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UV-induced photocatalytic degradation of aqueous acetaminophen: the role of adsorption and reaction kinetics

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Abstract

Nanostructured titania supported on activated carbon (AC), termed as integrated photocatalytic adsorbents (IPCAs), were prepared by ultrasonication and investigated for the photocatalytic degradation of acetaminophen (AMP), a common analgesic and antipyretic drug. The IPCAs showed high affinity towards AMP (in dark adsorption studies), with the amount adsorbed proportional to the TiO2 content; the highest adsorption was at 10 wt% TiO2. Equilibrium isotherm studies showed that the adsorption followed the Langmuir model, indicating the dependence of the reaction on an initial adsorption step, with maximum adsorption capacity of 28.4 mg/g for 10 % TiO2 IPCA. The effects of initial pH, catalyst amount and initial AMP concentration on the photocatalytic degradation rates were studied. Generally, the AMP photodegradation activity of the IPCAs was better than that of bare TiO2. Kinetic studies on the photocatalytic degradation of AMP under UV suggest that the degradation followed Langmuir–Hinshelwood (L–H) kinetics, with an adsorption rate constant (K) that was considerably higher than the photocatalytic rate constant (k r), indicating that the photocatalysis of AMP is the rate-determining step during the adsorption/photocatalysis process.

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References

  • Aksu Z, Kutsal TA (1991) Bioseparation process for removing lead(II) ions from waste water by using C. vulgaris. Chem Technol Biotechnol 52:109–118

    Article  CAS  Google Scholar 

  • Allen SJ, Mckay G, Khader KYH (1988) Multicomponent sorption isotherms of basic dyes onto peat. Environ Pollut 52:39–53

    Article  CAS  Google Scholar 

  • Ao Y, Xu J, Fu D, Shen X, Yuan C (2008) Low temperature preparation of anatase TiO2-coated activated carbon. Colloid Surf A Physicochem Eng Asp 312:125–130

    Article  CAS  Google Scholar 

  • Basha S, Keane D, Nolan K, Morrissey A, Oelgemöller M, Tobin J (2010) Studies on the adsorption and kinetics of photodegradation of pharmaceutical compound, Indomethacin using novel photocatalytic adsorbents. Ind Eng Chem Res 49(22):11302–11309

  • Basha S, Barr C, Keane D, Nolan K, Morrissey A, Oelgemöller M, Tobin JM (2011) On the adsorption/photodegradation of amoxicillin in aqueous solutions by an integrated photocatalytic adsorbent (IPCA): experimental studies and kinetics analysis. Photochem Photobiol Sci 10:1014–1022

    Article  CAS  Google Scholar 

  • Bayarri B, Gimenez J, Curco D, Esplugas S (2005) Photocatalytic degradation of 2,4-dichlorophenol by TiO2/UV: kinetics, actinometries and models. Catal Today 101:227–236

    Article  CAS  Google Scholar 

  • Bhattacharyya A, Kawi S, Ray MB (2004) Photocatalytic degradation of orange II by TiO2 catalysts supported on adsorbents. Catal Today 98:431–439

    Article  CAS  Google Scholar 

  • Bolton JR, Bircher KG, Tumas W, Tolman CA (2001) Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems (IUPAC Technical Report). Pure Appl Chem 73:627–637

    Article  CAS  Google Scholar 

  • Brunner M, Schmiedberger A, Schmid R, Jager D, Piegler E, Eichler HG, Muller M (1998) Direct assessment of peripheral pharmacokinetics in humans: comparison between cantharides blister fluid sampling, in vivo microdialysis and saliva sampling. Br J Clin Pharmacol 46:425–431

    Article  CAS  Google Scholar 

  • Burgina EB, Baltakhinov VP, Boldyreva EV, Shakhtschneider TP (2004) IR spectra of paracetamol and phenacetin. 1. Theoretical and experimental studies. J Struct Chem 45:64–73

