Subsurface tropical Pacific nitrogen isotopic composition of nitrate: Biogeochemical signals and their transport

We report measurements of the nitrogen isotopic composition of nitrate (the δ15N of NO3−) across the equatorial Pacific, for zonal transects from 165°E to 95°W and meridional transects across 95° and 110°W. The δ15N of NO3− is similar in the equatorial thermocline (≈100 m) and intermediate depth waters (≈150 to 600 m), averaging (7.1 ± 0.3)‰ and (7.1 ± 0.1)‰, respectively. These values are more than 2‰ higher than subthermocline waters of the Southern and Atlantic Oceans and are ≈1‰ higher than putative source waters in the high latitude South Pacific (Subantarctic Mode Water, SAMW). The combined constraints of nitrate concentration and δ15N of NO3−in the equatorial Pacific require (1) lateral exchange between the high‐latitude source waters and the zones of denitrification in the eastern tropical Pacific and (2) the accumulation of remineralized nutrients at depth. The zonal uniformity of the subsurface equatorial Pacificδ15N of NO3− indicates rapid transport within the equatorial zone, which works to homogenize the δ15N of NO3− across the Pacific basin. Against this backdrop of high δ15N of NO3−in the tropical Pacific, we find a discrete off‐equatorial core of lowerδ15N of NO3− (5.5 ± 0.3)‰ concentrated at 5°S and 150 to 200 m along the 110° and 95°W transects and in apparent association with the Southern Subsurface Counter Current (SSCC). We propose that the remineralized products of nitrogen fixation, at the source of the SSCC in the western south Pacific, are the origin of the low δ15N of NO3− in these waters

Uptake of groundwater nitrogen by a near-shore coral reef community on Bermuda

Nutrient enrichment can slow growth, enhance bioerosion rates, and intensify algal competition for reef-building corals. In areas of high human population density and/or limited waste management, submarine groundwater discharge can transfer anthropogenic nutrients from polluted groundwater to coastal reefs. In this case study, we investigate the impact of submarine groundwater discharge on a near-shore reef in Bermuda, where over 60% of sewage generated by the island’s 64,000 residents enters the groundwater through untreated cesspits. Temperature, salinity, pH, and alkalinity were monitored at a groundwater discharge vent, three locations across the adjacent coral reef (0–30 m from shore), and a comparison patch reef site 2 km from shore. Groundwater discharge was characterized by low salinity, low aragonite saturation state (Ω_(ar)), high alkalinity, elevated nitrate + nitrite (NO₃₋ + NO₂₋; hereafter, “NO₃₋”) concentrations (> 400 µM), and an elevated ¹⁵N/¹⁴N ratio of NO₃₋ (δ¹⁵N = 10.9 ± 0.02‰ vs. air, mean ± SD). Rainfall and tidal cycles strongly impacted groundwater discharge, with maximum discharge during low tide. NO₃₋ concentrations on the near-shore reef averaged 4 µM, ten times higher than that found at the control site 2 km away, and elevated NO₃₋ δ¹⁵N at the near-shore reef indicated sewage-contaminated groundwater as a significant nitrogen source. Tissue δ¹⁵N of Porites astreoides, a dominant reef-building coral, was elevated by ~ 3‰ on the near-shore reef compared to the control site, indicating that corals across the near-shore reef were assimilating groundwater-derived nitrogen. In addition, coral skeletal density and calcification rates across the near-shore reef were inversely correlated with NO₃₋ concentration and δ¹⁵N, indicating a negative coral health response to groundwater-borne nutrient inputs. P. astreoides bioerosion rates, in contrast, did not show an effect from the groundwater input

Nitrogen isotope evidence for expanded ocean suboxia in the early Cenozoic

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the ^(15)N/^(14)N ratio (δ^(15)N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ^(15)N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ^(15)N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. Δ^(15)N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed

Origin of the deep Bering Sea nitrate deficit : constraints from the nitrogen and oxygen isotopic composition of water column nitrate and benthic nitrate fluxes

Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 19 (2005): GB4005, doi:10.1029/2005GB002508.On the basis of the normalization to phosphate, a significant amount of nitrate is missing from the deep Bering Sea (BS). Benthic denitrification has been suggested previously to be the dominant cause for the BS nitrate deficit. We measured water column nitrate 15N/14N and 18O/16O as integrative tracers of microbial denitrification, together with pore water-derived benthic nitrate fluxes in the deep BS basin, in order to gain new constraints on the mechanism of fixed nitrogen loss in the BS. The lack of any nitrate isotope enrichment into the deep part of the BS supports the benthic denitrification hypothesis. On the basis of the nitrate deficit in the water column with respect to the adjacent North Pacific and a radiocarbon-derived ventilation age of ∼50 years, we calculate an average deep BS (>2000 m water depth) sedimentary denitrification rate of ∼230 μmol N m−2 d−1 (or 1.27 Tg N yr−1), more than 3 times higher than high-end estimates of the average global sedimentary denitrification rate for the same depth interval. Pore water-derived estimates of benthic denitrification were variable, and uncertainties in estimates were large. A very high denitrification rate measured from the base of the steep northern slope of the basin suggests that the elevated average sedimentary denitrification rate of the deep Bering calculated from the nitrate deficit is driven by organic matter supply to the base of the continental slope, owing to a combination of high primary productivity in the surface waters along the shelf break and efficient down-slope sediment focusing along the steep continental slopes that characterize the BS.This study was supported by NSF grants OCE-0136449 and OCE-9981479 to D. M. S., OCE-0118126 and OCE-0324987 to D. C. M., and DFG grant LE 1326/1-1 to M. F. L. The BS cruise was funded by grant OPP-9912122

Evidence from diatom-bound nitrogen isotopes for subarctic Pacific stratification during the last ice age and a link to North Pacific denitrification changes

Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 22 (2007): PA1215, doi:10.1029/2005PA001205.In a piston core from the central Bering Sea, diatom microfossil-bound N isotopes and the concentrations of opal, biogenic barium, calcium carbonate, and organic N are measured over the last glacial/interglacial cycle. Compared to the interglacial sections of the core, the sediments of the last ice age are characterized by 3‰ higher diatom-bound δ 15N, 70 wt % lower opal content and 1200 ppm lower biogenic barium. Taken together and with constraints on sediment accumulation rate, these results suggest a reduced supply of nitrate to the surface due to stronger stratification of the upper water column of the Bering Sea during glacial times, with more complete nitrate consumption resulting from continued iron supply through atmospheric deposition. This finding extends the body of evidence for a pervasive link between cold climates and polar ocean stratification. In addition, we hypothesize that more complete nutrient consumption in the glacial age subarctic Pacific contributed to the previously observed ice age reduction in suboxia and denitrification in the eastern tropical North Pacific by lowering the nutrient content of the intermediate-depth water formed in the subpolar North Pacific. In the deglacial interval of the Bering Sea record, two apparent peaks in export productivity are associated with maxima in diatom-bound and bulk sediment δ 15N. The high δ 15N in these intervals may have resulted from greater surface nutrient consumption during this period. However, the synchroneity of the deglacial peaks in the Bering Sea with similar bulk sediment δ 15N changes in the eastern Pacific margin and the presence of sediment lamination within the Bering Sea during the deposition of the productivity peaks raise the possibility that both regional and local denitrification worked to raise the δ 15N of the nitrate feeding Bering Sea surface waters at these times.Financial support for this work was provided by NSF grants OCE-0136449, OCE-9981479, ANT-0453680, by BP and Ford Motor Company through the Princeton Carbon Migration Initiative, and by a NDSEG fellowship to B.G.B. Work conducted aboard the USCG Healy (Healy 0202) was funded by grant OPP-9912122

Nitrogen isotopic analysis of carbonate-bound organic matter in modern and fossil fish otoliths

