Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.     

Origins of black carbon from anthropogenic emissions and open biomass burning transported to Xishuangbanna, Southwest China

Black carbon (BC) has importance regarding aerosol composition, radiative balance, and human exposure. This study adopted a backward-trajectory approach to quantify the origins of BC from anthropogenic emissions ($\mathrm{B}{\mathrm{C}}_{\text{An}}$) and open biomass burning ($\mathrm{B}{\mathrm{C}}_{\text{BB}}$) transported to Xishuangbanna in 2017. Haze months, between haze and clean months, and clean months in Xishuangbanna were defined according to daily PM_2.5 concentrations of >75, 35–75, and <35 µg/m³, respectively. Results showed that the transport efficiency density (TED) of BC transported to Xishuangbanna was controlled by the prevailing winds in different seasons. The yearly contributions to the effective emission intensity of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were 52% and 48%, respectively. However, when haze occurred in Xishuangbanna, the average $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ contributions were 23% and 77%, respectively. This suggests that open biomass burning (BB) becomes the dominant source in haze months. Myanmar, India, and Laos were the dominant source regions of BC transported to Xishuangbanna during haze months, accounting for 59%, 18%, and 13% of the total, respectively. Furthermore, India was identified as the most important source regions of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ transported to Xishuangbanna in haze months, accounting for 14%. The two countries making the greatest contributions to $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were Myanmar and Laos in haze months, accounting for 55% and 13%, respectively. BC emissions from Xishuangbanna had minimal effects on the results of the present study. It is suggested that open BB in Myanmar and Laos, and anthropogenic emissions in India were responsible for poor air quality in Xishuangbanna.     

Chemical and olfactive impacts of organic matters on odor emission patterns from the simulated construction and demolition waste landfills

The explosive increase of construction and demolition waste (CDW) caused the insufficient source separation and emergency disposal at domestic waste landfills in many developing countries. Some organic fractions were introduced to the CDW landfill process and resulted in serious odor pollution. To comprehensively explore the impacts of organic matters on odor emission patterns, five CDW landfills (OIL), with organic matters/ inert CDW components (O/I) from 5% to 30%, and the control group only with inert components (IL) or organics (OL) were simulated at the laboratory. The chemical and olfactive characters of odors were evaluated using the emission rate of 94 odorants content (ER_total), theory odor concentration (TOC_total), and e-nose concentration (ER_ENC), and their correlations with waste properties were also analyzed. It was found that the main contributors to ER_total (IL: 93.0% NH₃; OIL: 41.6% sulfides, 31.0% NH₃, 25.9% oxygenated compounds) and TOC total (IL: 64.1% CH₃SH, 28.2% NH₃; OIL: 71.7% CH₃SH, 24.8% H₂S) changed significantly. With the rise of O/I, ER_total, TOC_total, and ER_ENC increased by 10.9, 20.6, and 2.1 times, respectively. And the organics content in CDW should be less than 10% (i.e., DOC<101.3 mg/L). The good regressions between waste properties (DOC, DN, pH) and ${\mathrm{ER}}_{\stackrel{?}{\mathrm{ENC}}}$ (r=0.86, 0.86, -0.88, p<0.05), ${\mathrm{TOC}}_{\stackrel{?}{\mathrm{total}}}$ (r=0.82, 0.79, -0.82, p<0.05) implied that the carbon sources and acidic substances relating to organics degradation might result in that increase. Besides, the correlation analysis results (${\mathrm{ER}}_{\stackrel{?}{\mathrm{ENC}}}$ vs. ${\mathrm{TOC}}_{\stackrel{?}{\mathrm{total}}}$, r=0.96, p<0.01; vs. ${\mathrm{ER}}_{\stackrel{?}{\mathrm{total}}}$, r=0.86, p<0.05) indicated that e-nose perhaps was a reliable odor continuous monitoring tool for CDW landfills.     

Effectiveness evaluation of water-sprinkling in controlling urban fugitive road dust based on TRAKER method: A case study in Baoding, China

Fugitive road dust (FRD) contributes a great deal to urban rainwater and air pollution and is commonly controlled by water-sprinkling in most Chinese cities. However, there is a lack of information on its effectiveness. We used the Testing Re-entrained Aerosol Kinetic Emissions from Roads (TRAKER) method to monitor different types of roads in Baoding city before and within 1 hr after water-sprinkling and obtained the road dirtiness index (a) and PM concentration in the road environment ($T_{\mathrm{T}}^{*}$), to evaluate the removal efficiency for PM deposited on the road surface (${\eta }_a$) and the reduction efficiency for the PM concentration in the road environment (${\eta }_{\text{PM}}$). The results give that the ${\eta }_a$ for three types of roads is ranked: branch road (87%-–100%) > major arterial road (80%-83%) > minor arterial road (68%-77%), and the ${\eta }_{\text{PM}}$ ranked: minor arterial road (70%) > branch road (46%-58%) > major arterial road (37%-53%). The ${\eta }_a$ and ${\eta }_{\text{PM}}$ varied non-linearly with time and presented a quadratic curve. The average effective control time (${\eta }_{\mathit{a}}$> 0) was 62 min on the major and minor arterial roads, and much longer than 1 hr on branch roads. The ${\eta }_{\text{PM}}$ values diminished completely by 72 min on average from the end of sprinkling for the three types of roads. Water-sprinkling can remove PM₁₀ particles from the road surface and reduce their concentration in the road environment more thoroughly than PM_2.5. Our findings could be helpful for controlling urban FRD emissions more efficiently and precisely.     

Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2

Based on the experimental and theoretical methods, the NO selective catalytic oxidation process was proposed. The experimental results indicated that lattice oxygen was the active site for NO oxide over the $\mathrm{\alpha }$-MnO₂(110) surface. In the theoretical study, DFT (density functional theory) and periodic slab modeling were performed on an $\mathrm{\alpha }$-MnO₂(110) surface, and two possible NO oxidation mechanisms over the surface were proposed. The non-defect $\mathrm{\alpha }$-MnO₂(110) surface showed the highest stability, and the surface O_s (the second layer oxygen atoms) position was the most active and stable site. O₂ molecule enhanced the joint adsorption process of two NO molecules. The reaction process, including O₂ dissociation and O=N-O-O-N=O formation, was calculated to carry out the NO catalytic oxidation mechanism over $\mathrm{\alpha }$-MnO₂(110). The results showed that NO oxidation over the $\mathrm{\alpha }$-MnO₂(110) surface exhibited the greatest possibility following the route of O=N-O-O-N=O formation. Meanwhile, the formation of O=N-O-O-N=O was the rate-determining step.     

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

Retrieval of refractive index of ultrafine single particle using hygroscopic growth factor obtained by high sensitive surface plasmon resonance microscopy

When exposed to different relative humidities (RHs), the optical properties of atmospheric aerosols will change because of changes in the aerosol particle size and complex refractive index (RI), which will affect haze formation and global climate change. The potential contributions of ultrafine particles to the atmospheric optical characteristics and to haze spreading cannot be ignored because of their high particle number concentrations and strong diffusibility; measurement of the optical properties of wet ultrafine particles is thus highly important for environmental assessment. Therefore, a surface plasmon resonance microscopy with azimuthal rotation illumination (SPRM-ARI) system is designed to determine the RIs of single particle aerosols with diameters of less than 100 nm in the hygroscopic growth process. Measurements are taken using mixed single particles with different mass ratios. The RIs of mixed single aerosols at different RHs are retrieved by measuring the scattering light intensity using the SPRM-ARI system and almost all the RIs of the bicomponent particles with different mass ratios decrease with increasing water content under high RH conditions. Finally, for each of the bicomponent particles, the maximum standard deviations for the retrieved RI values are only $2.06\times {10}^{-3}$, $3.08\times {10}^{-3}$ and $3.83\times {10}^{-3}$, corresponding to the NaCl and NaNO₃ bicomponent particles with a 3:1 mass ratio at 76.0% RH, the NaCl and glucose particles with a 1:3 mass ratio at 89.0% RH, and the NaCl and OA particles with a 1:1 mass ratio at 78.0% RH, respectively; these results indicate that the high-sensitivity SPRM-ARI system can measure the RI effectively and accurately.     

Adsorptive removal of phosphate by the bimetallic hydroxide nanocomposites embedded in pomegranate peel

This study aimed to fabricate new and effective material for the efficiency of phosphate adsorption. Two types of adsorbent materials, the zirconium hydroxides embedded in pomegranate peel (Zr/Peel) and zirconium-lanthanum hydroxides embedded in pomegranate peel (Zr–La/Peel) were developed. Scanning electronic microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) were evaluated to give insight into the physicochemical properties of these adsorbents. Zr–La/Peel exceeded the adsorption efficiency of Zr/Peel adsorbents in batch adsorption experiments at the same pH level. The peel as a host can strive to have a strong “shielding effect” to increase the steadiness of the entrenched Zr and La elements. La and Zr are hydroxide metals that emit many hydrogen ions during the hydrolysis reaction, which contribute to protonation and electrostatic attraction. The highest adsorption capacity of La–Zr/Peel for phosphate was calculated to be 40.21 mg/g, and pseudo second-order equation is very well fitted for kinetic adsorption. Phosphate adsorption efficiency was reduced by an increase of pH. With the background of coexisting Cl^?, little effect on adsorption efficiency was observed, while adsorption capacities were reduced by almost 20–30% with the coexistence of ${{\text{SO}}_4}^{2?}$, ${{\text{NO}}_3}^{?}$ and humic acid (HA).     

