Zhen-yu Du

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.

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.

Evaluation of fungal spore characteristics in Beijing, China, based on molecular tracer measurements

PM2:5 (particulate matter with aerodynamic diameters less than 2:5 m) and PM10 (particulate matter with aerodynamic diameters less than 10 m) samples were collected by high-volume air samplers simultaneously at a rural site and an urban site in Beijing, China. Various carbohydrates were quantified by high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD), including the sugar alcohols mannitol and arabitol, recently proposed as molecular tracers for fungal aerosol. The annual average concentrations of arabitol in PM2:5 and PM10 at the urban site were 7:4 9:4 and 21:0 20:4 ng m 3 , and the respective mannitol concentrations were 10:3 9:5 and 31:9 26:9 ng m 3 . During summer and autumn, higher arabitol and mannitol levels than during spring and winter were observed in coarse particles, probably due to different dominant sources of fungal spores in different seasons. In the dry season (i.e., winter and spring) in Beijing, probably only the suspension from exposed surfaces (e.g., soil resuspension, transported dust, etc) can be regarded as the main sources for fungal aerosols. On the other hand, in summer and autumn, fungal spores in the atmosphere can be derived from more complex sources, including plants, vegetation decomposition and agricultural activity, such as ploughing; these fungal spore sources may contribute more to coarse PM. Moreover, statistical analysis according to typical seasonal patterns, including a dry season (December 2010 to March 2011) and a wet season (July to September 2011), revealed different variations of fungal spores in different seasons. Although fungal spore levels at rural sites were reported to be consistently higher than those at urban sites in other studies, our findings showed the opposite pattern, indicating a high abundance of fungal spores in the urban area of this Chinese megacity.

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.

Seasonal variations and source estimation of saccharides in atmospheric particulate matter in Beijing, China

Saccharides are important constituents of atmospheric particulate matter (PM). In order to better understand the sources and seasonal variations of saccharides in aerosols in Beijing, China, saccharide composition was measured in ambient PM samples collected at an urban site in Beijing. The highest concentrations of total saccharides in Beijing were observed in autumn, while an episode with abnormal high total saccharide levels was observed from 15 to 23 June, 2011, due to extensive agricultural residue burning in northern China during the wheat harvest season. Compared to the other two categories of saccharides, sugars and sugar alcohols, anhydrosugars were the predominant saccharide group, indicating that biomass burning contributions to Beijing urban aerosol were significant. Ambient sugar and sugar alcohol levels in summer and autumn were higher than those in spring and winter, while they were more abundant in PM2.5 during winter time. Levoglucosan was the most abundant saccharide compound in both PM2.5 and PM10, the annual contributions of which to total measured saccharides in PM2.5 and PM10 were 61.5% and 54.1%, respectively. To further investigate the sources of the saccharides in ambient aerosols in Beijing, the PM10 datasets were subjected to positive matrix factorization (PMF) analysis. Based on the objective function to be minimized and the interpretable factors identified by PMF, six factors appeared to be optimal as to the probable origin of saccharides in the atmosphere in Beijing, including biomass burning, soil or dust, isoprene SOA and the direct release of airborne fungal spores and pollen.

Brown and black carbon in Beijing aerosol: Implications for the effects of brown coating on light absorption by black carbon

Brown carbon (BrC) is increasingly included in climate models as an emerging category of particulate organic compounds that can absorb solar radiation efficiently at specific wavelengths. Water-soluble organic carbon (WSOC) has been commonly used as a surrogate for BrC; however, it only represents a limited fraction of total organic carbon (OC) mass, which could be as low as about 20% in urban atmosphere. Using methanol as the extraction solvent, up to approximately 90% of the OC in Beijing aerosol was isolated and measured for absorption spectra over the ultraviolet-to-visible wavelength range. Compared to methanol-soluble OC (MSOC), WSOC underestimated BrC absorption by about 50% at 365nm. The mass absorption efficiencies measured for BrC in Beijing aerosol were converted to the imaginary refractive indices of BrC and subsequently used to compute BrC coating-induced enhancement of light absorption (Eabs) by black carbon. Eabs attributed to lensing was reduced in the case of BrC coating relative to that caused by purely-scattering coating. However, this reduction was overwhelmed by the effect of BrC shell absorption, indicating that the overall effect of BrC coating was an increase in Eabs. Methanol extraction significantly reduced charring of OC during thermal-optical analysis, leading to a large increase in the measured elemental carbon (EC) mass and an apparent improvement in the consistency of EC measurements by different thermal-optical methods.

The characteristics of carbonaceous aerosol in Beijing during a season of transition

Carbonaceous aerosol was measured during fall of 2010 in Beijing. Daily variation of organic carbon (OC) was found to coincide with that of relative humidity (RH), and the OC to elemental carbon (EC) ratios were more than doubled during the more humid periods (RH above 0.75) compared to other conditions. This large increase in OC/EC could not be explained by the variations of primary biomass burning emissions but was accompanied by a five-fold increase in the sulfate to EC ratio. It was then inferred that secondary organic aerosol (SOA) formation was enhanced under the more humid conditions, presumably through aqueous-phase processes. This enhanced SOA formation might be partially associated with particles externally mixed with black carbon, as indicated by the RH-dependent relationships between aerosol optical attenuation and EC loading. In addition, organic aerosols exhibited different properties between the more humid and the other periods, such that they were less volatile and charred more significantly during thermal-optical analysis in the former case. These differences coincided with the evidence of enhanced SOA formation under the more humid conditions. This study highlights the necessity of incorporating aqueous-phase chemistry into air quality models for SOA.