凝并过程对亚微米灰霾颗粒中痕量重金属分布的影响

灰霾颗粒中痕量重金属物质对人体健康的危害,不仅仅与其重金属总含量有关,在很大程度上,与痕量重金属的尺度及其分布有直接的关联。为了研究凝并（coagulation）过程对不同初始条件的灰霾颗粒中重金属物质分布的影响,采用多重蒙特卡罗（multi-Monte Carlo,MMC）方法,模拟研究了亚微米灰霾颗粒中痕量重金属元素的分布规律。模拟发现,基于连续区布朗凝并机理下,在经过一段时间演化后,低初始数浓度的灰霾颗粒类中重金属物质质量百分比趋于均一,这表明凝并过程去除了初始重金属物质在灰霾颗粒中的富集效果;而在高初始数浓度灰霾颗粒类中重金属物质分布满足幂律关系。而且,进一步分析发现,在低初始数浓度灰霾颗粒类中重金属物质尺度分布趋于正态分布。     

Chemical characterization of fine particles from on-road vehicles in the Wutong tunnel in Shenzhen, China

Vehicle populations in China have been increasing sharply since 1990s. Vehicle emissions including various gaseous pollutants and particulate matter cause deterioration of air quality. However, measurements of particulate mater from on-road vehicles in China are scarcely reported, and thus the chemical compositions of particles emitted from vehicles in China are unknown. In this research, tunnel experiments were performed to measure PM2.5 in the Wutong tunnel, Shenzhen, China. Detailed PM2.5 chemical compositions, with organic compounds determined by GC/MS, in the tunnel were presented. Elemental carbon and organic matter composed 63% and 34% of the total PM2.5 mass in the Wutong tunnel, respectively. Alkanes, PAHs, hopanes, fatty acids, and dicarboxylic acids were the major identified organic compounds, and their source profiles in the PM2.5 in the Wutong tunnel were characterized. The comparisons of our measurements with those in the literature were also made to demonstrate the characteristics of the vehicle source profiles in the Wutong tunnel. The experimental results in this paper can improve understanding of particulate matter emitted from vehicles in China.     

Chemical characterization and source identification/apportionment of fine and coarse air particles in Thessaloniki,Greece

The distribution of air particulate mass and selected particle components (trace elements and polycyclic aromatic hydrocarbons (PAHs)) in the fine and the coarse size fractions was investigated at a traffic-impacted urban site in Thessaloniki, Greece. 76±6% on average of the total ambient aerosol mass was distributed in the fine size fraction. Fine-sized trace elemental fractions ranged between 51% for Fe and 95% for Zn, while those of PAHs were between 95% and 99%. A significant seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. Similar seasonal trend was exhibited by PAHs, whereas larger fine fractions in summer were shown by trace elements. The compositional signatures of fine and coarse particle fractions were compared to that of local paved-road dust. A strong correlation was found between coarse particles and road dust suggesting strong contribution of resuspended road dust to the coarse particles. A multivariate receptor model (multiple regression on absolute principal component scores) was applied on separate fine and coarse aerosol data for source identification and apportionment. Results demonstrated that the largest contribution to fine-sized aerosol is traffic (38%) followed by road dust (28%), while road dust clearly dominated the coarse size fraction (57%).     

The impact of day-old dilute smog on fresh smog systems: An outdoor chamber study

The effect of dilute day-old smog on fresh smog systems was studied in the UNC dual outdoor chamber. Smog systems which contained fresh smog precursors plus dilute residuals from the day before (0.04 ppm O₃, 0.1–0.3 ppm NMHC and 0.1 ppmC aldehydes) produced almost twice the ozone as fresh systems which had the same initial NMHC and NO_x injections. It is hypothesized that as much as 15–25% of this O₃ increase is due to residual first day aldehydes and that the remaining increase results from an increased morning percentage of NO₂ and the extra residual paraffinic hydrocarbons. The combined interactive effect of changes in initial aldehydes to NO₂ and aged paraffins appears to be greater than if each of these are considered separately.     

