Chemical characteristics and source apportionment of atmospheric particles during heating period in Harbin, China

Atmospheric particles（total suspended particles（TSPs）; particulate matter（PM） with particle size below 10 μm, PM10; particulate matter with particle size below 2.5 μm, PM2.5）were collected and analyzed during heating and non-heating periods in Harbin. The sources of PM10 and PM2.5were identified by the chemical mass balance（CMB） receptor model.Results indicated that PM2.5/TSP was the most prevalent and PM2.5was the main component of PM210, while the presence of PM10–100was relatively weak. SO-4and NO-3concentrations were more significant than other ions during the heating period. As compared with the non-heating period, Mn, Ni, Pb, S, Si, Ti, Zn, As, Ba, Cd, Cr, Fe and K were relatively higher during the heating period. In particular, Mn, Ni, S, Si, Ti, Zn and As in PM2.5were obviously higher during the heating period. Organic carbon（OC） in the heating period was 2–5 times higher than in the non-heating period. Elemental carbon（EC） did not change much. OC/EC ratios were 8–11 during the heating period, which was much higher than in other Chinese cities（OC/EC： 4–6）. Results from the CMB indicated that 11 pollution sources were identified, of which traffic, coal combustion, secondary sulfate, secondary nitrate, and secondary organic carbon made the greatest contribution. Before the heating period, dust and petrochemical industry made a larger contribution. In the heating period, coal combustion and secondary sulfate were higher. After the heating period, dust and petrochemical industry were higher. Some hazardous components in PM2.5were higher than in PM10, because PM2.5has a higher ability to absorb toxic substances. Thus PM2.5pollution is more significant regarding human health effects in the heating period.

Catalytic oxidation of CS_2 over atmospheric particles and oxide catalysts

The catalytic oxidization of CS2 over atmospheric particles and some oxide catalysts was explored through FT-IR, MS and a fixed-bed stainless steel reactor. The results show that atmospheric particles and some oxide catalysts exhibited considerable oxidizing activities for CS2 at ambient temperature. The reaction products are mainly COS and elemental sulfur, even CO2 on some catalysts. Among the catalysts, CaO has the strongest catalytic activity for oxidizing CS2. Fe2O3 is weaker than CaO. The catalytic activity for Al2O3 reduces considerably compared with the former two catalysts, and SiO2 the weakest. Atmospheric particle samples’ catalytic activity is between Fe2O3’s and Al2O3’s. The atmospheric particle sample collected mainly consists of Ca(Al2Si2O8) · 4H2O, which is also the main component of cement. COS, the main product, is formed by the catalytic oxidization of CS2 with adsorbed “molecular” oxygen over the catalysts’ surfaces. The concentration of adsorbed oxygen over catalysts’ surfaces may be the key factor contributed to the oxidizing activity. It is indicated that CS2 could be catalytically oxidized over atmospheric particles, which induced that this reaction may be another important source of atmospheric COS from CS2.

Characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China

To understand the pollution characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China, total suspended particulate （TSP） and PMI0 samples were collected in cities of Changsha, Zhuzhou and Xiangtan from December 2011 to January 2012, and heavy metals of Cd, Pb, Cr, and As were analyzed. It shows that the average TSP concentration in Changsha, Zhuzhou and Xiangtan were （183 ± 73）, （201± 84） and （190 ±66） μg/m3 respectively, and the average PM10 were （171 ± 82）, （178 ± 65） and （179 ± 55） μg/m3 respectively. The lowest TSP and PM10 concentrations occurred at the background Shaping site of Changsha. The average ratio of p（PM10）/p（TSP） was 91.9%, ranging from 81.3% to 98.9%. Concerning heavy metals, in TSP samples, the concentration of Cr, As, Cd and Pb were 28.8-56.5, 18.1-76.3, 3.9-26.1 and 148.0-460.9 ng/m3, respectively, while in PMI0 samples, were 16.4--42.1, 15.5-67.9, 3.3-22.2 and 127.9-389.3 ng/m3, respectively. The enrichment factor of Cd was the highest, followed by Pb and As, while that of Cr was the lowest.

