Oxygen Isotope Fractionation of O₂ Consumption through Abiotic Photochemical Singlet Oxygen Formation Pathways

Oxygen isotope ratios of O₂ are important tracers for assessing biological activity in biogeochemical processes in aquatic environments. In fact, changes in the ¹⁸O/¹⁶O and ¹⁷O/¹⁶O ratios of O₂ have been successfully implemented as measures for quantifying photosynthetic O₂ production and biological O₂ respiration. Despite evidence for light-dependent O₂ consumption in sunlit surface waters, however, photochemical O₂ loss processes have so far been neglected in the stable isotope-based evaluation of oxygen cycling. Here, we established the magnitude of the O isotope fractionation for abiotic photochemical O₂ elimination through formation of singlet O₂, ¹O₂, and the ensuing oxygenation and oxidation reactions with organic compounds through experiments with rose bengal as the ¹O₂ sensitizer and three different amino acids and furfuryl alcohol as chemical quenchers. Based on the kinetic analysis of light-dependent O₂ removal in the presence of different quenchers, we rationalize the observable O isotope fractionation of O₂ and the corresponding, apparent ¹⁸O kinetic isotope effects (¹⁸O-AKIE) with a pre-equilibrium model for the reversible formation of ¹O₂ and its irreversible oxygenation reactions with organic compounds. While ¹⁸O-AKIEs of oxygenation reactions amount to 1.03, the O isotope fractionation of O₂ decreased to unity with increasing ratio of the rates of oxygenation reaction of ¹O₂ vs ¹O₂ decay to ground state oxygen, ³O₂. Our findings imply that O isotope fractionation through photochemical O₂ consumption with isotope enrichment factors, ¹⁸O-ϵ, of up to -30‰ can match contributions from biological respiration at typical dissolved organic matter concentrations of lakes, rivers, and oceans and should, therefore, be included in future evaluations of biogeochemical O₂ cycling.