Oxidative degradation of ranitidine by UV and ultrasound: identification of transformation products using LC-Q-ToF-MS
Misha T. Elias A , Jisha Chandran B , Usha K. Aravind A and Charuvila T. Aravindakumar
B C D
+ Author Affiliations
- Author Affiliations
A Advanced Centre of Environmental Studies and Sustainable Development, Mahatma Gandhi University, Kottayam, 686560, Kerala, India.
B Inter University Instrumentation Centre, Mahatma Gandhi University, Kottayam, 686560, Kerala, India.
C School of Environmental Sciences, Mahatma Gandhi University, Kottayam, 686560, Kerala, India.
D Corresponding author. Email: cta@mgu.ac.in
Environmental Chemistry 16(1) 41-54 https://doi.org/10.1071/EN18155
Submitted: 16 July 2018 Accepted: 17 October 2018 Published: 3 December 2018
Environmental context. Ranitidine, a widely prescribed antiulcer drug commonly found in surface waters, has been identified as an emerging contaminant due to its toxicity and the enhanced toxicity displayed by its transformation products. Mechanisms for the formation of ranitidine transformation products and their degradation pathways induced by UV oxidation processes are presented. This work provides insight into treatment processes to remove these toxic chemicals from environmental water bodies.
Abstract. The transformation products (TPs) of pharmaceuticals formed during advanced oxidation processes (AOPs) are of great significance, but there are still gaps in our knowledge regarding the persistence of such compounds in the water matrices, their impact on human health and the applicability of such techniques during water treatment processes. Ranitidine (RAN), a highly prescribed gastrointestinal drug, has been widely detected in various surface waters and experiments, along with its TPs, which show enhanced toxicity. The present study analyses the TPs formed from the degradation of RAN in aqueous solution induced by three AOPs; namely UV-photolysis, UV/peroxodisulfate (PDS) and sonolysis. The degradations followed pseudo first-order kinetics, with removal efficiencies of 99.8, 100 and 98.8 % after 60 min under UV photolysis, UV/PDS, and sonolysis, respectively, with a corresponding decrease in chemical oxygen demand (COD) of 25, 100 and 75 %. Structures of the main TPs were elucidated by using LC-Q-ToF-MS in positive mode, and possible degradation pathways are proposed which mainly involved C-N and C-H bond cleavage, hydroxylation and reduction of nitro groups. Possible mechanisms for the formation of the identified TPs (elucidated by using electrospray ionisation–collisionally induced dissociation) support their structural assignments. Seven out of the 11 TPs presented here (namely TP-1, TP-4, TP-5, TP-6, TP-7, TP-9 and TP-10) were not reported in previous studies of RAN using any other AOPs, while four (m/z 331, 270, 288 and 286) were found to retain the NO2 group, which might contribute to the formation of halonitromethanes (HNMs) during chlorination of drinking water. Interestingly, we identified an additional sonolysis product, TP-3, whose formation can only be rationalised by invoking ozone.
Additional keywords: advanced oxidation processes, ESI-CID, halonitromethanes, pharmaceutical pollution, photodegradation.
References
Ali AMM, Kallenborn R, Sydnes LK, Rønning HT, Alarif WM, Al-Lihaibi S (2017). Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification. Environmental Science and Pollution Research International 24, 14657–14668.| Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identificationCrossref | GoogleScholarGoogle Scholar |
Anipsitakis GP, Dionysiou DD, Gonzalez MA (2006). Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ions. Environmental Science & Technology 40, 1000–1007.
| Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ionsCrossref | GoogleScholarGoogle Scholar |
Antoniou MG, de la Cruz AA, Dionysiou DD (2010). Intermediates and reaction pathways from the degradation of microcystin-LR with sulfate radicals. Environmental Science & Technology 44, 7238–7244.
| Intermediates and reaction pathways from the degradation of microcystin-LR with sulfate radicalsCrossref | GoogleScholarGoogle Scholar |
APHA (1992). ‘Standard methods for the examination of water and wastewater, 18th edn.’ (American Public Health Association: Washington, DC)
Babu SG, Ashokkumar M, Neppolian B (2016). The role of ultrasound on advanced oxidation processes. Topics in Current Chemistry 374, 75
| The role of ultrasound on advanced oxidation processesCrossref | GoogleScholarGoogle Scholar |
Bond T, Mokhtar Kamal NH, Bonnisseau T, Templeton MR (2014). Disinfection by-product formation from the chlorination and chloramination of amines. Journal of Hazardous Materials 278, 288–296.
