) were correlated significantly with the sorption of ametryn, whereas only soil pH was strongly correlated with imazethapyr sorption. No correlation was found between Kd values of the herbicides and the clay contents of the soils. Multiple regression analysis showed that Kd values were better correlated (r2=0.94 and 0.89 for ametryn and imazethapyr, respectively) if SOC and pH were simultaneously taken into account. The study indicated that sorption of these herbicides in the alkaline soils of Pakistan was low and consequently there is considerable risk of groundwater contamination.     

Thermodynamics of interaction of lindane on silty loam and silty clay loam Indian soils

Abstract

Interaction of lindane with silty loam and silty clay loam soils was studied in batch tests at 23, 30 and 37° C. Sorption experiments were carried out at four concentrations and for varying time of contact upto 72 hours. This was followed by desorption studies. No desorption was observed. The sorption data was analysed using sorption equations and evaluating the thermodynamic parameters. The sorption was found to be predominantly entropic in nature and a combined effect of adsorption and chemisorption. The effect of organic matter and other chemical and mineralogical constituents of soils has also been discussed. The sorption with single application of lindane with the two soil types indicates that the insecticide is less likely to reach groundwater.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

The effects of pH and soil type on concentrations of zinc, copper and nickel extracted by calcium chloride from sewage sludge-treated soils

The effects of pH on concentrations of zinc, copper and nickel extracted by calcium chloride from a clay loam and two sandy loam soils that had been treated with sewage sludge were studied. Concentrations of all the metals increased rapidly as pH decreased below a threshold value ranging from 6.2 to 7.0 for Zn, 6.2 to 7.2 for Ni and 4.7 to 5.7 for Cu. Both the total concentrations and the threshold pH values were influenced by differences in soil texture and (between the two light-textured soils) by differences in soil cation exchange capacity. The amount of zinc and copper extracted from the mixtures was considerably less than that extracted from the same quantity of sludge alone.     

The ratio of clay content to total organic carbon content is a useful parameter to predict adsorption of the herbicide butachlor in soils

Thirteen soils collected from 11 provinces in eastern China were used to investigate the butachlor adsorption. The results indicated that the total organic carbon (TOC) content, clay content, amorphous Fe2O3 content, silt content, CEC, and pH had a combined effect on the butachlor sorption on soil. Combination of the data obtained from the 13 soils in the present study with other 23 soil samples reported by other researchers in the literature showed that Koc would be a poor predictive parameter for butachlor adsorption on soils with TOC content higher than 4.0% and lower than 0.2%. The soils with the ratio of clay content to TOC content (RCO) values less than 60 adsorbed butachlor mainly by the partition into soil organic matter matrix. The soils with RCO values higher than 60 apparently adsorbed butachlor by the combination of the partition into soil organic matter matrix and adsorption on clay surface.     

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.