Sorptive behavior of the phenylamide fungicides,mefenoxam and metalaxyl,and their acid metabolite in typical Cameroonian and German soils

Laboratory soil sorption experiments were conducted on mefenoxam, formulated metalaxyl (F-metalaxyl), pure metalaxyl (P-metalaxyl) and metalaxyl acid metabolite to elucidate differences in their sorptive behaviour on typical Cameroonian forest soil (sand clay loam, pH 4.8 and 3.01% OC) and German soil (sandy loam, pH 7.2, 1.69% OC) using a batch equilibrium method. The data obtained on all test chemicals conformed to linear and Freundlich adsorption isotherms. The Langmuir equation failed to describe the sorption of the substances tested. All substances were adsorbed to a greater extent by the Cameroonian soil. The average percentage adsorptions for mefenoxam, F-metalaxyl, P-metalaxyl and the acid metabolite on the Cameroonian soil were 27.8%, 28.3%, 31.8% and 46.8% respectively while for the German soil they were 21.7%, 21.5%, 24.7% and 9.8% respectively. The KD and KF parameters and the Freundlich exponential term (1/n) were low, indicating that the interactions between soil particles and the fungicides were weak. The sorption parameters were lower in the German soil. P-metalaxyl exhibited a higher adsorption capacity than F-metalaxyl in both soils. Mefenoxam and F-metalaxyl exhibited similar sorption parameters in soils, whereas those of P-metalaxyl and acid metabolite differed. Differences observed in the adsorption between the two soils could be attributed to their properties. Desorption studies revealed that the adsorbed fungicides were not firmly retained by soil particles and their adsorption was reversible. Desorption of adsorbed mefenoxam, P-metalaxyl and of the acid metabolite from German soil was almost completely reversible with percentage desorption rates of more than 91.0%, whereas the rate for F-metalaxyl was 74.1%. All compounds exhibited some resistance to desorption from the Cameroonian soil, with percentage desorption rates less than 77.0%. Therefore if degradation in the soil is slow the fungicides described have a potential to leach to lower soil horizons.     

PAH desorption from river floodplain soils using supercritical fluid extraction

Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (ρ < 2 g cm⁻³), and <63 μm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of “slow” and “very slow” desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.     

Adsorption and desorption processes of MCPA in Polish mineral soils

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.     

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.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.     

Adsorption and desorption characteristics of hydrophobic pesticide endosulfan in four Indian soils

Adsorption and desorption characteristics of endosulfan in four Indian soils were studied extensively. The soils used were clayey soil (CL--lean clay with sand), red soil (GM--silty gravel with sand), sandy soil (SM--silty sand with gravel) and composted soil (PT--peat) as per ASTM (American Society for Testing and Materials) standards. Adsorption and desorption rates were calculated from kinetic studies. These values varied for alpha and beta endosulfan depending on the soil type. Maximum specific adsorption capacities (qmax) for different soils were calculated by Langmuir model. The values varied from 0.1 to 0.45 mg g(-1) for alpha endosulfan and 0.0942-0.2722 mg g(-1) for beta endosulfan. Maximum adsorption took place in clay soil followed by composted soil and red soil. Adsorptions of alpha and beta endosulfan were negligible in sand. The binding characteristics of various functional groups were calculated using Scatchard plot. Effect of functional groups was more predominant in clayey soil. Organic matter also played a significant role in adsorption and desorption of endosulfan. Endosulfan adsorption decreased drastically in clay soil when the pH was reduced. Desorption was higher at both acidic and alkaline pH ranges compared to neutral pH. Results indicated that alpha endosulfan is more mobile compared to beta endosulfan and mobility of endosulfan is maximum in sandy soil followed by red soil. It can be inferred that crystal lattice of the clay soil plays a significant role in endosulfan adsorption and desorption. Immobilization of endosulfan is more advisable in clay soil whereas biological and or chemical process can be applied effectively for the remediation of other soil types.     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

Sorption kinetics of chlorinated hydrophobic organic chemicals

This is the second of a two-part series describing the sorption kinetics of hydrophobic organic chemicals. Part I “The Use of First-Order Kinetic Multi-Compartment Models” is published in issue 1 of this journal, pp. 21–28. Sorption kinetics of chlorinated benzenes from a natural lake sediment have been investigated in gas-purge desorption experiments. Biphasic desorption curves, with an initial “fast” part and a subsequent “slow” part, were found for all tested chlorobenzenes. From these results first-order sorption uptake and desorption rate constants were calculated with a two-sediment compartment model, which is presented in the first paper. In three sets of experiments the sorption uptake period and sediment/water ratio were varied. Rate constants are not influenced by these experimental conditions, which supports the partitioning concept for the sorption of hydrophobic organic chemicals in sediments.     

Study on the kinetics of cerium(III) adsorption-desorption on different soils of China

The kinetics of Ce(III) adsorption-desorption on four typical soils in China has been studied by using the batch method with the radioactive nuclide 141Ce. Results indicated that Ce(III) adsorption was rapid and nearly finished in less than 0.5 min. Desorption procedure was about completed in 1-30 min in the tested soils. Ce(III) desorption equilibrium times vary with different soils. The amounts of Ce(III) desorption on different soils in the same time were different. The Elovich equation proved to be the best models for fitting the data of Ce(III) desorption reactions in fluvo-aquic soil and black soil; and the parabolic-diffusion equation was the best model in red earth and loess soil.     

