Source apportionment of atmospheric carbonaceous particulate matter based on the radiocarbon

A method was established to quantitatively estimate sources of atmospheric carbonaceous matter, using a combination of radiocarbon technology, linear regression of organic carbon (OC) -K⁺ and elemental carbon (EC) tracer method. Fractional contributions of fossil fuels, biomass burning, biogenic secondary organic carbon (BSOC) and soil dust to the atmospheric size-resolved carbonaceous matters in Shanghai suburb were estimated using this new method. The fossil carbon contributed most of the OC in particles smaller than 0.49 μm, and its fraction decreased with the increase of particle size. Biomass burning contributed 17–28 % to the OC. The BSOC contributed comparable proportions to the OC in particles smaller than 3.0 μm with the biomass burning, but larger in the particles lager than 3.0 μm. The soil dust contributed least fraction to the OC of each size with a proportion of 2–13 %. The biomass burning and fossil sources shared comparable fraction of the EC in all size range.     

Method development for the analysis of particle phase substituted methoxy phenols and aromatic acids from biomass burning using capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI-MS)

A method is developed for the determination of substituted methoxy phenols and aromatic acids in biomass burning aerosol using capillary electrophoresis (CE) coupled to an electrospray ionization mass spectrometer. Background electrolytes (BGEs) containing ammonium acetate, ammonium hydroxide and 10% (v/v) methanol at pH 9.1 and ammonium hydroxide at pH 11 are investigated for their suitability. A good linearity is found for all analytes in the range of 1-50 microM for the ammonium acetate based BGE and 1-40 microM for the ammonium hydroxide BGE. The detection limit ranged from 0.1 to 1.0 microM for the ammonium acetate based BGE and 0.3 to 0.7 microM for the ammonium hydroxide BGE. The relative standard deviation (R.S.D.) is typically less than 0.5% (ammonium acetate based BGE) and 4.2% (ammonium hydroxide BGE) for the migration time and 3-9% (ammonium acetate based BGE) and 2.5-8% (ammonium hydroxide BGE) for the peak area (n = 5). The analytical time was less than 10 min for both methods. The proposed methods are fast, sensitive and quantitative and can be applied to the analysis of complex biomass burning aerosol samples without complex pre-treatment. The results from the analysis of real biomass burning samples demonstrate the suitability of the proposed methods to the analysis of low concentration water soluble organic carbon (WSOC) in biomass burning samples. The fast analytical time and high sensitivity of the proposed methods enables the analysis of a large number of size segregated impactor samples from biomass burning aerosols.     

成都市工业区大气环境污染状况研究

以成都东郊工业区为例,采集气溶胶样品用中子活化分析测定了24种元素的含量,将分析结果与京津地区、广州地区进行比较,并用气溶胶中元素含量的均值做了富集因子分析。结果表明,该区的气溶胶污染与煤炭燃烧等有关。     

Significant Reduction of UVB Caused by Smoke from Biomass Burning in Brazil

Abstract— Solar UVB radiation, total ozone and the aerosol optical thickness (AOT) of the atmosphere were measured at various sites in Brazil during the burning season of 1995. Smoke from biomass burning caused very significant AOT and up to an 81% reduction in UVB at Cuiabd, hundreds of kilometers from the most widespread burning. Little or no smoke was apparent upwind of the major burning regions at and near Manaus, and UVB was close to the expected values. There is an increased incidence of respiratory, cardiopulmonary and other diseases associated with severe air pollution, but the responsible biological mechanisms are unknown. The bactericidal effects of solar UVB are well known, and significantly reduced UVB resulting from severe air pollution in regions where UVB levels are ordinarily high might enhance the survivability of pathogenic organisms in air and water and on surfaces exposed to sunlight.     

Study of PM2.5 in Beijing suburban site by neutron activation analysis and source apportionment

Airborne particulate matter (APM) was collected in coarse fraction and in PM_2.5 during spring of 2002 in Beijing suburban sampling site by Gent SFU sampler. More attention has been paid to the special “events” such as dust, storm and haze. Taking advantage of the combination of thermal or epithermal neutron irradiation with Compton suppression spectrometer system, twenty elemental (Al, Si, Ca, K, Dy, Cu, I, In, Ba, W, Sn, Sb, As, Ti, Br, V, Mn, Cl, Na, Zn) concentration were determined. Among them, several key trace elements that cannot be accomplished by the traditional neutron activation analysis (NAA) were determined. The analysis of trace elemental concentration in PM_2.5 shows that the anthropogenic elements such as As, In, Sn, Sb have different trends than crustal elements. The back-trajectories of the high concentration anthropogenic pollution elements revealed their source region. Six potential sources were resolved by positive matrix factorization (PMF), two area type and four source type, as soil, limestone quarry, crop burning and mixture of residue motor and coal burning sampling sites. Taking into account of everyday air particle back trajectories, source compositions together with source regions were also identified. This revised version was published online in July 2006 with corrections to the Cover Date.     

