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Evaluation of azamethiphos and dimethoate degradation using chlorine dioxide during water treatment

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Abstract

Chlorine dioxide (ClO2) degradation of the organophosphorus pesticides azamethiphos (AZA) and dimethoate (DM) (10 mg/L) in deionized water and in Sava River water was investigated for the first time. Pesticide degradation was studied in terms of ClO2 level (5 and 10 mg/L), degradation duration (0.5, 1, 2, 3, 6, and 24 h), pH (3.00, 7.00, and 9.00), and under light/dark conditions in deionized water. Degradation was monitored using high-performance liquid chromatography. Gas chromatography coupled with triple quadrupole mass detector was used to identify degradation products of pesticides. Total organic carbon was measured to determine the extent of mineralization after pesticide degradation. Real river water was used under recommended conditions to study the influence of organic matter on pesticide degradation. High degradation efficiency (88–100% for AZA and 85–98% for DM) was achieved in deionized water under various conditions, proving the flexibility of ClO2 degradation for the examined organophosphorus pesticides. In Sava River water, however, extended treatment duration achieved lower degradation efficiency, so ClO2 oxidized both the pesticides and dissolved organic matter in parallel. After degradation, AZA produced four identified products (6-chlorooxazolo[4,5-b]pyridin-2(3H)-one; O,O,S-trimethyl phosphorothioate; 6-chloro-3-(hydroxymethyl)oxazolo[4,5-b]pyridin-2(3H)-one; O,O-dimethyl S-hydrogen phosphorothioate) and DM produced three (O,O-dimethyl S-(2-(methylamino)-2-oxoethyl) phosphorothioate; e.g., omethoate; S-(2-(methylamino)-2-oxoethyl) O,O-dihydrogen phosphorothioate; O,O,S-trimethyl phosphorodithioate). Simple pesticide degradation mechanisms were deduced. Daphnia magna toxicity tests showed degradation products were less toxic than parent compounds. These results contribute to our understanding of the multiple influences that organophosphorus pesticides and their degradation products have on environmental ecosystems and to improving pesticide removal processes from water.

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References

  • Adityosulindroa S, Julcoura C, Barthea L (2018) Heterogeneous Fenton oxidation using Fe-ZSM5 catalyst for removal of ibuprofen in wastewater. J Environ Chem Eng 6:5920–5928

    Google Scholar 

  • Aguilar CAH, Narayanan J, Singh N, Thangarasu P (2014) Kinetics and mechanism for the oxidation of anilines by ClO2: a combined experimental and computational study. J Phys Org Chem 27:440–449

    CAS  Google Scholar 

  • Ahmed S, Rasul MG, Brown R, Hashib MA (2011) Influence of parameters on the heterogeneous photocatalytic degradation of pesticides and phenolic contaminants in wastewater: a short review. J Environ Menag 92:311–330

    CAS  Google Scholar 

  • Alvarez-Zaldívar P, Payraudeau S, Meite F, Masbou J, Imfeld G (2018) Pesticide degradation and export losses at the catchment scale: insights from compound-specific isotope analysis (CSIA). Water Res 139:198–207

    Google Scholar 

  • APHA (American Public Health Association) (1998) American Water Works Association, and Water Environment Federation, Standard methods for the examination of water and wastewater, 20th edn. American Public Health Association, Washington DC

    Google Scholar 

  • Arques A, Amat AM, Garcıa-Ripoll A, Vicente R (2007) Detoxification and/or increase of the biodegradability of aqueous solutions of dimethoate by means of solar photocatalysis. J Hazard Mater 146:447–452

    CAS  Google Scholar 

  • Aulakh JS, Malik AK, Mahajan RK (2005) Solid phase microextraction-high pressure liquid chromatographic determination of nabam, thiram and azamethiphos in water samples with UV detection: preliminary data. Talanta 66:266–270

    Google Scholar 

  • Azizian M, Boano F, Detwiler RL, Rippy MA (2017) Ambient groundwater flow diminishes nitrate processing in the hyporheic zone of streams. Water Resour Res 53:3941–3967

    CAS  Google Scholar 

  • Barisic J, Cannon S, Quinn B (2019) Cumulative impact of anti-sea lice treatment (azamethiphos) on health status of Rainbow trout (Oncorhynchus mykiss, Walbaum 1792) in aquaculture. Sci Rep 9:16217

