Preventing drift of oxygen isotopes of CO₂-in-air stored in glass sample flasks: new insights and recommendations

It is known that the oxygen isotope composition of CO₂-in-air, when stored over longer time periods in glass sample flasks, tends to drift to more negative values while the carbon isotope composition remains stable. The exact mechanisms behind this drift were still unclear. New experimental results reveal that water already inside the flasks during sampling plays a major role in the drift of the oxygen isotopes. A drying method to remove any water sticking to the inner walls by evacuating the flasks for more than 72 h while heating to 60 °C significantly decreases drift of the oxygen isotopes. Moreover, flasks not dried with this method showed higher differences among drift rates of individual flasks. This is explained through the buildup of H₂O molecules sticking to the inner walls. Humidity of the air samples in the flasks as well as surface characteristics will lead to differences among flasks. Results also show that permeability of water is higher through Viton O-ring flask seals than through polychlorotrifluoroethylene (PCTFE) shaft seals, and that the stability of flasks sealed with the latter is significantly better over time.