Relative abundance of atropisomer pairs in metolachlor metabolites, MESA and MOXA, vary with slope and hydric soils in subwatersheds of the Choptank River watershed, Maryland.

Metolachlor is the most heavily used member of acetanilide herbicides, which are noted for forming highly soluble metabolites in root zone soils soon after field application. The two primary metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), retain the same chiral chemistry as their source and are important tracers of nitrate loading from agricultural cropland. New analytical methods for separating the isomers of MESA and MOXA, enable studies assessing changes in the abundance of atropisomer pairs of the carbon chiral enantiomers in environmental samples.

enantiomeric separation of MESA and MOXA, two environmentally important metabolites of the herbicide, metolachlor.

Complete separation of the -enantiomers of the two most abundant, persistent polar metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), was achieved using UPLC equipped with a reverse phase chiral column and trace detection with an electrospray triple quadrupole mass spectrometer. Various conditions that influenced the separation and instrumental signal were investigated to achieve the optimum separation and instrument response within an analysis time of less than 30 minutes. Different eluting solvent compositions for each metabolite were required for optimized separation of of the 4 enantiomers.

Contribution of ketone/aldehyde-containing compounds to the composition and optical properties of Suwannee River fulvic acid revealed by ultrahigh resolution mass spectrometry and deuterium labeling.

A prior method of mass labeling ketone-/aldehyde-containing species in natural dissolved organic matter (DOM) is further developed and applied. This application involved the treatment of Suwannee River fulvic acid (SRFA) with increasing concentrations of sodium borodeuteride (NaBD), followed by detection of reduced species via negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). The extent of reduction, as determined by ESI FTICR MS, resulting from increasing concentrations of NaBD correlated well with changes in the absorption and emission spectra of the corresponding untreated and borodeuteride-reduced samples, providing evidence that ketone/aldehyde functional groups contribute substantially to the bulk optical properties of SRFA.

Combined Effects of pH and Borohydride Reduction on Optical Properties of Humic Substances (HS): A Comparison of Optical Models.

The combined effects of pH and borohydride reduction on the optical properties of a series of humic substances and a lignin model were examined to probe the molecular moieties and interactions that give rise to the observed optical properties of these materials. Increasing the pH from 2 to 12 produced significantly enhanced absorption across the spectra of all samples, with distinct spectral responses observed over pH ranges attributable to the deprotonation of carboxylic acids and phenols. Borohydride reduction substantially attenuated the broadband absorption enhancements with pH, clearly indicating that the loss of absorption due to ketone/aldehyde reduction is coupled with the pH-dependent increase in absorption due to deprotonation of carboxylic acids and phenols.