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
220 Publications
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…
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…
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…
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…
Ongoing human activities are known to affect nitrogen cycling on coral reefs, but the full history of anthropogenic impact is unclear due to a lack of continuous records. We have used the nitrogen isotopic composition of skeleton-bound organic matter (CS-δ15N) in a coastal Porites coral from Magnetic Island in the Great Barrier Reef as a proxy for…
Equatorial Pacific nitrate 15N/14N and 18O/16O (δ15N and δ18O) measurements from repeat station occupations are used to: (1) identify the source of surface waters, (2) estimate the nitrate assimilation isotope effect, (3) characterize the temporal relationship between the supply and consumption of nitrate in surface waters, and (4) quantify the…
Roughly 240 million years ago (Ma), scleractinian corals rapidly expanded and diversified across shallow marine environments. The main driver behind this evolution is uncertain, but the ecological success of modern reefbuilding corals is attributed to their nutritional symbiosis with photosynthesizing dinoflagellate algae. We show that a suite of…
In the Southern Ocean, the nitrogen (N) isotopes of organic matter and the N and oxygen (O) isotopes of nitrate (NO3 −) have been used to investigate NO3 − assimilation and N cycling in the summertime period of phytoplankton growth, both today and in the past. However, recent studies indicate the significance of processes in other seasons for…
Rationale The denitrifier method allows for highly sensitive measurement of the 15N/14N (δ15N value) and 18O/16O (δ18O value) of nitrate dissolved in natural waters and for highly sensitive δ15N measurement of other N forms (e.g., organic N) that can be converted into nitrate. Here, updates to instrumentation and protocols are described, and…
We present real-time optical polarization subtraction for calibration of Faraday rotation spectra. Noise analysis yields minor isotope sensitivity of 3.0 ppbv·Hz-1/2 and 1.7×10-8 rad·Hz-1/2 noise-equivalent angle. Sub-permil ratiometric precision is achieved at integration times >100 s. © 2016 OSA.
The isotopic composition of skeleton-bound organic nitrogen in shallow-water scleractinian corals (hereafter, CS-δ15N) is an emerging tool for studying the marine nitrogen cycle in the past. The CS-δ15N has been shown to reflect the δ15N of nitrogen (N) sources to corals, with most applications to date focusing on the anthropogenic/terrestrial N…
The equatorial Pacific Ocean is one of the major high-nutrient, low-chlorophyll regions in the global ocean. In such regions, the consumption of the available macro-nutrients such as nitrate and phosphate is thought to be limited in part by the low abundance of the critical micro-nutrient iron1. Greater atmospheric dust deposition2 could have…
We report wintertime nitrogen and oxygen isotope ratios (δ15N and δ18O) of seawater nitrate in the Southern Ocean south of Africa. Depth profile and underway surface samples collected in July 2012 extend from the subtropics to just beyond the Antarctic winter sea ice edge. We focus here on the Antarctic region (south of 50.3°S), where application…
We report concentration and nitrogen and oxygen isotopic measurements of nitrate, total dissolved nitrogen, and particulate nitrogen from Antarctic landfast sea ice, covering almost the complete seasonal cycle of sea ice growth and decay (from April to November). When sea ice forms in autumn, ice algae growth depletes nitrate and accumulates…
We tested the hypothesis that the nitrogen (N) isotopic signature (δ15N) of coral skeletal organic material (CS-δ15N) matches that of the coral tissue and also reflects the δ15N of water column fixed N, such that CS-δ15N can be used as a proxy for spatio-temporal oceanic N isotope distributions. Strong correlations between the δ15N of skeletal…
The stable nitrogen (N) and oxygen (O) isotope ratios (15N/14N and 18O/16O, respectively) of nitrate (NO3-) were measured during incubations of freshly collected seawater to investigate the effect of light intensity on the isotope fractionation associated with nitrate assimilation and possible co-occurring regeneration and nitrification by in situ…
The skeleton-bound organic nitrogen in reef-building symbiotic corals may be a high-resolution archive of ocean nitrogen cycle dynamics and a tool for understanding coral biogeochemistry and physiological processes. However, the existing methods for measuring the isotopic composition of coral skeleton-bound organic nitrogen (hereafter, CS-δ15N)…
We have developed a transportable spectroscopic nitrogen isotopic analyzer. The spectrometer is based on dual-modulation Faraday rotation spectroscopy of nitric oxide isotopologues with near shot-noise limited performance and baseline-free operation. Noise analysis indicates minor isotope (15NO) detection sensitivity of 0.36 ppbv·Hz−1/2,…
Reduced nitrate supply to the subarctic North Pacific (SNP) surface during the last ice age has been inferred from coupled changes in diatom-bound δ15N (DB-δ15N), bulk sedimentary δ15N, and biogenic fluxes. However, the reliability of bulk sedimentary and DB-δ15N has been questioned, and a previously reported δ15N minimum during Heinrich Stadial 1…
The fraction of phytoplankton growth that leads to the rain of organic carbon out of the sunlit surface ocean ("export production") is central to the ocean s sequestration of atmospheric carbon dioxide. Nitrate assimilation has long been taken as a measure of export production; however, this has recently been questioned by suggestions that much of…
In a sediment core from the Pacific sector of the Antarctic Zone (AZ) of the Southern Ocean, we report diatom-bound N isotope (δ15Ndb) records for total recoverable diatoms and two distinct diatom assemblages (pennate and centric rich). These data indicate tight coupling between the degree of nitrate consumption and Antarctic climate across the…
Reconstructed changes in seawater calcium and magnesium concentration ([Ca2+], [Mg2+]) predictably affect the ocean s acid/base and carbon chemistry. Yet inaccurate formulations of chemical equilibrium "constants" are currently in use to account for these changes. Here we develop an efficient implementation of the MIAMI Ionic Interaction Model to…
We report nitrogen (N) isotopic measurements of nitrate, total dissolved nitrogen, and particulate nitrogen from Antarctic pack ice in early and late spring. Salinity-normalized concentrations of total fixed N are approximately twofold higher than in seawater, indicating that sea ice exchanges fixed N with seawater after its formation. The…
The Sargasso Sea is characterized by strong summertime stratification that is thought to drive oligotrophy, but export production is surprisingly similar to that of high-latitude regions with ample major nutrient supply. Here we use the summer-to-fall progression in the northwestern Sargasso Sea to investigate the relationship between upper ocean…
During the last interglacial period, global temperatures were ∼2°C warmer than at present and sea level was 6 to 8 meters higher. Southern Ocean sediments reveal a spike in authigenic uranium 127,000 years ago, within the last interglacial, reflecting decreased oxygenation of deep water by Antarctic Bottom Water (AABW). Unlike ice age reductions…
The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEIs) as well as…
A dual-modulation Faraday rotation spectrometer is employed for isotopic ratiometry of nitric oxide (NO) converted from nitrate/nitrite. Excellent linearity of measured NO to dissolved nitrate is demonstrated. Ratiometry of IAEA-NO-3 standards indicates 3 % accuracy. © 2014 OSA.
