Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Mild hydrolysis of 2-trifluoromethylphenol: kinetics, mechanism and environmental relevance

2-Trifluoromethylphenol was hydrolysed in a phosphate buffer at neutral pH. At mild temperatures ranging from 34 degrees C to 69 degrees C this compound liberates consecutively fluorine anions to form salicylic acid. This process is energetically driven by the hydration of the fluorine anions. No intermediates have been detected by HPLC and (19)F-NMR and this was confirmed by computer calculations which favor the first step in the whole reaction sequence being rate-limiting. Accordingly, the reaction energy of the first dehalogenation of the trifluoromethyl anion is 28.4 kcal mol(-1) higher than for the second dehalogenation. The pseudo-first-order kinetic was determined and from an Arrhenius diagram an activation energy of E(a)=25.1 kcal mol(-1) has been estimated. At 37 degrees C and a pH of 7.4 the half-life was 6.9 h. The rate of hydrolysis was favored at higher pH and it was not influenced by oxygen, sunlight or trace elements found in natural water. The latter was shown by incubations with lake water instead of distilled water.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment

Natural zeolite and synthetic zeolite, MCM-22, were employed as effective adsorbents for a basic dye, methylene blue, removal from wastewater. Two methods, Fenton oxidation and high temperature combustion, have been used for regeneration of used materials. It is found that MCM-22 exhibits equilibrium adsorption at 1.7 x 10(-4) mol g(-1), much higher than the adsorption of natural zeolite (5 x 10(-5) mol g(-1)) at initial dye concentration of 2.7 x 10(-5)M and 30 degrees C. Solution pH will affect the adsorption behaviour of MCM-22. Higher solution pH results in higher adsorption capacity. The regenerated adsorbents show different capacity depending on regeneration technique. Physical regeneration by high temperature combustion will be better than chemical regeneration using Fenton oxidation in producing effective adsorbents. Regeneration of MCM-22 by high temperature treatment can make the adsorbent exhibit comparable or superior adsorption capacity as compared to the fresh sample depending on the temperature and time. The optimal temperature and time will be 540 degrees C and 1h. The Fenton oxidation will recover 60% adsorption capacity. For natural zeolite, regeneration can not fully recover the adsorption capacity with the two techniques and the regenerated natural zeolites by the two techniques are similar, showing 60% adsorption capacity of fresh sample. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetics.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Effect of anions and cations on cadmium sorption kinetics from aqueous solutions by chitin: experimental studies and modeling

The effect of ions, including Na(+), Mg(2+), Ca(2+), Cl(-), SO(4)(2-) and CO(3)(2-), at various initial concentrations, on the kinetics of cadmium sorption by chitin was studied at 25 degrees C and free initial pH solution in batch conditions. The presence of these ions in solution was found to inhibit the uptake of cadmium by chitin to different degrees: sodium and chloride ions have no significant effect. For Mg(2+), Ca(2+), SO(4)(2-) and CO(3)(2-) ions, the effects ranged from a large inhibition of cadmium by Ca(2+) and CO(3)(2-) to a weak inhibition by Mg(2+) and SO(4)(2-). These results indicate that the uptake sites of these ions are the same. No ion was found to enhance cadmium uptake. The results also showed that the kinetics of sorption are best described by a pseudo second-order expression than a first or second-order model.     

Study of inclusion complex of beta-cyclodextrin and nitrobenzene

beta-cyclodextrin can react with nitrobenzene to form an inclusion complex which is characterized by (1)H NMR and powder X-ray diffractometry. The ratio of beta-CD to NB in inclusion complex is determined as 1:1. At 25 degrees C, the dissociated constant, K(D), of the inclusion complex is measured as 6.5 x 10(-3) M in neutral solution (pH=7.0), but in alkali (pH=13.5), K(D) is 3.2 x 10(-2) M which is much larger than that measured in neutral.     