    Article  CAS  Google Scholar 

  • Chen H, Lee SW, Kim TH, Hur BY (2006) Photocatalytic decomposition of benzene with plasma sprayed TiO2-based coatings on foamed aluminum. J Eur Ceram Soc 26:2231–2239

    Article  CAS  Google Scholar 

  • Chen H, Li X, Zhu S (2012) Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels. Environ Sci Pollut Res 19:2381–2389

    Article  CAS  Google Scholar 

  • Chiron S, Fernandez-Alba A, Rodriguez A, Garcia-Calvo E (2000) Pesticide chemical oxidation: state-of-the-art. Water Res 34:366–377

    Article  CAS  Google Scholar 

  • Cojocaru B, Neatu S, Parvulescu VI, Somoghi V, Petrea N, Epure G, Alvaro M, Garcia H (2009) Synergism of activated carbon and undoped and nitrogen-doped TiO2 in the photocatalytic degradation of the chemical warfare agents Soman, VX, and Yperite. Chem Sustain Chem 2:427–436

    Article  CAS  Google Scholar 

  • Cunningham J, Al-Sayyed G, Srijaranai S (1994) In: Helz GR, Zepp RG, Crosby DG (eds) Aquatic and surface photochemistry. Lewis, Boca Raton, pp 317–348

    Google Scholar 

  • Daneshvar N, Aleboyeh A, Khataee AR (2005) The evaluation of electrical energy per order (EEo) for photooxidative decolorization of four textile dye solutions by the kinetic model. Chemosphere 59:761–767

    Article  CAS  Google Scholar 

  • Danten Y, Tassaing T, Besnard M (2006) Density functional theory (DFT) calculations of the Infrared absorption spectra of acetaminophen complexes formed with ethanol and acetone species. J Phys Chem A 110:8986–9001

    Article  CAS  Google Scholar 

  • Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938

    Article  CAS  Google Scholar 

  • Deegan AM, Shaik B, Nolan K, Urell K, Oelgemöller M, Tobin J, Morrissey A (2011) Treatment options for wastewater effluents from pharmaceutical companies Internat. J Environ Sci Technol 8:649–666

  • Federsel HJ (2013) En route to full implementation: driving the green chemistry agenda in the pharmaceutical industry. Green Chem 15:3105–3115

    Article  CAS  Google Scholar 

  • Flores JM, Zhao DF, Segev L, Schlag P, Kiendler-Scharr A, Fuchs H, Watne AK, Bluvshtein N, Mentel TF, Hallquist M, Rudich Y (2014) Evolution of the complex refractive index in the near UV spectral region in ageing secondary organic aerosol. Atmos Chem Phys Discus 14:4149–4187

    Article  Google Scholar 

  • Forrest JA, Clements JA, Prescott LF (1982) Clinical pharmacokinetics of paracetamol. Clin Pharmacokinet 7:93–107

    Article  CAS  Google Scholar 

  • Fritz W, Schluender EU (1974) Simultaneous adsorption equilibria of organic solutes in dilute aqueous solution on activated carbon. Ceram Eng Sci Proc 29:1279–1282

    CAS  Google Scholar 

  • Fujishima A, Zhang X, Tryk DA (2008) TiO2 photocatalysis and related surface phenomena. Surf Sci Rep 63:515–582

    Article  CAS  Google Scholar 

  • Gogate PR, Pandit AB (2004) A review of imperative technologies for wastewater treatment II: Hybrid methods. Adv Environ Res 8:553–597

    Article  CAS  Google Scholar 

  • Goncalves MST, Oliveira-Campos AMF, Pinto EMMS, Plasencia PMS, Queiroz MJRP (1999) Photochemical treatment of solutions of azo dyes containing TiO2. Chemosphere 39:781–786

    Article  CAS  Google Scholar 

  • Guettai N, Amar HA (2005) Photocatalytic oxidation of methyl orange in presence of titanium dioxide in aqueous suspension. Part II Kinetics study. Desalination 185:439–448

