Ozonation of Emergent Contaminants Renato Falcão Dantas

19 Abstract In this work, the ozonation of emergent contaminants represented by pharmaceuticals (Sulfamethoxazole and Bezafibrate) and surfactants (Quaternary Ammonium Compounds) was studied. Results in terms of target compound degradation and mineralization along with the biodegradability and toxicity assessment of formed intermediates are presented. Moreover, a previous study about the suitability of the combination ozonation-Sequencing Batch Biofilm Reactor (SBBR), using the model compound 4-chlorophenol, is shown. The first part of this work deals with the removal and mineralization of the compound 4-chlorophenol. The 4-CP is not included among the “new” or emerging contaminants. However this preliminary study allowed setting up our ozonation system as well as analytical methods. In addition, the coupling ozonation with SBBR constitute an innovative experimental procedure. The preliminary runs aimed to assess the mineralization of 100 and 200 mg L 4-chlorophenol (4-CP) solutions by ozonation and ozonation-biological treatment (SBBR). The experimental results showed that with an ozone flow rate of 5.44 and 7.57 g h, 4CP was completely removed from the solution in 15 and 30 minutes of ozonation, respectively. By the other hand, at the 4-CP abatement time, on average only 26 % of total organic carbon (TOC) removal was achieved. Quinone and hydroquinone were found as intermediates of reaction and a kinetic constant around 9·10 min was calculated for the ozone direct attack. The biodegradability (BOD5/COD) of the preozonated solutions increased from 0 until a range between 0.2-0.37. The combination of ozonation and aerobic biological treatment in an aerobic sequencing batch biofilm reactor (SBBR) gave an abatement of more than 90 % of the initial TOC. Moreover, the biofilter reactor showed fast recuperation after being submitted to absence of oxygen and feed. The Quaternary Ammonium Compounds (QACs) ozonation was carried out in order to assess the mineralization potential of ozonation processes for this class of compounds. To perform this study, the QACs 16-BAC (Benzyl-dimethylhexadecylammonium-chloride) and 18-BAC (Benzyl-dimethyl-stearylammonium-chloride) were treated by ozonation at different O3 dosage. The TOC (Total Organic Carbon) removal was monitored in order to follow the mineralization of the surfactants along the runs. According to experimental results, from an initial TOC concentration of 50 mg L, 90 minutes of ozonation reached at most 50% of mineralization at the used conditions (ozone flow rate 7.57 g h). Due to the experimental problems observed during the Renato F. Dantas Ozonation of Emergent Contaminants Abstract 20 ozonation of QACs, an alternative advanced oxidation process (photo-Fenton) was applied. In order to observe the mineralization of QACs by means of photo-Fenton, the runs were carried out with the same QAC concentration used in ozonation runs. Besides, two different lamps were used (UV and Xe). According to experimental results, after 90 minutes of treatment, the photo-Fenton process achieved up to 80% of mineralization when the UV lamp was used. The efficiency of the photo-Fenton with Xe lamp was lower. An overall view of the two used oxidation process allows to state that the photo-Fenton process seems to be the most suitable process to treat waters containing QACs. To carry out the study of the sulfamethoxazole (SMX) ozonation, 200 mg L SMX solutions were treated by ozonation at different pH. Results showed that ozonation was proved to be an efficient method to degrade sulfamethoxazole. After 15 minutes of ozonation (corresponding dose = 0.4 g of ozone L), the complete antibiotic abatement was almost achieved with just 10 % of mineralization. The biodegradability and toxicity of the ozonation intermediates were also studied. A biodegradability enhancement (increment of BOD5/COD ratio) from 0 to 0.28 was observed after 60 min of ozonation. The acute toxicity of the intermediates was followed by the Microtox test and the toxicity profile showed a slight acute toxicity increment in the first stage of ozonation. The pH variation had an important role in the TOC and COD removal, promoting their growth with the increment of alkalinity. The second order kinetic constants for the ozonation of the SMX in an order of magnitude of 10 L mol s were also determined for pH 5 and 7. Concerning the Bezafibrate (BZF) ozonation, the results showed that ozonation is an efficient method to degrade BZF: after 10 minutes of treatment (corresponding to a dose of 0.73 mmoles L of ozone), the complete BZF abatement is achieved, starting from an initial concentration of 0.5 mmoles L. However, only a small part of the substrate is mineralized. Two different experimental approaches (absolute and competition method) are adopted to estimate the second order kinetic constants for the ozone attack at pH=6.0, 7.0 and 8.0. A good agreement was observed between the two kinetic methods adopted. The identification of main intermediates, attempted by HPLCMS technique, indicates that the oxidation of BZF develops through both the hydroxylation of the aromatic ring and the attack of ozone on the unchlorinated aromatic one. The assessment of by-products biodegradability and acute toxicity demonstrates that ozonation is a suitable technique to improve the biodegradability and reduce the toxicity of waters containing BZF.20 ozonation of QACs, an alternative advanced oxidation process (photo-Fenton) was applied. In order to observe the mineralization of QACs by means of photo-Fenton, the runs were carried out with the same QAC concentration used in ozonation runs. Besides, two different lamps were used (UV and Xe). According to experimental results, after 90 minutes of treatment, the photo-Fenton process achieved up to 80% of mineralization when the UV lamp was used. The efficiency of the photo-Fenton with Xe lamp was lower. An overall view of the two used oxidation process allows to state that the photo-Fenton process seems to be the most suitable process to treat waters containing QACs. To carry out the study of the sulfamethoxazole (SMX) ozonation, 200 mg L SMX solutions were treated by ozonation at different pH. Results showed that ozonation was proved to be an efficient method to degrade sulfamethoxazole. After 15 minutes of ozonation (corresponding dose = 0.4 g of ozone L), the complete antibiotic abatement was almost achieved with just 10 % of mineralization. The biodegradability and toxicity of the ozonation intermediates were also studied. A biodegradability enhancement (increment of BOD5/COD ratio) from 0 to 0.28 was observed after 60 min of ozonation. The acute toxicity of the intermediates was followed by the Microtox test and the toxicity profile showed a slight acute toxicity increment in the first stage of ozonation. The pH variation had an important role in the TOC and COD removal, promoting their growth with the increment of alkalinity. The second order kinetic constants for the ozonation of the SMX in an order of magnitude of 10 L mol s were also determined for pH 5 and 7. Concerning the Bezafibrate (BZF) ozonation, the results showed that ozonation is an efficient method to degrade BZF: after 10 minutes of treatment (corresponding to a dose of 0.73 mmoles L of ozone), the complete BZF abatement is achieved, starting from an initial concentration of 0.5 mmoles L. However, only a small part of the substrate is mineralized. Two different experimental approaches (absolute and competition method) are adopted to estimate the second order kinetic constants for the ozone attack at pH=6.0, 7.0 and 8.0. A good agreement was observed between the two kinetic methods adopted. The identification of main intermediates, attempted by HPLCMS technique, indicates that the oxidation of BZF develops through both the hydroxylation of the aromatic ring and the attack of ozone on the unchlorinated aromatic one. The assessment of by-products biodegradability and acute toxicity demonstrates that ozonation is a suitable technique to improve the biodegradability and reduce the toxicity of waters containing BZF. Renato F. Dantas Ozonation of Emergent Contaminants Introduction 21