Enrichment of oxygen heavy isotopes during photosynthesis in phytoplankton

Some of the oxygen produced during oxygenic photosynthesis is consumed but little is known about the extent of the processes involved. We measured the (17)O/(16)O and (18)O/(16)O ratios in O(2) produced by certain marine and freshwater phytoplankton representing important groups of primary producers. When the cells were performing photosynthesis under very low dissolved oxygen concentrations (< 3 μM), we observed significant enrichment in both (18)O and (17)O with respect to the substrate water. The difference in δ(18)O between O(2) and water was about 4.5, 3, 5.5, and 7‱ in the diatom Phaeodactylum tricornutum, Nannochloropsis sp. (Eustigmatophyceae), the coccolithophore Emiliania huxleyi and the green alga Chlamydomonas reinhardtii, respectively. The difference in δ(17)O was about 0.52 that of δ(18)O. As explained, the observed enrichments most probably stem from considerable oxygen consumption during photosynthesis even when major O(2)-consuming reactions such as photorespiration were minimized. These enrichments increased linearly with rising O(2) levels but with different δ(17)O/δ(18)O slopes for the various organisms, suggesting engagements of different O(2)-consuming reactions with rising O(2) levels. Consumption of O(2) may be important for energy dissipation during photosynthesis. The isotope enrichment observed here, not accounted for in earlier assessments, closes an important gap in our understanding of the difference between the isotopic compositions of atmospheric oxygen and that of seawater, i.e., the Dole effect.