    Article  CAS  Google Scholar 

  • Halling-Sørensen B, Nors Nielsen S, Lanszky PF, Ingerslev F, Holten Lutzhaft HC, Jørgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment—a review. Chemosphere 36:357–393

    Article  Google Scholar 

  • Heberer T, Reddersen K, Mechlinski A (2002) From municipal sewage to drinking water: fate and removal of pharmaceutical residues in the aquatic environment in urban areas. Water Sci Technol 46:81–88

    CAS  Google Scholar 

  • Herrmann J (1999) Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants. Catal Today 53:115–129

    Article  CAS  Google Scholar 

  • Ho YS, McKay G (1998) Sorption of dye from aqueous solution by peat. Chem Eng J 70:115–124

    Article  CAS  Google Scholar 

  • Hoffmann MR, Martin ST, Choi WY, Bahnemann DW (1995) Environmental applications of semiconductor photocatalysis. Chem Rev 95:69–96

    Article  CAS  Google Scholar 

  • Jasper JT, Sedlak DL (2013) Phototransformation of wastewater-derived trace organic contaminants in open-water unit process treatment wetlands. Environ Sci Technol 47(19):10781–10790

    Article  CAS  Google Scholar 

  • Keane D, Basha S, Nolan K, Morrissey A, Oelgemöller M, Tobin J (2011) Photodegradation of famotodine by integrated photocatalytic adsorbent (IPCA) and kinetic study. Catal Lett 141(2):300–308

  • Khan AR, Ataullah R, Al-Haddad A (1997) Equilibrium adsorption studies of some aromatic pollutants from dilute aqueous solutions on activated carbon at different temperatures. J Colloid Interface Sci 194:154–165

    Article  CAS  Google Scholar 

  • Kim S-H, Ngo HH, Shon HK, Vigneswaran S (2008) Adsorption and photocatalysis kinetics of herbicide onto titanium oxide and powdered activated carbon. Sep Purif Technol 58:335–342

    Article  CAS  Google Scholar 

  • Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environ Int 35:402–417

    Article  CAS  Google 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. Environ Sci Technol 36:1202–1211

    Article  CAS  Google Scholar 

  • Kumar KV, Sivanesan S, Ramamurthy V (2005) Adsorption of malachite green onto Pithophora sp., a fresh water algae: equilibrium and kinetic modeling. Process Biochem 40:2865–2872.

  • Kummerer K (2008) Pharmaceuticals in the environment: sources, fate, effects and risks, 3rd edn. Springer, Berlin

    Book  Google Scholar 

  • Lacey C, Basha S, Morrissey A, Tobin J (2012) Occurrence of pharmaceutical compounds in wastewater process streams in Dublin, Ireland. Environ Monit Assess 184:1049–1062

    Article  CAS  Google Scholar 

  • Lagergren S, Svenska BK (1898) Zur theorie der sogenannten adsorption geloester stoffe. Veterskapsakad Handlingar 24:1–6

    Google Scholar 

  • Li Y, Li X, Li J, Yin J (2005) Photocatalytic degradation of methyl orange in a sparged tube reactor with TiO2-coated activated carbon composites. Catal Commun 6:650–655

    Article  CAS  Google Scholar 

  • Li Y, Li X, Li J, Yin J (2006) Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study. Water Res 40:1119–1126

    Article  CAS  Google Scholar 

  • Liu Z, He Y, Li F, Liu Y (2006) Photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (5 pp). Environ Sci Pollut Res 13:328–332

    Article  CAS  Google Scholar 

  • Liu Y, Wan K, Deng N, Wu F (2010) Photodegradation of paracetamol in montmorillonite KSF suspension. React Kinet Mech Catal 99:493–502

    CAS  Google Scholar 

  • Lu MC, Chen JN, Chang KT (1999) Effect of adsorbents coated with titanium dioxide on the photocatalytic degradation of propoxur. Chemosphere 38(3):617–627

