Tomas Undabeytia

Glyphosate adsorption on soils of different characteristics. Influence of copper addition

Results of glyphosate (GPS) adsorption on three soils of different characteristics show that the interaction of this pesticide with the soils was not related to their CEC and clay minerals content, but to the content of iron and aluminum amorphous oxides and organic matter. The presence of Cu in treatment solutions enhanced GPS adsorption, due to several reasons: GPS coordinates strongly to Cu, and Cu GPS complexes formed seem to have higher ability to be adsorbed on the soil than free GPS; GPS adsorption can take place on sites where Cu was previously adsorbed, acting as a bridge between the soil and GPS; when Cu was present the solution pH decreased, and GPS adsorption increased, since lower pHs lead to the formation of GPS species with lower negative charge, which are adsorbed more easily on the negatively charged soil surfaces.

Organo-clay formulations of pesticides: reduced leaching and photodegradation

Adsorption of organic cations on several clay minerals is reviewed with an emphasis on the effect of ionic strength and modeling. The clay exchanged with suitable organic cations forms a basis for ecologically acceptable formulations of herbicides with reduced leaching, ground water contamination and enhanced weed control efficacy. Incomplete neutralization of the clay surface charge by an organic cation may be advantageous in achieving maximal adsorption of hydrophobic herbicides. One conclusion from these studies is that optimization of clay-based herbicide formulations requires a selection of structurally compatible organic cations preadsorbed on the clay at optimal coverage. New experimental results are presented for alachlor formulations, which significantly reduce herbicide leaching under conditions of heavy irrigation. We were able to demonstrate that organo-clay formulations of alachlor and metolachlor can increase crop yields in a 1-year field experiment. The photostabilization of pesticides is reviewed and improved organo-clay formulations of the herbicides trifluralin and norflurazon are described. A pillared clay, nanocomposite micro- and/or meso porous material, was effective in reducing leaching and in conferring photostabilization, without added organic cations.

The effect of dissolved glyphosate upon the sorption of copper by three selected soils.

The effect of the pesticide glyphosate (GPS) on adsorption processes of copper onto three soils of different characteristics has been studied. Cu adsorption decreases in general with increasing GPS concentration in solution, due principally to the lower equilibrium pHs, although this is not the only variable affecting copper adsorption. For the same pH values, Cu adsorption is higher in two of the three soils in the presence of GPS, but for the third soil, Cu adsorption is higher in the absence of GPS. This behavior is explained by the possibility of GPS adsorption on these soils and by the formation of Cu-GPS complexes in solution. The soils showing a higher Cu adsorption in the presence of GPS than in its absence for the same pH are able to adsorb this pesticide. In these soils, copper can be adsorbed directly on the soil surfaces, and also through the formation of bonds with GPS previously adsorbed. The third soil was not able to adsorb GPS. Consequently, all the pesticide remained in solution, forming strong Cu complexes with low tendency to be adsorbed on this soil. For this reason, the concentration of free Cu in solution is drastically reduced, and the adsorption of copper on this soil is lower.

Adsorption of Cd and Zn on montmorillonite in the presence of a cationic pesticide

Abstract The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.

Novel system for reducing leaching of the herbicide metribuzin using clay-gel-based formulations

Metribuzin is an herbicide widely used for weed control that has been identified as a groundwater pollutant. It contaminates the environment even when it is used according to the manufacturers instructions. To reduce herbicide leaching and increase weed control, new controlled release formulations were developed by entrapping metribuzin within a sepiolite-gel-based matrix using two clay/herbicide proportions (0.5/0.2 and 1/0.2) (loaded at 28.6 and 16.7% a.i.) as a gel (G28, G16) or as a powder after freeze-drying (LF28, LF16). The release of metribuzin from the control released formulations into water was retarded, when compared with commercial formulation (CF) except in the case of G28. The mobility of metribuzin from control released formulations into soil columns of sandy soil was greatly diminished in comparison with CF. Most of the metribuzin applied as control released formulations (G16, LF28 and LF16) was found at a depth of 0-8 cm depth. In contrast, residues from CF and G28 along the column were almost negligible. Bioassays from these control released formulations showed high efficacy at 0-12 cm depth. The use of these novel formulations could minimize the risk of groundwater contamination while maintaining weed control for a longer period.

Cu(II)-glyphosate system: a study by anodic stripping voltammetry and the influence on Cu adsorption by montmorillonite

The influence of the pesticide glyphosate (GPS) on the adsorption of Cu (II) on montmorillonite has been examined. The complexation of Cu(II) with GPS was studied using anodic stripping voltammetry in differential pulse mode (DPASV). It has been concluded that the complexes present a labile behaviour and GPS shows a low but noticeable degree of heterogeneity, probably due to complexation of Cu bv more than one GPS species. Cu(II) adsorption on montmorillonite is drastically decreased in the presence of GPS, due to several reasons: decrease in free Cu concentration due to formation of Cu-GPS complexes; surface loading of GPS on montmorillonite, obstructing interlamellar Cu2+ adsorption and competitive effect between protons and Cu2+ for interlamellar positions.

