Chemical characterization of PM2.5 from a southern coastal city of China:applications of modeling and chemical tracers in demonstrationof regional transport

An intensive sampling campaign of airborne fine particles (PM2.5) was conducted at Sanya, a coastal city in Southern China, from January to February 2012. Chemical analyses and mass reconstruction were used identify potential pollution sources and investigate atmospheric reaction mechanisms. A thermodynamic model indicated that low ammonia and high relative humidity caused the aerosols be acidic and that drove heterogeneous reactions which led to the formation of secondary inorganic aerosol. Relationships among neutralization ratios, free acidity, and air-mass trajectories suggest that the atmosphere at Sanya was impacted by both local and regional emissions. Three major transport pathways were identified, and flow from the northeast (from South China) typically brought the most polluted air to Sanya. A case study confirmed strong impact from South China (e.g., Pearl River Delta region) (contributed 76.8% to EC, and then this result can be extended to primary pollutants) when the northeast winds were dominant. The Weather Research Forecasting Black carbon model and trace organic markers were used to apportion local pollution versus regional contributions. Results of the study offer new insights into the atmospheric conditions and air pollution at this coastal city

Brown Carbon Aerosol in Urban Xi’an, Northwest China: TheComposition and Light Absorption Properties

Light-absorbing organic carbon (i.e., brown carbon or BrC) in the atmospheric aerosol has significant contribution to light absorption and radiative forcing. However, the link between BrC optical properties and chemical composition remains poorly constrained. In this study, we combine spectrophotometric measurements and chemical analyses of BrC samples collected from July 2008 to June 2009 in urban Xi'an, Northwest China. Elevated BrC was observed in winter (5 times higher than in summer), largely due to increased emissions from wintertime domestic biomass burning. The light absorption coefficient of methanol-soluble BrC at 365 nm (on average approximately twice that of water-soluble BrC) was found to correlate strongly with both parent polycyclic aromatic hydrocarbons (parent-PAHs, 27 species) and their carbonyl oxygenated derivatives (carbonyl-OPAHs, 15 species) in all seasons (r(2) > 0.61). These measured parent-PAHs and carbonyl-OPAHs account for on average similar to 1.7% of the overall absorption of methanol-soluble BrC, about 5 times higher than their mass fraction in total organic carbon (OC, similar to 0.35%). The fractional solar absorption by BrC relative to element carbon (EC) in the ultraviolet range (300-400 nm) is significant during winter (42 +/- 18% for water-soluble BrC and 76 +/- 29% for methanol-soluble BrC), which may greatly affect the radiative balance and tropospheric photochemistry and therefore the climate and air quality

Biomass burning tracers in rural and urban ultrafine particles in Xi'an,China

To investigate the impact of biomass burning emissions on ultrafine particles (PM0.133: particulate matter with an aerodynamic diameter less than 0.133 μm), biomass burning tracers (including levoglucosan, mannonsan and K+) were measured at a rural and an urban sites in Xi'an during winter heating period. The average levoglucosan concentrations of rural and urban PM0.133 were 0.93 ± 0.32 μg m−3 and 0.29 ± 0.14 μg m−3, respectively. Comparable PM0.133 mannosan concentrations were observed in rural samples (0.16 ± 0.26 μg m−3) and urban samples (0.17 ± 0.10 μg m−3). Higher correlation between levoglucosan and K+ was obtained for urban samples (R = 0.86) than that for rural samples (R = 0.72). The levoglucosan to K+ ratio was found to be higher for rural samples (0.77 ± 0.39) compared to that for urban samples (0.32 ± 0.14). Levoglucosan to mannosan ratios averaged 7.86 and 2.83 for rural and urban samples, respectively. It can be concluded that the major source of rural biomass burning was the combustion of crop residuals and softwood. The contributions of biomass burning to OC ranged from 19% to 32%, with an average of 24% for rural samples. The results provide a better understanding on the rural and urban magnitude of levoglucosan and contributions of biomass burning in Xi'an

