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.     

Fate of napropamide herbicide in selected Malaysian soils

This study was carried out to determine the sorption-desorption, degradation and leaching of napropamide in selected Malaysian soils. The sorption capacities of the selected Malaysian soils for napropamide were the following in descending order: Linau > Teringkap > Gunung Berinchang > Jambu > Rudua > Baging soil. The results indicate that napropamide degradation decreased with increasing soil sorption capacity. Napropamide was leached out earlier in the Baging soil than the other soils. Overall, the application of napropamide in the selected Malaysian soils would not pose a threat to the environment except in soil with low organic matter and clay content and high hydraulic conductivity, such as the Baging 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.     

Comparison of batch, stirred flow chamber, and column experiments to study adsorption, desorption and transport of carbofuran within two acidic soils

Different methods (batch, column and stirred flow chamber experiments) used for adsorption and desorption of carbofuran studies were compared. All tested methods showed that the carbofuran adsorption was higher in the soil with the higher organic matter content, whereas the opposite behaviour was observed for the percentage of carbofuran desorbed. However, different methods have revealed some discrepancies in carbofuran adsorption/desorption kinetics. Although batch method showed interesting data on equilibrium experiments, such as a low heterogeneity for the carbofuran adsorption sites independent of soil organic matter content, it had some disadvantages for carbofuran adsorption/desorption kinetic studies. The disadvantages were related with the excessive limitations of this method on kinetics, i.e., no difference could be detected between different soils. However, with column and stirred flow chamber methods the carbofuran adsorption/desorption kinetics of different soils could be compared. Moreover, the absolute values of carbofuran adsorption/desorption and its rate were higher in the stirred flow chamber than in the batch and column experiments. Using stirred flow chamber experiments the carbofuran desorption was significantly faster than its adsorption, whereas carbofuran using column experiments they were similar. These discrepancies should be considered when the results obtained only with one method is discussed.     

Sorption of 2,4-D on Natural and Organic Amended Soils of Different Characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unamended soils. In contrast, the ST soil showed the largest adsorption for unamended soil.     

Sorption of 2,4-d on natural and organic amended soils of different characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unammended soils. In contrast, the ST soil showed the largest adsorption for unammended soil.     

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 of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

Mobility of adsorbed arsenic in two calcareous soils as influenced by water extract of compost

The mobility of arsenic (As) in soil affects both the bio-toxicity of As and the groundwater quality, which in turn indirectly affects the quality of edible part of crops and human health, if the crops were irrigated with As contaminated groundwater. A vertical soil column simulates the depth of a soil profile in a real soil environment. Thus soil column experiment is much more pertinent to soil environment than a batch experiment to simulate solute movement as well as leaching through soil profile. A laboratory soil column experiment was conducted to determine the extent of As leaching from soil percolated with influent that contained organic substances. The water extract of compost (WEC) was used as the source of organic substances. The results of As breakthrough curves (BTCs) showed that less pore volumes of influents were required to reach the relative concentration ratio of 1 (C/C0=1) for the two calcareous soils treated with influent that contained WEC. The concentrations of As in the column effluents of soils percolated with 0.01M KCl in WEC were significantly higher than those percolated with 0.01M KCl with the same volumes of effluents collected. This clearly indicates that dissolved as well as deprotonated organic substances which are negatively charged have higher potential for competing the adsorption sites with As on soils, leading to increasing mobility of As in soil and associated environments. Further, it is observed that the characteristics of soil components related to As adsorption affected the adsorption as well as desorption processes and subsequent mobility of As in soil environment as influenced by organic substances.     

Effects of thermal desorption on the composition of two coking plant soils: impact on solvent extractable organic compounds and metal bioavailability

To evaluate the efficiency and the influence of thermal desorption on the soil organic compartment, contaminated soils from coking plant sites (NM and H) were compared to their counterparts treated with thermodesorption. The extractable organic matter, and the metal content and distribution with soil compartments were studied.In both thermodesorbed soils, PAH (polycyclic aromatic hydrocarbon) degradation exceeded 90%. However, the thermal desorption led not only to a volatilization of the organic compounds but also to the condensation of extractable organic matter.The treatments only affected the Fe and Zn distribution within the more stable fractions, whereas the organic compound degradation did not affect their mobility and availability.     

