Abstract
The cardiovascular drugs (CDDs), such as metoprolol (MET), atenolol (ATE), bezafibrate (BZB), and atorvastatin (ATO), have been frequently detected in the water environment. They can cause potential threats to the ecological environment and human health due to their “pseudo-persistence” effect. In this study, the photolysis kinetics, degradation mechanisms, by-products, influencing factors, and acute toxicity of these four typical CDDs under polychromatic ultraviolet irradiation (200–400 nm) were investigated. The results showed that the photolysis of ATE, BZB, MET, and ATO all followed pseudo-first-order kinetics, and their average photon quantum yields of the wavelength studied were 0.14×10−2, 0.33×10−3, 0.78×10−4, and 0.24×10−4 mol einstein−1, respectively. Singlet oxygen (1O2), hydroxyl radical (·OH), and the triplet-excited state of the cardiovascular drug (3CDD*) were all involved in the photolysis while 1O2 was the dominator. The effects of NO3−, Cl−, HCO3−, and humic acid (HA) on the photolysis were the combination of light-shielding, quenching, and excitation of reactive species. Seven, four, four, and nine photolysis products of ATO, BZB, ATE, and MET were identified, respectively, and their possible degradation pathways were proposed. The acute toxicity of ATE was basically unchanged during photolysis; however, ATO, BZB, and MET toxicity all increased due to the generation of ketonization and hydroxylation products.
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References
Abshagen U, Bablok W, Koch K, Lang PD, Schmidt HA, Senn M, Stork H (1979) Disposition pharmacokinetics of bezafibrate in man. Eur J Clin Pharmacol 16:31–38. https://doi.org/10.1007/BF00644963
Agüera A, MDMG R, Fernández-Alba AR (2012) Chapter 2 - Chemical evaluation of water treatment processes by LC–(Q)TOF-MS: identification of transformation products. In: Fernandez-Alba AR (ed) Comprehensive Analytical Chemistry, vol 58. Elsevier, pp 61–109
Álvarez-Ruiz R, Picó Y, Alfarhan AH, El-Sheikh MA, Alshahrani HO, Barceló D (2020) Dataset of pesticides, pharmaceuticals and personal care products occurrence in wetlands of Saudi Arabia. Data Brief 31:105776. https://doi.org/10.1016/j.dib.2020.105776
Baena-Nogueras RM, González-Mazo E, Lara-Martín PA (2017) Degradation kinetics of pharmaceuticals and personal care products in surface waters: photolysis vs biodegradation. Sci Total Environ 590-591:643–654. https://doi.org/10.1016/j.scitotenv.2017.03.015
Barber LB, Antweiler RC, Flynn JL, Keefe SH, Kolpin DW, Roth DA, Schnoebelen DJ (2011) Lagrangian mass-flow investigations of inorganic contaminants in wastewater-impacted streams. Environ Sci Technol 45:2575–2583. https://doi.org/10.1021/es104138y
Behera SK, Kim HW, Oh J, Park H (2011) Occurrence and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea. Sci Total Environ 409:4351–4360. https://doi.org/10.1016/j.scitotenv.2011.07.015
Blough NV (1988) Electron paramagnetic resonance measurements of photochemical radical production in humic substances. 1. Effects of O2 and charge on radical scavenging by nitroxides. Environ Sci Technol 46:77–82
Bodhipaksha LC, Sharpless CM, Chin Y, MacKay AA (2017) Role of effluent organic matter in the photochemical degradation of compounds of wastewater origin. Water Res 110:170–179. https://doi.org/10.1016/j.watres.2016.12.016
Cai W, Peng T, Yang B, Xu C, Liu Y, Zhao J, Gu F (2020) Kinetics and mechanism of reactive radical mediated fluconazole degradation by the UV/chlorine process: experimental and theoretical studies. Chem Eng J 402:126224. https://doi.org/10.1016/j.cej.2020.126224
