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In this work, the characterization of the species produced in reactive plasmas by differentially pumped mass spectrometry is addressed. A H2/CH4/N2 mixture (90 : 5 : 5) was fed into a direct current glow discharge and analysed by conventional and cryo-trap assisted mass spectrometry. The gaseous mixture was chosen because of its particular relevance in the inhibition of tritium-rich carbon film deposition in fusion plasmas (scavenger technique) and in the deposition of amorphous hydrogenated carbon films by plasma-assisted chemical vapour deposition. Important changes in the composition of the detected species upon surface modification of the reactor walls (stainless steel or covered by an amorphous hydrogenated carbon layer) or in the way they are sampled (length and spatial configuration of the stainless steel duct) were detected. They are analysed in terms of radical formation and recombination on the reactor walls or into the sampling duct, thus providing some insight into the underlying chemistry. In general, when the reactor walls are covered by an amorphous hydrogenated carbon layer, more hydrocarbons are produced, but the radical production is lower and seem to be less reactive than in stainless steel. Also, two sources of oxygen contamination in the plasma have been identified, from the native oxide layer in stainless steel and from unintended water contamination in the chamber, which modify considerably the detected species., (Copyright © 2014 John Wiley & Sons, Ltd.)