Formation mechanism and control strategy for particulate nitrate in China

Over the past decade, fine particulate matter (PM) pollution in China has been abated significantly, benefiting from strict emission control measures, but particulate nitrate continues to rise. Here, we review the progress in particulate nitrate (pNO₃⁻) pollution characterization, nitrate formation mechanisms, and the proposed control strategies in China. The spatial and temporal distributions of pNO₃⁻ are summarized. The current status of knowledge on the chemical mechanism is updated, and the significance of its formation pathways is assessed by various approaches such as field observation and modelling of nitrate production rate, as well as isotopic analysis. The factors impacting pNO₃⁻ formation and the corresponding pollution regulation strategies are discussed, in which the importance of atmospheric oxidation capacity and ammonia are addressed. Finally, the challenges and open questions in pNO₃⁻ pollution control in China are outlined.     

Quantifying the characteristics of particulate matters captured by urban plants using an automatic approach

It is widely accepted that urban plant leaves can capture airborne particles. Previous studies on the particle capture capacity of plant leaves have mostly focused on particle mass and/or size distribution. Fewer studies, however, have examined the particle density, and the size and shape characteristics of particles, which may have important implications for evaluating the particle capture efficiency of plants, and identifying the particle sources. In addition, the role of different vegetation types is as yet unclear. Here, we chose three species of different vegetation types, and firstly applied an object-based classification approach to automatically identify the particles from scanning electron microscope(SEM)micrographs. We then quantified the particle capture efficiency, and the major sources of particles were identified. We found(1) Rosa xanthina Lindl(shrub species) had greater retention efficiency than Broussonetia papyrifera(broadleaf species) and Pinus bungeana Zucc.(coniferous species), in terms of particle number and particle area cover.(2) 97.9% of the identified particles had diameter ≤10 μm, and 67.1% of them had diameter ≤2.5 μm. 89.8% of the particles had smooth boundaries, with 23.4% of them being nearly spherical.(3) 32.4%–74.1% of the particles were generated from bare soil and construction activities, and 15.5%–23.0% were mainly from vehicle exhaust and cooking fumes.     

Study on superoxide and hydroxyl radicals generated in indirect electrochemical oxidation by chemiluminescence and UV-Visible spectra

The generation and transformation of radicals on the cathode of indirect electrochemical oxidation were studied by chemilumines- cence(CL)and UV-Visible spectra in the reactor with a salt bridge that connected the separated chambers.The CL intensity of 4×10~(-9)mol/L luminol on the cathode with bubbling oxygen was about seven times that of the intensity without it,which was because of the generation of reactive oxygen species(ROS).The existence of ROS,especially the generation of the superoxide radical,c...     

基于不同自由基的高级氧化技术对水中诺氟沙星的去除效果

抗生素在水中的赋存浓度较低,难以被常规的城市污水处理系统有效去除。考察了紫外光联合氯(UV/氯)、双氧水(UV/H2O2)、过硫酸盐(UV/PS) 3种高级氧化体系对诺氟沙星(NFX)的去除效果。结果表明:UV/氯体系降解NFX相比于其他2种具有显著的高效性,当溶液初始pH为7、氯浓度为30 μmol/L时,NFX在2 min内的去除率可达98.67%,相同氧化剂浓度下,UV/H2O2和UV/PS体系10 min内对NFX的去除率仅为41.41%和65.73%;对于UV/氯体系,NFX的去除率随氯浓度的升高而上升,同时考虑成本,最优氯浓度为30 μmol/L;pH影响3种体系对NFX的去除速率,但效果不同,对于UV/氯体系,强碱性条件有利于NFX的去除,对于UV/H2O2和UV/PS体系,中性及弱碱性更有利于NFX的去除;水体基质Cl-对UV/氯体系去除NFX有抑制作用,但对UV/H2O2和UV/PS体系影响不大; HCO 3 - 对3种体系去除NFX均有抑制作用。     

Physicochemical characterization of forest and sugarcane leaf combustion's particulate matters using electron microscopy, EDS, XRD and TGA

