Competitive Adsorption-Desorption Kinetics of Phenoxyacetic Acids and a Chlorophenol in Volcanic Soil

Susarla, Sridhar; Bhaskar, G. V.; Bhamidimarri, S. M. Rao

doi:10.1080/09593331808616613

Cited by 7 publications

(4 citation statements)

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“…The resulting chlorophenols may bear an additional risk for groundwater pollution (Garrison et al, 1996). Due to their chemical structures phenoxyalkanoic acid herbicides have one polar carboxylic group and one lipophilic phenyl moietysthey are suitable model substances for studying adsorption/desorption processes in soil Bolan and Baskaran, 1996;Socias-Viciana et al, 1999;Susarla et al, 1997). Factors dominating the sorption of phenoxyalkanoic acid herbicides are postulated to be both interactions of the carboxylic groups with surfaces of organic matter and negatively charged clay via metal ion bridges (Parker and Rate, 1998) and partition via lipophilic interactions in soil organic matter (Benoit et al, 1998;Pignatello and Xing, 1995).…”

Section: Introductionmentioning

confidence: 99%

Influence of Molecular Structure on Sorption of Phenoxyalkanoic Herbicides on Soil and Its Particle Size Fractions

Haberhauer

Pfeiffer

Gerzabek

2000

J. Agric. Food Chem.

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The sorption and desorption behaviors of four phenoxyalkanoic acid herbicides and their metabolites on four agricultural soils and soil particle size fractions were examined. Generally, there was a trend of increasing adsorption and decreasing desorption in the order mecoprop < MCPA < dichlorprop < 2,4-D. The significant increase in adsorption of the phenolic metabolites can be explained by their lower polarity and enhanced partition in the organic soil matrix. Estimation of sorption distribution coefficients from particle size fraction adsorption data was possible for a sandy soil and a silty Cambisol soil only. It is suggested that increasing steric demand, for example, molecular volume, and slight changes in the polarity of the compounds affect their adsorption properties. Comparison of adsorption and desorption data of structurally similar compounds obtained from a variety of soils allows investigation of structure-induced differences in sorption strength.

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Section: Introductionmentioning

confidence: 99%

Influence of Molecular Structure on Sorption of Phenoxyalkanoic Herbicides on Soil and Its Particle Size Fractions

Haberhauer

Pfeiffer

Gerzabek

2000

J. Agric. Food Chem.

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“…The polar carboxyl group is primarily responsible for their relatively high chemical activity and dominates in interactions with clay mineral surfaces. Many experimental studies have been devoted to the study of the sorption/desorption processes of phenoxyalkanoic acid herbicides in soils and/or soil components, respectively (Pignatello and Xing, 1995;Benoit et al, 1996Benoit et al, , 1998Bolan and Baskaran, 1996;de Paolis and Kukkonen, 1997;Sannino et al, 1997;Susarla et al, 1997;Socias-Viciana et al, 1999;Celis and Koskinen, 1999a and b;Celis et al, 1999;Haberhauer et al, 2000Haberhauer et al, , 2001Hsu et al, 2000;Inacio et al, 2001;Clausen et al, 2001;Dubus et al, 2001;Vasudevan et al, 2002;Spadotto and Hornsby, 2003). These experiments describe sorption of phenoxyalkanoic acid herbicides from aqueous solutions at various solid matrixes and provide the distribution coefficient K D and, eventually, the adsorption energy or enthalpy that is calculated from fits to experimental data.…”

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confidence: 98%

Sorption of Phenoxyacetic Acid Herbicides on the Kaolinite Mineral Surface – An Ab Initio Molecular Dynamics Simulation

Tunega¹,

Haberhauer

Gerzabek³

et al. 2004

Soil Science

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Full atomic position optimizations and ab initio molecular dynamics simulations at room temperature were performed in a study of the adsorption of phenoxyacetic acid herbicides on the octahedral surface of a kaolinite layer formed from hydroxyl groups. The studied molecules are bound strongly to the surface hydroxyl groups via hydrogen bonds formed through the carboxyl group. Particularly strong bonding with the hydrogen atom approximately midway between the two adjacent oxygen atoms was observed between the OH group of the carboxyl group and one of the surface OH groups. Molecular dynamics simulations showed proton jumps within this strong hydrogen bond. Kaolinite surface hydroxyl groups are chemically active and able to act as proton donors or acceptors. Additional interactions were observed between atoms of the aromatic parts of the adsorbed molecules and the surface hydroxyl groups. The phenoxyacetic acids are significantly more strongly bound than acetic acid to the octahedral kaolinite surface. This strong bonding of the phenoxyacetic acids to the kaolinite layer surface indicates a strong retention capability in the soil matrix and a significant contribution of kaolinite clay minerals to the "bound residue" phenomenon. (Soil Science 2004;Volume 169:44-54)

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“…These herbicides contain one or more polar carboxylic groups responsible for their relatively high chemical reactivity with soil components. The physical and chemical processes of phenoxyacetic acid-based herbicides in soils and/or soil components (solubility, adsorption-desorption, chemical resistance, bio-, and photodegradation) were extensively investigated by a variety of experiments [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. A strong dependence of the adsorbed amount on pH and on the presence of electrolytes in solution was observed [12,13,17].…”

Section: Introductionmentioning

confidence: 99%

Molecular modeling of MCPA herbicide adsorption by goethite (110) surface in dependence of pH

2020

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The sorption mechanism between 4-chloro-2-methylphenoxyacetic acid (MCPA) herbicide and the dominating (110) surface of the mineral goethite was studied by molecular modeling of the full set of possible surface complexes using density functional theory with periodic boundary conditions for the structural surface models. The most stable arrangements of the MCPA species were predicted taking into account the type and topology of the surface OH groups, protonation states (pH effect), the structure of carboxyl/carboxylate group of MCPA, and the binding type (outer-or inner-sphere complexes). Acid-base properties of MCPA and the goethite surface OH groups led to creation of several pH ranges (3-4, 4-9, 9) for combining neutral/deprotonated MCPA with neutral/protonated goethite surface. The predicted strongest adsorption (physisorption) for the complexes in the pH 4-9 range was followed by largest solvent destabilization of the outer-sphere complexes due to the high solvent energy of the MCPA and surface hydration of the hydroxylated goethite surface. In line with experimental data, the adsorption of MCPA should increase with decreasing pH owing to the presence of neutral MCPA molecule (pK a ~ 3) and its lower solvation energy that can produce more stable complexes in solution than that of anionic MCPA in pH 4-9 range. The formation of the inner-sphere chemisorbed surface complex contributes significantly to the overall adsorption of MCPA at acidic pH range. In the chemisorbed inner-sphere complexes, monodentate binding was revealed through the formation of a Fe-O-C bridge.

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Competitive Adsorption-Desorption Kinetics of Phenoxyacetic Acids and a Chlorophenol in Volcanic Soil

Cited by 7 publications

References 0 publications

Influence of Molecular Structure on Sorption of Phenoxyalkanoic Herbicides on Soil and Its Particle Size Fractions

Influence of Molecular Structure on Sorption of Phenoxyalkanoic Herbicides on Soil and Its Particle Size Fractions

Sorption of Phenoxyacetic Acid Herbicides on the Kaolinite Mineral Surface – An Ab Initio Molecular Dynamics Simulation

Molecular modeling of MCPA herbicide adsorption by goethite (110) surface in dependence of pH

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