Fate of atrazine and chlorpyrifos during solid state fermentation—examination of processes

Abstract

Solid state fermentation (SSF) was investigated as a means to dispose of two commonly used pesticides, chlorpyrifos (O, O‐diethyl O‐(3,5,6‐trichloro‐2‐pyridyl) phosphorothioate) and atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐1,3,5‐triazine). SSF experiments were carried out in bench‐scale bioreaetors (equipped with CO₂ and volatile organic traps) containing a mixture of lignocellulosic materials and a radiolabeled pesticide. Ethyl acetate‐extractable, alkali soluble, and alkali insoluble fractions were evaluated for radioactivity following a 60‐d incubation period at 40°C. The majority of the 2, 6‐pyridyl‐¹⁴C]chlorpyrifos was associated with the ethyl acetate extract (about 74%), 17% was trapped as organic volatiles by polyurethane foam traps and < 0.5% of the chlorpyrifos was mineralized to CO². Only small amounts of the radioactivity were associated with alkali soluble (0.0003%) and alkali insoluble (0.3%) fractions. In the ¹⁴C‐U‐ring] atrazine bioreactors, very little of the radioactivity volatilized (<0.5%) and less than 0.5% was mineralized to CO₂. Approximately 57% of the applied radioactivity was associated with the ethyl acetate extract while 9% and 24% of the radioactivity was associated with the alkali soluble (humic and fulvic acids) and alkali insoluble fractions, respectively. Possible reaction mechanisms by which covalent bonds could be formed between atrazine (or metabolites) and humic substances were investigated. The issue of bound atrazine residue (alkali soluble fraction) was at least partially resolved. Oxidative coupling experiments revealed that formation of covalent bond linkages between amino substituent groups of atrazine residue and humic substances is highly unlikely.