Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity.

Hydroxymethanesulfonate (HMS) has been found to be an abundant organosulfur aerosol compound in the Beijing-Tianjin-Hebei (BTH) region with a measured maximum daily mean concentration of up to 10 µg per cubic meter in winter. However, the production medium of HMS in aerosols is controversial, and it is unknown whether chemical transport models are able to capture the variations of HMS during individual haze events. In this work, we modify the parametrization of HMS chemistry in the nested-grid GEOS-Chem chemical transport model, whose simulations provide a good account of the field measurements during winter haze episodes. We find the contribution of the aqueous aerosol pathway to total HMS is about 36% in winter in Beijing, due primarily to the enhancement effect of the ionic strength on the rate constants of the reaction between dissolved formaldehyde and sulfite. Our simulations suggest that the HMS-to-inorganic sulfate ratio will increase from the baseline of 7% to 13% in the near future, given the ambitious clean air and climate mitigation policies for the BTH region. The more rapid reductions in emissions of SO2 and NOx compared to NH3 alter the atmospheric acidity, which is a critical factor leading to the rising importance of HMS in particulate sulfur species.

Review on recent progress in observations, source identifications and countermeasures of PM2.5.

Recently, PM2.5 (atmospheric fine particulate matter with aerodynamic diameter ≤ 2.5 µm) have received so much attention that the observations, source appointment and countermeasures of it have been widely studied due to its harmful impacts on visibility, mood (mental health), physical health, traffic safety, construction, economy and nature, as well as its complex interaction with climate. A review on the PM2.5 related research is necessary. We start with summary of chemical composition and characteristics of PM2.5 that contains both macro and micro observation results and analysis, wherein the temporal variability of concentrations of PM2.5 and major components in many recent reports is embraced. This is closely followed by an overview of source appointment, including the composition and sources of PM2.5 in different countries in the six inhabitable continents based on the best available results. Besides summarizing PM2.5 pollution countermeasures by policy, planning, technology and ideology, the World Air Day is proposed to be established to inspire and promote the crucial social action in energy-saving and emission-reduction. Some updated knowledge of the important topics (such as formation and evolution mechanisms of hazes, secondary aerosols, aerosol mass spectrometer, organic tracers, radiocarbon, emissions, solutions for air pollution problems, etc.) is also included in the present review by logically synthesizing the studies. In addition, the key research challenges and future directions are put forward. Despite our efforts, our understanding of the recent reported observations, source identifications and countermeasures of PM2.5 is limited, and subsequent efforts both of the authors and readers are needed.

[Composition and Source Apportionments of Saccharides in Atmospheric Particulate Matter in Beijing].

Based on the newly established high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD), the saccharides in PM2.5 and PM10 in Beijing from 2011 - 2012 were quantified. Fourteen saccharides were synchronously detected in the aerosols samples in Beijing, which can be divided into three categories, i. e. anhydrosugar, sugar and sugar alcohol. Anhydrosugar, coming from biomass burning, include levoglucosan, mannosan and galactosan. Sugar and sugar alcohol, emitted by the primary biogenic emission, include glucose, fructose, trehalose, arabitol, mannitol, glycerol, threitol, 2-meythltrtols (2-methylthreitol and 2-methylerythrito), xylitol and inositol. The concentrations of monosaccharide anhydrides in summer and autumn were obviously higher than those in spring and winter, while the concentrations of sugar and sugar alcohol in winter were significantly lower than those in other seasons. The results of positive matrix factorization analysis suggested that saccharides compounds in atmospheric PM in Beijing can be derived from biomass burning, suspended soil or dust, isoprene SOA, as well as direct release of airborne fungal spores and pollen.

Humidity plays an important role in the PM2.5 pollution in Beijing.

Heavily-polluted PM2.5 (fine particulate matter) episodes frequently impacting Beijing, especially during winter, have become a substantial concern. We found that during winter, the daily variation of PM2.5 in Beijing tracked the pattern of relative humidity (RH). With the increase of PM2.5 (or RH), water-soluble components (especially inorganic ions) became more abundant, and the water-soluble organic carbon to organic carbon ratios increased. The nitrate to sulfate ratios also exhibited dependence on RH, and were higher than those measured about a decade ago, consistent with the increasing trend of nitrogen oxides emissions. Surprisingly, the ratios of water-insoluble organic carbon to elemental carbon showed significant increase at high RH levels, presumably indicating the formation of secondary organic aerosol that is not soluble in water. In addition, humid winters were occasionally identified during 1996-2013 which are expected to be favorable for the formation of air pollution episodes with high PM2.5 concentrations.

The characteristics of Beijing aerosol during two distinct episodes: impacts of biomass burning and fireworks.

The chemical composition of Beijing aerosol was measured during summer and winter. Two distinct episodes were identified. Water-soluble potassium (K(+)) increased significantly during the firework episode in winter with an episode to non-episode ratio of 4.97, whereas the biomass burning (BB) episode in summer was characterized by high episode to non-episode ratios of levoglucosan (6.38) and K(+) (6.90). The BB and firework episodes had only a minor influence on the water-soluble OC (organic carbon) to OC ratio. Based on separate investigations of episode and non-episode periods, it was found that: (i) sulfate correlated strongly with both relative humidity and nitrate during the typical winter period presumably indicating the importance of the aqueous-phase oxidation of sulfur dioxide by nitrogen dioxide, (ii) oxalate and WSOC during both winter and summer in Beijing were mainly due to secondary formation, and (iii) high humidity can significantly enhance the formation potential of WSOC in winter.

