Effects of protein concentration on the extent of gamma-ray-mediated oxidative labeling studied by electrospray mass spectrometry

Exposure of aqueous protein solutions to gamma-rays results in the formation of *OH radicals that readily react with solvent-exposed amino acid side chains. The incorporation of oxygen leads to peak progressions with a spacing of 16 Da in the mass distribution of the polypeptide chain. Unlike some other oxidative labeling strategies, these radiolysis experiments do not require solution additives that could interfere with the analysis or that might cause secondary oxidation processes. Using myoglobin as a model system, we demonstrate that the level of oxidative labeling depends critically on the protein concentration. If ignored, this effect may lead to ambiguities in the interpretation of experiments employing *OH labeling for monitoring solvent-accessible surface areas, protein folding, and protein-protein interactions. We present a simple analysis that allows oxidation to be interpreted as a process with exponential kinetics, characterized by an apparent rate constant of the form kapp=kRAD/([P]tot+B), where kRAD is the primary rate of hydroxyl radical production, B is a constant, and [P]tot is the total protein concentration. While oxidative labeling may trigger some changes in protein conformation, it is found that the magnitude of this effect is surprisingly small, a result that is consistent with observations previously made by others.     

Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III) two-stage oxidation process

A two-stage oxidation (UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III)) process was applied to mineralize bisphenol A (BPA) at pH(i) (initial pH) 7. We take advantage of the high oxidation potential of sulfate radicals and use persulfate as the 1st-stage oxidant to oxidize BPA to less complex compounds (stoichiometric ratio: [S(2)O(8)(2-)](0)/[BPA](0)=1). Afterwards, the traditional photo-Fenton process was used to mineralize those compounds to CO(2). To the best of our knowledge, this is the first attempt to utilize the two processes in conjunction for the complete degradation of BPA. During the 2nd-stage reaction, other oxidants (H(2)O(2) and Iron alone) were also employed to observe the extent of enhancement of photo-Fenton. Further, qualitative identification of both hydroxyl and sulfate radicals was performed to evaluate their dominance under different conditions. The BPA degradation in this UV/persulfate process formulated a pseudo-first-order kinetic model well, with a rate constant of approximately 0.038 min(-1) (25 degrees C), 0.057 min(-1) (35 degrees C), and 0.087 min(-1) (50 degrees C), respectively. The much lower activation energy (DeltaE = 26 kJ mol(-1)) was further calculated to clarify that the thermal-effect of an illuminated system differs from single heat-assisted systems described in other research. Final total organic carbon (TOC) removal levels of BPA by the use of such two-stage oxidation processes were 25-34%, 25%, and 87-91% for additional Fe(II,III) activation, H(2)O(2) promotion, and Fe(II,III)/H(2)O(2) promotions, respectively.     

Photochemical degradation of diethyl phthalate with UV/H2O2

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.     

Oxidative degradation of dimethyl phthalate (DMP) by UV/H(2)O(2) process

The photochemical degradation of dimethyl phthalate (DMP) in UV/H(2)O(2) advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H(2)O(2) alone. In contrast, the combined UV/H(2)O(2) process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H(2)O(2) concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H(2)O(2) advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10(9) M(-1)s(-1) through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H(2)O(2) advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal.     

Ozonation of Cationic Red X-GRL in aqueous solution: kinetics and modeling

Ozonation of Cationic Red X-GRL was investigated in a semi-batch column reactor under various operating conditions such as gas flow rate Q(G), temperature T, initial concentration C(D,0), and pH. The relative contributions of ozone direct oxidation and OH-facilitated indirect oxidation of the dyestuff were quantified, and the overall rate constant k(T) and the kinetic regime of the reaction were determined by interpreting the experimental data with a newly derived kinetic model. The Hatta number of the reaction was found between 0.053 and 0.080, indicating that the reaction occurred in the liquid bulk, i.e. the slow kinetic regime. The ratio γ of indirect oxidation rate constant k(R) to k(T) decreased from 11.50% at pH 9.24 to 2.47% at pH 3.15. A mechanistically sounder model was derived to describe the reaction kinetics, which takes into account mechanisms of ozone decomposition and dyestuff degradation, and gas-liquid mass transfer. Good agreements were obtained between the experimental and calculated concentrations of Cationic Red X-GRL C(D), dissolved ozone C(A), ozone in off gas C(A,G), and nitrate. Furthermore, a model-based sensitivity analysis of C(D)/C(D,0), C(A), and C(A,G) was performed with respect to various model parameters.     

Photo-degradation of chlorophenols in the aqueous solution

The review presents the chlorophenols photo-degradation kinetics and mechanism in the aquatic environment under UV-vis in the presence of hydroxyl radicals and singlet oxygen. The influence of experimental parameters e.g. pH, dissociation degree, presence of oxidants in solution, number and position of Cl atoms on the quantum yield and reaction rate constant of chlorophenols are discussed. Mechanisms of photolysis, reaction with hydroxyl radicals, singlet oxygen and secondary reactions for mono-, di-, tri-, tetra- and pentachlorophenol are proposed. The pathways for intermediate reactions e.g. dechlorination, oxidation, dimerization for chlorophenols are also presented.     

Ammonia removal in electrochemical oxidation: mechanism and pseudo-kinetics

This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO(2)/Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl(-). The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L(-1)h(-1) and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl(-). About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N(2) in the produced gas. The rate at which Cl(-) lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl(-) concentration affected the constant of the pseudo zero-order kinetics, expressed by k=0.0024[Cl(-)]xj. The ammonia was reduced to less than 0.5 mg N L(-1) after 2h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements.     

Degradation of picloram by the electro-Fenton process

The degradation of the picloram, a widely used herbicide, has been undertaken by the electrochemical advanced oxidation process, namely electro-Fenton in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Degradation kinetics of picloram was investigated. Kinetic results evidence a pseudo first-order degradation, with a rate constant of reaction between picloram and hydroxyl radicals of (2.73+/-0.08) x 10(9) M(-1) s(-1). The effect of applied current and catalyst concentration on the degradation and mineralization of picloram was also investigated. The optimum applied current and catalyst concentration values for the degradation of picloram was determined as 300 mA and 0.2 mM Fe(3+), respectively. Mineralization of picloram was followed by the total organic carbon (TOC) analysis. At the end of 8h of electrolysis, 95% of the initial TOC was removed. Several degradation products were identified by using HPLC, LC-MS, GC-MS, and IC analysis. The identified by-products allowed to propose a mineralization pathway for the picloram degradation.     

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.     

Degradation of carbofuran by using ozone, UV radiation and advanced oxidation processes.

The degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate), a frequently used carbamate derivative pesticide that is considered a priority pollutant, is carried out in batch reactors by means of single oxidants: ozone, UV radiation and Fenton's reagent; and by the advanced oxidation processes (AOPs) constituted by combinations of ozone plus UV radiation, UV radiation plus H(2)O(2), and UV radiation plus Fenton's reagent (photo-Fenton system). For all these reactions, the apparent pseudo-first-order rate constants are evaluated in order to compare the efficiency of each process. In addition and by means of a competition kinetic model, the rate constants for the reaction of carbofuran with ozone and with hydroxyl radicals are also determined. The improvement in the decomposition levels of carbofuran reached by the combined processes in relation to the single oxidants, due to the generation of the very reactive hydroxyl radicals, is also established in every process. For the oxidant concentrations applied, the most effective process in removing carbofuran was the photo-Fenton system.     

Verification of competitive kinetics technique and oxidation kinetics of 2,6-dimethyl-aniline and o-toluidine by Fenton process

The competitive kinetics technique is shown to be a useful and reliable tool for determining rate constants. Regardless of the conditions of the reaction and the operation mode, the intrinsic second-order rate constants of 2,6-dimethyl-aniline and hydroxyl radicals were 1.65 × 10(10), 1.60 × 10(10), and 1.71 × 10(10)M(-1)s(-1) in the absence of SiO(2) under complete-mix conditions, in the presence of SiO(2) under complete-mix conditions, and in a fluidized-bed Fenton reactor with SiO(2) as the media, respectively, demonstrating that the rates are comparable under a variety of reaction conditions. The average intrinsic second-order rate constant of o-toluidine and hydroxyl radicals obtained in a homogeneous system under various conditions was 7.36 × 10(9)M(-1)s(-1), indicating that o-toluidine is less susceptible to hydroxyl radicals than 2,6-dimethyl-anilne. Hydroxyl radicals primarily attacked the amine group rather than the methyl group of the o-toluidine to form o-cresol and 2-nitrotoluene, which sequentially transformed to carboxylic acids including acetic, oxalic, lactic, and maleic acids after the collapse of the benzene ring.     

