Enzymatically catalyzed CO
O equilibration for oxygen isotope analyses of aqueous samples
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RATIONALE: The classic CO2 -H2 O equilibration method is a very popular technique for the measurement of the oxygen isotope composition of aqueous samples in stable isotope geochemistry. This study examined whether enzymatically controlled CO2 -H2 O equilibration by carbonic anhydrase (CA) could reduce the time for oxygen isotope equilibrium between CO2 and H2 O at 25°C. METHODS: Four types of aqueous samples containing CA were equilibrated with CO2 gases using a continuous flow isotope ratio mass spectrometer equipped with an automated gas sample collection device. We examined the effect of CA concentration in an aqueous sample, the influence of drying technique for the preparation of sample vials containing dried CA, the age of CA stock solution, and the ionic strength and the oxygen isotope composition of aqueous samples. RESULTS: CA rapidly catalyzed the oxygen isotope exchange between CO2 and H2 O and was unaffected by drying technique or stock solution age. Compared with aqueous samples with no CA or 0.2 μmolal CA, samples containing 4 μmolal CA significantly reduced the CO2 -H2 O equilibration time for deionized water and artificial seawater (ionic strength = ~0.6) from ~19 h and ~23 h to ~0.30 h and ~0.77 h, respectively at 25°C. CONCLUSIONS: This enzymatically catalyzed CO2 -H2 O equilibration method is time-efficient, cost-effective, requires no additional data correction procedure, and can be used for most commercially available CO2 -H2 O equilibration devices without any modification.
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