Adsorption Of Paraquat Research Articles

Effect of humic acids on the adsorption of paraquat by goethite

The adsorption of the herbicide paraquat (PQ2+) on goethite and on the binary system humic acid–goethite has been studied in batch experiments by performing adsorption isotherms under different conditions of pH, supporting electrolyte concentration and temperature. The results were completed with capillary electrophoresis (CE) in order to measure the binding isotherm between PQ2+ and humic acid (HA) molecules in solution. PQ2+ adsorption is negligible on the bare goethite surface but important on the HA–goethite adsorbent. In this last case, the adsorption increases by increasing pH and decreasing electrolyte concentration. There are no significant effects of temperature on the adsorption. The adsorption takes place by direct binding of PQ2+ to adsorbed HA molecules leading to the formation of surface species of the type goethite–HA–PQ2+. The results are consistent with a mechanism where PQ2+ binds negatively charged groups of HA (carboxylates and phenolates) forming ionic pairs or outer-sphere complexes. Since goethite in nature usually contains adsorbed HA molecules, it may act as a good adsorbent for cationic herbicides. This will not only benefit the deactivation of the herbicides but also reduce their leaching and transport through groundwater.

Adsorption of paraquat on goethite and humic acid-coated goethite

Adsorption of cationic pesticides in soils is generally attributed to mineral clays and organic matter components. However, iron oxides may also contribute to such adsorption or affect it by associating with other components. Using goethite and humic acid as models for iron oxides and organic matter respectively, we studied the adsorption of the cationic pesticide paraquat on goethite and humic acid-coated goethite. At pH 4.0 the adsorption on goethite was not significant, and at pH 10.0, although the surface of the oxide was negatively charged, much less pesticide was adsorbed than on mineral clays. At this pH the adsorption of paraquat decreased as the ionic strength increased, and application of the charge distribution multisite complexation model (CD-MUSIC model) enabled interpretation of the results. At pH 4, the adsorption of paraquat on the humic acid-coated goethite was similar to the adsorption on mineral clays, but was considerably less than the adsorption on humic acid in solution. The lower adsorption on solid organic matter is attributed to a decrease in the number of “active” binding sites on the humic acid as a result of the binding to iron oxide.

Adsorption study of 14C-paraquat in two Malaysian agricultural soils

The adsorption equilibrium time and effects of pH and concentration of (14)C-labeled paraquat (1,1(')-dimethyl-4,4(')-bipyridylium dichloride) in two types of Malaysian soil were investigated. The soils used in the study were clay loam and clay soils from rice fields. Equilibrium studies of paraquat in a soil and pesticide solution were conducted. Adsorption equilibrium time was achieved within 2 h for both soil types. The amount of (14)C-labeled paraquat adsorbed onto glass surfaces increased with increasing shaking time and remained constant after 10 h. It was found that paraquat adsorbed by the two soils was very similar: 51.73 (clay loam) and 51.59 μ g g(-1) (clay) at 1 μ g/ml. The adsorption of paraquat onto both types of soil was higher at high pH, and adsorption decreased with decreasing pH. At pH 11, the amounts of (14)C-labeled paraquat adsorbed onto the clay loam and clay soil samples were 4.08 and 4.05 μ g g(-1), respectively, whereas at pH 2, the amounts adsorbed were 3.72 and 3.57 μ g g(-1), respectively. Results also suggested that paraquat sorption by soil is concentration dependent.

LAJU ADSORPSI DAN DESORPSI PARAQUAT PADA TANAH PERTANIAN DESA OESAO KECAMATAN KUPANG TIMUR

The research about determination of kinetic adsorption and desorption rate of paraquat on agriculture area Oesao-east Kupang has been done. The aim of this research was to determine the kinetic of paraquat adsorption before and after saturated and to model the desorption. The research consisted of evaluation of the analitycal procedure for paraquat, pattern of soil kinetic adsorption and paraquat desorption. The result of procedure evaluation showed that reduced paraquat absorbed at λ maximum 606 nm and relative stability at 0-150 minutes. Constant of paraquat kinetic adsorption at natural state bigger than saturated state. k1 value at natural state was 0,011 per minute whereas k1 value at saturated state was 0,003 per minute. Desorption model of paraquat by using three desorbents were ammonium chloride, 29,2% of sea water salinity and aquadest showed the best desorbent was ammonium chloride, followed by sea water and aquadest.