Kinetics of aqueous base and acid hydrolysis of aldicarb, aldicarb sulfoxide and aldicarb sulfone

The kinetics of degradation of aqueous solutions of aldicarb, aldicarb sulfoxide and aldicarb sul fone by base hydrolysis were investigated. Pseudo first order rate constants of 37 micrograms/l solutions were determined at different hydroxide concentrations by acid-base titration. Second order rate constants were calculated, and it was found that aldicarb sulfone is more sensitive to hydroxide ion concentration than aldicarb sulfoxide which is more sensitive than aldicarb. Temperature effects were determined by measuring the base hydrolysis rate constant for aldicarb sulfone at 5, 15, 20, 25, 30, and 35 degrees C. An activation energy of 15.2 +/- 0.1 kcal/mole was calculated. Addition of a neutral electrolyte decreased the rate constant for base hydrolysis. Acid catalyzed hydrolysis rate constants were also measured for aldicarb sulfone, and, as expected, the reaction was much slower. The second order (reaction) rate constant for base hydrolysis of aldicarb sulfone is 40.3 (+/- 0.5) liter mole-1min-1; for acid catalyzed hydrolysis it is 7.33 (+/- 0.06) X 10(-4) liter mole-1min-1.     

The potential inhalation hazard posed by dioxin contaminated soil.

Mathematical models and field data were used to estimate the airborne concentrations of 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD) vapor and particulates which could originate from soil containing 100 ppb TCDD. The model of Jury et al. (1983) and the box approach were used to predict the concentration of TCDD vapor from soil. The daily soil temperature was assumed to vary between 20 degrees C and 40 degrees C for six months of the year to account for diurnal warming and cooling of the soil. The depth of contamination was 50 mm. The model predicted average vapor flux rate for TCDD from soil for this temperature profile was 1.5 x 10(-14) mg/sec-cm2. The upper-bound estimates of the TCDD vapor concentration on-site at 40 degrees C and 20 degrees C were 2.5 pg/m3 and 1.8 pg/m3, respectively. Using a recently proposed unit risk value (URV) of 2.9 x 10(-6) (pg/m3)-1 [slope factor = 1.0 x 10(-14) (mg/kg-day)-1], the maximum plausible cancer risk is about 1 x 10(-5). If one accepts the EPA URV of 3.3 x 10(-5) (pg/m3)-1 (slope factor = 1.2 x 10(-13) (mg/kg-day)-1), then the risk is no greater than 1 x 10(4). A maximum TCDD vapor concentration of 0.21 pg/m3 was predicted 100 meters downwind (for summer days). The on-site concentration of TCDD in suspended particulate was estimated to be 1.4 pg/m3 (based on a TSP level of 0.07 mg/m3 from site soil). For persons exposed to vapors and particulates about 100 meters off-site, the exposure was about 10-fold less.(ABSTRACT TRUNCATED AT 250 WORDS)     

On the thermally induced isomerisation of hexabromocyclododecane stereoisomers

The interconversion of the stereoisomers contained in technical 1,2,5,6,9,10-hexabromocyclododecane, a major brominated flame retardant increasingly found in the environment and in biota, was investigated at elevated temperatures. The application of pure enantiomers of the three constituents alpha-, beta-, and gamma-HBCD enabled the unambiguous elucidation of the individual isomerisation reactions as well as the quantification of all respective rate constants. At 160 degrees C the rate constants range over two orders of magnitude from 1.50x10(-3) to 1.88x10(-5)mol(%)s(-1). A preliminary mechanistic explanation for the differences of the rate constants which govern the composition of HBCD diastereomers at equilibrium is given.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

Photo-oxidation of cork manufacturing wastewater

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).     