Nanosecond laser-induced photochemical oxidation method for protein surface mapping with mass spectrometry

We have developed an ultrafast pulse method for protein surface footprinting by laser-induced protein surface oxidations. This method makes use of a pulse UV laser that produces, in nanoseconds, a high concentration of hydroxyl (OH) free radicals by photodissociation of a hydrogen peroxide (H2O2) solution. The OH radicals oxidize amino acid residues located on the protein surface to produce stable covalent modifications. The oxidized protein is then analyzed by mass spectrometry to map the oxidized amino acid residues. Ubiquitin and apomyoglobin were used as model proteins in this study. Our results show that a single laser pulse can produce extensive protein surface oxidations. We found that monooxidized ubiquitins were more susceptible to further oxidations by subsequent laser irradiation, as compared to nonoxidized ones. This is due to the conformational changes of proteins by oxidation that increases the solvent-accessible surface area. Therefore, it is crucial to perform this experiment with a single pulse of laser so as to avoid oxidation of proteins after conformation of the protein changes. Subsequently, to obtain a high frequency and coverage of the oxidation sites while keeping the number of laser shots to one, we further optimized the laser power and concentration of hydrogen peroxide as well as the concentration of protein. This ultrafast OH radical generation method allows for rapid and accurate detection of surface residues, enabling mapping of the solvent-accessible regions of a protein in its native state.     

Electrochemically mediated reduction of horseradish peroxidase by 1,1'-ferrocenedimethanol in organic solvents

Cyclic voltammetry is an efficient means of analyzing the catalytic reduction of H2O2 at immobilized horseradish peroxidase (HRP)-Eastman AQ 55 electrodes in the presence of 1,1'-ferrocenedimethanol as a one-electron reversible cosubstrate. This system was employed to study the kinetics of the reduction of compound II of HRP in a number of organic solvents. An electrocatalytic response was detected in methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, 2-butanone, 1,2-propanediol, acetonitrile, ethyl acetate, and ethylene glycol. Unusual bell-shaped variations of the peak or plateau catalytic current with the substrate concentration were observed in all solvents tested. The results obtained in methanol, acetonitrile, and 1-propanol were analyzed using the model developed by Saveant (Limoges, B.; Saveant, J.-M.; Yazidi, D. J. Am. Chem. Soc. 2003, 125, 9192-9203). The values of k3Gamma0 and K3,M, where k3 = k3,1k3,2/(k3,-1 + k3,2), Gamma0 is the surface concentration of active enzyme, and K3,M = (k3,-1 + k3,2)/k3,1, were determined. The values of k3Gamma0 for the mediated reduction of compound II of HRP in methanol, 1-propanol, and acetonitrile (in the presence of 5% aqueous buffer) were not affected by the solvent dielectric constant but decreased with solvent hydrophobicity. The value of K3,M obtained in methanol was similar to that obtained for [Os(bpy)2pyCl]2+ in aqueous buffer.     

Time-resolved fluorescence monitoring of aromatic radicals in photoinitiated processes

