Size-resolved airborne particulate oxalic and related secondary organicaerosol species in the urban atmosphere of Chengdu, China

Size-segregated (9-stages) airborne particles during winter in Chengdu city of China were collected on a day/night basis and determined for dicarboxylic acids (diacids), ketocarboxylic acids (ketoacids), α-dicarbonyls, inorganic ions, and water-soluble organic carbon and nitrogen (WSOC and WSON). Diacid concentration was higher in nighttime (1831 ± 607 ng m− 3) than in daytime (1532 ± 196 ng m− 3), whereas ketoacids and dicarbonyls showed little diurnal difference. Most of the organic compounds were enriched in the fine mode (< 2.1 μm) with a peak at the size range of 0.7–2.1 μm. In contrast, phthalic acid (Ph) and glyoxal (Gly) presented two equivalent peaks in the fine and coarse modes, which is at least in part due to the gas-phase oxidation of precursors and a subsequent partitioning into pre-existing particles. Liquid water content (LWC) of the fine mode particles was three times higher in nighttime than in daytime. The calculated in-situ pH (pHis) indicated that all the fine mode aerosols were acidic during the sampling period and more acidic in daytime than in nighttime. Robust correlations of the ratios of glyoxal/oxalic acid (Gly/C2) and glyoxylic acid/oxalic acid (ωC2/C2) with LWC in the samples suggest that the enhancement of LWC is favorable for oxidation of Gly and ωC2 to produce C2. Abundant K+ and Cl− in the fine mode particles and the strong correlations of K+ with WSOC, WSON and C2 indicate that secondary organic aerosols in the city are significantly affected by biomass burning emission

Atmospheric oxalic acid and related secondary organic aerosols inQinghai Lake, a continental background site in Tibet Plateau

Summertime PM2.5 aerosols collected from Qinghai Lake (3200ma.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2-C11), ketocarboxylic acids and &alpha;-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231&plusmn;119ngm-3), ketocarboxylic acids (8.4&plusmn;4.3ngm-3), and &alpha;-dicarbonyls (2.7&plusmn;2.1ngm-3) at the Tibetan background site are 2-5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30-400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and &alpha;-dicarbonyls at this background site.</p

Column-Integrated Aerosol Optical Properties during Summer and Autumn of 2012 in Xi'an, China

Column-integrated aerosol optical properties were derived systematically from measurements made in Xi&#39;an, which is located in Guanzhong Plain of central China with a ground-based CIMEL sun photometer from May to November 2012. Aerosol optical depths (AODs), Angstrom exponents, water vapor contents, and aerosol optical and micro-physical properties, including aerosol volume size distribution, complex refractive indices and single scattering albedo (SSA), were determined. Daily variations in AODs at 440 nm (tau(440)) generally followed those of the 24-hr PM2.5 mass concentrations, but there were differences in the relationships in summer and autumn. August showed the highest monthly tau(440) (1.13) while the largest monthly Angstrom exponent (alpha(440-870) = 1.30) and water vapor content (C-w = 4.28) both occurred in July. Monthly averages of the aerosol size distributions showed the dominance of coarse mode aerosols, except in July and August, when the contribution of the accumulation and coarse modes were fairly comparable. Monthly changes in the complex refractive index (including both real and imaginary parts) and SSA were also studied, including their wavelength dependences; these analyses implied changes in the abundances of the aerosol types. Finally, an episode involving urban and dust aerosols was analyzed using sun photometer aerosol retrievals; MODIS images captured by Aqua satellite and average wind vectors from the NCEP operational global analyses were also considered in the case study.</p

Seasonal characteristics of oxalic acid and related SOA in the free troposphere of Mt. Hua, central China: Implications for sources and formation mechanisms

PM10 aerosols from the summit of Mt. Hua (2060 m a.s.l) in central China during the winter and summer of 2009 were analyzed for dicarboxylic acids, ketocarboxylic acids and alpha-dicarbonyls. Molecular composition of dicarboxylic acids (C-2-C-11) in the free tropospheric aerosols reveals that oxalic acid (C-2, 399 +/- 261 ng m(-3) in winter and 522 +/- 261 ng m(-3) in summer) is the most abundant species in both seasons, followed by malonic (C-3) and succinic (C-4) acids, being consistent with that on ground levels. Most of the diacids are more abundant in summer than in winter, but adipic (C-6) and phthalic (Ph) acids are twice lower in summer, suggesting more significant impact of anthropogenic pollution on the wintertime alpine atmosphere. Moreover, glyoxal (Gly) and methylglyoxal (mGly) are also lower in summer (12 +/- 6.1 ng m(-3)) than in winter (22 +/- 13 ng m(-3)). As both dicarbonyls are a major precursor of C-2, their seasonal variation patterns, which are opposite to those of the diacids, indicate that the mountain troposphere is more oxidative in summer. C-2 showed strong linear correlations with levoglucosan in winter and oxidation products of isoprene and monoterpane in summer. PCA analysis further suggested that the wintertime C-2 and related SOA in the Mt Hua troposphere mostly originate from photochemical oxidations of anthropogenic pollutants emitted from biofuel and coal combustion in lowland regions. On contrast, the summertime C-2 and related SOA mostly originate from further oxidation of the mountainous isoprene and monoterpene oxidation products. The AIM model calculation results showed that oxalic acid concentration well correlated with particle acidity (R-2 = 0.60) but not correlated with particle liquid water content, indicating that particle acidity favors the organic acid formation because aqueous-phase C-2 production is the primary mechanism of C-2 formation in ambient aerosols and is driven by acid-catalyzed oxidation.</p

