Abstract
The carbon, nitrogen, and phosphorus (C, N, and P, respectively) composition and elemental ratios were measured in the 20–200 μ m size fraction during July 2015 in the surface waters of an anticyclonic eddy encountered north of Hawaii in the oligotrophic North Pacific Subtropical Gyre. The observed particulate N : P ratio fluctuated by approximately a factor of two over the diel cycle. We present a simple mathematical argument connecting this change to a rate of biological nitrogen fixation, and calculate the nitrogen fixation rate to be ≥ 13 nmol L −1 d −1 for this size class. This value is higher than simultaneous bottle‐incubation based rates measured with isotopic tracers, yet is consistent with historic rate measurements from the region. As confirmation of our methods, diurnal changes in C : N : P of laboratory cultures of the diazotrophic genus Trichodesmium were measured. In the laboratory, we show that estimates of nitrogen fixation from stoichiometric time series are equivalent to those derived directly from mass balance. The disparity between nitrogen fixation rates derived from tracer measurements and particulate stoichiometry in the field suggests that large diazotrophs may be underestimated in small volume (∼ 4 L) bottle incubations as a result of either spatial heterogeneity or vertical migration of large cells. Otherwise, processes other than diazotrophy must cause the observed changes in stoichiometry. This approach represents a novel and scalable means of quantifying in situ nitrogen fixation rates from diurnal changes in size‐fractionated stoichiometry. We also infer carbon fixation, growth rates, and phosphorus uptake in the 20–200 μm size class.