Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Sorption and desorption of diuron on Typic Argiudoll,Oxic Argiudoll and on their clay fractions: environmental aspects

Abstract

The sorption and desorption of diuron by soil samples from Horizons A and B (HA and HB) and by their different clay fractions were investigated, using two soil samples, classified as Typic Argiudoll and Oxic Argiudoll. The sorption and desorption curves were adjusted to the Freundlich model and evaluated by parameters K_f, K_d and K_oc. Based on the data of groundwater ubiquity score (GUS), leachability index (LIX) and hysteresis index (HI), the risk of groundwater pollution was evaluated. The K_d values obtained for soil samples were between 4.5?mL g^?1 (Oxic Argiudoll – HB) and 15.9?mL g^?1 (Typic Argiudoll – HA) and between 1.13 and 14.0?mL g^?1 for the different mineral fractions, whereas the K_oc values varied between 276 (Oxic Argiudoll – HB) and 462 (Typic Argiudoll – HA). According to the parameter GUS, only Oxic Argiudoll – HB presented leaching potential, and based on the LIX index this same soil presented the highest leaching potential. Some samples presented low LIX and GUS values, indicating no leaching potential, but none presented HI results indicative of hysteresis, suggesting weak bonds between diuron and the soil samples and, hence, the risk of groundwater pollution by diuron.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

Sorption and photodegradation of chlorpyrifos on riparian and aquatic macrophytes

Surface water bodies may become contaminated via spray drift following pesticide application. In this investigation, the photodegradation and sorption of chlorpyrifos was studied in four riparian macrophytes representative of Mediterranean flora (Phragmites australis, Iris pseudacorus, Equisetum pratense and Typha latifolia). The results of experiments with both the active ingredient and the formulation DURSBAN 48® EC confirm the ability of these species to interact with chemicals such as chlorpyrifos. The maximum sorption of chlorpyrifos at equilibrium was observed in Phragmites australis (22%). And, the maximum instantaneous sorption of chlorpyrifos was observed in the dried biomass of Phragmites australis (49%). The epicuticular waxes present on leaves influence photodegradation processes, resulting in a decrease in chlorpyrifos persistence depending on the nature of the extract. The half-life of chlorpyrifos residues in leaf waxes decreased from 34 to 99 minutes when irradiated.     

有机膨润土吸附苯胺的性能及工艺条件的优化

以钙基膨润土为原料，钠化后用溴化十六烷基三甲铵（CTMAB）进行有机改性，制得有机膨润土。在单因素吸附实验的基础上，采用L16（4^4）正交实验法对有机膨润土吸附水中苯胺的工艺条件进行了优化研究。结果表明，当矿物的粒径小于74／μm、振荡速度为150r／min、吸附液为25mL，并且以此三者为固定因素时，其优化工艺条件为有机膨润土投加量2．0g，温度40℃，pH7，吸附时间1．5h。     

粘土矿物与重金属界面反应的研究进展

介绍了3种粘土吸附剂：蒙脱石、高岭石和伊利石对重金属的吸附、脱附等界面反应机理，以及粘土矿物对重金属的选择性及对吸附的影响因素。另外，还探讨了为提高其吸附性能而进行的改性方法。     

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 and Desorption of Three Endocrine Disrupters in Soils

Sorption of the estrogens estrone (E1), 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL^?1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL^?1 and reached levels ≥80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31–22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94–83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin–Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K_f.1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g^?1) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Sorption kinetic characteristics of polybrominated diphenyl ethers on natural soils

Sorption kinetic characteristics of BDE-28 and BDE-47 on five natural soils with different organic carbon fractions were investigated, and could be satisfactorily described by a two (fast and slow)-compartment first-order model with the ratio of rate constants ranged from 9 to 94 times. The fast compartment made a dominant contribution (71% ∼ 94%) to the total sorption amount in the whole process, and accounted for over 90% of the increase in the total sorption amount at initial 5 h. The influence of the slow compartment on the increase in the total sorption amount became principal (above 90%) in the subsequent stage approximately from 9 h or 25 h to the apparent equilibrium at 265 h. The results proposed the different sorption behaviors of the mathematically classified compartments for BDE-28 and BDE-47, which may correspond to the different soil components, such as soil organic fractions with amorphous and condensed structures, respectively.     

