北京地区臭氧污染的来源分析

光化学烟雾污染是影响北京地区夏季空气质量的一个重要环境问题．利用区域空气质量模（CAMx）对2000年6月底至7月初发生在北京地区的臭氧污染过程进行模拟,运用臭氧源识别技术（OSAT）和地区臭氧评估技术（GOAT）,量化了不同地区的污染源排放对北京市城近郊区臭氧污染的贡献,探讨了周边地区排放的臭氧贡献方式问题,分析了北京地区臭氧污染的化学机制特征．研究表明,北京地区臭氧污染分布存在显著差异,并且具有明显的区域性特征,定陵地区的超标臭氧主要受到城近郊区烟羽的严重影响（占55％）,城近郊区则除了受到北京市的前体物排放影响外（占46％）,来自天津市、河北省南部地区的贡献往往也占有重要份额;周边地区对北京市城近郊区的贡献中,直接输入的臭氧约占七层,其余部分以输入前体物的方式贡献臭氧;北京城近郊区的臭氧生成主要受挥发性有机物控制,而在远郊区县和农村地区臭氧生成对氮氧化物变得更为敏感．对北京地区臭氧污染的源排放控制,需要综合考虑各种臭氧来源和不同贡献方式的重要性,以及臭氧生成机制的变化规律．     

Ground-based on-line measurements of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in the Pearl River Delta,China

Aiming at understanding the regional O₃ problem and the impacts of city to rural areas, ambient peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were measured by an on-line instrument at a back garden site (BGS), and a receptor site for urban plume from Guangzhou city. The highest mixing ratios for PAN and PPN were 3.9 and 0.7 ppbv, respectively. PAN and PPN had a similar diurnal pattern as that of O₃. As revealed by the slope of the linear regression line between PPN and PAN, anthropogenic volatile organic compounds (AVOCs) dominated photochemical O₃ production most of the time. From the correlation between PAN and O₃, the regional background level of O₃ was derived to be 28 ± 15 ppbv. Two night-time plumes containing elevated PAN and O₃ were observed, and the backward-trajectory analysis supported the transport of urban plume from Guangzhou city. Based on the temporal variation of PPN/PAN, two day-time episodes were also selected to discuss the influence from Guangzhou.     

Synthesis and light-emitting properties of 2-(<Emphasis Type="Italic">N</Emphasis>-phenyl-α-naphthylamino) and 2-dimesitylboron-7-(<Emphasis Type="Italic">N</Emphasis>-phenyl-α-naphthylamino)-9,9-diethylfluorene

A fluorescent organic triarylamine with a symmetric structure, 2,7-bis(N-α-naphthyl-phenylamino)-9,9-diethylfluorene (NPAEF) was synthesized using two methods, modified Ullmann coupling and modified palladium-catalyzed amination. An activated copper and a combination of Pd(OAc)₂/P(t-Bu)₃ and Pd(dba)₂/P(t-Bu)₃ were selected as catalysts to improve yields of reactions. These synthetic procedures were also successfully applied to an asymmetric 2-dimesitylboron-7-(N-phenyl-α-naphthylamino)-9,9-diethylfluorene (BNPEF). Photoluminescent emission peaks in solid film and in diluted solution of NPAEF were both observed at 461 nm, while the main emission peaks of BNPEF appeared at 422 nm in hexane, and at 480 nm in methanol. The double emission peaks of BNPEF in hexane reflected fine structure in the vibrational state. With an increasing polarity of solvent, the main PL emission peaks were red-shifted and vibrational fine structure disappeared. Additionally, energy levels of NPAEF were investigated and an electroluminescence (EL) device of ITO/PVK:NPAEF/Al was fabricated, which showed a turn-on voltage of 9 V and peaked at 462 nm. The EL spectrum was in good agreement with PL spectrum, which indicated that they were from the same emitting center in the device. Supported by the National Natural Science Foundation of China (Grant Nos. 20674004, 60776039, 60825407 & 10434030), Beijing Commission of Education (Grant No. KM200710015009), Beijing Sustentation Fund for Elitist (Grant No. 20041D0500410), Laboratory of Printing and Packaging Material and Technology and Beijing Area Major Laboratory Project (Grant No. KF200811) and BJTU Fund (Grant No. 2006XM043).     

