Predicting pharmaceutical degradation by UV (LP)/H2O2 processes: A kinetic model

Abstract Pharmaceuticals and other organic micropollutants are increasingly found in water sources. The UV/H2O2 process is a suitable technology to degrade these pharmaceuticals. A kinetic model is presented to predict pharmaceutical degradation during UV/H2O2 treatment. Reactions with background constituents in the water matrix, such as (bi)carbonate, nitrate and NOM were considered as well as hydroxyl radical and carbonate radical reactions with the pharmaceuticals. The kinetic model is validated by collimated beam experiments. In several water matrices a good agreement between measured and modelled degradation was found, for direct photolysis as well as advanced oxidation. For only 5 of the 36 compounds, the model over or under predicted the measured results. Possible explanations are: pH effects during photolysis and radical scavenging by NOM. The influence of each reaction incorporated in the kinetic model was studied by a sensitivity analysis. The sensitivity study showed that nitrate reactions can also be relevant in UV (LP) applications when there is no hydrogen peroxide and low concentrations of NOM.

[1]  C.H.M. Hofman-Caris,et al.  Prediction of advanced oxidation performance in UV/H2O2 reactor systems with LP-UV lamps , 2011 .

[2]  K. Linden,et al.  UV photolysis of nitrate: effects of natural organic matter and dissolved inorganic carbon and implications for UV water disinfection. , 2001, Environmental science & technology.

[3]  J. Crittenden,et al.  A kinetic model for H2O2/UV process in a completely mixed batch reactor , 1999 .

[4]  K. Linden,et al.  UV and UV/H2O2 treatment of methylisoborneol (MIB) and geosmin in water , 2005 .

[5]  G. Beck.  Elektrische leitfähigkeitsmessungen zum nachweis geladener zwischenprodukte der pulsradiolyse , 1969 .

[6]  C. Adams,et al.  Determination of Hydroxyl Radical Rate Constants for Fuel Oxygenates , 2007 .

[7]  H. Fricke,et al.  Rate constants of OH with HO2,O2-, and H2O2+ from hydrogen peroxide formation in pulse-irradiated oxygenated water , 1968 .

[8]  W. J. Cooper,et al.  Free Radical Destruction of β-Blockers in Aqueous Solution , 2008 .

[9]  I. Katsoyiannis,et al.  Efficiency and energy requirements for the transformation of organic micropollutants by ozone, O3/H2O2 and UV/H2O2. , 2011, Water research.

[10]  H. Christensen,et al.  Reactions of Hydroxyl Radicals with Hydrogen Peroxide at Ambient and Elevated Temperatures , 1982 .

[11]  H. Ngo,et al.  A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. , 2014, The Science of the total environment.

[12]  P. Neta,et al.  Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution , 1979 .

[13]  Mehrdad Raisee,et al.  Modeling hydroxyl radical distribution and trialkyl phosphates oxidation in UV-H2O2 photoreactors using computational fluid dynamics. , 2010, Environmental science & technology.

[14]  M. Sillanpää,et al.  Recent developments in photochemical and chemical AOPs in water treatment: a mini-review , 2010 .

[15]  B. Wols,et al.  Degradation of 40 selected pharmaceuticals by UV/H2O2. , 2013, Water research.

[16]  K. Linden,et al.  The ROH,UV concept to characterize and the model uv/H202 process in natural waters. , 2007, Environmental science & technology.

[17]  A. Negrón-Mendoza,et al.  Radiolysis of aqueous solutions of ammonium bicarbonate over a large dose range , 1991 .

[18]  K. Linden,et al.  Experimental and model comparisons of low- and medium-pressure Hg lamps for the direct and H2O2 assisted UV photodegradation of N-nitrosodimethylamine in simulated drinking water. , 2003, Environmental science & technology.

[19]  G. Buxton,et al.  Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in Aqueous Solution , 1988 .

[20]  Shane A. Snyder,et al.  Transformation of atrazine, carbamazepine, diclofenac and sulfamethoxazole by low and medium pressure UV and UV/H2O2 treatment , 2012 .

[21]  J. Bolton,et al.  Photochemistry of nitrite and nitrate in aqueous solution: a review , 1999 .

[22]  G. Mark,et al.  The photochemistry of aqueous nitrate ion revisited , 1996 .

[23]  W. Koppenol,et al.  THE HABER‐WEISS CYCLE , 1978 .

[24]  I Nopens,et al.  Application of a mechanistic UV/hydrogen peroxide model at full-scale: sensitivity analysis, calibration and performance evaluation. , 2011, Communications in agricultural and applied biological sciences.

