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The oceans are a key source of a number of atmospherically importantvolatile gases. The accurate and robust determination of trace gasesin seawater is a significant analytical challenge, requiringreproducible and ideally automated sample handling, a high efficiencyof seawater–air transfer, removal of water vapour from the samplestream, and high sensitivity and selectivity of the analysis. Here wedescribe a system that was developed for the fully automated analysisof dissolved very short-lived halogenated species (VSLS) sampled froman under-way seawater supply. The system can also be used forsemi-automated batch sampling from Niskin bottles filled during CTD(conductivity, temperature, depth) profiles. The essential componentscomprise a bespoke, automated purge and trap (AutoP & T) unitcoupled to a commercial thermal desorption and gas chromatograph massspectrometer (TD-GC-MS). The AutoP & T system has completed fiveresearch cruises, from the tropics to the poles, and collected over2500 oceanic samples to date. It is able to quantify >25 species overa boiling point range of 34–180 °C with Henry's lawcoefficients of 0.018 and greater (CH22l, kHccdimensionless gas/aqueous) and has been used to measure organicsulfurs, hydrocarbons, halocarbons and terpenes. In the eastern tropicalPacific, the high sensitivity and sampling frequency provided newinformation regarding the distribution of VSLS, including novelmeasurements of a photolytically driven diurnal cycle ofCH22l within the surface ocean water

ocean science

Technical Note: A fully automated purge and trap GC-MS system for quantification of volatile organic compound (VOC) fluxes between the ocean and atmosphere