We have developed new methods for natural abundance isotope ratio measurement of several biologically available and typically dissolved forms of N that are common in the environment: the 15N/14N, 18O/16O, and 18O/17O/16O of nitrate, the 15N/14N of total dissolved N (i.e. dissolved organic N in waters lacking nitrate and ammonium), and the 15N/14N of ammonium. For paleoceanographic work, we developed new techniques for the 15N/14N of the microfossil-bound N of diatoms (made of opal), planktonic foraminifera (calcite), and scleractinian corals (aragonite). All of these approaches have as their cornerstone the “denitrifier” method for nitrate isotopic analysis, in which nitrate (NO3-) is converted to nitrous oxide (N2O) gas by a strain of denitrifying bacteria that lacks an active N2O reductase, followed by analysis of the product N2O with a stable isotope ratio mass spectrometer.
Coupling of the denitrifier method, which yields the 15N/14N and 18O/16O of nitrate (NO3-)(1,2), with other steps to yield the 15N/14N of dissolved organic N (DON, 3), microfossil-bound organic N (4), and dissolved ammonium (NH4+, 5). “MS” indicate mass spectrometric analysis.
References
206 Publications
The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10 increase in…
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…
Dissolved oxygen (O2) is essential for most ocean ecosystems, fuelling organisms’ respiration and facilitating the cycling of carbon and nutrients. Oxygen measurements have been interpreted to indicate that the ocean’s oxygen-deficient zones (ODZs) are expanding under global warming1,2. However, models provide an unclear picture of future ODZ…
Fossil-bound organic material holds great potential for the reconstruction of past changes in nitrogen (N) cycling. Here, with a series of laboratory experiments, we assess the potential effect of oxidative degradation, fossil dissolution, and thermal alteration on the fossil-bound N isotopic composition of different fossil types, including…
The nitrogen isotopes (δ15N) in the organic fraction of accretionary hard part structures, such as fish otoliths, may provide life histories of dietary change. We performed controlled experiments to validate the dynamics of the isotopic signal incorporation into biominerals following dietary shifts and also compared whole-otolith and serial…
Background: Cancerous cells can recycle metabolic ammonium for their growth. As this ammonium has a low nitrogen isotope ratio (15N/14N), its recycling may cause cancer tissue to have lower 15N/14N than surrounding healthy tissue. We investigated whether, within a given tissue type in individual mice, tumoral and healthy tissues could be…
Ocean circulation supplies the surface ocean with the nutrients that fuel global ocean productivity. However, the mechanisms and rates of water and nutrient transport from the deep ocean to the upper ocean are poorly known. Here, we use the nitrogen isotopic composition of nitrate to place observational constraints on nutrient transport from the…
Salinity-driven density stratification of the upper Arctic Ocean isolates sea-ice cover and cold, nutrient-poor surface waters from underlying warmer, nutrient-rich waters. Recently, stratification has strengthened in the western Arctic but has weakened in the eastern Arctic; it is unknown if these trends will continue. Here we present…
For times prior to those represented by the air trapped in Antarctic ice core records, the concentration of CO2 in the atmosphere must be reconstructed using geochemical proxies. The δ13C of particulate organic carbon (POC) produced in ocean surface waters has previously been observed to covary with the concentration of CO2 in the water…
Bulk sediment δ15N records from the eastern tropical Pacific (ETP) extending back to the last ice age most often show low glacial δ15N, then a deglacial δ15N maximum, followed by a gradual decline to a late Holocene δ15N that is typically higher than that of the Last Glacial Maximum (LGM). The lower δ15N of the LGM has been interpreted to reflect…
Nitrogen isotope ratios (δ15N) are a well-established tool for investigating the dietary and trophic behavior of animals in terrestrial and marine food webs. To date, δ15N values in fossils have primarily been measured in collagen extracted from bone or dentin, which is susceptible to degradation and rarely preserved in deep time (>100,000…
The Southern Ocean is widely recognized as a potential cause of the lower atmospheric concentration of CO2 during ice ages, but the mechanism is debated. Focusing on the Southern Ocean surface, we review biogeochemical paleoproxy data and carbon cycle concepts that together favor the view that both the Antarctic and Subantarctic Zones (AZ and SAZ)…
The15N/14N ratio of the fish-native organic matter preserved in fish otoliths (or δ15Noto) may allow for reconstruction of fish trophic history and changes in food webs. To support this application, ground-truthing data are needed on the relationships among the δ15N of diet, of fish tissue (e.g., white muscle tissue, δ15Nwmt), and δ15Noto. Using a…
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…
