The efficient adsorption of toxic organic species from humid airstreams by active carbons is impeded by the competitive adsorption of water vapour which, at low values of p/p(s), occurs at specific (polar) adsorption sites located at the edges of the carbon layer-planes and at in-plane defects. At higher pressures, adsorption in micropores and mesopores also occurs. The concentration of polar adsorption sites therefore determines the hydrophilicity of the carbon structure and their accelerated formation, by exposure to air and water vapour, is also responsible for the 'ageing' of active carbons. Overall, the adsorption of water reduces the volume of porosity available for the adsorption of target species and the hydrophilic nature of active carbons is recognized as a major barrier to their effective use in many applications. We present here results for the adsorption of nitrogen, organic and water vapours by a hydrophobic respirator granular active carbon produced by the thermal treatment of a base carbon, to desorb polar oxygen groups, followed by use of a plasma enhanced chemical vapour deposition (PECVD) treatment to apply a hydrophobic, fluorine containing, surface nanolayer. We show that at equivalent %RH values the treated carbon adsorbs significantly less water compared to an untreated (control) carbon and that the treatment does not reduce the levels of open porosity or impede the adsorption of a range of organic vapours at ambient temperatures. Preliminary evidence for the presence, after treatment, of constrictions at pore entrances which act as molecular gates is also presented. The treated carbon (after ageing for 6 weeks at 80%RH) is shown to have greater adsorptivity than an untreated base carbon toward hexane present in a humid (80%RH) airstream. This results in a 39% increase in break-through time. These hydrophobic properties persist one year after manufacture. The mechanism leading to the modified water adsorption properties is the partial desorption of polar oxygen sites followed by deposition at the external carbon surfaces of hydrophobic plasma polymer species. This reduces the polar surface free energy of the carbon and hence the amount of water adsorption occurring by the primary mechanism. This in turn retards the diffusion of water molecules into the micropores and leads to lower adsorption volumes at higher pressures. (C) 2010 Elsevier B.V. All rights reserved.