Organic contamination may decrease the targeted performances of coated surfaces. To study the contamination induced by surrounding materials, a method using a thermal extractor is presented in the first part of this work. Besides its normal operation (analyses of outgassing compounds from a material), this device is used in an original way to contaminate and decontaminate samples. Efficiency of contamination and decontamination protocols are assessed by automated thermal desorption and gas chromatography coupled with mass spectrometry and by secondary ion mass spectrometry coupled with a time of flight mass analyzer. This enables to study the contamination induced by a bulk material outgassing and to take in consideration the possible competition between outgassed species. This method is then applied to investigate contamination of Laser MegaJoule sol-gel coated optics by a retractable sheath. The impact of the temperature on the outgassing of the sheath has been highlighted. Increasing temperature from 30 to 50 C enables the outgassing of organophosphorous compounds and increases the outgassing of oxygenated compounds and phthalates. Chemical analyses of contaminated optics have highlighted affinities between the sol-gel coating and phthalates and organophosphorous, and low affinities with aromatics and terpens. Finally, samples with increasing levels of contamination have been realized. However a saturation phenomenon is observed at 90 ng cm(-2). (C) 2014 Elsevier B.V. All rights reserved.