Airborne particulate endocrine disrupting compounds in China:Compositions, size distributions and seasonal variations ofphthalate esters and bisphenol A

Phthalate esters and bisphenol A (BPA) are endocrine disrupting compounds (EDCs) and ubiquitously occur in the environment. In the past decade we have characterized atmospheric organic aerosols from various environments (e.g., urban, rural, mountain and marine) of East Asia on a molecular level, but not investigated EDCs in the samples. In the current study we re-analyzed our database for concentrations, compositions and size distributions of phthalates and BPA and compared with those in the literature to improve the understanding on air pollution status in China. Our results showed that airborne particulate phthalates and BPA are 63&ndash;1162 ng m&minus;3 and 1.0&ndash;20 ng m&minus;3 in the urban regions in China, respectively, being one to two orders of magnitude higher than those in the developed countries. Among the detected phthalates in Chinese urban areas, bis(2-ethylhexyl) phthalate (BEHP) is the predominant congener, contributing to 23&ndash;79% (ave. 53 &plusmn; 15%) of the total phthalates. Concentrations of phthalates and bisphenol A in Shanghai and Xi&#39;an (two mega-cities in China) in 2009 were 3&ndash;84% lower than those in 2003, probably indicating a positive effect of the government&#39;s air pollution control in the recent years. Phthalates are higher in summer than in winter, because they are not chemically bonded to the polymeric matrix and more easily evaporate into the air under higher temperature conditions. Based on the size distribution observation, we found that diisobutyl and dibutyl phthalates mainly exist in coarse particles because of high volatilities, in contrast to BEHP and BPA, which are dominant in fine particles due to less volatility. Our results also indicate that BPA is mostly derived from the open burning of solid waste while phthalates are derived from both direct evaporation from the matrix and solid waste combustion.</p

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

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

Characteristics of surface ozone at an urban site of Xi'an in Northwest China

Surface ozone concentrations in Xi&#39;an, China were monitored from March 23, 2008 to January 12, 2009 using the Model ML/EC9810 ozone analyzer. The daily average O(3) ranged from &lt;1 ppb to 64.2 ppbv with an annual average of 16.0 ppbv. The seasonal average of O(3) in summer (32.5 ppbv) was more than 10 times higher than that in winter (3.0 ppbv). A significant positive correlation was found between ozone concentration and ambient temperature, indicating that the intensity of solar radiation was one of the several major factors controlling surface ozone production. Using the NOAA HYSPLIT 4 trajectory model, the three longest O(3) pollution episodes were found to be associated with the high biogenic volatile organic carbon (BVOC) emissions from the vegetation of Qinling Mountains. No significant weekday and weekend difference in O(3) levels was detected due to the non-significant change in NO(x) emissions. O(3) depletion by NO emission directly emitted from vehicles, low oxygenated VOC concentrations, and low-level solar radiation caused by high aerosol loading all contributed to the low levels of O(3) found in Xi&#39;an compared to other cities and rural areas.</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

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

Molecular distribution and seasonal variation of hydrocarbons in PM2.5 from Beijing during 2006

Normal (n)-alkanes and polycyclic aromatic hydrocarbons (PAHs) in PM2.5 were collected from Beijing in 2006 and analyzed using a thermal desorption-GC/MS technique. Annual average concentrations of n-alkanes and PAHs were 282 +/- 96 and 125 +/- 150 ng/m(3), respectively: both were highest in winter and lowest in summer. C-19-C-25 compounds dominated the n-alkanes while benzo[b]fluoranthene, benzo[e]pyrene, and phenanthrene were the most abundant PAHs. The n-alkanes exhibited moderate correlations with organic carbon (OC) and elemental carbon (EC) throughout the year, but the relationships between the PAHs, OC and EC differed between the heating and non-heating seasons. The health risks associated with PAHs in winter were more than 40 times those in spring and summer even though the PM2.5 loadings were comparable. Carbon preference index values (&lt;1.5) indicated that the n-alkanes were mostly from fossil fuel combustion. The ratios of indeno[123-cd]pyrene to benzo[ghi]pyrelene in summer and spring were 0.58 +/- 0.12 and 0.63 +/- 0.09, respectively, suggesting that the PAHs mainly originated from motor vehicles, but higher ratios in winter reflected an increased influence from coal, which is extensively burned for domestic heating. A comprehensive comparison showed that PAH pollution in Beijing has decreased in the past 10 years.</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