Sorption of glyphosate and Cu(II) on a natural fulvic aced complex: Mutual influence

The mutual influence of the pesticide glyphosate (Gps) and copper on their adsorption on a natural metal-fulvic acid complex (M-FA) has been studied. The complex was extracted from a podsol and contains 22.16% Fe and 7.54% Al. High adsorption of Gps on M-FA is observed, but it decreases slightly in the presence of Cu(II) in solution. This is due to formation of very strong metal-Gps complexes, either with the added Cu or with Fe and Al desorbed from the M-FA complex. These complexes have a lower tendency to be adsorbed than the free Gps. Al and Fe desorption is more marked as higher is the concentration of Cu and GPS in solution, due to the decrease of equilibrium pH, to their displacement from the FA complex by Cu2+ ions and to ligand exchange of Gps for FA in the complex. In contrast, the adsorption of Cu increases as the concentration of Gps increases, since the formation of Gps complexes with Al and Fe in solution originates vacant positions on M-FA, facilitating copper adsorption.

Cyclodextrin Inclusion Complex to Improve Physicochemical Properties of Herbicide Bentazon: Exploring Better Formulations

The knowledge of the host-guest complexes using cyclodextrins (CDs) has prompted an increase in the development of new formulations. The capacity of these organic host structures of including guest within their hydrophobic cavities, improves physicochemical properties of the guest. In the case of pesticides, several inclusion complexes with cyclodextrins have been reported. However, in order to explore rationally new pesticide formulations, it is essential to know the effect of cyclodextrins on the properties of guest molecules. In this study, the inclusion complexes of bentazon (Btz) with native βCD and two derivatives, 2-hydroxypropyl-β-cyclodextrin (HPCD) and sulfobutylether-β-cyclodextrin (SBECD), were prepared by two methods: kneading and freeze-drying, and their characterization was investigated with different analytical techniques including Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), X-ray diffractometry (XRD) and differential pulse voltammetry (DPV). All these approaches indicate that Btz forms inclusion complexes with CDs in solution and in solid state, with a stoichiometry of 1∶1, although some of them are obtained in mixtures with free Btz. The calculated association constant of the Btz/HPCD complex by DPV was 244±19 M−1 being an intermediate value compared with those obtained with βCD and SBECD. The use of CDs significantly increases Btz photostability, and depending on the CDs, decreases the surface tension. The results indicated that bentazon forms inclusion complexes with CDs showing improved physicochemical properties compared to free bentazon indicating that CDs may serve as excipient in herbicide formulations.

Effect of contact time and the use of hydroxypropyl-β-cyclodextrin in the removal of fluorene and fluoranthene from contaminated soils

Sorption-desorption experiments of fluorene (FLU) and fluoranthene (FLT) in soils were carried out and correlated to their removal from aged contaminated soils using aqueous solutions in the absence and in the presence of hydroxypropyl-β-cyclodextrin (HPBCD) as the extraction agent. FLU became more resistant to extraction in aged contaminated soils due to its initial adsorption onto the mineral and amorphous soil organic matter (SOM) domains, sites of lower binding energy from which, due to its small size, it could spread towards the condensed SOM as the contact time increased. Therefore, FLU will not be easily desorbed from aged contaminated soils due to physical entrapment mechanisms, even when using HPBCD as extractant, presenting FLU low risks to the environment. On the contrary, FLT was extracted from aged soils in the presence of HPBCD in solutions to a much greater extent than in its absence. Due to its more hydrophobic character FLT sorption in soils was relatively quicker, remaining more or less fixed on hydrophobic sites of the organic matter (OM) with different energies, and therefore the amount of FLT extracted was almost constant for different ageing times. During extraction experiments, the influence of the OM quality of the soils was also highlighted because an inverse proportionality between OM content of soil and extractability of sorbed FLT was observed. It was concluded that soils with lower OM content that had more diagenetically processed OM could block the extraction of FLT more effectively than soils with higher OM content that are less humified. This indicates the need to use not only adsorption-desorption data in contaminant fate and transport models, but also extraction studies in aged contaminated soils and other complementary analytical approaches when assessing soil contamination-related risks.

Environmentally-friendly formulations of alachlor and atrazine: preparation, characterization and reduced leaching

Atrazine and alachlor formulations were designed by encapsulating the herbicide molecules into phosphatidylcholine (PC) vesicles, which subsequently were adsorbed on montmorillonite. PC and montmorillonite are classified as substances of minimal toxicological risk by the U.S. EPA. PC enhanced alachlor and atrazine solubilities by 15- and 18-fold, respectively. A 6 mM PC:5 g/L clay ratio was found as optimal for PC adsorption on the clay. Active ingredient contents of the PC-clay formulations ranged up to 8.6% for atrazine and 39.5% for alachlor. Infrared spectroscopy showed hydrophobic interactions of herbicide molecules with the alkyl chains of PC, in addition to hydrophilic interactions with the PC headgroup. Release experiments in a sandy soil showed a slower rate from the PC-clay formulations than the commercial ones. Soil column experiments under moderate irrigation and bioactivity experiments indicate that a reduction in the recommended dose of alachlor and atrazine can be accomplished by using PC-clay formulations.