Local and non-local sources of airborne particulate pollution at Beijing--The ratio of Mg/Al as an element tracer for estimating the contributions of mineral aerosols from outside Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%―67% of total suspended particles (TSP), 10%―70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%―86%) of the total mineral aerosols in TSP, 69% (52%―90%) in PM10, and 76% (59%―93%) in PM2.5 in spring, and 69% (52%―83%), 79% (52%―93%), and 45% (7%―79%) in TSP, PM10, and PM2.5, respectively, in winter, while only ～20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

Evidence of coal combustion contribution to ambient VOCs during winter in Beijing

Volatile organic compounds(VOCs)play an important role in ozone and secondary organic aerosol(SOA)formation,but VOCs sources during winter are not fully understood.To investigate VOCs sources during winter,mixing ratios of C2–C12 VOCs were measured at an urban site in Beijing from December 29,2011to January 17,2012.Correlation analysis of toluene to benzene and i-pentane to n-pentane suggest that coal combustion could also be an important source for VOCs besides vehicular emissions.Source apportionment results show that coal combustion and vehicular emissions contributed 28%–39%and31%–45%to ambient VOCs during winter,respectively.Backward trajectory analyses demonstrated that contributions from the burning of coal were higher when air masses came from southern regions outside Beijing.Close attention should be paid to VOCs emissions from coal combustion in Beijing city and the vicinity to the South.     

Combined application of INAA and PIXE for studying the regional aerosol composition in Southern Africa

As part of the SAFARI-92 biomass buming experiment, aerosol collections were carried out with several size-fractionating sampling devices at a number of sites in Southern Africa. One of the samplers used at all ground-based sites was a stacked filter unit (SFU). The SFU samples were analyzed by both INAA and PIXE analysis. The present paper gives an intercomparison of the analytical results obtained in order to assess the accuracy and to check the quality assurance of the analytical procedures. Twenty-one common elements were determined by both INAA and PIXE. Concentrations of 13 elements (i.e., Na, Mg, Al, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Zn and Br) were generally measured with sufficient precision in both techniques for performing the intercomparison. The INAA and PIXE data were compared in terms of PIXE/INAA concentration ratios on a sample by sample basis for the coarse and fine size fraction separately. the atmospheric concentrations for K, Mn and Fe agreed within 5–10%, the agreement between the data for the other common elements was typically better than 15%. Possible explanations for lower than 1.0 ratios for Cl, Br and Na are presented. The common elements were classified into groups according to their detectability and sensitivity in each technique.     

Local and non-local sources of airborne particulate pollution at Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%–-67% of total suspended particles (TSP), 10% –70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM_2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%–-86%) of the total mineral aerosols in TSP, 69% (52%–-90%) in PM₁₀, and 76% (59%–-93%) in PM_2.5 in spring, and 69% (52%–-83%), 79% (52%–-93%), and 45% (7% – 79%) in TSP, PM₁₀, and PM_2.5, respectively, in winter, while only ≈20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions

The composition of the water-soluble organic matter from fine aerosols collected in a rural location during two different meteorological conditions (summer and autumn) was investigated by UV-vis, synchronous fluorescence (with Δλ = 20 nm), FT-IR and CPMAS-¹³C NMR spectroscopies. A seasonal variation in the concentration of total carbon, organic carbon and water-soluble organic carbon was confirmed, with higher values during the autumn and lower values during the summer season. The chemical characterisation of the water-soluble organic matter showed that both samples are dominated by a high content of aliphatic structures, carboxyl groups and aliphatic carbons single bonded to one oxygen or nitrogen atom. However, the autumn sample exhibits a higher aromatic content than the summer sample, plus signals due to carbons of phenol, ketones and methoxyl groups. These signals were attributed to lignin breakdown products which are likely to be released during wood combustion processes. The obtained results put into evidence the major contribution of biomass burning processes in domestic fireplaces during low temperature conditions into both the concentration and the bulk chemical properties of the WSOC from fine aerosols.     

