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In situ field measurements of glyoxal at the surface in the tropical marine boundary layer have been made with a temporal resolution of a few minutes during two 4-week campaigns in June–July and August–September 2014 at the Cape Verde Atmospheric Observatory (CVAO; 16∘52′ N, 24∘52′ W). Using laser-induced phosphorescence spectroscopy with an instrumental detection limit of ∼1 pptv (1 h averaging), volume mixing ratios up to ∼10 pptv were observed, with 24 h averaged mixing ratios of 4.9 and 6.3 pptv observed during the first and second campaigns, respectively. Some diel behaviour was observed, but this was not marked. A box model using the detailed Master Chemical Mechanism (version 3.2) and constrained with detailed observations of a suite of species co-measured at the observatory was used to calculate glyoxal mixing ratios. There is a general model underestimation of the glyoxal observations during both campaigns, with mean midday (11:00–13:00) observed-to-modelled ratios for glyoxal of 3.2 and 4.2 for the two campaigns, respectively, and higher ratios at night. A rate of production analysis shows the dominant sources of glyoxal in this environment to be the reactions of OH with glycolaldehyde and acetylene, with a significant contribution from the reaction of OH with the peroxide HC(O)CH2OOH, which itself derives from OH oxidation of acetaldehyde. Increased mixing ratios of acetaldehyde, which is unconstrained and potentially underestimated in the base model, can significantly improve the agreement between the observed and modelled glyoxal during the day. Mean midday observed-to-modelled glyoxal ratios decreased to 1.3 and 1.8 for campaigns 1 and 2, respectively, on constraint to a fixed acetaldehyde mixing ratio of 200 pptv, which is consistent with recent airborne measurements near CVAO. However, a significant model under-prediction remains at night. The model showed limited sensitivity to changes in deposition rates of model intermediates and the uptake of glyoxal onto aerosol compared with sensitivity to uncertainties in chemical precursors. The midday (11:00–13:00) mean modelled glyoxal mixing ratio decreased by factors of 0.87 and 0.90 on doubling the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively, and increased by factors of 1.10 and 1.06 on halving the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively. Although measured levels of monoterpenes at the site (total of ∼1 pptv) do not significantly influence the model calculated levels of glyoxal, transport of air from a source region with high monoterpene emissions to the site has the potential to give elevated mixing ratios of glyoxal from monoterpene oxidation products, but the values are highly sensitive to the deposition rates of these oxidised intermediates. A source of glyoxal derived from production in the ocean surface organic microlayer cannot be ruled out on the basis of this work and may be significant at night.

The oceans are a key source of a number of atmospherically important volatile gases. The accurate and robust determination of trace gases in seawater is a significant analytical challenge, requiring reproducible and ideally automated sample handling, a high efficiency of seawater–air transfer, removal of water vapour from the sample stream, and high sensitivity and selectivity of the analysis. Here we describe a system that was developed for the fully automated analysis of dissolved very short-lived halogenated species (VSLS) sampled from an under-way seawater supply. The system can also be used for semi-automated batch sampling from Niskin bottles filled during CTD (conductivity, temperature, depth) profiles. The essential components comprise a bespoke, automated purge and trap (AutoP & T) unit coupled to a commercial thermal desorption and gas chromatograph mass spectrometer (TD-GC-MS). The AutoP & T system has completed five research cruises, from the tropics to the poles, and collected over 2500 oceanic samples to date. It is able to quantify >25 species over a boiling point range of 34–180 °C with Henry's law coefficients of 0.018 and greater (CH22l, kHcc dimensionless gas/aqueous) and has been used to measure organic sulfurs, hydrocarbons, halocarbons and terpenes. In the eastern tropical Pacific, the high sensitivity and sampling frequency provided new information regarding the distribution of VSLS, including novel measurements of a photolytically driven diurnal cycle of CH22l within the surface ocean water.