Abstract. Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM1 mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (Dva) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00–02:00 p.m. EST due to photochemical production. The average (±1σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012(±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NOx. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern peaking around local lunch and dinner times. In addition, NOA is characterized with prominent CxH2x+2N+ peaks likely from amine compounds. Our results indicate that cooking-related activities are a major source of POA in NYC, releasing comparable amounts of POA as traffic emissions. POA=HOA+COA) on average accounts for ~30% of the total OA mass during this study while SOA dominates the OA composition with SV-OOA and LV-OOA on average accounting for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC involves a~continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that nitrogen-containing organic species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving acid-base chemistry. Analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city.
Identification of new transformation products during enzymatic treatment of tetracycline and erythromycin antibiotics at laboratory scale by an on-line turbulent flow liquid-chromatography coupled to a high resolution mass spectrometer LTQ-Orbitrap