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Extreme haze episodes repeatedly shrouded Beijing during the winter of 2012–2013, causing major environmental and health problems. To better understand these extreme events, we performed a model-assisted analysis of the hourly observation data of PM<sub>2.5</sub> and its major chemical compositions. The synthetic analysis shows that (1) the severe winter haze was driven by stable synoptic meteorological conditions over northeastern China, and not by an abrupt increase in anthropogenic emissions. (2) Secondary species, including organics, sulfate, nitrate, and ammonium, were the major constituents of PM<sub>2.5</sub> during this period. (3) Due to the dimming effect of high loading of aerosol particles, gaseous oxidant concentrations decreased significantly, suggesting a reduced production of secondary aerosols through gas-phase reactions. Surprisingly, the observational data reveals an enhanced production rate of secondary aerosols, suggesting an important contribution from other formation pathways, most likely heterogeneous reactions. These reactions appeared to be more efficient in producing secondary inorganics aerosols than organic aerosols resulting in a strongly elevated fraction of inorganics during heavily polluted periods. (4) Moreover, we found that high aerosol concentration was a regional phenomenon. The accumulation process of aerosol particles occurred successively from cities southeast of Beijing. The apparent sharp increase in PM<sub>2.5</sub> concentration of up to several hundred μg m<sup>−3</sup> per hour recorded in Beijing represented rapid recovery from an interruption to the continuous pollution accumulation over the region, rather than purely local chemical production. This suggests that regional transport of pollutants played an important role during these severe pollution events.
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Vehicle emissions are a major source of urban air pollution. In recent decade, the Chinese government has introduced a range of policies to reduce vehicle emissions. In order to understand the chemical characteristics of PM<sub>2.5</sub> from on-road vehicle emissions in the Pearl River Delta (PRD) region and to evaluate the effectiveness of control policies on vehicle emissions, the emission factors of PM<sub>2.5</sub> mass, elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), water-soluble inorganic ions (WSII), metal elements, organic compounds and stable carbon isotopic composition were measured in the Zhujiang tunnel of Guangzhou, in the PRD region of China in 2013. Emission factors of PM<sub>2.5</sub> mass, OC, EC and WSOC were 92.4, 16.7, 16.4 and 1.31 mg vehicle<sup>−1</sup> km<sup>−1</sup> respectively. Emission factors of WSII were 0.016 (F<sup>-</sup>) ~ 4.17 (Cl<sup>−</sup>) mg vehicle<sup>−1</sup> km<sup>−1</sup>, contributing about 9.8% to the PM<sub>2.5</sub> emissions. The sum of 27 measured metal elements accounted for 15.2% of PM<sub>2.5</sub> emissions. Fe was the most abundant metal element, with an emission factor of 3.91 mg vehicle<sup>−1</sup> km<sup>−1</sup>. Emission factors of organic compounds including n-alkanes, polycyclic aromatic hydrocarbons, hopanes and steranes were 91.9, 5.02, 32.0 and 7.59 μg vehicle<sup>−1</sup> km<sup>−1</sup>, respectively. Stable carbon isotopic composition δ<sup>13</sup>C value was −25.0‰ on average. An isotopic fractionation of 3.2‰ was found during fuel combustion. Compared to a previous study in Zhujiang tunnel in 2004, emission factors of PM<sub>2.5</sub>mass, EC, OC, WSII except Cl<sup>-</sup> and organic compounds decreased by 16.0 ~ 93.4%, which could be attributed to emission control policy from 2004 to 2013. However, emission factors of most of the metal elements increased significantly, which could be partially attributed to the changes in motor oil additives and vehicle conditions. There are no mandatory national standards to limit metal content from vehicle emissions, which should be a concern of the government. A snapshot of the 2013 characteristic emissions of PM<sub>2.5</sub> and its constituents from the on-road vehicular fleet in the PRD region retrieved from our study would be helpful for the assessment of past and future implementations of vehicle emission control policy.
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We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 10<sup>8</sup> to 2.2 × 10<sup>10</sup> molec cm<sup>−3</sup> over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 10<sup>6</sup> to 2 × 10<sup>7</sup> molec cm<sup>−3</sup> over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 10<sup>11</sup> and 2 × 10<sup>11</sup> molec cm<sup>−3</sup> s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.
