Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants

Ozonation of drinking water: part I. Oxidation kinetics and product formation.

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

This study investigates the oxidation of pharmaceuticals during conventional ozonation and advanced oxidation processes (AOPs) applied in drinking water treatment. In a first step, second-order rate constants for the reactions of selected pharmaceuticals with ozone (k(O3)) and OH radicals (k(OH)) were determined in bench-scale experiments (in brackets apparent k(O3) at pH 7 and T = 20 degrees C): bezafibrate (590 +/- 50 M(-1) s(-1)), carbamazepine (approximately 3 x 10(5) M(-1) s(-1)), diazepam (0.75 +/- 0.15 M(-1) s(-1)), diclofenac (approximately 1 x 10(6) M(-1) s(-1)), 17alpha-ethinylestradiol (approximately 3 x 10(6) M(-1) s(-1)), ibuprofen (9.6 +/- 1.0 M(-1) s(-1)), iopromide ( 5 x 10(4) M(-1) s(-1), indicating that these compounds are completely transformed during ozonation processes. Values for k(OH) ranged from 3.3 to 9.8 x 10(9) M(-1) s(-1). Compared to other important micropollutants such as MTBE and atrazine, the selected pharmaceuticals reacted about two to three times faster with OH radicals. In the second part of the study, oxidation kinetics of the selected pharmaceuticals were investigated in ozonation experiments performed in different natural waters. It could be shown that the second-order rate constants determined in pure aqueous solution could be applied to predict the behavior of pharmaceuticals dissolved in natural waters. Overall it can be concluded that ozonation and AOPs are promising processes for an efficient removal of pharmaceuticals in drinking waters.

Oxidation of pharmaceuticals during ozonation and advanced oxidation processes

This paper presents a review of catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. It is also an attempt to propose general ideas about mechanisms governing catalytic ozone reactions. Catalytic ozonation is a new means of contaminants removal from drinking water and wastewater. Its application is mainly limited to laboratory use. However, due to successful results further investigation is to be carried out. The majority of models proposed represent more of a speculative approach to the problem than a hypothesis based on experimental data. It is therefore useful to provide a summary of the accomplishments concerning catalytic ozonation and methods of enhancing molecular ozone reactions that were published so far. A survey of the application of several homo- and heterogeneous catalysts, their activity and the parameters influencing the efficiency of catalytic systems is presented here as a short overview, the aim of which is to raise awareness of possible new approaches to water purification.

Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment

Different dissolved natural organic materials photosensitize the transformation of a series of methyl and methoxy phenols at pH 8 with a very similar high selectivity (reactivity range 50). This selectivity falls in the range of that achieved using the aromatic ketones benzophenone (BP), 3'-methoxyacetophenone (3'-MAP), and 2-acetonaphthone (2-AN) as model photosensitizers. For both natural and model sensitizers, the photooxidation at pH 8 is not controlled by singlet oxygen. Deuterium isotope effects (k H /k D ) of different phenols are 0.7-1.3 for humic and fulvic acids and 1.1-1.7 for BP, suggesting an electron transfer mechanism. In contrast, the isotope effect for 2-AN of 4 indicates an H-atom abstraction reaction. The results show that reactive excited triplet states are important photooxidants in natural waters and should be considered for assessing the abiotic degradation of chemicals. The reactive triplet state concentration is estimated to be 10 -14 M in the top meter of Lake Greifensee under summer noon sunlight, and this leads to a half-life of 7 h for 2,4,6-trimethylphenol. Further still uncharacterized photooxidants derived from the dissolved organic material are also involved in the phototransformation of the phenols.

Transformation kinetics of phenols in water: photosensitization by dissolved natural organic material and aromatic ketones.

In an ozone-containing water a suspension of a few milligrams per liter of activated carbon (AQ or carbon black (CB) initiates a radical-type chain reaction that then proceeds in the aqueous phase and accelerates the transformation of O3 into secondary radicals, such as hydroxyl radicals (°OH). This results in an Advanced Oxidation Process (AOP) that is similar to an O3-based AOP involving application of H2O2 or UV-irradiation. We have studied these phenomena by observing the effect of suspensions of AC and CB on the rate of transformation of O3 in lakewater and in well-characterized solutions. In addition, the stoichiometric yield factor of the AC-catalyzed conversion of O3, into °OH has been shown to be comparable to that which is achieved by a slower process in the absence of AC. This comparison has been based on the measured depletion of an O3-resistant organic °OH probe that was added as a trace reference compound and that competed with a kinetic excess of solutes that controlled the lifetim...

Activated Carbon and Carbon Black Catalyzed Transformation of Aqueous Ozone into OH-Radicals

Textural and chemical factors affecting adsorption capacity of activated carbon in highly efficient desulfurization of diesel fuel

The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment.

Kinetics and Mechanism of the Degradation of Methyl Parathion in Aqueous Hydrogen Sulfide Solution: Investigation of Natural Organic Matter Effects

The reactions of five organophosphorus insecticides (OPs) (chlorpyrifos-methyl, parathion-methyl, fenchlorphos, chlorpyrifos, and parathion) with hydrogensulfide/ bisulfide (H2S/HS-) and polysulfides (S(n)2-) were examined in well-defined aqueous solutions over a pH range from 5 to 9. The rates are first-order in the concentration of the different reduced sulfur species. Experiments at 25 degrees C demonstrated that the reaction of the five OPs with the reduced sulfur species follows a SN2 mechanism. The activation parameters of the reaction of OPs with bisulfide were determined from the measured second-order rate constants over a temperature range of 5-60 degrees C. The determined second-order rate constants show that the reaction of an OP with polysulfides is from 15 to 50 times faster than the reaction of the same OP with bisulfide. The dominant transformation products are desalkyl OPs, which indicate that the nucleophilic substitution of reduced sulfur species occurs at the carbon atom of the alkoxy groups. And also the results show that these reduced sulfur species are much better nucleophiles, and thus degrade these pesticides faster than the well-studied base hydrolysis by OH-. When the determined second-order rate constants are multiplied with the concentration of HS- and S(n)2- reported in salt marshes and porewater of sediments, predicted half-lives show that abiotic degradation by sulfide species may be of comparable importance to microbially mediated degradation in anoxic environments.

Urs Jans

Papers

Transformation kinetics of phenols in water: photosensitization by dissolved natural organic material and aromatic ketones.

Activated Carbon and Carbon Black Catalyzed Transformation of Aqueous Ozone into OH-Radicals

Textural and chemical factors affecting adsorption capacity of activated carbon in highly efficient desulfurization of diesel fuel

Kinetics and Mechanism of the Degradation of Methyl Parathion in Aqueous Hydrogen Sulfide Solution: Investigation of Natural Organic Matter Effects

Nucleophilic Substitution of Phosphorothionate Ester Pesticides with Bisulfide (HS-) and Polysulfides (Sn2-)