| Disinfection by-product formation from the chlorination and chloramination of aminesCrossref | GoogleScholarGoogle Scholar |
Bu L, Zhou S, Shi Z, Deng L, Li G, Yi Q, Gao N (2016). Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways. Environmental Science and Pollution Research International 23, 2848–2855.
| Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathwaysCrossref | GoogleScholarGoogle Scholar |
Buckley T, Cashin A, Stuart M, Browne G, Dunn SV (2013). Nurse practitioner prescribing practices: the most frequently prescribed medications. Journal of Clinical Nursing 22, 2053–2063.
| Nurse practitioner prescribing practices: the most frequently prescribed medicationsCrossref | GoogleScholarGoogle Scholar |
Busker RW, Beijersbergen van Henegouwen GMJ (1987). The photolysis of 5‐nitrofurfural in aqueous solutions: nucleophilic substitution of the nitro‐group. Photochemistry and Photobiology 45, 331–335.
| The photolysis of 5‐nitrofurfural in aqueous solutions: nucleophilic substitution of the nitro‐groupCrossref | GoogleScholarGoogle Scholar |
Calza P, Pelizzetti E, Minero C (2005). The fate of organic nitrogen in photocatalysis: an overview. Journal of Applied Electrochemistry 35, 665–673.
| The fate of organic nitrogen in photocatalysis: an overviewCrossref | GoogleScholarGoogle Scholar |
Chandran J, Aravind UK, Aravindakumar CT (2015). Sonochemical transformation of thymidine: A mass spectrometric study. Ultrasonics Sonochemistry 27, 178–186.
| Sonochemical transformation of thymidine: A mass spectrometric studyCrossref | GoogleScholarGoogle Scholar |
Christophoridis C, Nika M-C, Aalizadeh R, Thomaidis NS (2016). Ozonation of ranitidine: Effect of experimental parameters and identification of transformation products. The Science of the Total Environment 557–558, 170–182.
| Ozonation of ranitidine: Effect of experimental parameters and identification of transformation productsCrossref | GoogleScholarGoogle Scholar |
Chu W, Li D, Gao N, Templeton MR, Tan C, Gao Y (2015). The control of emerging haloacetamide DBP precursors with UV/persulfate treatment. Water Research 72, 340–348.
| The control of emerging haloacetamide DBP precursors with UV/persulfate treatmentCrossref | GoogleScholarGoogle Scholar |
Deng L, Huang C-H, Wang Y-L (2014). Effects of combined UV and chlorine treatment on the formation of trichloronitromethane from amine precursors. Environmental Science & Technology 48, 2697–2705.
| Effects of combined UV and chlorine treatment on the formation of trichloronitromethane from amine precursorsCrossref | GoogleScholarGoogle Scholar |
Dimitrakopoulou D, Rethemiotaki I, Frontistis Z, Xekoukoulotakis NP, Venieri D, Mantzavinos D (2012). Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO2 photocatalysis. Journal of Environmental Management 98, 168–174.
| Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO2 photocatalysisCrossref | GoogleScholarGoogle Scholar |
Dirany A, Sirés I, Oturan N, Özcan A, Oturan MA (2012). Electrochemical treatment of the antibiotic sulfachloropyridazine: Kinetics, reaction pathways, and toxicity evolution. Environmental Science & Technology 46, 4074–4082.
| Electrochemical treatment of the antibiotic sulfachloropyridazine: Kinetics, reaction pathways, and toxicity evolutionCrossref | GoogleScholarGoogle Scholar |
Dong H, Qiang Z, Lian J, Qu J (2017). Degradation of nitro-based pharmaceuticals by UV photolysis: Kinetics and simultaneous reduction on halonitromethanes formation potential. Water Research 119, 83–90.
| Degradation of nitro-based pharmaceuticals by UV photolysis: Kinetics and simultaneous reduction on halonitromethanes formation potentialCrossref | GoogleScholarGoogle Scholar |
Fang J, Ma J, Yang X, Shang C (2010). Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa. Water Research 44, 1934–1940.
| Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosaCrossref | GoogleScholarGoogle Scholar |
Fang J-Y, Ling L, Shang C (2013). Kinetics and mechanisms of pH-dependent degradation of halonitromethanes by UV photolysis. Water Research 47, 1257–1266.
