Abstract. During the ARK XXV 1 + 2 expedition in the Arctic Ocean carried out in June–July 2010 aboard the R/V Polarstern, we measured carbon monoxide (CO), non-methane hydrocarbons (NMHC) and phytoplankton pigments at the sea surface and down to a depth of 100 m. The CO and NMHC sea-surface concentrations were highly variable; CO, propene and isoprene levels ranged from 0.6 to 17.5 nmol L⁻¹, 1 to 322 pmol L⁻¹ and 1 to 541 pmol L⁻¹, respectively. The CO and alkene concentrations as well as their sea–air fluxes were enhanced in polar waters off of Greenland, which were more stratified because of ice melting and richer in chromophoric dissolved organic matter (CDOM) than typical North Atlantic waters. The spatial distribution of the surface concentrations of CO was consistent with our current understanding of CO-induced UV photoproduction in the sea. The vertical distributions of the CO and alkenes were comparable and followed the trend of light penetration, with the concentrations displaying a relatively regular exponential decrease down to non-measurable values below 50 m. However, no diurnal variations of CO or alkene concentrations were observed in the stratified and irradiated surface layers. On several occasions, we observed the existence of subsurface CO maxima at the level of the deep chlorophyll maximum. This finding suggests the existence of a non-photochemical CO production pathway, most likely of phytoplanktonic origin. The corresponding production rates normalized to the chlorophyll content were in the range of those estimated from laboratory experiments. In general, the vertical distributions of isoprene followed that of the phytoplankton biomass. These data support the existence of a dominant photochemical source of CO and light alkenes enhanced in polar waters of the Arctic Ocean, with a minor contribution of a biological source of CO. The biological source of isoprene is observed in the different water masses but significantly increases in the warmer Atlantic waters.