Adsorption, desorption, soil mobility and aqueous persistence of fensulfothion and its sulfide and sulfone metabolites

Soil/water interactions with the insecticide fensulfothion and its sulfide and sulfone metabolites and described. Adsorption to, and desorption from four soils were studied. There was a general inverse relationship between water solubilities of the three chemicals and their adsorption K values. Order of adsorption was f. sulfide greater than f. sulfone greater than fensulfothion. Adsorption K values correlated significantly with soil organic content. Desorption of fensulfothion and the sulfone were similar whereas the less soluble sulfide desorbed to a lesser extent. To facilitate comparison of desorption tendencies of the three compounds of desorption index was developed. Mobilities through the soils were directly related to the water solubilities of the three chemicals. Mobilities in decreasing order were - fensulfothion greater than f. sulfone greater than f. sulfide. Persistence of fensulfothion was similar in both sterile and non-sterile natural water - about 50% remaining at the end of the 16 wk experiment. Under reducing conditions fensulfothion disappeared from water in 8-12 wk with almost complete conversion to the sulfide.     

Effect of wheat and rice straw biochars on pyrazosulfuron-ethyl sorption and persistence in a sandy loam soil

The objective of this research was to investigate the effect of wheat and rice biochars on pyrazosulfuron-ethyl sorption in a sandy loam soil. Pyrazosulfuron-ethyl was poorly sorbed in the soil (3.5–8.6%) but biochar amendment increased the herbicide adsorption, and the effect varied with the nature of the feedstock and pyrolysis temperature. Biochars prepared at 600°C were more effective in adsorbing pyrazosulfuron-ethyl than biochars prepared at 400°C. Rice biochars were better than wheat biochars, and higher herbicide adsorption was attributed to the biochar surface area/porosity. The Freundlich constant 1/n suggested nonlinear isotherms, and nonlinearlity increased with increase in the level of biochar amendment. Desorption results suggested sorption of pyrazosulfuron-ethyl was partially irreversible, and the irreversibility increased with increase in the level of biochar. Both sorption and desorption of pyrazosulfuron-ethyl correlated well with the content of biochars. The free energy change (ΔG) indicated that the pyrazosulfuron-ethyl sorption process was exothermic, spontaneous and physical in nature. Persistence studies indicated that biochar (0.5%) amendment did not have significant effect on herbicide degradation, and its half-life values in the control, 0.5% WBC600- and RBC600-amended rice planted soils were 7, 8.6, and 10.4 days, respectively.     

Desorption of chlorinated hydrocarbons from spiked and anthropogenically contaminated sediments

The desorption of 20 chlorinated organics from sediments has been studied using a nitrogen purge/Tenax trap system for separating the “dissolved” and “sorbed” fractions in sediment/water slurries. The desorption partition coefficient, K_D, was found to decrease with increasing temperature and suspended sediment concentration. While some differences in K_D and desorption rates were observed for the study chemicals, considering their wide range of physical/chemical properties such as K_OW, these changes were small. Desorption half-lives averaged about 60d at 4°C, 40d at 20°C and 10d at 40°C under continuous gaseous purging. Estimates of the loadings of chemicals via desorption from bottom sediments in Lake Ontario are compared to loadings of these chemicals to the lake from the Niagara River.     

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.     

弱碱性树脂吸附-解吸苦味酸

考察了水中苦味酸在弱碱性离子交换树脂D301R上的吸附与解吸。研究了吸附热力学、动力学特性及吸附机理。结果表明,树脂在pH=2.7～10.2时,吸附能力最好。等温平衡吸附遵循Freundlich模型。吸附过程为吸热、熵增的自发过程。吸附动力学符合Lagergren准二级速率方程,颗粒内扩散为吸附速率的主要控制步骤,吸附速率常数为7.23×10-5～1.20×10-4g/(mg.min),吸附活化能为19.4 kJ/mol。树脂上吸附的苦味酸可用HNO3+丙酮混合液定量洗脱,洗脱率达99%。静态吸附和脱附的比较结果证实了吸附过程中存在不可逆化学吸附。树脂对苦味酸的吸附主要是通过静电吸附、酸碱络合吸附、氢键吸附等协同作用来完成的。     

