Adsorption of Monobutyl Phthalate from Aqueous Phase onto Two Macroporous Anion-Exchange Resins

As new emerging pollutants, phthalic acid monoesters (PAMs) pose potential ecological and human health risks. In the present study, adsorption performance of monobutyl phthalate (MBP) onto two macroporous base anion-exchange resins (D-201 and D-301) was discussed. It was found that the adsorption isotherms were best fitted by the Langmuir equation while the adsorption kinetics were well described by pseudo-first-order model. Analyses of sorption isotherms and thermodynamics proved that the adsorption mechanisms for DBP onto D-201 were ion exchange. However, the obtained enthalpy values indicate that the sorption process of MBP onto D-301 is physical adsorption. The equilibrium adsorption capacities and adsorption rates of DBP on two different resins increased with the increasing temperature of the solution. D-301 exhibited a higher adsorption capacity of MBP than D-201. These results proved that D-301, as an effective sorbent, can be used to remove phthalic acid monoesters from aqueous solution

BiOCl Decorated NaNbO3 Nanocubes: A Novel p-n Heterojunction Photocatalyst With Improved Activity for Ofloxacin Degradation

BiOCl/NaNbO3 p-n heterojunction photocatalysts with significantly improved photocatalytic performance were fabricated by a facile in-situ growth method. The obtained BiOCl/NaNbO3 samples were characterized by UV-vis absorption spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), photocurrent (PC) and photoluminescence spectroscopy (PL). The photocatalytic activity of the BiOCl/NaNbO3 samples was investigated by the degradation of a typical antibiotic Ofloxacin (OFX). The experimental results showed that BiOCl/NaNbO3 composites exhibited much higher photocatalytic activity for OFX degradation compared to pure NaNbO3 and BiOCl. The degradation percent of OFX reached 90% within 60 min, and the apparent rate constant was about 8 times as that of pure NaNbO3 and BiOCl. The improved activity can be attributed to the formation of p-n junction between NaNbO3 and BiOCl. The formed p-n junction facilitated the separation of photogenerated holes and electrons, thereby enhancing photocatalytic activity. In addition, the composite photocatalyst showed satisfactory stability for the degradation of OFX. Due to the simple synthesis process, high photocatalytic activity, and the good recyclability of these composite photocatalysts, the results of this study would provide a good example for the rational design of other highly efficient heterojunction photocatalytic materials

Differences of characteristics and performance with Bi3+ and Bi2O3 doping over TiO2 for photocatalytic oxidation under visible light

Bi-doped TiO2 photocatalysts were synthesized by sol with a high-pressure hydrothermal method and developed for the photocatalytic degradation of formaldehyde under the visible light irradiation and ambient temperature. According to characterization, it could be found that some Bi-doped TiO2 could be transformed into the distinctive crystals phase of Bi4Ti3O12, which was crucial for improving activity. The excess Bi2O3 doping into TiO2, such as Bi2O3-N/TiO2 and Bi2O3-C/TiO2, generated a mixed oxides with Bi2O3 and Bi4Ti3O12, was not beneficial to increase the activity of HCHO oxidation, whereas Bi3+/TiO2 composed of TiO2 and Bi4Ti3O12 displayed a higher activity with good stability. It was worth noteworthy that Bi3+/TiO2 didn’t show the lowest binding energy. However, it exhibited a lower PL intensity, higher adsorption, and activity due to the uniform particulates, high surface areas, and the strong interaction between TiO2 and Bi4Ti3O12, attributing to create superoxide radical anion (•O2-) and hydroxyl radical (•OH). The present results of Bi3+/TiO2 indicated that HCHO could be effectively oxidized from 1.094 to 0.058 mg/m3 (94.7%) under visible light irradiation within 36 h. The current research made effort to draw out the existing state of Bi, which would be better, Bi3+ or Bi2O3, doped in the TiO2

Development of Ag/MnCeOx catalysts synthesized with ethanol or water for HCHO decomposition at ambient temperature

Formaldehyde, one of important pollutants in the indoor air, has received increasing attention due to damage to human health. To mitigate formaldehyde pollution, MnCeOx mixed oxides were synthesized by solvothermal method with different solvents and complexing agents, including water or ethanol, and citric acid or glycol, and these catalysts were investigated to catalytic oxidation of formaldehyde at ambient temperature under a real indoor environment, as a super low concentration of indoor formaldehyde (1.0 ± 0.5 mg/m3) and the air under static condition. The result indicated that the MnCeOx catalysts prepared with ethanol exhibited higher activities than samples synthesized with H2O. Structure and performance analysis by BET, XRD, SEM, TEM, TG, Raman, XPS, H2-TPR, and O2-TPD displayed that the MnCeOx oxides synthesized with ethanol (instead of using water) greatly promoted the structure and reducibility, resulting in a high activity for HCHO degradation. More than 90% conversion for HCHO degradation was finished at 36 h and no deactivation could be detected by a series of tests. More importantly, the MnCeOx oxides supported by an increasing of Ag exhibited the increased activity. Promoting effect of Ag over the MnCeOx oxides indicated a strong interplay between Ag and MnCeOx greatly affected the property of Ag/MnCeOx catalysts. The HCHO concentration could be decreased to less than 0.08 mg/m3 at 24 h over 2.0 wt%Ag/MnCeOx (E/G). The performance improvement was ascribed to the high reducibility and high distribution of metallic silver, which could increase the surface active oxygen species and improve the oxygen mobility, and also could weaken the surface Mn–O bond