Photolytic initiation of free radical reactions is important to many areas of technology; time-resolved monitoring of submicromolar concentrations of radicals produced during the course of these reactions is needed to provide information about the rate of initiation and its competition with radical recombination. In this work, time-resolved laser-induced fluorescence is evaluated for monitoring of diphenylketyl radicals produced by photoreduction of the triplet state of benzophenone. Fluorescence from the doublet-doublet transition of the radical is excited with a continuous wave laser and provides a sensitive method to detect these intermediates at nanomolar concentrations and to study their kinetics in solution on time scales from a few microseconds to hundreds of milliseconds. The ketyl radical fluorescence measurements of radical initiation reactions allowed the H atom abstraction rate constant by triplet benzophenone from both 2-propanol and benzhydrol to be determined, where k(H) = (2.1 ± 0.1) × 10(6) M(-)(1) s(-)(1) for 2-propanol and k(H) = (4.4 ± 0.1) × 10(6) M(-)(1) s(-)(1) for benzhydrol. The diphenylketyl radical recombination rate constant was also determined by time-resolved fluorescence monitoring of the decay of the radical population and found to be k(r) = (1.9 ± 0.2) × 10(8) M(-)(1) s(-)(1). Formation kinetics could be measured on a microsecond time scale from radical populations as low as 45 nM; decay kinetics could be followed on a millisecond time scale from 20 nM radical concentrations.     

Kinetic analysis and energy efficiency of phenol degradation in a plasma-photocatalysis system

Combination of two kinds of advanced oxidation processes (AOPs) is an effective approach to control wastewater pollution. In this research, a pulsed discharge plasma system with multi-point-to-plate electrode and an immobilized TiO(2) photocatalysis system is coupled to oxidize target pollutant in aqueous solution. Kinetic analysis (pseudo-first order kinetic constant, k) and energy efficiency (energy yield value at 50% phenol conversion, G(50)) of phenol oxidation in different reaction systems (plasma alone and plasma-photocatalysis) are reviewed to account for the synergistic mechanism of plasma and photocatalysis. The experimental results show that higher k and G(50) of phenol oxidation can be obtained in the plasma-photocatalysis system under the conditions of different gas bubbling varieties, initial solution pH and radical scavenger addition. Moreover, the investigation tested hydroxyl radical (OH) is the most important species for phenol removal in the synergistic system of plasma-photocatalysis as well as in the plasma alone system.     

Removal of C.I. Acid Orange 7 from aqueous solution by UV irradiation in the presence of ZnO nanopowder

The removal of C.I. Acid Orange 7 (AO7) from aqueous solution under UV irradiation in the presence of ZnO nanopowder has been studied. The average crystallite size of ZnO powder was determined from XRD pattern using the Scherrer equation in the range of 33 nm. The experiments showed that ZnO nanopowder and UV light had a negligible effect when they were used on their own. The effects of some operational parameters such as pH, the amount of ZnO nanopowder and initial dye concentration were also examined. The photodegradation of AO7 was enhanced by the addition of proper amount of hydrogen peroxide, but it was inhibited by ethanol. From the inhibitive effect of ethanol, it was deducted that hydroxyl radicals played a significant role in the photodegradation of the dye. The kinetic of the removal of AO7 can be explained in terms of the Langmuir-Hinshelwood model. The values of the adsorption equilibrium constant, K(AO7), and the kinetic rate constant of surface reaction, k(c), were 0.354(mg l(-1))(-1) and 1.99 mg l(-1)min(-1), respectively. The electrical energy consumption per order of magnitude for photocatalytic degradation of AO7 was lower in the UV/ZnO/H(2)O(2) process than that in the UV/ZnO process. Accordingly, it could be stated that the complete removal of color, after selecting desired operational parameters could be achieved in a relatively short time, about 60 min.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

Standard electrochemical behavior of high-quality, boron-doped polycrystalline diamond thin-film electrodes