[25]  B. Wols,et al.  Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water. , 2012, Water research.

[26]  J. K. Hurst,et al.  Hydroxyl Radical Formation during Peroxynitrous Acid Decomposition , 1999 .

[27]  T. Heberer.  Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. , 2002, Toxicology letters.

[28]  B. Legube,et al.  Phototransformation of selected organophosphorus pesticides in dilute aqueous solutions. , 2004, Water research.

[29]  S. Goldstein,et al.  Formation of Peroxynitrate from the Reaction of Peroxynitrite with CO2: Evidence for Carbonate Radical Production , 1998 .

[30]  P. Neta,et al.  PULSE RADIOLYSIS STUDIES. XIII. RATE CONSTANTS FOR THE REACTION OF HYDROXYL RADICALS WITH AROMATIC COMPOUNDS IN AQUEOUS SOLUTIONS. , 1968 .

[31]  S. Canonica,et al.  Photosensitizer method to determine rate constants for the reaction of carbonate radical with organic compounds. , 2005, Environmental science & technology.

[32]  Karl G. Linden,et al.  Standardization of Methods for Fluence (UV Dose) Determination in Bench-Scale UV Experiments , 2003 .

[33]  K. Linden,et al.  Phototransformation of selected organophosphorus pesticides: roles of hydroxyl and carbonate radicals. , 2010, Water research.

[34]  Joel J Ducoste,et al.  Modeling the UV/hydrogen peroxide advanced oxidation process using computational fluid dynamics. , 2010, Water research.

[35]  M. Belosevic,et al.  Photodegradation of emerging micropollutants using the medium-pressure UV/H2O2 Advanced Oxidation Process. , 2013, Water research.

[36]  Karl G Linden,et al.  Degradation of endocrine disrupting chemicals bisphenol A, ethinyl estradiol, and estradiol during UV photolysis and advanced oxidation processes. , 2004, Environmental science & technology.

[37]  J. D. Laat,et al.  Transformation of carbendazim induced by the H2O2/UV system in the presence of hydrogenocarbonate ions : involvement of the carbonate radical , 2002 .

[38]  S. Goldstein,et al.  Mechanism of nitrite formation by nitrate photolysis in aqueous solutions: the role of peroxynitrite, nitrogen dioxide, and hydroxyl radical. , 2007, Journal of the American Chemical Society.

[39]  R. Huie,et al.  Temperature dependence of the rate constants for reactions of the sulfate radical, SO4-, with anions , 1990 .

[40]  Benjamin D. Stanford,et al.  Pharmaceuticals and endocrine disrupting compounds in U.S. drinking water. , 2009, Environmental science & technology.

[41]  Juner Chen,et al.  The Photochemical Decomposition of Hydrogen Peroxide in Aqueous Solutions of Allyl Alcohol at 2537 Å.1 , 1959 .

[42]  S. Mabury,et al.  A new method for measuring carbonate radical reactivity toward pesticides , 2000 .

[43]  J. Baxendale,et al.  The photolysis of hydrogen peroxide at high light intensities , 1957 .

[44]  S. Canonica.  Oxidation of aquatic organic contaminants induced by excited triplet states , 2007 .

[45]  K. Linden,et al.  The role of effluent nitrate in trace organic chemical oxidation during UV disinfection. , 2012, Water research.

[46]  K. Linden,et al.  Impact of hydrogen peroxide on nitrite formation during UV disinfection. , 2003, Water research.

[47]  W. Glaze,et al.  Advanced Oxidation Processes. A Kinetic Model for the Oxidation of 1,2-Dibromo-3-chloropropane in Water by the Combination of Hydrogen Peroxide and UV Radiation , 1995 .

[48]  J. Kruithof,et al.  UV/H2O2 treatment: an essential process in a multi barrier approach against trace chemical contaminants , 2012 .

[49]  K. Linden,et al.  Nitrate photosensitized degradation of atrazine during UV water treatment , 2003, Aquatic Sciences.

[50]  J. de Laat,et al.  Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution. , 2008, Chemosphere.

[51]  D. Meyerstein,et al.  Absorption spectra of NO–3 in solution , 1961 .

[52]  W. Arnold,et al.  Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct. , 2005, Environmental science & technology.

[53]  B. Bielski,et al.  Kinetics of the interaction of HO/sub 2/ and O/sub 2//sup -/ radicals with hydrogen peroxide. The Haber--Weiss reaction. [Gamma radiation] , 1979 .

[54]  A. Ross,et al.  Reactivity of HO2/O−2 Radicals in Aqueous Solution , 1985 .