Dissolved organic nitrogen (DON) is the dominant form of fixed nitrogen in most low and middle latitude ocean surface waters. Here, we report measurements of DON isotopic composition (δ15N) from the west South China Sea (SCS), with the goal of providing new insight into DON cycling. The concentration of DON in the surface ocean is correlated (r =…
(Figure Presented) Figure 4. Cycle of biologically driven N transformations that occur in natural and human-influenced terrestrial and marine environments. Nitrogen (N2) fixation (step 1) and N assimilation (from ammonium, nitrate, or organic N, step 2) are anabolic processes, whereas mineralization (step 3), nitrification (steps 4−6), DNRA (steps 7,…
Nitrogen (N) is used in many of life s fundamental biomolecules, and it is also a participant in environmental redox chemistry. Biogeochemical processes control the amount and form of N available to organisms ("fixed"N). These interacting processes result in N acting as the proximate limiting nutrient in most surface environments. Here, we review…
Historical coral skeleton (CS) δ18O and δ15N records were produced from samples recovered from sedimentary deposits, held in natural history museum collections, and cored into modern coral heads. These records were used to assess the influence of global warming and regional eutrophication, respectively, on the decline of coastal coral communities…
We present the first nitrogen isotope (δ15N) measurements of planktic foraminifera, paleoceanographically important zooplankton, from the nutrient-rich waters of the modern Southern Ocean. Foraminifera were collected from net tows in the Subantarctic and Polar Frontal Zones (SAZ and PFZ, respectively) south of Africa during winter 2015 and late…
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…
The shoaling of the Central American Seaway (CAS) around 4.6 Ma (million years ago) is thought to have enhanced the Gulf Stream, strengthening the Atlantic Meridional Overturning Circulation and potentially influencing the evolution of Pliocene climate. Paleoclimate records indicate a buildup of heat and salt in the Caribbean and changes in the…
Biogeochemical processes within the Atlantic basin alter the nitrogen (N) and oxygen (O) isotopic compositions (δ 15 N and δ 18 O) of nitrate before this nutrient is carried from the upper water column into the deep ocean by the formation of North Atlantic Deep Water (NADW). Here, nitrate δ 15 N and δ 18 O measurements along the 2013 CLIVAR/GO…
Both the nitrogen (N) isotopic composition (δ 15 N) of the nitrate source and the magnitude of isotope discrimination associated with nitrate assimilation are required to estimate the degree of past nitrate consumption from the δ 15 N of organic matter in Southern Ocean sediments (e.g., preserved within diatom microfossils). It has been suggested…
The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the 15N/14N ratio (d15N) 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, d15N declined by 13 to 16 per mil in the…
From 1.25 million to 700,000 years ago, the ice age cycle deepened and lengthened from 41,000- to 100,000-year periodicity, a transition that remains unexplained. Using surface- and bottom-dwelling foraminifera from the Antarctic Zone of the Southern Ocean to reconstruct the deep-to-surface supply of water during the ice ages of the past 1.5…
Most biological nitrogen transformations have characteristic kinetic isotope effects used to track these processes in modern and past environments. The isotopic fractionation associated with nitrogen fixation, the only biological source of fixed nitrogen (N), provides a particularly important constraint for studies of nitrogen cycling. Nitrogen…
This article outlines the isotope systematics of processes in the ocean nitrogen (N) cycle and their impact on the isotopic compositions of the major N forms, with an eye toward how the N isotopes may record current N fluxes and past changes. The dominant dynamic is of kinetic isotope discrimination, in which the light isotope of N (14N) is…
The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the…
The nitrogen isotopic composition (δ15N) of otolith-bound organic matter (OM) is a potential source of information on dietary history of bony fishes. In contrast to the δ15N of white muscle tissue, the most commonly used tissue for ecological studies, the δ15N of otolith-bound OM (δ15Noto) provides a record of whole life history. More importantly,…
In the Antarctic Zone of the Southern Ocean, the coupled observations of elevated diatom-bound 15 N/ 14 N (δ 15 N db ) and reduced export production during the ice ages indicates more complete nitrate (NO 3 − ) consumption. This evidence points to an ice age decline in gross NO 3 − supply from the deep ocean to the surface wind-mixed layer, which…
Planktonic foraminifer tests are major archives of environmental change and provide a multitude of proxies in paleoceanography and paleoclimatology. The application of such proxies is contingent upon a collaborative effort to better understand how the living organisms record the properties of their environment and how the resulting signals are…
