Fate of chlorpyrifos bound residues in paddy soils: Release, transformation, and phytoavailability.

Chlorpyrifos (CPF) is a widely used organophosphorus insecticide that tends to form bound residues (BRs) in soils. However, the stability and biological activity of CPF-BRs remain to be explored. Facilitated by carbon-14 tracing, this study obtained CPF-BRs initially formed in two typical paddy soils (14C-CPF-BRin), and further investigated their release, transformation and phytoavailability using duckweed (Lemna minor) as a model aquatic organism. Most 14C-CPF-BRin in soils were composed of the parent CPF and its metabolite 3,5,6-trichloro-2-pyridinol (2-OH-TCP), which was mainly formed through reversible entrapment by soil fulvic acids and humin (>80%). At 36 d, 66.67-80.90% of the 14C-CPF-BRin was released, of which only 2-OH-TCP could be released into the water and absorbed by the duckweed, with bioconcentration factors ranging from 247.99 to 324.68 L kg-1. The subsequent metabolism of released 14C-CPF-BRin in duckweed included phase I metabolism from 2-OH-TCP to 4-OH-TCP and phase II metabolism of conjugation of TCP with plant endogenous amino acids. The study suggested that CPF bound residues have high bioavailability in paddy field environments. Given that many pesticides and non-pesticide chemicals share structures analogous to CPF, the findings have important implications for better understanding the environmental and human health risks of man-made chemicals.

The fate of erythromycin in soils and its effect on soil microbial community structure.

Erythromycin is one of the most commonly used macrolide antibiotics. However, little is known currently about the environmental behavior and fate of erythromycin in soils. Here erythromycin was 14C-labeled to investigate its degradation, mineralization and bound residues (BRs) in three typical agricultural soils. Results indicated the fate of 14C-erythromycin in soils varied greatly with soils types. Erythromycin was rapidly mineralized in black soil (BS) and fluvo-aquic soil (FS), whereas it rapidly formed large amounts of BRs in red soil (RS) with slow mineralization. At 120 d, about 90% of the introduced 14C-erythromycin was mineralized as 14CO2 in BS and FS, but only 30% in RS. There was still a certain proportion of BRs in all soils, especially in RS, up to 50%. Erythromycin residues (ERs) may be underestimated if its residues are only assessed by extractable residues. We recommend to include a practical silylation procedure to quantify Type I BRs in regular erythromycin residue monitoring, which can be used as signal of the need to initiate further laboratory BRs experiments. The degradation of erythromycin was mainly attributed to soil microorganisms, which promote erythromycin mineralization and lead to the re-release of BRs. Microbial analysis showed that erythromycin persisted longer in soils with lower microbial diversity and richness. Erythromycin at 2.5 mg kg-1 showed no significant impact on soil microbial diversity in all treatments, but caused changes in soil community composition. This study provides a reference for scientific evaluation and pollution remediation of erythromycin in soils.

Reducing environmental risks of chlorpyrifos application in typical soils by adding appropriate exogenous organic matter: Evidence from a simulated paddy field experiment.

Chlorpyrifos (CPF), as an organophosphate insecticide extensively used in the modern agricultural system, has been gradually banned in many countries due to its reported health risks to organisms, including humans. This study used simulated paddy field experiments and carbon-14 tracing to explore the possibility of reducing environmental risks of chlorpyrifos application through appropriate agronomic practice. Results showed 14C-CPF concentration in rice plants planted in the red soil (RS) was significantly higher than that in black soil (BS) and fluvo-aquic soil (FS). The application of biochar and chicken manure in RS reduced 14C-CPF accumulation in rice plants, and the content of 14C-CPF in rice grains decreased by 25% and 50%, respectively. Adding biochar to all three soils reduced the migration of 14C-CPF, especially in FS with the highest risk of 14C-CPF migration. The addition of chicken manure in FS reduced the migration of 14C-CPF and the total residual amount of 14C-CPF in the soil. In addition, chicken manure treatment increased the formation of 14C-bound residues (BRs) in soils and changed the distribution 14C-BRs in humus. The results indicated that the degree of environmental risks associated with the CPF application varies with soil types and could be reduced by introducing suitable exogenous organic matter into different soils, which is of great significance for guiding the scientific application of chlorpyrifos in agronomic practices.

Combination of high specific activity carbon-14 labeling and high resolution mass spectrometry to study pesticide metabolism in crops: Metabolism of cycloxaprid in rice.

