Qingqing Yu

Spatial distributions of secondary organic aerosols from isoprene, monoterpenes, β-caryophyllene and aromatics over China during summer

Filter-based particle samples were simultaneously collected at 14 sites across 6 regions of China during the summer of 2012. These filters were analyzed for secondary organic aerosol (SOA) tracers from biogenic precursors (isoprene, monoterpenes, and β-caryophyllene) and anthropogenic aromatics. The sum of all SOA tracers ranged from 29.9 to 371 ng m−3 with the majority from isoprene (123 ± 78.8 ng m−3), followed by monoterpenes (10.5 ± 6.64 ng m−3), β-caryophyllene (5.07 ± 3.99 ng m−3), and aromatics (2.90 ± 1.52 ng m−3). The highest levels of biogenic SOA tracers were observed in East China, whereas the highest concentrations of the aromatic SOA tracer, 2,3-dihydroxy-4-oxopentanoic acid (DHOPA), occurred in North China. All biogenic SOA tracers exhibited positive correlations with temperature, most likely resulting from enhanced biogenic volatile organic compounds (BVOCs) emissions and photochemistry in high-temperature regions. Among the isoprene SOA tracers, the low-NOx products 2-methyltetrols were the largest by mass concentration. However, at certain urban sites, the contribution of the high-NOx product 2-methylglyceric acid was significantly higher, implying a greater influence of NOx on isoprene SOA formation in urban areas. For the monoterpene SOA tracers, the ratio of the first-generation products (cis-pinonic acid plus pinic acid) to the high-generation product (3-methyl-1,2,3-butanetricarboxylic acid) exhibited a negative correlation with the amount of high-generation products, indicating that this ratio could serve as an indicator of the aging of monoterpene SOA. The ratio ranged from 0.89 to 21.0, with an average of 7.00 ± 6.02, among the observation sites, suggesting that monoterpene SOA was generally fresh over China during the summer. As a typical anthropogenic SOA tracer, DHOPA exhibited higher levels at urban sites than at remote sites. These SOA tracers were further used to attribute SOA origins via the SOA-tracer method. The total concentrations of secondary organic carbon (SOC) and SOA were estimated to be in the range of 0.37 to 2.47 μgC m−3 and 0.81 to 5.44 µg m−3, respectively, with the highest levels observed in the eastern regions of China. Isoprene (46 ± 14%) and aromatics (27 ± 8%) were the two major contributors to SOC in every region. In North China, aromatics were the largest SOA contributor. Our ground-based observations suggest that anthropogenic aromatics are important SOA precursors in China.

Spatial and seasonal variations of isoprene secondary organic aerosol in China: Significant impact of biomass burning during winter.

Isoprene is a substantial contributor to global secondary organic aerosol (SOA). The formation of isoprene SOA (SOAI) is highly influenced by anthropogenic emissions. Currently, there is rare information regarding SOAI in polluted regions. In this study, one-year concurrent observation of SOAI tracers was undertaken at 12 sites across China for the first time. The tracers formed from the HO2-channel exhibited higher concentrations at rural sites, while the tracer formed from the NO/NO2-channel showed higher levels at urban sites. 3-Methyltetrahydrofuran-3,4-diols exhibited linear correlations with their ring-opening products, C5-alkenetriols. And the slopes were steeper in the southern China than the northern China, indicating stronger ring-opening reactions there. The correlation analysis of SOAI tracers with the factor determining biogenic emission and the tracer of biomass burning (levoglucosan) implied that the high level of SOAI during summer was controlled by biogenic emission, while the unexpected increase of SOAI during winter was largely due to the elevated biomass burning emission. The estimated secondary organic carbon from isoprene (SOCI) exhibited the highest levels in Southwest China. The significant correlations of SOCI between paired sites implied the regional impact of SOAI in China. Our findings implicate that isoprene origins and SOAI formation are distinctive in polluted regions.

Changes in visibility with PM2.5 composition and relative humidity at a background site in the Pearl River Delta region.