Raman micro-spectrometry as a technique for investigating heterogeneous reactions on individual atmospheric particles

Investigating the heterogeneous reaction on individual atmospheric particles is important because it approximates actual atmospheric conditions and can aid in reducing artifacts in elucidating real mechanisms and processes,and determining real kinetic parameters of the atmosphere relevance.This study developed a Raman microspectrometry method to investigate heterogeneous reactions on individual particles.The method was applied to the reaction of NO2 with individual CaCO3 particles.It was demonstrated that Raman microspectrometry can obtain information on both chemical composition and microscopic morphology at the same time,as well as information on chemical characteristics,such as the phase,which is useful for studying reaction processes.Raman spectra of individual particles deposited on a substrate showed no interference by morphological resonance,which is helpful for obtaining high-quality spectra.Moreover,Raman microspectrometry was compared with other methods for investigating heterogeneous reactions on individual particles and was found to have several advantageous characteristics.

Concentration Characteristics and Sources of Chemical Elements in Atmospheric Fine Particles (PM_(2.5)) in Autumn in Xi'an City

[Objective] The aim was to study the concentration characteristics and sources of chemical elements in atmospheric fine particles (PM2.5) in autumn in Xi’an City. [Method] By means of mini-volume sampler, PM2.5 samples in atmosphere in Xi’an were collected in October 2009, and the concentration characteristics and sources of elements in PM2.5 were analyzed. [Result] The average mass concentration of PM2.5 in atmosphere in autumn in Xi’an City was 168.44 μg/m3 which was higher than that of Beijing and Pearl River Delta area, and the minimum and maximum value were 53.29 and 358.16 μg/m3, respectively. The mass concentration of S, Zn, K, Cl, Ca and Fe in PM2.5 was above 1.0 μg/m3, being at high pollution level. In addition, K had obvious correlation with organic carbon (OC) and element carbon (EC), with the correlation coefficients of 0.76 and 0.75 (P<0.000 1), respectively, and it showed that OC and EC had the same source as K, namely biomass burning had certain contribution to OC and EC. Enrichment factors analysis revealed that K, Ca, Fe, Ti, Mn and Cr mainly came from earth crust, rock weathering and other natural sources, while anthropogenic pollution sources had great effects on S, Zn, Cl, Pb, Br, Mo, Cd and As which were affected by soil dust and other natural sources slightly, and Cd had the highest enrichment factor and mainly came from metal smelting. In a word, coal combustion, biomass burning, vehicle emissions, metallurgical, chemical industry and dust were the main sources of PM2.5 in autumn in Xi’an. [Conclusion] The study could provide theoretical foundation for the control of urban environmental pollution.

Diurnal Variation of Atmospheric Aerosol Particles in the Phyllostachys heterocycla Forest in Spring

Taking the Phyllostachys heterocycla forest in Qishan National Forest Park of Fuzhou for example, this study observed the diurnal variation of atmospheric aerosol particles in the forest in the growing season.The results showed that:(1) The diurnal variation curves of the particle concentration of the forest and the forest edge had "two peaks and two troughs", but the peaks and troughs of the forest edge were advanced or delayed.The concentrations of the particles in the forest and at the forest edge had two peaks at 11:00–13:00 and 17:00–19:00 and two troughs at 7:00–9:00 and 15:00–17:00.(2) For the forest and the forest edge, the diurnal variation trends of the particles of different particle sizes were generally similar, except that the peaks and troughs of fine particles were slightly earlier or lagging than that of coarse particles.(3) The concentrations of the particles were positively correlated with temperature, humidity and light, and negatively correlated with wind speed, and the concentrations of the particles at the forest edge were significantly negatively correlated with wind speed.

Estimate Totel Number of the Earth Atmospheric Particle with Standard Atmosphere model

The total number of atmospheric particle (AP) is an important datum for planetary science and geoscience. Estimating entire AP number is also a familiar question in general physics. With standard atmosphere model, considering the number difference of AP caused by rough and uneven in the earth surface below, the sum of dry clean atmosphere particle is . So the whole number of AP including water vapor is . The rough estimation for the total number of AP on other planets (or satellites) in condensed state is also discussed on the base of it.

Determination of trace lead and mercury in airborne particles by hydride generation atomic fluorescence spectrometry

A new method for determination of trace lead and mercury by hydride generation atomic fluorescence spectrometry （HG-AFS） was established. Lead was determined in the medium of citric acid using potassium ferricyanide （K3Fe（CN）6） as oxidant. Ni enhanced the fluorescence signals in this system. Mercury was determined in the medium of nitric acid using mixture of thiourea and ascorbic acid as masking reagent, sodium dioctylsulphosuccinate （SDSS） as enhancing reagent. The working mechanism of the hydride generation of lead and mercury was discussed. Interferences of some coexisting ions were studied systematically and the determination conditions were optimized. Under the optimized conditions, the detection limits of the method were 0.31μg.L^-1 for lead and 0.023 μg·L^-1 for mercury, and the relative standard deviations based on eleven determinations of 5.00 μg·L^-1 standard of Pb and Hg, were 2.6% for Pb and 2.2 % for Hg. This method was applied to the analysis of lead and mercury in four different diameter airborne particles after microwave digestion. Results suggested heavy metal elements easily concentrated in smaller particles.

