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This study investigates the changes in sorption/desorption, dissipation and leaching of the two enantiomeric forms of the allelochemical carvone, R-carvone and S-carvone, after amending an agricultural soil sample with two nanoengineered sorbents: biochar (BC) and organoclay (OCl). The sorption of carvone enantiomers was non-enantioselective and similarly improved by the addition of OCl and BC to the soil. However, OCl-amended soil showed reversible sorption, whereas BC-amended soil displayed sorption-desorption hysteresis. Dissipation of carvone enantiomers was enantioselective. Both amendments increased the half-life of the enantiomers in the soil. This effect was more pronounced for BC-amended soil and for S-carvone. Leaching of R- and S-carvone through soil columns was scarce in unamended soil (< 7%), due to their rapid degradation during leaching, and null for OCl- and BC-amended soil, for which much of the applied R- and S-carvone remained in the top 0-5 cm amended soil layer. Addition of biochars and organoclays could help increase the persistence of carvone enantiomers in the rhizosphere, which may favor their use as residual pest management substances.

The activity of allelochemicals in agroecosystems are highly dependent on their soil persistence. The aim of this work was to establish a link between the soil persistence of salicylic acid (SA) and its bioactivity, to better understand the mechanisms of allelochemical-mediated soil-plant interactions. Incubation and bioassay experiments were conducted for this purpose. The addition of HgCl₂ and decreasing temperature to 4 °C increased the persistence of SA in soil. Since these treatments greatly decreased the soil respiration, they probably slowed the SA dissipation by reducing the soil microbial activity. To a lesser extent, soil humidity and soil pH also influenced the SA dissipation rate. Exogenous olive-mill organic waste (ALP) increased the soil respiration, but interestingly, delayed the degradation of SA, presumably because ALP acted as an alternative source of C for soil microorganisms. The phytotoxicity of SA towards Eruca vesicaria in soil increased by the addition of ALP. Applied to soil at 0.5%, ALP reduced the SA dose for 50% Eruca vesicaria aerial biomass inhibition to 40%. Our results show how certain agronomic practices, such as the application of agri-industrial biosolids, could be used to modulate the persistence of allelochemicals in the rhizosphere and control their biological functions in soils.

Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (l-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with l-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves. Keywords: Adsorption; clay minerals; diuron; MCPA; organoclays; terbuthylazine

New designs of pesticide formulations based on organoclays are receiving increasing attention in reducing offsite movement of pesticides in the environment and in prolonging the efficacy of soil-applied pesticides. In the present article, we report the results of laboratory and field experiments conducted to evaluate the influence of the saturating cation, the sorbent : herbicide ratio, and the type of preparation on the controlled release properties of organoclay-based formulations of the herbicide hexazinone. Two organoclays with different affinities for hexazinone (hexadecyltrimethylammonium-exchanged Arizona montmorillonite, HDTMA-SA, and phenyltrimethylammonium-exchanged Arizona montmorillonite, PTMA-SA), two herbicide loadings (10% and 20% AI), and three types of preparation were assayed. Laboratory experiments showed that hexazinone formulations based on HDTMA-SA displayed slow-release properties in water, retarded herbicide leaching through soil columns, and maintained a herbicidal efficacy similar to that of the currently available commercial hexazinone formulation (wettable powder). In contrast, PTMA-SA formulations released the herbicide instantaneously and did not display slow-release properties. High organoclay-herbicide ratios and the use of organic solvent made the interaction between HDTMA-SA and the herbicide more intimate and reduced the release rate of hexazinone, suggesting that a range of release and leaching behaviours can be achieved by selecting the type of preparation and the herbicide loading in the formulations. A field experiment confirmed the usefulness of HDTMA-SA formulations of hexazinone to reduce herbicide leaching while maintaining weed-control efficacy.