In fall-winter, 2007-2013, visibility and light scattering coefficients (bsp) were measured along with PM2.5 mass concentrations and chemical compositions at a background site in the Pearl River Delta (PRD) region. The daily average visibility increased significantly (p<0.01) at a rate of 1.1 km/year, yet its median stabilized at ~13 km. No haze days occurred when the 24-hr mean PM2.5 mass concentration was below 75 μg/m(3). By multiple linear regression on the chemical budget of particle scattering coefficient (bsp), we obtained site-specific mass scattering efficiency (MSE) values of 6.5 ± 0.2, 2.6 ± 0.3, 2.4 ± 0.7 and 7.3 ± 1.2m(2)/g, respectively, for organic matter (OM), ammonium sulfate (AS), ammonium nitrate (AN) and sea salt (SS). The reconstructed light extinction coefficient (bext) based on the Interagency Monitoring of Protected Visual Environments (IMPROVE) algorithm with our site-specific MSE revealed that OM, AS, AN, SS and light-absorbing carbon (LAC) on average contributed 45.9% ± 1.6%, 25.6% ± 1.2%, 12.0% ± 0.7%, 11.2% ± 0.9% and 5.4% ± 0.3% to light extinction, respectively. Averaged bext displayed a significant reduction rate of 14.1/Mm·year (p<0.05); this rate would be 82% higher if it were not counteracted by increasing relative humidity (RH) and hygroscopic growth factor (f(RH)) at rates of 2.5% and 0.16/year(-1) (p<0.01), respectively, during the fall-winter, 2007-2013. This growth of RH and f(RH) partly offsets the positive effects of lowered AS in improving visibility, and aggravated the negative effects of increasing AN to impair visibility.

Significant Increase of Aromatics-Derived Secondary Organic Aerosol during Fall to Winter in China

Human activities release large amounts of anthropogenic pollutants into the air, and thereby produce substantial secondary organic aerosol (SOA). Aromatic hydrocarbons (AHs) that mainly emitted from coal combustion, transportation, solvent use and biofuel/biomass burning, are a major class of anthropogenic SOA precursors. At present, there are few field studies focusing on AH-derived SOA (SOAA) on a continental scale, especially in polluted regions of the world. In this study, a one-year concurrent observation of the SOAA tracer, 2,3-dihydroxy-4-oxopentanoic acid (C5H8O5, DHOPA) was carried out at 12 sites across six regions of China for the first time. The annual averages of DHOPA among the 12 sites ranged from 1.23 to 8.83 ng m-3 with a mean of 3.48 ± 1.96 ng m-3. At all observation sites, the concentrations of DHOPA from fall to spring were significantly higher than those in summertime, and positive correlations were observed between DHOPA and the biomass burning tracer (levoglucosan). This indicated that such a nationwide increase of SOAA during the cold period was highly associated with the enhancement of biomass burning emission. In the northern China, the highest levels of DHOPA were observed in the coldest months during winter, probably due to the enhancement of biofuel and coal consumption for household heating. In the southern China, the highest levels of DHOPA were mostly observed in fall and spring, which were associated with the enhancement of open biomass burning. The apparent increases of DHOPA and levoglucosan levels during the cold period and the negative correlations of visibility with DHOPA and levoglucosan imply that the reduction of SOAA amount and biomass burning emission is an efficient way to reduce haze pollution during fall to winter in China.

Ambient PM 2.5 -bound polycyclic aromatic hydrocarbons (PAHs) in rural Beijing: Unabated with enhanced temporary emission control during the 2014 APEC summit and largely aggravated after the start of wintertime heating

For human health benefits it is crucial to see if carcinogenic air pollutants like polycyclic aromatic hydrocarbons (PAHs) are reduced accordingly along with the control of the criteria pollutants including fine particles (PM2.5). A number of studies documented that enhanced temporary emission control during the 2014 Asia-Pacific Economic Cooperation summit (APEC) in Beijing resulted in substantial drops of observed ambient PM2.5, as well as PAHs, in urban areas of Beijing, yet it is not clear whether PM2.5-bound PAHs in the rural areas were also lowered during the APEC. Here filter-based PM2.5 samples were collected at a rural site in northeast of Beijing, and analyzed for 25 PAHs before (Oct. 27-Nov. 2, 2014), during (Nov. 3-12, 2014) and after (Nov. 13, 2014-Jan. 14, 2015) the APEC. Observed concentrations of PM2.5, OC and EC during the APEC dropped by about 30%, however, average PM2.5-bound PAHs and their incremental lifetime cancer risk (ILCR), 25.65 ng/m3 and 3.2 × 10-4, remained almost unchanged when compared to that of 25.48 ng/m3 and 3.5 × 10-4, respectively, before the APEC. After the APEC with the start of wintertime central heating in urban Beijing on Nov. 15, 2014, average total concentration of PAHs and their ILCR highly elevated and reached 118.25 ng/m3 and 1.5 × 10-3, respectively. Source apportioning by positive matrix factorization (PMF) revealed that coal combustion was the largest source that contributed 63.2% (16.1 ng/m3), 78.5% (20.1 ng/m3) and 56.1% (66.3 ng/m3) to the total PAHs before, during and after the APEC, respectively. Uncontrolled residential coal use during the APEC was found to be the reason for unabated levels of PAHs, and the largely aggravated PAHs after the APEC was resulted from increased coal consumption for wintertime residential heating. Our results suggested reducing emission from residential coal combustion is crucial to mitigate carcinogenic PAHs in ambient air, especially in rural areas.