    Google Scholar 

  • Ben W, Shi Y, Li W, Zhang Y, Qiang Z (2017) Oxidation of sulfonamide antibiotics by chlorine dioxide in water: kinetics and reaction pathways. Chem Eng J 327:743–750

    CAS  Google Scholar 

  • Bi X, Wang P, Jiao C, Cao H (2009) Degradation of remazol golden yellow dye wastewater in microwave enhanced ClO2 catalytic oxidation process. J Hazard Mater 168:895–900

    CAS  Google Scholar 

  • Brausch JM, Salice CJ (2011) Effects of an environmentally realistic pesticide mixture on Daphnia magna exposed for two generations. Arch Environ Contam Toxicol 61:272–279

    CAS  Google Scholar 

  • Canty MN, Hagger JA, Moore RTB, Cooper L, Galloway TS (2007) Sublethal impact of short term exposure to the organophosphate pesticide azamethiphos in the marine mollusc Mytilus edulis. Mar Pollut Bull 54:396–402

    CAS  Google Scholar 

  • Chamberlain E, Shi H, Wang T, Ma Y, Fulmer A, Adams C (2012) Comprehensive screening study of pesticide degradation via oxidation and hydrolysis. J Agric Food Chem 60:354–363

    CAS  Google Scholar 

  • Chen J-Q, Wang D, Zhu M-X, Gao C-J (2007) Photocatalytic degradation of dimethoate using nanosized TiO2 powder. Desalination 207:87–94

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Colovic MB, Krstic DZ, Lazarevic-Pasti TD, Bondzic AM, Vasic V (2013) Acetylcholinesterase inhibitors: pharmacology and toxicology. Curr Neuropharmacol 11:315–335

    CAS  Google Scholar 

  • Deshpande NM, Sarnaik SS, Paranjpe SA, Kanekar PP (2004) Optimization of dimethoate degradation by Brevundimonas sp. MCM B-427 using factorial design: studies on interactive effects of environmental factors. World J Microb Biot 20:455–462

    CAS  Google Scholar 

  • Evgenidou E, Fytianos K, Poulios I (2005) Photocatalytic oxidation of dimethoate in aqueous solutions. J Photoch Photobio A 175:29–38

    CAS  Google Scholar 

  • Evgenidou E, Konstantinou I, Fytianos K, Albanis T (2006) Study of the removal of dichlorvos and dimethoate in a titanium dioxide mediated photocatalytic process through the examination of intermediates and the reaction mechanism. J Hazard Mater B137:1056–1064

    Google Scholar 

  • Evgenidou E, Konstantinou I, Fytianos K, Poulios I (2007) Oxidation of two organophosphorous insecticides by the photo-assisted Fenton reaction. Water Res 41:2015–2027

    CAS  Google Scholar 

  • Fei X, Sun G (2009) Oxidative degradation of organophosphorous pesticides by N-halamine fabrics. Ind Eng Chem Res 48:5604–5609

    CAS  Google Scholar 

  • Fu XR, Gu XG, Lu SG, Sharma VK, Brusseau ML, Xue YF, Danish M, Fu GY, Qiu ZF, Sui Q (2017) Benzene oxidation by Fe(III)-activated percarbonate: matrix-constituent effects and degradation pathways. Chem Eng J 309:22–29

    CAS  Google Scholar 

  • Huber MM, Korhonen S, Ternes TA, Gunten U (2005) Oxidation of pharmaceuticals during water treatment with chlorine dioxide. Water Res 39:3607–3617

    CAS  Google Scholar 

  • Hwang E, Cash JN, Zabik MJ (2002) Chlorine and chlorine dioxide treatment to reduce or remove EBDCs and ETU residues in a solution. J Agric Food Chem 50:4734–4742

    CAS  Google Scholar 

  • Hwang E-S, Cash JN, Zabik MJ (2003) Determination of degradation products and pathways of mancozeb and ethylenethiourea (ETU) in solutions due to ozone and chlorine dioxide treatments. J Agric Food Chem 51:1341–1346

    CAS  Google Scholar 

  • Intorre L, Soldani G, Cognetti-Varriale AM, Monni G, Meucci V, Pretti C (2004) Safety of azamethiphos in eel, seabass and trout. Pharmacol Res 49:171–176

    CAS  Google Scholar 

  • ISO 6341:2012, Water quality -Determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea) - Acute toxicity test, October, 2012.

