Chemical formation and source apportionment of PM2.5 at an urban site at the southern foot of the Taihang mountains

The region along the Taihang Mountains in the North China Plain (NCP) is characterized by serious fine particle pollution. To clarify the formation mechanism and controlling factors, an observational study was conducted to investigate the physical and chemical properties of the fine particulate matter in Jiaozuo city, China. Mass concentrations of the water-soluble ions (WSIs) in PM_2.5 and gaseous pollutant precursors were measured on an hourly basis from December 1, 2017, to February 27, 2018. The positive matrix factorization (PMF) method and the FLEXible PARTicle (FLEXPART) model were employed to identify the sources of PM_2.5. The results showed that the average mass concentration of PM_2.5 was 111 μg/m³ during the observation period. Among the major WSIs, sulfate, nitrate, and ammonium (SNA) constituted 62% of the total PM_2.5 mass, and NO₃⁻ ranked the highest with an average contribution of 24.6%. NH₄⁺ was abundant in most cases in Jiaozuo. According to chemical balance analysis, SO₄²⁻, NO₃⁻, and Cl⁻ might be present in the form of (NH₄)₂SO₄, NH₄NO₃, NH₄Cl, and KCl. The liquid-phase oxidation of SO₂ and NO₂ was severe during the haze period. The relative humidity and pH were the key factors influencing SO₄^2- formation. We found that NO₃⁻ mainly stemmed from homogeneous gas-phase reactions in the daytime and originated from the hydrolysis of N₂O₅ in the nighttime, which was inconsistent with previous studies. The PMF model identified five sources of PM_2.5: secondary origin (37.8%), vehicular emissions (34.7%), biomass burning (11.5%), coal combustion (9.4%), and crustal dust (6.6%).     

Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai,Central East China

To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai Experiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers for the oxidation of isoprene, α/β-pinene, and β-caryophyllene were measured using gas chromatography/mass spectrometry. Most of the biogenic SOA tracers did not show clear diurnal variations, suggesting that they are formed during long-range atmospheric transport or over relatively long time scales. Although isoprene- and α/β-pinene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that crop residue burning may be a source for this acid. Total concentrations of isoprene oxidation products are much higher than those of α/β-pinene and β-caryophyllene oxidation products. The averaged ratio of isoprene to α/β-pinene oxidation products (R_iso/pine) was 4.9 and 6.7 for the daytime and nighttime samples, respectively. These values are among the highest in the aerosols reported in different geographical regions, which may be due to the large isoprene fluxes and relatively high levels of oxidants such as OH in CEC. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/β-pinene, and β-caryophyllene to be 0.42–3.1 μgC m⁻³ (average 1.6 μgC m⁻³) during the daytime and 0.11–4.2 μgC m⁻³ (1.7 μgC m⁻³) during the nighttime. These values correspond to 2.9–23% (10%) and 3.2–28% (9.8%) of the total OC concentrations, in which isoprene-derived SOC accounts for 58% and 63% of total SOC during the daytime and nighttime, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than α/β-pinene and β-caryophyllene at high altitudes in CEC.     

Evolutionary processes and sources of high-nitrate haze episodes over Beijing, Spring

Rare and consecutive high-nitrate haze pollution episodes were observed in Beijing in spring2012. We present detailed characterization of the sources and evolutionary mechanisms of this haze pollution, and focus on an episode that occurred between 15 and 26 April. Submicron aerosol species were found to be substantially elevated during haze episodes, and nitrates showed the largest increase and occupation(average: 32.2%) in non-refractory submicron particles(NR-PM_1), which did not occur in other seasons as previously reported. The haze episode(HE) was divided into three sub-episodes, HEa, HEb, and HEc. During HEa and HEc, a shallow boundary layer, stagnant meteorological conditions, and high humidity favored the formation of high-nitrate concentrations, which were mainly produced by three different processes —daytime photochemical production, gas-particle partitioning, and nighttime heterogeneous reactions — and the decline in visibility was mainly induced by NR-PM_1.However, unlike HEa and HEc, during HEb, the contribution of high nitrates was partly from the transport of haze from the southeast of Beijing — the transport pathway was observed at ~800–1000 m by aerosol Lidar —and the decline in visibility during HEb was primarily caused by PM_(2.5). Our results provide useful information for air quality improvement strategies in Beijing during Spring.     

Sensitivity of ozone to precursor emissions in urban Beijing with a Monte Carlo scheme

In order to understand the formation mechanisms of high surface ozone and identify the main contributor sources in Beijing, this study investigates the sensitivity of surface ozone to NO, NO₂ and nine types of NMVOC emissions during a photochemical smog episode. Monte Carlo sensitivity analysis scheme with fifty simulations is established based on the Nested Air Quality Prediction Model System (NAQPMS). At every simulation, each of the eleven precursor emissions is perturbed with a distinct set of perturbations. The sensitivities of ozone to emissions are identified by multiple linear regressions. The stability of sensitivity results is validated by two experiments with standard deviations of log-normal perturbations set as 30% and 50% respectively. The sensitivity results suggest that the current high surface ozone is strongly stimulated by NMVOC emissions. Among NMVOC emissions, formaldehyde, ethylene and olefins emissions present the greatest impacts on ozone. On the other hand, NOx emissions have a strong inhibitory effect on ozone formation, even after 50% NOx emission reduction. This indicates that the current ozone formation in Beijing is under NOx-saturated conditions. A transition of ozone formation is observed from NOx-saturated to NOx-limited sensitivity behavior with a 75% reduction of NOx emissions. This study gives the implication that abatement of the four NMVOC types mentioned above could be efficient on reducing the high levels of surface ozone in central urban Beijing, while inadequate abatement in NOx emissions probably induces reverse effects.