Sorption-desorption behavior of metsulfuron-methyl and sulfosulfuron in soils

Sorption of metsulfuron-methyl and sulfosulfuron were studied in five Indian soils using batch sorption method. Freundlich adsorption equation described the sorption of herbicides with K_f (adsorption coefficient) values ranging between 0.21 and 1.88 (metsulfuron-methyl) and 0.37 and 1.17 (sulfosulfuron). Adsorption isotherms were L-type suggesting that the herbicides sorption decreased with increase in the initial concentration of the herbicide in the solution. The K_f for metsulfuron-methyl showed good positive correlation with silt content (significant at p = 0.01) and strong negative correlation with the soil pH (significant at p = 0.05) while sorption of sulfosulfuron did not correlate with any of the soil parameter. Desorption of herbicides was concentration dependent and, in general, sulfosulfuron showed higher desorption than the metsulfuron-methyl. The study indicates that these herbicides are poorly sorbed in the Indian soil types and there may be a possibility of their leaching to lower soil profiles.     

生物质炭添加量对BDE-47在土壤中吸附和解吸行为的影响

研究了添加生物质炭对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中吸附和解吸行为的影响。结果表明,在受试天然土壤中添加不同量的生物质炭,土壤对BDE-47吸附能力的变化程度也将不同,当生物质炭添加量为2.0%(质量分数,下同)以下时,随着生物质炭添加量的增加,土壤对BDE-47吸附能力的提高程度越明显,BDE-47的解吸滞后性则呈现先上升后下降的趋势。当生物质炭添加量为0.1%、0.5%时,土壤单点分配系数分别为原土壤的0.98~1.39、1.02~1.50倍;当生物质炭添加量为1.0%、2.0%时,土壤单点分配系数分别为原土壤的1.44~1.68、3.25~3.27倍;生物质炭添加量为1.0%时,BDE-47的解吸滞后性最显著。     

pH和温度对2,2’,4,4’-四溴联苯醚在土壤中吸附和解吸行为的影响研究

研究了pH和温度对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中的吸附和解吸行为的影响。结果表明,pH和温度都可以影响BDE-47在受试土壤中的吸附和解吸行为。pH升高或降低均会使土壤对BDE-47的吸附能力提高,且在碱性环境中提高的程度更大;酸性或碱性条件下BDE-47在土壤中的解吸滞后性显著增强。温度降低后,土壤对BDE-47的吸附能力提高,5℃时的单点分配系数(Kd,表征土壤对BDE-47的吸附能力)是25℃时的1.03~1.67倍;温度由25℃降低到5℃后,BDE-47在土壤中的解吸滞后性增强。     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

Two-Compartment Sorption of Phenanthrene on Eight Soils with Various Organic Carbon Contents

Sorption characteristics of phenanthrene (PHE) were studied on eight soils with organic carbon contents spanning over an order of magnitude using phase distribution relationships (PDRs) at 1 h, 48 h, and 720 h contact times. A new algebraic method was employed to describe the sorption characteristics at different time intervals (between 1 h and 48 h, and 1 h and 720 h). It was found that nonlinearity increased with increasing contact time and sorption that occurred in the subsequent time interval following the initial 1 h exhibited stronger isotherm nonlinearity. Sorption coefficients were positively correlated with the organic carbon contents of the soils. Detailed sorption dynamics were also examined on these soils. A two-compartment, first-order model was used to describe the sorption dynamics. The rate constants of the two compartments differed 18–170 times, suggesting the dissimilar sorption behaviors of the mathematically separated compartments. These two compartments were labeled fast and slow sorption compartment according to the rate constants. Calculation showed that the fast compartment accounted for over 80% of the overall sorption at the initial 1 h, while the slow compartment predominated the total sorption in the following 47 h. By combining the discussion of PDRs and sorption dynamics, the contributions of the two compartments to linear and nonlinear sorption were differentiated. The slow sorption compartment made a major contribution to nonlinear sorption and possibly to sequestration of organic pollutants by these soils.     

Physical,chemical and biological behaviour of fumigants on cottonseed

Fumigation is required to protect cottonseed in storage and pre-shipment from insect pests and/or microorganisms. Fumigation of cottonseed with carbon disulphide (CS₂), carbonyl sulphide (COS), ethanedinitrile (C₂N₂), ethyl formate (EF), methyl bromide (MB) and phosphine (PH₃) showed that >85% of the fumigants disappeared within 5?h of exposure. COS maintained >20?mg L^–1 for 24?h. After 1?day of aeration, 75%–85% of the absorbed COS and MB and 20%–40% of the absorbed CS₂, EF and PH₃ were released from treated cottonseed. The fumigant residues were reduced by 80% for COS, 50% for EF or MB and 25% for CS₂ after 1?day of aeration. After 13?days of aeration, fumigant residues were reduced by 95% for MB, 65% for EF, 55% for CS₂ and to natural levels in the COS residue. Carbon disulphide, COS, PH₃, EF and C₂N₂ had no effect on the germination of cottonseed, but germination was reduced to 50% by MB. COS has potential as a fumigant for control of insect pests in cottonseed because it dissipates quickly and does not negatively impact germination. On the other hand, MB appears to strongly absorb and requires an extended period for residues to dissipate, and it negatively impacts germination.     

