LEE- Çevre Bilimleri Mühendisliği ve Yönetimi-Doktora
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ÖgeDegradation of industrial micropollutants with sulfate radical–based advanced oxidation processes(Lisansüstü Eğitim Enstitüsü, 2021) Montazeri, Bahareh ; Arslan Alaton, İdil ; 693111 ; Çevre MühendisliğiOccurrence of micropollutants in wastewaters from the industries poses a serious threat to the environment and many of these contaminants are recalcitrant and/or toxic and/or biologically non-degradable. Therefore, the major concern is to treat the wastewater before being discharge into the environment. Among all these industrial micropollutants, in particular 3,5-dichlorophenol (3,5-DCP) from chlorophenols (CPs), 2,4-dichloroaniline (2,4-DCA) from chloroanilines (CAs) and iprodione (IPR) from hydantoins, have been drawn specific attention due to their commercial importance as raw materials, potential toxicity and refractory nature. 3,5-DCP is directly released to the aquatic environment through various waste streams such as wood pulp bleaching processes. 2,4-DCA is extensively used in manufacturing of pigments, optical brighteners and pharmaceutical agents. IPR as a fungicide is used to prevent gray mold on crops; however, its usage has been banned recently by the European Food Safety Authority. Considering the wide spread usage of the above-mentioned micropollutants and their incomplete removal in conventional industrial and urban wastewater treatment plants; they may end up in the aquatic environment, becoming threats to wildlife. Sulfate radicals (SO4●-)-based advanced oxidation processes (AOPs) have demonstrated that they have the potential to be efficiently applied in removing many organic pollutants from wastewater. In the first part of this study, three persulfate (PS)-mediated AOPs including one homogenous photochemical oxidation processes; ultraviolet-C (UV-C)-activated PS oxidation process (UV-C/PS), and two heterogeneous catalytic oxidation processes; zero-valent iron-activated persulfate oxidation process (ZVI/PS) and zero-valent aluminum-activated persulfate oxidation process (ZVA/PS) were employed in order to investigate the three micropollutants removal in distilled water (DW) and examine the influence of initial PS concentration (0.00 mM-1.00 mM) and pH on the treatment performances. UV-C/PS treatment of 3,5-DCP for all studied PS concentrations resulted in complete 3,5-DCP removal and the 3,5-DCP degradation rate increased by increasing the initial PS concentration which can be explained by an increase in the steady-state concentration of SO4●- generation in reaction solution. Increasing the initial pH to values more than 7.5, resulted in rapid 3,5-DCP degradation. Maximum 3,5-DCP removal efficiency was as 59% by 120 min ZVI/PS (PS=1.00 mM; pH=5.0); however, complete 3,5-DCP removal was obtained by decreasing pH to more acidic value after 20 min ZVI/PS (PS=0.50 mM; pH=3.0) treatment. ZVA/PS could not provide complete 3,5-DCP removal after 120 min treatment such that for the highest tried PS concentration.(1.00 mM; pH=3.0) resulted in only 31% 3,5-DCP removal. 2,4-DCA degradation by UV-C/PS, at all studied initial PS concentrations and pH values resulted in complete pollutant removal. PS activation with ZVI resulted in complete 2,4-DCA removal for initial PS concentration exceeding 0.50 mM such that after 80 min ZVI/PS (PS=0.75 mM; pH=5.0) treatment, complete 2,4-DCA was obtained; however, the required time to achieve complete 2,4-DCA with initial PS of 1.00 mM was longer (100 min) most probably as a result of SO4●- scavenging reaction with excess PS and/or ferrous ion. The highest 2,4-DCA removal (47%) by 120 min ZVA/PS (pH=3.0) treatment was obtained with initial PS concentration of 0.25 mM, below or beyond which the 2,4-DCA removal decreased. 2,4-DCA removal by 120 min ZVA/PS (PS=0.50 mM) treatment increased remarkably from 20% to 89% , when pH decreased from 3.0 to 1.5 suggesting that more acidic pH facilitated effective removal of 2,4-DCA due to ZVA corrosion. Complete IPR removal was achieved by UV-C/PS at all studied initial PS concentrations such that even with low PS (0.03 mM), complete IPR was obtained in 20 min. Increasing initial PS concentration in the range of 0.01 mM to 1.00 mM led to higher SO4●- concentrations and consequently faster IPR degradation rates. Alkaline hydrolysis of IPR was observed at initial pH of 9.0 and 11.0 during UV-C/PS treatment; however, complex pH effect on IPR degradation rate was observed at neutral and acidic pH values. ZVI/PS (pH=5.0) treatment of IPR, demonstrated that increasing initial PS concentration to more than 0.50 mM, appreciably improved ZVI/PS treatment of IPR. ZVA/PS was an efficient treatment only in IPR degradation such that even low PS concentrations (0.10 mM and 0.25 mM) with initial pH of 3.0 resulted in almost 80% IPR removal after 120 min treatment and for higher PS concentrations, complete IPR was obtained. In both heterogeneous treatments of all three model industrial micropollutants acidic pH values showed a better performance. Those oxidation processes from treatability of the micropollutants in DW resulted in complete micropollutant removal, were investigated under selected PS and pH conditions to correlate each micropollutant removal with chloride ion (Cl-) release, metal ion release, dissolved organic carbon (DOC) removal and PS consumption. Experiments conducted in DW indicated that for all three model industrial micropollutants, complete removals were achieved by UV-C/PS accompanied with dechlorination and appreciable mineralizations. 