The enzyme-amplified amperometric DNA sensor using an electrodeposited polymer redox mediator

A highly sensitive method for the detection of a breast cancer-associated BRCA-1 gene is reported. The detection is based on a classical sandwich-type assay using horseradish peroxidase (HRP) as a catalytic label and electrodeposited Os^2+/3+ conducting polymer (PAA-PVI-Os) as a redox mediator. Target DNA could be detected by the HRP-catalyzed reduction of H₂O₂, leading to a limit of detection as low as 10 fM. Supported by the National Natural Science Foundation of China (Grant Nos. 20725516, 20704043, 20873175 & 20805055), Shanghai Municipal Commission for Science and Technology (Grant Nos. 0752nm021 & 07ZR14136), Ministry of Science and Technology (Grant Nos. 2006CB933000, 2007CB936000 & 2007AA06A406), Ministry of Health (Grant No. 2009ZX10603), and China Postdoctoral Science Foundation and Shanghai Postdoctoral Scientific Program (Grant No. 07R214160).     

Sulfonate-based fluorescent probes for imaging hydrogen peroxide in living cells

Based on the mechanism of H₂O₂-mediated hydrolysis of sulfonates, two fluorescein disulfonates compounds (FS-1 and FS-2) were designed and synthesized as the highly selective and sensitive fluorescent probes for imaging H₂O₂ in living cells. The probes were detected with elemental analysis, IR, ¹H NMR and ¹³C NMR. Upon reaction with H₂O₂, the probes exhibit strong fluorescence responses and high selectivity for H₂O₂ over other reactive oxygen species and some biological compounds. Furthermore, the sulfonate-based probes, as novel fluorescent reagents, are cell-permeable and can detect micromolar changes in H₂O₂ concentrations in living cells by using confocal microscopy. Supported by the National Basic Research Program of China (Grant No. 2007CB936000), the National Natural Science Funds for Distinguished Young Scholar (Grant No. 20725518), Major Program of the National Natural Science Foundation of China (Grant No. 90713019), the National Natural Science Foundation of China (Grant No. 20875057), the Natural Science Foundation of Shandong Province, China (Grant No. Y2007B02), and the Science and Technology Development Programs of Shandong Province, China (Grant No. 2008GG30003012)     

New bienzymatic strategy for glucose determination by immobilized-gold nanoparticle-enhanced chemiluminescence

Bienzymatic biosensor for the determination of glucose by flow injection chemiluminescence (CL) detection was proposed. Hybrids of gold nanoparticles (GNPs) and chitosan were chosen as the immobilization matrix of glucose oxidase (GOD) and horseradish peroxidase (HRP) to fabricate the biosensors with silane-pretreated glass microbeads. After the enzyme catalyzing oxidation of glucose in GOD biosensor, the produced H₂O₂ flowed into HRP biosensor to react with luminol. The doped GNPs in chitosan were found to enhance the classical CL reaction of luminol-H₂O₂-HRP. The CL enhancement was investigated in detail by CL and UV-visible spectrum. Under the optimized experimental conditions, glucose could be determined in a linear range from 0.01 to 6.0 mmol/L with a detection limit of 5.0 μmol/L at 3σ. The accuracy of the proposed method was examined by detecting the glucose level in four clinical serum samples from hospital. The proposed method provides a new alternative to determine glucose. Supported by the Natural Science Foundation of Shandong Province (Grant No. Q2007B03), the Doctoral Fund of Qingdao University of Science and Technology (Grant No. 0022141), and the National Natural Science Foundation of China (Grant No. 20775038)     

Assessment of the sequential principal component analysis chemometric tool to identify the soluble atmospheric pollutants in rainwater