C1-C2 alkyl aminiums in urban aerosols: Insights from ambient and fuel combustion emission measurements in the Yangtze River Delta region of China

We measured low molar-mass alkyl aminiums (methylaminium, dimethylaminium, ethylaminium and diethylaminium) in urban aerosols in the Yangtze River Delta region of eastern China in August 2014 and from November 2015 to May 2016. After examining artifact formation on sample filters, methylaminium, dimethylaminium and ethylaminium concentrations were quantified. The three C1-C2 aminiums exhibited a unimodal size distribution that maximized between 0.56 and 1.0 μm. Their concentrations in PM2.5 were 5.7 ± 3.2 ng m−3, 7.9 ± 5.4 ng m−3 and 20.3 ± 16.6 ng m−3, respectively, with higher concentrations during the daytime and in warm seasons. On new particle growth days, amine uptake to particles larger than 56 nm was barely enhanced. The molar ratios of individual aminium/NH4+ in PM2.5 were on the order of 10−4 and 10−3. Aminiums were thus far less to out-compete ammonium (NH4+) in neutralizing acidic species in particle sizes down to 56 nm. Abundant nitrate (NO3−/SO42− molar ratio = ∼3) and its correlation to methylaminium and ethylaminium implied that nitrate might be more important aminium salt than sulfate in urban aerosols of this area. Direct measurement of particle-phase amine emission from coal and biomass burning showed that coal burning is an important atmospheric amine source, considering coal burning is top-ranked particulate matter source in China

Electric-field-induced selective catalysis of single-molecule reaction

随着单分子电学检测技术的迅速发展，分子电子学的研究不再局限于分子电子学器件的构筑及其电学性质的测量，而且扩展到单分子尺度化学反应过程的探索。然而目前相关的研究仍然局限于理论计算方面，在单分子尺度上实时监测和调控化学反应的活性和选择性是化学领域的长期目标和挑战。针对这一挑战，洪文晶教授课题组与程俊教授课题组合作，自主研发了精密科学仪器，将单个有机分子定向连接在两个末端尺寸为原子级的电极之间，解决了化学反应中分子取向控制的问题.理论计算结果证实了定向电场可以有效地稳定化学反应的过渡态，从而降低反应能垒。该研究工作在化学化工学院洪文晶教授、程俊教授、能源材料化学协同创新中心（iChEM）刘俊扬副研究员的共同指导下完成，由硕士研究生黄晓艳、iChEM博士研究生唐淳、博士研究生李洁琼以及兰州大学的陈力川博士作为共同第一作者，化学化工学院师佳副教授、陈招斌高级工程师、夏海平教授和田中群教授，萨本栋微纳研究院杨扬副教授、环境与生态学院白敏冬教授以及兰州大学张浩力教授参与了研究工作的讨论并给予指导，博士后乐家波、博士研究生郑珏婷、张佩（已毕业）、李瑞豪、李晓慧也参与了研究工作。Oriented external electric fields (OEEFs) offer a unique chance to tune catalytic selectivity by orienting the alignment of the electric field along the axis of the activated bond for a specific chemical reaction; however, they remain a key experimental challenge. Here, we experimentally and theoretically investigated the OEEF-induced selective catalysis in a two-step cascade reaction of the Diels-Alder addition followed by an aromatization process. Characterized by the mechanically controllable break junction (MCBJ) technique in the nanogap and confirmed by nuclear magnetic resonance (NMR) in bottles, OEEFs are found to selectively catalyze the aromatization reaction by one order of magnitude owing to the alignment of the electric field on the reaction axis. Meanwhile, the Diels-Alder reaction remained unchanged since its reaction axis is orthogonal to the electric fields. This orientation-selective catalytic effect of OEEFs reveals that chemical reactions can be selectively manipulated through the elegant alignment between the electric fields and the reaction axis.This work was supported by the National Key R&D Program of China (2017YFA0204902), the National Natural Science Foundation of China (21722305, 21703188, 21673195, 21621091, 51733004, 51525303, and 91745103), the China Postdoctoral Science Foundation (2017M622060), and the Young Thousand Talents Project of China. 该工作得到国家自然科学基金委（21722305、21703188、21673195、51733004、51525303、91745103），国家重点研发计划课题（2017YFA0204902），中国博士后面上基金（2017M622060）的资助，以及固体表面物理化学国家重点实验室、醇醚酯化工清洁生产国家工程实验室、能源材料化学协同创新中心的支持

Twelve-Year Trends of PM10 and Visibility in the Hefei Metropolitan Area of China

