Sorption of the fumigant 1,3-dichloropropene on soil

The fumigant 1,3-dichloropropene (1,3-D) is considered a major replacement to methyl bromide, which is to be phased out of use in the United States by 2005. The main purpose of this study was to evaluate soil-water partitioning of 1,3-D in two California agricultural soils (Salinas clay loam and Arlington sandy loam). The partition coefficients (Kd and Kf) were determined by directly measuring the concentration of 1,3-D in the solid phase (Cs) and aqueous phase (Cw) after batch equilibration. In the Salinas clay loam, the Kf of cis-1,3-D in adsorption and desorption isotherms was 0.47 and 0.54, respectively, with respective values of 0.39 and 0.49 for trans-1,3-D. This slight hysteric effect suggests that a different range of forces are involved in the adsorption and desorption process. Since n was near unity in the Freundlich equation, the Freundlich isotherms can also be approximated using the liner isotherm. At 25 degrees C, the Kd of the 1,3-D isomers in both soils ranged from 0.46 to 0.56, and the Koc (organic matter partition coefficient) ranged from 58 to 70. The relatively low Kd values and a Koc that falls within the range of 50-150, suggests that 1,3-D is weakly sorbed and highly mobile in these soils. Understanding the sorption behavior of 1,3-D in soil is important when developing fumigation practices to reduce the movement of 1,3-D to the air and groundwater.     

A comparative study of adsorption of an anionic and a non-ionic surfactant by soils based on physicochemical and mineralogical properties of soils

In the present work we performed a comparative study on the adsorption of the surfactants sodium dodecyl sulphate (SDS) (anionic), and octylphenoxypolyethoxyethanol (Triton X-100) (non-ionic) to 18 soils with organic matter (OM) and clay fraction contents varying over a broad range. The objective of the study was to gain further insight into the influence of the physicochemical and mineralogical properties of soils on the adsorption of surfactants by soils. Adsorption isotherms were obtained using concentrations below the critical micellar concentration (cmc) of the surfactants. The adsorption coefficients, Kf, determined from the Freundlich equation were lower for SDS (range 1.77-82.1, mean value 36.3) than for Triton X-100 (range 0.01-913, mean value 257). Simple and multiple correlation coefficients were obtained between Kf values and soil characteristics. The results obtained indicate the influence of the OM content on the adsorption of SDS (r=0.64, p<0.01) and of the clay fraction content on that of Triton X-100 (r=0.83, p<0.001). Additionally, we observed a preferential adsorption of SDS by the 1:1 mineral kaolinite (r=0.54, p<0.05), while Triton X-100 was adsorbed mainly by the 2:1 minerals, montmorillonite (r=0.66, p<0.01) and illite (r=0.87, p<0.001). According to the influence of different soil parameters on adsorption, different mechanisms of adsorption are proposed for each surfactant. Our findings point to the interest of considering the physicochemical properties of soils and also the mineralogy of the soil clay fraction when selecting a surfactant in technologies involving enhanced solubilization and removal of contaminants from soils and sediments.     

Sorption of thiamethoxam in three Indian soils

The sorption behavior of the insecticide thiamethoxam [3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine] on three Indian soils with different physico-chemical properties was investigated. The soils represent the major grapevine growing areas of India, where the vineyards frequently receive thiamethoxam applications as foliar spray, soil drenching and through drip irrigation for the management of various insect pests. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation and free energy indicated physical adsorption of thiamethoxam on soil. The adsorptivity of different soils might be attributed to the organic matter and clay contents. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. Thiamethoxam could be categorized as a chemical with medium leaching potential.     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

Adsorption characteristics of pesticides methamidophos and glyphosate by two soils

Contributions of organic matter and minerals in soil were evaluated by comparing changes in adsorption of methamidophos (MDP) and glyphosate (GPS) before and after removal of organic matter from argaltoll (mollisol) and typustalf (alfisol) soils. Adsorption isotherms of MDP and GPS by the two soils comforted to Freundlich equation, and the adsorption capacity of GPS by argaltoll soil was higher than that of MDP. Due to the removal of organic matter from soils, K(f) values of MDP and GPS adsorbed by argaltoll soil, which were calculated from Freundlich equations and the measure of adsorption capacity, decreased by 46.1% and 75.0%, and these by typustalf soil decreased by 34.9% and 52.5%, respectively. Results from this study suggested that soil organic matter made greater contributions to adsorption of GPS, but soil minerals could provide more available adsorption sites for MDP.     