Physical characteristics and quantitative elemental composition of PM and residual ash produced from sugarcane leaves (SCL) combustion were investigated using TEM-EDS compared with forest leaves (FRL). SEM-EDS was used to analyze the microstructure and chemical composition of biomass raw leaves and PM. XRD analysis was also performed to investigate the characterization of the crystalline nanostructure, structure of PM, and residual ash compared to the TEM image processing method. The oxidation kinetics of biomass raw materials, PM, and residual ash were investigated by TGA. The morphology of fine and ultrafine agglomerate structure of SCL soot and residual ash are not significantly different from the FRL soot and residual ash. The average diameter sizes of single primary nanoparticles of SCL and FRL soot are approximately 37 nm and 35 nm, while the sizes of residual ash are about 18 nm and 22 nm, respectively. The single primary nanoparticles of soot are mainly composed of curve line crystallites of carbon fringes, while residual ash is composed of straight-line lattice fringes. The average fringe lengths of SCL and FRL soot are about 1.25 nm and 1.04 nm from the outer shell and 0.89 nm and 0.74 nm from the inner core. The interlayer spacing of curve line carbon fringes of SCL and FRL soot is approximately 0.359 nm and 0.362 nm by the TEM image analysis and it was matched with XRD analysis. The biomass PMs are mainly composed of soot, Si, Ca, and K compounds: SiO₂, CaCO₃, and KCl.     

Emission factors of particulate matter, CO and CO2 in the pyrolytic processing of typical electronic wastes

A self-designed experimental device was employed to simulate the pyrolytic dismantling process of selected electronic wastes(E-wastes), including printed wiring boards(PWBs)and plastic casings. The generated particulate matter(PM) of different particle sizes, carbon monoxide(CO) and carbon dioxide(CO_2) were determined, and the corresponding emission factors(EFs) were estimated. Finer particles with particle sizes of 0.4–2.1 μm accounted for78.9% and 89.3% of PM emitted by the pyrolytic processing of PWBs and plastic casings,respectively, and the corresponding EFs were 9.68 ± 4.81 and 18.49 ± 7.2 g/kg, respectively.The EFs of CO and CO_2 from PWBs and plastic casings were 55.9 ± 26.9 and 1182 ± 439 g/kg,and 133.6 ± 34.6 and 2827 ± 276 g/kg, respectively. Compared with other emission sources,such as coal, biomass, and traffic exhaust, the EFs of E-wastes were relatively higher,especially for PM. There were significant positive correlations(p 0.05) of the initial contents of carbon and nitrogen in PWBs with the related EFs of PM, CO, and CO_2, while the correlations for plastic casings were insignificant. The EFs of CO of PWBs were significantly positively correlated with the corresponding EFs of PM and the parent polycyclic aromatic hydrocarbons(PAHs); however, the same result was not observed for plastic casings.     

DOC对柴油机燃用生物柴油颗粒物微观形貌及SOF组分的影响

为研究氧化催化转化器（DOC）对柴油机燃用调合生物柴油（B0,B20）后排放颗粒物微观形貌及可溶性有机组分（SOF）的影响规律,对DOC作用前后的排气颗粒物进行采样,利用透射电镜（TEM）和气相色谱-质谱仪（GC-MS）开展颗粒物理化特性研究.结果表明：未加装DOC时,与B0相比,B20排放颗粒物基本碳粒子粒径减小,分形维数增加,团聚堆积现象加剧;SOF组分中的脂类和酸类物质质量分数增加,烷烃类、芳香烃和酚类物质质量分数减少,C26~C35的质量分数降低.加装DOC后,B0和B20排气颗粒物团簇程度降低,分形维数降幅分别为10.1%和15.5%;SOF组分中芳香烃类和酚类物质质量分数增加,烷烃类、脂类、酸类质量分数减小,C15~C25质量分数下降;B0排放颗粒物SOF中C26~C35质量分数降低41.4%,而B20增加865.8%.     

Sister chromatid exchange and DNA damage in human lymphocytes induced by air-dust in Lanzhou City: involvement in free radicals

The air-dust samples collected from petro-chemical industrial region in the suburb of Lanzhou and from a certain rural region 64 km away from the city were extracted, with a mixed solvent (benzene: hexane: isopropanol=7:2:1) for 8 hours. A strong free radical signal at g= 2.00 of air-dust itself and a hyperfine splitting EPR signal of extract from air-dust have been detected. The sister chromatid exchange frequency (SCE) was increased by extracts of both dusts from the industrial region and from the rural region. If a chemical is able to increase SCE up to twice as high as the control, this chemical is considered to be mutagenic and/or carcinogenic. The double SCE frequency concentration is 23 μg/ml for the dust extract obtained from the industrial region and 47μg/ml for that from the rural region. Extracts were able to damage to DNA template. Results indicated that the mutagenicity and/or carcinogenicity of the extracts obtained from the petro-chemical industrial region were stronger than that of the     

