RESUMO
The analysis of the nitrogen (N) isotopic composition of organic matter bound to fossil biomineral structures (BB-δ15 N) using the oxidation-denitrifier (O-D) method provides a novel tool to study past changes in N cycling processes. METHODS: We report a set of methodological improvements to the O-D method, including (a) a method for sealing the reaction vials in which the oxidation of organic N to NO3 - takes place, (b) a recipe for bypassing the pH adjustment step before the bacterial conversion of NO3 - to N2 O, and (c) a method for storing recrystallized dipotassium peroxodisulfate (K2 S2 O8 ) under Ar atmosphere. RESULTS: The new sealing method eliminates the occasional contamination and vial breakage that occurred previously while increasing sample throughput. The protocol for bypassing pH adjustment does not affect BB-δ15 N, and it significantly reduces the processing time. Storage of K2 S2 O8 reagent under Ar atmosphere produces stable oxidation blanks over more than 3.5 years. We report analytical blanks, accuracy, and precision for this methodology from eight users over the course of ~3.5 years of analyses at the Max Planck Institute for Chemistry. Our method produces analytical blanks characterized by low N content (0.30 ± 0.13 nmol N, 1σ, n = 195) and stable δ15 N (-2.20 ± 3.13, n = 195). The analysis of reference amino acid standards USGS 40 and USGS 65 indicates an overall accuracy of -0.23 ± 0.35 (1σ, n = 891). The analysis of in-house fossil standards gives similar analytical precision (1σ) across a range of BB-δ15 N values and biominerals: zooxanthellate coral standard PO-1 (6.08 ± 0.21, n = 267), azooxanthellate coral standard LO-1 (10.20 ± 0.28, n = 258), foraminifera standard MF-1 (5.92 ± 0.28, n = 243), and tooth enamel AG-Lox (4.06 ± 0.49, n = 78). CONCLUSIONS: The methodological improvements significantly increase sample throughput without compromising analytical precision or accuracy down to 1 nmol of N.
RESUMO
Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean's Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind-driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode-which arises from the meridional temperature gradient as affected by Earth's obliquity (axial tilt)-can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles.