Abstract
Benzotriazoles (BTs) are highly produced chemicals that are commonly used in the manufacture of aircraft de-icing/antifreeze fluids (ADAFs), coolants, etc. BTs have been detected in a variety of water environments, causing health hazards to aquatic species and humans. In this study, 1H-benzotriazole (BTri) and 4-methyl-1H-benzotriazole (4-TTri) were selected to investigate their degradation mechanisms in the aqueous phase initiated by ·OH using a theoretical calculation method. Addition reactions are the main type of reactions of ·OH with BTri and 4-TTri. The total rate constants for the reactions of BTri and 4-TTri with ·OH at 298 K are 8.26 × 109 M−1 s−1 and 1.81 × 1010 M−1 s−1, respectively. The reaction rate constants increase as the temperature rises, indicating that rising temperatures promote the degradation of BTri and 4-TTri. 7-hydroxy-1H-benzotriazole (1-P1) and 4-hydroxy-benzotriazoles (1-P2) produced via multiple reaction pathways are important transformation products of BTri. After successive reactions with ·OH, 1-P1 and 1-P2 can be successively converted to 4,7-dihydroxy-1H-benzotriazole (1-P7), 4,7-dione-1H-benzotriazole (1-P8), and 1,2,3-triazole-4,5-dicarboxylic acid (1-P9), which is consistent with the product compositions detected in the experiments. The toxicity assessment indicated that the acute toxicity and chronic toxicity of the resulting transformation products are significantly reduced compared to BTri as the degradation process progressed, and ultimately showed no harm to all three aquatic organisms (fish, daphnia, and green algae). Hence, advanced oxidation processes (AOPs) can not only effectively remove BTs from water, but also reduce their toxic effects on aquatic organisms.
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An Z, Sun J, Han D, Mei Q, Wei B, Wang X, He M (2019) Theoretical study on the mechanisms, kinetics and ecotoxicity assessment of OH-initiated reactions of guaiacol in atmosphere and wastewater. Sci Total Environ 685:729–740
An Z, Han D, Sun J, Mei Q, Wei B, Li M, Qiu Z, Bo X, Wang X, Xie J, Zhan J, He M (2021) Full insights into the roles of pH on hydroxylation of aromatic acids/bases and toxicity evaluation. Water Res 190:116689
An Z, Bo X, Mei Q, Wei B, Xie J, Zhan J, He M (2022) Theoretical insights into the degradation of swep by hydroxyl radicals in atmosphere and water environment: mechanisms, kinetics and toxicity. Sci Total Environ 816:151651
Asimakopoulos AG, Ajibola A, Kannan K, Thomaidis NS (2013) Occurrence and removal efficiencies of benzotriazoles and benzothiazoles in a wastewater treatment plant in Greece. Sci Total Environ 452–453:163–171
Baduel C, Lai FY, van Nuijs ALN, Covaci A (2019) Suspect and nontargeted strategies to investigate in vitro human biotransformation products of emerging environmental contaminants: the benzotriazoles. Environ Sci Technol 53:10462–10469
Bahnmüller S, Loi CH, Linge KL, Von Gunten U, Canonica S (2015) Degradation rates of benzotriazoles and benzothiazoles under UV-C irradiation and the advanced oxidation process UV/H2O2. Water Res 74:143–154
Benitez FJ, Acero JL, Real FJ, Roldan G, Rodriguez E (2015) Ozonation of benzotriazole and methylindole: kinetic modeling, identification of intermediates and reaction mechanisms. J Hazard Mater 282:224–232
Bo X, Sun J, Mei Q, Wei B, An Z, Qiu Z, Han D, Xie J, He M (2021) Theoretical insights into the degradation of tyrosol stimulated by hydroxyl and sulfate radicals in wastewater and ecotoxicity evaluation. J Clean Prod 293:126161
Borowska E, Felis E, Kalka J (2016) Oxidation of benzotriazole and benzothiazole in photochemical processes: kinetics and formation of transformation products. Chem Eng J 304:852–863
Canneaux S, Bohr F, Henon E (2014) KiSThelP: a program to predict thermodynamic properties and rate constants from quantum chemistry results. J Comput Chem 35:82–93
Collins FC, Kimball GE (1949) Diffusion-controlled reaction rates. J Colloid Interface Sci 4:425–437
Deng Y, Zhao R (2015) Advanced oxidation processes (AOPs) in wastewater treatment. Curr Pollut Rep 1:167–176
Ding Y, Yang C, Zhu L, Zhang J (2010) Photoelectrochemical activity of liquid phase deposited TiO2 film for degradation of benzotriazole. J Hazard Mater 175:96–103
Duan Z, Xing Y, Feng Z, Zhang H, Li C, Gong Z, Wang L, Sun H (2017) Hepatotoxicity of benzotriazole and its effect on the cadmium induced toxicity in zebrafish Danio rerio. Environ Pollut 224:706–713
Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, Scalmani G, Barone V, Petersson G, Nakatsuji HJ (2016) Gaussian 16 revision a. 03. 2016; gaussian inc. 2
Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154–2161
Janna H, Scrimshaw MD, Williams RJ, Churchley J, Sumpter JP (2011) From dishwasher to tap? Xenobiotic substances benzotriazole and tolyltriazole in the environment. Environ Sci Technol 45:3858–3864
Jia J, Zhu Q, Liu N, Liao C, Jiang G (2019) Occurrence of and human exposure to benzothiazoles and benzotriazoles in mollusks in the Bohai Sea. China Environ Int 130:104925
Lee J-E, Kim M-K, Lee J-Y, Lee Y-M, Zoh K-D (2019) Degradation kinetics and pathway of 1H-benzotriazole during UV/chlorination process. Chem Eng J 359:1502–1508