Preparation of methacrylic acid-modified rice husk improved by an experimental design and application for paraquat adsorption

Methacrylic acid (MAA) grafted rice husk was synthesized using graft copolymerization with Fenton's reagent as the redox initiator and applied to the adsorption of paraquat. The highest grafting percentage of 44.3% was obtained using the traditional kinetic method. However, a maximum grafting percentage of 65.3% was calculated using the central composite design. Experimental results based on the recipes predicted from the statistical analysis are consistent with theoretical calculations. A representative polymethacrylic acid-g-rice husk (PMAA-g-rice husk) copolymer was hydrolyzed to a salt type and applied to the adsorption of paraquat. The adsorption equilibrium data correlate more closely with the Langmuir isotherm than with the Freundlich equation. The maximum adsorption capacity of modified rice husk is 292.5 mg/g-adsorbent. This value exceeds those for Fuller's earth and activated carbon, which are the most common binding agents used for paraquat. The samples at various stages were characterized by solid-state 13C NMR spectroscopy.

Adsorption Effect on the Degradation of Carbaryl, Mecoprop, and Paraquat by Anodic Fenton Treatment in an SWy-2 Montmorillonite Clay Slurry

The Fenton reaction-based anodic Fenton treatment (AFT) was applied to three widely used organic agrochemicals, carbaryl, mecoprop, and paraquat, in a clay slurry. The adsorption and degradation behaviors of these neutral (carbaryl), anionic (mecoprop), and cationic (paraquat) agrochemicals were studied in a slurry of SWy-2 Na(+)-montmorillonite clay, and adsorption isotherms were obtained at given experimental conditions. The d spacing (d 001) of the clay layer before and after adsorption or degradation was measured by X-ray diffraction (XRD). On the basis of the change of d spacing, molecular disposition at the clay interlayer was inferred: both mecoprop and paraquat form a monolayer sitting flat and parallel to the clay siloxane surfaces. Results show that, due to different adsorption mechanisms, the adsorption effect on chemical degradation by AFT varies with pesticide: strong and tight adsorption of paraquat at the clay interlayer protects paraquat from being attacked by hydroxyl radicals; loosely adsorbed carbaryl or mecoprop is readily degraded. XRD analysis clearly indicates that AFT is capable of effectively degrading interlayer noncationic organic chemicals that are not usually available for biodegradation.

Quaternary herbicides retention by the amendment of acid soils with a bentonite-based waste from wineries

The agronomic utility of a solid waste, waste bentonite (WB), from wine companies was assessed. In this sense, the natural characteristics of the waste were measured, followed by the monitoring of its effects on the adsorption/desorption behaviour of three quaternary herbicides in acid soils after the addition of increasing levels of waste. This was done with the intention of studying the effect of the added organic matter on their adsorption. The high content in C (294 g kg −1), N (28 g kg −1), P (584 mg kg −1) and K (108 g kg −1) of WB turned it into an appropriate amendment to increase soil fertility, solving at the same time its disposal. WB also reduced the potential Cu phytotoxicity due to a change in Cu distribution towards less soluble fractions. The adsorption of the herbicides paraquat, diquat and difenzoquat by acid soils amended with different ratios of WB was measured. In all cases, Langmuir equation was fitted to the data. Paraquat (PQ) and diquat (DQ) were adsorbed and retained more strongly than difenzoquat (DFQ) in the acid soil studied. However, the lowest retention of DFQ in an acid soil can be increased by amendment with organic matter through a solid waste from wineries, and it is enough for duplicate retention a dosage rate of 10 t/ha. Anyway, detritivores ecology can still be affected. Detritivores are the organisms that consume organic material, and in doing so contribute to decomposition and the recycling of nutrients. The term can also be applied to certain bottom-feeders in wet environments, which play a crucial role in benthic ecosystems, forming essential food chains and participating in the nitrogen cycle.

