ALBERT

Description: Ground-based PM2.5 samples collected at four different sites in Pearl River Delta region (PRD) during winter and summer (from 14 December 2006 to 28 January 2007 in winter and from 4 July to 9 August 2007 in summer) were analyzed for 30 water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids and dicarbonyls, nine fatty acids, and benzoic acid. Molecular distributions of dicarboxylic acids demonstrated that oxalic acid (C2) was the most abundant species followed by phthalic acid (Ph) in PRD region. The concentrations of total dicarboxylic acids ranged from 99 to 1340 ng m−3, with an average of 438 ± 267 ng m−3 in PRD. The concentrations of total ketocarboxylic acids ranged from 0.6 to 207 ng m−3 (43 ± 48 ng m−3 on average) while the concentrations of total α-dicarbonyls, including glyoxal and methylglyoxal, ranged from 0.2 to 89 ng m−3, with an average of 11 ± 18 ng m−3 in PRD. The total quantified water-soluble compounds (TQWOC) (organic carbon) accounted for 3.4 ± 2.2% of OC and 14.3 ± 10.3% of water-soluble OC (WSOC). Hexadecanoic acid (C16:0), octadecanoic acid (C18:0) and oleic acid (C18:1) were the three most abundant fatty acids in PRD. The distributions of fatty acids were characterized by a strong even carbon number predominance with a maximum (Cmax) at hexadecanoic acid (C16:0). Ratio of C18:1 to C18:0 acts as an indicator for aerosol aging. In PRD, an average of C18:1/C18:0 ratio was 0.53 ± 0.39, suggesting an enhanced photochemical degradation of unsaturated fatty acid. Moreover, the concentrations of benzoic acid ranged from 84 to 306 ng m−3, (165 ± 48 ng m−3 on average), which can be emitted as primary pollutant from motor vehicles exhaust, or formed from photochemical degradation of aromatic hydrocarbons. Seasonal variations of the organic specie concentrations were found in the four sampling cities. Higher concentrations of TQWOC were observed in winter (598 ± 321 ng m−3) than in summer (372 ± 215 ng m−3). However, the abundances of TQWOC in OC mass were higher in summer (0.9–12.4%, 4.5 ± 2.7% on average) than in winter (1.1–5.7, 2.5 ± 1.2% on average), being consistent with enhanced secondary production of dicarboxylic acids in warmer weather. Spatial variations of water-soluble dicarboxylic acids were characterized by higher concentrations in Hong Kong and lower concentrations in Guangzhou (GZ)/Zhaoqing (ZQ) during winter whereas the highest concentrations were observed in GZ/ZQ during summer. These spatial and seasonal distributions are consistent with photochemical production and the subsequent accumulation under different meteorological conditions.

Description: Vehicle emissions of volatile organic compounds (VOCs) were determined at the Shing Mun Tunnel, Hong Kong in summer and winter of 2003. One hundred and ten VOCs were quantified in this study. The average concentration of the total measured VOCs at the inlet and outlet of the tunnel were 81 250 pptv and 117 850 pptv, respectively. Among the 110 compounds, ethene, ethyne and toluene were the most abundant species in the tunnel. The total measured VOC emission factors ranged from 67 mg veh−1 km−1 to 148 mg veh−1 km−1, with an average of 115 mg veh−1 km−1. The five most abundant VOCs observed in the tunnel were, in decreasing order, ethene, toluene, n-butane, propane and i-pentane. These five most abundant species contributed over 38% of the total measured VOCs emitted. The high propane and n-butane emissions were found to be associated with liquefied petroleum gas (LPG)-fueled taxis. Fair correlations were observed between marker species (ethene, i-pentane, n-nonane, and benzene, toluene, ethylbenzene and xylenes – BTEX) with fractions of gasoline-fueled or diesel-fueled vehicles. Moreover, ethene, ethyne, and propene are the key species that were abundant in the tunnel but not in gasoline vapors or LPG. The ozone formation potential from the VOCs in Hong Kong was evaluated by the maximum increment reactivity (MIR). It was found to be 568 mg of ozone per vehicle per kilometer traveled. Among them, ethene, propene and toluene contribute most to the ozone-formation reactivity.