Real-time,single-particle chemical composition,volatility and mixing state measurements of urban aerosol particles in southwest China

To investigate the volatility of atmospheric particulates and the evolution of other particulate properties(chemical composition,particle size distribution and mixing state)with temperature,a thermodenuder coupled with a single particle aerosol mass spectrometer was used to conduct continuous observations of atmospheric fine particles in Chengdu,southwest China.Because of their complex sources and secondary reaction processes,the average mass spectra of single particles contained a variety of chemical components(including organic,inorganic and metal species).When the temperature rose from room temperature to280℃,the relative areas of volatile and semi-volatile components decreased,while the relative areas of less or non-volatile components increased.Most(>80%)nitrate and sulfate existed in the form of NH_(4)NO_(3)and(NH_(4))_(2)SO_(4),and their volatilization temperatures were50–100℃and 150–280℃,respectively.The contribution of biomass burning(BB)and vehicle emission(VE)particles increased significantly at 280℃,which emphasized the important role of regional biomass burning and local motor vehicle emissions to the core of particles.With the increase in temperature,the particle size of the particles coated with volatile or semi-volatile components was reduced,and their mixing with secondary inorganic components was significantly weakened.The formation of K-nitrate(KNO_(3))and K-sulfate(KSO_(4))particles was dominated by liquid-phase processes and photochemical reactions,respectively.Reducing KNO_(3)and BB particles is the key to improving visibility.These new results are helpful towards better understanding the initial sources,pollution formation mechanisms and climatic effects of fine particulate matter in this megacity in southwest China.

Origin,evolution,and distribution of atmospheric aerosol particles in Asia

In recent years, Asia became the region with the highest increase in rate of urbanization and economic development in the world. According to recent estimates from the United Nations, the world population will increase 36% between 2000 and 2030, leading to a doubling of the number of urban dwellers in less developed regions, like Asia. Such rapid economic development has many associated environmental problems, including development of heavy aerosol pollution over Asia.

Source Apportionment of Ambient PM_(10) in the Urban Area of Longyan City,China:a Comparative Study Based on Chemical Mass Balance Model and Factor Analysis Method

In order to identify the day and night pollution sources of PM10 in ambient air in Longyan City,the authors analyzed the elemental composition of respirable particulate matters in the day and night ambient air samples and various pollution sources which were collected in January 2010 in Longyan with inductivity coupled plasma-mass spectrometry（ICP-MS）.Then chemical mass balance（CMB） model and factor analysis（FA） method were applied to comparatively study the inorganic components in the sources and receptor samples.The results of factor analysis show that the major sources were road dust,waste incineration and mixed sources which contained automobile exhaust,soil dust/secondary dust and coal dust during the daytime in Longyan City,China.There are two major sources of pollution which are soil dust and mixture sources of automobile exhaust and secondary dust during the night in Longyan.The results of CMB show that the major sources are secondary dust,automobile exhaust and road dust during the daytime in Longyan.The major sources are secondary dust,soil dust and automobile exhaust during the night in Longyan.The results of the two methods are similar to each other and the results will guide us to plan to control the PM10 pollution sources in Longyan.

Effect of non-spherical atmospheric charged particles and atmospheric visibility on performance of satellite-ground quantum link and parameters simulation

In order to study the relationship between the non-spherical atmospheric charged particles and satellite-ground quantum links attenuation. The relationship among the particle concentration, equivalent radius, charge density of the charged particle, the attenuation coefficient and entanglement of the satellite-ground quantum link can be established first according to the extinction cross section and spectral distribution function of the non-spherical atmospheric charged particles. The quantitative relationship between atmospheric visibility and communication fidelity of satellite-ground quantum link were analyzed then. Simulation results show that the ellipsoid, Chebyshev atmospheric charged particle influences on attenuation of the satellite-ground quantum link increase progressively. When the equivalent particle radius is 0.2 gm and the particle concentration is 50 μg/m^3, the attenuation coefficient and entanglement of the satellite-ground quantum link is 9.21 dB/km, 11.46 dB/km and 0.453, 0.421 respectively; When the atmospheric visibility reduces from 8 km to 2 kin, the communication fidelity of satellite-ground quantum link decreases from 0.52 to 0.08. It is shown that the non-spherical atmospheric charged particles and atmospheric visibility influence greatly on the performance of the satellite-ground quantum link communication system. Therefore, it is necessary to adjust the parameters of the quantum-satellite communication system according to the visibility values of the atmosphere and the shapes of the charged particles in the atmosphere to improve reliability of the satellite-ground quantum link.

