Graciela P. Zanini

Effect of humic acids on the adsorption of paraquat by goethite.

The adsorption of the herbicide paraquat (PQ(2+)) 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 PQ(2+) and humic acid (HA) molecules in solution. PQ(2+) 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 PQ(2+) to adsorbed HA molecules leading to the formation of surface species of the type goethite-HA-PQ(2+). The results are consistent with a mechanism where PQ(2+) 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.

Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics.

The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters.

A real time in situ ATR-FTIR spectroscopic study of glyphosate desorption from goethite as induced by phosphate adsorption: Effect of surface coverage

The desorption of glyphosate from goethite as induced by the adsorption of phosphate was investigated by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy in combination with adsorption isotherms. Desorption of glyphosate was very low in the absence of phosphate. Addition of phosphate promoted glyphosate desorption. At low initial surface coverages, added phosphate adsorbed on free surface sites, mainly, displacing a small amount of glyphosate. At high initial surface coverages, on the contrary, phosphate adsorption resulted in a significant glyphosate desorption. In the latter conditions, the ratio desorbed glyphosate to adsorbed phosphate was 0.60. The desorption process can be explained by assuming that phosphate adsorbs first forming a monodentate mononuclear complex, which rapidly evolves into a bidentate binuclear complex that displaces glyphosate.

On the dissolution kinetics of humic acid particles. Effect of monocarboxylic acids

The dissolution kinetics of humic acid particles has been studied in batch experiments, and the effects of monocarboxylic (formic, acetic, and propionic) acids are reported. The dissolution rate of the particles is significantly affected by the presence of monocarboxylic acids in the pH range 4-10. At pH 7, for example, propionic acid increases 30 times this dissolution rate. The capacity of increasing the dissolution rate is in the order formic acid<acetic acid<propionic acid, and this dissolving capacity of carboxylics seems to be directly related to their affinity for HA molecules located at the surface of the solid particles. The results indicate that carboxylics and related compounds may affect markedly the mobility and transport of humic substances in the environment.

Effect of the surfactant benzalkonium chloride in the sorption of paraquat and cadmium on montmorillonite

Pesticides, heavy metals and surfactants can share the same region or site in the environment and thus they may compete for the surface of minerals. A competitive study of the adsorption between the cationic surfactant benzalkonium chloride (BAC) with the heavy metal cadmium (Cd(II)) and the cationic herbicide paraquat (PQ) on montmorillonite is presented. Adsorption isotherms for BAC, PQ and Cd(II) were performed in single solute systems and also in binary solute systems, PQ+BAC and Cd(II)+BAC to evaluate the effects of BAC on the adsorption of the other two substances. The affinities of BAC and PQ were strong and similar, thus BAC affected significantly the adsorption of PQ and vice versa. The affinity of Cd(II) for the montmorillonite surface was low, thus BAC affected appreciably Cd(II) adsorption, but the heavy metal did not modify BAC adsorption. XRD data show that BAC molecules control the magnitude of the basal spacing.

Desorption rate of glyphosate from goethite as affected by different entering ligands: hints on the desorption mechanism

Environmental context Glyphosate is a heavily used herbicide that is mobilised in soil and sediments through adsorption–desorption processes from the surface of mineral particles. We demonstrate that the desorption rate of glyphosate from goethite, a ubiquitous mineral, is nearly independent of the concentration and nature of the substance that is used to desorb it. The results elucidate the desorption mechanism and are relevant to understand and predict the environmental mobility of glyphosate. Abstract The desorption kinetics of glyphosate (Gly) from goethite was studied in a flow cell using attenuated total reflectance Fourier-transform infrared spectroscopy. Because Gly forms an inner-sphere surface complex by coordinating to Fe atoms at the goethite surface, the desorption process is actually a ligand-exchange reaction, where Gly is the leaving ligand and water molecules or dissolved substances are the entering ligands. A series of possible entering ligands that can be found in nature was tested to evaluate their effect on the desorption kinetics of Gly. Contrarily to expectations, the desorption rate was quite independent of the entering ligand concentration. Moreover, the identity of this ligand (phosphate, citrate, sulfate, oxalate, EDTA, thiocyanate, humic acid, water) had only a small effect on the value of the desorption rate constant. By analogy with the reactivity of transition metal complexes in solution, it is concluded that the rate is mainly controlled by the breaking of the Fe–Gly bond, through a dissociative or a dissociative interchange mechanism. The results are relevant in understanding and predicting the environmental mobility of Gly: irrespective of the identity of the entering ligand, Gly will always desorb from iron (hydr)oxides in nature at nearly the same rate, simplifying calculations and predictions enormously. The importance of studying desorption kinetics using mineral surfaces and environmentally relevant molecules is also highlighted.

Aggregation Kinetics of Humic Acid: Effects of Ca2+ Concentration

The aggregation kinetics of a humic acid (HA) sample as a function of Ca2+ concentration at pH 5, 7 and 9 was investigated. UV-visible spectroscopy was used to quantify the progress of the aggregation reaction, and zeta potential measurements were used to evaluate the charging state of the HA molecules. The aggregation rate increases by increasing Ca2+ concentration. The rate is also higher at pH 9 than at pH 5 and 7. The proposed reaction mechanism consists of two steps: a rapid binding of calcium to humic molecules followed by a slower step, where HA molecules approach each other and become aggregated. This aggregation is possible because calcium binding decreases the zeta potential of HA from −37 to −15 mV. The study also reveals that the resulting aggregates have a core with a composition very similar to the composition of the whole HA sample and an outermost surface enriched with larger or more condensed molecules.

Surface speciation of phosphate on goethite as seen by InfraRed Surface Titrations (IRST)

Phosphate adsorption at the metal oxide-water interface has been intensely studied, and the system phosphate-goethite in aqueous media is normally used as a model system with abundant information regarding adsorption-desorption under very different conditions. In spite of this, there is still discussion on whether the main inner-sphere surface complexes that phosphate forms on goethite are monodentate or bidentate. A new spectroscopic technique, InfraRed Surface Titration (IRST), is presented here and used to systematically explore the surface speciation of phosphate on goethite in the pH range 4.5-9.5 at different surface coverages. IRST enabled to construct distribution curves of surface species and distribution curves of dissolved phosphate species. In combination with the CD-MUSIC surface complexation model it was possible to conclude that surface complexes are monodentate. Very accurate distribution curves were obtained, showing a crossing point at pH5.5 at a surface coverage of 2.0μmolm-2, with a mononuclear monoprotonated species predominating at pH>5.5 and a mononuclear diprotonated species prevailing at pH<5.5. On the contrary, at the low surface coverage of 0.7μmolm-2 there is no crossing point, with the mononuclear monoprotonated species prevailing at all pH. IRST can become a powerful technique to investigate structure, properties and reactions of any IR-active surface complex at the solid-water interface.