The isotopic ratios 17O/16O and 18O/16O in molecular oxygen and their significance in biogeochemistry

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (delta O-17 and delta O-18) of dissolved O-2 in the ocean and of air O-2 in ice cores. This method is based on the deviations ((17)Delta) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O-2. To apply this method, the slope in the O-17/O-16 VS. O-18/O-16 relationship used for (17)Delta calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the (17)Delta of O-2 in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O-2 consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 +/- 0.0006) in ln(delta O-17 + 1) vs. ln(delta O-18 + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating (17)Delta of dissolved O-2. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O-2 in air records of ice cores. Copyright (c) 2005 Elsevier Ltd.