Evaluation of sorption-desorption processes for metalaxyl in natural and artificial soils

The main process controlling soil-pesticide interaction is the sorption-desorption as influenced by active soil surfaces. The sorption phenomena can influence translocation, volatility, persistence and bioactivity of a pesticide in soil. The present investigation was conducted on natural and artificial soils in order to enumerate the effect of soil components such as montmorillonite and ferrihydrite on the sorption behaviour of the fungicide metalaxyl and if sorption-desorption of the chiral pesticide affects the enantiomeric ratio. The sorption-desorption characteristics of metalaxyl were investigated by batch equilibration technique in a natural soil, two artificial soils, and in pure montmorillonite and ferrihydrite. After extraction, pesticide residues were analyzed by conventional and chiral chromatography using tandem mass spectrometry. A K_dSorp (2.3–6.5) suggests low level sorption of metalaxyl with an appreciable risk of run-off and leaching. Thus, metalaxyl poses a threat to surface and ground water contamination. Furthermore, desorption tests revealed a hysteretic effect (H ≤ 0.8) in natural and artificial soils. Significant amount of metalaxyl was found tightly bound to the adsorbents without desorbing readily after desorption cycle. Desorption of 22–56% of the total amount of the retained metalaxyl was determined. This study reveals that an artificial soil derived from different soil constituents can be used to assess their influence on sorption/desorption processes. The present investigation showed that both montmorillonite and ferrihydrite play a significant role in the sorption of metalaxyl. The sorption doesn't influence the enantiomeric ratio of racemic metalaxyl.     

盐碱地区沉积物磷释放特性及影响因素

为研究沉积物磷释放对盐碱地区景观水体富营养化的影响,以天津滨海新区泰达河道为对象,应用沉积物中磷形态的标准测试方法（SMT）,分析了沉积物中磷的形态;研究了沉积物中磷的解吸动力学,并探讨了水力扰动、pH和盐度对沉积物中磷解吸的影响。结果表明,无机磷（IP）为沉积物中磷的主要形态,总量为0.637 mg/g,IP中又以钙磷（Ca-P）为主,约占IP的80%,而铁/铝磷（Fe/Al-P）仅占20%。0-4 h为磷的快速解吸阶段,4-24 h为慢速解吸阶段,并逐渐达到平衡。泰达河道沉积物对磷具有一定的吸持能力,不易解吸。增强水力扰动的强度会促进磷的解吸,但影响不大;在碱性条件下,增加pH对磷的解吸没有显著影响;增加水体盐度,能促进磷的解吸。     

Sorption of the herbicides diquat and difenzoquat from aqueous medium by polymeric resins in the presence of sodium dodecylsulfate: Kinetic and mechanistic study

The goal of this work was to propose a novel method for the solid-phase extraction of the herbicides diquat (DQT²⁺) and difenzoquat (DFQT⁺) from aqueous medium using polymeric Amberlite XAD-2 and XAD-4 resins in the presence of sodium dodecylsulfate (SDS). The addition of SDS to the medium was of fundamental importance in order to allow the formation of a negatively charged surface able to sorb the cationic solutes. Several factors that could influence the sorption process, such as SDS concentration in the medium, sorbent mass, pH, ionic strength, and initial concentration of the solutes were investigated. Kinetic studies were also performed to model the system and to identify the mechanisms that operate the sorption process of the herbicides. SDS concentration in the medium presented remarkable influence on the extraction efficiency, achieving maximum values when the ratios [SDS]/[herbicide] were approximately 90, for XAD-2, and 22 and 11 for DQT²⁺ and DFQT⁺, respectively, for XAD-4. The sorption process followed a pseudo second-order kinetic in all cases studied. It was also found that an intraparticle diffusion process controlled exclusively the sorption of the herbicides by the Amberlite XAD-2 and XAD-4 resins in the first 15 min, becoming less active with time.