Organosulfates from pinene and isoprene over the Pearl River Delta, South China: seasonal variation and implication in formation mechanisms.

Biogenic organosulfates (OSs) are important markers of secondary organic aerosol (SOA) formation involving cross reactions of biogenic precursors (terpenoids) with anthropogenic pollutants. Until now, there has been rare information about biogenic OSs in the air of highly polluted areas. In this study, fine particle (PM2.5) samples were separately collected in daytime and nighttime from summer to fall 2010 at a site in the central Pearl River Delta (PRD), South China. Pinene-derived nitrooxy-organosulfates (pNOSs) and isoprene-derived OSs (iOSs) were quantified using a liquid chromatograph (LC) coupled with a tandem mass spectrometer (MS/MS) operated in negative electrospray ionization (ESI) mode. The pNOSs with MW 295 exhibited higher levels in fall (151 ± 86.9 ng m(-3)) than summer (52.4 ± 34.0 ng m(-3)), probably owing to the elevated levels of NOx and sulfate in fall when air masses mainly passed through city clusters in the PRD and biomass burning was enhanced. In contrast to observations elsewhere where higher levels occurred at nighttime, pNOS levels in the PRD were higher during the daytime in both seasons, indicating that pNOS formation was likely driven by photochemistry over the PRD. This conclusion is supported by several lines of evidence: the specific pNOS which could be formed through both daytime photochemistry and nighttime NO3 chemistry exhibited no day-night variation in abundance relative to other pNOS isomers; the production of the hydroxynitrate that is the key precursor for this specific pNOS was found to be significant through photochemistry but negligible through NO3 chemistry based on the mechanisms in the Master Chemical Mechanism (MCM). For iOSs, 2-methyltetrol sulfate ester which could be formed from isoprene-derived epoxydiols (IEPOX) under low-NOx conditions showed low concentrations (below the detection limit to 2.09 ng m(-3)), largely due to the depression of IEPOX formation by the high NOx levels over the PRD.

Tracer-based source apportionment of polycyclic aromatic hydrocarbons in PM2.5 in Guangzhou, southern China, using positive matrix factorization (PMF).

From 28 November to 23 December 2009, 24-h PM2.5 samples were collected simultaneously at six sites in Guangzhou. Concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) together with certain molecular tracers for vehicular emissions (i.e., hopanes and elemental carbon), coal combustion (i.e., picene), and biomass burning (i.e., levoglucosan) were determined. Positive matrix factorization (PMF) receptor model combined with tracer data was applied to explore the source contributions to PAHs. Three sources were identified by both inspecting the dominant tracer(s) in each factor and comparing source profiles derived from PMF with determined profiles in Guangzhou or in the Pearl River Delta region. The three sources identified were vehicular emissions (VE), biomass burning (BB), and coal combustion (CC), accounting for 11 ± 2%, 31 ± 4%, and 58 ± 4% of the total PAHs, respectively. CC replaced VE to become the most important source of PAHs in Guangzhou, reflecting the effective control of VE in recent years. The three sources had different contributions to PAHs with different ring sizes, with higher BB contributions (75 ± 3%) to four-ring PAHs such as pyrene and higher CC contributions (57 ± 4%) to six-ring PAHs such as benzo[ghi]perylene. Temporal variations of VE and CC contributions were probably caused by the change of weather conditions, while temporal variations of BB contributions were additionally influenced by the fluctuation of BB emissions. Source contributions also showed some spatial variations, probably due to the source emission variations near the sampling sites.

Polycyclic aromatic hydrocarbons in PM2.5 in Guangzhou, southern China: spatiotemporal patterns and emission sources.

Fine particulate samples were simultaneously collected at six sites in Guangzhou in November-December 2009. Eighteen polycyclic aromatic hydrocarbons (PAHs) and tracers, i.e. hopanes, elemental carbon, picene and levoglucosan were measured. Three high level episodes were observed during the sampling period, likely due to accumulation effects. Back trajectory analysis revealed that the air masses for the three episodes were from eastern inland Pearl River Delta (PRD) region. There was no obvious concentration gradient for total and 5-6 ring PAHs such as benzo[g,h,i]perylene (BghiP) from urban to rural sites. However, 4-ring PAHs such as pyrene (Pyr) exhibited significantly higher levels at rural site than that at urban/suburban sites (p<0.01). BghiP correlated well with hopanes, elemental carbon and picene, indicating vehicular emissions and coal combustion were the sources of 5-6 ring PAHs, which were further confirmed by comparing the four tracers/BghiP ratios and IcdP/BghiP ratios in ambient samples with those from source profiles. Results indicated that vehicular emissions were no longer the dominant sources in winter season in Guangzhou.