Comparison of abundances, compositions and sources of elements, inorganic ions and organic compounds in atmospheric aerosols from Xi'an and New Delhi, two megacities in China and India

Wintertime TSP samples collected in the two megacities of Xi&#39;an, China and New Delhi, India were analyzed for elements, inorganic ions, carbonaceous species and organic compounds to investigate the differences in chemical compositions and sources of organic aerosols. The current work is the first time comparing the composition of urban organic aerosols from China and India and discussing their sources in a single study. Our results showed that the concentrations of Ca, Fe, Ti, inorganic ions, EC, PAHs and hopanes in Xi&#39;an are 1.3-2.9 times of those in New Delhi, which is ascribed to the higher emissions of dust and coal burning in Xi&#39;an. In contrast, Cl- levoglucosan, n-alkanes, fatty alcohols, fatty acids, phthalates and bisphenol A are 0.4-3.0 times higher in New Delhi than in Xi&#39;an, which is attributed to strong emissions from biomass burning and solid waste incineration. PAHs are carcinogenic while phthalates and bisphenol A are endocrine disrupting. Thus, the significant difference in chemical compositions of the above TSP samples may suggest that residents in Xi&#39;an and New Delhi are exposed to environmental hazards that pose different health risks. Lower mass ratios of octadecenoic acid/octadecanoic acid (C-18:1/C-18:0) and benzo(a)pyrene/benzo(e)pyrene (BaP/BeP) demonstrate that aerosol particles in New Delhi are photochemically more aged. Mass closure reconstructions of the wintertime TSP indicate that crustal material is the most abundant component of ambient particles in Xi&#39;an and New Delhi, accounting for 52% and 48% of the particle masses, respectively, followed by organic matter (24% and 23% in Xi&#39;an and New Delhi, respectively) and secondary inorganic ions (sulfate, nitrate plus ammonium, 16% and 12% in Xi&#39;an and New Delhi, respectively).</p

Day-night differences and seasonal variations of chemical species in PM10 over Xi'an, northwest China

To investigate day-night differences and seasonal variations of PM10 and its chemical composition in an urban environment in Xi&#39;an, northwest China, day- and nighttime PM10 mass and its chemical components including water-soluble ions (Na+, NH4 (+), K+, Mg2+, Ca2+, F-, Cl-, NO3 (-), and SO4 (2-)), organic carbon (OC), elemental carbon, and water-soluble organic carbon (WSOC) were measured on selected representative days from 20 December 2006 to 12 November 2007. Annual mean PM10 concentration in this city was five times of the China Ambient Air Quality Standard for annual average (70 mu g m(-3)). Carbonaceous fractions and water-soluble ions accounted for nearly one third and 12.4 %, respectively, of the annual mean PM10 mass. No dramatic day-night differences were found in the loadings of PM10 or its chemical components. Spring samples were highlighted by abundance of Ca2+, while the secondary aerosol species (SO4 (2-), NO3 (-), and NH4 (+)) and OC dominated in summer, autumn, and winter samples. Relatively low NO3 (-)/SO4 (2-) ratio suggested that stationary source emissions were more important than vehicle emissions in the source areas in this city. Strong relationships between WSOC and biomass markers (water-soluble K+, OC1, and OP) were observed in winter and autumn, indicating that WSOC was derived mainly from biomass burning in these seasons. This was also supported by analysis results on the biomass burning events. In contrast, poor correlations between WSOC and biomass markers were demonstrated in summer and spring, implying that WSOC was mainly formed as secondary organic carbon through photochemical activities.</p