Estimating simazine-treated area in watersheds based on annual stream loads.

Existing data in the United States are insufficient for estimating pesticide-treated crop areas at the watershed scale. The objective of this research was to evaluate an approach for estimating simazine usage on corn (Zea mays L.) based on its transport to streams of the Salt River Basin (SRB) of Missouri, USA. Annual loads of total simazine and atrazine (parent + metabolites) were quantified for seven SRB watersheds from 2005 to 2017. Simazine-treated corn area was computed as the total simazine load (g) divided by total atrazine load (g ha-1 ) on a treated area basis; atrazine was used as surrogate in the absence of treated area simazine load data. From 2005 to 2010, an estimated 3.8-31% of the corn area within SRB watersheds was treated with simazine, and four of six watersheds had <10% of corn treated. In contrast, Long Branch Creek (2005-2017) and its sub-watersheds (2012-2017) had ≥20% of corn area treated with simazine. Key sources of variation in treated area estimates included extremely dry years with little simazine transport and disparities between spring-applied atrazine and fall-applied simazine transport. However, compared with national estimates for the SRB, these results estimated simazine usage that was generally one to two orders of magnitude greater and showed far more spatial and temporal variation among watersheds. These results demonstrated that this broadly applicable output-based method is a significant improvement over existing input-based national data for estimating pesticide usage in watersheds.

A simple method for isolation and purification of DIBOA-Glc from Tripsacum dactyloides.

Naturally occurring benzoxazinones (Bx) are a highly reactive class of compounds that have received particular attention in the past several decades. Recently, we identified 2-ß-D-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one (DIBOA-Glc) as the compound present in the roots of Eastern gamagrass {Tripsacum dactyloides (L.)} responsible for atrazine degradation. However, characterization of the DIBOA-Glc/atrazine degradation reaction has been limited due to difficulties in attaining sufficient quantities of purified DIBOA-Glc. The objective of the study was to develop a simple purification and isolation method for obtaining bulk quantities of highly purified DIBOA-Glc. T. dactyloides roots were extracted with 90% aqueous methanol, and the crude extract was fractionated using an HPLC equipped with a C8 semi-prep column and fraction collector. UHPLC-DAD-MS/MS was used to confirm the identity of DIBOA-Glc in the fractions collected. Analysis by 13C and 1H NMR and DAD indicated that 542 mg of DIBOA-Glc with a purity of > 99% was obtained. The reactivity of the DIBOA-Glc was confirmed in a 16 hour assay with atrazine, which resulted in 48.5% ± 1.2% (SD) atrazine degradation. The method described here offers several advantages over existing extraction and synthesis methods, which are more cumbersome, use hazardous chemicals, and yield only small quantities of purified compound. The newly developed method will facilitate future research characterizing the chemical behavior of DIBOA-Glc and determine its potential as an atrazine mitigation and remediation tool.

Identification of an atrazine-degrading benzoxazinoid in Eastern gamagrass (Tripsacum dactyloides).

This study was part of a broader effort to identify and characterize promising atrazine-degrading phytochemicals in Eastern gamagrass (Tripsacum dactyloides ; EG) roots for the purpose of mitigating atrazine transport from agroecosystems. The objective of this study was to isolate and identify atrazine-degrading compounds in EG root extracts. Eastern gamagrass roots were extracted with methanol, and extracts were subjected to a variety of separation techniques. Fractions from each level of separation were tested for atrazine-degrading activity by a simple assay. Compounds were identified using high-performance liquid chromatography-tandem mass spectrometry. Results from the experiments identified 2-ß-d-glucopyranosyloxy-4-hydroxy-1,4-benzoxazin-3-one (DIBOA-Glc) as the compound responsible for atrazine degradation in the root extract fractions collected. 2-ß-d-Glucopyranosyloxy-1,4-benzoxazin-3-one (HBOA-Glc) was also identified in the root extract fractions, but it did not demonstrate activity against atrazine. Estimated root tissue concentrations were 210 mg kg(-1) (wet wt basis) for DIBOA-Glc and 71 mg kg(-1) for HBOA-Glc (dry wt basis, 710 ± 96 and 240 ± 74 mg kg(-1), respectively). This research was the first to describe the occurrence and concentrations of an atrazine-degrading benzoxazinone compound isolated from EG tissue.