Despite slow nutrient supply to the subtropical surface ocean, its rates of annual inorganic carbon drawdown and net oxygen production are similar to those of nutrient-rich high latitude waters. This surprisingly rapid carbon drawdown, if due to the production and export of marine biomass, cannot be explained in terms of known nutrient supply…
Human alteration of the global nitrogen cycle intensified over the 1900s. Model simulations suggest that large swaths of the open ocean, including the North Atlantic and the western Pacific, have already been affected by anthropogenic nitrogen through atmospheric transport and deposition. Here we report an ∼130-yearlong record of the 15N/14N of…
A rise in the atmospheric CO2 concentration of 20 parts per million over the course of the Holocene has long been recognized as exceptional among interglacials and is in need of explanation. Previous hypotheses involved natural or anthropogenic changes in terrestrial biomass, carbonate compensation in response to deglacial outgassing of oceanic…
We report the nitrogen (N) isotope ratios (δ15N) of planktic foraminifera collected from upper-ocean net tows (surface to 200 m), moored sediment traps, and core-top sediments at the Bermuda Time-series Site in the northern Sargasso Sea between 2009 and 2013. Consistent with previous measurements from low-latitude core-top sediments, the annually…
Nitrogen is a limiting nutrient for primary production in the western Arctic Ocean. Measurements of the nitrogen (15N/14N) and oxygen (18O/16O) isotope ratios of nitrate in the southeastern Beaufort Sea provide insight into biogeochemical cycling of nitrogen in the western Arctic Ocean. Nitrate O isotope ratios in the Pacific halocline evidence a…
Nitrification, the oxidation of ammonium to nitrite and then nitrate, is often discounted as a source of nitrate in euphotic zone waters due to photoinhibition of nitrifying microorganisms and/or competition for ammonium with phytoplankton. However, there have also been counterarguments that nitrification represents a significant “regenerated”…
The original version of this Article contained errors in Fig. 2b and Table 2. In Fig. 2b, the white circle labels were incorrectly positioned as they referred to scenarios that were used in an earlier version of the Article. In Table 2, the following three sentences were removed from the legend The last two calculations are discussed in the …
Nitrate persists in eastern equatorial Pacific surface waters because phytoplankton growth fueled by nitrate (new production) is limited by iron. Nitrate isotope measurements provide a new constraint on the controls of surface nitrate concentration in this region and allow us to quantify the degree and temporal variability of nitrate consumption…
To investigate the controls on N2 fixation and the role of the Atlantic in the global ocean s fixed nitrogen (N) budget, Atlantic N2 fixation is calculated by combining meridional nitrate fluxes across World Ocean Circulation Experiment sections with observed nitrate 15N/14N differences between northward and southward transported nitrate. N2…
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…
With the rapid rise in pollution-associated nitrogen inputs to the western Pacific, it has been suggested that even the open ocean has been affected. In a coral core from Dongsha Atoll, a remote coral reef ecosystem, we observe a decline in the 15N/14N of coral skeleton-bound organic matter, which signals increased deposition of anthropogenic…
The Southern Ocean regulates the ocean s biological sequestration of CO2 and is widely suspected to underpin much of the ice age decline in atmospheric CO2 concentration, but the specific changes in the region are debated. Although more complete drawdown of surface nutrients by phytoplankton during the ice ages is supported by some sediment core…
The North Atlantic Ocean is considered a nitrogen (N) limited system once vernal stabilisation of the water column alleviates light limitation and allows phytoplankton growth to deplete surface nutrients to virtually undetectable levels. Ammonium and other regenerated N forms are then the main surface N source for phytoplankton production. The…
The nitrogen (N) isotopes provide an integrative geochemical tool for constraining the fixed N budget of the ocean. However, N isotope budgeting requires a robust estimate for the organism-scale nitrogen isotope effect of denitrification, in particular as it occurs in water column denitrification zones (εwcd). Ocean field data interpreted with the…
An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world’s largest ocean, where relatively fresh surface waters inhibit North Pacific…
We investigated the potential of coral skeleton δ15N (CS-δ15N) records for tracking anthropogenic-N sources in coral reef ecosystems. We produced a 56 yr-long CS-δ15N record (1958–2014) from a reef flat in Guam that has been exposed to varying 1) levels of sewage treatment 2) population density, and 3) land use. Increasing population density (from…
Global models estimate that the anthropogenic component of atmospheric nitrogen (N) deposition to the ocean accounts for up to a third of the ocean s external N supply and 10% of anthropogenic CO2 uptake. However, there are few observational constraints from the marine atmospheric environment to validate these findings. Due to the paucity of…