Adsorption, desorption, and mobility of permethrin in Malaysian soils

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r2 = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10-15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

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.     

Sodium dodecyl sulphate-enhanced desorption of atrazine: effect of surfactant concentration and of organic matter content of soils

A study was made of the adsorption-desorption of atrazine in aqueous medium in five soils with organic matter (OM) contents in the range 1.4-10.3% and also of the desorption of the herbicide in aqueous solutions of the anionic surfactant sodium dodecyl sulphate (SDS) at critical micelle concentrations (cmc) of 0.75, 1.50, 5 and 10. The adsorption and desorption isotherms in water together with the desorption isotherms in SDS solutions with concentrations of 0.75 and 1.50 cmc fit the Freundlich adsorption equation. All the desorption isotherms displayed hysteresis. The increase or reduction in hysteresis of the desorption isotherms in SDS solutions with respect to those of desorption in water depend on the SDS concentration and on the OM content of the soils. Below the cmc, SDS only increases the desorption of atrazine in the soil with the highest OM content (10.3%). However, above the cmc (5 and 10 cmc) the desorption of atrazine increases in all soils, the efficiency of desorption increasing with the OM content of the soils.     

Adsorption of arsenate on soils. Part 1: laboratory batch experiments using 16 Chinese soils with different physiochemical properties

Laboratory batch experiments were carried out to study the adsorption of arsenate on 16 Chinese soils with different physicochemical properties. Wide differences in arsenate adsorption were observed, and the Jiangxi and Hubei soils were more effective sorbents for arsenate than other soils. The Langmuir one-surface and two-surface equations were used to model the arsenate adsorption data. Except for the Jiangxi and Hubei soils, the Langmuir one-surface equation gave reasonably good fits to the arsenate adsorption data. However, the Langmuir two-surface equation generally provided a better fit than the Langmuir one-surface equation. For soils with relative high organic matter (OM), dissolved organic carbon (DOC) or extractable phosphate, the Langmuir one-surface and two-surface equations described the adsorption isotherms similarly. In contrast, for soils with relatively low contents of OM, DOC or extractable phosphate, the Langmuir two-surface equation gave the better fit to the arsenate adsorption data.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Sorption behaviour of acetochlor,atrazine, carbendazim,diazinon, imidacloprid and isoproturon on Hungarian agricultural soil

Laboratory studies were conducted to determine the sorption behaviour of six commonly used pesticides (acetochlor, atrazine, carbendazim, diazinon, imidacloprid and isoproturon) on Hungarian brown forest soil with clay alluviation (Luvisol) using the batch equilibrium technique. The sorption isotherms could be described by the Freundlich equation in non-linear form (n < 1) for all compounds, however in case of diazinon using the extended Freundlich equation proved to be a better approach. The adsorption constant related soil organic carbon content (Koc) calculated from Freundlich equation were 314 for acetochlor, 133 for atrazine, 2805 for carbendazim, 1589 for diazinon, 210 for imidacloprid and 174 for isoproturon. The octanol-water partition coefficients (Pow), which can be a useful parameter to predict of adsorption behaviour of a chemical on soil, and dissociation coefficients of these pesticides were calculated based on the chemical structure of them using a computerized expert system. The octanol-water partition coefficients were determined experimentally from high performance liquid chromatographic parameters as well. Good agreement was observed between experimental and the computer expert system estimated data. Computer estimated log Pow values ranged 0.5 and 3.86 for the examined pesticides, with imidacloprid and diazinon being the least and most hydrophobic respectively. Experimentally determined logPow ranged between 0.92 and 3.81 with the same tendency. It can be concluded that the Freundlich adsorption constants (Kf) are slightly related to the octanol-water partition coefficients of investigated chemicals, nevertheless no close correlation could be established because of the influence of further characteristics of solutes and soil.     