Elemental compositions of PM2.5 and TSP in Lijiang, southeastern edge of Tibetan Plateau during pre-monsoon period

PM2.5 and total suspended particulate (TSP) samples were collected at Lijiang, southeastern Tibetan Plateau, China. Sixteen elements (Al, Si, S, K, Ca, Cr, Mn, Ti, Fe, Ni, Zn, As, Br, Sb, Pb and Cu) were analyzed to investigate their elemental compositions during the pre-monsoon period. The results showed that Ca was the most abundant element in both PM2.5 and TSP samples. The enrichment factors (EFs) of Si, Ti, Ca, Fe, K and Mn were all below 10 for both PM2.5 and TSP, and these elements also had lower PM2.5/TSP ratios (0.32-0.34), suggesting that they were mainly derived from crustal sources. Elements Cu, Zn, S, Br and Sb showed strong enrichment in PM2.5 and TSP samples, with their PM2.5/TSP ratios ranging from 0.66 to 0.97, indicating that they were enriched in the fine fractions and influenced by anthropogenic sources. Analysis of the wind field at 500 hPa and calculations of back trajectories indicated that Al, Si, Ca, Ti, Cr, Mn and Fe can be influenced by transport from northwestern China during the dust-storm season, and that S, K, Ni, Br and Pb reached high concentrations during westerly transport from south Asia. Combined with the principle component analysis and correlation analysis, elements of PM2.5 samples were mainly from crustal sources, biomass burning emissions and regional traffic-related sources.</p

Seasonal variations and chemical characteristics of sub-micrometer particles (PM1) in Guangzhou, China

Daily samples of ambient sub-micrometer particles (PM1, particles with an aerodynamic diameter &le; 1.0 &mu;m) were collected from July 2009 to April 2010 at an urban site over Guangzhou in southern China. Mass concentrations of water-soluble inorganic ions, organic carbon (OC) and elemental carbon (EC) were determined to characterize the chemical composition of PM1. The mass concentration of PM1 ranged from 14.6 &mu;g m&minus; 3 to 143.3 &mu;g m&minus; 3, with an annual mean value of 52.4 &plusmn; 27.3 &mu;g m&minus; 3. Seasonally-averaged PM1 concentrations decreased in the order winter &gt; autumn &gt; spring &gt; summer. The annual mean concentrations of OC and EC were 6.2 &plusmn; 3.5 and 5.0 &plusmn; 2.9 &mu;g m&minus; 3, respectively. The OC and EC concentrations were measured following the IMPROVE_A thermal/optical reflectance (TOR) protocol. Total carbonaceous aerosol (the sum of organic matter and elemental carbon) accounted for 23.0 &plusmn; 4.4% of PM1 mass. Clear seasonal variations in OC and EC suggested sources of these two constituents were remarkable difference among the four seasons. Seasonally averaged OC/EC ratios were 1.2, 1.7, 1.4, and 1.5, from spring to winter respectively. Low OC/EC ratios in comparison with other cities in China revealed that vehicle emissions play an important role in carbonaceous aerosol levels in Guangzhou. SO42 &minus;, NO3&minus; and NH4+ were the three major inorganic ions in PM1, collectively contributing 30.0% &plusmn; 6.3% of the PM1 mass. SO42 &minus; and NH4+ were both the highest in autumn and the lowest in summer. In contrast, NO3&minus; was the highest in winter. Sulfur oxidation ratio was positively correlated with solar radiation and O3, but negatively correlated with SO2. Nitrogen oxidation ratio was positively correlated with NO2, NH4+ and Cl&minus;, but showed a negative correlation with temperature. By applying the IMPROVE equation, PM1 mass was reconstructed and showed that (NH4)2SO4, NH4NO3, OM and EC accounted for (30.7 &plusmn; 11.4) %, (9.7 &plusmn; 5.2) %, (22.6 &plusmn; 5.0) % and (9.7 &plusmn; 2.3) % of PM1, respectively. Finally, source apportionment by positive matrix factorization revealed that (1) secondary aerosol and biomass burning, (2) diesel emissions, (3) gasoline emissions and sea salt, and (4) coal combustion were the greatest contributors to PM1.</p

