Abstract
Chlorine dioxide has been reported as very efficiently removing pesticides and other organic compounds from water matrixes. Due to pesticide toxicity and potential toxicity of their degradation products, it is important to monitor these compounds as environmental pollutants in ground and surface waters. Evaluating the effects of chlorine dioxide treatment is necessary, and toxicity studies are used to ascertain the severity of effects of intermediates due to incomplete degradation of the parent compounds. In this paper, for the first time, chlorine dioxide is applied and evaluated for the removal of chloroacetamide herbicides (pethoxamid and metazachlor) from waters (deionized water and Sava River water). The degradation degree of herbicides was measured by high-performance liquid chromatography, the main degradation products were identified using gas chromatography with a triple quadrupole mass detector, and the degree of mineralization was monitored by total organic carbon analysis. Four and two degradation products were identified after pethoxamid and metazachlor degradation, respectively. Total organic carbon analysis showed mineralization occurred, but it was incomplete. The mineralization and the characteristics of the degradation products obtained were tested using Daphnia magna and showed lower toxicity than the parent herbicides. The advantage of the applied treatment was a very high degradation percentage for pethoxamid removal from deionized water and Sava River water (100% and 97%, respectively), with higher mineralization efficiency (65%) than metazachlor. Slightly lower degradation efficiency in the Sava River water was due to chlorine dioxide oxidizing the herbicides and dissolved organic matter simultaneously.
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References
American Public Health Association, American Water Works Association, & Water Environment Federation. (1998). Standard methods for the examination of water and wastewater (20th ed.). Washington: APHA-AWWA-WEF.
Arques, A., Amat, A. M., García-Ripoll, A., & Vicente, R. (2007). Detoxification and/or increase of the biodegradability of aqueous solutions of dimethoate by means of solar photocatalysis. Journal of Hazardous Materials, 146(3), 447–452. https://doi.org/10.1016/j.jhazmat.2007.04.046.
Ben, W., Shi, Y., Li, W., Zhang, Y., & Qiang, Z. (2017). Oxidation of sulfonamide antibiotics by chlorine dioxide in water: kinetics and reaction pathways. Chemical Engineering Journal, 327, 743–750. https://doi.org/10.1016/j.cej.2017.06.157.
Casado, J., Santillo, D., & Johnston, P. (2018). Multi-residue analysis of pesticides in surface water by liquid chromatography quadrupole-Orbitrap high resolution tandem mass spectrometry. Analytica Chimica Acta, 1024, 1–17. https://doi.org/10.1016/j.aca.2018.04.026.
Cerejeira, M. J., Viana, P., Batista, S., Pereira, T., Silva, E., Valério, M. J., Silva, A., Ferreira, M., & Silva-Fernandes, A. M. (2003). Pesticides in Portuguese surface and ground waters. Water Research, 37(5), 1055–1063. https://doi.org/10.1016/S0043-1354(01)00462-6.
Chamberlain, E., Shi, H., Wang, T., Ma, Y., Fulmer, A., & Adams, C. (2012). Comprehensive screening study of pesticide degradation via oxidation and hydrolysis. Journal of Agricultural and Food Chemistry, 60(1), 354–363. https://doi.org/10.1021/jf2033158.
Chen, Q., Wang, Y., Chen, F., Zhang, Y., & Liao, X. (2014). Chlorine dioxide treatment for the removal of pesticide residues on fresh lettuce and in aqueous solution. Food Control, 40, 106–112. https://doi.org/10.1016/j.foodcont.2013.11.035.
D’Archivio, A. A., Fanelli, M., Mazzeo, P., & Ruggieri, F. (2007). Comparison of different sorbents for multiresidue solid-phase extraction of 16 pesticides from groundwater coupled with high-performance liquid chromatography. Talanta, 71(1), 25–30. https://doi.org/10.1016/j.talanta.2006.03.016.
Friedman, C. L., Lemley, A. T., & Hay, A. (2006). Degradation of chloroacetanilide herbicides by anodic Fenton treatment. Journal of Agricultural and Food Chemistry, 54(7), 2640–2651. https://doi.org/10.1021/jf0523317.
