Biwu Chu

Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days

Haze in China has been increasing in frequency of occurrence as well as the area of the affected region. Here, we report on a new mechanism of haze formation, in which coexistence with NOx can reduce the environmental capacity for SO2, leading to rapid conversion of SO2 to sulfate because NO2 and SO2 have a synergistic effect when they react on the surface of mineral dust. Monitoring data from five severe haze episodes in January of 2013 in the Beijing-Tianjin-Hebei regions agreed very well with the laboratory simulation. The combined air pollution of motor vehicle exhaust and coal-fired flue gases greatly reduced the atmospheric environmental capacity for SO2, and the formation of sulfate was found to be a main reason for the growth of fine particles, which led to the occurrence of haze. These results indicate that the impact of motor vehicle exhaust on the atmospheric environment might be underestimated.

Decreasing effect and mechanism of FeSO4 seed particles on secondary organic aerosol in α-pinene photooxidation

α-Pinene/NOx and α-pinene/HONO photooxidation experiments at varying humidity were conducted in smog chambers in the presence or absence of FeSO4 seed particles. FeSO4 seed particles decrease SOA mass as long as water was present on the seed particle surface, but FeSO4 seed particles have no decreasing effect on SOA under dryer conditions at 12% relative humidity (RH). The decreasing effect of FeSO4 seed particles on the SOA mass is proposed to be related to oxidation processes in the surface layer of water on the seed particles. Free radicals, including OH, can be formed from catalytic cycling of Fe(2+) and Fe(3+) in the aqueous phase. These radicals can react further with the organic products of α-pinene oxidation on the seed particles. The oxidation may lead to formation of smaller molecules which have higher saturation vapor pressures and favor repartitioning to the gas phase, and therefore, reduces SOA mass.

Role of ammonia in forming secondary aerosols from gasoline vehicle exhaust

Ammonia (NH3) plays vital roles in new particle formation and atmospheric chemistry. Although previous studies have revealed that it also influences the formation of secondary organic aerosols (SOA) from ozonolysis of biogenic and anthropogenic volatile organic compounds (VOCs), the influence of NH3 on particle formation from complex mixtures such as vehicle exhausts is still poorly understood. Here we directly introduced gasoline vehicles exhausts (GVE) into a smog chamber with NH3 absorbed by denuders to examine the role of NH3 in particle formation from GVE. We found that removing NH3 from GVE would greatly suppress the formation and growth of particles. Adding NH3 into the reactor after 3 h photo-oxidation of GVE, the particle number concentration and mass concentrations jumped explosively to much higher levels, indicating that the numbers and mass of particles might be enhanced when aged vehicle exhausts are transported to rural areas and mixed with NH3-rich plumes. We also found that the presence of NH3 had no significant influence on SOA formation from GVE. Very similar oxygen to carbon (O:C) and hydrogen to carbon (H:C) ratios resolved by aerosol mass spectrometer with and without NH3 indicated that the presence of NH3 also had no impact on the average carbon oxidation state of SOA from GVE.

Comparisons of measured nitrous acid (HONO) concentrations in a pollution period at urban and suburban Beijing, in autumn of 2014

To study the HONO formation mechanisms during a pollution period, a continuous measurement was performed in both urban and suburban aeras of Beijing. During this period, the PM2.5 concentrations increased to 201 and 137 μg/m3 in urban and suburban areas, respectively. The concentrations of HONO, CO, SO2, O3, NO, NO2, NOx were 1.45 ppbv, 0.61 ppmv, 8.7 ppbv, 4.3 ppbv, 44.4 ppbv, 37.4 ppbv, 79.4 ppbv and 0.72 ppbv, 1.00 ppmv, 1.2 ppbv, 7.9 ppbv, 3.7 ppbv, 8.2 ppbv, 11.9 ppbv, in urban and suburban areas, respectively. To compare possible pathways of HONO formation in both sites, the contributions of direct emissions, heterogeneous formations, and homogeneous productions were studied. HONO/NO2 ratios in the two sites indicated that heterogeneous reactions of NO2 were more efficient in suburban areas. And in both urban and suburban areas, the increase of PM2.5 concentrations and RH would promote the conversion efficiency in RH that ranged from 0% to 85%. However, when RH was above 85%, the HONO formation slowed down. Moreover, the study of direct emissions and homogeneous reactions showed that they contributed to a majority of HONO increase in urban areas than the 20% contributions in suburban areas. It implied that the high NOx concentrations and NO concentrations in urban areas or in pollution periods would make direct emissions and homogeneous reactions become dominant in HONO formations.

Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NOx photooxidation

Aerosol phase reactions play a very important role on secondary organic aerosol (SOA) formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate (MnSO4) and zinc sulfate (ZnSO4), on the photochemical reactions of a toluene/NOx photooxidation system in a 2 m3 smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NOx conversion and the formation of ozone and SOA. MnSO4 and ZnSO4 seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO4 and ZnSO4 seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.

Heterogeneous Kinetics of cis-Pinonic Acid with Hydroxyl Radical under Different Environmental Conditions.

