An improved head-space analysis method for methane in seawater

A widely used degassing method for methane in seawater employing vacuum was tested and subsequently improved. It yielded 62 ± 3.8% of the total dissolved methane, hence a reproducible correction factor was established. The method was then applied to measure CH4 in the sea-air boundary layer and simultaneously in the overlying air along two transects in the eastern Equatorial Pacific off Peru in March of 1992. The results showed surprising small-scale reversals of the methane exchange between ocean and atmosphere in this region. Generally the ocean acted as a source of methane but also methane uptake by the ocean was found. This was mainly a consequence of high CH4 concentrations in the air which deviated considerably from the long-term and large-scale average. If applied to the flux rate calculations, the observed variabilities indicate that both rate and direction of the methane flux through the air-sea interface vary considerably depending on the atmospheric CH4 content. The implications are that even ocean areas with high concentrations of dissolved CH4 can be considerably weaker sources than would be expected on the basis of 1.7 ppmv mean atmospheric methane content. Based on improved simultaneous analyses of both air and water samples, the ocean-atmosphere flux of methane would therefore be more dynamic than previously thought.