Chemical composition of fine particles in the Tennessee Valley region

Fine particles in the atmosphere have elicited new national ambient air quality standards (NAAQS) because of their potential role in health effects and visibility-reducing haze. Since April 1997, Tennessee Valley Authority (TVA) has measured fine particles (PM2.5) in the Tennessee Valley region using prototype Federal Reference Method (FRM) samplers, and results indicate that the new NAAQS annual standard will be difficult to meet in this region. The composition of many of these fine particle samples has been determined using analytical methods for elements, soluble ions, and organic and elemental carbon. The results indicate that about one-third of the measured mass is SO4(-2), one-third is organic aerosol, and the remainder is other materials. The fraction of SO4(-2) is highest at rural sites and during summer conditions, with greater proportions of organic aerosol in urban areas throughout the year. Additional measurements of fine particle mass and composition have been made to obtain the short-term variability of fine mass as it pertains to human exposure. Measurements to account for semi-volatile constituents of fine mass (nitrates, semi-volatile organics) indicate that the FRM may significantly under-measure organic constituents. The potentially controllable anthropogenic fraction of organic aerosols is still largely unknown.     

Chemical characterization of rainwater at Singapore

A short term study of the chemical composition of rainwater was carried out from November 1999 to October 2000 in Singapore. The rainwater was typically acidic with a mean pH of 4.2. Sulfate was the most abundant ion and comparable to the results reported for other industrialized regions. The concentrations of major ions (NH(4)(+), Ca(2+), K(+), Na(+), Mg(2+), SO(4)(2+), NO(3)(2-), Cl(-), HCOO(-), CH(3)COO(-)) varied monthly. Results show that local meteorological conditions influence the chemical compositions to a significant extent. The pollutants in rainwater were derived from long range and local (industry and traffic) sources.     

A mechanism describing the photochemical oxidation of toluene in smog

The photo-oxidation of toluene/NO_x exhibits several features that distinguish it from olefin and paraffin smog systems: highly photolytic products, a relatively low production rate of peroxy radicals, and strong sinks for NO_x. The underlying chemical behavior of the toluene smog system is discussed and a kinetic simulation mechanism is presented. The mechanism simulates toluene smog chamber experiments conducted at two facilities: the University of California at Riverside evacuable chamber, and the outdoor smog chamber at the University of North Carolina.     

A long-path infra-red study of Los Angeles smog

Gaseous air pollutants have been measured in Los Angeles smog by the method of long-path infra-red absorption spectroscopy. A Fourier transform spectrometer operated at 0.25cm⁻¹ resolution was used in conjunction with a 1260-m optical path folded along a base path of 23 m. Detection sensitivities were in the parts-per-billion range. Compounds measured included NH₃, CO, H₂CO, HCOOH, CH₃OH, HNO₃, NO, NO₂, O₃, peroxyacetyl nitrate, alkyl nitrates and various hydrocarbons. The rise and fall of pollutant concentrations is reported in detail for the smoggy two-day period of 26 and 27 June 1980. Reactive hydrocarbons and nitrogen oxides were oxidized during the daytime, yielding ozone, aldehyde, nitric acid and peroxyacetyl nitrate. The observed gaseous reaction products only accounted for about 20 % of the nitrogen oxides that disappeared during the day. It is deduced that the “missing” 80% of the nitrogen was removed heterogeneously into aerosol particles or on surfaces at ground level.     

The influence of aerosols on photochemical smog in Mexico City

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J_NO2) for the key reaction NO₂+hν→NO+O (λ<430 nm). The calculated values are in good agreement with previously published measurements of J_NO2at two sites in Mexico City: Palacio de Minerı́a (19°25′59″N, 99°07′58″W, 2233 masl), and IMP (19°28′48″N, 99°11′07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03′N, 99°14′W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J_NO2 by 10–30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.     

The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

Turbulence effects on chemical reactions in smog chamber flows

Turbulent mixing effects on the reaction rate of a non-premixed flow are presented for a moderately slow second-order irreversible chemical reaction. The turbulent mixing process leads to inhomogeneities in the concentration of the reactants. Chemical reactions are normally highly non-linear and large errors can result from using average concentrations in the computation of mean reaction rates. A brief review of the literature on this problem and its application areas is made with particular emphasis placed on near isothermal flows where the fluctuation in the reaction rate constant can be neglected. The reaction between mixing air jets containing dilute nitric oxide, NO, and ozone, O₃, is studied in a large Turbulent Smog Chamber (TSC) under conditions of high Reynolds number, three-dimensional flow. The measured reactant concentrations, obtained with good time and space resolution, are used to investigate the effects of the reactant species concentration fluctuations on the mean reactant species concentration field through their contribution to the mean reaction rate. Two flow geometries have been studied: two opposed jets issuing into a large chamber and a plume-like source issuing into a turbulent background flow. A three-dimensional finite-difference computation has been carried out for the flow in the chamber using the k-ε-g model of turbulence and mixing. The reacting species concentration field is calculated by considering the transport of a ‘perturbation variable’ equal to the mean of the difference between the species concentration and its corresponding fast chemistry value. A closure for the mean chemical reaction rate based on this quantity is presented and its experimental validation discussed.     