  • Ison A, Odeh IN, Margerum DW (2006) Kinetics and mechanisms of chlorine dioxide and chlorite oxidations of cysteine and glutathione. Inorg Chem 45:8768–8775

    CAS  Google Scholar 

  • Jariyal M, Jindal V, Mandal K, Guptab VK, Singh B (2018) Bioremediation of organophosphorus pesticide phorate in soil by microbial consortia. Ecotox Environ Safe 159:310–316

    CAS  Google Scholar 

  • Jia X-H, Feng L, Liu Y-Z, Zhang L-Q, Jia X-H, Feng L, Liu Y-Z, Zhang L-Q (2017) Oxidation of antipyrine by chlorine dioxide: reaction kinetics and degradation pathway. Chem Eng J 309:646–654

    CAS  Google Scholar 

  • 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. J Hazard Mater 260:1092–1099

    Google Scholar 

  • Kanade SN, Adeland AB, Khilare VC (2012) Malathion degradation by Azospirillum lipoferum Beijerinck. Sci Res Reporter 2:94–103

    Google Scholar 

  • Katsumata H, Okada T, Kaneco S, Suzuki T, Ohta K (2010) Degradation of fenitrothion by ultrasound/ferrioxalate/UV system. Ultrason Sonochem 17:200–206

    CAS  Google Scholar 

  • Klüttgen B, Dülmer U, Engels M, Ratte TH (1994) ADaM, an artificial freshwater for the culture of zooplankton. Water Res 28:743–746

    Google Scholar 

  • Leal JKF, Adjobo-Hermans MJW, Brock R, Bosman GJCGM (2017) Acetylcholinesterase provides new insights into red blood cell ageing in vivo and in vitro. Blood Transfus 15:232–238

    Google Scholar 

  • Li R, Zheng J, Wang R, Song YZ, Chen Q, Yang X, Li S-P, Jiang J (2010) Biochemical degradation pathway of dimethoate by Paracoccus sp. Lgjj-3 isolated from treatment wastewater. Int Biodeter Biodegr 64:51–57

    CAS  Google Scholar 

  • 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 Sci Technol 35(129–130):132–136

    Google Scholar 

  • Mao Q, Li Q, Li H, Yuan S, Zhang J (2020) Oxidative paraben removal with chlorine dioxide: reaction kinetics and mechanism. Sep Purif Technol 237:116327

    Google Scholar 

  • Matsushita T, Morimoto A, Kuriyama T, Matsumoto E, Matsui Y, Shirasaki N, Kondo T, Takanashi H, Kameya T (2018) Removals of pesticides and pesticide transformation products during drinking water treatment processes and their impact on mutagen formation potential after chlorination. Water Res 138:67–76

    CAS  Google Scholar 

  • Milojković JV, Popović Djordjević JB, Pezo LL, Brčeski ID, Kostić AZ, Miločević VD, Stojanović MD (2018) Applying multi-criteria analysis for preliminary assessment of the properties of alginate immobilized Myriophyllum spicatum in lake water samples. Water Res 141:163–171

    Google Scholar 

  • Miodragović ZM, Jokić A, Pfendt PA (1992) Fulvic acid characterization in an alluvial sediment sequence: differences between clay and sand environments. Org Geochem 18:481–487

    Google Scholar 

  • Moreira AJ, Pinheiro BS, Araújo AF, Freschi GPG (2016) Evaluation of atrazine degradation applied to different energy systems. Environ Sci Pollut Res 23:18502–18511

    CAS  Google Scholar 

  • Nandan S, Tailor D, Yadav A (2016) Malathion pesticide degradation by advanced oxidation process (UV-irradiation). IRJAES 1:153–156

    Google Scholar 

  • Nie SX, Liu XL, Wu ZM, Zhan L, Yin GD, Yao SQ, Song HN, Wang SF (2014) Kinetics study of oxidation of the lignin model compounds by chlorine dioxide. Chem Eng J 241:410–417

    CAS  Google Scholar 

  • OECD Guideline for testing of chemicals (2004) Daphnia sp. Acute immobilisation test. OECD Guideline 202.