Sorption of fipronil and its metabolites on soils from South Australia

This paper reports on the sorption of fipronil [(+/-)-5-amino-1-(2,6-dichloro-alpha,alpha,alpha-trifluoro-p-tolyl)-4-trifluoromethyl-sulfinylpyrazole-3-carbonitrile] and its two main metabolites, desulfynil and sulfide derivatives on a range of soils from South Australia. The Freundlich sorption coefficient (Kf) values for fipronil on the soils ranged from 1.94 to 4.84 using a 5% acetonitrile/water mixture as the soil solution. Its two metabolites had a higher sorption affinity for soils, with Kf values ranging from 11.09 to 23.49 for the sulfide derivative and from 4.70 to 11.77 for the desulfynil derivative. Their sorption coefficients were found to be better related to the soil organic carbon than clay content. The presence of cosolvents in soil solutions had a significant influence on the sorption of fipronil. The Freundlich sorption coefficients showed a log linear relationship with the fractions of both acetonitrile and methanol in solutions. The sorption coefficient of fipronil on Turretfield soil in the aqueous solution was estimated to be from 13.80 to 19.19. Methanol had less effect on the sorption of fipronil than acetonitrile. The Kd values for fipronil on the eight soils using a 5% methanol/water mixture were from 5.34 to 13.85, which reflect more closely the sorption in the aqueous solution. The average Koc value for fipronil on the eight South Australian soils was calculated to be 825+/-214.     

Sorption of paraquat on clay components in Taiwan's oxisol

The sorption of herbicides in soils is mainly influenced by clay components. The objectives of this study were to evaluate the contribution of clay components on paraquat sorption. The surface soils (0-20 cm) of a Laopi pedon (Fine, mixed, Hyperthermic Typic Hapludox) were separated clays into whole (< 2.0 microm), coarse (0.2-2.0 microm), and fine (< 0.2 microm) fractions with the treatments of removals of organic matter (OM) and free Fe (Fed) oxides. Results indicated that sorption isotherm of paraquat was fitted by the nonlinear Freundlich equation with R2 values ranged in 0.79-0.96, respectively. The shape of paraquat adsorption isotherm on the fine fraction was H-type, but their shapes on the whole and coarse fractions were L-types. The fine clay fractions gave higher contribution on paraquat sorption than the coarse clay fractions identified by their K(f) values. Organic matter associated with fine clay fraction had high CEC contributing to relatively high affinity for paraquat. The DCB treatment created high-affinity sites for paraquat on the fine clay, but had little effect on paraquat sorption for the coarse clay. Chemisorption is the major mechanism for retention of paraquat on clay components, not ion exchange. However, the silicate clay had the highest affinity for paraquat and free Fe compound had the lowest.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.     

Sorption of the Fumigant 1,3-Dichloropropene on Soil

Abstract

The fumigant 1,3-dichloropropene (1,3-D) is considered a major replacement to methyl bromide, which is to be phased out of use in the United States by 2005. The main purpose of this study was to evaluate soil–water partitioning of 1,3-D in two California agricultural soils (Salinas clay loam and Arlington sandy loam). The partition coefficients (K _d and K _f ) were determined by directly measuring the concentration of 1,3-D in the solid phase (C _s ) and aqueous phase (C _w ) after batch equilibration. In the Salinas clay loam, the K _f of cis-1,3-D in adsorption and desorption isotherms was 0.47 and 0.54, respectively, with respective values of 0.39 and 0.49 for trans-1,3-D. This slight hysteric effect suggests that a different range of forces are involved in the adsorption and desorption process. Since n was near unity in the Freundlich equation, the Freundlich isotherms can also be approximated using the liner isotherm. At 25°C, the K _d of the 1,3-D isomers in both soils ranged from 0.46 to 0.56, and the K _oc (organic matter partition coefficient) ranged from 58 to 70. The relatively low K _d values and a K _oc that falls within the range of 50–150, suggests that 1,3-D is weakly sorbed and highly mobile in these soils. Understanding the sorption behavior of 1,3-D in soil is important when developing fumigation practices to reduce the movement of 1,3-D to the air and groundwater.     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.     