Detection and quantification of levoglucosan in atmospheric aerosols: a review

Levoglucosan is a tracer for biomass burning sources in atmospheric aerosol particles. Therefore, much effort has been recently put into developing methods for its quantification. This review describes and compares both established and emerging analytical methods for levoglucosan quantification in ambient aerosol samples, with the special needs of the environmental analytical chemist in mind.     

Methods for the determination of levoglucosan and other sugar anhydrides as biomass burning tracers in environmental samples – A review

Nowadays, there is a great pressure on finding an alternative source of energy. One such source is biomass combustion. Biomass is any organic matter such as wood, crops, seaweed, and animal wastes that during combustion emits energy but also smoke and solid residue. Biomass burning tracers, such as levoglucosan, mannosan and galactosan, are sugar anhydrides produced during burning of biomass that contain cellulose and hemicellulose. Analysis of environmental samples for tracers is the source of information about the type of biofuel burned. In this article, a literature review of the preparation and determination of biomass burning tracers for environmental samples was presented. The review discusses the preparation of different samples (particulate matter, soils, sediments, biological samples), extraction, derivatization, and determination. Amongst determination methods the most popular was gas chromatography with mass spectrometry but other techniques were also used, such as high‐performance liquid chromatography with aerosol charge detection, capillary electrophoresis with pulsed amperometric detection, and ion chromatography with pulsed amperometric detection.     

A simplified method for levoglucosan quantification in wintertime atmospheric particulate matter by high performance anion-exchange chromatography coupled with pulsed amperometric detection

Levoglucosan, a tracer for the assessment of the biomass burning contribution to atmospheric particulate matter (PM) concentrations, was determined by means of high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD). In this work we propose a modification in the instrumental set-up aiming at an improvement in the detector response by adding NaOH after chromatographic separation to increase the pH. The comparison between this technique and the gas chromatography/mass spectrometry (GC/MS) method commonly used showed good agreement. Repeatability is 4.8% RSD, limits of detection for pevoglucosan, mannosan and galactosan are in the range 0.001–0.002 µg mL^?1 in solution, corresponding to 3–4 ng m^?3 for 24 m³ of air sampled. PM10 samples were characterised for levoglucosan and for organic and elemental carbon contents. The preliminary results reported here for five sites in the Lombardy region (Northern Italy) are, as far as we know, the first data on levoglucosan contribution to OC in Italy. The levoglucosan concentrations observed in Lombardy vary in the range 173–963 ng m^?3 with an average levoglucosan-C to OC ratio ranging from 1.5% to 2.5%.     

Radon Dose and Aerosols

The equilibrium factor value (F) was measured in the NRPB radon chamber and the corresponding track density ratio (r = D/D ₀) of bare (D) and diffusion (D ₀) LR-115 nuclear track detectors was determined, as well as the regression equation F(r). Experiments with LR-115 nuclear track detectors and aerosol sources (burning candle and cigarette) were carried out in the Osijek University radon chamber and afterwards an empirical relationship between the equilibrium factor and aerosol concentration was derived. For the purpose of radon dose equivalent assessment, procedures for determining the unattached fraction of radon progeny were introduced using two nuclear track detectors.     

Quantitative infrared intensity studies of vapor-phase glyoxal, methylglyoxal, and 2,3-butanedione (diacetyl) with vibrational assignments

Glyoxal, methylglyoxal, and 2,3-butanedione (diacetyl) are all known biomass burning effluents and suspected aerosol precursors. Pressure-broadened quantitative infrared spectra of glyoxal, methylglyoxal, and diacetyl vapors covering the 520-6500 cm(-1) range are reported at 0.112 cm(-1) resolution, each with a composite spectrum derived from a minimum of 10 different sample pressures for the compound, representing some of the first quantitative intensity data for these analytes. Many vibrational assignments for methylglyoxal are reported for the first time, as are some near-IR and far-IR bands of glyoxal and diacetyl. To complete the vibrational assignments, the far-infrared spectra (25-600 cm(-1)) of all three vapors are also reported, those of methylglyoxal for the first time. Density functional theory and ab initio MP2 theory are used to help assign vibrational modes. Potential bands for atmospheric monitoring are discussed.     

