Abstract
The influences of HCO3 −, Cl−, and other components on the UV/TiO2 degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO3 −, Cl−, NO3 −, and SO4 2− in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO2 loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO3 − in the UV/TiO2/HCO3 − system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of •CO3 − in the system. The results also showed that •CO3 − likely induces a preferred ketonization pathway. Besides the inorganic anions HCO3 −, Cl−, NO3 −, and SO4 2−, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO3 − or Cl− during UV/TiO2 treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.
Similar content being viewed by others
References
Autin O, Hart J, Jarvis P, MacAdam J, Parsons SA, Jefferson B (2013) The impact of background organic matter and alkalinity on the degradation of the pesticide metaldehyde by two advanced oxidation processes: UV/H2O2 and UV/TiO2. Water Res 47:2041–2049. doi:10.1016/j.watres.2013.01.022
Besse JP, Latour JF, Garric J (2012) Anticancer drugs in surface waters: what can we say about the occurrence and environmental significance of cytotoxic, cytostatic and endocrine therapy drugs? Environ Int 39:73–86. doi:10.1016/j.envint.2011.10.002
Boreen AL, Arnold WA, McNeill K (2005) Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct. Environ Sci Technol 39:3630–3638. doi:10.1021/es048331p
Buerge IJ, Buser HR, Poiger T, Muller MD (2006) Occurrence and fate of the cytostatic drugs cyclophosphamide and ifosfamide in wastewater and surface waters. Environ Sci Technol 40:7242–7250. doi:10.1021/es0609405
Burns RA, Crittenden JC, Hand DW, Selzer VH, Sutter LL, Salman SR (1999) Effect of inorganic ions in heterogeneous photocatalysis of TCE. J Environ Engin 125:77–85. doi:10.1061/(ASCE)0733-9372(1999)125:1(77)
Bus JS, Gibson JE (1973) Teratogenicity and neonatal toxicity of ifosfamide in mice. Proc Soc Exp Biol Med 143:965–970. doi:10.3181/00379727-143-37450
Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical-review of rate constants for reactions of hydrated electrons, hydrogen-atoms and hydroxyl radicals (.Oh/.O-) in aqueous-solution. J Phys Chem Ref Data 17:513–886. doi:10.1063/1.555805
Castiglioni S, Bagnati R, Fanelli R, Pomati F, Calamari D, Zuccato E (2006) Removal of pharmaceuticals in sewage treatment plants in Italy. Environ Sci Technol 40:357–363. doi:10.1021/es050991m
Cavalcante RP, Dantas RF, Wender H, Bayarri B, Gonzalez O, Gimenez J, Esplugas S, Machulek A (2015) Photocatalytic treatment of metoprolol with B-doped TiO2: effect of water matrix, toxicological evaluation and identification of intermediates. Appl Catal B-Environ 176:173–182. doi:10.1016/j.apcatb.2015.04.007
Česen M, Kosjek T, Busetti F, Kompare B, Heath E (2016) Human metabolites and transformation products of cyclophosphamide and ifosfamide: analysis, occurrence and formation during abiotic treatments. Environ Sci Pollut Res:1–15. doi:10.1007/s11356-016-6321-1
Cesen M, Kosjek T, Laimou-Geraniou M, Kompare B, Sirok B, Lambropolou D, Heath E (2015) Occurrence of cyclophosphamide and ifosfamide in aqueous environment and their removal by biological and abiotic wastewater treatment processes. Sci Total Environ 527:465–473. doi:10.1016/j.scitotenv.2015.04.109
Choi J, Lee H, Choi Y, Kim S, Lee S, Lee S, Choi W, Lee J (2014) Heterogeneous photocatalytic treatment of pharmaceutical micropollutants: effects of wastewater effluent matrix and catalyst modifications. Appl Catal B-Environ 147:8–16. doi:10.1016/j.apcatb.2013.08.032
Chong MN, Jin B, Chow CWK, Saint C (2010) Recent developments in photocatalytic water treatment technology: a review. Water Res 44:2997–3027. doi:10.1016/j.watres.2010.02.039
Diebold U (2003) The surface science of titanium dioxide. Surf Sci Rep 48:53–229. doi:10.1016/S0167-5729(02)00100-0
Fang JY, Fu Y, Shang C (2014) The roles of reactive species in micropollutant degradation in the UV/free chlorine system. Environ Sci Technol 48:1859–1868. doi:10.1021/es4036094
