Seasonal and diurnal variations of COO in air: Initial observations from Pasadena, CA

The budget of atmospheric CO2 is widely studied using records of temporal and spatial variations of concentrations, d C and dO values. However, the number and diversity of sources and sinks prevents these alone from fully constraining the budget. Molecules containing two rare isotopes can serve as additional tracers and potentially provide additional, independent, constraints. We present data documenting seasonal and diurnal variations of CO2 having a mass of 47 u (mostly COO) in air from Pasadena, CA. We report these data using the ‘mass 47 anomaly’ (D47), which is defined as the deviation of R(=[47]/[44]) from that expected for a random distribution of isotopologues. Between February 2004 and December 2005, D47 showed a seasonal pattern that differed significantly from that expected based on thermodynamic equilibrium. During the year 2004 D47 was 0.76‰ in winter, increased to 0.87‰ in summer and gradually decreased through the autumn to 0.81‰ at the end of the year. D47 then increased again through the winter and spring of 2005 to 0.97‰ in summer followed by a decrease to 0.88‰ at the end of 2005. The seasonal variations cannot be accounted for by variations in the relative contribution of local fossil fuel sources. Diurnal variations were the combined effect of both fuel combustion and respiration having D47 values of 0.41‰ and ca. 0.77‰, respectively. The seasonal cycle may be interpreted as a competition between low D47 values in respiration and higher D47 values resulting from CO2-water exchange in photosynthesis. 2007 Elsevier Ltd. All rights reserved.