Analytical improvements and assessment of long-term performance of the oxidation-denitrifier method.

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.

Evidence for a Northern Hemispheric trigger of the 100,000-y glacial cyclicity.

The causes of the Mid-Pleistocene Transition, the shift from ∼41-ky to 100-ky interglacial-glacial cycles and more intense ice ages, remain intensely debated, as this fundamental change occurred between ∼1,250 and 650 ka without substantial changes in astronomical climate forcings. Recent studies disagree about the relative importance of events and processes in the Northern and Southern Hemispheres, as well as whether the shift occurred gradually over several interglacial-glacial cycles or abruptly at ∼900 ka. We address these issues using a north-to-south reconstruction of the Atlantic arm of the global meridional overturning ocean circulation, a primary means for distributing heat around the globe, using neodymium (Nd) isotopes. Results reveal a period of intense erosion affecting the cratonic shields surrounding the North Atlantic between Marine Isotope Stages (MIS) 27 and 25 (∼980 and 950 ka), reflected by unusually low Nd isotope ratios in deep North Atlantic seawater. This episode preceded a major ocean circulation weakening between MIS 25 and 21 (950 and 860 ka) that coincided with the first ∼100-ky-long interglacial-glacial onset of Northern Hemisphere glaciation at around 2.4 to 2.8 Ma. The data point to a Northern Hemisphere-sourced initiation for the transition, possibly induced through regolith loss and increased exposure of the crystalline bedrock, which would lead to increased friction, enabling larger ice sheets that are characteristic of the 100-ky interglacial-glacial cycles.