Technical Note: Inexpensive Modification Of Exetainers For The Reliable Storage Of Trace-Level Hydrogen And Carbon Monoxide Gas Samples

Atmospheric trace gases such as dihydrogen (H-2), carbon monoxide (CO) and methane (CH4) play important roles in microbial metabolism and biogeochemical cycles. Analysis of these gases at trace levels requires reliable storage of discrete samples of low volume. While commercial sampling vials such as Exetainers (R) have been tested for CH4 and other greenhouse gases, no information on reliable storage is available for H-2 and CO. We show that vials sealed with butyl rubber stoppers are not suitable for storing H-2 and CO due to release of these gases from rubber material. Treating butyl septa with NaOH reduced trace-gas release, but contamination was still substantial, with H-2 and CO mixing ratios in air samples increasing by a factor of 3 and 10 after 30 d of storage in conventional 12 mL Exetainers. All tested materials showed a near-linear increase in H-2 and CO mixing ratios, indicating a zero-order reaction and material degradation as the underlying cause. Among the rubber materials tested, silicone showed the lowest potential for H-2 and CO release. We thus propose modifying Exetainers by closing them with a silicone plug to minimise contamination and sealing them with a stainless-steel bolt and O-ring as a secondary diffusion barrier for long-term storage. Such modified Exetainers exhibited stable mixing ratios of H-2 and CH4 exceeding 60 d of storage at atmospheric and elevated (10 ppm) mixing ratios. The increase of CO was still measurable but was 9 times lower than in conventional Exetainers with treated septa; this can be corrected for due to its linearity by storing a standard gas alongside the samples. The proposed modification is inexpensive, scalable and robust, and thus it enables reliable storage of large numbers of low-volume gas samples from remote field locations.