Ambient organic carbon to elemental carbon ratios: influence of the thermal-optical temperature protocol and implications.

Ambient organic carbon (OC) to elemental carbon (EC) ratios are strongly associated with not only the radiative forcing due to aerosols but also the extent of secondary organic aerosol (SOA) formation. An inter-comparison study was conducted based on fine particulate matter samples collected during summer in Beijing to investigate the influence of the thermal-optical temperature protocol on the OC to EC ratio. Five temperature protocols were used such that the NIOSH (National Institute for Occupational Safety and Health) and EUSAAR (European Supersites for Atmospheric Aerosol Research) protocols were run by the Sunset carbon analyzer while the IMPROVE (the Interagency Monitoring of Protected Visual Environments network)-A protocol and two alternative protocols designed based on NIOSH and EUSAAR were run by the DRI analyzer. The optical attenuation measured by the Sunset carbon analyzer was more easily biased by the shadowing effect, whereas total carbon agreed well between the Sunset and DRI analyzers. The EC(IMPROVE-A) (EC measured by the IMPROVE-A protocol; similar hereinafter) to EC(NIOSH) ratio and the EC(IMPROVE-A) to EC(EUSAAR) ratio averaged 1.36 ± 0.21 and 0.91 ± 0.10, respectively, both of which exhibited little dependence on the biomass burning contribution. Though the temperature protocol had substantial influence on the OC to EC ratio, the contributions of secondary organic carbon (SOC) to OC, which were predicted by the EC-tracer method, did not differ significantly among the five protocols. Moreover, the SOC contributions obtained in this study were comparable with previous results based on field observation (typically between 45 and 65%), but were substantially higher than the estimation provided by an air quality model (only 18%). The comparison of SOC and WSOC suggests that when using the transmittance charring correction, all of the three common protocols (i.e., IMPROVE-A, NIOSH and EUSAAR) could be reliable for the estimation of SOC by the EC-tracer method.

Intercomparison of thermal-optical methods for the determination of organic and elemental carbon: influences of aerosol composition and implications.

An intercomparison of organic carbon (OC) and elemental carbon (EC) measurements was conducted based on ambient aerosol samples collected during four seasons in Beijing, China. Dependence of OC and EC values on the temperature protocol and the charring correction method is presented and influences of aerosol composition are investigated. EC was found to decrease with the peak inert mode temperature (T(peak)) such that EC determined by the IMPROVE (the Interagency Monitoring of Protected Visual Environments)-A protocol (T(peak) was 580 °C) was 2.85 ± 1.31 and 3.83 ± 2.58 times that measured by an alternative protocol with a T(peak) of 850 °C when using the transmittance and reflectance correction, respectively. It was also found that reflectance correction tends to classify more carbon as EC compared with transmittance; results from the IMPROVE-A protocol showed that the ratio of EC defined by reflectance correction (EC(R)) to that based on transmittance (EC(T)) averaged 1.50 ± 0.42. Moreover, it was demonstrated that emissions from biomass burning would increase the discrepancy between EC values determined by different temperature protocols. On the other hand, the discrepancy between EC(R) and EC(T) was strongly associated with secondary organic aerosol (SOA) which was shown to be an important source of the organics that pyrolyze during the inert mode of thermal-optical analysis.

[Characteristics of polycyclic aromatic hydrocarbons (PAHS) on airborne particulates in Beijing].

Total suspended particulates (TSP) samples were collected from Sep., 2003 to Jul., 2004 in Beijing, and 15 kinds of PAHs, ranging from 3 to 7 rings were analyzed. The maximum concentrations sigma PAHs and BaP were 705 ng/m3 and 52 ng/m3 respectively. Average sigma PAHs concentrations in four seasons were 46 ng/m3, 16 ng/m3, 52 ng/m3 and 268 ng/m3 respectively; and the average BaP concentrations in four seasons were 2.8 ng/m3, 0.23 ng/m3, 3.3 ng/m3, 16 ng/m3 respectively. Regarding to the meteorological parameters, precipitation distinctly lowered the concentration; in heating period, PAHs concentrations fall with the temperature goes up, but there is no obvious relation between concentration and temperature in non-heating period; the increase of wind speed level causes the decrease of PAH concentrations in the heating period, but relation between PAH concentrations and wind speed varied with aromatic rings of PAHs and levels of wind speed in the non-heating period.

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols.

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F- , Cl- , NO2(-), NO3(-), SO3(2-), SO4(2-) , PO4(3-)), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 microg/m3 to 500 microg/m3 ( r = 0.999-0.9999). The relative standard deviation (RSD) were 0.43%-2.00% and the detection limits were from 2.7 ng/m3 to 88 ng/m3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM2.5 of Beijing.