  • Pergal MV, Kodranov ID, Pergal MP, Dojčinović BP, Stanković DS, Petković BB, Manojlović DD (2018) Assessment of degradation of sulfonylureah Herbicides in water by chlorine dioxide. Water Air Soil Poll 229:310

    Google Scholar 

  • Persoone G, Marsalek B, Blinova I, Törökne A, Zarina D, Manusadzianas L, Nalecz-Jawecki G, Tofan L, Stepanova N, Tothova L, Kolar BA (2003) Practical and user-friendly toxicity classification system with microbiotests for natural waters and wastewaters. Environ Toxicol 18:395–402

    CAS  Google Scholar 

  • Pfendt P, Jokic A (1993) Characterization and ecochemical significance of Lake Celije sediment humic acids. J Serb Chem Soc 58:833–842

    CAS  Google Scholar 

  • Pohlman FW, Stivarius MR, McElyea KS, Johnson ZB, Johnson MG (2002) Reduction of microorganisms in ground beef using multiple intervention technology. Meat Sci 61:315–322

    CAS  Google Scholar 

  • Priya DN, Modak JM, Trebše P, Žabarc R, Raichura AM (2011) Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films. J Hazard Mater 195:214–222

    CAS  Google Scholar 

  • Raj P, Singh A, Singh A, Singh N (2017) Dalton transactions (Cambridge, England: 2003) 46:985–994.

  • Ratna Kumari A, Jeevan G, Ashok M, Koteswara Rao C, Vamsi KSK (2012) Malathion degradation by Bacillus spp. isolated from soil. J Pharm 2:37–42

  • Rodgers SL, Cash JN, Siddiq M, Ryser ETA (2004) Comparison of different chemical sanitizers for inactivating Escherichia coli O157:H7 and Listeria monocytogenes in solution and on apples, lettuce, strawberries, and cantaloupe. J Food Prot 67:721–731

    CAS  Google Scholar 

  • Roglić GPergal MV, Kodranov ID, Pergal MM, Dojčinović BP, Manojlović D (2017) Degradation herbicides with chlorine dioxide: degradation efficiency and toxicity test, XXV International Conference "Ecological Truth" (EcoIst’17), Proceedings, pp. 392-397, Vrnjacka banja, Serbia, ISBN 978-86-6305-062-4.

  • Roth M, Richards RH, Sommerville C (1993) Current practices in the chemotherapeutic control of sea lice infestations in aquaculture: a review. J Fish Dis 16:1–26

    CAS  Google Scholar 

  • Rougé V, Allard S, Croué JP, von Gunten U (2018) In-situ formation of free chlorine during ClO2 treatment: implications on the formation of disinfection byproducts. Environ Sci Technol 52:13421–13429

    Google Scholar 

  • Şener Ş, Şener E, Davraz A (2017) Evaluation of water quality using water quality index (WQI ) method and GIS in Aksu River (SW-Turkey ). Sci Total Environ J 584-585:131–144

    Google Scholar 

  • Sievers G, Palacios P, Inostroza R, Dölz H (1995) Evaluation of the toxicity of 8 insecticides in Salmo salar and the in vitro effects against the isopode parasite, Ceratothoa gaudichaudii. Aquaculture 134:9–16

    CAS  Google Scholar 

  • Simo OP, Zhang Q (2002) The degradation of organophosphorus pesticides in natural waters: a critical review. Crit Rev Environ Sci Technol 32:17–72

    Google Scholar 

  • Stewart DJ, Napolitano MJ, Bakhmutova-Albert EV, Margerum DW (2008) Kinetics and mechanisms of chlorine dioxide oxidation of tryptophan. Inorg Chem 47:1639–1647

    CAS  Google Scholar 

  • Teodorovic I, Mauric N. (2003) TesTox version 1.0.

