Effect of surfactants at low concentrations on the sorption of atrazine by natural sediment.

A series of experiments were carried out to determine the effect of surfactants at low concentrations on the sorption of atrazine by natural sediments. With surfactant concentrations ranging from 0 to 20 mg/ L, anionic and cationic surfactants appreciably reduce the adsorption of atrazine, while nonionic surfactant decreases the adsorption of atrazine at concentrations equal to or less than 1 mg/L and increases adsorption at higher concentrations. Desorption of atrazine in the presence of different sodium dodecylbenzene sulfonate (SDBS) concentrations shows that a portion of the bound pesticide resists desorption in the SDBS free system. However, the addition of SDBS accelerates the desorption of atrazine. Furthermore, the nature of sediment and the contacting sequence of SDBS, at 10 mg/L, with the sediment, also influence the adsorption of atrazine. The conclusions in this study could be explained partially by the effect of the type and concentration of surfactants and the characteristics of sediments.     

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.     

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.     

Mobility of atrazine from alginate-bentonite controlled release formulations in layered soil

The mobility of atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine] from alginate-bentonite-based controlled release (CR) formulations was investigated by using soil columns. Two CR formulations based on sodium alginate (14.0 g kg(-1), atrazine (6.0 g kg(-1), natural or acid-treated bentonite (50 g kg(-1), and water (924 g kg(-1) were compared to technical grade product and commercial liquid (CL) formulation (Gesaprim 500FW). All herbicide treatments were applied to duplicate layered bed systems simulating the typical arrangement under a plastic greenhouse, which is composed of sand (10 cm), peat (2 cm), amended soil (20 cm) and native soil (20 cm). The columns were leached with 39 cm (1500 ml) and 156 cm (6000 ml) of 0.02 M CaCl2 solution to evaluate the effect of water volume applied on herbicide movement. When 39 cm of 0.02 M CaCl2 solution was applied, there was no presence of herbicide in the leachate for the alginate-bentonite CR treatments. However, 0.11% and 0.14% of atrazine appeared in the leachate when the treatment was carried out with technical grade and CL formulations, respectively. When 156 cm of 0.02 M CaCl2 solution was applied, the use of the alginate-acid treated bentonite CR formulation retards and reduces the presence of atrazine in the leachate as compared to technical product. Analysis of the soil columns showed the highest atrazine concentration in the peat layer. Alginate-bentonite CR formulations might be an efficient system for reducing atrazine leaching in layered soil and thus, it could reduce the risks of pollution of groundwater.     

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.     

Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.     

Behavior of Chlorpyrifos-methyl in soil and sediment

This research was carried out with the aim of obtaining information regarding the possible environmental impact of Chlorpyrifos-methyl, an organophosphoric insecticide used in agriculture for its phytoiatric action against Hemiptera, Lepidoptera, Coleoptera, and Diptera. Studies relating to the degradation kinetics of the insecticide in two soils and one sediment have shown a rapid degradation process in all three. The prevalent form of degradation would appear to be the chemical type, because the degradation kinetics in a sterile soil have not demonstrated that micro-organisms play a significant part. The adsorption isotherms showed that the insecticide has a greater affinity for the sediment (Kf=143) as opposed to the soils (Kf=65) and that the adsorption process is practically irreversible. Moreover, hydrolysis tests in buffered solutions at pH 4, 7, and 9 revealed that the molecule is particularly unstable with a basic pH.     

Assessment of adsorption behavior of dibutyltin (DBT) to clay-rich sediments in comparison to the highly toxic tributyltin (TBT)

The sorption behavior of dibutyltin (DBT) to four types of natural clay-rich sediments as a function of pH and salinity was studied. The strongest affinity of DBT was found to the montmorillonite-rich sediment, which is characterized by the highest specific surface area and cation exchange capacity of the four used sediments. Kd values range between 12 and 40 (l/kg) on simulated marine conditions (pH 8, salinity 32%). A maximum of DBT adsorption was found at a salinity of 0% and pH 6. Desorption occurred over the entire studied pH range (4-8) when contaminated sediments interact with butyltin-free water. The maximum of desorption coincided with the minimum of adsorption, and vice versa. The results of DBT adsorption are compared with tributyltin (TBT), and the mechanism of the adsorption process is discussed.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

Effects of ionic strength and temperature on adsorption of atrazine by a heat treated kerolite

The adsorption of 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on a heat treated kerolite sample at 600 degrees C (K-600) from pure water solution at 10 degrees C, 25 degrees C and 40 degrees C has been studied. The influence of the presence of 0.1 M KCl in the medium was also investigated for a better understanding of variables affecting the adsorption of this herbicide. The experimental adsorption data points were fitted to the Langmuir equation in order to calculate the adsorption capacities (Xm) of the samples; Xm values range from 2.3x10(3) mg kg-1 (pure water solution at 40 degrees C) up to 15.2x10(3) mg kg-1 (0.1 M KCl solution at 10 degrees C). The adsorption data were also fitted to the Freundlich equation in order to clarify the influence of the presence of 0.1 M KCl on atrazine adsorption. The parameter K10 obtained from this equation (adsorption capacity at an equilibrium solution concentration of atrazine equal to 10 mg l-1) shows clearly that the presence of 0.1 M KCl in the medium tends to increase the adsorption of atrazine in the range of temperature studied. The adsorption experiment also showed that the lower temperature, the more effective the adsorption of atrazine from both, pure water and 0.1 M KCl solutions. The values of the removal efficiency (R) obtained ranged from 39% at 40 degrees C (pure water solution) up to 93% at 10 degrees C (0.1 M KCl solution).     

