Yajie Qian

Fe(III)-promoted transformation of β-lactam antibiotics: Hydrolysis vs oxidation

The widely used β-lactam antibiotics are susceptible to oxidative and/or hydrolytic degradation promoted by some metal ions (e.g., Cu(II)). Ferric ions (Fe(III)) are among the most common metal ions, but their role in the environmental transformation and fate of β-lactam antibiotics is still unknown. This study elucidates that Fe(III) can promote degradation of β-lactam antibiotics under environmental aquatic conditions. Degradation rate constants of ampicillin (AMP) linearly increased with increasing Fe(III) concentration, but were independent of AMP concentration when AMP was higher than Fe(III) concentration. Neutral pH was most favorable for Fe(III)-promoted degradation of AMP, and the promoted degradation was also significant in real surface water and wastewater matrix. Among the various β-lactam antibiotics, Fe(III)-promoted degradation of penicillins was faster than that of cephalosporins. Product analysis indicated that only two isomers of hydrolysis products were observed without detection of oxidation products. The Fe(III)-promoted degradation likely occurred via complexation of β-lactam antibiotics with carboxyl group and tertiary nitrogen, and then enhancing the hydrolytic cleavage of β-lactam ring. This study is among the first to identify the role of Fe(III) in the degradation of β-lactam antibiotics and elucidate the mechanism. The new findings indicate iron species are among the factors affecting the environmental fate of β-lactam antibiotics.

Long-term impact of a tetracycline concentration gradient on the bacterial resistance in anaerobic-aerobic sequential bioreactors

Wastewater treatment systems are considered as hotspots for release of antibiotic resistance genes (ARGs) into the environment. Anaerobic-aerobic sequential (AAS) bioreactors now are intensively used for wastewater treatment worldwide. However, the occurrence of ARGs in wastewater treatment systems exposed to low-level (i.e., sub-inhibitory) antibiotic is poorly known. Here, we studied the distribution patterns of seven tetracycline resistance genes (tet genes) including tet(A), tet(C), tet(G), tet(X), tet(M), tet(O), and tet(W), as well as one mobile element [class 1 integron (intI1)] in AAS bioreactors under exposure to tetracycline from 50u202fμg/L to 500u202fμg/L. Additionally, effect on the removal performance of nutrients and tetracycline in both anaerobic and aerobic units was also investigated. A tetracycline concentration gradient selected for bacterial resistance in the anaerobic reactor, with the exception of tet(A) and tet(W), and the tetracycline removal deteriorated by 47%. However, the abundance of tet and intI1 genes reduced in the subsequent aerobic unit, and the removal of tetracycline, soluble COD, and NH4+-N maintained at average efficiencies of 91%, 90%, and 93%, respectively. The level of tet(X) was largely unaffected by AAS treatment. It is notable that intI1 genes probably played a crucial role on the horizontal dissemination of tet genes. The tetracycline levels and intI1 genes appear to be the primary factors influencing the occurrence of tet genes in AAS bioreactors. Nonetheless, AAS treatments still show promise for reducing antibiotics, ARGs and mobile elements without affecting nutrient removal, and need further research for practical applications.

Efficient bioconversion of organic wastes to high optical activity of l -lactic acid stimulated by cathode in mixed microbial consortium

Lactic acid is one of the emerging top biomass derived platform chemicals that can be fermented from organic wastes. This study evaluated the potential of Cathodic Electro-Fermentation (CEF) as a novel approach to enhance the yield of high optical activity (OA) of l-lactic acid from organic wastes using mixed microbial consortium. The fermentation process was stimulated through the cathode applied withxa0-100u202fmV versus standard hydrogen electrode (SHE), which contributed to 4.73 times higher lactic acid productivity (0.6578u202fgu202fL-1 h-1) compared to that in the open circuit control (0.1392u202fgu202fL-1 h-1), and an improved OA of l-lactic acid was also observed (42.3% vs. 3.6% of the open circuit control). The study elucidated that the optimal voltage atxa0-100u202fmV promoted the conversion of pyruvate to l-lactate by 77.9% compared to the Blank, which triggered the generation of l-lactic acid to occur rapidly even at low concentration of pyruvate. The significant variation of microbial community in family- and genus-level distributions were observed in CEF system. Furthermore, the open-circuit operation test demonstrated that the cathode providing in-situ electron supply was essential to achieve high efficient bioconversion of organic wastes to lactic acid. Our work highlights the feasibility of CEF to steer high value-added fermentation products deriving from organic wastes by the mixed microbial consortium.

