Catalytic degradation of dimethomorph by nitrogen-doped rice husk biochar.

N-doped biochar is widely used for activating persulfate to degrade organic pollutants. Which type of N atom is the key factor for activation is still unclear and needs to be further explored and analyzed. In this study, four kinds of biochar were prepared using urea and rice husk as precursors, and tested for the catalytic degradation of dimethomorph. Increasing the nitrogen doping level caused the catalytic removal efficiency of dimethomorph in the presence of peroxymonosulfate increased from 16.6% to 86.8%. A correlation analysis showed that the ability of N-doped biochar to activate PMS is mainly related to the content of pyrrole N, graphite N and carbonyl and the degree of defects. In experiments on electron paramagnetic resonance and free radical suppression, the reactive species of SO4•-, 1O2,·OH and O2.- were detected, among which 1O2 was found to be the main agent in the nonradical pathway. The degradation pathways for dimethomorph were analyzed based on a total of 8 degradation products identified by high-performance liquid chromatography-time of flight mass spectrometry (HPLC-Q-TOFMS). The results of this study provide a fundamental basis for using agricultural waste to produce inexpensive and efficient nonmetal catalysts that are highly effective in reducing dimethomorph levels in agricultural lands.

Abiotic transformation of kresoxim-methyl in aquatic environments: Structure elucidation of transformation products by LC-HRMS and toxicity assessment.

In this study, abiotic transformation of an important strobilurin fungicide, kresoxim-methyl, was investigated under controlled laboratory conditions for the first time by studying its kinetics of hydrolysis and photolysis, degradation pathways and toxicity of possibly formed transformation products (TPs). The results indicated that kresoxim-methyl showed a fast degradation in pH9 solutions with DT50 of 0.5 d but relatively stable under neutral or acidic environments in the dark. It was prone to photochemical reactions under simulated sunlight, and the photolysis behavior was easily affected by different natural substances such as humic acid (HA), Fe3+and NO3-which are ubiquitous in natural water, showing the complexity of degradation mechanisms and pathways of this chemical compound. The potential multiple photo-transformation pathways via photoisomerization, hydrolyzation of methyl ester, hydroxylation, cleavage of oxime ether and cleavage of benzyl ether were observed. 18 TPs generated from these transformations were structurally elucidated based on an integrated workflow combining suspect and nontarget screening by high resolution mass spectrum (HRMS), and two of them were confirmed with reference standards. Most of TPs, as far as we know, have never been described before. The in-silico toxicity assessment showed that some of TPs were still toxic or very toxic to aquatic organisms, although they exhibit lower aquatic toxicity compared to the parent compound. Therefore, the potential hazards of the TPs of kresoxim-methyl merits further evaluation.

Characterization of peanut-shell biochar and the mechanisms underlying its sorption for atrazine and nicosulfuron in aqueous solution.

The aim of the present study was to investigate the sorption of atrazine and nicosulfuron onto several experimentally produced biochars, as well as to understand the influence of biochar structure on sorption mechanisms. Nine biochars were generated by pyrolyzing peanut shell at 300, 450, or 600 °C and exposing samples to each of the several deashing treatments: none, water or HCl. The sorption of atrazine and nicosulfuron by the nine biochars were evaluated. Biochars were characterized via elemental analyzer, BET-N2 surface area, FTIR and XPS. Three kinetic models were used to fit the sorption kinetics data and both the Freundlich and dual-mode models described the sorption isotherms well. All the biochar samples exhibited high sorption affinity for both atrazine and nicosulfuron. The sorption mechanisms of the biochar included hydrophobic partition, π-π electron donor-acceptor interactions, H-bonding, and pore-filling mechanism, and these mechanisms were dependent on both the degree of biochar carbonization and the concentration of atrazine or nicosulfuron. Ash could bind to atrazine and nicosulfuron by specific interactions but played a negative role in the sorption, especially on high pyrolyzing temperature biochars. These results will facilitate the production of efficient and cheap adsorbents for reducing the risk of atrazine and nicosulfuron.