Removal of congo red from aqueous solution by bagasse fly ash and activated carbon: kinetic study and equilibrium isotherm analyses

Present investigation deals with the utilisation of bagasse fly ash (BFA) (generated as a waste material from bagasse fired boilers) and the use of activated carbons-commercial grade (ACC) and laboratory grade (ACL), as adsorbents for the removal of congo red (CR) from aqueous solutions. Batch studies were conducted to evaluate the adsorption capacity of BFA, ACC and ACL and the effects of initial pH (pH(0)), contact time and initial dye concentration on adsorption. The pH(0) of the dye solution strongly affected the chemistry of both the dye molecules and BFA in an aqueous solution. The effective pH(0) was 7.0 for adsorption on BFA. Kinetic studies showed that the adsorption of CR on all the adsorbents was a gradual process. Equilibrium reached in about 4h contact time. Optimum BFA, ACC and ACL dosages were found to be 1, 20 and 2 g l(-1), respectively. CR uptake by the adsorbents followed pseudo-second-order kinetics. Equilibrium isotherms for the adsorption of CR on BFA, ACC and ACL were analysed by the Freundlich, Langmuir, Redlich-Peterson, and Temkin isotherm equations. Error analysis showed that the R-P isotherm best-fits the CR adsorption isotherm data on all adsorbents. The Freundlich isotherm also shows comparable fit. Thermodynamics showed that the adsorption of CR on BFA was most favourable in comparison to activated carbons.     

A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils

Batch adsorption and desorption experiments were performed using thirteen agricultural soil samples and five pesticides. Experimental data indicated a gradient in pesticide adsorption on soil: trifluralin > 2,4-D > isoproturon> atrazine > bentazone. Atrazine, isoproturon and trifluralin adsorption were correlated to soil organic matter content (r2 = 0.7, 0.82, 0.79 respectively). Conversely, bentazone adsorption was governed by soil pH (r2 = 0.68) while insignificant effect has been shown in the case of 2,4-D. Multiple linear regressions were used to combine relationships between the various soil parameters and the Freundlich adsorption coefficient (K(f)) of each pesticide. Then desorption was assessed since it may reflect some of the interactions involved between the pesticides and the soil components. Adsorbed molecules were released into aqueous solution in the following order: bentazone > atrazine> isoproturon> 2,4-D > trifluralin. The occurrence of hysteresis did not allow an accurate interpretation of the pesticide desorption data because of the possible interplay of several processes.     

凹凸棒粘土对水中亚甲蓝的吸附性能

用焦磷酸钠和盐酸纯化了地产凹凸棒粘土,SEM、XRD和FT-IR表征其结构。研究了凹凸棒粘土对亚甲蓝的吸附性能及热力学和动力学特征,考察了吸附时间、温度、初始浓度、pH和离子强度下对亚甲蓝吸附的影响。结果表明,不同实验条件下,吸附过程均符合准二级动力学特征。凹凸棒粘土对亚甲蓝是放热的物理吸附过程,吸附符合Langmuir模式,在303 K时最大吸附量为114.02 mg/g。与其他吸附材料相比,凹凸棒粘土对亚甲蓝有较快的吸附速率和较大的吸附量,可以作为价廉的吸附剂用于亚甲蓝的消除。     

Impact of coexistence of carbendazim, atrazine, and imidacloprid on their adsorption, desorption, and mobility in soil

The effect of coexisting pesticide on adsorption/desorption and mobility of another one was investigated with carbendazim (CBD), imidacloprid (IDP), and atrazine (ATR). The data indicated that adsorption of CBD, ATR, and IDP on the tested soil was fitted well by Freundlich equation and increased with an order of IDP < ATR ? CBD. Adsorption of a pesticide was decreased by the coexistence of another one through their competitive adsorption. The presence of coexisting solute of the more adsorbability played a more important role than that of the lesser adsorbability. The adsorption of IDP and ATR was easier to be affected by 28.9–52.0 % and 31.1–60.7 % with the addition of CBD, while that of CBD was much less influenced by 3.4–18.1 % and 6.9–31.8 % with the presence of ATR and IDP, respectively. An adsorbability-related enhancement in desorption of the three pesticides by the co-adsorbed solute was also observed. As a result of competitive adsorption/desorption, the mobility of the pesticides estimated from soil thin-layer chromatography was altered. The results clearly illustrated that adsorbability and concentration-related alteration in adsorption/desorption and mobility will be caused by the coexistence of pesticides.     