| Kinetics and mechanisms of pH-dependent degradation of halonitromethanes by UV photolysisCrossref | GoogleScholarGoogle Scholar |
Fent K, Weston AA, Caminada D (2006). Erratum to “Ecotoxicology of human pharmaceuticals”. Aquatic Toxicology (Amsterdam, Netherlands) 78, 207
| Erratum to “Ecotoxicology of human pharmaceuticals”Crossref | GoogleScholarGoogle Scholar | [Aquatic Toxicology 76 (2006), 122–159]
Gros M, Petrović M, Barceló D (2007). Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro river basin (Northeast Spain). Environmental Toxicology and Chemistry 26, 1553–1562.
| Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro river basin (Northeast Spain)Crossref | GoogleScholarGoogle Scholar |
Isidori M, Parrella A, Pistillo P, Temussi F (2009). Effects of ranitidine and its photoderivatives in the aquatic environment. Environment International 35, 821–825.
| Effects of ranitidine and its photoderivatives in the aquatic environmentCrossref | GoogleScholarGoogle Scholar |
Ji Y, Fan Y, Liu K, Kong D, Lu J (2015). Thermo activated persulfate oxidation of antibiotic sulfamethoxazole and structurally related compounds. Water Research 87, 1–9.
| Thermo activated persulfate oxidation of antibiotic sulfamethoxazole and structurally related compoundsCrossref | GoogleScholarGoogle Scholar |
Jovanovic SV, Simic MG (1986). Mechanism of OH radical reactions with thymine and uracil derivatives. Journal of the American Chemical Society 108, 5968–5972.
| Mechanism of OH radical reactions with thymine and uracil derivativesCrossref | GoogleScholarGoogle Scholar |
Khetan SK, Collins TJ (2007). Human pharmaceuticals in the aquatic environment: A challenge to green chemistry. Chemical Reviews 107, 2319–2364.
| Human pharmaceuticals in the aquatic environment: A challenge to green chemistryCrossref | GoogleScholarGoogle Scholar |
Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002). Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: A national reconnaissance. Environmental Science & Technology 36, 1202–1211.
| Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: A national reconnaissanceCrossref | GoogleScholarGoogle Scholar |
Krzeminski P, Schwermer C, Wennberg A, Langford K, Vogelsang C (2017). Occurrence of UV filters, fragrances and organophosphate flame retardants in municipal WWTP effluents and their removal during membrane post-treatment. Journal of Hazardous Materials 323, 166–176.
| Occurrence of UV filters, fragrances and organophosphate flame retardants in municipal WWTP effluents and their removal during membrane post-treatmentCrossref | GoogleScholarGoogle Scholar |
Kümmerer K (2003). Significance of antibiotics in the environment. The Journal of Antimicrobial Chemotherapy 52, 5–7.
| Significance of antibiotics in the environmentCrossref | GoogleScholarGoogle Scholar |
Lawton LA, Robertson PKJ (1999). Physico-chemical treatment methods for the removal of microcystins (cyanobacterial hepatotoxins) from potable waters. Chemical Society Reviews 28, 217–224.
| Physico-chemical treatment methods for the removal of microcystins (cyanobacterial hepatotoxins) from potable watersCrossref | GoogleScholarGoogle Scholar |
Legrini O, Oliveros E, Braun AM (1993). Photochemical processes for water treatment. Chemical Reviews 93, 671–698.
| Photochemical processes for water treatmentCrossref | GoogleScholarGoogle Scholar |
Li R, Kong J, Liu H, Chen P, Liu G, Li F, Lv W (2017). A sulfate radical based ferrous-peroxydisulfate oxidative system for indomethacin degradation in aqueous solutions. RSC Advances 7, 22802–22809.
| A sulfate radical based ferrous-peroxydisulfate oxidative system for indomethacin degradation in aqueous solutionsCrossref | GoogleScholarGoogle Scholar |
Liu Z, Zhou X, Chen X, Dai C, Zhang J, Zhang Y (2013). Biosorption of clofibric acid and carbamazepine in aqueous solution by agricultural waste rice straw. Journal of Environmental Sciences (China) 25, 2384–2395.
| Biosorption of clofibric acid and carbamazepine in aqueous solution by agricultural waste rice strawCrossref | GoogleScholarGoogle Scholar |
Llor C, Bjerrum L (2014). Antimicrobial resistance: risk associated with antibiotic overuse and initiatives to reduce the problem. Therapeutic Advances in Drug Safety 5, 229–241.