    Article  CAS  Google Scholar 

  • Matos J, Laine J, Hermann JM (2001) Effect of the type of activated carbons on the photocatalytic degradation of aqueous organic pollutants by UV-irradiated titania. J Catal 200:10–20

    Article  CAS  Google Scholar 

  • Nikolaou A, Meric S, Fatta D (2007) Occurrence patterns of pharmaceuticals in water and wastewater environments. Anal Bioanal Chem 387:1225–1234

    Article  CAS  Google Scholar 

  • Ocampo-Pereza R, Sanchez-Polo M, Rivera-Utrilla J, Leyva-Ramos R (2011) Enhancement of the catalytic activity of TiO2 by using activated carbon in the photocatalytic degradation of cytarabine. Appl Catal B Environ 104:177–184

    Article  Google Scholar 

  • Peuravuori J (2012) Aquatic photochemistry of paracetamol in the presence of dissolved organic chromophoric material and nitrate. Environ Sci Pollut Res 19:2259–2270

    Article  Google Scholar 

  • Roberts PH, Thomas KV (2006) The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment. Sci Total Environ 356:143–153

    Article  CAS  Google Scholar 

  • Salgado R, Marques R, Noronha JP, Carvalho G, Oehmen A, Reis MAM (2012) Assessing the removal of pharmaceuticals and personal care products in a full-scale activated sludge plant. Environ Sci Pollut Res 19:1818–1827

    Article  CAS  Google Scholar 

  • Santos LHMLM, Araujo AN, Fachini A, Pena A, Delerue-Matos C, Montenegro MCBSM (2010) Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment. J Hazard Mater 175:45–95

    Article  CAS  Google Scholar 

  • Shimizu K, Kaneko T, Fujishima T, Kodama T, Yoshida H, Kitayama Y (2002) Selective oxidation of liquid hydrocarbons over photoirradiated TiO2 pillared clays. Appl Catal A Gen 225:185–191

    Article  CAS  Google Scholar 

  • Stackelberg PE, Gibs J, Furlong ET, Meyer MT, Zaugg SD, Lippincott RL (2007) Efficiency of conventional drinking-water-treatment processes in removal of pharmaceuticals and other organic compounds. Sci Total Environ 377:255–272

    Article  CAS  Google Scholar 

  • Tang WZ, Huang CP (1995) Photocatalyzed oxidation pathways of 2,4-dichlorophenol by CdS in basic and acidic aqueous solutions. Water Res 29:745–756

    Article  CAS  Google Scholar 

  • Ternes TA (1998) Occurrence of drugs in German sewage treatment plants and rivers. Water Res 32:3245–3260

    Article  CAS  Google Scholar 

  • Terzyk AP (2001) The influence of activated carbon surface chemical composition on the adsorption of acetaminophen (paracetamol) in vitro. Part II. TG, FTIR, and XPS analysis of carbons and the temperature dependence of adsorption kinetics at the neutral pH. Colloids and Surfaces A: Physicochem. Eng. Aspects 177:23–45

  • Usher C, Teeling M, Bennett K, McGowan B, Feely J (2005) Usage of paracetamol-containing combination analgesics remains high in primary care. Br J Clin Pharmacol 60:648–652

    Google Scholar 

  • Vadivelan V, Kumar VK (2005) Equilibrium, kinetics, mechanism, and process design for the sorption of methylene blue onto rice husk. J Colloid Interface Sci 286:90–100

    Article  CAS  Google Scholar 

  • Velegraki T, Mantzavinos D (2008) Conversion of benzoic acid during TiO2-mediated photocatalytic degradation in water. Chem Eng J 140:15–21

    Article  CAS  Google Scholar 

  • Vohra MS, Tanaka K (2003) Photocatalytic degradation of aqueous pollutants using silica-modified TiO2. Water Res 37:3992–3996