In this study a new method of principal component (PC) analysis, sequential PC analysis (SPCA), is proposed and assessed on real samples. The aim was to identify the atmospheric emission sources of soluble compounds in rainwater samples, and the sample collection was performed with an automatic sampler. Anions and cations were separated and quantified by ion chromatography, whereas trace metals and metalloids were determined by inductively coupled plasma mass spectrometry. SPCA results showed eight interfering PCs and ten significant PCs. The interfering cases originated from different atmospheric sources, such as resuspended crustal particles, marine aerosols, urban traffic and a fertilizer factory. The significant PCs explained 84.6% of the total variance; 28.1% accounted for the main contribution, which was resuspended industrial soil from a fertilizer factory containing NO₂^-, NH₄⁺, NO₃^-, SO₄^2-, F^-, Al, K⁺, Mn, Sb and Ca²⁺ as indicators of the fertilizer factory. Another important source (15.0%) was found for Na⁺, Mg²⁺, K⁺, Cl^- and SO₄^2-, which represents the marine influence from south and southwest directions. Emissions of Ba²⁺, Pb, Sr²⁺, Sb and Mo, which represent a traffic source deposited in soils, were identified as another abundant contribution (12.1%) to the rainwater composition. Other important contributions to the rainwater samples that were identified through SPCA included the following: different urban emissions (Cu, As, Cd, Zn, Mo and Co, 18.1%), emissions from vegetation (HCOO^-, 7.7%) and emissions from industrial combustion processes (Ni, V 15.6%). The application of SPCA proved to be a useful tool to identify the complete information on rainwater samples as indicators of urban air pollution in a city influenced mainly by vehicle traffic emissions and resuspended polluted soils.     

Analysis of ambient ozone and precursor monitoring data in a densely populated residential area of Kuwait

Analysis of ozone (O₃) pollution in the Salmiyah residential area of Kuwait was conducted over a period of 12 months, from March 2008 to February 2009. Salmiyah is a densely populated area, mainly by expatriates. Apartment buildings are the dominant type of dwellings available in Salmiyah. The area is surrounded by major highways that get congested with traffic at peak hours of the day. The objectives of this work were: to monitor ambient tropospheric levels of O₃ and its precursors both for test comparing such levels to international standard limits and for assessing their health effects, to understand their diurnal behaviors, and to study their seasonal trends. The results of this study indicated that O₃, nitrogen dioxide (NO₂), and non-methane hydrocarbons (NMHC) exceeded the ambient air quality standards during specific times of the year. The diurnal patterns for NO₂ and NMHC showed three peaks which were directly dependent on high traffic density, while only two daily maxima were observed in the case of O₃. Finally, O₃ compared to its precursors exhibited a completely opposite monthly mean distribution with the highest concentration levels detected during the summer season (July and August).     

Preparation and Characterization of FeCo-Al2O3 and Al2O3 Aerogels

Nanocrystalline γ-Al₂O₃ and FeCo-Al₂O₃ nanocomposites containing FeCo alloy nanoparticles well dispersed in the nanocrystalline γ-Al₂O₃ matrix were successfully obtained by the sol-gel method using aluminum tri-sec-butoxide and iron and cobalt nitrates as precursors. The gels were submitted to high temperature supercritical drying which allowed to obtain aerogels with high surface areas and pore volumes.     

V2O5/C catalyst for liquid phase oxidation of glyoxal to glyoxylic acid

A study of the catalytic activity of V₂O₅/C catalyst for the oxygen oxidation of glyoxal has been made, showing that glyoxylic acid can be formed without control of pH value and there is little oxalic acid from the excessive oxidation of glyoxylic acid. The studies of XRD and TEM have shown that V₂O₅ diffraction peaks gradually strengthen with the increase of the content of V₂O₅. With the content of 3% V₂O₅ and the calcination temperature of 573 K, V₂O₅/C catalyst displayed the best activity and selectivity. The conversion of glyoxal and the selectivity of glyoxylic acid reached 18.76% and 77.70% after 5 h, respectively. Moreover, V₂O₅/C catalyst showed small deactivation after recycling three times, which indicates that V₂O₅/C has a higher stability than noble metal catalysts in the reaction medium. Supported by the Technology Research and Development Project for University of Shanxi Province of China (Grant No. 20051272)     

Preparation of magnesium and calcium ferrites from the thermolysis of M3[Fe(cit)2]2·xH2O precursors

Magnesium and calcium ferrites have been prepared from the thermolysis of M₃[Fe(C₆H₅O₇)₂]₂·xH₂0 (M=Mg, Ca) precursors. Thermal decomposition of the precursors has been studied employing various physico-chemical techniques, i.e., TG-DSC, XRD, IR and Mössbauer spectroscopy. After dehydration the anhydrous precursors undergo an abrupt oxidative pyrolysis to yield α-Fe₂O₃ and a metastable acetone-dicarboxylate intermediate. A subsequent exothermic decomposition leads to the formation of MgO and CaCO₃ from the respective intermediates. Finally ferrite is formed as a result of solid state reaction between MO/MCO₃ and α-Fe₂O₃. Nanosized ferrites of the stoichiometry MgFe₂O₄ and Ca₂Fe₂O₅ have been obtained from magnesium and calcium bis(citrato) ferrates(III). The temperature of ferrite formation is much lower than possible in conventional ceramic method. The results have been compared with the respective oxalate and maleate precursors.     

Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

A study of the atmospheric photochemical reaction of CF₃ radical with CO and O₂ was performed by using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS). The electronic structures and mechanism of ionization and dissociation of CF₃OC(O)OOC(O)-OCF₃ were investigated. It was indicated that the two bands on the photoelectron spectrum of CF₃OC(O)OOC(O)OCF₃ are the result of ionization of an electron from a lone pair of oxygen and a fluorine lone pair of CF₃ group. The outermost electrons reside in the oxygen lone pair. The experimental and theoretical first vertical ionization energy is 13.21 and 13.178 eV, respectively, with the PES and OVGF method. They are in good agreement. The photo ionization and dissociation processes were discussed with the help of theoretical calculations and PES-PIMS experiment. After ionization, the parent ions prefer the dissociation of the C—O bond and giving the fragments CF₃OCO⁺ and CF₃⁺. It demonstrated that the ultraviolet photoelectron and photoionization mass spectrometer could be applied widely in the study of atmospheric photochemical reaction. Supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KZCX2-YW-205), Hundred Talents Fund, 973 Program of Ministry of Science and Technology of China (Grant No. 2006CB403701) and the National Natural Science Foundation of China (Grant Nos. 20577052, 20673123)     

In-situ synthesis of PHEMA magnetic nanogels via photochemical method

One-pot synthesis of magnetic nanogels via photochemical method is reported in this paper. Poly(2-hydroxyethyl methacrylate)(PHEMA) magnetic nanogels are synthesized by in-situ polymerization of 2-hydroxyethyl methacrylate (HEMA) and N,N′-methylene-bis-(acrylamide)(MBA) in Fe₃O₄ aqueous suspension under UV irradiation. The structure and compositions of magnetic nanogels are characterized by FTIR, TGA, SEM, TEM and PCS. TGA measurement indicates that magnetic nanogels contain 90% magnetite. Both naked Fe₃O₄ and magnetic nanogels are superparamagnatic at room temperature according to magnetization curves. The swollen capability of the hydrogel shell is proved by contrasting the particles sizes obtained by SEM, TEM and PCS. Particle diameters can be manipulated by changing monomer concentration and irradiation time. A mechanism of the coating process is proposed. Supported by the Shanghai Municipal Commission for Special Project of Nanometer Science and Technology (Grant No. 0452nm068)     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Highly efficient heterogeneous procedure for the conjugate addition of amines to electron deficient alkenes

The novel efficient procedure has been developed for the conjugate addition of amines to electron deficient alkenes. K₂CO₃ supported on different carriers have been synthesized for the conjugate addition of amines and alkenes. After optimizing the reaction conditions, K₂CO₃/MgO was chosen as the most efficient catalyst for the reactions. The results showed that the catalyst was very efficient for the conjugate addition of amines to electron deficient alkenes with the excellent yields in several minutes. Operational simplicity, without need of any solvent, low cost of the catalyst used, high yields, reusability, excellent chemoselectivity, and applicability to large-scale reactions are the key features of this methodology. Supported by the National Key Project of Scientific and Technical Supporting Programs Funded by Ministry of Science and Technology of China (Grant No. 2006BAE03B06), Shanghai Leading Academic Discipline Project (Grant No. B409), and Shanghai International Cooperation of Science and Technology Project (Grant No. 06SR07101)     

Application of receptor models to airborne particulate matter

The human activities in their various aspects cause a change in the natural air quality. This change results more marked in very populated and in high industrialized areas. Some pollutants emitted are typical of a particular activity. Each source of pollution is identified by its profile in the composition of the emissions in the environment. Multivariate receptor models can be used in order to apportion pollutants to the different sources assessing the contribution of each source to the total pollution.This paper deals with the application of Absolute Principal Component Scores (APCS) receptor model to data obtained from the automatic network of air quality monitoring in the city of Bari (South Italy). The parameters monitored by automatic networks, as bihourly values, are PM₁₀, NO_x, CO, Benzene, Toluene, Xilene. The data shown in this paper concerning 1 month almost of sampling in different monitoring stations of Bari Municipality during the period of time from January 2005 to April 2006. Moreover preliminary results obtained applying the APCS model to daily PM_2.5 samples collected during SITECOS PRIN project are shown. The results concerning data collected in corso Cavour (Bari) during the month of October 2005.The results obtained by APCS receptor model seem to suggest a poor contribution of the “vehicular traffic source” and a relevant contribution of the “secondary particulate source” to particulate matter concentrations.     