Effects of sludge age on anaerobic acidification of waste activated sludge: Volatile fatty acids production and phosphorus release

Effects of sludge age on volatile fatty acids (VFAs) production and Phosphorus (P) release during anaerobic acidification of waste activated sludge (WAS) were investigated. Sequencing batch reactors (SBR) fed with simulating domestic sewage were applied to produce WAS of different sludge ages, and batch tests were used for anaerobic acidification. The maximum dissolved total organic carbon, release of  ${\text{PO}}_4^{3+}?\mathrm{P}$, and accumulation of acetate (C2), propionate (C3), butyrate (C4), and valerate (C5) decreased by 56.2%, 55.8%, 52.6%, 43.7%, 82.4% and 84.8%, respectively, as the sludge age of WAS increased from 5 to 40 days. Limited degradation of protein played a dominating role in decreasing DTOC and VFAs production. Moreover, the increase in molecular weight of organics and organic nitrogen content in the supernatant after acidification suggested that the refractory protein in WAS increased as sludge age extended. Although the production of C2, C3, C4, and C5 from WAS decreased as the sludge age increased, the proportions of C2 and C3 in VFAs increased, which might be due to the declined production of C5 from protein and the faded genus Dechlorobacter. Keeping sludge age of WAS at a relatively low level (<10 days) is more appropriate for anaerobic acidification of WAS as internal carbon sources and P resource.     

Formation mechanisms of nitrous acid (HONO) during the haze and non-haze periods in Beijing, China

As an important precursor of hydroxyl radical (OH), nitrous acid (HONO) plays a significant role in atmospheric chemistry. Here, an observation of HONO and relevant air pollutants in an urban site of Beijing from 14 to 28 April, 2017 was performed. Two distinct peaks of HONO concentrations occurred during the observation. In contrast, the concentration of particulate matter in the first period (period Ⅰ) was significantly higher than that in the second period (period Ⅱ). Comparing to HONO sources in the two periods, we found that the direct vehicle emission was an essential source of the ambient HONO during both periods at night, especially in period Ⅱ. The heterogeneous reaction of NO₂ was the dominant source in period Ⅰ, while the homogeneous reaction of NO with OH was more critical source at night in period Ⅱ. In the daytime, the heterogeneous reaction of NO₂ was a significant source and was confirmed by the good correlation coefficients (R²) between the unknown sources (P_unknown) with NO₂, PM_2.5, NO₂ × PM_2.5 in period Ⅰ. Moreover, when solar radiation and OH radicals were considered to explore unknown sources in the daytime, the enhanced correlation of P_unknown with photolysis rate of NO₂ and OH ($J_{{\mathrm{NO}}_2}$ × OH) were 0.93 in period Ⅰ, 0.95 in period Ⅱ. These excellent correlation coefficients suggested that the unknown sources released HONO highly related to the solar radiation and the variation of OH radicals.     

臭氧层耗损研究的进展评述

８０年代以业南极上空平流层臭氧层不断减少，１９９８年９月臭氧洞的面积和深度达历史最高记录。平流层臭氧耗损会导致到达在面地的有害紫外线增加，损害人类的健康和破坏地球生态。介绍了了臭氧层损耗的机理、现状、该领域的研究进展和复旦大学的研究结果。     

黄磷诱发臭氧化处理废水实验研究

黄磷与氧气在潮湿空气中反应诱发臭氧等活性粒子,可应用于难降解的有机废水处理。实验结果表明,聚乙烯废水、乙醇废水脱色率可达77％－87％。对分散染料废水脱色率仅达26．3％。半黄磷直接投加入聚乙烯废水,乙醛废水诱发反应产生的臭氧等活性粒子通入废水的实验结果表明,以废水体积1L计,投加黄磷5g,脱色反应基本完成,脱色率达80％;CODCr去除量与黄磷投加量成正比。     

Characteristics of one-year observation of VOCs, NOx, and O3 at an urban site in Wuhan, China