Standard electrochemical data for high-quality, boron-doped diamond thin-film electrodes are presented. Films from two different sources were compared (NRL and USU) and both were highly conductive, hydrogen-terminated, and polycrystalline. The films are acid washed and hydrogen plasma treated prior to use to remove nondiamond carbon impurity phases and to hydrogen terminate the surface. The boron-doping level of the NRL film was estimated to be in the mid 1019 B/cm3 range, and the boron-doping level of the USU films was approximately 5 x 10(20) B/cm(-3) based on boron nuclear reaction analysis. The electrochemical response was evaluated using Fe-(CN)6(3-/4-), Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, dopamine, ascorbic acid, Fe(3+/2+), and chlorpromazine. Comparisons are made between the apparent heterogeneous electron-transfer rate constants, k0(app), observed at these high-quality diamond films and the rate constants reported in the literature for freshly activated glassy carbon. Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, and chlorpromazine all involve electron transfer that is insensitive to the diamond surface microstructure and chemistry with k0(app) in the 10(-2)-10(-1) cm/s range. The rate constants are mainly influenced by the electronic properites of the films. Fe(CN)6(3-/4-) undergoes electron transfer that is extremely sensitive to the surface chemistry with k0(app) in the range of 10(-2)-10(-1) cm/s at the hydrogen-terminated surface. An oxygen surface termination severely inhibits the rate of electron transfer. Fe(3+/2+) undergoes slow electron transfer at the hydrogen-terminated surface with k0(app) near 10(-5) cm/s. The rate of electron transfer at sp2 carbon electrodes is known to be mediated by surface carbonyl functionalities; however, this inner-sphere, catalytic pathway is absent on diamond due to the hydrogen termination. Dopamine, like other catechol and catecholamines, undergoes sluggish electron transfer with k0(app) between 10(-4) and 10(-5) cm/s. Converting the surface to an oxygen termination has little effect on k0(app). The slow kinetics may be related to weak adsorption of these analytes on the diamond surface. Ascorbic acid oxidation is very sensitive to the surface termination with the most negative Ep(ox) observed at the hydrogen-terminated surface. An oxygen surface termination shifts Ep(ox) positive by some 250 mV or more. An interfacial energy diagram is proposed to explain the electron transfer whereby the midgap density of states results primarily from the boron doping level and the lattice hydrogen. The films were additionally characterized by scanning electron microscopy and micro-Raman imaging spectroscopy. The cyclic voltammetric and kinetic data presented can serve as a benchmark for research groups evaluating the electrochemical properties of semimetallic (i.e., conductive), hydrogen-terminated, polycrystalline diamond.     

Ozone direct oxidation kinetics of Cationic Red X-GRL in aqueous solution

This study characterizes the ozonation of the azo dye Cationic Red X-GRL in the presence of TBA (tert-butyl alcohol), a scavenger of hydroxyl radical, in a bubble column reactor. Effects of oxygen flow rate, temperature, initial dye concentration, and pH were investigated through a series of batch tests. Generally, enhancing oxygen flow rate enhanced the removal of dye. However, there was a minimum removal of dye at temperature 298 K. Increasing or decreasing temperature enhanced the degradation of dye. Increasing the initial dye concentration decreased the removal of dye while the ozonation rate increased. The rate constants and the kinetic regime of the reaction between ozone and dye were obtained by fitting the experimental data to a kinetics model based on a second order overall reaction, first order with respect to both ozone and dye. The Hatta numbers of the reactions were between 0.039 and 0.083, which indicated that the reaction occurred in the liquid bulk. The direct oxidation rate constant k(D) was correlated with temperature by a modified Arrhenius Equation with an activation energy E(a) of 15.538 kJ mol(-1).     

Modeling of nonylphenol degradation by photo-nanocatalytic process via multivariate approach

Modeling of photocatalytic degradation of nonylphenol (NP), an endocrine disrupter and toxic compound, has been investigated in synthetic aqueous solutions containing ZnO nanoparticles as semiconductor using multivariate approach. In this regard, a full factorial experimental design was performed in order to study the main variables affecting the degradation process as well as their most significant interactions. Initial NP concentrations ([NP](0)) of 0.454-9.08 μM, were treated with UV-vis/ZnO using different pH and nanocatalyst loading rates. Effect of experimental parameters on the NP degradation rate constant was established by the response surface plots. The degradation rate constant decreased with an increase in the initial concentration of NP, while it increased with ZnO loading until a concentration of 0.5 g L(-1). The rate constant increases with increase in pH up to 10, after which a significant decrease is observed. The results showed that most influential factors on NP degradation constant are the [NP](0), pH of reaction media, and ZnO loading rate, and the most significant interaction is [NP]-pH. Finally, two mathematical models have been proposed to estimate NP degradation rate constant (k) on the basis of the significant variables and interactions. Predicted results of models showed good agreement with the experimental data (R(2) = 0.83 and 0.93).