Airborne particulate organic markers at the summit (2060 m,a.s.l.) of Mt. Hua in central China during winter: Implications for biofuel and coal combustion

Sugars, n-alkanes and PAHs in PM10 and size-segregated samples collected from the summit (2060 m, altitude) of Mt. Hua in Guanzhong Plain, central China during the winter of 2009 were characterized using a GC/MS technique. Concentrations of sugars, n-alkanes and PAHs in PM10 are 107&plusmn;52, 121&plusmn;63, 7.3&plusmn;3.4 ng m&minus;3, respectively. Levoglucosan and fossil fuel derived n-alkanes are more abundant in the air masses transported from southern China than in those from northern China with no spatial difference found for PAHs, suggesting that emissions from biomass burning and vehicle exhausts are more significant in southern part of the country. Dehydrated sugars, fossil fuel derived n-alkanes and PAHs presented a unimode size distribution, peaking at the size of 0.7&ndash;1.1 &mu;m, whereas non-dehydrated sugars and plant wax derived n-alkanes showed a bimodal pattern, peaking at 0.7&ndash;2.1 and 5.8&ndash;9.0 &mu;m, respectively. Principal component analysis showed that biofuel combustion plus plant emission is the most important source in Mt. Hua, being different from the cases in Chinese urban areas where fossil fuel combustion is the major source. By comparison with previous mountain and lowland observations and aircraft measurements we found that wintertime PAHs in China are still characterized by coal burning emissions especially in the inland regions, although in the country increasing rate of SO2 emission from coal combustion has decreased and emissions of vehicle exhaust has sharply increased.</p

Characteristics and major sources of carbonaceous aerosols in PM2.5 fromSanya, China

PM2.5 samples were collected in Sanya, China in summer and winter in 2012/2013. Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including n-alkanes (n-C14-n-C40) and polycyclic aromatic hydrocarbons (PAHs) were quantified. The concentrations of these carbonaceous matters were generally higher in winter than summer. The estimated secondary organic carbon (OCsec) accounted for 38% and 54% of the total organic carbon (TOC) in winter and summer, respectively. The higher value of OCsec in addition to the presences of photochemically-produced PAHs in summer supports that photochemical conversions of organics are much active at the higher air temperatures and with stronger intense solar radiation. Carbon preference index (CPI) and percent contribution of wax n-alkanes suggest that anthropogenic sources were more dominant than derivation from terrestrial plants in Sanya. Diagnostic ratios of atmospheric PAHs further indicate that there was a wide mix of pollution sources in winter while fossil fuel combustion was the most dominant in summer. Positive Matrix Factorization (PMF) analysis with 18 PAHs in the winter samples found that motor vehicle emissions and biomass burning were the two main pollution sources, contributing 37.5% and 24.6% of the total quantified PAHs, respectively.</p

Chemical composition and size distribution of wintertime aerosols in the atmosphere of Mt. Hua in central China

TSP, PM(10) and size-segregated aerosols were collected at the summit (2060 m, a.s.l.) of Mt. Hua in central China during the winter of 2009, and determined for organic (OC) and elemental carbon (EC), pH of water-extracts and inorganic ions. OC in TSP and PM(10) are 6.9 +/- 2.9 and 5.9 +/- 2.5 mu g m(-3), while EC in TSP and PM(10) are 0.9 +/- 0.6 and 0.9 +/- 0.5 mu g m(-3), respectively. SO(4)(2-), NO(3)(-), NH(4)(+) and Ca(2)(+) are major ions in PM(10) with concentrations of 5.8 +/- 3.7, 2.7 +/- 1.6, 1.6 +/- 0.9 and 1.5 +/- 0.7 mu g m(-3), respectively. OC/EC ratios (8.2 +/- 3.1 in TSP and 6.6 +/- 1.8 in PM(10)) at the mountaintop are 2-4 times higher than those in lowland surface, suggesting an enhanced transformation of organics from gas- to solid- phase because of an increased photochemical oxidation and/or an increased condensation due to lower temperature, as well as an increased organic input from mountain plant emission. Air mass backward trajectories showed that compared with those derived from north/northwest China aerosols transported from the south contained higher concentrations of SO(4)(2-) and NH(4)(+) and lower concentrations of Ca(2+). Size distributions of NH(4)(+) and K(+) presented as an accumulation mode with a peak at 0.7-1.1 mu m, in contrast to Ca(2+) and Mg(2+), which maximized at the size 4.7-5.8 mu m as a coarse mode. SO(4)(2-) and NO(3)(-) showed a bimodal pattern with a large peak at the range 0.7-1.1 mu m and a small peak at the size of 4.7-5.8 mu m, whereas Na(+) and Cl(-) displayed a bimodal pattern with two equivalent peaks in the fine (&lt; 2.1 mu m) and coarse (&gt;= 2.1 mu m) ranges. pH values of the water-extracts demonstrate that aerosols originate from southern China are more acidic than those from the north/northwest, and the particles with a diameter of 0.7-11 mu m are most acidic.</p

