New insights on the structure of the picloram-montmorillonite surface complexes.

HYPOTHESIS: The environmental mobility and bioavailability of Picloram (PCM) are determined by the amine and carboxylate chemical groups interaction with the soils mineral phases. Clay particles, such as montmorillonite (Mt), and the pH value of the media could play an important role in adsorption processes. Thus, the study of the role of soil components other than organic matter deserves further investigation for a more accurate assessment of the risk of groundwater contamination. EXPERIMENTS: Samples with PCM adsorbed on Mt dispersions were prepared at pH 3-9. Subsequently, the dispersions were separated, washed, centrifuged and stored at room temperature. Picloram (PCM) herbicide interaction with surface groups of montmorillonite (Mt) was studied using XRD, DTA, FTIR and XPS techniques. FINDINGS: The entrance of PCM into the Mt basal space, in two different arrangements, perpendicular and planar, is proposed and the final arrangement depends on PCM concentration. The interaction of PCM with Mt surface sites through the nitrogen of the pyridine ring and carboxylic group of PCM, forming bidentate and bridge inner-sphere complexes was confirmed by FTIR and XPS analysis. The acidity constant of the PCM adsorbed on the Mt surface was calculated.

Adsorption of Cu(II), Zn(II), Cd(II) and Pb(II) by dead Avena fatua biomass and the effect of these metals on their growth.

The biosorption of copper(II), zinc(II), cadmium(II) and lead(II) from aqueous solutions by dead Avena fatua biomass and the effect of these metals on the growth of this wild oat were investigated. Pseudo-first- and second-order and intra-particle diffusion models were applied to describe the kinetic data and to evaluate the rate constants. The adsorption kinetics of all the metals follows a pseudo-second-order model. The adsorption capacity was determined, and the Freundlich and Langmuir models were applied. The experimental data obtained for all the metals are best described by the Langmuir model. A. fatua was characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and zeta potential. The results obtained evidence the presence of Zn(II), Cu(II), Cd(II) or Pb(II) on the surface of the weed. The growth of A. fatua was affected by the presence of all metals. The decrease in the growth rate with increasing metal concentration was more noticeable for zinc.

Co-biosorption of copper and glyphosate by Ulva lactuca.

This study investigated the adsorption of glyphosate (PMG) onto the green algae Ulva lactuca. PMG was not adsorbed by U. lactuca but PMG was adsorbed when the process was mediated by Cu(II) with molar ratios Cu(II):PMG≥1.5:1. U. lactuca was characterized by water adsorption surface area, FTIR, SEM and EDS. The Langmuir and Freundlich models were applied. Results showed that the biosorption processes for copper and PMG in the presence of copper were described described by the Langmuir model (qmax=0.85±0.09 mmol g(-1), KL=0.55±0.14 l mmol(-1) and qmax=3.65±0.46 mmol g(-1), KL=0.103±0.03 l mmol(-1), respectively). Copper adsorption was greater in the presence of PMG than in the absence of the pesticide and the adsorption can only be represented by the Freundlich model (KF=0.08±0.01, 1/n=1.86±0.07). In all cases studied, the maximum metal uptake (qmax) increased with increasing pH. Surface complexes with a stoichiometry ranging from ≡Cu-PMG-Cu to ≡Cu-PMG-Cu3 are suggested as reaction products of the process. Due to the increasing amounts of PMG applied in Argentina, natural reservoirs present considerable amounts of this herbicide. The value of this work resides in using U. lactuca, a marine seaweed commonly found along coastlines all over the world, as a biosorbent for PMG.