催化湿式过氧化氢氧化处理垃圾渗滤液及其DOM光谱分析

采用催化湿式过氧化氢氧化法对转运站垃圾渗滤液进行了处理,研究了影响催化湿式过氧化氢氧化效果的多个因素,并采用三维荧光和紫外-可见光谱对催化湿式过氧化氢氧化处理后水样中的溶解性有机物(DOM)成分变化进行了表征分析.结果显示,在最优实验条件下,COD去除率可达90%以上.光谱分析结果表明,渗滤液中的DOM组分降解效果明显,含有芳香环、双键和羰基共轭体系的有机物的去除效果也比较显著.     

华北地区颗粒物浓度时空分布特征及其因素

利用2017年华北地区各地级及以上城市空气质量浓度等有关数据,对该区域内的颗粒物浓度时空分布特征进行研究,在此基础上进一步利用空间自相关分析方法对该区域内的颗粒物浓度的空间聚集特征进行定量描述,并利用空间计量模型分析了影响华北地区城市颗粒物浓度的因素。结果表明：整体上,华北地区PM_2.5和PM₁₀的污染日出现的平均频率分别为17.25%和14.23%,需重点关注细颗粒物造成的污染。在时间分布上,各省市的颗粒物月均浓度存在“U”型变化,呈现出冬季>秋季≈春季>夏季的规律。在空间分布上,各地级市颗粒物年均浓度具有明显的空间聚集特性,高聚集主要出现在河北南部,低聚集主要出现在内蒙古。空间计量模型表明,风速、降雨量和人均GDP对华北地区城市的PM_2.5和PM₁₀年均浓度均具有显著的负向影响,而第二产业占比、煤炭使用量和机动车保有量均对颗粒物浓度有正向影响,其中煤炭消耗量的影响最大,其次是机动车保有量。上述研究结果可为制定华北地区大气污染控制提供有效的措施和科学依据。     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation

Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature, persulfate concentration and pH conditions were examined in batch experiments. The results showed that, the aniline degradation followed pseudo first-order reaction model. Aniline degradation rate increased with increasing temperature or persulfate concentration. In the pH range of 3 to 11, a low aniline degradation rate was obtained at strong acid system (pH 3), while a high degradation rate was achieved at strong alkalinity (pH 11). Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5, 7 and 9). Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology. And nitrobenzene, 4-4’-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation mechanism of aniline was also tentatively proposed.     

DOC技术对柴油机排放颗粒物数浓度的影响

利用ELPI(电子低压冲击器)对不同转速、不同负荷以及安装DOC(氧化催化转化器)前后颗粒物排放及粒径分布进行了研究. 结果表明:无论安装DOC与否,柴油机排放颗粒物数浓度均随发动机转速的增加而增加. 增大负荷,颗粒物数浓度峰值处的粒径也随之增大. 经过DOC催化转化后,柴油机排放颗粒物的大部分仍呈单峰正态分布,且DOC对核模态粒子的氧化转化效率较高. 经过DOC后,在低转速下,不同粒径的颗粒物数浓度均有所降低;中、高转速下,DOC对粒径大于120 nm的颗粒物数浓度无明显降低作用.      

The oxidation damage of type II collagen by oxy free radicals and fulvic acid

The features of oxidative damage to type II collagen from pig cartilage, induced by · OH, O2- and fulvic acid from epidemic district of KBD, were studied in vitro. The results from amino acid analysis of the damaged collagen are characterized by a decrease in hydroxyproline and proline contents, and an increase in glutamic acid content. The change arc dependent on·OH and FA concentration. It is postulated that the FA or other toxic xenobiotics induce the generation of free radicals, which play the role of the trigger in KBD development.     

Seasonal variation characteristics of hydroxyl radical pollution and its potential formation mechanism during the daytime in Lanzhou

Hydroxyl free radicals(OH radicals) play the main role in atmospheric chemistry and their involving reactions are the dominant rate determining step in the formation of secondary fine particulate matter and in the removal of air pollutants from the atmosphere.In this paper,we studied the seasonal variation characteristics of OH radicals during the daytime in Lanzhou and explored the potential formation mechanism of high concentration OH radicals.We found that the OH radicals in four seasons was ...     