Comparison of dicarboxylic acids and related compounds in aerosol samples collected in Xi'an, China during haze and clean periods

PM10 aerosols from Xi&#39;an, a mega city of China in winter and summer, 2009 were measured for secondary organic aerosols (SOA) (i.e., dicarboxylic acids (DCA), keto-carboxylic acids, and &alpha;-dicarbonyls), water-soluble organic (WSOC) and inorganic carbon (WSIC), elemental carbon (EC) and organic carbon (OC). Molecular compositions of SOA on haze and clean days in both seasons were compared to investigate their sources and formation mechanisms. DCA in the samples were 1843&plusmn;810ngm-3 in winter and 1259&plusmn;781ngm-3 in summer, respectively, which is similar and even higher than those measured in 2003. Oxalic acid (C2, 1162&plusmn;570ngm-3 in winter and 1907&plusmn;707ngm-3 in summer) is the predominant species of DCA, followed by t-phthalic (tPh) in winter and phthalic (Ph) in summer. Such a molecular composition is different from those in other Asian cities where succinic acid (C4) or malonic acid (C3) is the second highest species, which is mostly due to significant emissions from household combustion of coal and open burning of waste material in Xi&#39;an. Mass ratios of C2/diacids, diacids/WSOC, WSOC/OC and individual diacid-C/WSOC are higher on the haze days than on the clean days in both seasons, suggesting an enhanced SOA production under the haze condition. We also found that the haze samples are acidic while the clean samples are almost neutral. Such a difference in particle acidity is consistent with the enhanced SOA production, because acid-catalysis is an important aqueous-phase formation pathway of SOA. Gly/mGly mass ratio showed higher values on haze days than on clean day in both seasons. We comprehensively investigated the ratio in literature and found a consistent pattern. Based on our observation results and those documented data we proposed for the first time that concentration ratio of Gly/mGly can be taken as an indicator of aerosol ageing.</p

N-Alkanes and polycyclic aromatic hydrocarbons in total suspended particulates from the southeastern Tibetan Plateau: Concentrations, seasonal variations, and sources

Sixty-two suspended particle (TSP) samples were collected from Lulang on the southeastern Tibetan Plateau from July 2008 and July 2009 to investigate the concentrations, seasonal variations, and sources of n-alkanes and polycyclic aromatic hydrocarbons (PAHs). Samples were analyzed using thermal-deposition gas chromatography mass spectrometry. The concentrations of particulate total n-alkanes ranged from 0.10 to 21.83ngm-3, with an annual mean of 1.25ngm-3; the PAHs ranged from 0.06 to 2.53, with a mean of 0.59 ngm-3. Up to 70% of PAHs were 5- and 6-ring compounds. The n-alkanes and PAHs both showed higher concentrations in winter and lower concentrations in summer. Analyses of diagnostic ratios indicate that 6.4% to 58.9% (mean 24.9%) of the n-alkanes were from plant waxes. Source characterization studies, i.e. diagnostic ratio and positive factor matrix analysis, suggest that the PAHs were from biomass burning as well as from fossil fuel combustion. Backward trajectory analysis suggests that the biomass mass burning pollutants could be from South Asia and western China via long distance transport. The study contributes to a more comprehensive understanding of the concentrations, seasonal variations, and sources of n-alkanes and PAHs in a remote background area in Tibetan Plateau.</p

Selected water-soluble organic compounds found in size-resolved aerosols collected from urban, mountain and marine atmospheres over East Asia

Primary (i.e. sugars and sugar-alcohols) and secondary (i.e. carboxylic acids) water-soluble organic compounds (WSOCs) in size-segregated aerosols from the urban and mountain atmosphere of China and from the marine atmosphere in the outflow region of East Asia were characterized on a molecular level. Levoglucosan is the most abundant compound among the quantified WSOCs in the urban and mountain atmosphere, whose concentration at the urban site was 1-2 orders of magnitude higher than that at the mountain and marine sites. In contrast, malic, succinic and phthalic acids were dominant among the measured WSOCs at the marine site. In the urban air, sugars except levoglucosan gave a bimodal size distribution with a large peak in fine range (&lt;2.1 mu m) and a small peak in coarse range (&gt;= 2.1 mu m) during winter, being opposite to those in spring. In contrast, these WSOCs at the mountain and marine sites dominated in the coarse range but diminished and even disappeared in the fine range. Geometric mean diameters (GMDs) of the measured WSOCs in the fine mode at the urban site were larger in winter than in spring. Levoglucosan and carboxylic acids except for azelaic and benzoic acids showed a larger GMD in the coarse mode at the marine site probably due to an increased hygroscopic growth.</p