Study of Sorption Kinetics and Sorption-Desorption Models to Assess the Transport Mechanisms of 2,4-Dichlorophenoxyacetic Acid on Volcanic Soils.

The sorption behavior of 2,4-dichlorophenoxyacetic acid (2,4-D) in the abundant agricultural volcanic ash-derived soils (VADS) is not well understood despite being widely used throughout the world, causing effects to the environment and human health. The environmental behavior and risk assessment of groundwater pollution by pesticides can be evaluated through kinetic models. This study evaluated the sorption kinetics and 2,4-D sorption-desorption in ten VADS through batch sorption experiments. Differences in the sorption extent for the fast and slow phases was observed through the IPD model where 2,4-D sorption kinetics was controlled by external mass transfer and intra organic matter diffusion in Andisols (C1 ≠ 0). We confirmed from the spectroscopic analysis that the carboxylate group directly drives the interaction of 2,4-D on Andisol soil. The MLR model showed that IEP, FeDCB, and pH×Silt are important soil descriptors in the 2,4-D sorption in VADS. The Freundlich model accurately represented sorption equilibrium data in all cases (Kf values between 1.1 and 24.1 µg1-1/n mL1/ng-1) with comparatively higher sorption capacity on Andisols, where the highest hysteresis was observed in soils that presented the highest and lowest OC content (H close to 0).

Nicosulfuron sorption kinetics and sorption/desorption on volcanic ash-derived soils: Proposal of sorption and transport mechanisms.

Nicosulfuron sorption/desorption kinetics were studied through batch sorption studies in ten volcanic ash-derived Andisol and Ultisol soils with acidic pH and variable surface charge. Two different kinetic models were used to fit the experimental data: i) Models to establish kinetic parameters (Pseudo-First and Pseudo-Second-Order), and ii) Models to describe solute transport mechanisms of organic compounds on sorbents (Intraparticle Diffusion, Dimensionless Intraparticle, Boyd, and Two-Site Nonequilibrium). Sorption kinetic data best fit the pseudo-second-order model. Application of these models to describe solute transport suggests that underlying mechanisms are complex in all soils due to: i) surface sorption, with mass transfers controlling sorption kinetics across the boundary layer; and ii) pore diffusion (i.e. intraparticle diffusion into macropores and micropores). The Freundlich model explained equilibrium sorption data in all cases (R2 > 0.9979) with Kf values higher than those reported for different class of soils (6.85-16.08 µg1-1/n mL1/n  g-1). The hysteresis was significant in all studied soils. The lower sorption rate on Ultisols must be considered in regards to Nicosulfuron leaching potential.

Electrochemical method to study the environmental behavior of Glyphosate on volcanic soils: Proposal of adsorption-desorption and transport mechanisms.

Glyphosate is used extensively worldwide, but current evidence suggests detrimental effects on the environment, pollinators, and human health. Glyphosate adsorption kinetics and adsorption/desorption were studied through batch sorption experiments in ten typical volcanic ash-derived soils from Andisol and Ultisol orders. Two kinetic models were used to fit the experimental data: i. Models that allowed establishment of principally kinetic parameters and modeling of the adsorption process, and ii. Models described solute transport mechanisms commonly used for remediation purposes. Adsorption kinetic data were best fitted by the pseudo-second-order kinetic model and Two-Site Nonequilibrium model. These models suggest that mechanisms are complex due to rapid surface adsorption in ultisols with mass transfer controlling adsorption kinetics across the boundary layer, as indicated by the highhand lowt1/2values. High intraparticle diffusion into macropores and micropores was observed for Andisols. The Freundlich model accurately represented adsorption equilibrium data in all cases (R2 > 0.9580) with comparatively higher adsorption capacity on Andisols. Kf values (2.50-52.28 µg1-1/n mL1/n g-1) and hysteresis were significant in all studied soils. Taken together, these data suggest that Glyphosate may be adsorbed more on Andisol soils in comparison to Ultisols.