Geerdink, R. B., Kooistra-Sijpersma, A., Tiesnitsch, J., Kienhuis, P. G. M., & Brinkman, U. A. T. (1999). Determination of polar pesticides with atmospheric pressure chemical ionisation mass spectrometry–mass spectrometry using methanol and/or acetonitrile for solid-phase desorption and gradient liquid chromatography. Journal of Chromatography A, 863(2), 147–155. https://doi.org/10.1016/S0021-9673(99)00898-5.
Hanot, V., Goscinny, S., & Deridder, M. (2015). A simple multi-residue method for the determination of pesticides in fruits and vegetables using a methanolic extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry: optimization and extension of scope. Journal of Chromatography A, 1384, 53–66. https://doi.org/10.1016/j.chroma.2015.01.040.
Hey, G., Grabic, R., Ledin, A., la Cour Jansen, J., & Andersen, H. R. (2012). Oxidation of pharmaceuticals by chlorine dioxide in biologically treated wastewater. Chemical Engineering Journal, 185-186, 236–242. https://doi.org/10.1016/j.cej.2012.01.093.
Hladik, M. L., Bouwer, E. J., & Roberts, A. L. (2008). Neutral chloroacetamide herbicide degradates and related compounds in Midwestern United States drinking water sources. Science of the Total Environment, 390(1), 155–165. https://doi.org/10.1016/j.scitotenv.2007.09.042.
Huntscha, S., Singer, H. P., McArdell, C. S., Frank, C. E., & Hollender, J. (2012). Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography–tandem mass spectrometry. Journal of Chromatography A, 1268, 74–83. https://doi.org/10.1016/j.chroma.2012.10.032.
Hurtado-Sánchez, M. C., Romero-González, R., Rodríguez-Cáceres, M. I., Durán-Merás, I., & Frenich, A. G. (2013). Rapid and sensitive on-line solid phase extraction-ultra high performance liquid chromatography–electrospray-tandem mass spectrometry analysis of pesticides in surface waters. Journal of Chromatography A, 1305, 193–202. https://doi.org/10.1016/j.chroma.2013.07.045.
Hvězdová, M., Kosubová, P., Košíková, M., Scherr, K. E., Šimek, Z., Brodský, L., Šudoma, M., Škulcová, L., Sáňka, M., Svobodová, M., Krkošková, L., Vašíčková, J., Neuwirthová, N., Bielská, L., & Hofman, J. (2018). Currently and recently used pesticides in Central European arable soils. Science of the Total Environment, 613-614, 361–370. https://doi.org/10.1016/j.scitotenv.2017.09.049.
Hwang, E., Cash, J. N., & Zabik, M. J. (2002). Chlorine and chlorine dioxide treatment to reduce or remove EBDCs and ETU residues in a solution. Journal of Agricultural and Food Chemistry, 50(16), 4734–4742. https://doi.org/10.1021/jf020307c.
Jardim, W. F., Moraes, S. G., & Takiyama, M. M. K. (1997). Photocatalytic degradation of aromatic chlorinated compounds using TiO2: toxicity of intermediates. Water Research, 31(7), 1728–1732. https://doi.org/10.1016/S0043-1354(96)00349-1.
Jevtić, S., Vukojević, V., Djurdjić, S., Pergal, M. V., Manojlović, D. D., Petković, B. B., & Stanković, D. M. (2018). First electrochemistry of herbicide pethoxamid and its quantification using electroanalytical approach from mixed commercial product. Electrochimica Acta, 277, 136–142. https://doi.org/10.1016/j.electacta.2018.05.004.
Jia, X.-H., Feng, L., Liu, Y.-Z., & Zhang, L.-Q. (2017). Oxidation of antipyrine by chlorine dioxide: reaction kinetics and degradation pathway. Chemical Engineering Journal, 309, 646–654. https://doi.org/10.1016/j.cej.2016.10.062.
Jokić, A., Srejić, R., Pfendt, P. A., & Zakrzewska, J. (1995). Characterization of lake sediment humic acids from the Ćelije Lake system near Kruševac (Central Serbia) by 13C and 1H solution NMR and 13C cpmas NMR. Water, Air, and Soil Pollution, 84(1), 159–173. https://doi.org/10.1007/BF00479595.
Jović, M., Manojlović, D., Stanković, D., Dojčinović, B., Obradović, B., Gašić, U., & Roglić, G. (2013). Degradation of triketone herbicides, mesotrione and sulcotrione, using advanced oxidation processes. Journal of Hazardous Materials, 260, 1092–1099. https://doi.org/10.1016/j.jhazmat.2013.06.073.
