Enhanced database creation with in silico workflows for suspect screening of unknown tebuconazole transformation products in environmental samples by UHPLC-HRMS.

The search and identification of organic contaminants in agricultural watersheds has become a crucial effort to better characterize watershed contamination by pesticides. The past decade has brought a more holistic view of watershed contamination via the deployment of powerful analytical strategies such as non-target and suspect screening analysis that can search more contaminants and their transformation products. However, suspect screening analysis remains broadly confined to known molecules, primarily due to the lack of analytical standards and suspect databases for unknowns such as pesticide transformation products. Here we developed a novel workflow by cross-comparing the results of various in silico prediction tools against literature data to create an enhanced database for suspect screening of pesticide transformation products. This workflow was applied on tebuconazole, used here as a model pesticide, and resulted in a suspect screening database counting 291 transformation products. The chromatographic retention times and tandem mass spectra were predicted for each of these compounds using 6 models based on multilinear regression and more complex machine-learning algorithms. This comprehensive approach to the investigation and identification of tebuconazole transformation products was retrospectively applied on environmental samples and found 6 transformation products identified for the first time in river water samples.

Fate of phosphorus from treated wastewater in soil-based constructed wetlands.

In France, soil-based constructed wetlands for the discharge of treated wastewater have become a popular technique to both reduce flow to surface receiving water bodies and perform complementary treatments. This study focuses on the fate of phosphorus in three different soils, as well as its assimilation by Phragmites australis. The experimental set-up consisted of three lysimeters containing three soils selected to be representative of those typically found near wastewater treatment plants (i.e. a silt loam Fluvisol, a sandy loam Fluvisol and a sandy-clay loam Technosol). Lysimeters are undisturbed soil monoliths (1.5 m3 in volume), whose masses are continuously monitored in order to obtain an accurate water mass balance. The lysimeters here were intermittently fed for 3.5 days and then left to rest for 3.5 days. The experiment lasted 26 months, including 18 months of feeding with phosphorus (PO4-P, TP) fluxes in and out being monitored along with water content, oxygen content and redox potential at various depths. The quantities of phosphorus stored in the soils and assimilated in the Phragmites australis were measured. Phosphorus fractionation in soils was performed to better understand its distribution and potential remobilization. Low phosphate concentrations were measured at the outlets of all three lysimeters, thereby highlighting satisfactory phosphorus retention in the three soils (removal efficiencies >90%). A significant amount of phosphorus can be exported by harvesting Phragmites australis aerial parts (26%, 17% and 13% of the yearly incoming phosphorus mass for the silt loam Fluvisol, sandy loam Fluvisol and sandy-clay loam Technosol, respectively). The fractionation step served to determine that the phosphorus retained in the soil was primarily bound to iron oxides/hydroxides, calcium and clay. Moreover, it was found to be preferable to hold oxidizing (aerobic) conditions and pH close to neutral in order to maintain conditions under which the complexes formed with phosphorus remain stable.