Artificial neural network (ANN) modeling of adsorption of methylene blue by NaOH-modified rice husk in a fixed-bed column system

In this study, rice husk was modified with NaOH and used as adsorbent for dynamic adsorption of methylene blue (MB) from aqueous solutions. Continuous removal of MB from aqueous solutions was studied in a laboratory scale fixed-bed column packed with NaOH-modified rice husk (NMRH). Effect of different flow rates and bed heights on the column breakthrough performance was investigated. In order to determine the most suitable model for describing the adsorption kinetics of MB in the fixed-bed column system, the bed depth service time (BDST) model as well as the Thomas model was fitted to the experimental data. An artificial neural network (ANN)-based model was also developed for describing the dynamic dye adsorption process. An extensive error analysis was carried out between experimental data and data predicted by the models by using the following error functions: correlation coefficient (R ²), average relative error, sum of the absolute error and Chi-square statistic test (χ ²). Results show that with increasing bed height and decreasing flow rate, the breakthrough time was delayed. All the error functions yielded minimum values for the ANN model than the traditional models (BDST and Thomas), suggesting that the ANN model is the most suitable model to describe the fixed-bed adsorption of MB by NMRH. It is also more rational and reliable to interpret dynamic dye adsorption data through a process of ANN architecture.     

Tributyltin partitioning in sediments: effect of aging

The effect of aging on the solid/pore-water partitioning and desorption behaviour of tributyltin (TBT) in sediments was examined. Three sediment samples with contrasting physical and chemical properties were spiked with 10 mg/kg TBT and aged under sterile conditions for periods of time ranging from 1 to 84 days. Aging had a negligible effect on partitioning and desorption behaviour in a sandy sample with very low organic carbon content (0.2% w/w). In contrast, for samples with larger amounts of organic carbon (2.6% and 4.8% w/w), aging caused substantial increases in TBT sorption. For these samples, apparent distribution coefficients (KD,app) obtained from sequential 2 h desorption experiments also exhibited a twofold increase between spiked sediments subjected to aging for 1 day and 84 days. This study demonstrates that aging effects may be an important aspect of TBT fate in contaminated sediments.     

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.     

Formation of shaped barium sulfate-dye hybrids: waste dye utilization for eco-friendly treatment of wastewater

Purpose

Owing to the present complexity and difficulty of concentrated dye wastewater treatment, this work aimed to synthesize a reproducible waste-sorbing material for the treatment of wastewater by forming the dye-conjugating complex hybrid.

Methods

The inorganic/organic hybridization was applied to prepare the objective material by immobilizing waster dye-Mordant blue 9 (MB) with barium sulfate (BaSO₄). The composition and pattern of the formed material were determined by spectrometry and characterized by SEM and XRD, and their formation process was clarified. The adsorption of cationic dye-basic blue BO (BB) and copper ion was investigated..

Results

The hybrid of MB alone into growing BaSO₄ formed the pineapple-like particles while that of the MB/BB-conjugating complex was the rhombus material. The adsorption of BB on the MB–BaSO₄ hybrid was probably attributed to ion-pair equilibrium and that of Cu²⁺ may result from the complexation. The treatment of dye and heavy metal wastewaters indicated that the MB hybrid material removed 99.8% BB and 97% Cu²⁺ and the dye-conjugating hybrid with growing BaSO₄ 100% MB, 99.5% BB, and 44% Cu²⁺.

Conclusion

The waste MB–BaSO₄ hybrid material is efficient to treat cationic dye and Cu²⁺ wastewater. The dye-conjugating hybridization method is the first to be advanced for in situ wastewater treatment, and it showed a combined effect for the removal of both organic dyes and heavy metals.     

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.     

Effects of zero-valent iron (Fe0) and temperature on the transformation of DDT and its metabolites in lake sediment

Zero-valent iron improves the transformation of DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] and its metabolites in aged and highly contaminated lake sediment under biotic conditions. The addition of Fe0 has a strong effect on transformation rates at 22 degrees C and 9 degrees C, the most enhanced degradation being obtained for DDT and DDOH [2,2-bis(p-chlorophenyl)ethanol]. At 22 degrees C and 10 weeks' incubation, the DDT concentration is reduced from 2.75 micromol g(-1) (974 mg kg(-1)) to 0.98 micromol g(-1) (346 mg kg(-1)) and 1.98 micromol g(-1) (702 mg kg(-1)) in samples with and without the addition of iron, respectively. After 40 weeks' incubation these concentrations have further decreased to 0.19 micromol g(-1) (66 mg kg(-1)) and 0.74 micromol g(-1) (264 mg kg(-1)).There is no significant transformation of any of the compounds at 9 degrees C without the addition of Fe0. In the presence of iron, however, DDT is reduced to 1.25 micromol g(-1) (442 mg kg(-1)) within 40 weeks' incubation. This study demonstrates the ability of adapted microorganisms to transform DDT under elevated temperatures in original, aged sediments, and also the stimulating effect of zero-valent iron, which is significant even at low temperatures.