Influence of Copper on the Adsorption and Desorption of Paraquat, Diquat, and Difenzoquat in Vineyard Acid Soils

Retention of the cationic herbicides paraquat (PQ), diquat (DQ), and difenzoquat (DFQ) in two vineyard soils with a different management history and retention capacity was examined. The influence of copper on the ability of the soils to retain the herbicides was determined by comparing the results of adsorption and desorption tests on untreated and Cu-enriched soil samples, and also on soils that were previously treated with EDTA to extract native copper. The three herbicides were strongly adsorbed by both soils. Soil 1 exhibited linear adsorption isotherms for PQ and DFQ with partition coefficients, KD, of 1.28 x 103 and 1.37 x 103 L kg-1, respectively, and a Freundlich-type isotherm for DQ with a linearized partition coefficient, KD*, of 1.01 x 103 L kg-1. On the other hand, soil 2 exhibited curved isotherms and smaller KD* values (viz. 106, 418, and 28 L kg-1 for PQ, DQ, and DFQ, respectively). Using EDTA to extract copper from the soils released new sites for the herbicides to bind. The three herbicides exhibited strong hysteresis in the adsorption-desorption process. Extracting copper decreased the percent desorption of PQ and DQ; on the other hand, it decreased the affinity of DFQ for the resulting vacant adsorption sites. Similarly, competitive adsorption tests with copper and the herbicides revealed that the metal was only capable of displacing DFQ from adsorption sites. The behavior of this herbicide in the soils was consistent with a specific adsorption model. The disparate behavior of the two soils toward the herbicides was a result of the adsorption sites in soil 1 being less extensively occupied than those of soil 2 in the adsorption tests. The effect of copper on the adsorption of DFQ in the two soils was acceptably reproduced by an adsorption model involving Coulombic and specific sorption with competition from the metal.

Development of a Spectrophotometric Sequential Injection Methodology for Online Monitoring of the Adsorption of Paraquat on Clay Mineral and Soil

The reduction of paraquat by sodium dithionite in alkaline solution was explored to develop an automated, spectrophotometric, sequential injection method for online determination of the herbicide in suspensions of solid adsorbents. A tangential filter was used for interfacing the suspension and the analyzer. The linear dynamic range was between 0.1 and 20 mg L−1, with detection and quantification limits of 0.039 and 0.10 mg L−1, respectively. Sampling throughput was 102 hr−1. Precision at the 5 mg L−1 paraquat concentration was 2.9%, with a consumption of dithionite of 1 mg per analysis. The method revealed that adsorption of paraquat onto vermiculite is faster and quantitative in comparison with a tropical soil. The authors were invited to contribute this paper to a special issue of the journal entitled “Spectroscopy and Automation”. This special issue was organized by Miguel de la Guardia, Professor of Analytical Chemistry at Valencia University, Spain. The special issue was published in volume 39, issue 6.

Adsorption of paraquat using methacrylic acid-modified rice husk

This work investigates the adsorption of paraquat from aqueous medium using a methacrylic acid (MAA)-modified rice husk. The carboxyl groups were chemically bound to the surface of the rice husk by graft copolymerization using Fenton’s reagent as a redox initiator. The graft copolymerization was examined to determine the H 2O 2 concentration and the amount of MAA monomer used. FT-IR spectra confirmed the presence of carbonyl groups on the structural units of the rice husk derivative. The MAA-modified rice husks were hydrolyzed to sodium salt and used to adsorb paraquat. The adsorption was rapid in the first few minutes and quickly reached equilibrium. Equilibrium adsorption data are more consistent with the Langmuir isotherm equation than with the Freundlich equation. The maximum adsorption capacity of modified rice husks was 317.7 mg/g-adsorbent. This value clearly exceeds the 60 mg/g of Fuller’s earth and the 90 mg/g of activated carbon, which are the most commonly used binding agents for paraquat.

Paraquat Adsorption, Degradation, and Remobilization in Tropical Soils of Thailand