A continuous online observation of ozone and its precursors(NOx, VOCs) was carried out in central urban Wuhan from September 2016 to August 2017. The concentration levels of ozone,NOx, VOCs and their variations in urban Wuhan were analyzed, as well as effects of VOCs on ozone photochemical generation and the main controlling factors for ozone production. During the observation period, the average concentrations of ozone and NOx in Wuhan was 22.63 and30.14 ppbv, respectively, and the average concentration of VOCs was 32.61 ppbv(42.3% alkanes,13.0% alkenes, 10.0% aromatics, 7.3% acetylene, 9.9% OVOCs, and 10.5% halohydrocarbons).Ozone concentration was higher in spring and summer as compared with autumn and winter,wheras VOCs and NOx concentratios were lower in spring and summer but higher in autumn and winter. Aromatics and alkenes, two of VOCs species, showed the highest contributions to ozone formation potential in Wuhan(35.7% alkenes, 35.4 aromatics, 17.5% alkanes, 8.6% OVOCs,1.6% halogenated hydrocarbons, and 1.4% acetylene). Among all VOCs species, those with the highest contribution were ethylene, m-xylene, toluene, propylene and o-xylene. The contribution of these five compounds to the total ozone formation potential concentration was 43.90%.Ozone-controlling factors in Wuhan changed within one day; during the early morning hours(6:00–9:00), VOCs/NOx was low, and ozone generation followed a VOCs-limited regime.However, during the peak time of ozone concentration(12:00–16:00), the ratio of VOCs/NOx was relatively high, suggesting that ozone generation followed a NOx-limited regime.     

氯氟烃及其替代物

近年来,臭氧衰竭比原先预料的更严重,对人类健康和环境构成了严重威胁。“蒙特利尔议定书”和“大气清洁法案”要求2000年要完全清除致臭氧衰竭物质——氯氟烃(CFCs)的生产和使用。目前,世界各地积极开发CFCs的替代物,以加速转换。虽然已开发的氧氯氟烃(HCFCs)、氢氟烃(HFCs)等替代物与CFCs相比还有一定缺点,但最终一定会实现替代转换。     

Surface ozone scenario and air quality in the north-central part of India

Tropospheric pollutants including surface ozone(O_3), nitrogen dioxide(NO_2), carbon monoxide(CO) and meteorological parameters were measured at a traffic junction(78°2′ E and 27°11′ N) in Agra, India from January 2012 to December 2012. Temporal analysis of pollutants suggests that annual average mixing ratios of tropospheric pollutants were: O_3— 22.97 ± 23.36 ppbV,NO_2— 19.84 ± 16.71 ppb V and CO — 0.91 ± 0.86 ppm V, with seasonal variations of O_3 having maximum mixing ratio during summer season(32.41 ± 19.31 ppbV), whereas lowest was found in post-monsoon season(8.74 ± 3.8 ppbV). O_3 precursors: NO_2 and CO, showed inverse relationship with O_3. Seasonal variation and high O_3 episodes during summer are associated with meteorological parameters such as high solar radiation, atmospheric temperature and transboundary transport. The interdependence of these variables showed a link between the daytime mixing ratios of O_3 with the nighttime level of NO_2. The mixing ratios of CO and NO_2 showed tight correlations, which confirms the influence of vehicular emissions combined with other anthropogenic activities due to office/working hours, shallowing, and widening of boundary layer. FLEXTRA backward trajectories for the O_3 episode days clearly indicate the transport from the NW and W to S/SE and SW direction at Agra in different seasons.     

臭氧对蚕豆外部形态的影响及叶绿素a的表征作用

本文通过臭氧对蚕豆急性伤害的研究，描述了蚕豆遭受臭氧急性伤害的反应症状，并阐明蚕豆叶片叶绿素a的变化对蚕豆受害程度的表征作用。     

臭氧发生器应用技术现状

概述了臭氧在环境保护中的重要作用，介绍了臭氧发生器应用现状及其处理技术的进展，强调了高效臭氧发生器在废水处理中的现实意义。     

水中臭氧分解动力学研究

在磷酸盐缓冲液中研究了臭氧的自分解,根据臭氧分解机理推导出其动力学方程。由不同温度和pH值下的实验结果确定出kT,0,n以及活化能E。      

有机废水湿式O_3氧化降解过程的研究

采用 O3 湿式氧化降解含氯乙烯的有机废水 ,实验研究了不同 p H、不同温度以及不同初始氯乙烯浓度对反应过程的影响 ,初步探讨了在高 p H时 O3 的自分解催化产生自由基 OH·机理和污染物的氧化降解过程。通过实验研究与分析 ,获得了氯乙烯有机废水 O3 氧化过程的动力学方程     

新型铅合金电极用于电解法制备臭氧的研究

探讨了Pb、Pb-0.5％Sn、Pb-0.8％Sn、Pb-1.78%Sn、Pb-1.35%Sn-0.049?、Pb-0.8％Sn-0.1％Ca-0.1％Ce铅合金电极的电化学性能、耐腐蚀性能和电解产生臭氧的产率，及铅合金电极在不同电流强度条件下电解产生臭氧的最佳条件。实验结果表明：掺杂了Sn，Ce等金属能提高铅合金电极的析氧电位和臭氧产率，其中当以PB-0.8％Sn-0.1％Ca-0.1％Ce合金电极为阳极，铂电极为阴极。饱和硫酸钾溶液为电解液，电流强度为7.5mA时，臭氧产率最高达到19％。