Chemical composition of nucleation and accumulation mode particles collected in Vienna,Austria

Atmospheric aerosol samples were collected by six-stage low pressure impactors in Vienna downtown. Aerosol particles were deposited on aluminum foils in five size fractions in the size range of 0.04–25 μm AD. The concentration of the components Cl⁻, Br⁻, NO₃⁻, SO₄²⁻, Ca, Cu, Fe, Mg, Pb. Sr, Zn and total C was determined by multi-element analytical methods. A comparison of the relative composition of the size fractions containing nucleation mode and accumulation mode particles showed the components derived from traffic emissions (Pb, Br⁻ and C) to be significantly enriched in the nucleation mode size fraction. On the other hand, each of the components Cl⁻, SO₄²⁻,Ca, Cu, Fe, Mg and Sr has a similar relative concentration in the nucleation mode and in the accumulation mode size fraction. For all samples collected on days with prevailing westerly winds a strong negative correlation between wind speed and sulfate particle size as well as sulfate concentration was observed.     

Chemical composition of fine particles from incense burning in a large environmental chamber

 This study is aimed to characterize the major chemical compositions of PM_2.5 from incense burning in a large environmental chamber. Chemical analyses, including X-ray fluorescence for elemental species, ion chromatography for water soluble inorganic species (chloride, nitrate, sulfate, sodium, potassium, ammonium) and thermal/optical reflectance analysis for carbon species were carried out for combustion of three incense categories (traditional, aromatic and church incense). The average concentrations from incense burning ranged from 139.8 to 4414.7 μg m⁻³ for organic carbon (OC), and from 22.8 to 74.0 μg m⁻³ for elemental carbon (EC), respectively. The average OC and EC concentrations in PM_2.5 of three incense categories were in the order of church incense>traditional incense>aromatic incense. OC/EC ratios ranged from 7.0 to 39.1 for the traditional incense, with an average of 21.7; from 3.2 to 11.9 for the aromatic incense, with an average of 7.7. The concentrations of Cl⁻, SO₄²⁻, Na⁺ and K⁺ were highly variable. On average, the inorganic ion concentration sequence was traditional incense>church incense>aromatic incense. The profiles for elements were dominated by Na, Cl and K. In general, the major components in PM_2.5 fraction from incense burning are OC (especially OC2, OC3 and OC4), EC and K.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

The wall as a source of hydroxyl radicals in smog chambers

The role of the wall of a smog chamber as a radical source has been investigated in several ways. From data in the literature evidence is obtained that HNO₃, present on the reactor wall, may react with NO in the gas phase according to the reaction HNO₃(wall) + 2NO + H₂O → 3HNO₂ to give nitrous acid. Nitrous acid may subsequently photolyze to give hydroxyl radicals.Experimental evidence about the occurrence of this reaction was obtained by u.v.-irradiation of propane-NO_x mixtures with and without NH₃. The presence of NH₃ resulted in a drastically reduced photochemical reactivity, suggesting that neutralization of nitric acid prevented the reaction of HNO₃ with NO. Inclusion of the reaction mentioned above into a computer-model gave a good agreement between experimental and calculated concentration profiles of NO, NO₂ and O₃ in experiments with CO-NO_x and propane-NO_x, mixtures. The results of our findings and those from others are discussed.     

Comparative analysis of chemical reaction mechanisms for photochemical smog

Six chemical reaction mechanisms for photochemical smog are analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. Answers to previously inaccessible questions such as the relative contributions of individual organic species to photochemical ozone formation are obtained. Based on the results of the analysis we have identified specific aspects of each mechanism that are responsible for the discrepancies with other mechanisms and with an explicit mechanism based on the latest understanding of atmospheric chemistry. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Thus, we identify why the predictions of the mechanisms are different, and have recommended research efforts that are needed to eliminate many of the discrepancies.     