Difference between low-volume and high-volume Andersen samplers in measuring atmospheric aerosols

The mass concentration and size distribution of aerosols in Tokaimura were investigated using a high-volume and a low-volume Andersen sampler. A difference was found using the two samplers： the concentration of total aerosols determined with the high-volume sampler is smaller than that of the low-volume sampler by 70-90% throughout the year. Compared to the high-volume sampler, low-volume sampler gave lower concentration for aerosols 〉7 μm, higher concentration for aerosols of 3.3-7.0 μm and 〈 1.1 μm, though similar results for aerosols of 1.1-3.3 μm. The low-volume sampler was found to have better separation efficiency and higher accuracy.

Concentration-dependent effects of reductive pulmonary inhalants on ultrafine particle-induced oxidative stress:Insights for health risk assessment

The impact of reductive pulmonary inhalants on ultrafine particles(UFPs)-induced pulmonary oxidative stress remains a crucial consideration,yet the concentration-dependent effects of these inhalants have remained unexplored.Here we synthesized composite UFPs simulating atmospheric UFPs,primarily composed of metals and quinones.We subjected these UFPs to varying concentrations(0e7000 mM)of two reductive pulmonary inhalants,N-acetylcysteine and salbutamol,to assess their influence on oxidative potential,measured through the dithiothreitol assay(OP^(DTT)).Simultaneously,we analysed the soluble metal content of UFPs to uncover potential relationships between oxidative potential and metal solubility.Our results unveil a dual role played by these inhalants in shaping the OPDTT of composite UFPs.Specifically,OP^(DTT) generally increased as inhalant concentrations rose from 0 to 300 mM.However,an intriguing reversal occurred when concentrations exceeded 500 mM,resulting in a decline in OPDTT.Relative to untreated UFPs,these inhalants induced promotion and inhibition effects within concentration ranges of 100e500 and>1000 mM,respectively.While no significant correlation emerged between OP^(DTT) and soluble metal content as inhalant concentrations ranged from 0 to 7000 mM,noteworthy positive correlations emerged at lower inhalant concentrations(e.g.,N-acetylcysteine at 0 e300 mM).These findings provide insights into the potential influence of reductive pulmonary inhalants on health risks associated with UFP exposure,further underscoring the need for continued research in this critical area.

Determination of particulate polycyclic aromatic hydrocarbons in ambient air by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction

A solid phase extraction procedure(SPE)is described for the quantitative analysis of polycyclic aromatic hydrocarbons(PAHs)in atmospheric particulate matter(PM),as ubiquitous environmental pollutants routinely measured in air qualitymonitoring.A SPE cartridge was used based on a molecular imprinted polymer(MIP-SPE)properly tailored for selective retention of PAHs with 4 and more benzene fused rings.The performance of the clean-up procedure was evaluated with the specific concern of selective purification towards saturated hydrocarbons,which are the PM components mostly interfering GC analysis of target PAHs.Under optimized operative conditions,the MIP-SPE provided analyte recovery close to 95%for heavier PAHs,from benzo(α)pyrene to benzo(ghi)perylene,and close to 90%for four benzene rings PAHs,with good reproducibility(RSDs:2.5%-5.9%).Otherwise,C_(17)-C_(32) n-alkanes were nearly completely removed.The proposed method was critically compared with Solid Phase Micro Extraction(SPME)using a polyacrylate fiber.Both methods were successfully applied to the analysis of ambient PM2.5 samples collected at an urban polluted site.Between the two procedures,the MIP-SPE provided the highest recovery(R%≥93%)for PAHs with 5 and more benzene rings,but lower for lighter PAHs.In contrast,SPME showed a mean acceptable R%value(∼80%)for all the investigated PAHs,except for the heaviest PAHs in the most polluted samples(R%:110%-138%),suggesting an incomplete purification from the interfering n-hydrocarbons.