The study of pesticide metabolism in crops is critical for assessing the mode of action and environmental risks of pesticides. However, the study of pesticide metabolism in crops is usually complicated and it is often a daunting challenge to accurately screen the metabolites of novel pesticides in complex matrices. This study demonstrated a combined use of high-specific activity carbon-14 labeling and high-resolution mass spectrometry (HSA-14C-HRMS) for metabolism profiling of a novel neonicotinoid cycloxaprid in rice. By generating the characteristic radioactive peaks on the liquid chromatogram, the use of 14C can eliminate the severe interference of complex matrices and quickly probe target compounds; by producing ion pairs with unique abundance ratios on HRMS, high-specific activity labeling can effectively exclude false matrix positives and promote the elucidation of metabolite structure. The structures of 15 metabolites were identified, three of which were further confirmed by authentic standards. Based on these metabolites, a metabolic profile of cycloxaprid was established, which includes denitrification, demethylation, imidazolidine hydroxylation and ring cleavage olefin formation, oxidation and carboxylation reactions. The strategy of combining high-specific activity 14C labeling and HRMS offers unique advantages and provides a powerful solution for profiling unknown metabolites of novel pesticides in complex matrices, especially when traditional non-labeling methods are not feasible.

Reducing the Environmental Risk of Chlorpyrifos Application through Appropriate Agricultural Management: Evidence from Carbon-14 Tracking.

Chlorpyrifos (CPF) is one of the most critical insecticides in the world. However, many countries are gradually banning its use due to its reported hazardous impacts on humans. This study explored the possibility of reducing the environmental risk of CPF through appropriate agricultural management practices. Results showed that the environmental risk of CPF is lower under drainage conditions because there is more mineralization and less bound residues (BRs) than under submerged conditions. Bioaugmentation significantly enhanced the CPF mineralization and inhibited the formation of CPF-BRs. Biochar adsorbed CPF and thus reduced its bioavailability, but it could not completely eliminate the toxicity of CPF. In addition, bioaugmentation did not significantly affect the native microbial community of CPF-contaminated soil, suggesting its safety in reducing the environmental risk of CPF. The study indicated that the environmental risk of CPF could be reduced by appropriate agricultural management such as water management, bioaugmentation, soil biochar amendment, and selecting suitable soil types.

Enhanced mineralization of chlorpyrifos bound residues in soil through inoculation of two synergistic degrading strains.

Bioaugmentation methods are frequently employed for pesticide pollution remediation; however, it is not clear whether the introduced bacteria affect the pesticide bound residue (BRs) composition and whether the BRs can be catabolized by the introduced strains. This study aimed at answering these questions by using 14C-chlorpyrifos (14C-CPF) and two CPF-degrading strains (Pseudomonas sp. DSP-1 and Cupriavidus sp. P2). The results showed that the BRs can be up to 83.0%, and that the CPF-BRs formed can be further transformed into 14CO2 by the strains. Indeed, the microbial inoculation can increase the CPF mineralization by 1.0-22.1 times and can decrease the BRs by up to ~50% of the control (on day 20). Compared with the control without bioaugmentation, microbial inoculation enhanced the release of BRs by 2.2-18.0 times. Adding biochar to the soil can greatly inhibit CPF mineralization and maintain the BR content at a relatively stable level. The CPF residue can affect the composition of the indigenous soil microbial community, but the introduction of bacteria for remediation did not have a significant effect. The results indicate that Pseudomonas sp. DSP-1 and Cupriavidus sp. P2 are useful for remediating both CPF extractable and bound residues.

Characterization, Pathogenicity, and Phylogenetic Analyses of Colletotrichum Species Associated with Brown Blight Disease on Camellia sinensis in China.

Brown blight disease caused by Colletotrichum species is a common and serious foliar disease of tea (Camellia sinensis). Fungal isolates from several tea plantations causing typical brown blight symptoms were identified as belonging to the Colletotrichum acutatum species complex and the Colletotrichum gloeosporioides species complex based on morphological characteristics as well as DNA analysis of the internal transcribed spacer (ITS) and glyceraldehyde 3-phosphate dehydrogenase (GAPDH). Colletotrichum acutatum, a new causal agent associated with C. sinensis, showed high phenotypic and genotypic diversity compared with the more commonly reported C. gloeosporioides. Phylogenetic analysis derived from individual and combined ITS and GAPDH sequences clearly clustered C. acutatum and C. gloeosporioides into separate species. Pathogenicity tests validated that both species were causal agents of tea brown blight disease and were highly pathogenic to tea leaves. However, the two groups of C. gloeosporioides with low levels of variability within their ITS and GAPDH regions differed in their virulence. This study reports for the first time the characterization of C. acutatum and C. gloeosporioides causing brown blight disease on tea (Camellia sinensis (L.) O. Kuntze) in China.