Temperature effects on chlorinated-benzene sorption to hydrophobic surfaces

Sorption and desorption of chlorinated benzenes were investigated in a series of column experiments using porous silica that had phenyl groups bonded to the surface; the mass-fraction organic carbon was 0.016. Both sorption and desorption curves were asymmetrical, but they were mirror images of each other for most experiments, indicating good sorption reversibility. The resulting breakthrough curves were fit to an advection-dispersion mathematical model, with sorption as a first-order, reversible reaction. Significantly greater tailing in the chlorinated-benzene breakthrough curves versus the salt-tracer ones was evidence of slow sorption and desorption. ΔH° values for di-, tri- and tetra-chlorobenzene were 13–21 kJ mol₋₁, indicative of strong van der Waals binding. Despite these small values, slow desorption was attributed to slow binding and release rather than diffusion through the bonded organic phase. Desorption rates decreased in going from di- to tri- to tetra- to penta-chlorobenzene. This decrease was significantly more than the decrease in molecular-diffusion coefficients in the same series, suggesting a chemical rather than a physical rate control. There was less difference in sorption rates through the series, suggesting an inverse relation between partition coefficient and desorption rate. ΔG° values were −17 to −23 kJ mol⁻¹, giving TΔS° values of about 4 kJ mol⁻¹. Thus enthalpic contributions to sorption appear to be of greater importance than entropic contributions.     

Some models for the adsorption kinetics of pesticides in soil

Abstract

Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, The first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a numerical solution for local equilibration were compared. Concentration‐time relationships for the solution and adsorbed phases were calculated for different rate constants, initial conditions, and partition ratios at equilibrium. The second model described simultaneous adsorption‐desorption equilibration with two mechanisms, both with their own rate constants. After a comparatively fast equilibration with the first mechanism, there was a gradual increase in extent of overall‐adsorption, accompanied with a shift to greater amounts adsorbed by the second mechanism. With the third model, adsorption equilibration occurred by diffusion into a stagnant region. With diffusion distances ranging from 0.1 to 4.0 cm, the time needed for approach to adsorption equilibrium varied from about 0.25 days to about one year. Some of the possibilities of these models were discussed considering published experimental results.     

Modeling the effects of concentration history on the slow desorption of trichloroethene from a soil at 100% relative humidity

To determine the effects of concentration history on slow sorption processes, desorption kinetic profiles for trichloroethene (TCE) were measured for a soil at 100% relative humidity subject to different exposure concentrations and exposure times. Exposure concentrations ranged from 1% to 80% of the saturation vapor pressure (Ps) for TCE, and exposure times (i.e., time allowed for sorption before desorption begins) ranged from 1 to 96 days. A spherical diffusion model based on a gamma distribution of sorption rates and a gamma distribution of desorption rates was developed and applied to the data. At 80% P/Ps, the entire gamma distributions of sorption and desorption rates were available for TCE. In accordance with a micropore filling mechanism, the fraction of these distributions available for TCE sorption decreased with decreasing P/Ps. Experimental results are consistent with a micropore-filling mechanism, where the amount of slow desorbing mass decreased with decreasing exposure time, and the fraction of slow desorbing sites filled decreased with decreasing exposure concentration. Simulation results suggest that diffusion limits the rates that micropores fill, and that rates of sorption and desorption for soil contaminated at smaller values of P/Ps are, on average, less than those at larger values of P/Ps (i.e., slow desorption rates are a function of exposure concentration). Simulation results also suggest that the model adequately describes the effects of exposure concentration and exposure time on the rates of sorption and desorption, but not on the capacity of the slow sites for TCE. This work is important because contaminant concentrations in the subsurface vary in space and time, and the proposed model represents a new and mechanistically based approach to capture the effects of this heterogeneity on slow desorption.     

BDE-47 sorption and desorption to soil matrix in single- and binary-solute systems

Three loamy-clay soil samples (LC1-3) with different properties were collected as the geosorbents to preliminarily investigate the sorption and desorption of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in single system and binary system with the presence of decabromodiphenyl ether (BDE-209), which can provide information in order to further understand the sorption mechanisms and evaluate the adsorption sites. A concentration of 10 μg L⁻¹ BDE-209 suppressed the sorption of BDE-47, and the trend became more and more significant with the increase of BDE-47 equilibrium concentration, however, BDE-47 caused no competitive effect on BDE-209 sorption, which was related with the better accessibility of more hydrophobic molecules to adsorption sites. In the binary system, nonlinearity of the BDE-47 sorption isotherms for the three samples changed in different ways, which originated from the varied soil properties. Desorption hysteresis was observed in all cases, which was estimated due to irreversible surface adsorption between sorbent and sorbate. BDE-209 made desorption of BDE-47 more hysteretic from soil samples, which was estimated to be ascribed to the accelerated sorbent state transition and new sites creation caused by BDE-209 sorption.     

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.     

Immobilization of pentachlorophenol in soil using carbonaceous material amendments

In this study, three pentachlorophenol (PCP) laboratory-spiked and one field-contaminated soil were amended with 2.0% char, humic acid (HA) and peat, respectively. The amended soils were aged for either 7 or 250 days. After amendment, CaCl₂ extractability of PCP was significantly decreased. Desorption kinetics indicated that the proposed amendment could lead to a strong binding and slow desorption of PCP in soils. Amendment with char reduced the bioaccumulation factor (BAF) of PCP most significantly for earthworms (Eisenia fetida) in all soils studied. The results of both physicochemical and biological tests suggested that amendment reduced PCP bioavailability quickly and enduringly, implying that carbonaceous material amendment, especially char amendment, was a potentially attractive in situ remediation method for sequestration of PCP in contaminated soil.