The adsorptive capacity of vapor-phase mercury chloride onto powdered activated carbon derived from waste tires

Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury-containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl2) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150 degrees C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer-Emmett-Teller (BET) surface area could adsorb more HgCl2 at room temperature. The equilibrium adsorptive capacity of HgCl2 for WPAC measured in this study was 1.49 x 10(-1) mg HgCl2/g PAC at 25 degrees C with an initial HgCI2 concentration of 25 microg/m3. With the increase of adsorption temperature < or = 150 degrees C, the equilibrium adsorptive capacity of HgCl2 for WPAC was decreased to 1.34 x 10(-1) mg HgCl2/g PAC. Furthermore, WPAC with higher sulfur contents could adsorb even more HgCl2 because of the reactions between sulfur and Hg2+ at 150 degrees C. It was demonstrated that the mechanisms for adsorbing HgCl2 onto WPAC were physical adsorption and chemisorption at 25 and 150 degrees C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) > 0.998 for HgCl2 adsorption at 25 and 150 degrees C. Moreover, the equilibrium adsorptive capacity of HgCl2 for virgin WPAC was similar to that for CPAC at 25 degrees C, whereas it was slightly higher for sulfurized WPAC than for CPAC at 150 degrees C.     

The marine macroalga Cystoseira baccata as biosorbent for cadmium(II) and lead(II) removal: kinetic and equilibrium studies

This work reports kinetic and equilibrium studies of cadmium(II) and lead(II) adsorption by the brown seaweed Cystoseira baccata. Kinetic experiments demonstrated rapid metal uptake. Kinetic data were satisfactorily described by a pseudo-second order chemical sorption process. Temperature change from 15 to 45 degrees C showed small variation on kinetic parameters. Langmuir-Freundlich equation was selected to describe the metal isotherms and the proton binding in acid-base titrations. The maximum metal uptake values were around 0.9 mmol g(-1) (101 and 186 mg g(-1) for cadmium(II) and lead(II), respectively) at pH 4.5 (raw biomass), while the number of weak acid groups were 2.2 mmol g(-1) and their proton binding constant, K(H), 10(3.67) (protonated biomass). FTIR analysis confirmed the participation of carboxyl groups in metal uptake. The metal sorption was found to increase with the solution pH reaching a plateau above pH 4. Calcium and sodium nitrate salts in solution were found to affect considerably the metal biosorption.     

Bromate formation on the non-porous TiO2 photoanode in the photoelectrocatalytic system

The increasing use of ozone in water disinfection processes has been the focus of considerable concern in regards to inorganic disinfection by product formation of bromate in waters containing bromide. Due to the public health risk caused by the presence of bromate as a suspected carcinogen, attention had been addressed to the conditions under which bromate is formed. In this study, photoanodic bromine generation and bromate (BrO(3)(-)) formation were investigated using a TiO(2) electrode in a photoelectrocatalytic (PEC) treatment process. The separation of anodic and cathodic reactions in the PEC system resulted in a pH decrease from 9.3 to 3.0 in the photoanode compartment and an increase to 11.0 in the cathode compartment. Under a photo-illumination intensity of 5.7 m W cm(-2) UV, a biasing potential of +1.0V vs SCE, a pH of 6.0 and at a NaBr concentration of 1.0 x 10(-2) M, active bromine formation increased over time with 2.4 x 10(-6) M min(-6) rate and reached a steady-state concentration of 1.44 x 10(-4) M in 60 min. Bromate formation was detected after a lag-period of 15 min and exhibited a continuous increasing trend with respect to irradiation time. No bromate formation was observed below pH 6.5 whereas an increasing bromate concentrations and pH up to pH=8.5 were noted.     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Solubility of nonylphenol and nonylphenol ethoxylates. On the possible role of micelles

The water solubility of nonylphenol (NP) has been estimated to be 4.9 +/- 0.4 mg/l corresponding to (2.22 +/- 0.18) x 10(-5) mol/l at 25 degrees C using shake flask and surface tension techniques. The low solubility in combination with an observed rather slow dissolution process will limit the leachability of NP in the terrestrial environment. Based on indirect evidence, it is suggested that NP, in contrast to nonylphenol ethoxylate (NPEO) with, e.g., 12 ethoxylate moieties, is not subject to micelle formation, and as such does not constitute a potential vehicle for the transport of hydrophobic pollutants in the environment. For NPEOs with a very high number of ethoxy moieties, e.g., 100, the compounds appear water soluble without micelle formation.