3,5-DCP was completely degraded by UV-C/PS (PS=0.30 mM; pH=6.3) treatment in 40 min accompanied with 95% DOC removal that was achieved after 120 min treatment. Maximum Cl- concentrations of 3.91 mg/L was obtained after 120 min UV-C/PS treatment of 3,5-DCP corresponding to practically 90% of the highest possible theoretical Cl- release of 4.35 mg/L. Practically complete 2,4-DCA removal was achieved after 10 min UV-C/PS (PS=1.00 mM; pH=6.0); however, with the progress of the treatment, dechlorination and DOC removal were proceeded such that 93% DOC removal and Cl- concentration of 3.64 mg/L were obtained after 40 min treatment. Beyond this treatment time, both DOC removal and dechlorination were practically stopped and remained constant probably due to PS depletion. IPR degradation was accompanied with rapid dechlorination and PS consumption. UV-C/PS (PS=0.30 mM; pH=6.2) treatment was also effective in IPR mineralization; 78% DOC was removed after 120 min treatment and maximum Cl- concentrations of 1.50 mg/L was obtained at the end of the reaction. For all three studied industrial micropollutants, complete/near-complete removals were achieved by ZVI/PS accompanied with iron (Fe) release; however, their mineralizations were partially (21%-50% DOC removal) after 120 min treatment. ZVA/PS was only effective in IPR removal; however poor mineralization was obtained after 120 min treatment. Treatability of the selected micropollutants was also examined in a synthetic tertiary treated urban wastewater (SWW) during the studied treatments due to the fact that the presence of different water constituents in the reaction solution may inhibit the oxidation performance. Experimental results of three model industrial pollutants by the selected treatments (UV-C/PS and ZVI/PS) in SWW, revealed complete micropollutant removals; however, their mineralizations were partially and different compared to DW. UV-C/PS treatment of 3,5-DCP in DW that exhibited appreciable mineralization of 3,5-DCP, demonstrated worse treatment performance compared to ZVI/PS when applied in SWW (26% DOC removal and 41% DOC removal in SWW after 120 min treatment by UV-C/PS and ZVI/PS, respectively). Partial mineralizations of 2,4-DCA in SWW by 120 min UV-C/PS and ZVI/PS treatments were obtained as 57% and 35% DOC removals, respectively which were lower compared to DW revealing performance of both treatments decreased in complex medium. The experiments in DW exhibited the superior performance of the UV-C/PS for IPR mineralization (78% DOC removal after 120 min); however, the oxidation performance of UV-C/PS in SWW decreased appreciably and resulted in 24% DOC removal after 120 min. 40% DOC removal after 120 min was observed with ZVI/PS being the most efficient process in SWW. UV-C/PS treatment of all three selected micropollutants, was most negatively affected when apply in SWW most probably due to UV-C light absorption of SWW constituents hindering effective absorption by the target pollutant. Vibrio fischeri (V. fischeri) and Pseudokirchneriella subcapitata (P. subcapitata) were employed as the organism tests to assess changes in acute toxicity during application of the studied treatments. Responses of the two mentioned test organisms were rather different; higher inhibition rates were observed on P. subcapitata than V. fischeri. While the percent relative inhibition of the original 3,5-DCP on P. subcapitata was almost 20%, the inhibitory effect increased after 80 min UV-C/PS treatment reaching to 47%. After 80 min ZVI/PS treatment of 3,5-DCP, the percent relative inhibition of treated samples on P. subcapitata did not change appreciably. The percent relative inhibition of the original 2,4-DCA on P. subcapitata was in the range of 20%-28%; however, the inhibitory effect increased and reached 72% after 120 min UV-C/PS treatment. The percent relative inhibition of original IPR samples on P. subcapitata was obtained as <10%; however, it reached 56% and 39% after 120 min UV-C/PS and ZVI/PS, respectively. During the application of selected treatments in DW, the genotoxicity of original micropollutants and their AOPs-treated samples were explored using a mutant strain of Salmonella typhimurium TA 1535; however, no significant genotoxic effect was observed. At the final stage of this study, the type and nature of possible evolved degradation products during the selected treatments of three model industrial pollutants in DW were examined by ion chromatography, liquid chromatography and mass spectrometry analysis in order to gain a deeper insight into the formed radical reactions with the target pollutants. Hydroquinone, acetic acid and Cl- could be detected and quantified in the reaction solution during UV-C/PS and ZVI/PS treatments of 3,5-DCP. Aniline and acetic acid formations were evidenced during UV-C/PS treatment of 2,4-DCA accompanied with dechlorination; however only acetic acid was identified during ZVI/PS. LC analysis confirmed the formation of 2,4-DCA, hydroquinone, acetic acid and formic acids as the major aromatic and aliphatic degradation products of IPR during UV-C/PS while hydroquinone, lactic acid and acetic acid was evidenced for ZVI/PS treatment of IPR.