Oxidation of cefalexin by thermally activated persulfate: Kinetics, products, and antibacterial activity change

While the widely used β-lactam antibiotics, such as cephalosporins, are known to be susceptible to oxidation by sulfate radical (SO4-), comprehensive study about SO4--induced oxidation of cephalosporins is still limited, such as the impact of water matrices, and the structure and antibacterial activity of transformation products. Herein, the oxidation of cefalexin (CFX), a most frequently detected cephalosporin, was systematically investigated by thermally activated persulfate (PS). CFX oxidation followed pseudo-first-order kinetics, and SO4- dominantly contributed to the overall oxidation of CFX. The impact of water matrices, such as Cl-, HCO3- and natural organic matter, on CFX degradation was predicted using a pseudo-steady-state kinetic model. The secondary reactive species, such as chlorine and carbonate radicals, were found to contribute to CFX degradation. Product analysis indicated oxidation of CFX to six products (molecular weight of 363), with two stereoisomeric sulfoxides as the primary oxidation products. It was thus suggested that the primary amine on the side chain, and the thioether sulfur and double bond on the six-membered ring were the reactive sites of CFX towards SO4- oxidation. Antibacterial activity assessment showed that the biological activity of CFX solution was significantly diminished after treatment by the thermally activated PS.

Oxidation of Cefalexin by Permanganate: Reaction Kinetics, Mechanism, and Residual Antibacterial Activity

The oxidation of cefalexin (CFX), a commonly used cephalosporin antibiotic, was investigated by permanganate (PM) in water. Apparent second-order rate constant of the reaction between CFX and PM was determined to be 12.71 ± (1.62) M−1·s−1 at neutral pH. Lower pH was favorable for the oxidation of CFX by PM. The presence of Cl− and HCO3− could enhance PM-induced oxidation of CFX, whereas HA had negligible effect on CFX oxidation by PM. PM-induced oxidation of CFX was also significant in the real wastewater matrix. After addition of bisulfite (BS), PM-induced oxidation was significantly accelerated owing to the generation of Mn(III) reactive species. Product analysis indicated oxidation of CFX to three products, with two stereoisomeric sulfoxide products and one di-ketone product. The thioether sulfur and double bond on the six-membered ring were the reactive sites towards PM oxidation. Antibacterial activity assessment indicated that the activity of CFX solution was significantly reduced after PM oxidation.

Correction to: Ultrasound enhanced activation of peroxydisulfate by activated carbon fiber for decolorization of azo dye

The correct name of the 5th Author is Jiabin Chen.

Ultrasound enhanced activation of peroxydisulfate by activated carbon fiber for decolorization of azo dye

Activated carbon fiber (ACF) has become an emerging activator for peroxydisulfate (PDS) to generate sulfate radical (SO4•−). However, the relative low activation efficiency and poor contaminant mineralization limited its widespread application. Herein, ultrasound (US) was introduced to the ACF activated PDS system, and the synergistic effect of US and ACF in PDS activation and the enhancement of contaminant mineralization were investigated. The synergistic effect of US and ACF was observed in the PDS activation to decolorize orange G (OG). The decolorization efficiency increased with increasing ACF loading and US power, and PDS/OG ratio from 1 to 40. The activation energy was determined to be 24.065xa0kJ/mol. The radical-induced decolorization of OG took place on the surface of ACF, and both SO4•− and hydroxyl radical (•OH) contributed to OG decolorization. The azo bond and naphthalene ring on OG were destructed to other aromatic intermediates and finally mineralized to CO2 and H2O. The introduction of US in the ACF/PDS system significantly enhanced the mineralization of OG. The combination of US and PDS was highly efficient to activate PDS to decolorize azo dyes. Moreover, the introduction of US remarkably improved the contaminant mineralization.

Factors controlling the formation of persistent free radicals in hydrochar during hydrothermal conversion of rice straw

In the environment, persistent free radicals (PFR) have adverse effects on human health. PFR are generated by thermal conversion of biomass, such as hydrothermal carbonization to produce hydrochar. So far, the mechanism and control factors of PFR production in hydrochar are poorly known. Therefore, we investigated here the impacts of hydrothermal temperature, residence time and solid load on the formation of PFR in hydrochar from hydrothermal carbonization of rice straw, by electron paramagnetic resonance (EPR) coupled with Fourier transform infrared spectrometers. Results show that the EPR signal intensity increased with increasing hydrothermal temperature from 180 to 240xa0°C and then decreased at 260xa0°C. A shorter residence time and a higher solid load led to formation of more PFR in hydrochar. The types of PFR also depended on hydrothermal temperature, residence time and solid load. This is the first report on the formation of PFR and relevant influencing factors during hydrothermal conversion of biomass. Based on these results, hydrochar from hydrothermal conversion of biomass at relatively higher temperature, i.e., 260xa0°C, longer residence time, i.e., 4xa0h, and lower solid load, i.e., 1:10, isxa0suggested for safer application.