Paraquat adsorption, degradation, and remobilization were investigated in representative tropical soils of Yom River Basin, Thailand. Adsorption of paraquat in eight soil samples using batch equilibration techniques indicated that adsorption depended on soil characteristics, including exchangeable basic cations and iron content. Multiple regression analysis indicated significant contribution of exchangeable calcium percentage (ECP), total iron content (TFe) and exchangeable sodium percentage (ESP) to paraquat sorption (Q). ESP and TFe were significant at all adsorption stages, whereas ESP was significant only at the initial stage of paraquat adsorption. Adsorption studies using two soils representing clay and sandy loam textures showed that paraquat adsorption followed the Freundlich model, exhibiting a nonlinear sorption curve. Paraquat adsorption was higher in the clay soil compared to the sandy loam soil with K f values of 787 and 18, respectively. Desorption was low with 0.04 to 0.17% and 0.80 to 5.83% desorbed in clay and sandy loam soil, respectively, indicating some hysteresis effect. Time-dependent paraquat adsorption fitted to the Elovich kinetic model indicated that diffusion was a rate-limiting process. Paraquat mobility and degradation studies conducted using both field and laboratory soil column experiments with clay soil showed low mobility of paraquat with accumulation only in the surface 0–5 cm layer under field conditions and in the 0–1 cm layer in a laboratory soil column experiment. Degradation of paraquat in soil was faster under field conditions than at ambient laboratory conditions. The degradation rate followed a first-order kinetic model with the DT50 at 36–46 days and DT90 around 119–152 days.

Adsorption of herbicide paraquat by clay mineral regenerated from spent bleaching earth

The adsorption of herbicide paraquat (as model adsorbate) in aqueous solution onto regenerated clay mineral from bleaching earth waste has been studied in a batch reaction system. The adsorption rate has been investigated under the controlled process parameters including initial pH, salinity and temperature. Based on the high affinity between cationic paraquat and clay mineral, a pseudo-second order model has been developed using experimental data to predict the rate constant of adsorption, and equilibrium adsorption capacity. The results showed that the adsorption process could be satisfactorily described with the reaction model and were reasonably explained by assuming a competitive adsorption mechanism in the ion exchange process. Further, the fitted adsorption capacity at equilibrium decreased with increasing temperature. It implied that the strong interaction might play an important role in the paraquat–clay system. Overall, the results from this study demonstrated that the clay resource regenerated from bleaching earth waste could be used as a low-cost mineral adsorbent for the removal of environmental cationic organic pollutants from the aqueous solution.

Paraquat adsorption onto clays and organoclays from aqueous solution

Clays were compared with organoclays for the sorption of paraquat from aqueous solution. Sepiolite (S), bentonite (B), and illite (I) were used as clay samples. Organoclays were prepared by the modification of the clays with nonyl- and dodecylammonium chlorides, denoted as NS, DS, NB, DB, NI, and DI, respectively. Specific surface area and pore size distribution of the samples were determined by N 2 adsorption–desorption at 77 K using the BET method. X-ray powder diffraction analysis of the samples was used to determine the effects of modifying agents on the layer structure of the clays. In the adsorption experiments, C m values increased from 0.038 mmol/g for DS to 0.223 mmol/g for NI. K d 0.3 values ranged from 0.177 for DS to 0.843 for NI. The adsorption data indicated that illite and NI are the most effective adsorbents among these clays and organoclay samples, respectively.

Simultaneous adsorption of a mixture of paraquat and dye by NaY zeolite covered with alkylsilane

The surfaces of NaY zeolite particles were modified by the alkylsilylation of n-octadecyltrichlorosilane (OTS). Two kinds of modified NaY zeolites were prepared; one with its external surface partially and the other fully covered with alkylsilyl groups. Since the size of OTS is bigger than the pore diameter of NaY, it is attached on the external surface, leaving the internal pore accessible to adsorbate molecules. As a result of alkylsilylation, the adsorption properties of these sorbents were improved. The adsorption properties of these materials were tested by their reaction in a mixture of paraquat and blue dye. The results demonstrate that the alkysilylated NaY materials are capable of simultaneous adsorption of paraquat and blue dye. Paraquat was selectively adsorbed into the internal pore of the zeolite whereas the dye on the externally attached alkylsilyl groups of the sorbent; displaying the unique bimodal amphiphilic character of the alkylsilylated NaY zeolites.

Removal of herbicide paraquat from an aqueous solution by adsorption onto spent and treated diatomaceous earth

A spent diatomaceous earth from the beer brewery has been tentatively activated by sodium hydroxide at about 100 °C. The resulting product was used as a novel adsorbent for the adsorption of herbicide paraquat from an aqueous solution in a continuously stirred adsorber and batch flasks, respectively. The results showed that the adsorption process could be well described by the pseudo-second-order reaction model. From the view of the negatively charged surface of diatomaceous earth and cationic property of paraquat, the results were also reasonable to be explained by physical adsorption in the ion-exchange process under the effects of pH and temperature. Further, it was found that the Freundlich model appeared to fit the isotherm data better than the Langmuir model.