Description: Continuous measurements of atmospheric organic and elemental carbon (OC and EC) were taken during the high-pollution fall and winter seasons at Xi'an, Shaanxi Province, China from September 2003 through February 2004. Battery-powered mini-volume samplers collected PM2.5 samples daily and PM10 samples every third day. Samples were also obtained from the plumes of residential coal combustion, motor-vehicle exhaust, and biomass burning sources. These samples were analyzed for OC/EC by thermal/optical reflectance (TOR) following the Interagency Monitoring of Protected Visual Environments (IMPROVE) protocol. OC and EC levels at Xi'an are higher than most urban cities in Asia. Average PM2.5 OC concentrations in fall and winter were 34.1±18.0 μg m−3 and 61.9±;33.2 μg m−3, respectively; while EC concentrations were 11.3±6.9 μg m−3 and 12.3±5.3 μg m−3, respectively. Most of the OC and EC were in the PM2.5 fraction. OC was strongly correlated (R〉0.95) with EC in the autumn and moderately correlated (R=0.81) with EC during winter. Carbonaceous aerosol (OC×1.6+EC) accounted for 48.8%±10.1% of the PM2.5 mass during fall and 45.9±7.5% during winter. The average OC/EC ratio was 3.3 in fall and 5.1 in winter, with individual OC/EC ratios nearly always exceeding 2.0. The higher wintertime OC/EC corresponded to increased residential coal combustion for heating. Total carbon (TC) was associated with source contributions using absolute principal component analysis (APCA) with eight thermally-derived carbon fractions. During fall, 73% of TC was attributed to gasoline engine exhaust, 23% to diesel exhaust, and 4% to biomass burning. During winter, 44% of TC was attributed to gasoline engine exhaust, 44% to coal burning, 9% to biomass burning, and 3% to diesel engine exhaust.

Description: To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM2.5 and PM10 samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ13C) of OC and EC were –26.9±0.5‰ and –25.6±0.1‰, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC 13C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.

Description: This work presents a case study which includes regions of large rapidly varying vertical velocities observed by a VHF wind-profiler at Aberystwyth (52.4° N, 4.1° W). Analysis indicates that this region is associated with gravity waves above the tropopause level and simultaneous regions of convective activity below the tropopause level. This case study also suggests that convective activity can be identified effectively by finding periods of large uncertainties on the derived velocities. These regions are hypothesized to be related to regions of small-scale inhomogeneity in the wind field. Examination suggests that the large vertical velocity fluctuations above these convective regions are short period gravity wave packets as expected from theory. In addition the vertical flux of the horizontal momentum associated with the gravity waves also displays the pattern of reversal observed in previous studies.

Description: Numerous definitions and analytical techniques for elemental (or black) carbon (EC) have been published in the scientific literature, but still no generally accepted interdisciplinary definition exists. EC is not a single chemical compound, but is mainly composed of two parts of carbon contents: combustion residues from pyrolysis and combustion emissions formed via gas-to-particle conversion. Accordingly EC is subdivided into two classes: char and soot. Char is defined as carbonaceous materials obtained by heating organic substances and formed directly from pyrolysis, or as an impure form of graphitic carbon obtained as a residue when carbonaceous material is partially burned or heated with limited access of air. Soot is defined as only those carbon particles that form at high temperature via gas-phase processes. Since the different classes of EC have different chemical and physical properties, their optical light-absorbing properties differ, so that it is essential to differentiate them in the environment. The thermal optical reflectance (TOR) method was used to differentiate between char-EC and soot-EC according to its stepwise thermal evolutional oxidation of different carbon fractions under different temperatures and atmosphere. Char-EC and soot-EC are operationally defined as EC1-OP and EC2+EC3 (EC1, EC2 and EC3 corresponding to carbon fractions evolved at 550, 700 and 800 °C in a 98% He/2% O2 atmosphere, respectively), respectively. One year of observations of the daily and seasonal variations of carbonaceous particles were conducted in Xi'an, China in 2004 to demonstrate the different characteristics of char and soot in the atmosphere. Total carbon (TC), organic carbon (OC), EC and char-EC showed similar seasonal trends, with high concentrations in winter and low concentrations in summer, while soot-EC revealed relatively small seasonal variations, with maximum concentration (1.85±0.72 μg m−3) in spring and minimum concentration (1.15±0.47 μg m−3) in summer. The strong correlation between EC and char-EC (R2 = 0.99) and poor correlation between EC and soot-EC (R2 = 0.31) indicate that previously reported total EC in the literature reflected the distribution characteristics of char only, while overlooking that of soot. However, soot exhibits stronger light-absorbing characteristics than char, and merits greater focus in climate research. The small seasonal variation of soot-EC indicates that soot may be the background fraction in total EC, and is likely to have an even longer lifetime in the atmosphere than previously estimated for total EC, which suggests that soot may has a greater contribution to global warming. While both char-EC/soot-EC and primary OC/EC ratios vary with emission sources, only OC/EC ratio is affected by SOA. Thus char-EC/soot-EC may be a more effective indicator than OC/EC in source identification of carbonaceous aerosol. Comparison of seasonal variations of OC/EC and char-EC/soot-EC ratios in Xi'an confirms this point. However, wet scavenging by snow and rain was more effective for char than for soot and influenced the char-EC/soot-EC ratio, and this factor should be considered in source identification as well.