| Antimicrobial resistance: risk associated with antibiotic overuse and initiatives to reduce the problemCrossref | GoogleScholarGoogle Scholar |
Low GKC, McEvoy SR, Matthews RW (1991). Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atoms. Environmental Science & Technology 25, 460–467.
| Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atomsCrossref | GoogleScholarGoogle Scholar |
Martin LE, Oxford J, Tanner RJN (1981). The use of on-line high-performance liquid chromatography-mass spectrometry for the identification of ranitidine and its metabolites in urine. Xenobiotica 11, 831–840.
| The use of on-line high-performance liquid chromatography-mass spectrometry for the identification of ranitidine and its metabolites in urineCrossref | GoogleScholarGoogle Scholar |
Molinari R, Pirillo F, Loddo V, Palmisano L (2006). Heterogeneous photocatalytic degradation of pharmaceuticals in water by using polycrystalline TiO2 and a nanofiltration membrane reactor. Catalysis Today 118, 205–213.
| Heterogeneous photocatalytic degradation of pharmaceuticals in water by using polycrystalline TiO2 and a nanofiltration membrane reactorCrossref | GoogleScholarGoogle Scholar |
Muñoz F, von Sonntag C (2000). The reactions of ozone with tertiary amines including the complexing agents nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA) in aqueous solution. Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry 2029–2033.
| The reactions of ozone with tertiary amines including the complexing agents nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA) in aqueous solutionCrossref | GoogleScholarGoogle Scholar |
Naim S, Ghauch A (2016). Ranitidine abatement in chemically activated persulfate systems: Assessment of industrial iron waste for sustainable applications. Chemical Engineering Journal 288, 276–288.
| Ranitidine abatement in chemically activated persulfate systems: Assessment of industrial iron waste for sustainable applicationsCrossref | GoogleScholarGoogle Scholar |
Nejumal KK, Manoj PR, Aravind UK, Aravindakumar CT (2014). Sonochemical degradation of a pharmaceutical waste, atenolol, in aqueous medium. Environmental Science and Pollution Research International 21, 4297–4308.
| Sonochemical degradation of a pharmaceutical waste, atenolol, in aqueous mediumCrossref | GoogleScholarGoogle Scholar |
Olvera-Vargas H, Oturan N, Brillas E, Buisson D, Esposito G, Oturan MA (2014). Electrochemical advanced oxidation for cold incineration of the pharmaceutical ranitidine: Mineralization pathway and toxicity evolution. Chemosphere 117, 644–651.
| Electrochemical advanced oxidation for cold incineration of the pharmaceutical ranitidine: Mineralization pathway and toxicity evolutionCrossref | GoogleScholarGoogle Scholar |
Oturan MA, Aaron J-J (2014). Advanced oxidation processes in water/wastewater treatment: principles and applications. A review. Critical Reviews in Environmental Science and Technology 44, 2577–2641.
| Advanced oxidation processes in water/wastewater treatment: principles and applications. A reviewCrossref | GoogleScholarGoogle Scholar |
Oturan N, Trajkovska S, Oturan MA, Couderchet M, Aaron J-J (2008). Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process ‘electro-Fenton’. Chemosphere 73, 1550–1556.
| Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process ‘electro-Fenton’Crossref | GoogleScholarGoogle Scholar |
Prosser RS, Sibley PK (2015). Human health risk assessment of pharmaceuticals and personal care products in plant tissue due to biosolids and manure amendments, and wastewater irrigation. Environment International 75, 223–233.
| Human health risk assessment of pharmaceuticals and personal care products in plant tissue due to biosolids and manure amendments, and wastewater irrigationCrossref | GoogleScholarGoogle Scholar |
Radjenović J, Petrović M, Barceló D (2009). Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment. Water Research 43, 831–841.
| Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatmentCrossref | GoogleScholarGoogle Scholar |
Radjenović J, Sirtori C, Petrović M, Barceló D, Malato S (2010). Characterization of intermediate products of solar photocatalytic degradation of ranitidine at pilot-scale. Chemosphere 79, 368–376.