Occurrence,evolution and degradation of heavy haze events in Beijing traced by iodine-127 and iodine-129 in aerosols

Heavy haze events have become a serious environment and health problem in China and many developing countries, especially in big cities, like Beijing. However, the factors and processes triggered the formation of secondary particles from the gaseous pollutants are still not clear, and the processes driving evolution and degradation of heavy haze events are not well understood. Iodine isotopes (¹²⁷I and ¹²⁹I) as tracers were analyzed in time series aerosol samples collected from Beijing. It was observed that the ¹²⁷I concentrations in aerosols peaked during the heavy haze events. The conversion of gaseous iodine to particular iodine oxides through photochemical reactions provides primary nuclei in nucleation and formation of secondary air particles, which was strengthened as the external iodine input from the fossil fuel burning in the south/southeast industrial cities and consequentially induced heavy haze events. Anthropogenic ¹²⁹I concentrations peaked during clean air conditions and showed high levels in spring and later autumn compared to that in summer. ¹²⁹I originated from the direct air discharges and re-emissions from contaminated seawaters by the European nuclear fuel reprocessing plants was transported to Beijing by the interaction of Westerlies and East Asian winter monsoon. Three types of mechanisms were found in the formation and evolution of heavy haze events in Beijing by the variation of ¹²⁷I and ¹²⁹I, i.e., iodine oxides intermediated secondary air particles, dust storm and mixed mode by both secondary air particles and dust storm induced processes.     

Resuspension of radionuclides into the atmosphere due to forest fires

Two major wild fire episodes occurred in north-western Russia in April/May and August 2008. The burning biomass and heating of the surface soil released several hazardous components into the atmosphere. During the spring smoke episode the ¹³⁷Cs activity concentration in the air in southern Finland increased by a factor of 10 compared to values just before the episode. Simultaneously there was an increase of a same order of magnitude in the concentrations of PM₁₀, trace metals (e.g. lead), polycyclic aromatic hydrocarbons (e.g. benzo[a]pyrene) and potassium. The ²¹⁰Po/²¹⁰Pb activity ratio increased from the usual 3–5% to even as high as 35% because Po is more volatile than Pb. The summer episode was less severe but still the mercury concentration in the air increased by a factor of two while ¹³⁷Cs activity concentration rose by a factor of eight. From the radiological point of view the exposure to the increased radionuclide concentration was insignificant compared to health hazards due to the increased concentration of aerosol particles and their chemical components.     

Carbonaceous aerosol in the breathable particulate matter (PM10) in urban area

Carbonaceous material is a large fraction of urban aerosol and it is classified into Elemental Carbon (EC) and Organic Carbon (OC). EC particles are emitted from combustion sources. Because most combustion sources are anthropogenic and generally EC does not undergo chemical transformations, EC is a good indicator of primary anthropogenic primary pollution. OC particles species are emitted from primary emission sources either anthropogenic or biogenic sources. In this paper we have measured the ground concentration of Particulate Matter (PM), Total Carbon (TC), EC and OC in two Monitoring Stations in Rome. The first station is situated downtown Rome (near S.M. Maggiore Cathedral) where the traffic emission flux is strong. The second station is located in the inner a green park (Villa Ada Park): this site is not directly influenced by anthropogenic emissions. The results show that in Rome the TC contribution is about 30% of PM and the OC/EC vary between 0.5 and 1.5 according to the site we are considering. About the chemical particle composition the long-chain carboxylic have been identified as major constituent of organic aerosol and a range values are reported for two important compound class, the Polyciclic Aromatic Hydrocarbons and the nitro-PAHs wich are at very low levels.     

Isotope effect in the carbonyl sulfide reaction with O(3P)

The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC(34)S relative to OC(32)S was found to be 0.9783 ± 0.0062 ((34)ε = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be (34)ε = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)ε in OCS photolysis and OH oxidation are not larger than 10‰, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.     

Experimental approach of co-firing and anaerobic fermentation of biomass and coal, and their thermochemical properties

This article studied two sorts of biomass (corn and beech sawdust) and two varieties of coal (bituminous coal and lignite), which can produce energy using two different technologies: co-firing and anaerobic fermentation in pilot installations, in order to determine the future perspectives of those materials for large scale applications. By thermal analysis, the thermochemical characteristics of biomass (corn and beech sawdust) and of coal (bituminous coal from Jiu Valley and lignite from Oltenia basin) were determined. The co-firing tests have been achieved at a ratio of 15?% biomass, the rest being coal. At biomass?Ccoal co-firing, the SO₂, NO_x, CO, CO₂ and fly ash concentrations in the flue gases is lower than the burning of fossil fuels. In the anaerobic fermentation of biomass, the maximum concentration of methane inside the produced biogas was 50?C55?% by volume in the beech sawdust batch and 67?C68?% by volume in the corn batch.