Campanha MB, Awan AT, de Sousa DNR, Grosseli GM, Mozeto AA, Fadini PS (2015) A 3-year study on occurrence of emerging contaminants in an urban stream of São Paulo State of Southeast Brazil. Environ Sci Pollut R 22:7936–7947. https://doi.org/10.1007/s11356-014-3929-x
Chattaraj PK, Sarkar U, Roy DR (2006) Electrophilicity index. Chem Rev 106:2065–2091. https://doi.org/10.1021/cr040109f
Contardo-Jara V, Lorenz C, Pflugmacher S, Nützmann G, Kloas W, Wiegand C (2011) Exposure to human pharmaceuticals Carbamazepine, Ibuprofen and Bezafibrate causes molecular effects in Dreissena polymorpha. Aquat Toxicol 105:428–437. https://doi.org/10.1016/j.aquatox.2011.07.017
Cronin MTD, Manga N, Seward JR, Sinks GD, Schultz TW (2001) Parametrization of electrophilicity for the prediction of the toxicity of aromatic compounds. Chem Res Toxicol 14:1498–1505. https://doi.org/10.1021/tx015502k
Dalrymple RM, Carfagno AK, Sharpless CM (2010) Correlations between dissolved organic matter optical properties and quantum yields of singlet oxygen and hydrogen peroxide. Environ Sci Technol 44:5824–5829. https://doi.org/10.1021/es101005u
Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938. https://doi.org/10.1289/ehp.99107s6907
Deaton C, Froelicher ES, Wu LH, Ho C, Shishani K, Jaarsma T (2017) The global burden of cardiovascular disease. Eur J Cardiovasc Nurs 10:S5–S13. https://doi.org/10.1016/S1474-5151(11)00111-3
Ding Y, Jiang W, Liang B, Han J, Cheng H, Haider MR, Wang H (2020) UV photolysis as an efficient pretreatment method for antibiotics decomposition and their antibacterial activity elimination. J Hazard Mater 392:122321. https://doi.org/10.1016/j.jhazmat.2020.122321
Fasnacht MP, Blough NV (2003) Mechanisms of the aqueous photodegradation of polycyclic aromatic hydrocarbons. Environ Sci Technol 37:5767–5772. https://doi.org/10.1021/es034389c
Fuentes A, Pineda M, Venkata K (2018) Comprehension of top 200 prescribed drugs in the US as a resource for pharmacy teaching, training and practice. Pharmacy 6:43. https://doi.org/10.3390/pharmacy6020043
Gan Z, Sun H, Wang R, Hu H, Zhang P, Ren X (2014) Transformation of acesulfame in water under natural sunlight: joint effect of photolysis and biodegradation. Water Res 64:113–122. https://doi.org/10.1016/j.watres.2014.07.002
Gros M, Petrović M, Ginebreda A, Barceló D (2010) Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ Int 36:15–26. https://doi.org/10.1016/j.envint.2009.09.002
Gurke R, Rößler M, Marx C, Diamond S, Schubert S, Oertel R, Fauler J (2015) Occurrence and removal of frequently prescribed pharmaceuticals and corresponding metabolites in wastewater of a sewage treatment plant. Sci Total Environ 532:762–770. https://doi.org/10.1016/j.scitotenv.2015.06.067
Harper CR, Jacobson TA (2007) The broad spectrum of statin myopathy: from myalgia to rhabdomyolysis. Curr Opin Lipidol 18:401–408. https://doi.org/10.1097/MOL.0b013e32825a6773
Hoigné J, Faust BC, Haag WR, Scully FE, Zepp RG (1988) Aquatic humic substances as sources and sinks of photochemically produced transient reactants. American Chemical Society, Washington, DC
Hwang S, Huling SG, Ko S (2010) Fenton-like degradation of MTBE: effects of iron counter anion and radical scavengers. Chemosphere 78:563–568. https://doi.org/10.1016/j.chemosphere.2009.11.005
Kang Y, Kim M, Zoh K (2018) Effect of nitrate, carbonate/bicarbonate, humic acid, and H2O2 on the kinetics and degradation mechanism of Bisphenol-A during UV photolysis. Chemosphere 204:148–155. https://doi.org/10.1016/j.chemosphere.2018.04.015