To understand the atmospheric fate of secondary organic aerosol (SOA), heterogeneous degradation behaviors of a specific tracer derived from α-pinene-cis-pinonic acid (CPA), initiated by hydroxyl radicals (OH), were investigated under different environmental conditions using a flow reactor. The second-order rate constant (k2) of the CPA-OH reaction was determined to be (6.17 ± 1.07) × 10(-12) cm(3)·molecule(-1)·s(-1) at 25 °C and 40% relative humidity (RH). Higher temperature promoted this reaction, while relative humidity had a little inhibiting effect on it. The atmospheric lifetime of CPA varied from 2.1 to 3.3 days under different environmental conditions. Infrared spectrometry (IR), density functional theory (DFT) calculation and gas chromatography coupled mass spectrometry (GC-MS) results indicated that the oxidation products should be ascribed to poly(carboxylic acid)s. This study shows that the heterogeneous degradation of CPA initiated by OH radical is appreciable, and the concentrations of CPA measured in field measurements may underestimate the corresponding precursors of SOA.

Effect of aluminium dust on secondary organic aerosol formation in m -xylene/NO x photo-oxidation

As an important anthropogenic volatile organic compound (VOC), m-xylene has attracted numerous attentions due to its potential in secondary organic aerosol (SOA) formation. In this study, effects of aluminium dust seeds (boehmite and alumina) on SOA yield and aerosol size in m-xylene/NOx photo-oxidation were investigated in a 2 m3 smog chamber at 30°C and 50% relative humidity. Compared to the seed-free system, the presence of aluminium seeds resulted in an increase in the SOA yield, and also enhanced the O3 concentration in the chamber. The photolysis of O3 is a major source of OH radical, which is the most important oxidant of m-xylene. The increase in O3 concentration could result in the generation of more OH radicals, and finally contribute to the SOA formation. Seed particles influence the SOA size mainly by acting as condensation nuclei. Semi-volatile organic compounds (SVOCs) were condensed onto these nuclei, resulting in the increase in SOA size. However, when aluminium seeds with high concentrations were introduced into the system, SVOCs that had been condensed onto each particle were dispersed by these seeds, leading to the reduction in aerosol size.

Secondary aerosol formation and oxidation capacity in photooxidation in the presence of Al2O3 seed particles and SO2

To investigate the sensitivity of secondary aerosol formation and oxidation capacity to NOx in homogeneous and heterogeneous reactions, a series of irradiated toluene/NOx/air and α-pinene/NOx/air experiments were conducted in smog chambers in the absence or presence of Al2O3 seed particles. Various concentrations of NOx and volatile organic compounds (VOCs) were designed to simulate secondary aerosol formation under different scenarios for NOx. Under “VOC-limited” conditions, the increasing NOx concentration suppressed secondary aerosol formation, while the increasing toluene concentration not only contributed to the increase in secondary aerosol formation, but also led to the elevated oxidation degree for the organic aerosol. Sulfate formation was suppressed with the increasing NOx due to a decreased oxidation capacity of the photooxidation system. Secondary organic aerosol (SOA) formation also decreased with the presence of high concentration of NOx, because organoperoxy radicals (RO2) react with NOx instead of with peroxy radicals (RO2 or HO2), resulting in the formation of volatile organic products. The increasing concentration of NOx enhanced the formation of sulfate, nitrate and SOA under “NOx-limited” conditions, in which the heterogeneous reactions played an important role. In the presence of Al2O3 seed particles, a synergetic promoting effect of mineral dust and NOx on secondary aerosol formation in heterogeneous reactions was observed in the photooxidation. This synergetic effect strengthened the positive relationship between NOx and secondary aerosol formation under “NOx-limited” conditions but weakened or even overturned the negative relationship between NOx and secondary aerosol formation under “VOC-limited” conditions. Sensitivity of secondary aerosol formation to NOx seemed different in homogeneous and heterogeneous reactions, and should be both taken into account in the sensitivity study. The sensitivity of secondary aerosol formation to NOx was further investigated under “winter-like” and NH3-rich conditions. No obvious difference for the sensitivity of secondary aerosol formation except nitrate to NOx was observed.

Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of alpha-pinene/NO(x) with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer (TDMA) in terms of hygroscopic growth factor (Gf), with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols (SOA) formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor (ACSM) and matrix factorization (PMF) method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.

NO x promotion of SO 2 conversion to sulfate: An important mechanism for the occurrence of heavy haze during winter in Beijing

In this study, concentrations of NOx, SO2, O3 and fine particles (PM2.5) were measured at three monitoring stations in Beijing during 2015. For extreme haze episodes during 25 Nov. - 3 Dec. 2015, observation data confirmed that high concentrations of NOx promoted the conversion of SO2 to sulfate. Annual data confirmed that this is an important mechanism for the occurrence of heavy haze during winter in Beijing. Furthermore, in situ perturbation experiments in a potential aerosol mass (PAM) reactor were carried out at Shengtaizhongxin (STZX) station during both clean and polluted days. The concentrations of SO42-, NH4+, NO3- and organic aerosol were positively related to the concentration of added NO2. These results provide definitive evidence that NO2 can promote the conversion of SO2 to sulfate. At the same time, we found that NO2 can promote the formation of NH4+ and organic compounds in the aerosols. Our results illustrate that strengthened controls of nitrogen oxides is a key step in reducing the fine particles level in China.