Direct and indirect photodegradation of atrazine and S-metolachlor in agriculturally impacted surface water and associated C and N isotope fractionation.

Knowledge of direct and indirect photodegradation of pesticides and associated isotope fractionation can help to assess pesticide degradation in surface waters. Here, we investigated carbon (C) and nitrogen (N) isotope fractionation during direct and indirect photodegradation of the herbicides atrazine and S-metolachlor in synthetic agriculturally impacted surface waters containing nitrates (20 mg L-1) and dissolved organic matter (DOM, 5.4 mgC L-1). Atrazine and S-metolachlor were quickly photodegraded by both direct and indirect processes (half-lives <5 and <7 days, respectively). DOM slowed down photodegradation while nitrates increased degradation rates. The analysis of transformation products showed that oxidation mediated by hydroxyl radicals (HO˙) predominated during indirect photodegradation. UV light (254 nm) led to significant C and N isotope fractionation, yielding isotopic fractionation values εC = 2.7 ± 0.3 and 0.8 ± 0.1‰, and εN = 2.4 ± 0.3 and -2.6 ± 0.7‰ for atrazine and S-metolachlor, respectively. In contrast, photodegradation under simulated sunlight led to negligible C and slight N isotope fractionation, emphasizing the effect of the radiation wavelengths on the isotope fractionation induced by direct photodegradation. Altogether, these results highlight the importance of using simulated sunlight to obtain environmentally-relevant isotopic fractionation values and to distinguish photodegradation and other dissipation pathways in surface waters.

Phase Transfer and Biodegradation of Pesticides in Water-Sediment Systems Explored by Compound-Specific Isotope Analysis and Conceptual Modeling.

Current approaches are often limited to evaluating the contribution of pesticide dissipation processes in water-sediment systems as both degradation and phase transfer, that is, sorption-desorption, contribute to the apparent decrease of pesticide concentration. Here, the dissipation of widely used herbicides acetochlor and S-metolachlor was examined in laboratory by water-sediment microcosm experiments under oxic and anoxic conditions. Compound-specific isotope analysis (CSIA) emphasized insignificant carbon isotope fractionation in the sediment, indicating prevailing pesticide degradation in the water phase. Conceptual modeling accounting for phase transfer and biodegradation indicated that biodegradation may be underestimated when phase transfer is not included. Phase transfer does not affect carbon isotope fractionation for a wide spectrum of molecules and environmental conditions, underscoring the potential of pesticide CSIA as a robust approach to evaluate degradation in water-sediment systems. CSIA coupled with the identification of transformation products by high-resolution tandem mass spectrometry suggests the degradation of acetochlor and S-metolachlor to occur via nucleophilic substitution and the predominance of oxalinic acids as transformation products under both anoxic and oxic conditions. Altogether, combining the pesticide CSIA, the identification of transformation products, and the use of conceptual phase-transfer models improves the interpretation of pesticide dissipation in water-sediment systems.

Carbon and nitrogen stable isotope fractionation during abiotic hydrolysis of pesticides.

Compound-specific Stable Isotope Analysis (CSIA) has been recently established as a tool to study pesticide degradation in the environment. Among degradative processes, hydrolysis is environmentally relevant as it can be chemically or enzymatically mediated. Here, CSIA was used to examine stable carbon and nitrogen isotope fractionation during abiotic hydrolysis of legacy or currently used pesticides (chloroacetanilide herbicides: Acetochlor, Alachlor, S-Metolachlor and Butachlor, acylalanine fungicide: Metalaxyl, and triazine herbicide: Atrazine). Degradation products analysis and CN dual-CSIA allowed to infer hydrolytic degradation pathways from carbon and nitrogen isotopic fractionation. Carbon isotopic fractionation for alkaline hydrolysis revealed similar apparent kinetic isotope effects (AKIEC = 1.03-1.07) for the 6 pesticides, which were consistent with SN2 type nucleophilic substitutions. Neither enantio-selectivity (EF ≈ 0.5) nor enantio-specific isotope fractionation occurred during hydrolysis of R (AKIEC = 1.04 ±â€¯0.01) and S (AKIEC = 1.04 ±â€¯0.02) enantiomers of a racemic mixture of Metalaxyl. Dual element isotope plots enabled to tease apart CCl bond breaking of alkane (Λ ≈ εN/εC ≈ 0, Acetochlor, Butachlor) and aromatic π-system (Λ ≈ 0.2, Atrazine) from CO bond breaking by dealkylation (Λ ≈ 0.9, Metalaxyl). Reference values for abiotic versus biotic SN2 reactions derived from carbon and nitrogen CSIA may be used to untangle pesticide degradation pathways and evaluate in situ degradation during natural and engineered remediation.

Regioselective pivaloylation of N-phthaloylchitosan: a promising soluble intermediate for chitosan chemistry.

A simple and efficient pivaloylation of primary alcohols was realized on N-phthaloylchitosan that was regioselectively and entirely protected. The selectivity of this mild esterification was demonstrated by comparison with (1)H NMR chemical shifts of H-1 and H-3 of complete 3,6-O-dipivaloylated derivatives. The selective hydrazinolysis of N-phthaloyl groups in the presence of pivaloyl ester was achieved in ethanol/water. High molecular weight 6-O-pivaloylchitosan, purified by ultrafiltration, with solubility in organic solvents was obtained. The selective introduction of a phosphorus moiety in O-3 using chlorodiphenylphosphine has led to 3-O-diphenylphosphinito-N-phthaloyl-6-O-pivaloylchitosan with a ds of 0.97 from energy dispersive X-ray spectroscopy, which demonstrates the potential applications of O-6 pivaloyl protection. The pivaloylation of O-6 alcohols can enhance the solubility of some chitosan derivatives and therefore contributes to the development of applications involving chitosan through regioselective modifications of alcohol and amino groups.