Description: We simulated elemental carbon (EC) and organic carbon (OC) aerosols in China and compared model results to surface measurements at Chinese rural and background sites, with the goal of deriving "top-down" emission estimates of EC and OC, as well as better quantifying the secondary sources of OC. We included in the model state-of-the-science Chinese "bottom-up" emission inventories for EC (1.92 TgC yr−1) and OC (3.95 TgC yr−1), as well as updated secondary OC formation pathways. The average simulated annual mean EC concentration at rural and background sites was 1.1 μgC m−3, 56% lower than the observed 2.5 μgC m−3. The average simulated annual mean OC concentration at rural and background sites was 3.4 μgC m−3, 76% lower than the observed 14 μgC m−3. Multiple regression to fit surface monthly mean EC observations at rural and background sites yielded the best estimate of Chinese EC source of 3.05 ± 0.78 TgC yr−1. Based on the top-down EC emission estimate and observed seasonal primary OC/EC ratios, we estimated Chinese OC emissions to be 6.67 ± 1.30 TgC yr−1. Using these top-down estimates, the simulated average annual mean EC concentration at rural and background sites was significantly improved to 1.9 μgC m−3. However, the model still significantly underestimated observed OC in all seasons (simulated average annual mean OC at rural and background sites was 5.4 μgC m−3), with little skill in capturing the spatiotemporal variability. Secondary formation accounts for 21% of Chinese annual mean surface OC in the model, with isoprene being the most important precursor. In summer, as high as 62% of the observed surface OC may be due to secondary formation in eastern China. Our analysis points to four shortcomings in the current bottom-up inventories of Chinese carbonaceous aerosols: (1) the anthropogenic source is underestimated on a national scale, particularly for OC; (2) the spatiotemporal distributions of emissions are misrepresented; (3) there is a missing source in western China, likely associated with the use of biofuels or other low-quality fuels for heating; and (4) sources in fall are not well represented, either because the seasonal shifting of emissions and/or secondary formation are poorly captured or because specific fall emission events are missing. In addition, secondary production of OC in China is severely underestimated. More regional measurements with better spatiotemporal coverage are needed to resolve these shortcomings.

Description: We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 year-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant due to vigorous photochemistry and secondary organic aerosol (OA) production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matter constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We report, for the first time, a high regional correlation between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic properties of aerosol dicarboxylic acids.

Description: Thirty water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids, and benzoic acid were determined as well as organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) in PM2.5 samples collected during the Campaign of Air Quality Research in Beijing 2007 (CAREBeijing-2007) in the urban and suburban areas of Beijing. The objective of this study is to identify the influence of traffic emissions and regional transport to the atmosphere in Beijing during summer. PM2.5 samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measure on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOC), total fatty acids and benzoic acid during the entire sampling period were 1184 ± 241 ng m−3, 597 ± 159 ng m−3 and 1496 ± 511ng m−3 in PKU, and 1050 ± 303 ng m−3, 475 ± 114 ng m−3 and 1278 ± 372 ng m−3 in Yufa. Oxalic acid (C2) was found as the most abundant dicarboxylic acid at PKU and Yufa, followed by phthalic acid (Ph). A strong even carbon number predominance with the highest level at palmitic acid (C16:0), followed by stearic acid (C18:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from northeast, passing over southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from north or northwest sector (mountain areas without serious anthropogenic pollution sources) during cleaner events. The data with wind only from the same sector (minimizing the difference from regional contribution) but with and without traffic restriction in Beijing were analyzed to evaluate the effectiveness of local traffic restriction measure on the reduction of local air pollution in Beijing. The results suggested that the "traffic restriction" measure can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of elemental carbon (EC) value indicates elevated primary emissions in Yufa during restriction period than non-restriction period. This study demonstrates that even when primary exhaust was controlled by traffic restriction, the contribution of secondary organic species formed from photochemical processes was critical with long-range atmospheric transport of pollutants.

Description: We calculated the organic matter to organic carbon mass ratios (OM/OC mass ratios) in PM2.5 collected from 14 Chinese cities during summer and winter of 2003 and analyzed the causes for their seasonal and spatial variability. The OM/OC mass ratios were calculated two ways. Using a mass balance method, the calculated OM/OC mass ratios averaged 1.92 ± 0.39 yr-round, with no significant seasonal or spatial variation. The second calculation was based on chemical species analyses of the organic compounds extracted from the PM2.5 samples using dichloromethane/methanol and water. The calculated OM/OC mass ratio in summer was relatively high (1.75 ± 0.13) and spatially-invariant, due to vigorous photochemistry and secondary OA production throughout the country. The calculated OM/OC mass ratio in winter (1.59 ± 0.18) was significantly lower than that in summer, with lower values in northern cities (1.51 ± 0.07) than in southern cities (1.65 ± 0.15). This likely reflects the wider usage of coal for heating purposes in northern China in winter, in contrast to the larger contributions from biofuel and biomass burning in southern China in winter. On average, organic matters constituted 36% and 34% of Chinese urban PM2.5 mass in summer and winter, respectively. We reported, for the first time, high correlations between Zn and oxalic acid in Chinese urban aerosols in summer. This is consistent with the formation of stable Zn oxalate complex in the aerosol phase previously proposed by Furukawa and Takahashi (2011). We found that many other dicarboxylic acids were also highly correlated with Zn in the summer Chinese urban aerosol samples, suggesting that they may also form stable organic complexes with Zn. Such formation may have profound implications for the atmospheric abundance and hygroscopic property of aerosol dicarboxylic acids.