Bioavailability of organoclay formulations of atrazine in soil

Pesticide formulations based on organoclays have been proposed to prolong the efficacy and reduce the environmental impact of pesticides in soil. This research addressed the question of whether atrazine in organoclay-based formulations is irreversibly sorbed or is bioavailable for bacterial degradation in soil. Different cations of l-carnitine (CAR), tyramine (TYRAM), hexadimethrine (HEXADIM), phenyltrimethylammonium (PTMA), hexadecyltrimethylammonium (HDTMA), and Fe(III) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at 100% of the cation exchange capacity (CEC) of the clays as a strategy to enhance the affinity of the clay minerals for atrazine. A Buse loam soil from Becker, MN, was treated with three organoclay-based formulations of 14C-atrazine or free herbicide and incubated for 2 weeks. To determine the bioavailability of 14C-atrazine, the soil was inoculated with Pseudomonas sp. strain ADP, which rapidly mineralizes atrazine. At day 0, and after a 2 week incubation, mineralization and the amount of 14C-atrazine residues distributed between the aqueous-extractable, methanol-extractable, and bound fractions in the soil were determined to characterize the availability of nonaged and aged atrazine residues. By the end of the 2 week incubation, the microorganisms had mineralized >80% of the initial readily available (water-extractable) and >70% of the less readily available (methanol-extractable) 14C-atrazine in the soil. Bound residues increased from <4% at day 0 to ～17% after the 2 week incubation for both the formulated and free forms of atrazine. The results of these incubation experiments show that the bioavailabilities of atrazine were similar in the case of the organoclay formulations and as free atrazine. This indicated that whereas more atrazine was sorbed and less likely to be transported in soil, when formulated as organoclay complexes, it was ultimately accessible to degrading bacteria, so that the herbicide is likely to be naturally attenuated by soil microorganisms.