Electrochemical-enhanced nanoscale oxygen-vacancy CuFe2O4 to activate persulfate (E/oxygen-vacancy CuFe2O4/PS) for separation of Ebselen from wastewater.

To enhance the catalytic activity of CuFe2O4 on PS, a nanoscale oxygen-vacancy CuFe2O4 was prepared by hydrogenation reduction technique to construct an advanced oxidation system of electrochemical-enhanced nanoscale oxygen-vacancy CuFe2O4-activated persulfate. Using Ebselen (EBS) as a model pollutant, the degradation efficiency, activation mechanism and degradation pathway were studied. The oxygen-vacancy CuFe2O4 was characterized and analysed by FESEM, EDS and XPS. The results show that under the optimal reaction conditions (PS = 0.8 g/L, oxygen-vacancy CuFe2O4 = 0.3 g/L, initial pH = 6.5), the removal rate of 20 mg/L EBS can reach 92% after reaction for 60 min, which proves that the formation of oxygen-vacancy changed the catalytic inertness of CuFe2O4 on PS. It is speculated that in the E/oxygen-vacancy CuFe2O4/PS system, the existence of oxygen holes enhances the electron transfer ability and reducibility of the catalyst, so the oxygen-vacancy CuFe2O4 can efficiently activate PS to degrade EBS. The quenching experiments show that both SO4⋅- and ⋅OH are involved in the oxidation reaction as reactive radicals in the system, with SO4⋅- being the main reactive radical. In addition, both dissolved oxygen (DO) and anions in the solution inhibit the oxidative degradation of EBS by oxygen-vacancy CuFe2O4/PS system. Through GC-MS detection, a possible degradation pathway is proposed.

Removal of Pharmaceuticals and Personal Care Products (PPCPs) by Free Radicals in Advanced Oxidation Processes.

As emerging pollutants, pharmaceutical and personal care products (PPCPs) have received extensive attention due to their high detection frequency (with concentrations ranging from ng/L to µg/L) and potential risk to aqueous environments and human health. Advanced oxidation processes (AOPs) are effective techniques for the removal of PPCPs from water environments. In AOPs, different types of free radicals (HO·, SO4·-, O2·-, etc.) are generated to decompose PPCPs into non-toxic and small-molecule compounds, finally leading to the decomposition of PPCPs. This review systematically summarizes the features of various AOPs and the removal of PPCPs by different free radicals. The operation conditions and comprehensive performance of different types of free radicals are summarized, and the reaction mechanisms are further revealed. This review will provide a quick understanding of AOPs for later researchers.

Dissolved organic matter heightens the toxicity of tetrabromobisphenol A to aquatic organisms.

Tetrabromobisphenol A (TBBPA) is a new type of persistent organic pollutant, which causes environmental pollution and health problems, and has attracted the attention of the international research community. Once released into the environment, TBBPA can interact with dissolved organic matter (DOM), which affects its behavior. However, the effect of DOM on the biological toxicity of TBBPA remains unclear. The toxic effects of TBBPA on three model aquatic organisms (Chlorella pyrenoidosa, Daphnia magna, and Danio rerio), in the absence and presence of DOM were investigated. The order of acute toxicity of TBBPA to the three aquatic organisms was D. magna > D. rerio > C. pyrenoidosa. In the presence of DOM the median effect/lethal concentrations values of TBBPA to the three aquatic organisms decreased by at least 32 (C. pyrenoidosa), 52 (D. magna), and 6.6% (D. rerio), implying that DOM enhanced the acute toxicity of TBBPA to all the organisms. Moreover, the higher the concentration of DOM, the higher the acute toxicity of TBBPA. Furthermore, the presence of DOM increased total reactive oxygen species (ROS) induced by TBBPA in a concentration-dependent manner. A tracking analysis of total ROS in the three aquatic organisms also showed that the presence of DOM aggravated the accumulation of total ROS induced by TBBPA, indicating that oxidative stress is a characteristic mechanism of toxicity of TBBPA to aquatic organisms when DOM is present. In addition, the evaluated risk quotient indicated that the ecological risk of TBBPA to aquatic organisms can increase in environments rich in DOM.

Performance and Mechanisms of PropS-SH/HA Coatings in the Inhibition of Pyrite Oxidation.