Jović, M. S., Dojčinović, B. P., Kovačević, V. V., Obradović, B. M., Kuraica, M. M., Gašić, U. M., & Roglić, G. M. (2014). Effect of different catalysts on mesotrione degradation in water falling film DBD reactor. Chemical Engineering Journal, 248, 63–70. https://doi.org/10.1016/j.cej.2014.03.031.
Katsumata, H., Okada, T., Kaneco, S., Suzuki, T., & Ohta, K. (2010). Degradation of fenitrothion by ultrasound/ferrioxalate/UV system. Ultrasonics Sonochemistry, 17(1), 200–206. https://doi.org/10.1016/j.ultsonch.2009.06.011.
Kiljanek, T., Niewiadowska, A., Semeniuk, S., Gaweł, M., Borzęcka, M., & Posyniak, A. (2016). Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry—honeybee poisoning incidents. Journal of Chromatography A, 1435, 100–114. https://doi.org/10.1016/j.chroma.2016.01.045.
Klüttgen, B., Dülmer, U., Engels, M., & Ratte, H. T. (1994). ADaM, an artificial freshwater for the culture of zooplankton. Water Research, 28(3), 743–746. https://doi.org/10.1016/0043-1354(94)90157-0.
Komives, T. (2016). Chemical plant protection. Past. Present. Future? Ecocycles, 2(1), 1–2. https://doi.org/10.19040/ecocycles.v2i1.47.
Kralova, M., Levchuk, I., Kasparek, V., Sillanpaa, M., & Cihlar, J. (2015). Influence of synthesis conditions on physical properties of lanthanide-doped titania for photocatalytic decomposition of metazachlor. Chinese Journal of Catalysis, 36(10), 1679–1684. https://doi.org/10.1016/S1872-2067(15)60943-3.
Kuster, M., López de Alda, M., & Barceló, D. (2009). Liquid chromatography–tandem mass spectrometric analysis and regulatory issues of polar pesticides in natural and treated waters. Journal of Chromatography A, 1216(3), 520–529. https://doi.org/10.1016/j.chroma.2008.08.031.
Lopez, A., Mascolo, G., Tiravanti, G., & Passino, R. (1997). Degradation of herbicides (ametryn and isoproturon) during water disinfection by means of two oxidants (hypochlorite and chlorine dioxide). Water Science and Technology, 35(4), 129–136. https://doi.org/10.1016/S0273-1223(97)00018-8.
Marković, M., Jović, M., Stanković, D., Kovačević, V., Roglić, G., Gojgić-Cvijović, G., & Manojlović, D. (2015). Application of non-thermal plasma reactor and Fenton reaction for degradation of ibuprofen. Science of the Total Environment, 505, 1148–1155. https://doi.org/10.1016/j.scitotenv.2014.11.017.
Miodragović, Z. M., Jokić, A., & Pfendt, P. A. (1992). Fulvic acid characterization in an alluvial sediment sequence: differences between clay and sand environments. Organic Geochemistry, 18(4), 481–487. https://doi.org/10.1016/0146-6380(92)90111-A.
Nödler, K., Licha, T., Bester, K., & Sauter, M. (2010). Development of a multi-residue analytical method, based on liquid chromatography–tandem mass spectrometry, for the simultaneous determination of 46 micro-contaminants in aqueous samples. Journal of Chromatography A, 1217(42), 6511–6521. https://doi.org/10.1016/j.chroma.2010.08.048.
Nolet, L. M. L., & Rathore, H. S. (2012). Pesticides: evaluation of environmental pollution. Boca Raton: CRC Press.
OECD (2004). Guideline 202: Daphnia sp., acute immobilisation test. OECD Guidel Test Chem 1–12. doi:https://doi.org/10.1787/20745761.
Pérez, A., Otero, R., Romero Esquinas, A., Jiménez, J. R., & Fernández, J. M. (2017). Potential use of modified hydrotalcites as adsorbent of bentazon and metazachlor. Applied Clay Science, 141, 300–307. https://doi.org/10.1016/j.clay.2017.03.007.