Kim D, Lee J, Ryu J, Kim K, Choi W (2014) Arsenite oxidation initiated by the UV photolysis of nitrite and nitrate. Environ Sci Technol 48:4030–4037. https://doi.org/10.1021/es500001q
Klementová Á, Petráňová P, Fojtíková P (2021) Photodegradation of atorvastatin under light conditions relevant to natural waters and photoproducts toxicity assessment. Open J Appl Sci 11:489–499. https://doi.org/10.4236/ojapps.2021.104035
Lei Y, Lei X, Westerhoff P, Zhang X, Yang X (2021) Reactivity of chlorine radicals (Cl• and Cl2•–) with dissolved organic matter and the formation of chlorinated byproducts. Environ Sci Technol 55:689–699. https://doi.org/10.1021/acs.est.0c05596
Lester Y, Sharpless CM, Mamane H, Linden KG (2013) Production of photo-oxidants by dissolved organic matter during UV water treatment. Environ Sci Technol 47:11726–11733. https://doi.org/10.1021/es402879x
Li H, Duan L, Wang H, Chen Y, Wang F, Zhang S (2020) Photolysis of sulfadiazine under UV radiation: effects of the initial sulfadiazine concentration, pH, NO3− and Cd2+. Chem Phys Lett 739:136949. https://doi.org/10.1016/j.cplett.2019.136949
Lin W, Zhang X, Li P, Tan Y, Ren Y (2020) Ultraviolet photolysis of metformin: mechanisms of environmental factors, identification of intermediates, and density functional theory calculations. Environ Sci Pollut R 27:17043–17053. https://doi.org/10.1007/s11356-020-08255-9
Liu H, Sun P, Liu H, Yang S, Wang L, Wang Z (2015) Acute toxicity of benzophenone-type UV filters for Photobacterium phosphoreum and Daphnia magna: QSAR analysis, interspecies relationship and integrated assessment. Chemosphere 135:182–188. https://doi.org/10.1016/j.chemosphere.2015.04.036
Luo S, Wei Z, Spinney R, Zhang Z, Dionysiou DD, Gao L, Chai L (2018) UV direct photolysis of sulfamethoxazole and ibuprofen: an experimental and modelling study. J Hazard Mater 343:132–139. https://doi.org/10.1016/j.jhazmat.2017.09.019
Ma J, Lv W, Chen P, Lu Y, Wang F, Li F, Yao K (2016) Photodegradation of gemfibrozil in aqueous solution under UV irradiation: kinetics, mechanism, toxicity, and degradation pathways. Environ Sci Pollut R 23:14294–14306. https://doi.org/10.1007/s11356-016-6451-5
Maafi M, Maafi W (2015) Quantification of unimolecular photoreaction kinetics: determination of quantum yields and development of actinometers—the photodegradation case of cardiovascular drug nisoldipine. Int J Photoenergy 2015:1–12. https://doi.org/10.1155/2015/454895
Martínez-Rodríguez H, Donkor K, Brewer S, Galar-Martínez M, SanJuan-Reyes N, Islas-Flores H, Sánchez-Aceves L (2018) Metoprolol induces oxidative damage in common carp (Cyprinus carpio). Aquat Toxicol 197:122–135. https://doi.org/10.1016/j.aquatox.2018.02.012
Missi C, Atekwana EA (2020) Physical, chemical and isotopic characteristics of groundwater and surface water in the Lake Chilwa Basin, Malawi. J Afr Earth Sci 162:103737. https://doi.org/10.1016/j.jafrearsci.2019.103737
Muñoz I, López Doval JC, Ricart M, Villagrasa M, Brix R, Geiszinger A, Ginebreda A (2009) Bridging levels of pharmaceuticals in river water with biological community structure in the llobregat river basin (northeast spain). Environ Toxicol Chem 28:2706–2714. https://doi.org/10.1897/08-486.1
Neves CMB, Filipe OMS, Mota N, Santos SAO, Silvestre AJD, Santos EBH, Neves MGPM (2019) Photodegradation of metoprolol using a porphyrin as photosensitizer under homogeneous and heterogeneous conditions. J Hazard Mater 370:13–23. https://doi.org/10.1016/j.jhazmat.2018.11.055
Orellana-García F, Álvarez MA, López-Ramón MV, Rivera-Utrilla J, Sánchez-Polo M (2015) Effect of HO., SO4.− and CO3.−/HCO3. radicals on the photodegradation of the herbicide amitrole by UV radiation in aqueous solution. Chem Eng J 267:182–190. https://doi.org/10.1016/j.cej.2015.01.019
