Mark

Mass spectrometry (MS) has become a primary tool for identifying and quantifying biological molecules. In combination with other orthogonal techniques, such as gas-phase hydrogen/deuterium exchange (gHDX), MS is also capable of probing the structure of ions.

However, gHDX kinetics can depend strongly on many factors, including laboratory temperature, instrumental conditions, and instrument platform selection. These effects can lead to high variability with gHDX measurements, which has hindered the broader adoption of gHDX for structural MS. Here we introduce an approach for standardizing gHDX measurements using co-sampled standards.

Quantifying the exchange kinetics for analytes relative to the exchange kinetics of the standards results in greater accuracy and precision than the underlying absolute measurements. The standardization was found to be effective for several types of analytes including small molecules and intact proteins.

A subset of analytes showed deviations in their standardized exchange profiles that are attributed to field heating and the concomitant conformational isomerization. Inclusion of helium during the gHDX process for collisional cooling helps mitigate such variations in exchange kinetics related to ion heating. We anticipate that the outcomes of this research will enable the broader use of gHDX in MS-based workflows for molecular identification and isomer differentiation.

Reactive VOC Production from Photochemical and Heterogeneous Reactions Occurring at the Air-Ocean Interface

ConspectusThe ocean surface serves as a source and sink for a diverse set of reactive trace gases in the atmosphere, including volatile organic compounds (VOCs), reactive halogens, and oxidized and reduced nitrogen compounds.

The exchange of reactive trace gases between the atmosphere and ocean has been shown to alter atmospheric oxidant concentrations and drive particle nucleation and growth. Uncertainties in cloud radiative forcing and aerosol-cloud interactions are among the largest uncertainties in current global climate models. Climate models are particularly sensitive to cloud cover over the remote ocean due to large changes in albedo between the ocean surface and cloud tops.

Oceanic emissions contribute to cloud condensation nuclei concentrations, either through the direct emission of particles during wave breaking or through the formation of secondary aerosol particles following the emission of reactive gas-phase compounds. Despite generally small and diffuse oceanic emission rates for reactive trace gases, it has been shown that oxidant and particle number concentrations are acutely sensitive to air-sea trace gas exchange rates and the chemical composition of emitted species.

To date, field measurements of air-sea reactive gas exchange have focused primarily on the emission of gases of biological origin, such as dimethyl sulfide (DMS). While DMS emissions are relatively well constrained, the gas-phase oxidation that connects DMS to sulfate aerosol is less well understood.

Recent laboratory measurements suggest that heterogeneous and photochemical reactions occurring at the air-sea interface can also lead to the production and emission of a wide array of reactive VOC. When laboratory-based measurements are used to derive global scale emissions, the calculated sea-to-air fluxes of reactive VOC generated from heterogeneous and photochemical processes are comparable or larger in magnitude to the sea-to-air flux of DMS.

It is not yet clear how the mechanisms proposed in these laboratory experiments translate to atmospheric conditions. The proposed abiotic emissions are also a potential source of VOC in regions of low biological activity, which carries important implications for regional and global modeling.

This Account reviews recent laboratory and field experiments of biotic and abiotic ocean VOC emissions, with a specific focus on exploring open questions related to proposed abiotic reactive VOC emissions and the impact of including a large, abiotic VOC emission source on atmospheric oxidants and aerosol particles.

To date, abiotic emissions are not typically included in global chemical transport models. The proposed abiotic emissions mechanisms discussed here have the potential to drive significant changes to current understanding of chemistry in the marine atmosphere if present at the magnitudes suggested by laboratory studies. In order to validate their proposed significance, a coordinated set of laboratory, field, and modeling studies under ocean-relevant conditions are necessary.