Fernandez LA, Hernandez C, Bataller M, Veliz E, Lopez A, Ledea O, Padron S (2010) Cyclophosphamide degradation by advanced oxidation processes. Water Environ J 24:174–180. doi:10.1111/j.1747-6593.2009.00169.x
Ferrando-Climent L, Rodriguez-Mozaz S, Barcelo D (2013) Development of a UPLC-MS/MS method for the determination of ten anticancer drugs in hospital and urban wastewaters, and its application for the screening of human metabolites assisted by information-dependent acquisition tool (IDA) in sewage samples. Anal Bioanal Chem 405:5937–5952. doi:10.1007/s00216-013-6794-4
Jelic A, Gros M, Ginebreda A, Cespedes-Sanchez R, Ventura F, Petrovic M, Barcelo D (2011) Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Res 45:1165–1176. doi:10.1016/j.watres.2010.11.010
Jia YF, Zhou L, Ferronato C, Yang X, Salvador A, Zeng C, Chovelon JM (2013) Photocatalytic degradation of atenolol in aqueous titanium dioxide suspensions: kinetics, intermediates and degradation pathways. J Photochem Photobiol A-Chem 254:35–44. doi:10.1016/j.jphotochem.2013.01.003
Johnson AC, Jurgens MD, Williams RJ, Kummerer K, Kortenkamp A, Sumpter JP (2008) Do cytotoxic chemotherapy drugs discharged into rivers pose a risk to the environment and human health? An overview and UK case study. J Hydrol 348:167–175. doi:10.1016/j.jhydrol.2007.09.054
Kummerer K, Steger-Hartmann T, Meyer M (1997) Biodegradability of the anti-tumour agent ifosfamide and its occurrence in hospital effluents and communal sewage. Water Res 31:2705–2710. doi:10.1016/S0043-1354(97)00121-8
Lai WW-P, Hsu M-H, Lin AY-C (2017) The role of bicarbonate anions in methotrexate degradation via UV/TiO 2: mechanisms, reactivity and increased toxicity. Water Res 112:157–166. doi:10.1016/j.watres.2017.01.040
Lai WW-P, Lin Y-C, Tung H-H, Lo S-L, Lin AY-C (2016) Occurrence of pharmaceuticals and perfluorinated compounds and evaluation of the availability of reclaimed water in Kinmen. Emerg Contam 2:135–144. doi:10.1016/j.emcon.2016.05.001
Lai WWP, Lin HHH, Lin AYC (2015) TiO2 photocatalytic degradation and transformation of oxazaphosphorine drugs in an aqueous environment. J Hazard Mat 287:133–141. doi:10.1016/j.jhazmat.2015.01.045
Li YY, Song WH, Fu WJ, Tsang DCW, Yang X (2015) The roles of halides in the acetaminophen degradation by UV/H2O2 treatment: kinetics, mechanisms, and products analysis. Chem Eng J 271:214–222. doi:10.1016/j.cej.2015.02.090
Lin AYC, Hsueh JHF, Hong PKA (2015) Removal of antineoplastic drugs cyclophosphamide, ifosfamide, and 5-fluorouracil and a vasodilator drug pentoxifylline from wastewaters by ozonation. Environ Sci Pollut Res 22:508–515. doi:10.1007/s11356-014-3288-7
Lin AYC, Lin YC, Lee WN (2014) Prevalence and sunlight photolysis of controlled and chemotherapeutic drugs in aqueous environments. Environ Pollut 187:170–181. doi:10.1016/j.envpol.2014.01.005
Lin HHH, Lin AYC (2014) Photocatalytic oxidation of 5-fluorouracil and cyclophosphamide via UV/TiO2 in an aqueous environment. Water Res 48:559–568. doi:10.1016/j.watres.2013.10.011
Liu Y, He X, Duan X, Fu Y, Fatta-Kassinos D, Dionysiou DD (2016) Significant role of UV and carbonate radical on the degradation of oxytetracycline in UV-AOPs: kinetics and mechanism. Water Res 95:195–204. doi:10.1016/j.watres.2016.03.011
Lutterbeck CA, Machado EL, Kammerer K (2015) Photodegradation of the antineoplastic cyclophosphamide: a comparative study of the efficiencies of UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2 processes. Chemosphere 120:538–546. doi:10.1016/j.chemosphere.2014.08.076
Mazellier P, Busset C, Delmont A, De Laat J (2007) A comparison of fenuron degradation by hydroxyl and carbonate radicals in aqueous solution. Water Res 41:4585–4594. doi:10.1016/j.watres.2007.06.066
Mohrmann M, Ansorge S, Schmich U, Schonfeld B, Brandis M (1994) Toxicity of ifosfamide, cyclophosphamide and their metabolites in renal tubular cells in culture. Pediatr Nephrol 8:157–163. doi:10.1007/BF00865466