Pereira VJ, Weinberg HS, Linden KG, Singer PC (2007a) UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254 nm. Environ Sci Technol 41:1682–1688. https://doi.org/10.1021/es061491b
Pereira VJ, Linden KG, Weinberg HS (2007b) Evaluation of UV irradiation for photolytic and oxidative degradation of pharmaceutical compounds in water. Water Res 41:4413–4423. https://doi.org/10.1016/j.watres.2007.05.056
Rivas FJ, Gimeno O, Borralho T, Carbajo M (2010) UV-C radiation based methods for aqueous metoprolol elimination. J Hazard Mater 179:357–362. https://doi.org/10.1016/j.jhazmat.2010.03.013
Rocco L, Frenzilli G, Zito G, Archimandritis A, Peluso C, Stingo V (2012) Genotoxic effects in fish induced by pharmacological agents present in the sewage of some Italian water-treatment plants. Environ Toxicol 27:18–25. https://doi.org/10.1002/tox.20607
Roth GA, Mensah GA, Johnson CO, Addolorato G, Ammirati E, Baddour LM, Barengo NC (2020) Global burden of cardiovascular diseases and risk factors, 1990–2019. J Am Coll Cardiol 76:2982–3021. https://doi.org/10.1016/j.jacc.2020.11.010
Schwarzenbach RP, Gschwend PM, Imboden DM (2002) Direct photolysis. In: Environmental organic chemistry, pp 611–654
Sharma J, Mishra IM, Dionysiou DD, Kumar V (2015) Oxidative removal of Bisphenol A by UV-C/peroxymonosulfate (PMS): kinetics, influence of co-existing chemicals and degradation pathway. Chem Eng J 276:193–204. https://doi.org/10.1016/j.cej.2015.04.021
Šojić D, Despotović V, Orčić D, Szabó E, Arany E, Armaković S, Illés E (2012) Degradation of thiamethoxam and metoprolol by UV, O3 and UV/O3 hybrid processes: kinetics, degradation intermediates and toxicity. J Hydrol 472-473:314–327. https://doi.org/10.1016/j.jhydrol.2012.09.038
Solís RR, Rivas FJ, Chávez AM, Dionysiou DD (2019) Simulated solar photo-assisted decomposition of peroxymonosulfate. Radiation filtering and operational variables influence on the oxidation of aqueous bezafibrate. Water Res 162:383–393. https://doi.org/10.1016/j.watres.2019.06.063
Steinbach C, Burkina V, Fedorova G, Grabicova K, Stara A, Velisek J, Zlabek V (2014) The sub-lethal effects and tissue concentration of the human pharmaceutical atenolol in rainbow trout (Oncorhynchus mykiss). Sci Total Environ 497-498:209–218. https://doi.org/10.1016/j.scitotenv.2014.07.111
Swanson MB, Ivancic WA, Saxena AM, Allton JD, O’Brien GK, Suzuki T, Nishizawa H (1995) Direct photolysis of fenpyroximate in a buffered aqueous solution under a xenon lamp. J Agric Food Chem 43:513–518. https://doi.org/10.1021/jf00050a048
Vakondios N, Koukouraki EE, Diamadopoulos E (2014) Effluent organic matter (EfOM) characterization by simultaneous measurement of proteins and humic matter. Water Res 63:62–70. https://doi.org/10.1016/j.watres.2014.06.011
Valcárcel Y, Alonso SG, Rodríguez-Gil JL, Maroto RR, Gil A, Catalá M (2011) Analysis of the presence of cardiovascular and analgesic/anti-inflammatory/antipyretic pharmaceuticals in river- and drinking-water of the Madrid Region in Spain. Chemosphere 82:1062–1071. https://doi.org/10.1016/j.chemosphere.2010.10.041
Varga R, Somogyvári I, Eke Z, Torkos K (2013) Seasonal monitoring of cardiovascular and antiulcer agents’ concentrations in stream waters encompassing a capital city. J Pharmaceut 2013:1–9. https://doi.org/10.1155/2013/753928
Wan HB, Wong MK, Mok CY (1994) Comparative study on the quantum yields of direct photolysis of organophosphorus pesticides in aqueous solution. J Agric Food Chem 42:2625–2630. https://doi.org/10.1021/jf00047a046