Acid mine drainage (AMD) entering the environment will cause long-term environmental pollution and ecological damage, the treatment or remediation for which has become a difficult worldwide problem. To control AMD at the source, a novel composite coating, hydroxyapatite (HA) as the filler embedded in a γ-mercaptopropyltrimethoxysilane (PropS-SH) coating, was introduced in this study. The performance and mechanisms of PropS-SH/HA coatings in the inhibition of pyrite oxidation were investigated by chemical leaching testing and material structure characterization. The results of the investigations revealed that the addition of an appropriate amount of HA can enhance the passivation efficiency of the PropS-SH coating. The best coating was obtained from 3% (v/v) of PropS-SH solution with 16 wt % HA, as this coating decreased pyrite oxidation by 78.7% (based on total Fe release). The main mechanism of PropS-SH/HA for the inhibition of pyrite oxidation involved the generation of a PropS-SH network through a polycondensation reaction. The addition of HA increased the stability of the passivation film composed of PropS-SH as well as the combining capacity of PropS-SH/HA through the formation of Si-O-Si and Fe-O-Si bonds, respectively.

Screening and ecological risk of 1200 organic micropollutants in Yangtze Estuary water.

The Yangtze River, the third largest river in the world, has been polluted by various organic chemicals. In 2018, China decided to implement ecological restoration of the Yangtze River to protect the river. However, except for some conventional pollution indices such as COD (Chemical Oxygen Demand) and NH4+-N, the overall levels and risks of a wide variety of organic micropollutants (OMPs) in the Yangtze Estuary is not clear. Herein, results from a wide-range screening on levels and risks of OMPs in the Yangtze Estuary water were reported. 36 water samples were collected at 9 sites in the Yangtze Estuary in 2012 and 2013. Approximately 1200 OMPs were screened. A total of 131 OMPs were detected with total concentrations ranging from 1.8×103 to 9.7×103 ng/L. A tiered strategy was proposed to simplify the assessment of multi-substance ecological risks. Results showed that risk quotient (RQ) for 77% of the OMPs was less than 0.1. For 20 OMPs with RQ ≥ 0.1, joint probabilistic risks were assessed by species sensitivity distribution models. The joint risks as expressed by multi-substance potentially affected fractions are > 5%, and are not insignificant. The results may serve as a benchmark for protecting biodiversity in the Yangtze Estuary, as China motivated to have a fundamental improvement on the environmental quality by 2035.

Mitochondria-Targetable Ratiometric Time-Gated Luminescence Probe for Carbon Monoxide Based on Lanthanide Complexes.

As a critical gasotransmitter, carbon monoxide (CO) has been demonstrated to be related with mitochondrial respiration, but the monitoring of CO in mitochondria remains a great challenge. In this work, a unique ratiometric time-gated luminescence (TGL) probe, Mito-NBTTA-Tb3+/Eu3+, that can specifically respond to mitochondrial CO has been developed. The probe was designed by incorporating a mitochondria-targeting moiety, triphenylphosphonium, into a CO-activatable terpyridine polyacid derivative, 4'-(4-nitrobenzyloxy-2,2':6',2''-terpyridine-6,6''-diyl) bis(methylenenitrilo) tetrakis(acetic acid), for coordinating to Eu3+ and Tb3+ ions to construct lanthanide complex-based probe for ratiometric TGL detection of CO. Upon reaction with CO, accompanied by the conversion of nitro group to amino group, a 1,6-rearrangement-elimination reaction occurs, which leads to the cleavage of 4-nitrobenzyl group from Mito-NBTTA-Tb3+/Eu3+, resulting in the significant increase of Tb3+ emission at 540 nm and moderate decrease of Eu3+ emission at 610 nm. After the reaction, the I540/ I610 ratio was found to be 48-fold enhanced. This feature allowed Mito-NBTTA-Tb3+/Eu3+ to be employed as a ratiometric TGL probe for CO detection with the I540/ I610 ratio as a signal. In addition, the probe showed outstanding mitochondria-localization characteristic, which enabled the probe to be successfully applied to imaging CO within mitochondria of living cells under TGL and ratiometric modes. The application of Mito-NBTTA-Tb3+/Eu3+ was demonstrated by the visualization and quantitative detection of exogenous and endogenous CO in living cells and mouse liver tissue slices, as well as in living Daphnia magna and mice. All of the results suggested the potential of Mito-NBTTA-Tb3+/Eu3+ for the quantitative monitoring of CO in vitro and in vivo.

