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An analytical method for the determination of the alpha dicarbonyls glyoxal(GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles ispresented. The method is based on derivatization witho-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solventextraction and GC-MS (SIM) analysis. The method showed good precision(RSD < 10%), sensitivity (detection limits in the low ng L−1 range),and accuracy (good agreement between external calibration and standardaddition). The method was applied to determine GLY and MGLY in oceanic watersampled during the Polarstern cruise ANT XXVII/4 from Capetown toBremerhaven in spring 2011. GLY and MGLY were determined in the sea surfacemicrolayer (SML) of the ocean and corresponding bulk water (BW) with averageconcentrations of 228 ng L−1 (GLY) and 196 ng L−1 (MGLY). Theresults show a significant enrichment (factor of 4) of GLY and MGLY in theSML. Furthermore, marine aerosol particles (PM1) were sampled duringthe cruise and analyzed for GLY (average concentration 0.19 ng m−3) andMGLY (average concentration 0.15 ng m−3). On aerosol particles, bothcarbonyls show a very good correlation with oxalate, supporting the idea ofa secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLYand MGLY in seawater and on aerosol particles were correlated toenvironmental parameters such as global radiation, temperature, distance tothe coastline and biological activity. There are slight hints for aphotochemical production of GLY and MGLY in the SML (significant enrichmentin the SML, higher enrichment at higher temperature). However, a clearconnection of GLY and MGLY to global radiation as well as to biologicalactivity cannot be concluded from the data. A slight correlation between GLYand MGLY in the SML and in aerosol particles could be a hint forinteractions, in particular of GLY, between seawater and the atmosphere

atmospheric chemistry and physics

Glyoxal and methylglyoxal in Atlantic seawater and marine aerosol particles: method development and first application during the Polarstern cruise ANT XXVII/4