The sediment core TN057-06-PC4 (hereafter TN057-6) was retrieved from the Agulhas Ridge (42º 54.8' S, 8º 54.0' E, 3751 m) during the pre-site survey of the Ocean Drilling Program (ODP) Leg 177 at nearly the same position as ODP Site 1090 (42° 54.5′ S, 8° 54.0′ E, at 3,702 m). The high-resolution XRF Fe concentration records from ODP Site 1090 and TN57-06 were used to align the two cores using the software Analyseries (46). The good correlation of the two records after the alignment allows us to directly compare the measurements performed in the two cores with minimal stratigraphic uncertainty (Fig. S1a). This indicates that the 230 Th measurements performed in can be used to reconstruct sedimentary fluxes of different elements and/or organic compounds in both records.For example, in Figure S1c, the high-resolution 230 Th-normalized mass flux (Fig.S1b) was used to calculate iron fluxes both in ODP Site 1090 and TN057-6 ( The age model of our record was generated by graphic correlation of the highresolution 230 Th-normalized Fe flux from ODP Site 1090 to the most recent ice core dust reconstruction from EPICA Dome C (44), using ice core chronology (AICC2012) (47,48) (Fig. S2). This new age model is generally in good agreement with the original ages proposed by Venz and Hodell 2002 (65) using benthic δ 18 O stratigraphy (Fig. S3). The good correlation of ODP Site 1090 Fe flux and EDC dust records down to sub-millennial timescales allows us to directly compare our marine data to other ice core measurements (e.g., atmsopheric pCO 2 ) with minimal stratigraphic uncertainty (Fig. S2). Foraminifera-bound δ 15 N analysisAround 600-800 specimens of G. bulloides and O. universa were picked manually under a dissecting microscope (250-425--6 mg of clean foraminiferal calcite. Foraminifera-bound δ 15 N was measured at Princeton University following the protocol described in (23,32). In the intervals where foraminifera abundances were adequate, samples were measured in duplicate. The reported error 2 bars in Fig. S9 represent the standard deviation estimated from the means of duplicated measurements. The average standard deviation of all the replicated measurements (from foraminifera-bound organic matter oxidation onward) was 0.19‰. Bulk sediment δ 15 N and %Nitrogen analysisThe N content and δ 15 N of the bulk sediment were analyzed using a Thermo FisherSeries 1112 elemental analyzer coupled with a Thermo Fisher Delta V Plus mass spectrometer at ETH Zurich. Between 50 and 100 mg of sediment were used for eachanalysis. An in-house peptone standard, which has been referenced to international reference materials (IAEA-N1 and IAEA-N2), was measured in each sample run and used for the final corrections. The standard deviation for the peptone standard among the different runs was <0.1‰. 230 Th and opal analysisConcentrations of U and Th isotopes were measured by inductively coupled-plasma mass spectrometry after strong acid sediment digestion and chromatographic separation as described by Fleisher and Anderson, 2003 (49). Opal...
In the ocean, the chemical forms of nitrogen that are readily available for biological use (known collectively as 'fixed' nitrogen) fuel the global phytoplankton productivity that exports carbon to the deep ocean. Accordingly, variation in the oceanic fixed nitrogen reservoir has been proposed as a cause of glacial-interglacial changes in atmospheric carbon dioxide concentration. Marine nitrogen fixation, which produces most of the ocean's fixed nitrogen, is thought to be affected by multiple factors, including ocean temperature and the availability of iron and phosphorus. Here we reconstruct changes in North Atlantic nitrogen fixation over the past 160,000 years from the shell-bound nitrogen isotope ratio ((15)N/(14)N) of planktonic foraminifera in Caribbean Sea sediments. The observed changes cannot be explained by reconstructed changes in temperature, the supply of (iron-bearing) dust or water column denitrification. We identify a strong, roughly 23,000-year cycle in nitrogen fixation and suggest that it is a response to orbitally driven changes in equatorial Atlantic upwelling, which imports 'excess' phosphorus (phosphorus in stoichiometric excess of fixed nitrogen) into the tropical North Atlantic surface. In addition, we find that nitrogen fixation was reduced during glacial stages 6 and 4, when North Atlantic Deep Water had shoaled to become glacial North Atlantic intermediate water, which isolated the Atlantic thermocline from excess phosphorus-rich mid-depth waters that today enter from the Southern Ocean. Although modern studies have yielded diverse views of the controls on nitrogen fixation, our palaeobiogeochemical data suggest that excess phosphorus is the master variable in the North Atlantic Ocean and indicate that the variations in its supply over the most recent glacial cycle were dominated by the response of regional ocean circulation to the orbital cycles.
The continental shelves are the most biologically dynamic regions of the ocean, and they are extensive worldwide, especially in the western North Pacific. Their area has varied dramatically over the glacial/interglacial cycles of the last million years, but the effects of this variation on ocean biological and chemical processes remain poorly understood. Conversion of nitrate to N by denitrification in sediments accounts for half or more of the removal of biologically available nitrogen ("fixed N") from the ocean. The emergence of continental shelves during ice ages and their flooding during interglacials have been hypothesized to drive changes in sedimentary denitrification. Denitrification leads to the occurrence of phosphorus-bearing, N-depleted surface waters, which encourages N fixation, the dominant N input to the ocean. An 860,000-y record of foraminifera shell-bound N isotopes from the South China Sea indicates that N fixation covaried with sea level. The N fixation changes are best explained as a response to changes in regional excess phosphorus supply due to sea level-driven variations in shallow sediment denitrification associated with the cyclic drowning and emergence of the continental shelves. This hypothesis is consistent with a glacial ocean that hosted globally lower rates of fixed N input and loss and a longer residence time for oceanic fixed N-a "sluggish" ocean N budget during ice ages. In addition, this work provides a clear sign of sea level-driven glacial/interglacial oscillations in biogeochemical fluxes at and near the ocean margins, with implications for coastal organisms and ecosystems.
Surface nitrate concentration is a potentially useful diagnostic in reconstructing the past circulation of high‐latitude North Atlantic waters. Moreover, nutrient consumption in the North Atlantic surface impacts the atmospheric concentration of carbon dioxide. To reconstruct nutrient conditions in the subpolar North Atlantic region during the last ice age, a record of foraminifera‐bound δ15N was measured in Neogloboquadrina pachyderma (sin.) from core V28‐73 south of Iceland (57.2°N, 20.9°W). Foraminifera‐bound δ15N is up to 2‰ lower during the last ice age than during the Holocene, suggesting as much as ~25% less complete nitrate consumption during the former. This is consistent with stronger light limitation associated with a deeper summer surface mixed layer, perhaps related to the formation of Glacial North Atlantic Intermediate Water previously suggested to have occurred near the core site. However, three single‐point maxima in δ15N in the glacial section and the sharp deglacial δ15N rise coincide with Heinrich event layers. This suggests that increased water column stratification during Heinrich events, presumably due to surface freshening, reduced the nutrient supply from below and led to nearly complete nitrate consumption in the summertime mixed layer. The Heinrich layers in V28‐73 are not accompanied by δ18O minima in either N. pachyderma (sin.) or Globigerinoides bulloides, which we tentatively attribute to extreme mixed‐layer shoaling. The reconstructed subpolar North Atlantic upper water column changes—both glacial/interglacial and millennial—are inverse to those inferred for the Antarctic.
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