Vesicle-clay complexes in which positively charged vesicles composed of didodecyldimethylammonium bromide (DDAB) were adsorbed on montmorillonite removed efficiently anionic (sulfentrazone, imazaquin) and neutral (alachlor, atrazine) pollutants from water. These complexes (0.5% w:w) removed 92-100% of sulfentrazone, imazaquin and alachlor and 60% of atrazine from a solution containing 10mg/L of it. A synergistic effect on the adsorption of atrazine was observed when all pollutants were present simultaneously (30 mg/L each), its percentage of removal being 85.5. Column filters (18 cm) filled with a mixture of quartz sand and vesicle-clay (100:1, w:w) were tested. For the passage of 1L (25 pore volumes) of a solution including all the pollutants at 10mg/L each, removal was complete for sulfentrazone and imazaquin, 94% for alachlor and 53.1% for atrazine, whereas removal was significantly less efficient when using activated carbon. A similar advantage of the vesicle-clay filter was observed for the capacities of removal.
The influence of two organic amendments consisting of an urban waste compost (SUW) and a commercial amendment from olive mill wastes (OW) was assessed on the sorption properties and leaching of the ionizable herbicide imazaquin on four soils with different physicochemical characteristics. A loamy sand soil (CR), a loam soil (P44), a silt loam soil (AL), and a clay soil (TM), with low-medium organic matter contents, were chosen. Sorption-desorption experiments were performed on the original soils and on a mixture of these soils with the organic amendments at a rate of 6.25% (w/w). These mixtures were used just after preparation and after aging for 3 months. Imazaquin adsorption was higher on AL soil because of its high content of amorphous iron oxides, whereas it was related to the soils' organic matter (OM) contents on TM and CR soils and to acid pH on P44 soil. Addition of exogenous OM to soils caused a decrease in the adsorption of the herbicide with the only exception of CR soil, due to blocking of adsorptive surfaces and/or equilibrium pH rise. The extent of this decrease was dependent only on the nature of the added amendment on AL soil. The adsorbed amounts of imazaquin on aged organic fertilized soils were usually fairly close to that on original soils. Results of soil column experiments indicate that addition of exogenous organic matter cannot be considered as a regular practice for retarded movement of imazaquin.
A new clay-liposome complex was developed for reducing leaching of herbicides and contamination of groundwater. The liposomes were composed of the neutral and Environmental Protection Agency approved phospholipid phosphatidylcholine (PC). Adsorption of PC liposomes on the clay mineral montmorillonite could exceed the cation exchange capacity of the clay, and was well simulated by the Langmuir equation. X-ray diffraction results for 6 mM PC and 1.6 g/L clay (3 day incubation) yielded a basal spacing of 7.49 nm, which was interpreted as the formation of a supported planar bilayer on montmorillonite platelets. Fluorescence methods demonstrated structural changes which reflected adsorption of PC followed by loss of vesicle integrity as measured by the penetration of dithionite into the internal monolayer of fluorescently labeled liposomes, resulting in a decrease in fluorescence intensity to 18% of initial after 4 h. Energy transfer was demonstrated after 1 h from labeled liposomes to montmorillonite labeled by an acceptor. The neutral herbicide alachlor adsorbed on the liposome-clay complex, yielding a formulation of up to 40% active ingredient, and 1.6-fold reduction in herbicide release in comparison to the commercial formulation. Hence, the PC-montmorillonite complex can form a basis for environmentally friendly formulations of herbicides, which would yield 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 USEPA. PC enhanced 15-and 18-fold alachlor and atrazine solubilities, respectively. A 6 mM PC:5g/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.3
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