Upper ocean nitrogen fluxes in the Polar Antarctic Zone: Constraints from the nitrogen and oxygen isotopes of nitrate

We report nitrate nitrogen (N) and oxygen (O) isotope measurements from the seasonally sea ice covered Polar Antarctic Zone (PAZ) south of the Southern Antarctic Circumpolar Front. The 15 N/14 N and 18 O/16 O ratios of nitrate both increase into the summertime surface mixed layer, in strong correlation with the upward decrease in nitrate concentration, the expected result of nitrate assimilation by phytoplankton. Culture studies indicate that algal assimilation of nitrate fractionates the nitrate N and O isotopes equally, while previous field studies suggest that nitrate N and O isotope behavior can be decoupled by euphotic zone nitrification. Our data for the PAZ show strong coupling of the dual isotopes of nitrate, and a numerical model of Antarctic summertime surface layer N cycling fits our observations (including isotopic compositions of both nitrate and suspended particulate N) if the nitrification rate is no more than 6% of the nitrate assimilation rate by phytoplankton. The model estimates that the N isotope effect of nitrate assimilation is 5.0 +/- 0.7%. This estimate lacks some of the uncertainties associated with previous studies within the Antarctic Circumpolar Current, and it is at the low end of most recent estimates from the Southern Ocean, the range of which we speculatively attribute to an effect of mixed layer depth on the amplitude of isotope discrimination.