Identifying bound compounds in non-extractable residues of pesticides in soil by 4-pool kinetic analysis

• Published in: The Science of the total environment 2024-12, Vol.955, p.176814, Article 176814
• Main Authors: Huang, Michael Xiao, Lynn, Kari, Cryer, Steven, Wijntjes, Christiaan
• Format: Article
• Language: English
• Subjects: Bound compounds; Environmental Monitoring - methods; Kinetics; Models, Chemical; Non-extractable residues; Pesticide Residues - analysis; Pesticides; Pesticides - analysis; Soil - chemistry; Soil Pollutants - analysis; Speciation
• ISSN: 0048-9697; 1879-1026; 1879-1026
• DOI: 10.1016/j.scitotenv.2024.176814

This study explores the feasibility of identifying bound compounds in non-extractable residues (NERs) of pesticides in soil by 4-pool kinetic analysis. The 4-pools refer to parent compound, metabolites, NERs, and CO2 in 14C-labeled pesticide soil degradation studies. We discovered the following two characteristic 4-pool kinetic behaviors of formation of NERs: (1) if parent compound is bound as NERs, the metabolites (m(t) in % applied radioactivity (AR)) kinetically drive the evolution of CO2 only; and (2) if a metabolite (x) in a sequential degradation pathway is bound as NERs, m(t) is split into m1(t) and m2(t) at the metabolite (x) that is bound as NERs, which kinetically drive the formation of NERs and evolution of CO2 respectively. We developed two (i.e., Parent➔NER and metabolite➔NER) 4-pool models to capture the kinetic behaviors respectively. By fitting the models to a set of 4-pool data, we not only determine whether NERs form from parent compound or metabolites but also identify the bound metabolite (x) by resolving the metabolites into M1(t) and M2(t) (i.e., the variables used to simulate m1(t) and m2(t)) and then matching m1(t) (i.e., the sum of the bound metabolite (x) and its metabolite precursors) with M1(t). By applying the models to 14C-labeled parent compound-dosed studies and then sequentially to metabolite-dosed studies for 7 pesticides with ≥70 % AR NERs, we identified the bound compounds, which have the moieties known to be responsible for NERs, are bound as NERs instantaneously when dosed into soil, and account for pH dependency of NER formation. [Display omitted] •By 4-pool kinetic analysis, we can identify bound compounds in NERs of pesticides.•Identified compounds have the moieties which are known to be responsible for NERs.•Identified compounds are also bound instantaneously as NERs when dosed into soil.•The binding mechanism explains the pH dependency of NER formation.•Pesticides with NER-responsible moieties generate similar levels of NERs.