Comparison and implications of PM2.5 carbon fractionsin different environments

The concentrations of PM2.5 carbon fractions in rural, urban, tunnel and remote environments were measured using the IMPROVE thermal optical reflectance (TOR) method. The highest OC1 and EC1 concentrations were found for tunnel samples, while the highest OC2, OC3, and OC4 concentrations were observed for urban winter samples, respectively. The lowest levels of most carbon fractions were found for remote samples. The percentage contributions of carbon fractions to total carbon (TC) were characterized by one peak (at rural and remote sites) and two peaks (at urban and tunnel sites) with different carbon fractions, respectively. The abundance of char in tunnel and urban environments was observed, which might partly be due to traffic-related tire-wear. Various percentages of optically scattering OC and absorbing EC fractions to TC were found in the four different environments. In addition, the contribution of heating carbon fractions (char and soot) indicated various warming effects per unit mass of TC. The ratios of OC/EC and char/soot at the sites were shown to be source indicators. The investigation of carbon fractions at different sites may provide some information for improving model parameters in estimating their radiative effects.</p

Light attenuation cross-section of black carbon in an urbanatmosphere in northern China

Fine particulate matter (PM2.5) samples were collected over two years in Xi&rsquo;an, China to investigate the relationships between the aerosol composition and the light absorption efficiency of black carbon (BC). Real-time light attenuation of BC at 880&nbsp;nm was measured with an aethalometer. The mass concentrations and elemental carbon (EC) contents of PM2.5 were obtained, and light attenuation cross-sections (&sigma;ATN) of PM2.5 BC were derived. The mass of EC contributed &sim;5% to PM2.5 on average. BC &sigma;ATN exhibited pronounced seasonal variability with values averaging 18.6, 24.2, 16.4, and 26.0&nbsp;m2/g for the spring, summer, autumn, and winter, respectively, while averaging 23.0&nbsp;m2/g overall. &sigma;ATN varied inversely with the ratios of EC/PM2.5, EC/[SO42&minus;], and EC/[NO3&minus;]. This study of the variability in &sigma;ATN illustrates the complexity of the interactions among the aerosol constituents in northern China and documents certain effects of the high EC, dust, sulfate and nitrate loadings on light attenuation.</p

Measuring and Modeling Black Carbon (BC) Contamination in the SE Tibetan Plateau,

Black carbon (BC) concentrations were measured in the southeast (SE) Tibetan Plateau along the valley of the Yarlung Tsangpo River during winter (between November, 2008 and January, 2009). The measured mean concentration (0.75 &mu;g m&minus;3) is significantly higher than the concentrations (0.004&ndash;0.34 &mu;g m&minus;3) measured in background and remote regions of the globe, indicating that Tibetan glaciers are contaminated by BC particles in the Plateau. Because BC particles play important roles for the climate in the Tibetan Plateau, the sources and causes of the BC contamination need to be understood and investigated. In this study, a mesocale dynamical model (WRF) with BC particle modules is applied for analyzing the measurement. The analysis suggests that the major sources for the contamination in the SE Plateau were mainly from the BC emissions in eastern Indian and Bangladesh. Because of the west prevailing winds, the heavy emissions in China had no significant effects on the SE Plateau in winter. Usually, the high altitude of the Himalayas acts a physical wall, inhibiting the transport of BC particles across the mountains to the plateau. This study, however, finds that the Yarlung Tsangpo River valley causes a &#39;leaking wall&#39;, whereby under certain meteorological conditions, BC particles are being transported up onto the glacier. This too causes variability of BC concentrations (ranging from 0.3 to 1.5 &mu;g m&minus;3) in a time scale of a few days. The analysis of the variability suggests that the &ldquo;leaking wall&rdquo; effect cannot occur when the prevailing winds were northwest winds, during which the BC transport along the valley of the Yarlung Tsangpo River was obstructed. As a result, large variability of BC concentration was observed due to the change of prevailing wind directions.</p