Pergal, M. V., Kodranov, I. D., Pergal, M. M., Dojčinović, B. P., Stanković, D. M., Petković, B. B., et al. (2018). Correction to: Assessment of degradation of sulfonylurea herbicides in water by chlorine dioxide. Water, Air, & Soil Pollution, 229(9), 310. https://doi.org/10.1007/s11270-018-3967-y.
Persoone, G., Marsalek, B., Blinova, I., Törökne, A., Zarina, D., Manusadzianas, L., Nalecz-Jawecki, G., Tofan, L., Stepanova, N., Tothova, L., & Kolar, B. (2003). A practical and user-friendly toxicity classification system with microbiotests for natural waters and wastewaters. Environmental Toxicology, 18(6), 395–402. https://doi.org/10.1002/tox.10141.
PPDB - Pesticides Properties DataBase, University of Hertfordshire (2019). http://sitem.herts.ac.uk/aeru/ppdb/en/index.htm. Accessed 4 April 2020.
Priya, D. N., Modak, J. M., Trebše, P., Žabar, R., & Raichur, A. M. (2011). Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films. Journal of Hazardous Materials, 195, 214–222. https://doi.org/10.1016/j.jhazmat.2011.08.030.
Raczyk-Stanisławiak, U., Świetlik, J., Dąbrowska, A., & Nawrocki, J. (2004). Biodegradability of organic by-products after natural organic matter oxidation with ClO2—case study. Water Research, 38(4), 1044–1054. https://doi.org/10.1016/j.watres.2003.10.032.
Rav-Acha, C. (1984). The reactions of chlorine dioxide with aquatic organic materials and their health effects. Water Research, 18(11), 1329–1341. https://doi.org/10.1016/0043-1354(84)90001-0.
Reemtsma, T., Alder, L., & Banasiak, U. (2013a). Emerging pesticide metabolites in groundwater and surface water as determined by the application of a multimethod for 150 pesticide metabolites. Water Research, 47(15), 5535–5545. https://doi.org/10.1016/j.watres.2013.06.031.
Reemtsma, T., Alder, L., & Banasiak, U. (2013b). A multimethod for the determination of 150 pesticide metabolites in surface water and groundwater using direct injection liquid chromatography–mass spectrometry. Journal of Chromatography A, 1271(1), 95–104. https://doi.org/10.1016/j.chroma.2012.11.023.
Shi, L., Li, N., Wang, C., & Wang, C. (2010). Catalytic oxidation and spectroscopic analysis of simulated wastewater containing o-chlorophenol by using chlorine dioxide as oxidant. Journal of Hazardous Materials, 178(1), 1137–1140. https://doi.org/10.1016/j.jhazmat.2010.01.125.
Singh, J., & Kadapakkam Nandabalan, Y. (2018). Prospecting Ammoniphilus sp. JF isolated from agricultural fields for butachlor degradation. 3 Biotech, 8(3), 164. https://doi.org/10.1007/s13205-018-1165-7.
Solís, R., Rivas, F. J., & Gimeno, O. (2017). Removal of aqueous metazachlor, tembotrione, tritosulfuron and ethofumesate by heterogeneous monopersulfate decomposition on lanthanum-cobalt perovskites. Applied Catalysis B: Environmental, 200, 83–92. https://doi.org/10.1016/j.apcatb.2016.06.058.
Souissi, Y., Bouchonnet, S., Bourcier, S., Kusk, K. O., Sablier, M., & Andersen, H. R. (2013). Identification and ecotoxicity of degradation products of chloroacetamide herbicides from UV-treatment of water. Science of the Total Environment, 458-460, 527–534. https://doi.org/10.1016/j.scitotenv.2013.04.064.
Teodorović, I., & Maurić, N. (2003). TesTox Version 1.0.
Tian, F.-X., Xu, B., Zhang, T.-Y., & Gao, N.-Y. (2014). Degradation of phenylurea herbicides by chlorine dioxide and formation of disinfection by-products during subsequent chlor(am)ination. Chemical Engineering Journal, 258, 210–217. https://doi.org/10.1016/j.cej.2014.07.094.
Tian, F., Qiang, Z., Liu, C., Zhang, T., & Dong, B. (2010). Kinetics and mechanism for methiocarb degradation by chlorine dioxide in aqueous solution. Chemosphere, 79(6), 646–651. https://doi.org/10.1016/j.chemosphere.2010.02.015.
