Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment
Chlorination is a common method for drinking water disinfection due to its efficiency and low cost. The strong oxidative properties of chlorine can lead to reactions with dissolved organic compounds, resulting in various transformation products. This study investigates the chlorination-induced degra...
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| Format: | info:ar-repo/semantics/artículo |
| Language: | Inglés |
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Elsevier
2025
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| Online Access: | http://hdl.handle.net/20.500.12123/22665 https://www.sciencedirect.com/science/article/abs/pii/S0043135425004269 https://doi.org/10.1016/j.watres.2025.123513 |
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| author | De Geronimo, Eduardo Mosca, Agustín Ignacio Cabrerizo, Franco M. Vargas, Ronald |
| author_browse | Cabrerizo, Franco M. De Geronimo, Eduardo Mosca, Agustín Ignacio Vargas, Ronald |
| author_facet | De Geronimo, Eduardo Mosca, Agustín Ignacio Cabrerizo, Franco M. Vargas, Ronald |
| author_sort | De Geronimo, Eduardo |
| collection | INTA Digital |
| description | Chlorination is a common method for drinking water disinfection due to its efficiency and low cost. The strong oxidative properties of chlorine can lead to reactions with dissolved organic compounds, resulting in various transformation products. This study investigates the chlorination-induced degradation of the sulfonylurea herbicides metsulfuron-methyl and chlorimuron-ethyl, which are frequently found in surface and groundwater. The degradation of these herbicides follows a second-order kinetic model. The apparent second-order rate constants for metsulfuron-methyl range from 3.2 to 244 M⁻¹ s⁻¹, while those for chlorimuron-ethyl range from 2.2 to 287.7 M⁻¹ s⁻¹ within a pH range of 4 to 9. Reaction with HClO effectively reduced the concentration of pesticides. Under acidic conditions, the reaction was significantly enhanced, likely due to hydrolysis or changes in the speciation of the organic compounds. In fact, the rate constant under acidic conditions was approximately 35 and 27 times higher than the reaction rate at more neutral pH for chlorimuron-ethyl and metsulfuron-methyl, respectively. The reaction rate with ClO⁻ approached zero for both herbicides, suggesting a minor or negligible pathway involving the hypochlorite anion. Mass spectrometry identified six chlorination products for metsulfuron-methyl and five for chlorimuron-ethyl. Although the specific reaction mechanisms were not fully elucidated, these products provided valuable insights into the fate of sulfonylureas under chlorination. Under typical disinfection conditions (pH 7 and 4 mg L⁻¹ chlorine), the half-lives of 17.8 minutes for metsulfuron-methyl and 26.6 minutes for chlorimuron-ethyl demonstrate the potential for effective degradation in relatively short timeframes. This study underscores the potential for effective removal of these herbicides in drinking water treatment and highlights the importance of evaluating degradation products over time, as they remain detectable even after seven days. |
| format | info:ar-repo/semantics/artículo |
| id | INTA22665 |
| institution | Instituto Nacional de Tecnología Agropecuaria (INTA -Argentina) |
| language | Inglés |
| publishDate | 2025 |
| publishDateRange | 2025 |
| publishDateSort | 2025 |
| publisher | Elsevier |
| publisherStr | Elsevier |
| record_format | dspace |
| spelling | INTA226652025-06-12T14:37:55Z Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment De Geronimo, Eduardo Mosca, Agustín Ignacio Cabrerizo, Franco M. Vargas, Ronald Tratamiento del Agua Cloración del Agua Sulfonilúreas Herbicidas Degradación Water Treatment Water Chlorination Sulfonylureas Herbicides Degradation Chlorination is a common method for drinking water disinfection due to its efficiency and low cost. The strong oxidative properties of chlorine can lead to reactions with dissolved organic compounds, resulting in various transformation products. This study investigates the chlorination-induced degradation of the sulfonylurea herbicides metsulfuron-methyl and chlorimuron-ethyl, which are frequently found in surface