A REVIEW OF CURRENT KNOWLEDGE CONCERNING SIZE-DEPENDENT AEROSOL REMOVAL

The status of current knowledge on size-dependent aerosol removal by dry and wet processes, including dry deposition and impaction and nucleation scavenging, is reviewed. The largest discrepancies between theoretical estimations and measurement data on dry deposition and below-cloud scavenging are for submicron particles, Early dry deposition models, which developed based on chamber and wind tunnel measurements, tended to underestimate dry deposition velocity （Vσ） for submicron particles by around one order of magnitude compared to recent field measurements. Recently developed models are able to predict reasonable Vσ values for submicron particles but shift unrealistically the predicted minimum Vσ to larger particle sizes. Theoretical studies of impaction scavenging of aerosol particles by falling liquid drops also substantially underestimate the scavenging coefficients for submicron particles. Empirical formulas based on field measurements can serve as an alternative to the theoretical scavenging models. Future development of size-resolved impaction scavenging models needs to include more precipitation properties （e,g., droplet surface area） and to be evaluated by detailed cloud microphysical models and available measurements. Several recently developed nucleation scavenging parameterizations for in-cloud removal of interstitial aerosol give comparable results when evaluated against parcel models; however, they need to be verified once suitable field measurements are available. More theoretical and field studies are also needed in order to better understand the role of organic aerosols in the nucleation scavenging process.

N and O isotopes and the ore-forming mechanism of nitrate deposits in the Turpan-Hami Basin,Xinjiang,China

The recently discovered nitrate ore field in the Turpan-Hami Basin of western China represents an estimated resource of 2.5 billion tons, and is comparable in scale to the Atacama Desert super-scale nitrate deposit in Chile. The research on this area is rarely carried out, and the origin of the deposits remains uncertain. In this study, new methods were used to systematically analyze N and O isotopes in nitrate minerals collected from the Kumutage, Xiaocaohu, Wuzongbulak, Dawadi, Tuyugou, and Shaer ore deposits in the Turpan-Hami Basin. The data showed that the δ15NAir value ranges from 0.7‰ to 27.6‰, but mostly between 2‰ and 6‰, which was similar to atmospheric NO3-. The 18O was highly enriched with δ18OV-SMOW varying from 30.2‰ to 46.7‰. This differs from levels in deposits derived from microbial nitrogen fixation, but is similar to those in atmospheric nitrates. N and O isotopes data indicated that nitrate deposits in Turpan-Hami Basin must be the result of deposition of atmospheric nitrate particles. Although atmospheric nitrate particles are common, the nitrate deposits could form only under the condition of long-term extreme drought climate and very limited biological activity. This paper summarized the ore-forming mechanism of different types nitrate deposits based on their geological setting.

TOF–SIMS surface analysis of chemical components of size–fractioned urban aerosols in a typical heavy air pollution event in Beijing

Size–fractioned atmospheric aerosol particles were collected during a typical heavy air pollution event in Beijing. The organic and inorganic components on the surfaces of the samples were analyzed using time–of–flight secondary ion mass spectrometry（TOF–SIMS）.The variation characteristics of the surface chemical composition and influencing factors were studied, and the possible sources of these chemical compositions were identified through principal component analysis. The results showed that inorganic components such as crustal elements and sulfate, and organic components such as aliphatic hydrocarbons and oxygen–containing organic groups were present. Some surface components, such as polycyclic aromatic hydrocarbons, heavy metals and fluorides may exert adverse effects on human health. The species and relative percentages of the chemical components varied with particle size, diurnal and pollution progress. During a heavy pollution event, the species and relative percentages of secondary components such as oxygen–containing organic groups and sulfurous compounds increased, indicating that particles aged during this event. The surface chemical composition of the aerosol particles was affected mainly by emissions from coal combustion and motor vehicles. In addition, air pollution, meteorological factors, and air mass transport also exerted a significant effect on the surface chemical composition of aerosol particles.

Origin of high particle number concentrations reaching the St. Louis, Midwest Supersite

Ultrafine particles are associated with adverse health effects. Total Particle Number Concentration（TNC） of fine particles were measured during 2002 at the St. Louis — Midwest supersite. The time series showed overall low level with frequent large peaks. The time series was analyzed alongside criteria pollutant measurements and meteorological observations. Multiple regression analysis was used to identify further contributing factors and to determine the association of different pollutants with TNC levels. This showed the strong contribution of sulfur dioxide（SO2） and nitrogen oxides（NO x） to high TNC levels. The analysis also suggested that increased dispersion resulting from faster winds and higher mixing heights led to higher TNC levels. Overall, the results show that there were intense particle nucleation events in a SO2 rich plume reaching the site which contributed around 29% of TNC. A further 40% was associated with primary emissions from mobile sources. By separating the remaining TNC by time of day and clear sky conditions,we suggest that most likely 8% of TNC are due to regional nucleation events and 23% are associated with the general urban background.