Adsorption,Desorption, and Mobility of Permethrin in Malaysian Soils

Abstract

The adsorption, desorption, and mobility of permethrin in six tropical soils was determined under laboratory and greenhouse conditions. The six soils were selected from vegetable growing areas in Malaysia. Soil organic matter (OM) was positively correlated (r ² = 0.97) with the adsorption of permethrin. The two soils, namely, Teringkap 1 and Lating series with the highest OM (3.2 and 2.9%) released 32.5 and 30.8% of the adsorbed permethrin after four consecutive repetitions of the desorption process, respectively, compared to approximately 75.4% of the Gunung Berinchang soil with the lowest OM (1.0%) under the same conditions. The mobility of permethrin down the soil column was inversely correlated to the organic matter content of the soil. Permethrin residue penetrated only to the 10–15 cm zone in the Teringkap 1 soil with 3.2% OM but penetrated to a depth of more than 20 cm in the other soils. The Berinchang series soil with the lowest OM (1.0%) yielded leachate with 14.8% permethrin, the highest level in leachates from all the soils tested. Therefore, the possibility for permethrin to contaminate underground water may be greater in the presence of low organic matter content, which subsequently allows a higher percentage of permethrin to move downwards through the soil column.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (Kf values) generally decreased in the order: soybean-fed > corn-fed > not-fed-earthworm-castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (Koc values) was significantly greater for corn-castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean- and corn-castings treatments was always less than desorption from soil and not-fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Effect on herbicide adsorption of organic forestry waste products used for soil remediation

Organic soil amendments can be useful for improving degraded soil, but this increase in organic matter (OM) may influence adsorption of herbicides subsequently applied to the treated soil, even though the particle size of amendments and their nature differ from typical soil OM. In this study, a batch equilibrium method was used to measure adsorption of five herbicides following application to two organic media, wood pulp and sawdust, comparing these with two cropping soils. Herbicide adsorption, quantified by distribution coefficients (k_d), was much higher in the two organic media than in the cropping soils. The increases in adsorption were strongly correlated to the percentage of organic carbon. When the k_d was normalized to adsorption coefficients corrected for OM content (k_oc), variation in results between the media was greatly reduced, indicating that OM is an important factor influencing adsorption in these media. The results of this study suggest that herbicides will be less effective when applied to soils in which sawdust and wood pulp have been added. Using organic amendments to remediate soil will increase adsorption of pesticides, reducing their bio-availability and efficacy, but also reducing their tendency to leach into root zones of deep-rooted crops and into groundwater.     

Predicting radium availability and uptake from soil properties

The results of a potted soil experiment to determine the soil and plant factors ruling radium availability and uptake by ryegrass and clover are described. Nine soils with distinct soil characteristics were spiked with 226 Ra. They were thoroughly characterized and the solid liquid partitioning coefficient, Kd, was determined. Kd ranged from 38 l kg(-1) to 446 l kg(-1) (average: 188+/-156 l kg(-1)) and was linearly related to cation exchange capacity (CEC) and organic matter (OM) content. The soil-to-plant transfer factor (TF) was significantly affected by the chemical properties of the soils and ranged from 0.054 kg kg(-1) to 0.719 kg kg(-1) for ryegrass and from 0.034 kg kg(-1) to 1.494 kg kg(-1) for clover. Overall, no significant difference in TF between ryegrass and clover was observed. TF was related to Kd, to CEC, OM (for ryegrass only when excluding one soil) and the calcium concentration in the soil solution (for both plants if excluding one soil). Radium flux were calculated from the radium concentration in the soil solution and the evapotranspiration, to predict total radium uptake derived from shoot radium concentration and biomass yield. It was found that radium uptake could be predicted from the radium flux (R2=0.61 and 0.83 for ryegrass and clover, respectively). Higher predictability (R2=0.70 and 0.91 for ryegrass and clover, respectively) was obtained when relating total radium uptake to a radium flow considering competition effects at the root surface by bivalent cations.