and groundwater. The degradation of these herbicides follows a second-order kinetic model. The apparent second-order rate constants for metsulfuron-methyl range from 3.2 to 244 M⁻¹ s⁻¹, while those for chlorimuron-ethyl range from 2.2 to 287.7 M⁻¹ s⁻¹ within a pH range of 4 to 9. Reaction with HClO effectively reduced the concentration of pesticides. Under acidic conditions, the reaction was significantly enhanced, likely due to hydrolysis or changes in the speciation of the organic compounds. In fact, the rate constant under acidic conditions was approximately 35 and 27 times higher than the reaction rate at more neutral pH for chlorimuron-ethyl and metsulfuron-methyl, respectively. The reaction rate with ClO⁻ approached zero for both herbicides, suggesting a minor or negligible pathway involving the hypochlorite anion. Mass spectrometry identified six chlorination products for metsulfuron-methyl and five for chlorimuron-ethyl. Although the specific reaction mechanisms were not fully elucidated, these products provided valuable insights into the fate of sulfonylureas under chlorination. Under typical disinfection conditions (pH 7 and 4 mg L⁻¹ chlorine), the half-lives of 17.8 minutes for metsulfuron-methyl and 26.6 minutes for chlorimuron-ethyl demonstrate the potential for effective degradation in relatively short timeframes. This study underscores the potential for effective removal of these herbicides in drinking water treatment and highlights the importance of evaluating degradation products over time, as they remain detectable even after seven days. EEA Balcarce Fil: De Gerónimo, Eduardo. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Balcarce. Instituto de Innovación para la Producción Agropecuaria y el Desarrollo Sostenible; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Innovación para la Producción Agropecuaria y el Desarrollo Sostenible; Argentina Fil: Mosca, Agustín. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Balcarce. Instituto de Innovación para la Producción Agropecuaria y el Desarrollo Sostenible; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Innovación para la Producción Agropecuaria y el Desarrollo Sostenible; Argentina Fil: Cabrerizo, Franco M. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; Argentina. Instituto Tecnológico de Chascomús; Argentina Fil: Vargas, Ronald. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; Argentina. Instituto Tecnológico de Chascomús; Argentina 2025-06-12T14:32:24Z 2025-06-12T14:32:24Z 2025-07 info:ar-repo/semantics/artículo info:eu-repo/semantics/article info:eu-repo/semantics/publishedVeresion http://hdl.handle.net/20.500.12123/22665 https://www.sciencedirect.com/science/article/abs/pii/S0043135425004269 1879-2448 (Online) 0043-1354 (Print) https://doi.org/10.1016/j.watres.2025.123513 eng info:eu-repo/semantics/restrictedAccess http://creativecommons.org/licenses/by-nc-sa/4.0/ Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0) application/pdf Elsevier Water Research 280 : 123513 (July 2025) |
| spellingShingle | Tratamiento del Agua Cloración del Agua Sulfonilúreas Herbicidas Degradación Water Treatment Water Chlorination Sulfonylureas Herbicides Degradation De Geronimo, Eduardo Mosca, Agustín Ignacio Cabrerizo, Franco M. Vargas, Ronald Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title | Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title_full | Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title_fullStr | Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title_full_unstemmed | Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title_short | Insights into chlorination-induced degradation of sulfonylurea herbicides: Unraveling kinetics and intermediates during water treatment |
| title_sort | insights into chlorination induced degradation of sulfonylurea herbicides unraveling kinetics and intermediates during water treatment |
| topic | Tratamiento del Agua Cloración del Agua Sulfonilúreas Herbicidas Degradación Water Treatment Water Chlorination Sulfonylureas Herbicides Degradation |
| url | http://hdl.handle.net/20.500.12123/22665 https://www.sciencedirect.com/science/article/abs/pii/S0043135425004269 https://doi.org/10.1016/j.watres.2025.123513 |
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