Elisabeth Salhi

OZONATION OF REVERSE OSMOSIS CONCENTRATE: KINETICS AND EFFICIENCY OF BETA BLOCKER OXIDATION

Reverse osmosis (RO) concentrate samples were obtained from a RO-membrane system that uses effluents of wastewater treatment plants (WWTP) as feed water for the production of drinking water. A number of different pharmaceuticals (e.g. antibiotics, contrast media, beta blockers) were found in the WWTP effluent as well as in the RO-concentrate. Overall, a concentration factor (feed:concentrate) of approximately 3-4 was measured. Beta blockers (acebutolol, atenolol, bisoprolol, celiprolol, metoprolol, propranolol, timolol) were found in the range of low ng/L to low microg/L. Because metoprolol and propranolol are classified as potentially toxic to aquatic organisms and all beta blocker molecules have moieties, which are reactive towards ozone (amine groups, activated aromatic rings), it was tested whether ozonation can be applied for their mitigation. Rate constants for the reaction of acebutolol, atenolol, metoprolol and propranolol with ozone and OH radicals were determined. At pH 7 acebutolol, atenolol and metoprolol react with ozone with an apparent second-order rate constant k(O)(3) of about 2,000 M(-1)s(-1), whereas propranolol reacts with approximately 10(5)M(-1)s(-1). The rate constants for the reaction of the selected compounds with OH radicals were determined to be 0.5-1.0 x 10(10)M(-1)s(-1). Experiments with RO concentrate showed that an ozone dose of only 5mg/L resulted in a quantitative removal of propranolol in 0.8s and 10mg O(3)/L oxidized 70% of metoprolol in only 1.2s. Tests with chlorinated and non-chlorinated WWTP effluent showed an increase of ozone stability but a decrease of hydroxyl radical exposure in the samples after chlorination. This may shift the oxidation processes towards direct ozone reactions and favor the degradation of compounds with high k(O)(3).

Prediction of Micropollutant Elimination during Ozonation of Municipal Wastewater Effluents: Use of Kinetic and Water Specific Information

Ozonation is effective in improving the quality of municipal wastewater effluents by eliminating organic micropollutants. Nevertheless, ozone process design is still limited by (i) the large number of structurally diverse micropollutants and (ii) the varying quality of wastewater matrices (especially dissolved organic matter). These issues were addressed by grouping 16 micropollutants according to their ozone and hydroxyl radical ((•)OH) rate constants and normalizing the applied ozone dose to the dissolved organic carbon concentration (i.e., g O3/g DOC). Consistent elimination of micropollutants was observed in 10 secondary municipal wastewater effluents spiked with 16 micropollutants (∼2 μg/L) in the absence of ozone demand exerted by nitrite. The elimination of ozone-refractory micropollutants was well predicted by measuring the (•)OH exposure by the decrease of the probe compound p-chlorobenzoic acid. The average molar (•)OH yields (moles of (•)OH produced per mole of ozone consumed) were 21 ± 3% for g O3/g DOC = 1.0, and the average rate constant for the reaction of (•)OH with effluent organic matter was (2.1 ± 0.6) × 10(4) (mg C/L)(-1) s(-1). On the basis of these results, a DOC-normalized ozone dose, together with the rate constants for the reaction of the selected micropollutants with ozone and (•)OH, and the measurement of the (•)OH exposure are proposed as key parameters for the prediction of the elimination efficiency of micropollutants during ozonation of municipal wastewater effluents with varying water quality.

Kinetics and Mechanisms of N-Nitrosodimethylamine Formation upon Ozonation of N,N-Dimethylsulfamide-Containing Waters: Bromide Catalysis

N,N-Dimethylsulfamide (DMS), a newly identified, ubiquitous degradation product of the fungicide tolylfluanide, has been shown to be a N-nitrosodimethylamine (NDMA) precursor during ozonation. In this study, batch ozonation experiments in ultrapure buffered water, surface water, and tap water were performed to determine the kinetics and elucidate the mechanism of NDMA formation from DMS. It was found that at circumneutral pH, DMS reacts slowly with ozone (k approximately 20 M(-1) s(-1)) and moderately with hydroxyl radicals (k=1.5x10(9) M(-1)s(-1)). The reaction of DMS with these oxidants does not lead to NDMA. NDMA was only formed if bromide was present during ozonation of DMS-containing waters. Bromide is oxidized to hypobromous acid (HOBr) by ozone which then reacts with the primary amine of DMS to form a Br-DMS species. The rate limiting step of the formation of Br-DMS is the formation of HOBr. The reaction to form Br-DMS has an apparent second order rate constant at pH 8 of >3x10(4) M(-1)s(-1). The Br-DMS is transformed by ozone to NDMA and nitrate (k>or=5000 M(-1) s(-1)), with yields of 54% and 39%, respectively, based on the primary amine nitrogen of DMS. These reactions release bromide, making bromide a catalyst. NDMA is also formed during ozonation of DMS in the presence of hypochlorous acid (20-30% yield). The last step of NDMA formation is an intramolecular rearrangement with sulfur dioxide extrusion. On the basis of the mechanistic and kinetic information, it was possible to model NDMA formation in DMS-containing Lake Zurich water.

By-products formation during drinking water disinfection: a tool to assess disinfection efficiency?