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Oxygenated volatile organic compounds (OVOCs) are important products of the photo-oxidation of hydrocarbons. They influence the oxidizing capacity and the ozone-forming potential of the atmosphere. In the summer of 2008, 2 months of emission restrictions were enforced in Beijing to improve air quality during the Olympic Games. Observational evidence reported in related studies that these control measures were efficient in reducing the concentrations of primary anthropogenic pollutants (CO, NO<sub>x</sub> and non-methane hydrocarbons, i.e., NMHCs) by 30–40%. In this study, the influence of the emission restrictions on ambient levels of OVOCs was explored using a neural network analysis with consideration of meteorological conditions. Statistically significant reductions in formaldehyde (HCHO), acetaldehyde (CH<sub>3</sub>CHO), methyl ethyl ketone (MEK) and methanol were found to be 12.9, 15.8, 17.1 and 19.6%, respectively, when the restrictions were in place. The effect of emission controls on acetone was not detected in neural network simulations, probably due to pollution transport from surrounding areas outside Beijing. Although the ambient levels of most NMHCs were reduced by ~35% during the full control period, the emission ratios of reactive alkenes and aromatics closely related to automobile sources did not present much difference (< 30%). A zero-dimensional box model based on the Master Chemical Mechanism version 3.2 (MCM3.2) was applied to evaluate how OVOC production responds to the reduced precursors during the emissions control period. On average, secondary HCHO was produced from the oxidation of anthropogenic alkenes (54%), isoprene (30%) and aromatics (15%). The importance of biogenic sources for the total HCHO formation was almost on par with that of anthropogenic alkenes during the daytime. Anthropogenic alkenes and alkanes dominated the photochemical production of other OVOCs such as acetaldehyde, acetone and MEK. The relative changes of modeled HCHO, CH<sub>3</sub>CHO, methyl vinyl ketone and methacrolein (MVK + MACR) before and during the pollution controlled period were comparable to the estimated reductions in the neural network, reflecting that current mechanisms can largely explain secondary production of those species under urban conditions. However, it is worth noting that the box model overestimated the measured concentrations of aldehydes by a factor of 1.4–1.7 without consideration of loss of aldehydes on aerosols, and simulated MEK was in good agreement with the measurements when primary sources were taken into consideration. These results suggest that the understanding of the OVOCs budget in the box model remains incomplete, and that there is still considerable uncertainty in particular missing sinks (unknown chemical and physical processes) for aldehydes and absence of direct emissions for ketones.
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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 PM<sub>2.5</sub> 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. PM<sub>2.5</sub> samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measures on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOCs), total fatty acids and benzoic acid during the entire sampling period were 1184±241, 597±159 and 1496±511 ng m<sup>−3</sup> in Peking University (PKU), and 1050±303, 475±114 and 1278±372 ng m<sup>−3</sup> in Yufa, Beijing. Oxalic acid (C<sub>2</sub>) 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 stearic acid (C<sub>18:0</sub>), followed by palmitic acid (C<sub>16:0</sub>) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from the northeast, passing over the southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from the north or northwest sector (mountain areas without serious anthropogenic pollution sources) during less pollution 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 measures on the reduction of local air pollution in Beijing. The results suggested that the traffic restriction measures can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of EC value indicates more elevated primary emissions in Yufa during restriction periods than in non-restriction periods. 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.