Adsorption of Paraquat dichloride from aqueous solution by activated carbon derived from used tires

The removal of pesticide from wastewater under different batch experimental conditions, using a car tire derived activated carbon was investigated. The pesticide utilized in the study was Paraquat dichloride (1,1-dimethyl-4,4-bipyridyl dichloride), which is a well known herbicide. The adsorbent was produced from the pyrolysis and activation of used tires (TAC). The performances of this adsorbent and a commercial activated carbon F300 (CAC) have been compared. It was determined that the adsorption of Paraquat was weakly pH dependent. The effects of particle size, carbon dosage, temperature and the initial concentration of the Paraquat were studied. Further experiments investigating the regeneration capabilities of the tire-supplied carbon were performed. The regenerated carbons that were washed with basic pH solution were found to have the best sorption capacity recovery. It was found that the rate of sorption of Paraquat onto the carbon is very fast with almost 90% of the maximum possible adsorption taking place in the first 5 min. Nevertheless, the batch sorption kinetics was fitted for a first-order reversible reaction, a pseudo-first-order reaction and a pseudo-second-order reaction. The pseudo-second-order chemical reaction model appears to provide the best correlation. The applicability of the Langmuir isotherm for the present system has been evaluated at different temperatures. The isotherms show that the sorption capacity of CAC decreases with temperature and the dominant mechanism of CAC adsorption is physical sorption.

Adsorption kinetics of herbicide paraquat from aqueous solution onto activated bleaching earth

In the present study, the activated bleaching earth was used as adsorbent for the herbicide paraquat adsorption in a batch adsorber. The rate of adsorption has been investigated under the controlled process parameters like agitation speed, initial paraquat concentration, adsorbent dosage and temperature. A batch kinetic model, based on the assumption of a pseudo-second order mechanism, has been tested to predict the rate constant of adsorption, equilibrium adsorption capacity, time of half-adsorption, and equilibrium concentration by the fittings of the experimental data. The results of the kinetic studies show that the adsorption process can be well described with the pseudo-second order equation. Based on the isotherm data obtained from the fittings of the adsorption kinetics, Freundlich model appears to fit the adsorption better than Langmuir model. In addition, the effective diffusion coefficient has also been estimated based on the restrictive diffusion model.

Preparation of adsorbents from sugarcane manufacturing by-product filter-mud by thermal activation

A series of experiments with thermal activation were carried out on filter-mud waste from the sugarcane refining process in a rotary reactor. The influence of activation parameters on the agro-industrial waste by varying the operation temperature of 600–800 °C was determined. The variations of pore properties as well as the change of chemical characteristics in the resulting solids (FM series) were also studied. The results show that the resulting samples are type IV with hysteresis loops corresponding to type H3 from nitrogen adsorption–desorption isotherms, indicating slit-shaped mesoporous characteristics (BET surface areas of 57–132 m 2 g −1). The results also show that the surface areas of the unwashed products and water-washed products are lower than those of the washed products because of residues left in the crude products. The adsorption of paraquat on FM sample was preliminarily evaluated. The isotherm showed that the FM adsorbent had a high affinity for this herbicide and can be well fitted by Freundlich model. Thus, the agro-industrial waste is one resource for producing the mesoporous materials, and it may be applied to the water treatment for the removal of organic contaminants.

The effects of pH and salinity on kinetics of paraquat sorption onto activated clay

In the present study, activated clay was used as adsorbent for the kinetics of paraquat adsorption from aqueous solution at 25 °C in a batch adsorber. The rate of adsorption has been investigated under the controlled process parameters like initial pH and salinity. A pseudo-second order model has been tested to predict the rate constant of adsorption, equilibrium adsorption capacity, and distribution coefficient by the fittings of the experimental data. The results showed that the adsorption process could be well described with the reaction model. Also, the results were reasonable to be explained by competitive adsorption in the ion exchange process. Further, the process kinetics was reasonably described by the proposed mechanism, which was based on the concepts of completely mixed batch reactor, mass conservation, and homogeneous elementary reaction.

Sorption of Paraquat on Clay Components in a Taiwan's Oxisol

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