Tian, H. (2011). Determination of chloramphenicol, enrofloxacin and 29 pesticides residues in bovine milk by liquid chromatography–tandem mass spectrometry. Chemosphere, 83(3), 349–355. https://doi.org/10.1016/j.chemosphere.2010.12.016.
Wang, Y., Liu, H., Liu, G., Xie, Y., & Ni, T. (2015). Oxidation of diclofenac with chlorine dioxide in aquatic environments: influences of different nitrogenous species. Environmental Science and Pollution Research, 22(12), 9449–9456. https://doi.org/10.1007/s11356-015-4118-2.
Wasim, A., Dwaipayan, S., & Ashim, C. (2009). Impact of pesticides use in agriculture: their benefits and hazards. Interdisciplinary Toxicology, 2(1), 1–12. https://doi.org/10.2478/v10102-009-0001-7.
Weisshaar, H., & Böger, P. (1987). Primary effects of chloroacetamides. Pesticide Biochemistry and Physiology, 28(2), 286–293. https://doi.org/10.1016/0048-3575(87)90027-7.
Weisshaar, H., Retzlaff, G., & Böger, P. (1988). Chloroacetamide inhibition of fatty acid synthesis. Pesticide Biochemistry and Physiology, 32(3), 212–216. https://doi.org/10.1016/0048-3575(88)90103-4.
Wenk, J., Aeschbacher, M., Salhi, E., Canonica, S., von Gunten, U., & Sander, M. (2013). Chemical oxidation of dissolved organic matter by chlorine dioxide, chlorine, and ozone: effects on its optical and antioxidant properties. Environmental Science & Technology, 47(19), 11147–11156. https://doi.org/10.1021/es402516b.
Włodarczyk, M. (2014). Influence of formulation on mobility of metazachlor in soil. Environmental Monitoring and Assessment, 186(6), 3503–3509. https://doi.org/10.1007/s10661-014-3633-9.
Wu, J. G., & Laird, D. A. (2003). Abiotic transformation of chlorpyrifos to chlorpyrifos oxon in chlorinated water. Environmental Toxicology and Chemistry, 22(2), 261–264.
Zhang, J., Zheng, J.-W., Liang, B., Wang, C.-H., Cai, S., Ni, Y.-Y., He, J., & Li, S. P. (2011). Biodegradation of chloroacetamide herbicides by Paracoccus sp. FLY-8 in vitro. Journal of Agricultural and Food Chemistry, 59(9), 4614–4621. https://doi.org/10.1021/jf104695g.
Zhang, L., Guo, X., Yan, F., Su, M., & Li, Y. (2007). Study of the degradation behaviour of dimethoate under microwave irradiation. Journal of Hazardous Materials, 149(3), 675–679. https://doi.org/10.1016/j.jhazmat.2007.04.039.
Zhang, Y., Xiao, Z., Chen, F., Ge, Y., Wu, J., & Hu, X. (2010). Degradation behavior and products of malathion and chlorpyrifos spiked in apple juice by ultrasonic treatment. Ultrasonics Sonochemistry, 17(1), 72–77. https://doi.org/10.1016/j.ultsonch.2009.06.003.
Zheng, J., Li, R., Zhu, J., Zhang, J., He, J., Li, S., & Jiang, J. (2012). Degradation of the chloroacetamide herbicide butachlor by Catellibacterium caeni sp. nov DCA-1T. International Biodeterioration & Biodegradation, 73, 16–22. https://doi.org/10.1016/j.ibiod.2012.06.003.
Acknowledgments
The authors would like to thank TwinOxide-RS d.o.o. for providing components for the preparation of chlorine dioxide (TWINS preparation).
Funding
This work was financially supported by the Ministry of Education, Science, and Technological Development of the Republic of Serbia (Grant No. 451-03-68/2020-14/200026; 451-03-68/2020-14/200168).
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Chemical structure of the chloracetamide herbicides; Photograph of the sampling site, the Sava River, Belgrade; Main Sava River water characteristics. (DOCX 911 kb)
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Kodranov, I.D., Pergal, M.V., Avdin, V.V. et al. Examination of degradation and ecotoxicology of pethoxamid and metazachlor after chlorine dioxide treatment. Environ Monit Assess 192, 422 (2020). https://doi.org/10.1007/s10661-020-08392-1
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DOI: https://doi.org/10.1007/s10661-020-08392-1