In drinking water treatment, the inactivation of microorganisms increases with increasing disinfectant exposure (product of concentration and contact time, CT). Also, the formation of undesired (toxic) disinfection by-products increases with CT. The present study proposes a new concept that uses this undesired side effect of chemical water disinfection for a fast and reliable test of treatment efficiency. In laboratory systems, bromate formation during ozonation and the formation of trihalomethanes during chlorination were used to calculate the disinfectant exposure, which is a measure for the achieved degree of disinfection.

Simultaneous determination of bromide, bromate and nitrite in low μg l-1 levels by ion chromatography without sample pretreatment

A new ipn chromatographic method has been developed for the simultaneous analysis of the major matrix anions (chloride, nitrate, phosphate, sulfate, etc.), lower concentrated bromide, oxyhalides (iodate, chlorite, bromate) and nitrite in fresh waters and sea water. The method is based on an anion exchange chromatographic separation followed by a sequential analysis through conductivity and subsequent postcolumn reaction with UV detection: Whereas the matrix anions are quantified by conductivity, the oxyhalides and nitrite are measured by the oxidation product I; which they generate from iodide in the postcolumn reaction. The detection limits as determined for bromide, bromate and nitrite are 3, 0.1 and 0.5 mu g l(-1), respectively

Chemical oxidation of dissolved organic matter by chlorine dioxide, chlorine, and ozone: effects on its optical and antioxidant properties.

In water treatment dissolved organic matter (DOM) is typically the major sink for chemical oxidants. The resulting changes in DOM, such as its optical properties have been measured to follow the oxidation processes. However, such measurements contain only limited information on the changes in the oxidation states of and the reactive moieties in the DOM. In this study, we used mediated electrochemical oxidation to quantify changes in the electron donating capacities (EDCs), and hence the redox states, of three different types of DOM during oxidation with chlorine dioxide (ClO2), chlorine (as HOCl/OCl(-)), and ozone (O3). Treatment with ClO2 and HOCl resulted in comparable and prominent decreases in EDCs, while the UV light absorbances of the DOM decreased only slightly. Conversely, ozonation resulted in only small decreases of the EDCs but pronounced absorbance losses of the DOM. These results suggest that ClO2 and HOCl primarily reacted as oxidants by accepting electrons from electron-rich phenolic and hydroquinone moieties in the DOM, while O3 reacted via electrophilic addition to aromatic moieties, followed by ring cleavage. This study highlights the potential of combined EDC-UV measurements to monitor chemical oxidation of DOM, to assess the nature of the reactive moieties and to study the underlying reaction pathways.

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts – Electrophilic aromatic substitution and oxidation

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS).

Iodate and Iodo-Trihalomethane Formation during Chlorination of Iodide-Containing Waters: Role of Bromide

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 μg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 μg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.

Combination of Ozone with Activated Carbon as an Alternative to Conventional Advanced Oxidation Processes

The objective of this study was to compare the efficiency of O3/granular activated carbon (GAC) to enhance ozone transformation into ·OH radicals, with the common advanced oxidation processes (O3/OH−, O3/H2O2). The results obtained with model systems under the given experimental conditions showed that the system O3/OH− (pH 9) and O3/H2O2 (pH 7, [H2O2] = 1·10−5 M) are more efficient than O3/GAC (pH 7, [GAC] = 0.5 g/L) to enhance ozone transformation into ·OH radicals. However, in Lake Zurich water the O3/GAC process has a similar efficiency as O3/H2O2 for ozone transformation into ·OH radicals. The results also show that the presence of GAC during Lake Zurich water ozonation leads to (i) removal of hydrophilic and hydrophobic micropollutants, (ii) reduction of the concentration of CO3 2−/HCO3 −, and (iii) decrease of the concentration of dissolved organic carbon (DOC) present in the system.

Novel test procedure to evaluate the treatability of wastewater with ozone

Organic micropollutants such as pharmaceuticals, estrogens or pesticides enter the environment continuously through the effluent of municipal wastewater treatment plants (WWTPs). Enhanced treatment of wastewater (WW) by ozone (O3) is probably one of the simplest measures for abatement of organic micropollutants to avoid their discharge to the aquatic environment. During ozonation most organic micropollutants present in treated WW are oxidized either by a direct reaction with O3 or by secondarily formed hydroxyl radicals (OH). However, undesired oxidation by-products from the oxidative transformation of matrix components can also be formed. A modular laboratory decision tool based on the findings of previous investigations is presented to test the feasibility of ozonation as an option to upgrade specific WWTPs. These modules consist of investigations to assess (i) the matrix effects on ozone stability, (ii) the efficiency of micropollutant removal, (iii) the oxidation by-product formation, as well as (iv) bioassays to measure specific and unspecific toxicity of the treated WWs. Matrix effects on ozone stability (quantified as O3 and OH exposures) can give first indications on the suitability of an ozonation step. Ozonation of WWs yielding O3 and OH exposures and micropollutant abatement similar to reference values evoked a significant improvement of the water quality as indicated by a broad range of bioassays. Irregular behavior of the ozonation points towards unknown compounds, possibly leading to the formation of undesired degradation products. It has been observed that in such WWs ozonation partly enhanced toxicity. In summary, the presented tiered laboratory test procedure represents a relatively cheap and straight-forward methodology to evaluate the feasibility of ozonation to upgrade specific WWTPs for micropollutant removal based on chemical and biological measurements.