Pesticide compounds can influence denitrification processes in groundwater in many ways. This study observed behavior of three selected pesticides under denitrifying conditions. Alachlor, terbuthylazine, and tebuconazole, in a concentration of 0.1 mL L-1, were examined using two laboratory denitrifications assays: a "short" 7-day and a "long" 28-day test. During these tests, removal of pesticides via adsorption and biotic decomposition, as well as the efficiency of nitrate removal in the presence of the pesticides, were measured. No considerable inhibition of the denitrification process was observed for any of the pesticides. On the contrary, significant stimulation was observed after 21 days for alachlor (49%) and after seven days for terbuthylazine (40%) and tebuconazole (36%). Adsorption was in progress only during the first seven days in the case of all tested pesticides and increased only negligibly afterwards. Immediate adsorption of terbuthylazine was probably influenced by the mercuric chloride inhibitor. A biotic loss of 4% was measured only in the case of alachlor.

Institute of Chemistry Faculty of Civil Engineering Brno University of Technology 602 00 Brno Czech Republic

Research Centre for Toxic Compounds in the Environment Faculty of Science Masaryk University 611 37 Brno Czech Republic

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FAO (Food and Agriculture Organization of the United Nations) Pesticides Use. 2022. [(accessed on 27 August 2023)]. Available online: http://www.fao.org/faostat/en/#data/RP/visualize.

European Commission Active Substances, Safeners and Synergists. 2023. [(accessed on 27 August 2023)]. Available online: https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/start/screen/active-substances.

de Souza R.M., Seibert D., Quesada H.B., de Jesus Bassetti F., Fagundes-Klen M.R., Bergamasco R. Occurrence, impacts and general aspects of pesticides in surface water: A review. Process Saf. Environ. Prot. 2020;135:22–37. doi: 10.1016/j.psep.2019.12.035. DOI

Pino N., Peñuela G. Simultaneous degradation of the pesticides methyl parathion and chlorpyrifos by an isolated bacterial consortium from a contaminated site. Int. Biodeterior. Biodegrad. 2011;65:827–831. doi: 10.1016/j.ibiod.2011.06.001. DOI

Schulz R. Field Studies on Exposure, Effects, and Risk Mitigation of Aquatic Nonpoint-Source Insecticide Pollution: A Review. J. Environ. Qual. 2004;33:419–448. doi: 10.2134/jeq2004.4190. PubMed DOI

Caldas S.S., Demoliner A., Costa F.P., D’Oca M.G.M., Primel E.G. Pesticide residue determination in groundwater using solid-phase extraction and high-performance liquid chromatography with diode array detector and liquid chromatography-tandem mass spectrometry. J. Braz. Chem. Soc. 2010;21:642–650. doi: 10.1590/S0103-50532010000400009. DOI

Nasiri M., Ahmadzadeh H., Amiri A. Sample preparation and extraction methods for pesticides in aquatic environments: A review. TrAC Trends Anal. Chem. 2020;123:115772. doi: 10.1016/j.trac.2019.115772. DOI

Barra Caracciolo A., Fajardo C., Grenni P., Saccà M.L., Amalfitano S., Ciccoli R., Martin M., Gibello A. The role of a groundwater bacterial community in the degradation of the herbicide terbuthylazine. FEMS Microbiol. Ecol. 2010;71:127–136. doi: 10.1111/j.1574-6941.2009.00787.x. PubMed DOI

Kodeš V. Problematika pesticidů v ochraně vod—Jaká data máme k dispozici a co nám říkají? In Proceedings of the Sborník Přednášek a Posterových Sdělení z 13; Bienální Konference a Výstavy VODA. Poděbrady; Czech Republic. 18–19 September 2019.

Moulisová A., Bendakovská L., Kožíšek F., Vavrouš A., Jeligová H., Kotal F. Pesticidy a jejich metabolity v pitné vodě. Vodn. Hospodářství Spec. Vědeckotechnický Časopis Pro Proj. Realiz. Plánování Vodn. Hospodářství Souvisejích Oborech Zivotn. Prostředí. 2018;68:4–10.