Hexazinone and simazine dissipation in forestry field nurseries

Hexazinone and simazine field dissipation was studied in two different soils from Spain (Toledo and Burgos), devoted to forest nurseries for Pinus nigra. Laboratory experiments (adsorption-desorption isotherms, leaching experiment and degradation study) were carried out to determine possible mechanisms of dissipation. Higher adsorption was observed for hexazinone in Toledo (KfT = 0.69) compare to in Burgos soil (KfB = 0.20) probably due to the higher organic matter (OM) content of Toledo soil. No differences in adsorption were obtained for simazine in both soils (KfT = 1.27; KfB = 1.34). In every case, adsorption was higher for simazine than for hexazinone, in both soils. The total recovery of hexazinone in the leachates from handpacked soil columns was higher in Burgos (100%) than in Toledo (80%), because of the larger adsorption of hexazinone in this last soil. No differences in simazine leaching between both soils were found, although the total amount of pesticide recovered in leachates (40% in the two soils) was lower for simazine than for hexazinone. Finally, lower degradation was found in Burgos (t1/2 = 91 d) vs Toledo (t1/2 = 47 d), directly related with the high OM content of Toledo. No half-life was calculated for simazine in Toledo because no changes in herbicide soil content were observed during the period of time studied. In the case of Burgos, the half-life for simazine was 50 days. The field residues study showed larger persistence of simazine than hexazinone mainly due to the higher adsorption and lower mobility of simazine in the two soils. The lower persistence of hexazinone in Toledo soil than in Burgos soil is related to the larger rainfall occurred in this soil besides the higher degradation of this herbicide observed in Toledo soil. The much lower temperature in Burgos than in Toledo soil during winter contribute to the higher persistence of the two herbicides in Burgos soil.     

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers’ breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils’ hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.     

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption–desorption through column experiments

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.     

Adsorption of arsenate on soils. Part 2: modeling the relationship between adsorption capacity and soil physiochemical properties using 16 Chinese soils

An attempt has been made to elucidate the effects of soil properties on arsenate adsorption by modeling the relationships between adsorption capacity and the properties of 16 Chinese soils. The model produced was validated against three Australian and three American soils. The results showed that nearly 93.8% of the variability in arsenate adsorption on the low-energy surface could be described by citrate-dithionite extractable Fe (Fe(CD)), clay content, organic matter content (OM) and dissolved organic carbon (DOC); nearly 87.6% of the variability in arsenate adsorption on the high-energy surface could be described by Fe(CD), DOC and total arsenic in soils. Fe(CD) exhibited the most important positive influence on arsenate adsorption. Oxalate extractable Al (Al(OX)), citrate-dithionite extractable Al (Al(CD)), extractable P and soil pH appeared relatively unimportant for adsorption of arsenate by soils.     

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.     

Leaching of terbumeton and terbumeton-desethyl from mini-columns packed with soil aggregates in laboratory conditions

Leaching of terbumeton (TER) and terbumeton-desethyl (TED) from mini-columns packed with natural soil aggregates was investigated. Five soil samples from the Champagne area (France) with different physicochemical parameters were used. The soil samples were hand-packed into a 50 mm column in laboratory conditions. An aqueous solution of TER or TED was percolated through the column and collected effluents were analyzed for TER or TED using HPLC-DAD. The leaching experiments showed that TER and TED were moderately mobile. TED was more mobile than TER, possibly because of its higher polarity. The proportion of organic matter affected the mobility of TER and TED through soil columns (r=0.971) and leaching was lowest for soil having the highest organic matter content (5.9%). TER and TED were not significantly influenced by leaching solution composition (deionized water or CaCl(2) solution), but were strongly affected by soil packing. Packing resulted in less rapid release of compounds suggesting that unpacking may have contributed to preferential pathways through the soil columns. Increasing contact time between TER and soils before leaching decreased the mobility of TER and increased its persistence in soils. Indeed, 76% of TER was released when leaching started after a 15 h contact time whereas it was down to 26% after an aging treatment of 360 h. A proportion of TER (from 8% to 32%) and TED (from 8% to 17%) remained in soil. Associated to its high stability in soils this could in part account for a very slow transfer over the years towards the groundwater.     

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil

Laboratory studies were conducted to characterise four different antibiotic compounds with regard to sorption and mobility in various soil types. Distribution coefficients (Kd values) determined by a batch equilibrium method varied between 0.5 and 0.7 for metronidazole, 0.7 and 1.7 for olaquindox and 8 and 128 for tylosin. Tylosin sorption seems to correlate positively with the soil clay content. No other significant interactions between soil characteristics and sorption were observed. Oxytetracycline was particularly strongly sorbed in all soils investigated, with Kd values between 417 in sand soil and 1026 in sandy loam, and no significant desorption was observed. Soil column leaching experiments indicated large differences in the mobility of the four antibiotic substances, corresponding to their respective sorption capabilities. For the weakly adsorbed substances metronidazole and olaquindox the total amounts added were recovered in the leachate of both sandy loam and sand soils. For the strongly adsorbed oxytetracyline and tylosin nothing was detected in the leachate of any of the soil types, indicating a much lower mobility. Results from defractionation and extraction of the columns (30 cm length) showed that 60-80% of the tylosin added had been leached to a depth of 5 cm in the sandy loam soil and 25 cm in the sand soil.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.