Li Y, Chen L, Li H, Peng F, Zhou X, Yang Z (2020) Occurrence, distribution, and health risk assessment of 20 personal care products in indoor and outdoor swimming pools. Chemosphere 254:126872
Liang X, Martyniuk CJ, Zha J, Wang Z (2016) Brain quantitative proteomic responses reveal new insight of benzotriazole neurotoxicity in female Chinese rare minnow (Gobiocypris rarus). Aquat Toxicol 181:67–75
Liu Y-S, Ying G-G, Shareef A, Kookana RS (2011) Simultaneous determination of benzotriazoles and ultraviolet filters in ground water, effluent and biosolid samples using gas chromatography-tandem mass spectrometry. J Chromatogr A 1218:5328–5335
Liu Y-S, Ying G-G, Kookana RS (2012) Occurrence and removal of benzotriazoles and ultraviolet filters in a municipal wastewater treatment plant. Environ Pollut 165:225–232
Liu W, Xue J, Kannan K (2017) Occurrence of and exposure to benzothiazoles and benzotriazoles from textiles and infant clothing. Sci Total Environ 592:91–96
Lu T, Chen FW (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580–592
Lu J, Li H, Luo Z, Lin H, Yang Z (2018) Occurrence, distribution, and environmental risk of four categories of personal care products in the Xiangjiang River, China. Environ Sci Pollut Res Int 25:27524–27534
Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem 113:6378–6396
Mei Q, Cao H, Han D, Li M, Yao S, Xie J, Zhan J, Zhang Q, Wang W, He M (2020) Theoretical insight into the degradation of p-nitrophenol by OH radicals synergized with other active oxidants in aqueous solution. J Hazard Mater 389:121901
Parajulee A, Lei YD, De Silva AO, Cao X, Mitchell CPJ, Wania F (2017) Assessing the source-to-stream transport of benzotriazoles during rainfall and snowmelt in urban and agricultural watersheds. Environ Sci Technol 51:4191–4198
Priyadarshini M, Das I, Ghangrekar MM, Blaney L (2022) Advanced oxidation processes: performance, advantages, and scale-up of emerging technologies. J Environ Manage 316:115295
Qu R, Liu J, Li C, Wang L, Wang Z, Wu J (2016) Experimental and theoretical insights into the photochemical decomposition of environmentally persistent perfluorocarboxylic acids. Water Res 104:34–43
Qu R, Li C, Liu J, Xiao R, Pan X, Zeng X, Wang Z, Wu J (2018) Hydroxyl radical based photocatalytic degradation of halogenated organic contaminants and paraffin on silica gel. Environ Sci Technol 52:7220–7229
Reemtsma T, Miehe U, Duennbier U, Jekel M (2010) Polar pollutants in municipal wastewater and the water cycle: occurrence and removal of benzotriazoles. Water Res 44:596–604
Shi ZQ, Liu YS, Xiong Q, Cai WW, Ying GG (2019) Occurrence, toxicity and transformation of six typical benzotriazoles in the environment: a review. Sci Total Environ 661:407–421
Truhlar DG, Garrett BC, Klippenstein SJ (1996) Current status of transition-state theory. J Phys Chem 100:12771–12800
Vel Leitner NK, Roshani B (2010) Kinetic of benzotriazole oxidation by ozone and hydroxyl radical. Water Res 44:2058–2066
Vetter W, Lorenz J (2013) Determination of benzotriazoles in dishwasher tabs from Germany and estimation of the discharge into German waters. Environ Sci Pollut Res Int 20:4435–4440
Wang JL, Xu LJ (2012) Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application. Crit Rev Environ Sci Technol 42:251–325
Wang N, He L, Sun X, Li X, Li M (2022) The transformation of benzophenone-3 in natural waters and AOPs: the roles of reactive oxygen species and potential environmental risks of products. J Hazard Mater 427:127941
Yao L, Zhao JL, Liu YS, Zhang QQ, Jiang YX, Liu S, Liu WR, Yang YY, Ying GG (2018) Personal care products in wild fish in two main Chinese rivers: bioaccumulation potential and human health risks. Sci Total Environ 621:1093–1102
Ye J, Zhou P, Chen Y, Ou H, Liu J, Li C, Li Q (2018) Degradation of 1H-benzotriazole using ultraviolet activating persulfate: mechanisms, products and toxicological analysis. Chem Eng J 334:1493–1501
Zhao Y, Truhlar DG (2007) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 120:215–241
Zhao Y, Truhlar DG (2008) Density functionals with broad applicability in chemistry. ACC Chem Res 41:157–167
Funding
This work was supported by the National Natural Science Foundation of China (No. 22006095, 22236004), “Future Plan for Young Scholars of Shandong University”, the Fundamental Research Funds of Shandong University (2020GN103) and Gansu Youth Science and Technology Fund Program (20JR5RA213).
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Li’ao Gao: reaction mechanism investigation and writing draft manuscript. Shibo Zhang: theoretical calculation. Juan Dang: supervision, reviewing, and editing. Qingzhu Zhang: reviewing and editing.
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Gao, L., Zhang, S., Dang, J. et al. Mechanistic insight into the degradation of 1H-benzotriazole and 4-methyl-1H-benzotriazole by •OH-based advanced oxidation process and toxicity assessment. Environ Sci Pollut Res 30, 49150–49161 (2023). https://doi.org/10.1007/s11356-023-25814-y
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DOI: https://doi.org/10.1007/s11356-023-25814-y