Fenner K., Canonica S., Wackett L.P., Elsner M. Evaluating Pesticide Degradation in the Environment: Blind Spots and Emerging Opportunities. Science. 2013;341:752–758. doi: 10.1126/science.1236281. PubMed DOI

Navarro S., Vela N., José Giménez M., Navarro G. Persistence of four s-triazine herbicides in river, sea and groundwater samples exposed to sunlight and darkness under laboratory conditions. Sci. Total Environ. 2004;329:87–97. doi: 10.1016/j.scitotenv.2004.03.013. PubMed DOI

Chen Z., Chen Y., Vymazal J., Kule L., Koželuh M. Dynamics of chloroacetanilide herbicides in various types of mesocosm wetlands. Sci. Total Environ. 2017;577:386–394. doi: 10.1016/j.scitotenv.2016.10.216. PubMed DOI

Howarth R.W. Coastal nitrogen pollution: A review of sources and trends globally and regionally. Harmful Algae. 2008;8:14–20. doi: 10.1016/j.hal.2008.08.015. DOI

Ju X.T., Zhang C. Nitrogen cycling and environmental impacts in upland agricultural soils in North China: A review. J. Integr. Agric. 2017;16:2848–2862. doi: 10.1016/S2095-3119(17)61743-X. DOI

WHO . Guidelines for Drinking-Water Quality. 3rd ed. WHO; Geneva, Switzerland: 2004.

Capodici M., Avona A., Laudicina V.A., Viviani G. Biological groundwater denitrification systems: Lab-scale trials aimed at nitrous oxide production and emission assessment. Sci. Total Environ. 2018;630:462–468. doi: 10.1016/j.scitotenv.2018.02.260. PubMed DOI

Hiscock K.M., Lloyd J.W., Lerner D.N. Review of natural and artificial denitrification of groundwater. Water Res. 1991;25:1099–1111. doi: 10.1016/0043-1354(91)90203-3. DOI

Michel C., Baran N., André L., Charron M., Joulian C. Side Effects of Pesticides and Metabolites in Groundwater: Impact on Denitrification. Front. Microbiol. 2021;12:662727. doi: 10.3389/fmicb.2021.662727. PubMed DOI PMC

Pániková K., Weigelhofer G., Bílková Z., Malá J. Denitrification Assays for Testing Effects of Xenobiotics on Aquatic Denitrification and Their Degradation in Aquatic Environments. Water. 2023;15:2536. doi: 10.3390/w15142536. DOI

Gikas G.D., Pérez-Villanueva M., Tsioras M., Alexoudis C., Pérez-Rojas G., Masís-Mora M., Lizano-Fallas V., Rodríguez-Rodríguez C.E., Vryzas Z., Tsihrintzis V.A. Low-cost approaches for the removal of terbuthylazine from agricultural wastewater: Constructed wetlands and biopurification system. Chem. Eng. J. 2018;335:647–656. doi: 10.1016/j.cej.2017.11.031. DOI

Elsayed O.F., Maillard E., Vuilleumier S., Millet M., Imfeld G. Degradation of chloroacetanilide herbicides and bacterial community composition in lab-scale wetlands. Sci. Total Environ. 2015;520:222–231. doi: 10.1016/j.scitotenv.2015.03.061. PubMed DOI

Colosio C., Rubino F.M., Moretto A. International Encyclopedia of Public Health. Elsevier; Amsterdam, The Netherlands: 2017. Pesticides; pp. 454–462. DOI

Cao D., Wu R., Dong S., Wang F., Ju C., Yu S., Xu S., Fang H., Yu Y. Triazole resistance in Aspergillus fumigatus in crop plant soil after tebuconazole applications. Environ. Pollut. 2020;266:115124. doi: 10.1016/j.envpol.2020.115124. PubMed DOI

European Food Safety Authority Conclusion regarding the peer review of the pesticide risk assessment of the active substance tebuconazole. [(accessed on 27 August 2023)];EFSA Sci. Rep. 2008 :4–6. Available online: https://efsa.onlinelibrary.wiley.com/doi/epdf/10.2903/j.efsa.2008.176r. DOI

Herrero-Hernández E., Andrades M.S., Marín-Benito J.M., Sánchez-Martín M.J., Rodríguez-Cruz M.S. Field-scale dissipation of tebuconazole in a vineyard soil amended with spent mushroom substrate and its potential environmental impact. Ecotoxicol. Environ. Saf. 2011;74:1480–1488. doi: 10.1016/j.ecoenv.2011.04.023. PubMed DOI

Fresenius W., Quentin K., Schneider W. Water Analysis—A Practical Guide to Physico-Chemical. 1st ed. Springer-Verlag; Berlin Heidelberg, Germany: 1988. Chemical and Microbiological Water Examination and Quality Assurance.