Synthesis and characterization of gallium oxide nanoparticles

This review is based on the literature describing several methods for the synthesis of gallium oxide nanoparticles. Several techniques have been used for the synthesis of gallium oxide Ga₂O₃ nanoparticles. Gallium oxide Ga₂O₃ nanoparticles have been synthesized from different precursors. Different synthetic methods and different precursors produce nanoparticles which vary in size and shape. Over a dozen of synthetic methods for preparation of gallium oxide Ga₂O₃ nanoparticles together with the characterization techniques used have been discussed.     

Controlling the morphology of yttrium oxide through different precursors synthesized by hydrothermal method

Y₂O₃ sheets, rods, needles and tubes were synthesized from three precursors through hydrothermal reactions followed by calcination. The phase distribution and decomposition behaviors of the three precursors, Y₂(OH)_5.14(NO₃)_0.86·H₂O, Y₄O(OH)₉(NO₃) and hexagonal Y(OH)₃, were investigated. The reaction temperature and initial pH value during the hydrothermal reaction showed great influence on the shape and particle size of the products. The precursors were converted to Y₂O₃ particles with the retained original morphology of the precursors.     

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady‐State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

Levels of the stabilized Criegee Intermediate (sCI), produced via the ozonolysis of unsaturated volatile organic compounds (VOCs), were estimated at two London urban sites (Marylebone Road and Eltham) and one rural site (Harwell) in the UK over the period of 1998–2012. The steady‐state approximation was applied to data obtained from the NETCEN (National Environmental Technology Centre) database, and the levels of annual average sCI were estimated to be in the range of 30–3000 molecules cm⁻³ for UK sites. A consistent diurnal cycle of sCI concentration is estimated for the UK sites with increasing levels during daylight hours, peaking just after midday. The seasonal pattern of sCI shows higher levels in spring with peaks around May due to the higher levels of O₃. The ozone weekend effect resulted in higher sCI in UK urban areas during weekend. The sCI data were modeled using the information provided by the Air Quality Improvement Research Program (AQIRP) and found that the modeled production was five‐ to six‐fold higher than our estimated data, and therefore the estimated sCI concentrations in this study are thought to be lower estimates only. Compared with nighttime, 1.3‐ to 1.8‐fold higher sCI exists under daytime conditions. Using the levels of sCI estimated at Marylebone Road, globally the oxidation rates of NO₂ + sCI (22.4 Gg/yr) and SO₂ + sCI (37.6 Gg/yr) in urban areas can increase their effect in the troposphere and potentially further alter the oxidizing capacity of the troposphere. Further investigations of modeled sCI show that CH₃CHOO (64%) and CH₂OO (13%) are dominant among all contributing sCI at the UK sites.     

High time resolution observation and statistical analysis of atmospheric light extinction properties and the chemical speciation of fine particulates

In recent years, the visibility deterioration caused by regional fine particulate pollution becomes one of the crucial air pollution problems in the urban areas of our country. The rapid variation of visibility and fine particulates make it difficult to estimate the relationship between them precisely and accurately unless high time resolution observation data can be accessed. This study aims to fill this gap in the field of atmospheric science by establishing a formula using multiple linear regressions. Excellent fitting goodness (R ² = 0.913, n = 3167) was obtained using 10 min average of high-resolution real-time light scattering coefficients, light absorption coefficients, main chemical speciation concentration in PM₁ and some meteorological parameters from 17 Jan to 16 Feb, 2009. It shows that the average light extinction coefficient during the observation in the winter of Shenzhen was measured to be 290 ± 183 Mm^?1, consisting of 72% of light scattering and 21% of absorption. In terms of the percentage contribution of PM₁ chemical species to the total light extinction, the organic matter was estimated to be most with an average of 45%, followed by ammonium sulfate with an average of 24%. The contributions of black carbon and ammonium nitrate were 17% and 12%, respectively. Besides, the diurnal variation of light extinction was investigated as well in this study.