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Organic compounds in the atmosphere vary widely in their molecular composition and chemical properties, so no single instrument can reasonably measure the entire range of ambient compounds. Over the past decade, a new generation of in situ, field-deployable mass spectrometers has dramatically improved our ability to detect, identify, and quantify these organic compounds, but no systematic approach has been developed to assess the extent to which currently available tools capture the entire space of chemical identity and properties that is expected in the atmosphere. Reduced-parameter frameworks that have been developed to describe atmospheric mixtures are exploited here to characterize the range of chemical properties accessed by a suite of instruments. Multiple chemical spaces (e.g. oxidation state of carbon vs. volatility, and oxygen number vs. carbon number) were populated with ions measured by several mass spectrometers, with gas- and particle-phase α-pinene oxidation products serving as the test mixture of organic compounds. Few gaps are observed in the coverage of the parameter spaces by the instruments employed in this work, though the full extent to which comprehensive measurement was achieved is difficult to assess due to uncertainty in the composition of the mixture. Overlaps between individual ions and regions in parameter space were identified, both between gas- and particle-phase measurements, and within each phase. These overlaps were conservatively found to account for little (＜10%) of the measured mass. However, challenges in identifying overlaps and in accurately converting molecular formulas into chemical properties (such as volatility or reactivity) highlight a continued need to incorporate structural information into atmospheric measurements. [ABSTRACT FROM AUTHOR]

Organosulfates are formed in the atmosphere from reactions between reactive organic compounds (such as oxidation products of isoprene) and acidic sulfate aerosol. Here we investigated speciated organosulfates in an area typically downwind of the city of Manaus situated in the Amazon forest in Brazil during "GoAmazon2014/5" in both the wet season (February-March) and dry season (August-October). We observe products consistent with the reaction of isoprene photooxidation products and sulfate aerosols, leading to formation of several types of isoprene-derived organosulfates, which contribute 3% up to 42% of total sulfate aerosol measured by aerosol mass spectrometry. During the wet season the average contribution of summed organic sulfate concentrations to total sulfate was 19 ± 10% and similarly during the dry season the contribution was 19 ± 8%. This is the highest fraction of speciated organic sulfate to total sulfate observed at any reported site. Organosulfates appeared to be dominantly formed from isoprene epoxydiols (IEPOX), averaging 104 ± 73 ng m-3 (range 15-328 ng m-3) during the wet season, with much higher abundance 610 ± 400 ng m-3 (range 86-1962 ng m-3) during the dry season. The concentration of isoprene-derived organic sulfate correlated with total inorganic sulfate (R2 = 0.35 and 0.51 during the wet and dry seasons, respectively), implying the significant influence of inorganic sulfate aerosol for the heterogeneous reactive uptake of IEPOX. Organosulfates also contributed to organic matter in aerosols (3.5 ± 1.9% during the wet season and 5.1 ± 2.5% during the dry season). The present study shows that an important fraction of sulfate in aerosols in the Amazon downwind of Manaus consists of multifunctional organic chemicals formed in the atmosphere, and that increased SO2 emissions would substantially increase SOA formation from isoprene.

A new analytical methodology combining comprehensive two-dimensional gas chromatography (GC×GC), dual ionization energies and high resolution time of flight mass spectrometry has been developed that improves molecular level identification of organic compounds in complex environmental samples. GC×GC maximizes compound separation providing cleaner mass spectra by minimizing erroneous fragments from interferences and co-eluting peaks. Traditional electron ionization (EI, 70 eV) provides MS fragmentation patterns that can be matched to published EI MS libraries while vacuum ultraviolet photoionization (VUV, 10.5 eV) yields MS with reduced fragmentation enhancing the abundance of the molecular ion providing molecular formulas when combined with high resolution mass spectrometry. We demonstrate this new approach by applying it to a sample of organic aerosol. In this sample, 238 peaks were matched to EI MS library data with FM ≥ 800 but a fifth (42 compounds) were determined to be incorrectly identified because the molecular formula was not confirmed by the VUV MS data. This highlights the importance of using a complementary technique to confirm compound identifications even for peaks with very good matching statistics. In total, 171 compounds were identified by EI MS matching to library spectra with confirmation of the molecular formula from the high resolution VUV MS data and were not dependent on the matching statistics being above a threshold value. A large number of unidentified peaks were still observed with FM < 800, which in routine analysis would typically be neglected. Where possible, these peaks were assigned molecular formulas from the VUV MS data (211 in total). In total, the combination of EI and VUV MS data provides more than twice as much molecular level peak information than traditional approaches and improves confidence in the identification of individual organic compounds. The molecular formula data from the VUV MS data was used, in conjunction with GC×GC retention times and the observed EI MS, to generate a new, searchable EI MS library compatible with the standard NIST MS search program. This library is deliberately dynamic and editable so that other end users can add new entries and update existing entries as new information becomes available.