Wang M, Li J, Shi H, Miao D, Yang Y, Qian L, Gao S (2018) Photolysis of atorvastatin in aquatic environment: influencing factors, products, and pathways. Chemosphere 212:467–475. https://doi.org/10.1016/j.chemosphere.2018.08.086
Wenk J, von Gunten U, Canonica S (2011) Effect of dissolved organic matter on the transformation of contaminants induced by excited triplet states and the hydroxyl radical. Environ Sci Technol 45:1334–1340. https://doi.org/10.1021/es102212t
Wols BA, Harmsen DJH, Beerendonk EF, Hofman-Caris CHM (2014) Predicting pharmaceutical degradation by UV (LP)/H2O2 processes: a kinetic model. Chem Eng J 255:334–343. https://doi.org/10.1016/j.cej.2014.05.088
Yang W, Zhou H, Cicek N (2014) Treatment of organic micropollutants in water and wastewater by UV-based processes: a literature review. Crit Rev Environ Sci Technol 44:1443–1476. https://doi.org/10.1080/10643389.2013.790745
Yu H, Park M, Wu S, Lopez IJ, Ji W, Scheideler J, Snyder SA (2019) Strategies for selecting indicator compounds to assess attenuation of emerging contaminants during UV advanced oxidation processes. Water Res 166:115030. https://doi.org/10.1016/j.watres.2019.115030
Zeng C, Ji Y, Zhou L, Zhang Y, Yang X (2012) The role of dissolved organic matters in the aquatic photodegradation of atenolol. J Hazard Mater 239-240:340–347. https://doi.org/10.1016/j.jhazmat.2012.09.005
Zhang J, Sun B, Guan X (2013) Oxidative removal of bisphenol A by permanganate: kinetics, pathways and influences of co-existing chemicals. Sep Purif Technol 107:48–53. https://doi.org/10.1016/j.seppur.2013.01.023
Zhang K, Zhao Y, Fent K (2020) Cardiovascular drugs and lipid regulating agents in surface waters at global scale: occurrence, ecotoxicity and risk assessment. Sci Total Environ 729:138770. https://doi.org/10.1016/j.scitotenv.2020.138770
Zhang Y, Del Vecchio R, Blough NV (2012) Investigating the mechanism of hydrogen peroxide photoproduction by humic substances. Environ Sci Technol 46:11836–11843. https://doi.org/10.1021/es3029582
Zhao X, Jiang J, Pang S, Guan C, Li J, Wang Z, Ma J (2019) Degradation of iopamidol by three UV-based oxidation processes: kinetics, pathways, and formation of iodinated disinfection byproducts. Chemosphere 221:270–277. https://doi.org/10.1016/j.chemosphere.2018.12.162
Zhou Y, Zhao J, Zhang Y, Qu J, Li C, Qin W, Zhao Y (2019) Trace amounts of fenofibrate acid sensitize the photodegradation of bezafibrate in effluents: mechanisms, degradation pathways, and toxicity evaluation. Chemosphere 235:900–907. https://doi.org/10.1016/j.chemosphere.2019.07.008
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This work was supported by the National Natural Science Foundation of China (Grant No. 41877466), Natural Science Foundation of Guangdong Province (Grant No. 2019A1515011037), Research Fund of SIT of Guangzhou (Grant No. 201707010158).
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Senwen **: Experimental operation, data analysis, writing—original draft preparation; Wenting Lin: Literature retrieval, data curation; Anchen Liu: Product identification; Zhihan Gao: Experimental operation; Han Lin: Experimental operation; Yuan Ren: Conceptualization, writing—reviewing and editing, supervision.
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**, S., Lin, W., Liu, A. et al. Ultraviolet photolysis of four typical cardiovascular drugs: mechanisms, influencing factors, degradation pathways, and toxicity trends. Environ Sci Pollut Res 28, 60663–60675 (2021). https://doi.org/10.1007/s11356-021-15000-3
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DOI: https://doi.org/10.1007/s11356-021-15000-3