Negreira N, de Aida ML, Barcelo D (2014) Cytostatic drugs and metabolites in municipal and hospital wastewaters in Spain: filtration, occurrence, and environmental risk. Sci Total Environ 497:68–77. doi:10.1016/j.scitotenv.2014.07.101
Ofiarska A, Pieczynska A, Borzyszkowska AF, Stepnowski P, Siedlecka EM (2016) Pt-TiO2-assisted photocatalytic degradation of the cytostatic drugs ifosfamide and cyclophosphamide under artificial sunlight. Chem Eng J 285:417–427. doi:10.1016/j.cej.2015.09.109
Pelaez M, de la Cruz AA, O'Shea K, Falaras P, Dionysiou DD (2011) Effects of water parameters on the degradation of microcystin-LR under visible light-activated TiO2 photocatalyst. Water Res 45:3787–3796. doi:10.1016/j.watres.2011.04.036
Rioja N, Zorita S, Penas FJ (2016) Effect of water matrix on photocatalytic degradation and general kinetic modeling. Appl Catal B-Environ 180:330–335. doi:10.1016/j.apcatb.2015.06.038
Santiago DE, Arana J, Gonzalez-Diaz O, Aleman-Dominguez ME, Acosta-Dacal AC, Fernandez-Rodriguez C, Perez-Pena J, Dona-Rodriguez JM (2014) Effect of inorganic ions on the photocatalytic treatment of agro-industrial wastewaters containing imazalil. Appl Catal B-Environ 156:284–292. doi:10.1016/j.apcatb.2014.03.022
Sirtori C, Zapata A, Malato S, Aguera A (2012) Formation of chlorinated by-products during photo-Fenton degradation of pyrimethanil under saline conditions. Influence on toxicity and biodegradability. J Hazard Mat 217:217–223. doi:10.1016/j.jhazmat.2012.03.017
Steger-Hartmann T, Kummerer K, Schecker J (1996) Trace analysis of the antineoplastics ifosfamide and cyclophosphamide in sewage water by two-step solid-phase extraction and gas chromatography mass spectrometry. J Chromatogr A 726:179–184. doi:10.1016/0021-9673(95)01063-7
Van Doorslaer X, Dewulf J, De Maerschalk J, Van Langenhove H, Demeestere K (2015) Heterogeneous photocatalysis of moxifloxacin in hospital effluent: effect of selected matrix constituents. Chem Eng J 261:9–16. doi:10.1016/j.cej.2014.06.079
Wang XH, Lin AYC (2012) Phototransformation of cephalosporin antibiotics in an aqueous environment results in higher toxicity. Environ Sci Technol 46:12417–12426. doi:10.1021/es301929e
Watkinson AJ, Murby EJ, Costanzo SD (2007) Removal of antibiotics in conventional and advanced wastewater treatment: implications for environmental discharge and wastewater recycling. Water Res 41:4164–4176. doi:10.1016/j.watres.2007.04.005
Wilde ML, Mahmoud WMM, Kummerer K, Martins AF (2013) Oxidation-coagulation of beta-blockers by (K2FeO4)-O-VI in hospital wastewater: assessment of degradation products and biodegradability. Sci Total Environ 452:137–147. doi:10.1016/j.scitotenv.2013.01.059
Yin J, Shao B, Zhang J, Li K (2010) A preliminary study on the occurrence of cytostatic drugs in hospital effluents in Beijing, China. Bull Environ Contam Toxicol 84:39–45. doi:10.1007/s00128-009-9884-4
Zepp RG, Hoigne J, Bader H (1987) Nitrate-induced photooxidation of trace organic-chemicals in water. Environ Sci Technol 21:443–450. doi:10.1021/es00159a004
Zhang GS, He XX, Nadagouda MN, O'Shea KE, Dionysiou DD (2015) The effect of basic pH and carbonate ion on the mechanism of photocatalytic destruction of cylindrospermopsin. Water Res 73:353–361. doi:10.1016/j.watres.2015.01.011
Acknowledgement
We are grateful for the financial support from the Ministry of Science and Technology (NSC 102-2221-E-002-009-MY3), Taiwan, ROC.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Suresh Pillai
Electronic supplementary material
ESM 1
(DOCX 606 kb)
Rights and permissions
About this article
Cite this article
Lai, W.WP., Chuang, YC. & Lin, A.YC. The effects and the toxicity increases caused by bicarbonate, chloride, and other water components during the UV/TiO2 degradation of oxazaphosphorine drugs. Environ Sci Pollut Res 24, 14595–14604 (2017). https://doi.org/10.1007/s11356-017-9005-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-017-9005-6