Filter-based measurement of light absorption by brown carbon in PM 2.5 in a megacity in South China

Carbonaceous aerosols represent an important nexus between air pollution and climate change. Here we collected filter-based PM2.5 samples during summer and autumn in 2015 at one urban and two rural sites in Guangzhou, a megacity in southern China, and got the light absorption by black carbon (BC) and brown carbon (BrC) resolved with a DRI Model 2015 multi-wavelength thermal/optical carbon analyzer apart from determining the organic carbon (OC) and elemental carbon (EC) contents. On average BrC contributed 12-15% of the measured absorption at 405nm (LA405) during summer and 15-19% during autumn with significant increase in the LA405 by BrC at the rural sites. Carbonaceous aerosols, identified as total carbon (TC), yielded average mass absorption efficiency at 405nm (MAE405) that were approximately 45% higher in autumn than in summer, an 83% increase was noted in the average MAE405 for OC, compared with an increase of only 14% in the average MAE405 for EC. The LA405 by BrC showed a good correlation (p<0.001) with the ratios of secondary OC to PM2.5 in summer. However, this correlation was poor (p>0.1) in autumn, implying greater secondary formation of BrC in summer. The correlations between levoglucosan (a marker of biomass burning) and the LA405 by BrC were significant during autumn but insignificant during summer, suggesting that the observed increase in the LA405 by BrC during autumn in rural areas was largely related to biomass burning. The measurements of light absorption at 550nm presented in this study indicated that the use of the IMPROVE algorithm with an MAE value of 10m2/g for EC to approximate light absorption may be appropriate in areas not strongly affected by fossil fuel combustion; however, this practice would underestimate the absorption of light by PM2.5 in areas heavily affected by vehicle exhausts and coal burning.

Fast screening compositions of PM 2.5 by ATR-FTIR: Comparison with results from IC and OC/EC analyzers

Chemical speciation of fine particles or PM2.5 collected on filters is still a costly and time-consuming task. In this study, filter-based PM2.5 samples were collected during November-December 2013 at four sites in Guangzhou, and the major components were fast screened (~7min per filter sample) by Attenuated Total Reflectance (ATR)-Fourier Transform Infrared Spectroscopic (FTIR) in comparison with that measured by Organic carbon/Element carbon (OC/EC) analyzer and Ion Chromatography (IC). The concentrations of nitrate, ammonium, sulfate, primary organic carbon (POC) and secondary organic carbon (SOC) measured by OC/EC and IC analyzers were better correlated with their infrared absorption peak heights at 1320cm-1 for nitrate, 1435, 3045 and 3215cm-1 for ammonium, 615cm-1 for sulfate, 690, 760 and 890cm-1 for POC and 1640 and 1660cm-1 for SOC respectively, during polluted days (PM2.5>75μg/m3) than during clean days (PM2.5≤75μg/m3). With the evolution of a haze episode during our field campaign, the concentrations of the major PM2.5 components displayed consistent variations with their infrared absorption peak heights, suggesting ATR-FTIR could be a fast and useful technique to characterize filter-based PM2.5 compositions particularly during pollution events although cautions should be taken when PM2.5 levels are low. Notably, elevated PM2.5 mass concentrations occurred with enhanced ratios of [NO3-]/[SO42-] and [NH4+]/[SO42-], implying that nitrogenous components play vital roles in the PM2.5 pollution events in the study region.