  • Teodorovic I, Planojevic I, Knezevic P, Radak S, Nemet I (2009) Sensitivity of bacterial vs. acute Daphnia magna toxicity tests to metals. Cent Eur J Biol 4:482–492

    CAS  Google Scholar 

  • Tian F, Qiang Z, Liu C, Zhang T, Dong B (2010) Kinetics and mechanism for methiocarb degradation by chlorine dioxide in aqueous solution. Chemosphere 79:646–651

    CAS  Google Scholar 

  • 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. Chem Eng J 258:210–217

    CAS  Google Scholar 

  • Tomlin C (2011) The pesticide manual; incorporating the agrochemicals handbook: a world compendium. British Crop Protection Council, Farnham, Surrey. https://doi.org/10.1006/pest.1996.0019

    Book  Google Scholar 

  • USEPA (2003) Long term 2 enhanced surface water treatment rule – toolbox guidance manual, United States Environmental Protection Agency. Cincinnati, OH

    Google Scholar 

  • Vandekinderen I, Van Camp J, De Meulenaer B, Veramme K, Bernaert N, Denon Q, Ragaert P, Devlieghere F (2009) Moderate and high doses of sodium hypochlorite, neutral electrolyzed oxidizing water, peroxyacetic acid, and gaseous chlorine dioxide did not affect the nutritional and sensory qualities of fresh-cut iceberg lettuce (Lactuca sativa Var. capitata L.) after washing. J Agric Food Chem 57:4195–4203

    CAS  Google Scholar 

  • Wang Y, Liu H, Liu G, Xie Y (2014) Oxidation of diclofenac by aqueous chlorine dioxide: Identification of major disinfection by products and toxicity evaluation. Sci Total Environ 473–474:437–445

    Google Scholar 

  • Wang Y, Liu H, Xie Y, Ni T, Liu G (2015) Oxidative removal of diclofenac by chlorine dioxide: reaction kinetics and mechanism. Chem Eng J 279:409–415

    CAS  Google Scholar 

  • Wenk J, Aeschbacher M, Salhi E, Canonica S, On Gunten U, Sander M (2013) Chemical oxidation of dissolved organic matter by chlorine dioxide, chlorine, and ozone: effects on its optical and antioxidant properties. Environ Sci Technol 47:11147–11156

    CAS  Google Scholar 

  • Xiao-yi B, Peng W, Hong J, Huan-yan X, Shu-jie S, Jun-li H (2007) Treatment of phenol wastewater by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process. J Environ Sci 19:1510–1515

    Google Scholar 

  • Zhang L, Guo X, Yan F, Su M, Li Y (2007) Study of the degradation behaviour of dimethoate under microwave irradiation. J Hazard Mater 149:675–679

    CAS  Google Scholar 

  • 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. Ultrason Sonochem 17:72–77

    CAS  Google Scholar 

  • Zoun PEF, Spierenburg TJ (1989) Determination of cholinesterase-inhibiting pesticides and some of their metabolites in cases of animal poisoning using thin-layer chromatography. J Chromatogr 462:448–453

    CAS  Google Scholar 

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Acknowledgments

The authors would like to thank 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) and TwinOxide-RS d.o.o.

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Authors and Affiliations

  1. University of Belgrade - Institute of Chemistry, Technology and Metallurgy, Njegoševa 12, Belgrade, 11000, Serbia

    Marija V. Pergal & Biljana Dojčinović

  2. Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, 11000, Serbia

    Igor D. Kodranov & Dragan D. Manojlović

  3. South Ural State University, Lenin prospekt 76, Chelyabinsk, Russia, 454080

    Viacheslav V. Avdin & Dragan D. Manojlović

  4. The Vinca Institute of Nuclear Sciences, University of Belgrade, POB 522, Belgrade, 11001, Serbia

    Dalibor M. Stanković

  5. Faculty of Sciences, University of Priština, Lole Ribara 29,, Kosovska Mitrovica, 38220, Serbia

    Branka B. Petković

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  1. Marija V. Pergal
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  2. Igor D. Kodranov
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Appendix A. Supporting Information

Appendix A. Supporting Information

HPLC chromatograms of parent organophosphorus pesticides (10 mg/L) and their degradation products in deionized water and in Sava River water, GC-QQQ chromatograms and mass spectra for degradation products of the organophosphorus pesticides, effects of humic acid on the reaction between AZA and DM with ClO2 as well as full characteristics of Sava River water.

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Pergal, M.V., Kodranov, I.D., Dojčinović, B. et al. Evaluation of azamethiphos and dimethoate degradation using chlorine dioxide during water treatment. Environ Sci Pollut Res 27, 27147–27160 (2020). https://doi.org/10.1007/s11356-020-09069-5

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