In this study, vanadium trioxide (V2O3) was adopted to activate PMS via a Fenton-like reaction to degrade metronidazole (MNZ). The V2O3-PMS system can almost completely degrade MNZ at 30 min with 42.4% TOC removal. Comparative tests reveal that V2O3 stands out among a variety of heterogeneous catalysts, including metallic oxides and carbon materials. Sulfate radicals (SO4•−) and hydroxyl radicals (•OH) derived from PMS decomposition are major reactive oxygen species, based on quenching tests, electron spin resonance (ESR) analysis, the steady-state concentrations of radicals ([SO4•−]ss = 5.1 × 10-13 M and [•OH]ss = 4.0 × 10-14 M), and kinetics model. The process of stepwise electron transfer from vanadium species to PMS to produce reactive radicals was proved by small-molecule simulation experiments and pickling experiments of vanadium oxides. Possible pathways of MNZ degradation were proposed based on the results of LC-MS and Fukui function, including two stages of the hydroxylation and bond cleavage of nitro and the subsequent ring-opening. This study reveals the high reusability and practicability of the V2O3-PMS system over a relatively wide pH range, which puts forward a new vision on V2O3 induced Fenton-like reactions and a new reference method for the removal of medical organic contaminants in water.
Design of high-efficiency visible light photocatalysts is critical in the degradation of antibiotic pollutants in water, a key step towards environmental remediation. In the present study, Mo-doped BiOBr nanocomposites are prepared hydrothermally at different feed ratios, and display remarkable visible light photocatalytic activity towards the degradation of sulfanilamide, a common antibacterial drug. Among the series, the sample with 2% Mo dopants exhibits the best photocatalytic activity, with a performance 2.3 times better that of undoped BiOBr. This is attributed to Mo doping that narrows the band gap of BiOBr and enhances absorption in the visible region. Additional contributions arise from the unique materials morphology, where the highly exposed (102) crystal planes enrich the photocatalytic active sites, and facilitate the adsorption of sulfanilamide molecules and their eventual attack by free radicals. The reaction mechanism and pathways are then unraveled based on theoretical calculations of the Fukui index and liquid chromatography/mass spectrometry measurements of the reaction intermediates and products. Results from this study indicate that deliberate structural engineering based on heteroatom doping and morphological control may serve as an effective strategy in the design of highly active photocatalysts towards antibiotic degradation.
Development of low-cost, high-performance photocatalysts for the effective degradation of antibiotics in wastewater is critical for environmental remediation. In this work, titanium dioxide/zirconium dioxide/graphitic carbon nitride (TiO2/ZrO2/g-C3N4) ternary composites are fabricated via a facile hydrothermal procedure, and photocatalytically active towards the degradation of berberine hydrochloride under visible light illumination. The performance is found to increase with the Ti:Zr atomic ratio in the nanocomposites, and obviously enhanced in comparison to that of the binary TiO2/g-C3N4 counterpart, due to the formation of type I/II heterojunctions that help separate the photogenerated electron-hole pairs and produce superoxide and hydroxy radicals. The mechanistic pathways are unraveled by a deliberate integration of liquid chromatography-mass spectrometry measurements with theoretical calculations of the condensed Fukui index. Furthermore, the ecotoxicity of the reaction intermediates is examined by utilizing the Toxicity Estimation Software Tool (TEST) and quantitative structure activity relationship calculations (QSAR).
Volatile methyl siloxanes (VMS) are ubiquitous in indoor environments due to their use in personal care products. This paper builds on previous work identifying sources of VMS by synthesizing time-resolved proton-transfer reaction time-of-flight mass spectrometer VMS concentration measurements from four multiweek indoor air campaigns to elucidate emission sources and removal processes. Temporal patterns of VMS emissions display both continuous and episodic behavior, with the relative importance varying among species. We find that the cyclic siloxane D5 is consistently the most abundant VMS species, mainly attributable to personal care product use. Two other cyclic siloxanes, D3 and D4, are emitted from oven and personal care product use, with continuous sources also apparent. Two linear siloxanes, L4 and L5, are also emitted from personal care product use, with apparent additional continuous sources. We report measurements for three other organosilicon compounds found in personal care products. The primary air removal pathway of the species examined in this paper is ventilation to the outdoors, which has implications for atmospheric chemistry. The net removal rate is slower for linear siloxanes, which persist for days indoors after episodic release events. This work highlights the diversity in sources of organosilicon species and their persistence indoors.
Rapid atmospheric warming since the mid-twentieth century has increased temperature-dependent erosion and sediment-transport processes in cold environments, affecting food, energy and water security. In this Review, we summarize landscape changes in cold environments and provide a global inventory of increases in erosion and sediment yield driven by cryosphere degradation. Anthropogenic climate change, deglaciation, and thermokarst disturbances are causing increased sediment mobilization and transport processes in glacierized and periglacierized basins. With continuous cryosphere degradation, sediment transport will continue to increase until reaching a maximum (peak sediment). Thereafter, transport is likely to shift from a temperature-dependent regime toward a rainfall-dependent regime roughly between 2100–2200. The timing of the regime shift would be regulated by changes in meltwater, erosive rainfall and landscape erodibility, and complicated by geomorphic feedbacks and connectivity. Further progress in integrating multisource sediment observations, developing physics-based sediment-transport models, and enhancing interdisciplinary and international scientific collaboration is needed to predict sediment dynamics in a warming world.
This paper proposes a Bayesian multilevel spatio-temporal model with a time-varying spatial autoregressive coefficient to estimate temporally heterogeneous network interdependence. To tackle the classic reflection problem, we use multiple factors to control for confounding caused by latent homophily and common exposures. We develop a Markov Chain Monte Carlo algorithm to estimate parameters and adopt Bayesian shrinkage to determine the number of factors. Tests on simulated and empirical data show that the proposed model improves identification of network interdependence and is robust to misspecifcation. Our method is applicable to various types of networks and provides a simpler and more flexible alternative to coevolution models.
The regime divide is one of the most studied cleavages in international politics, and the current discussion centers on whether the great power competition between the United States and China divides the world along regime lines. This paper focuses on the US-China competition in forming voting alignments in the United Nations General Assembly and disentangles the effects of regime type on actions, preferences, and strategic calculations of the rival powers and developing countries. We develop a formal model to theorize the competition and convert the game into a Bayesian statistical estimator. Empirical evidence suggests that the US-China competition increases the democracy/authoritarianism voting cleavage. States' regime-oriented voting or vote-buying choices, however, are not driven by their sincere preferences but by differential strategies shaped by regime type. These findings shed light on the nature of the US-China competition and its implications for the world order.
This paper proposes a Bayesian alternative to the synthetic control method for comparative case studies with a single or multiple treated units. We adopt a Bayesian posterior predictive approach to Rubin’s causal model, which allows researchers to make inferences about both individual and average treatment effects on treated observations based on the empirical posterior distributions of their counterfactuals. The prediction model we develop is a dynamic multilevel model with a latent factor term to correct biases induced by unit-specific time trends. It also considers heterogeneous and dynamic relationships between covariates and the outcome, thus improving precision of the causal estimates. To reduce model dependency, we adopt a Bayesian shrinkage method for model searching and factor selection. Monte Carlo exercises demonstrate that our method produces more precise causal estimates than existing approaches and achieves correct frequentist coverage rates even when sample sizes are small and rich heterogeneities are present in data. We illustrate the method with two empirical examples from political economy. (For software to implement the method, please visit https://github.com/liulch/bpCausal)