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Water vapor is the most important greenhouse gas and its spatiotemporal variability strongly exceeds that of all other greenhouse gases. However, this variability has hardly been studied quantitatively so far. We present an analysis of a 5-year period of water vapor measurements in the free troposphere above the Zugspitze (2962 m a.s.l., Germany). Our results are obtained from a combination of measurements of vertically integrated water vapor (IWV), recorded with a solar Fourier transform infrared (FTIR) spectrometer on the summit of the Zugspitze and of water vapor profiles recorded with the nearby differential absorption lidar (DIAL) at the Schneefernerhaus research station. The special geometrical arrangement of one zenith-viewing and one sun-pointing instrument and the temporal resolution of both instruments allow for an investigation of the spatiotemporal variability of IWV on a spatial scale of less than 1 km and on a timescale of less than 1 h. The standard deviation of differences between both instruments σ<sub>IWV</sub> calculated for varied subsets of data serves as a measure of variability. The different subsets are based on various spatial and temporal matching criteria. Within a time interval of 20 min, the spatial variability becomes significant for horizontal distances above 2 km, but only in the warm season (σ<sub>IWV</sub> =0.35 mm). However, it is not sensitive to the horizontal distance during the winter season. The variability of IWV within a time interval of 30 min peaks in July and August (σ<sub>IWV</sub> > 0.55 mm, mean horizontal distance = 2.5 km) and has its minimum around midwinter (σ<sub>IWV</sub> < 0.2 mm, mean distance > 5 km). The temporal variability of IWV is derived by selecting subsets of data from both instruments with optimal volume matching. For a short time interval of 5 min, the variability is 0.05 mm and increases to more than 0.5 mm for a time interval of 15 h. The profile variability of water vapor is determined by analyzing subsets of water vapor profiles recorded by the DIAL within time intervals from 1 to 5 h. For all altitudes, the variability increases with widened time intervals. The lowest relative variability is observed in the lower free troposphere around an altitude of 4.5 km. Above 5 km, the relative variability increases continuously up to the tropopause by about a factor of 3. Analysis of the covariance of the vertical variability reveals an enhanced variability of water vapor in the upper troposphere above 6 km. It is attributed to a more coherent flow of heterogeneous air masses, while the variability at lower altitudes is also driven by local atmospheric dynamics. By studying the short-term variability of vertical water vapor profiles recorded within a day, we come to the conclusion that the contribution of long-range transport and the advection of heterogeneous layer structures may exceed the impact of local convection by 1 order of magnitude even in the altitude range between 3 and 5 km.
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Our knowledge of the distribution of mercury concentrations in air of the Southern Hemisphere was until recently based mostly on intermittent measurements made during ship cruises. In the last few years continuous mercury monitoring has commenced at several sites in the Southern Hemisphere, providing new and more refined information. In this paper we compare mercury measurements at several remote sites in the Southern Hemisphere made over a period of at least 1 year at each location. Averages of monthly medians show similar although small seasonal variations at both Cape Point and Amsterdam Island. A pronounced seasonal variation at Troll research station in Antarctica is due to frequent mercury depletion events in the austral spring. Due to large scatter and large standard deviations of monthly average median mercury concentrations at Cape Grim, no systematic seasonal variation could be found there. Nevertheless, the annual average mercury concentrations at all sites during the 2007–2013 period varied only between 0.85 and 1.05 ng m<sup>−3</sup>. Part of this variability is likely due to systematic measurement uncertainties which we propose can be further reduced by improved calibration procedures. We conclude that mercury is much more uniformly distributed throughout the Southern Hemisphere than the distributions suggested by measurements made onboard ships. This finding implies that smaller trends can be detected in shorter time periods. We also report a change in the trend sign at Cape Point from decreasing mercury concentrations in 1996–2004 to increasing concentrations since 2007.
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Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM<sub>2.5</sub> and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and K<sup>+</sup> were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from <sup>14</sup>C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions from biomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μg m<sup>−3</sup> during the campaign in January–February 2012. Measurements on a 160 m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and K<sup>+</sup> concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.
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This study was performed to examine the relationship between isotopic composition in near-surface vapor (δ<sup>18</sup>O<sub>v</sub>) over western Africa during the monsoon season and El Niño–Southern Oscillation (ENSO) activity using the Isotope-incorporated Global Spectral Model. The model was evaluated using a satellite and in situ observations at daily to interannual timescales. The model provided an accurate simulation of the spatial pattern and seasonal and interannual variations of isotopic composition in column and surface vapor and precipitation over western Africa. Encouraged by this result, we conducted a simulation stretching 34 years (1979–2012) to investigate the relationship between atmospheric environment and isotopic signature on an interannual timescale. The simulation indicated that the depletion in the monsoon season does not appear every year at Niamey. The major difference between the composite fields with and without depletion was in the amount of precipitation in the upstream area of Niamey. As the interannual variation of the precipitation amount is influenced by the ENSO, we regressed the monsoon season averaged δ<sup>18</sup>O<sub>v</sub> from the model and annually averaged NINO3 index and found a statistically significant correlation (<i>R =</i> 0.56, <i>P</i> < 0.01) at Niamey. This relationship suggests that there is a possibility of reconstructing past western African monsoon activity and ENSO using climate proxies.