| Characterization of intermediate products of solar photocatalytic degradation of ranitidine at pilot-scaleCrossref | GoogleScholarGoogle Scholar |
Rahman MF, Yanful EK, Jasim SY (2009). Occurrences of endocrine disrupting compounds and pharmaceuticals in the aquatic environment and their removal from drinking water: Challenges in the context of the developing world. Desalination 248, 578–585.
| Occurrences of endocrine disrupting compounds and pharmaceuticals in the aquatic environment and their removal from drinking water: Challenges in the context of the developing worldCrossref | GoogleScholarGoogle Scholar |
Rayaroth MP, Aravind UK, Aravindakumar CT (2018). Role of in-situ nitrite ion formation on the sonochemical transformation of para-aminosalicylic acid. Ultrasonics Sonochemistry 40, 213–220.
| Role of in-situ nitrite ion formation on the sonochemical transformation of para-aminosalicylic acidCrossref | GoogleScholarGoogle Scholar |
Rivas J, Gimeno O, Carbajo M, Borralho T (2010). Aqueous ranitidine elimination in photolytic processes. International Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering 4, 449–451.
Rosal R, Rodríguez A, Perdigón-Melón JA, Petre A, García-Calvo E, Gómez MJ, Agüera A, Fernández-Alba AR (2010). Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Research 44, 578–588.
| Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonationCrossref | GoogleScholarGoogle Scholar |
Schulze T, Weiss S, Schymanski E, Carsten von der Ohe P, Schmitt-Jansen M, Altenburger R, Streck G, Brack W (2010). Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis. Environmental Pollution 158, 1461–1466.
| Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysisCrossref | GoogleScholarGoogle Scholar |
Sera L, McPherson ML, Holmes HM (2014). Commonly prescribed medications in a population of hospice patients. The American Journal of Hospice & Palliative Care 31, 126–131.
| Commonly prescribed medications in a population of hospice patientsCrossref | GoogleScholarGoogle Scholar |
Suslick KS (1989). The chemical effects of ultrasound. Scientific American 260, 80–86.
| The chemical effects of ultrasoundCrossref | GoogleScholarGoogle Scholar |
Tissot A, Boule P, Lemaire J (1984). Photochemistry and environment. VII. The photohydrolysis of chlorobenzene: Studies of the excited state involved. Chemosphere 13, 381–389.
| Photochemistry and environment. VII. The photohydrolysis of chlorobenzene: Studies of the excited state involvedCrossref | GoogleScholarGoogle Scholar |
Torres RA, Abdelmalek F, Combet E, Pétrier C, Pulgarin C (2007). A comparative study of ultrasonic cavitation and Fenton’s reagent for bisphenol A degradation in deionised and natural waters. Journal of Hazardous Materials 146, 546–551.
| A comparative study of ultrasonic cavitation and Fenton’s reagent for bisphenol A degradation in deionised and natural watersCrossref | GoogleScholarGoogle Scholar |
Trovó AG, Nogueira RFP, Agüera A, Sirtori C, Fernández-Alba AR (2009). Photodegradation of sulfamethoxazole in various aqueous media: Persistence, toxicity and photoproducts assessment. Chemosphere 77, 1292–1298.
| Photodegradation of sulfamethoxazole in various aqueous media: Persistence, toxicity and photoproducts assessmentCrossref | GoogleScholarGoogle Scholar |
Wang JL, Xu LJ (2012). Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application. Critical Reviews in Environmental Science and Technology 42, 251–325.
| Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and applicationCrossref | GoogleScholarGoogle Scholar |
Wu TY, Guo N, Teh CY, Hay JXW (2013) Theory and fundamentals of ultrasound. In ‘Advances in ultrasound technology for environmental remediation’. (Eds TY Wu, N Guo, CY Teh, JXW Hay) pp. 5–12. (Springer Netherlands: Dordrecht)
Xiao Y, Yaohari H, De Araujo C, Sze CC, Stuckey DC (2017). Removal of selected pharmaceuticals in an anaerobic membrane bioreactor (AnMBR) with/without powdered activated carbon (PAC). Chemical Engineering Journal 321, 335–345.
| Removal of selected pharmaceuticals in an anaerobic membrane bioreactor (AnMBR) with/without powdered activated carbon (PAC)Crossref | GoogleScholarGoogle Scholar |
Yan J, Lei M, Zhu L, Anjum MN, Zou J, Tang H (2011). Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfate. Journal of Hazardous Materials 186, 1398–1404.
| Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfateCrossref | GoogleScholarGoogle Scholar |
