Sampling considerations and assessment of E xetainer usage for measuring dissolved and gaseous methane and nitrous oxide in aquatic systems

Pre‐evacuated Exetainers are commonly used as measurement vials for the determination of methane (CH 4 ) and nitrous oxide (N 2 O) concentrations in liquid and gaseous samples from aquatic environments. The impact of residual air in these Exetainers on measurement accuracy is assessed. Residual air pressure in commercially available, pre‐evacuated Exetainers varied between 0.071 ± 0.008 atm and 0.180 ± 0.031 atm in examined batches. This background contamination can lead to large errors when determining dissolved and gaseous CH 4 and N 2 O concentrations particularly at low concentrations. A method for Exetainer pretreatment is suggested and verified, to reduce the residual CH 4 and N 2 O. Vials are flushed (needle 30 G × 0.5″, 0.3 mm) with nitrogen gas (N 2 ) for 5 min, which reduces the background CH 4 and N 2 O concentrations to 0.092 ± 0.008 ppm and 0.016 ± 0.001 ppm, respectively, approximately 3–4% of their respective concentrations in air. To avoid an alteration of sample concentration by variable residual gas levels left during a pre‐evacuation step, liquid and gaseous samples are injected into the N 2 filled Exetainers. For gaseous samples where large volumes of gas are available, Exetainers can alternatively be flushed with 100 mL of sampling gas. For gaseous samples, measured CH 4 and N 2 O concentrations of standard gases were statistically identical to their known concentrations. For liquid samples, measured CH 4 and N 2 O concentrations of liquid standard dilution series showed strong linear correlations with theoretically calculated concentrations (slope CH 4 : 1.04, slope N 2 O: 1.12). Sample concentrations remained constant over a minimum storage period of 6 weeks.