China has been experiencing severe air pollution and previous studies have mostly focused on megacities and a few hot spot regions. Hefei, the provincial capital city of Anhui province, has a population of near 5 million in its metropolitan area, but its air quality has not been reported in literature. In this study, daily PM10 and visibility data in 2001–2012 were analyzed to investigate the air quality status as well as the twelve-year pollution trends in Hefei. The results reveal that Hefei has been suffering high PM10 pollution and low visibility during the study period. The annual average PM10 concentrations are 2~3 times of the Chinese Ambient Air Quality Standard. PM10 shows fluctuating variation in 2001–2007 and has a slightly decreasing trend after 2008. The annual average visibility range is generally lower than 7 km and shows a worsening trend from 2001 to 2006 followed by an improving trend from 2007 to 2012. Wind speed, precipitation, and relative humidity have negative effects on PM10 concentrations in Hefei, while temperature could positively or negatively affect PM10. The results provide a general understanding of the status and long-term trends of PM10 pollution and visibility in a typical second-tier city in China

Effects of three pesticides on superoxide dismutase and glutathione-S-transferase activities and reproduction of Daphnia magna

Applying pesticides to crops is one of the causes of water pollution by surface runoff, and chlorpyrifos, trifluralin and chlorothalonil are used respectively as insecticide, herbicide and fungicide for crop plants widely. To explore effects of three pesticides on aquatic organisms, superoxide dismutase (SOD) and glutathione S-transferase (GST) activities were determined after 24 h and 48 h exposure of D. magna with ages of 6–24 h to several low concentrations of chlorpyrifos (0.36, 0.72, 1.43, 2.86, 5.72 μg∙L−1), trifluralin (0.17, 0.33, 0.66, 1.33, 2.65 mg∙L−1) and chlorothalonil (0.09, 0.18, 0.36, 0.72, 1.43 mg∙L−1) respectively. Main reproductive parameters including first pregnancy time, first brood time, the number of first brood and total fecundity after 21 d exposures at the same concentrations of pesticides as described above were also measured. The results showed that the activities of GST increased in lower concentrations and decreased in higher concentrations after 24 h exposure to three pesticides, respectively. The activities of SOD showed the same changes after 48 h exposure. With the time prolonged, the activities of GST decreased while the activities of SOD increased. After 21 d exposure, the first pregnancy time and first brood time were delayed, while the number of the first brood and total fecundity per female decreased with increasing concentrations. These results corroborated that GST activity was more sensitive to those pesticides than SOD activity, and there was a significant relationship between total fecundity and pesticides-dose(r>0.94, n=6), GST activity after 48 h exposure and total fecundity after 21 d exposure (r>0.92, n=6)

An Enhanced Stacking Ensemble Method for Granule Moisture Prediction in Fluidized Bed Granulation

Moisture is a crucial quality property for granules in fluidized bed granulation (FBG) and accurate prediction of the granule moisture is significant for decision making. This study proposed a novel stacking ensemble method to predict the granule moisture based on granulation process parameters. The proposed method employed k-nearest neighbor (KNN), random forest (RF), light gradient boosting machine (LightGBM) and deep neural networks (DNNs) as the base learners, and ridge regression (RR) as the meta learner. To improve the diversity of the base learners, perturbations of the input variables and network structures were adopted in the proposed method, implemented by feature construction and combination of multiple DNNs with a different number of hidden layers, respectively. In the feature construction, a SHapley Additive exPlanations (SHAP) approach was innovatively utilized to construct effective synthetic features, which enhanced the prediction performance of the base learners. The cross-validation results demonstrated that the proposed stacking ensemble method outperformed other machine learning (ML) algorithms in terms of performance evaluation criteria, for which the parameters MAE, MAPE, RMSE, and Adj. R2 were 0.0596, 1.5819, 0.0844, and 0.99485, respectively

The Research Progress of the Influence of Agricultural Activities on Atmospheric Environment in Recent Ten Years: A Review

In recent years, the industrial emission of air pollution has been reduced via a series of measures. However, with the rapid development of modern agriculture, air pollution caused by agricultural activities is becoming more and more serious. Agricultural activities can generate a large amount of air pollutants, such as ammonia, methane, nitrogen oxides, volatile organic compounds, and persistent organic pollutants, the sources of which mainly include farmland fertilization, livestock breeding, pesticide use, agricultural residue burning, agricultural machinery, and agricultural irrigation. Greenhouse gases emitted by agricultural activities can affect regional climate change, while atmospheric particulates and persistent organic pollutants can even seriously harm the health of surrounding residents. With the increasing threat of agricultural air pollution, more and more relevant studies have been carried out, as well as some recommendations for reducing emissions. The emissions of ammonia and greenhouse gases can be significantly reduced by adopting reasonable fertilization methods, scientific soil management, and advanced manure treatment systems. Regarding pesticide use and agricultural residues burning, emission reduction are more dependent on the restriction and support of government regulations, such as banning certain pesticides, prohibiting open burning of straw, and supporting the recycling and reuse of residues. This review, summarizing the relevant research in the past decade, discusses the current situation, health effects, and emission reduction measures of agricultural air pollutants from different sources, in order to provide some help for follow-up research