    Article  CAS  Google Scholar 

  • Wang C, Lee C, Lyu M, Juang L (2008) Photocatalytic degradation of C.I. Basic Violet 10 using TiO2 catalysts supported by Y zeolite: An investigation of the effects of operational parameters. Dyes Pigments 76:817–824

    Article  CAS  Google Scholar 

  • Wang X, Liu Y, Hu Z, Chen Y, Liu W, Zhao G (2009) Degradation of methyl orange by composite photocatalysts nano-TiO2 immobilized on activated carbons of different porosities. J Hazard Mater 169:1061–1067

    Article  CAS  Google Scholar 

  • Wong CC, Chu W (2003) The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources. Chemosphere 50:981–987

    Article  CAS  Google Scholar 

  • Xue G, Liu H, Chen Q, Hills C, Tyrer M, Innocent F (2011) Synergy between surface adsorption and photocatalysis during degradation of humic acid on TiO2/activated carbon composites. J Hazard Mater 186:765–772

    Article  CAS  Google Scholar 

  • Yamamoto H, Nakamura Y, Moriguchi S, Nakamura Y, Honda Y, Tamura I, Hirata Y, Hayashi A, Sekizawa J (2009) Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: laboratory photolysis, biodegradation, and sorption experiments. Water Res 43:351–362

    Article  CAS  Google Scholar 

  • Yang L, Yu LE, Ray MB (2008) Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis. Water Res 42:3480–3488

    Article  CAS  Google Scholar 

  • Zeng T, Arnold WA (2013) Pesticide photolysis in prairie potholes: probing photosensitized processes. Environ Sci Technol 47(13):6735–6745\

    CAS  Google Scholar 

  • Zhang X, Wu F, Wu X, Chen P, Deng N (2008) Photodegradation of acetaminophen in TiO2 suspended solution. J Hazard Mater 157:300–307

    Article  CAS  Google Scholar 

  • Zhang Y, Zhang C, Liu S, Xu Y-J (2013) Size effect induced activity enhancement and anti-photocorrosion of reduced graphene oxide/ZnO composites for degradation of organic dyes and reduction of Cr(VI) in water. Appl Catal B Environ 140–141:598–607

    Article  Google Scholar 

  • Zhu C, Wang L, Kong L, Yang X, Wang L, Zheng S, Chen F, Zhi FM, Zong H (2000) Photocatalytic degradation of AZO dyes by supported TiO2 + UV in aqueous solution. Chemosphere 41:303–309

    Article  CAS  Google Scholar 

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Acknowledgments

SB wishes to gratefully acknowledge financial support from the Irish Research Council for Science, Engineering and Technology (IRCSET) in the form of IRCSET EMPOWER postdoctoral fellowship and the Central Salt and Marine Chemicals Research Institute (CSMCRI) for grant of study/earned leave. DK gratefully acknowledges the financial support from the STRIVE program from the Environmental Protection Agency (EPA) Ireland and technical assistance from ENVA Ireland Ltd and National Chemical Company of Ireland.

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Authors and Affiliations

  1. Business School, Dublin City University, Dublin 9, Ireland

    Anne Morrissey

  2. Discipline of Marine Biotechnology and Ecology, CSIR-Central Salt and Marine Chemicals Research Institute, Bhavagnar, 364002, Gujarat, India

    Shaik Basha

  3. School of Biotechnology, Dublin City University, Dublin 9, Ireland

    David Keane, Jenny Lawler & John M. Tobin

  4. School of Chemical Sciences, Dublin City University, Dublin 9, Ireland

    Kieran Nolan

  5. College of Science, Technology and Engineering, James Cook University, Townsville, Queensland, 4811, Australia

    Michael Oelgemöller

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  1. Shaik Basha
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  2. David Keane
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Correspondence to Anne Morrissey.

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Basha, S., Keane, D., Nolan, K. et al. UV-induced photocatalytic degradation of aqueous acetaminophen: the role of adsorption and reaction kinetics. Environ Sci Pollut Res 22, 2219–2230 (2015). https://doi.org/10.1007/s11356-014-3411-9

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