Biodegradation of typical azole fungicides in activated sludge under aerobic conditions.

Widespread use of azole fungicides and low removal efficiency in wastewater treatment plants (WWTPs) have led to the elevated concentration of azole fungicides in receiving environment. However, there was limited research about the removal mechanism of azole fungicides in the biological treatment of WWTPs. Imidazole fungicide climbazole and triazole fungicide fluconazole were selected to investigate the biodegradation mechanism of azole fungicides in activated sludge under aerobic conditions. Climbazole was found to be adsorbed to solid sludge and resulted in quick biodegradation. The degradation of climbazole in the aerobic activated sludge system was fitted well by the first-order kinetic model with a half-life of 5.3 days, while fluconazole tended to stay in liquid and had only about 30% of loss within 77 days incubation. Ten biotransformation products of climbazole were identified by high resolution mass spectrometry using suspect and non-target screening method. But no biodegradation products of fluconazole were identified due to its limited removal. The possible biodegradation pathways for climbazole were proposed based on the products identification and pathway prediction system, and involves oxidative dehalogenation, side chain oxidation and azole ring loss. The findings from this study suggest that it should be a concern for the persistence of fluconazole in the environment.

Levofloxacin and sulfamethoxazole induced alterations of biomolecules in Pseudokirchneriella subcapitata.

Levofloxacin (LEV) and sulfamethoxazole (SMX) are two extensively used antibiotics. Most investigations have been concentrated on the toxic effects of antibiotics on algal species evaluated with traditional ecotoxicological endpoints; however, limited information is available on the alterations in biomolecules induced by antibiotics. Here we investigated alterations in the structure and function of biomolecules to a model species Pseudokirchneriella subcapitata following exposure of LEV and SMX by applying Fourier transform infrared spectroscopy (FTIR). The growth inhibition tests revealed that both LEV and SMX had negative effects on algal growth, while SMX was found to be more toxic to P. subcapitata than LEV. Based on the FTIR analysis, alterations in the structure, composition and function of lipids and proteins were observed on microalgal cells, which were correlated with the dosage of LEV and SMX. As a result of lipid peroxidation induced by LEV and SMX, an increase in the lipid/protein ratio and decrease in the ratios of CH2/lipid, CH3/lipid, carbonyl ester/lipid and olefinic = CH/lipid were observed in all treatment groups with respect to the reference control. Moreover, alterations in the composition and secondary structure of proteins were also observed in accompany with a decrease in the Amide I/Amide II ratio and an increase of the loose ß-sheet structure protein. LEV caused an elevated level of lipid peroxidation, while SMX induced a more obvious protein aggregation. The findings from this study showed that FTIR could reveal the toxic mechanism of these two antibiotics to algae at the biochemical level by linking alterations in biomolecules to biochemical dynamics and function.

Co-metabolism of sulfamethoxazole by a freshwater microalga Chlorella pyrenoidosa.

Microalgae-mediated biodegradation of antibiotics has recently gained increased attention from international scientific community. However, limited information is available regarding microalgae-mediated biodegradation of SMX in a co-metabolic system. Here we investigated the biodegradation of sulfamethoxazole (SMX) by five algal species (Pseudokirchneriella subcapitata, Scenedesmus quadricauda, Scenedesmus obliquus, Scenedesmus acuminatus and Chlorella pyrenoidosa), and its transformation pathways by C. pyrenoidosa in a sodium acetate (3 mM) co-metabolic system. The results showed that the highest SMX dissipation (14.9%) was detected by C. pyrenoidosa after 11 days of cultivation among the five tested algal species in the absence of other carbon sources. The addition of sodium acetate (0-8 mM) significantly enhanced the dissipation efficiency of SMX (0.4 µM) from 6.05% to 99.3% by C. pyrenoidosa after 5 days of cultivation, and the dissipation of SMX followed the first-order kinetic model with apparent rate constants (k) ranging from 0.0107 to 0.9811 d-1. Based on the results of mass balance analysis, biodegradation by C. pyrenoidosa was the main mechanism for the dissipation of SMX in the culture medium. Fifteen phase I and phase II metabolites were identified, and subsequently the transformation pathway was proposed, including oxidation, hydroxylation, formylation and side chain breakdown, as well as pterin-related conjugation. The majority of metabolites of SMX were only observed in the culture medium and varied with cultivation time. The findings of the present study showed effective co-metabolism of a sulfonamide by microalgae, and it may be applied in the aquatic environment remediation and wastewater treatment in the future.

Occurrence, toxicity and transformation of six typical benzotriazoles in the environment: A review.

Benzotriazoles (BTs) are a group of heterocyclic compounds which have been widely applied in industrial activities and domestic life mainly as corrosive inhibitors. BTs have been ubiquitously detected in receiving environments and cause potential toxicity to non-target organisms. This paper reviews the occurrence and fate of six selected benzotriazole compounds in different environmental and biological matrices, as well as the transformation and toxicity. Due to their high hydrophilicity and insufficient removal in wastewater treatment plants (WWTPs), these compounds were widely detected in aquatic environments with concentrations mainly from tens ng/L to tens µg/L. Considerable residual levels of BTs in plant, fish, air, tap water and human urine have implied the potential risks to various organsims. The reported acute toxicity of BTs are generally low (EC50 in mg/L level). Some observed sublethal effects including endocrine disrupting effects, hepatotoxicity and neurotoxicity, as well as the ability to promote the development of endometrial carcinoma still raise a concern. BTs are found often more recalcitrant to biodegradation compared to photolysis and ozonation. Environmental factors including pH, temperature, irradiation wavelength, redox condition as well as components of matrix are proved crucial to the removal of BTs. Further studies are needed to explore the precise environment fate and toxicity mechanism of BTs, and develop advanced treatment technologies to reduce the potential ecological risks of BTs.