Ozonation of chlortetracycline in the aqueous phase: Degradation intermediates and pathway confirmed by NMR.

Chlortetracycline (CTC) degradation mechanism in aqueous phase ozonation was evaluated for degradation mechanism and its correlation with the biodegradability and mineralization. CTC was removed within 8 and 4 min of ozonation at pH 2.2 and 7.0, respectively. At pH 2.2, HPLC-triple quadrupole mass spectrometry (MS) detected 30 products. The structures for some of these products were proposed on the basis of ozonation chemistry, CTC structure and MS data; these structures were then confirmed by nuclear magnetic resonance (NMR) spectra. Double bond cleavages, dimethyl amino group oxidation, opening and removal of the aromatic ring and dechlorination, mostly direct ozonation reactions, gave products with molecular weights (m.w.) 494, 510, 524, 495 and 413, respectively. Subsequent degradations gave products with m.w. 449, 465, 463 and 415. These products were arranged into a degradation pathway. At pH 7.0, the rate of reaction was increased, though the detected products were similar. Direct ozonation at pH 2.2 increased the biodegradability by altering the structures of CTC and its products. Nevertheless, direct ozonation alone remained insufficient for the mineralization, which was efficient at pH 7.0 due to the production of free radicals.

Chlortetracycline degradation by photocatalytic ozonation in the aqueous phase: mineralization and the effects on biodegradability.

Chlortetracycline (CTC) is a hazardous material in aquatic environments. This study was focused on optimization of photocatalytic ozonation processes for removal of CTC from wastewater at pH 2.2 and 7.0. In this study, the tested processes for CTC removal were arranged from the least efficient to the most efficient as: UV, UV/TiO2, O3, O3/UV and O3/UV/TiO2. Ozonation efficiency was due to ozone affinity for electron-rich sites on the CTC molecule. In the O3/UV and O3/UV/TiO2 processes, efficiency was increased by the photolysis of CTC and generation of *OH. At pH 7.0, all the processes were more efficient for CTC degradation than at pH 2.2 due to CTC speciation, ozone decay to *OH and the attractions between ionized CTC and TiO2 particles. UV/O3 at pH 7.0 showed an additive effect while other combination processes showed a synergistic effect that resulted in higher rates of reactions than the sums of individual reaction rates. The TOC removal ranged from 8% to 41% after one hour of reaction, with the above-mentioned order of efficiency. The biodegradability increased rapidly during the early minutes of the reaction. A reaction time of 10-15 min was sufficient for near maximum biodegradability, making these processes good pretreatments for the biological processes.

Optimizing the industrial wastewater pretreatment by activated carbon and coagulation: effects of hydrophobicity/hydrophilicity and molecular weights of dissolved organics.

This study addresses industrial wastewater treatment to remove dissolved organic compounds (DOC) using Fenton and coagulation processes, followed by granular activated carbon (GAC), and powdered activated carbon (PAC) as a pretreatment before reverse osmosis (RO). The effects of the hydrophobic / hydrophilic fractions and the molecular weights (MW) of the organics on DOC removal were tested and used to optimize the combination process. The raw wastewater (RWW) had a dominant hydrophobic fraction, as determined by polymeric resins Amberlite XAD-4. High performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) results showed that MW of organics were 256, 172, 258, 146, 392, 321, 182, 373, 276, 365, 409 and 453 in increasing order of hydrophobicity. GAC had higher adsorption capacity and was more selective for hydrophobic DOC removal than PAC. The removal efficiency of DOC by PAC and GAC was decreased after Fenton treatment, which decreased the hydrophobic fraction. Coagulation with ferric chloride efficiently removed the non-ionic hydrophilic and anionic hydrophilic organics. The coagulant doses selected as a pretreatment before GAC were 2.1 and 15.5 mg Fe(III)/mg DOC. The effluent total organic carbon (TOC) trends were correlated with the hydrophobic and hydrophilic fractions by using a rapid small-scale column test (RSSCT) for GAC breakthrough with a scale down factor of 5. GAC preferentially adsorbed the hydrophobic and the cationic hydrophilic organics. The effluent TOC trend could be divided into four stages: maximum adsorption, hydrophobic stage, exhaustion, and biological. The TOC removal after the exhaustion stage was almost equal to the hydrophilic fraction of TOC. Therefore these results demonstrated that the combination of coagulation and GAC adsorption was a highly efficient process for reducing DOC.

Tetracycline degradation by ozonation in the aqueous phase: proposed degradation intermediates and pathway.

During the ozonation of tetracycline (TC) in aqueous media at pHs 2.2 and 7.0, the effects of pH variations, protonation and dissociation of functional groups and variation in free radical exposure were investigated to elucidate the transformation pathway. Liquid chromatography-triple quadrupole mass spectrometry detected around 15 ozonation products, and uncovered their production and subsequent degradation patterns. During ozonation at pH 2.2, the TC degradation pathway was proposed on the basis of the structure, ozonation chemistry and mass spectrometry data of TC. Ozonation of TC at the C11a-C12 and C2-C3 double bonds, aromatic ring and amino group generated products of m/z 461, 477, 509 and 416, respectively. Further ozonation at the above mentioned sites gave products of m/z 432, 480, 448, 525 and 496. The removal of TOC reached a maximum of approximately 40% after 2 h of ozonation, while TC was completely removed within 4-6 min at both pHs. The low TOC removal efficiency might be due to the generation of recalcitrant products and the low ozone supply for high TC concentration. Ozonation decreased the acute toxicity of TC faster at pH 7.0 than pH 2.2, but the maximum decrease was only about 40% at both pHs after 2 h of ozonation. In this study, attempts were made to understand the correlation between the transformation products, pathway, acute toxicity and quantity of residual organics in solution. Overall, ozonation was found to be a promising process for removing TC and the products initially generated.