The nitrogen isotopic composition (δ^(15)N) of otolith-bound organic matter (OM) is a potential source of information on dietary history of bony fishes. In contrast to the δ^(15)N of white muscle tissue, the most commonly used tissue for ecological studies, the δ^(15)N of otolith-bound OM (δ^(15)N_(oto)) provides a record of whole life history. More importantly, δ^(15)N_(oto) can be measured in contexts where tissue is not available, for example, in otolith archives and sedimentary deposits. The utility and robustness of otolith δ^(15)N analysis was heretofore limited by the low N content of otoliths, which precluded the routine measurement of individual otoliths as well as the thorough cleaning of otolith material prior to analysis. Here, we introduce a new method based on oxidation to nitrate followed by bacterial conversion to N_2O. The method requires 200-fold less N compared to traditional combustion approaches, allowing for thorough pre-cleaning and replicated analysis of individual otoliths of nearly any size. Long term precision of δ^(15)N_(oto) is 0.3‰. Using an internal standard of Atlantic cod (Gadus morhua) otoliths, we examine the parameters of the oxidative cleaning step with regard to oxidant (potassium persulfate and sodium hypochlorite), temperature, and time. We also report initial results that verify the usefulness of δ^(15)N_(oto) for ecological studies. For three salmonid species, left and right otoliths from the same fish are indistinguishable. We find that the δ^(15)N_(oto) of pink salmon (Oncorhynchus gorbuscha) is related to the size of the fish for this species. We find that intra-cohort δ^(15)N_(oto) standard deviation for wild pink salmon, farmed brown trout (Salmo trutta), and farmed rainbow trout (Oncorhynchus mykiss) are all 0.4‰ or less, suggesting that δ^(15)N_(oto) will be valuable for population-level studies. Lastly, our protocol yields reproducible data for both δ^(15)N_(oto) and otolith N content in 17th century Atlantic cod otoliths. We find that 17th century cod are approximately 2 ‰ higher than modern cod, arguably consistent with either the larger size of the otoliths (and thus inferred for the fish) or with changes in baseline (primary producer) δ^(15)N in the modern coastal ocean compared to the past. All told, the results of this study bode well for the utility of otolith-bound δ15N for investigating the environment and ecology of modern and past fish

The Angola Gyre is a hotspot of dinitrogen fixation in the South Atlantic Ocean

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Marshall, T., Granger, J., Casciotti, K. L., Dahnke, K., Emeis, K.-C., Marconi, D., McIlvin, M. R., Noble, A. E., Saito, M. A., Sigman, D. M., & Fawcett, S. E. The Angola Gyre is a hotspot of dinitrogen fixation in the South Atlantic Ocean. Communications Earth & Environment, 3(1), (2022): 151, https://doi.org/10.1038/s43247-022-00474-x.Biological dinitrogen fixation is the major source of new nitrogen to marine systems and thus essential to the ocean’s biological pump. Constraining the distribution and global rate of dinitrogen fixation has proven challenging owing largely to uncertainty surrounding the controls thereon. Existing South Atlantic dinitrogen fixation rate estimates vary five-fold, with models attributing most dinitrogen fixation to the western basin. From hydrographic properties and nitrate isotope ratios, we show that the Angola Gyre in the eastern tropical South Atlantic supports the fixation of 1.4–5.4 Tg N.a−1, 28-108% of the existing (highly uncertain) estimates for the basin. Our observations contradict model diagnoses, revealing a substantial input of newly-fixed nitrogen to the tropical eastern basin and no dinitrogen fixation west of 7.5˚W. We propose that dinitrogen fixation in the South Atlantic occurs in hotspots controlled by the overlapping biogeography of excess phosphorus relative to nitrogen and bioavailable iron from margin sediments. Similar conditions may promote dinitrogen fixation in analogous ocean regions. Our analysis suggests that local iron availability causes the phosphorus-driven coupling of oceanic dinitrogen fixation to nitrogen loss to vary on a regional basis.This work was supported by the South African National Research Foundation (114673 and 130826 to T.M., 115335, 116142 and 129320 to S.E.F.); the US National Science Foundation (CAREER award, OCE-1554474 to J.G., OCE-1736652 to D.M.S. and K.L.C., OCE-05-26277 to K.L.C.); the German Federal Agency for Education and Research (DAAD-SPACES 57371082 to T.M.); the Royal Society (FLAIR fellowship to S.E.F.); and the University of Cape Town (T.M., J.G., S.E.F.). The authors also recognize the support of the South African Department of Science and Innovation’s Biogeochemistry Research Infrastructure Platform (BIOGRIP)