Abstract. Formaldehyde (HCHO), the most abundant carbonyl compound in the atmosphere, is generated as an intermediate product in the oxidation of nonmethane hydrocarbons. Proton transfer reaction mass spectrometry (PTR-MS) has the capability to detect HCHO from ion signals at m/z 31 with high time-resolution. However, the detection sensitivity is low compared to other detectable species, and is considerably affected by humidity, due to back reactions between protonated HCHO and water vapor prior to analysis. We performed a laboratory calibration of PTR-MS for HCHO and examined the detection sensitivity and humidity dependence at various field strengths. Subsequently, we deployed the PTR-MS instrument in a field campaign at Mount Tai

Ethylene ozonolysis was investigated in laboratory experiments using a Teflon bag reactor. A negative ion chemical ionization mass spectrometer (NI-CIMS) using SO2Cl(-) and Cl(-) as reagent ions was used for product analysis. In addition to the expected gas-phase products, such as formic acid and hydroperoxymethyl formate, oligomeric hydroperoxides composed of the Criegee intermediate (CH2OO) as a chain unit were observed. Furthermore, we observed secondary organic aerosol (SOA) formation from the ethylene ozonolysis, and the particle-phase products were also analyzed by NI-CIMS. The CH2OO oligomers were also observed as particle-phase components, suggesting that the oligomeric hydroperoxides formed in the gas phase partition into the particle phase. By adding methanol as a stabilized Criegee intermediate scavenger, both the gas-phase oligomer formation and SOA formation were strongly suppressed. This indicates that CH2OO plays a critical role in the formation of oligomeric hydroperoxides followed by SOA formation in ethylene ozonolysis. A new formation mechanism for the oligomeric hydroperoxides, which includes sequential addition of CH2OO to hydroperoxides, is proposed.

Abstract. An observation-based box model approach was undertaken to estimate concentrations of OH, HO2, and RO2 radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O3, H2O, CO, NO, NO2, hydrocarbon, HCHO, and CH3CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h−1 as a 6-h average (09:00–15:00 CST), suggesting 58±37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as ~23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once), in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NOx and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NOx-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions) in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO2 radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.

No abstract

Abstract. The emission characteristics of refractory black carbon (rBC) from biomass burning are essential information for numerical simulations of regional pollution and climate effects. We conducted combustion experiments in the laboratory to investigate the emission ratio and mixing state of rBC from the burning of wheat straw and rapeseed plants, which are the main crops cultivated in the Yangtze River Delta region of China. A single particle soot photometer (SP2) was used to measure rBC-containing particles at high temporal resolution and with high accuracy. The combustion state of each burning case was indicated by the modified combustion efficiency (MCE), which is calculated using the integrated enhancement of carbon dioxide and carbon monoxide concentrations relative to their background values. The mass size distribution of the rBC particles showed a lognormal shape with a mode mass equivalent diameter (MED) of 189 nm (ranging from 152 to 215 nm), assuming an rBC density of 1.8 g cm −3 . rBC particles less than 80 nm in size (the lower detection limit of the SP2) accounted for ∼ 5 % of the total rBC mass, on average. The emission ratios, which are expressed as rBC / CO ( indicates the difference between the observed and background values), displayed a significant positive correlation with the MCE values and varied between 1.8 and 34 ng m −3 ppbv −1 . Multi-peak fitting analysis of the delay time ( t, or the time of occurrence of the scattering peak minus that of the incandescence peak) distribution showed that rBC-containing particles with rBC MED = 200 ± 10 nm displayed two peaks at t = 1.7 µs and t = 3.2 µs, which could be attributed to the contributions from both flaming and smoldering combustion in each burning case. Both the t values and the shell / core ratios of the rBC-containing particles clearly increased as the MCE decreased from 0.98 (smoldering-dominant combustion) to 0.86 (flaming-dominant combustion), implying the great importance of the rapid condensation of semi-volatile organics. This laboratory study found that the mixing state of rBC particles from biomass burning strongly depends on its combustion processes, and overall MCE should be taken carefully into consideration while the climate effect of rBC particles from open biomass burning is simulated.

Laser-induced fluorescence spectra in the 330−370 nm region are assigned to the five expected methyl substituted vinoxy radicals:  1-methylvinoxy, 2-methylvinoxy, 1,2-dimethylvinoxy, 2,2-dimethylvinoxy, and 1,2,2-trimethylvinoxy radicals. Substituted vinoxy radicals were produced by photolyses or by chlorine or fluorine atom reactions with ketones, aldehydes, or ethers. These radicals were also observed when reacting oxygen atoms with olefins such as propene, cis- and trans-2-butene, isobutene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene. These results extend our knowledge of the replacement mechanism in O + olefin reactions, i.e., a methyl radical or a hydrogen atom can be expelled directly from the triplet biradical formed by an O atom addition to an olefin. Methyl substituted vinoxy radicals can also be produced by the release of a methyl radical from the 2-position carbon of an energized singlet aldehyde or ketone formed by a 1,2-migration of a hydrogen atom in the triplet biradical.

Open crop residue burning is one of the major sources of air pollutants including the precursors of photooxidants like ozone and secondary organic aerosol. We made measurements of trace gases including nonmethane volatile organic compounds (NMVOCs) in a rural area in central East China in June 2010. During the campaign, we identified six biomass burning events in total through the simultaneous enhancement of carbon monoxide and acetonitrile. Four cases represented fresh plumes (<2 h after emission), and two cases represented aged plumes (>3 h after emission), as determined by photochemical age. While we were not able to quantify formic acid, we identified an enhancement of major oxygenated volatile organic compounds (OVOCs) as well as low molecular alkanes and alkenes, and aromatic hydrocarbons in these plumes. The observed normalized excess mixing ratios (NEMRs) of OVOCs and alkenes showed dependence on air mass age, even in fresh smoke plumes, supporting the view that these species are rapidly produced and destructed, respectively, during plume evolution. Based on the NEMR data in the fresh plumes, we calculated the emission factors (EFs) of individual NMVOC. The comparison to previous reports suggests that the EFs of formaldehyde and acetic acid have been overestimated, while those of alkenes have been underestimated. Finally, we suggest that open burning of wheat residue in China releases about 0.34 Tg NMVOCs annually. If we applied the same EFs to all crops, the annual NMVOC emissions would be 2.33 Tg. The EFs of speciated NMVOCs can be used to improve the existing inventories.

Abstract. Traditional yield curve analysis shows that semi-volatile organic compounds are a major component of secondary organic aerosols (SOAs). We investigated the volatility distribution of SOAs from α-pinene ozonolysis using positive electrospray ionization mass analysis and dilution- and heat-induced evaporation measurements. Laboratory chamber experiments were conducted on α-pinene ozonolysis, in the presence and absence of OH scavengers. Among these, we identified not only semi-volatile products, but also less volatile highly oxygenated molecules (HOMs) and dimers. Ozonolysis products were further exposed to OH radicals to check the effects of photochemical aging. HOMs were also formed during OH-initiated photochemical aging. Most HOMs that formed from ozonolysis and photochemical aging had 10 or fewer carbons. SOA particle evaporation after instantaneous dilution was measured at  < 1 and  ∼ 40 % relative humidity. The volume fraction remaining of SOAs decreased with time and the equilibration timescale was determined to be 24–46 min for SOA evaporation. The experimental results of the equilibration timescale can be explained when the mass accommodation coefficient is assumed to be 0.1, suggesting that the existence of low-volatility materials in SOAs, kinetic inhibition, or some combined effect may affect the equilibration timescale measured in this study.