Effects of lomefloxacin on survival, growth and reproduction of Daphnia magna under simulated sunlight radiation.

Lomefloxacin, an antibacterial agent with known photo-induced toxicity in clinical studies, is frequently detected in aquatic environments. Investigating the photo-induced toxicity of lomefloxacin in aquatic organisms is therefore of importance for assessing its ecological risks. In this study, the effects of lomefloxacin on survival, growth and reproduction of Daphnia magna under simulated sunlight radiation (SSR) were investigated, and the mechanism of action was revealed. Results indicated that SSR containing UV radiation increased the acute toxicity of lomefloxacin to Daphnia magna relative to white fluorescent light irradiation. Under SSR, 100 µM lomefloxacin significantly enhanced reactive oxygen species (ROS) generation and lipid peroxidation, and decreased activities of superoxide dismutase and catalase. The biochemical observations and apparent effects on the organism indicate that oxidative stress plays a central role in the acute photo-induced toxicity. Chronic toxicity results showed that SSR significantly affected growth and reproduction of Daphnia magna, whereas lomefloxacin reduced the damage of UV radiation in SSR through light shielding. This study provides insight into the mechanism of photo-induced toxicity and can support the risk assessment of chemicals in the aquatic environment by including the impacts of sunlight irradiation on toxicity.

Extending the excitation wavelength from UV to visible light for a europium complex-based mitochondria targetable luminescent probe for singlet oxygen.

A visible-light-excitable Eu3+ complex-based luminescent probe, [Eu(pdap)3(DPBT)], has been proposed for time-gated luminescence imaging of singlet oxygen in the mitochondria of living cells, as well as in tumor tissues and laboratory animals. Extension of the excitation window to the visible-light region makes the probe more favorable for practical usage.

Time-gated luminescence imaging of singlet oxygen photoinduced by fluoroquinolones and functionalized graphenes in Daphnia magna.

Singlet oxygen (1O2) can be photogenerated by photoactive xenobiotics and is capable of causing adverse effects due to its electrophilicity and its high reactivity with biological molecules. Detection of the production and distribution of 1O2 in living organisms is therefore of great importance. In this study, a luminescent probe ATTA-Eu3+ combined with time-gated luminescence imaging was adopted to detect the distribution and temporal variation of 1O2 photoinduced by fluoroquinolone antibiotics and carboxylated/aminated graphenes in Daphnia magna. Results show that the xenobiotics generate 1O2 in living daphnids under simulated sunlight irradiation (SSR). The photogeneration of 1O2 by carboxylated/aminated graphenes was also confirmed by electron paramagnetic resonance spectroscopy. The strongest luminescence signals of 1O2 were observed in the hindgut of daphnids, and the signals in different areas of the daphnids (gut, thoracic legs and post-abdominal claw) displayed a similar trend of enhancement over irradiation time. Mean 1O2 concentrations at different regions of daphnids within one hour of SSR irradiation were estimated to be in the range of 0.5∼4.8µM. This study presented an efficient method for visualizing and quantifying the temporal and spatial distribution of 1O2 photogenerated by xenobiotics in living organisms, which can be employed for phototoxicity evaluation of xenobiotics.

Screening and health risk of organic micropollutants in rural groundwater of Liaodong Peninsula, China.

Groundwater serves as a main drinking water source for rural residents in China. However, little is known regarding the pollution of organic micropollutants in groundwater that may pose health risks. In this study, more than 1300 organic micropollutants were screened in the groundwater samples collected from 13 drinking water wells distributed across five rural regions of Liaodong Peninsula in China. A total of 80 organic micropollutants including 12 polycyclic aromatic hydrocarbons, 11 alkanes, 9 pesticides, 7 substituted phenols, 7 perfluoroalkyl acids, 6 heterocyclic compounds, 5 alcohols, 5 phthalic acid esters, 5 pharmaceutical and personal care products, 3 ketones, 2 polychlorinated biphenyls (PCBs), 2 alkylbenzenes and 2 chlorinated benzenes were detected, with their total concentration of 32-1.5 × 104 ng/L. Noncarcinogenic and carcinogenic risks of a part of pollutants were assessed. Exposure through skin absorption and oral ingestion was considered in the assessment. Generally the risks are within the acceptable limits, except for that the carcinogenic risk at two sites in Jinzhou is higher than 10-6. To the best of our knowledge, this is the first report on health risks of groundwater micropollutants in China.