Impacts of continuously regenerating trap and particle oxidation catalyst on the NO2 and particulate matter emissions emitted from diesel engine

Two continuously regenerating diesel particulate filter (CRDPF) with different configurations and one particles oxidation catalyst (POC) were employed to perform experiments in a controlled laboratory setting to evaluate their effects on NO₂, smoke and particle number emissions. The results showed that the application of the after-treatments increased the emission ratios of NO₂/NO_x significantly. The results of smoke emissions and particle number (PN) emissions indicated that both CRDPFs had sufficient capacity to remove more than 90% of total particulate matter (PM) and more than 97% of solid particles. However, the POC was able to remove the organic components of total PM, and only partially to remove the carbonaceous particles with size less than 30 nm. The negligible effects of POC on larger particles were observed due to its honeycomb structure leads to an inadequate residence time to oxidize the solid particles or trap them. The particles removal efficiencies of CRDPFs had high degree of correlations with the emission ratio of NO₂/NO_x. The PN emission results from two CRDPFs indicated that more NO₂ generating in diesel oxidation catalyst section could obtain the higher removal efficiency of solid particles. However this also increased the risk of NO₂ exposure in atmosphere.     

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb₂O₃) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb₂O₃, but few researches concerned the co-transformations of Sb₂O₃ and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb₂O₃. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb₂O₃ using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb₂O₃ was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb₂O₃ was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb₂O₃. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb₂O₃ not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO₃) was formed with the high Mn(II)/Sb₂O₃ ratio_, but without being observed in the low Mn(II)/Sb₂O₃ ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.     

不同离子在CCl4引发自由基反应中的作用及其环境生物学意义

报道了一种简便的ＣＣ１４体外引发自由基反应的模型，以小鼠肝匀浆脂质过氧化产物丙二醛（ＭＤＡ）的ＯＤ５３２ｍｍ值（ＭＤＡ－ＯＤ５３２ｍｍ）作为测定自由基反应的间接指标，研究了Ｈｇ＾２＋、Ｍｎ＾２＋、Ｎｉ＾２＋、Ｃｒ＾３＋、ＳｅＯ３＾２－等离子和Ｓs２Ｏ３水溶液在ＣＣ１４引发自由基反应体系中的作用。结果表明：Ｍn＾２＋能显著抑制自由基的生成，Ｃr＾３＋有一定的抑制作用，而ＨgＴ＾２＋对自由基产生有明显促进     

Simultaneous oxidation of NO, SO2 and Hg0 from flue gas by pulsed corona discharge

A process capable of oxidizing NO, SO2 and Hg0 was proposed simultaneously, which utilized a high-voltage and short-duration positive pulsed corona discharge. By focusing on NO, SO2, and Hg0 oxidation efficiencies, the influences of pulse peak voltage, pulse frequency, initial concentration, electrode number, residence time and water vapor addition were investigated. The results indicate that NO, SO2 and Hg0 oxidation efficiencies depend primarily on the radicals (OH, HO2, O) and the active species (O3, H2O2), etc. produced by the pulsed corona discharge. The NO, SO2 and Hg0 oxidation efficiencies improved as increasing pulse peak voltage, pulse frequency, electrode number and residence time, while they are reduced with an increasing initial concentration. By adding water vapor, SO2 oxidation efficiency is improved remarkably, while NO oxidation efficiency is decreased slightly. In our experiments, the simultaneous NO, SO2, and Hg0 oxidation efficiencies reached to 40%, 98% and 55% with the initial concentrations 479 mg/m3, 1040 mg/m3, and 15.0 ug/m3, respectively.     

不同离子在CCl_4引发自由基反应中的作用及其环境生物学意义

报道了一种简便的CCl_4 体外引发自由基反应的模型 ,以小鼠肝匀浆脂质过氧化产物丙二醛 (MDA)的OD_(53 2nm) 值(MDA OD_(53 2nm)作为测定自由基反应的间接指标 ,研究了Hg~(2 ) 、Mn~(2 ) 、Ni~(2 ) 、Cd~(2 ) 、Cr3 、SeO3 2 -等离子和As2 O3 水溶液在CCl4 引发自由基反应体系中的作用 .结果表明 :Mn2 能显著抑制自由基的生成 ,Cr3 有一定的抑制作用 ,而Hg2 对自由基产生有明显促进作用 ,其它离子的作用不明显 .就CCl4 与无机离子相互作用的环境生物学意义进行了探讨 .