Two distinct patterns of seasonal variation of airborne black carbon overTibetan Plateau

Airborne black carbon (BC) mass concentrations were measured from November 2012 to June 2013 at Ranwu and Beiluhe, located in the southeastern and central Tibetan Plateau, respectively. Monthly mean BC concentrations show a winter (November&ndash;February) high (413.2 ng m&minus;3) and spring (March&ndash;June) low (139.1 ng m&minus;3) at Ranwu, but in contrast a winter low and spring high at Beiluhe (204.8 and 621.6 ng m&minus;3, respectively). By examining the meteorological conditions at various scales, we found that the monthly variation of airborne BC over the southeastern Tibetan Plateau (TP) was highly influenced by regional precipitation and over the hinterland by winds. Local precipitation at both sites showed little impact on the seasonal variation of airborne BC concentrations. Potential BC source regions are identified using air mass backward trajectory analysis. At Ranwu, BC was dominated by the air masses from the northeastern India and Bangladesh in both winter and spring, whereas at Beiluhe it was largely contributed by air masses from the south slope of Himalayas in winter, and from the arid region in the north of the TP in spring. The winter and spring seasonal peak of BC in the southern TP is largely contributed by emissions from South Asia, and this seasonal variation is heavily influenced by the regional monsoon. In the northern TP, BC had high concentrations during spring and summer seasons, which is very likely associated with more efficient transport of BC over the arid regions on the north of Tibetan Plateau and in Central Asia. Airborne BC concentrations at the Ranwu sampling site showed a significant diurnal cycle with a peak shortly after sunrise followed by a decrease before noon in both winter and spring, likely shaped by local human activities and the diurnal variation of wind speed. At the Beiluhe sampling site, the diurnal variation of BC is different and less distinct.</p

Chemical Composition of PM(10) and PM(2.5) Collected at Ground Level and 100 Meters during a Strong Winter-Time Pollution Episode in Xi'an, China

An intensive sampling of aerosol particles from ground level and 100 m was conducted during a strong pollution episode during the winter in Xi&#39;an, China. Concentrations of water-soluble inorganic ions, carbonaceous compounds, and trace elements were determined to compare the composition of particulate matter (PM) at the two heights. PM mass concentrations were high at both stations: PM(10) (PM with aerodynamic diameter &lt;= 10 mu m) exceeded the China National Air Quality Standard Class II value on three occasions, and PM(2.5) (PM with aerodynamic diameter &lt;= 2.5 mu m) exceeded the daily U.S. National Ambient Air Quality Standard more than 10 times. The PM(10) organic carbon (OC) and elemental carbon (EC) were slightly lower at the ground than at 100 m, both in terms of concentration and percentage of total mass, but OC and EC in PM(2.5) exhibited the opposite pattern. Major ionic species, such as sulfate and nitrate, showed vertical variations similar to the carbonaceous aerosols. High sulfate concentrations indicated that coal combustion dominated the PM mass both at the ground and 100 m. Correlations between K(+) and OC and EC at 100 m imply a strong influence from suburban biomass burning, whereas coal combustion and motor vehicle exhaust had a greater influence on the ground PM. Stable atmospheric conditions apparently led to the accumulation of PM, especially at 100 m, and these conditions contributed to the similarities in PM at the two elevations. Low coefficient of divergence (CD) values reflect the similarities in the composition of the aerosol between sites, but higher CDs for fine particles compared with coarse ones were consistent with the differences in emission sources between the ground and 100 m.</p