Chemical and strontium isotope characterization of rainwater in Beijing,China

Major ion concentrations and Sr isotope ratios (⁸⁷Sr/⁸⁶Sr) were measured in rainwater samples collected at an urban site in Beijing over a period of one year. The pH value and major ion concentrations of samples varied considerably, and about 50% of the rainwater studied here were acidic rain with pH values less than 5.0. Ca²⁺ and NH₄⁺ were the dominant cations in rainwaters and their volume weighted mean (VWM) values were 608 μeq l^?1 (14–1781 μeq l^?1) and 186 μeq l^?1 (48–672 μeq l^?1), respectively. SO₄^2? was the predominant anion with VWM value of 316 μeq l^?1 (65–987 μeq l^?1), next was NO₃^? with VWM value of 109 μeq l^?1 (30–382 μeq l^?1).Using Na as an indicator of marine origin, and Al for the terrestrial inputs, the proportions of sea salt and terrestrial elements were estimated from elemental ratios. More than 99% of Ca²⁺ and 98% of SO₄^2? in rainwater samples are non-sea-salt origin. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize the different sources based on the data sets of this study and those from literatures. Such sources include sea salts (⁸⁷Sr/⁸⁶Sr～0.90917), soluble soil dust minerals originating from either local or the desert and loess areas (～0.7111), and anthropogenic sources (fertilizers, coal combustion and automobile exhausts). The high concentrations of alkaline ions (mainly Ca²⁺) in Beijing atmosphere have played an important role to neutralize the acidity of rainwater. However, it is worth noting that there is a remarkable acidification trend of rainwater in Beijing recent years.     

Chemical coupling between ammonia, acid gases, and fine particles

The concentrations of inorganic aerosol components in the fine particulate matter (PM(fine)< or =2.5 microm) consisted of primarily ammonium, sodium, sulfate, nitrate, and chloride are related to the transfer time scale between gas to particle phase, which is a function of the ambient temperature, relative humidity, and their gas phase constituent concentrations in the atmosphere. This study involved understanding the magnitude of major ammonia sources; and an up-wind and down-wind (receptor) ammonia, acid gases, and fine particulate measurements; with a view to accretion gas-to-particle conversion (GTPS) process in an agricultural/rural environment. The observational based analysis of ammonia, acid gases, and fine particles by annular denuder system (ADS) coupled with a Gaussian dispersion model provided the mean pseudo-first-order k(S-1) between NH(3) and H(2)SO(4) aerosol approximately 5.00 (+/-3.77)x10(-3) s(-1). The rate constant was found to increase as ambient temperature, wind speed, and solar radiation increases, and decreases with increasing relative humidity. The observed [NH(3)][HNO(3)] products exceeded values predicted by theoretical equilibrium constants, due to a local excess of ammonia concentration.     

Source characterization of ambient fine particles at multiple sites in the Seattle area

To identify major PM_2.5 (particulate matter ≤2.5 μm in aerodynamic diameter) sources with a particular emphasis on the ship engine emissions from a major port, integrated 24 h PM_2.5 speciation data collected between 2000 and 2005 at five United State Environmental Protection Agency's Speciation Trends Network monitoring sites in Seattle, WA were analyzed. Seven to ten PM_2.5 sources were identified through the application of positive matrix factorization (PMF). Secondary particles (12–26% for secondary nitrate; 17–20% for secondary sulfate) and gasoline vehicle emissions (13–31%) made the largest contributions to the PM_2.5 mass concentrations at all of the monitoring sites except for the residential Lake Forest site, where wood smoke contributed the most PM_2.5 mass (31%). Other identified sources include diesel vehicle emissions, airborne soil, residual oil combustion, sea salt, aged sea salt, metal processing, and cement kiln. Residual oil combustion sources identified at multiple monitoring sites point clearly to the Port of Seattle suggesting ship emissions as the source of oil combustion particles. In addition, the relationship between sulfate concentrations and the oil combustion emissions indicated contributions of ship emissions to the local sulfate concentrations. The analysis of spatial variability of PM_2.5 sources shows that the spatial distributions of several PM_2.5 sources were heterogeneous within a given air shed.