We conducted a survey of the natural abundance 15N/14N ratio (δ15N) of particulate organic matter (POM), diatom frustule-bound nitrogen (δ15NDB), and zooplankton from water column material collected with net tows across the eastern Bering Sea shelf in late winter of 2007 and 2008, to investigate the N dynamics of primary and secondary production…
A dual-modulation Faraday rotation spectrometer is employed for isotopic ratiometry of nitric oxide (NO) converted from nitrate/nitrite. Excellent linearity of measured NO to dissolved nitrate is demonstrated. Ratiometry of IAEA-NO-3 standards indicates ∼3 % accuracy. © 2014 Optical Society of America.
We report and interpret the nitrate δ15N and δ18O distributions in the cross-basin transect of the US GEOTRACES North Atlantic expedition. Lownitrate δ15N observed in the shallowthermocline of the centralwestern portion of the basin (reaching as lowas 2.5%vs. air; 2.3%lower than deep Atlantic nitrate) reflects the remineralization of nitrogen…
Emissions of anthropogenic nitrogen (N) to the atmosphere have increased tenfold since preindustrial times, resulting in increased N deposition to terrestrial and coastal ecosystems. The sources of N deposition to the ocean, however, are poorly understood. Two years of event-based rainwater samples were collected on the island of Bermuda in the…
Over the last two decades, the skeletal remains of deep-sea corals have arisen as a geochemical archive of Pleistocene oceanographic change. Here we report the exploration of the isotopic composition of the carbonate-bound organic nitrogen (hereafter, CB-δ15N) in the deep-sea scleractinian coral Desmophyllum dianthus as a possible tool for…
In the context of the atmospheric CO2 14C/C (δCatm14) changes since the last ice age, two episodes of sharp δCatm14 decline have been related to either the venting of deeply sequestered low-14C CO2 through the Southern Ocean surface or the abrupt onset of North Atlantic Deep Water (NADW) formation. In model simulations using an improved…
In order to strengthen environmental application of nitrate N and O isotopes, we measured the N and O isotopic fractionation associated with cellular nitrate uptake and efflux in the nitrate-assimilating marine diatom Thalassiosira weissflogii. We isolated nitrate uptake and efflux from nitrate reduction by growing the cells in the presence of…
Biological nitrogen fixation constitutes the main input of fixed nitrogen to Earth s ecosystems, and its isotope effect is a key parameter in isotope-based interpretations of the N cycle. The nitrogen isotopic composition (δ15N) of newly fixed N is currently believed to be∼-10/00, based on measurements of organic matter from diazotrophs using…
Taxon-specific nitrogen (N) isotope data from the summertime Sargasso Sea have previously suggested reliance of prokaryotic phytoplankton on regenerated N but a greater importance of nitrate assimilation for eukaryotic phytoplankton. To investigate this further, particles collected in the summer from 100 m at the Bermuda Atlantic Time-series…
John H. Martin, who discovered widespread iron limitation of ocean productivity, proposed that dust-borne iron fertilization of Southern Ocean phytoplankton caused the ice age reduction in atmospheric carbon dioxide (CO2). In a sediment core from the Subantarctic Atlantic, we measured foraminifera-bound nitrogen isotopes to reconstruct ice age…
The difference between nitrate δ15N and δ18O, or Δ(15-18), is sensitive to organic matter remineralization and tracks the modification of nitrate as it passes from the deep Pacific Ocean, through the Southern Ocean surface, and into the intermediate-depth Pacific. Circumpolar Deep Water (CDW) is upwelled with a nitrate Δ(15-18) of +3.0‰ and…
The ocean s biological pump refers to the coupled biological, chemical, and physical processes that work to concentrate carbon and other biologically active elements in the voluminous ocean interior, sequestering them from the surface ocean and the atmosphere. Current research seeks to understand the relationship of the ocean s biological pump…