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Parabens and salicylates were examined as disinfection byproduct (DBP) precursors to explore the possible influence of ipso substitution (i.e., halogen exchange) on the yield and speciation of trihalomethanes (THMs) formed during water chlorination. Substoichiometric conversion of C–Br bonds into C–Cl bonds was confirmed for several parabens and salicylates. The co-occurrence of (mono)brominated and nonhalogenated precursors in the presence of free chlorine (but in the absence of added Br–) generated polybrominated THMs, implicating ipso substitution. The THM molar yield, bromine incorporation, and bromine recovery from brominated and nonhalogenated precursor mixtures were commensurate with those observed from equimolar additions of NaBr, indicating efficient displacement of aromatic bromine by free chlorine followed by reincorporation of liberated HOBr into DBP precursors. The THM molar yield from brominated precursors was enhanced by a factor of ≤20 relative to that from nonhalogenated precursors. Trends in THM molar yields and bromine incorporation differed between brominated parabens and brominated salicylates, suggesting that the influence of ipso substitution on THM formation varies with the structure of the organic precursor. Collectively, these results provide new evidence of the often-overlooked role ipso substitution can play in promoting halogen exchange and bromine enrichment among DBPs in chlorinated waters. 

The toxic effects of herbicides are often incompletely selective and can harm crops. Safeners are “inert” ingredients commonly added to herbicide formulations to protect crops from herbicide-induced injury. Dichloroacetamide safeners have been previously shown to undergo reductive dechlorination in anaerobic abiotic systems containing an iron (hydr)oxide mineral (goethite or hematite) amended with Fe( ii ). Manganese oxides ( e.g. , birnessite) are important redox-active species that frequently co-occur with iron (hydr)oxides, yet studies examining the effects of more than one mineral on transformations of environmental contaminants are rare. Herein, we investigate the reactivity of dichloroacetamide safeners benoxacor, furilazole, and dichlormid in binary-mineral, anaerobic systems containing Fe( ii )-amended hematite and birnessite. As the molar ratio of Fe( ii )-to-Mn( iv ) oxide increased, the transformation rate of benoxacor and furilazole increased. The safener dichlormid did not transform appreciably over the sampling period (6 hours). The concentration of pH buffer ([MOPS] = 10–50 mM), ionic strength ([NaCl] = 10–200 mM), and order of solute addition ( e.g. , safener followed by Fe( ii ) or vice versa ) do not appreciably affect transformation rates of the examined dichloroacetamide safeners in Fe( ii ) + hematite slurries. The presence of agrochemical co-formulants, including the herbicide S -metolachlor and three surfactants, in solutions containing Cr(H 2 O) 6 2+ (as a model homogeneous reductant) also did not substantially influence rates of safener transformation. This study is among the first to examine laboratory systems of intermediate complexity ( e.g. , systems containing mixtures of agrochemical co-formulants or mineral phases) when assessing the environmental fate of emerging contaminants such as dichloroacetamide safeners.