Zhao J., He Q., Chen N., Peng T., Feng C. Denitrification behavior in a woodchip-packed bioreactor with gradient filling for nitrate-contaminated water treatment. Biochemical Engineering Journal. 2020;154 doi: 10.1016/j.bej.2019.107454. DOI

Paul E.A. Soil Microbiology, Ecology, and Biochemistry. 3rd ed. Elsevier Inc.; Oxford, UK: 2007.

Oh J., Silverstein J.A. Acetate Limitation and Nitrite Accumulation during Denitrification. J. Environ. Eng. 1999;125:234–242. doi: 10.1061/(ASCE)0733-9372(1999)125:3(234). DOI

Hu R., Zheng X., Zheng T., Xin J., Wang H., Sun Q. Effects of carbon availability in a woody carbon source on its nitrate removal behavior in solid-phase denitrification. J. Environ. Manag. 2019;246:832–839. doi: 10.1016/j.jenvman.2019.06.057. PubMed DOI

Qian W., Ma B., Li X., Zhang Q., Peng Y. Long-term effect of pH on denitrification: High pH benefits achieving partial-denitrification. Bioresour. Technol. 2019;278:444–449. doi: 10.1016/j.biortech.2019.01.105. PubMed DOI

Chung J., Bae W. Nitrite reduction by a mixed culture under conditions relevant to shortcut biological nitrogen removal. Biodegradation. 2002;13:163–170. doi: 10.1023/A:1020896412365. PubMed DOI

Lahdhiri A., Lesage G., Hannachi A., Heran M. Minimum COD needs for denitrification: From biological models to experimental set-up. Desalination Water Treat. 2017;61:326–334. doi: 10.5004/dwt.2017.11130. DOI

Novak P.J., Christ S.J., Parkin G.F. Kinetics of alachlor transformation and identification of metabolites under anaerobic conditions. Water Res. 1997;31:3107–3115. doi: 10.1016/S0043-1354(97)00151-6. DOI

Pozo C., Salmeron V., Rodelas B., Martinez-Toledo M.V., Gonzalez-Lopez J. Effects of the herbicide alachlor on soil microbial activities. Ecotoxicology. 1994;3:4–10. doi: 10.1007/BF00121384. PubMed DOI

Cycoń M., Piotrowska-Seget Z., Kaczyńska A., Kozdrój J. Microbiological characteristics of a sandy loam soil exposed to tebuconazole and λ-cyhalothrin under laboratory conditions. Ecotoxicology. 2006;15:639–646. doi: 10.1007/s10646-006-0099-8. PubMed DOI

Graham D.W., Miley M.K., deNoyelles F., Smith V.H., Thurman E.M., Carter R. Alachlor transformation patterns in aquatic field mesocosms under variable oxygen and nutrient conditions. Water Res. 2000;34:4054–4062. doi: 10.1016/S0043-1354(00)00147-0. DOI

Dehghani M., Nasseri S., Zamanian Z. Biodegradation of alachlor in liquid and soil cultures under variable carbon and nitrogen sources by bacterial consortium isolated from corn field soil. Iran. J. Environ. Health Sci. Eng. 2013;10:21. doi: 10.1186/1735-2746-10-21. PubMed DOI PMC

Čadková E., Komárek M., Kaliszová R., Vaněk A., Balíková M. Tebuconazole Sorption in Contrasting Soil Types. Soil Sediment Contam. Int. J. 2013;22:404–414. doi: 10.1080/15320383.2013.733448. DOI

Ilhan Z.E., Ong S.K., Moorman T.B. Dissipation of Atrazine, Enrofloxacin, and Sulfamethazine in Wood Chip Bioreactors and Impact on Denitrification. J. Environ. Qual. 2011;40:1816–1823. doi: 10.2134/jeq2011.0082. PubMed DOI

Krause Camilo B. Bioreactor reduces atrazine and nitrate in tile drain waters. Ecol. Eng. 2016;86:269–278. doi: 10.1016/j.ecoleng.2015.09.072. DOI

Ahmad K.S. Evaluating the Adsorption Potential of Alachlor and Its Subsequent Removal from Soils via Activated Carbon. Soil Sediment Contam. Int. J. 2018;27:249–266. doi: 10.1080/15320383.2018.1470604. DOI