Description: Subsurface nutrients on the Scotian Shelf, an ocean region at the convergence of the subpolar and subtropical western boundary currents (i.e., Labrador Current and Gulf Stream), are chiefly modulated by upstream shelf and slope waters. Yet little is known about long-term fluctuations in the advective transport of nutrients to the shelf. To examine the relationships between subsurface nutrient concentrations and dominant slope water masses at the Scotian Shelf break, we assembled all available hydrographic data (temperature, salinity) and dissolved nutrient data (nitrate, phosphate, silicate) for the period 1975-2020. Hydrographic and nutrient data were extracted from the Fisheries and Oceans Canada (DFO) data archives MEDS (Marine Environmental Data Section Archive; DFO, 2023a) and BioChem (DFO, 2023b; Devine et al., 2014), respectively, and predominantly include data from current DFO programs (e.g., Atlantic Zone Monitoring Program (AZMP)) and legacy datasets. Hydrographic data consist of vertical water column profiles collected using a conductivity-temperature-depth (CTD) profiler, generally mounted to a rosette sampler equipped with Niskin bottles for discrete water and nutrient sampling (Mitchel et al., 2002). Nutrient (nitrate, phosphate, silicate) measurements generally followed well established colorimetric techniques outlined in detail in the AZMP sampling protocol (Mitchell et al., 2002). Only nutrient data that passed initial quality control (i.e., BioChem quality flags of 1 and 0) are included in the datasets provided here (see Devine et al., 2014 for details on quality control (QC) procedures). In addition to hydrographic and nutrient parameters, datasets further include information on designated regions (e.g., WSS: Western Scotian Shelf, CSS: Central Scotian Shelf, ESS: Eastern Scotian Shelf) as defined in Lehmann et al (2023).

Description: Subsurface nutrients on the Scotian Shelf, an ocean region at the convergence of the subpolar and subtropical western boundary currents (i.e., Labrador Current and Gulf Stream), are chiefly modulated by upstream shelf and slope waters. Yet little is known about long-term fluctuations in the advective transport of nutrients to the shelf. To examine the relationships between subsurface nutrient concentrations and dominant slope water masses at the Scotian Shelf break, we assembled all available hydrographic data (temperature, salinity) and dissolved nutrient data (nitrate, phosphate, silicate) for the period 1975-2020. Hydrographic and nutrient data were extracted from the Fisheries and Oceans Canada (DFO) data archives MEDS (Marine Environmental Data Section Archive; DFO, 2023a) and BioChem (DFO, 2023b; Devine et al., 2014), respectively, and predominantly include data from current DFO programs (e.g., Atlantic Zone Monitoring Program (AZMP)) and legacy datasets. Hydrographic data consist of vertical water column profiles collected using a conductivity-temperature-depth (CTD) profiler, generally mounted to a rosette sampler equipped with Niskin bottles for discrete water and nutrient sampling (Mitchel et al., 2002). Nutrient (nitrate, phosphate, silicate) measurements generally followed well established colorimetric techniques outlined in detail in the AZMP sampling protocol (Mitchell et al., 2002). Only nutrient data that passed initial quality control (i.e., BioChem quality flags of 1 and 0) are included in the datasets provided here (see Devine et al., 2014 for details on quality control (QC) procedures). In addition to hydrographic and nutrient parameters, datasets further include information on designated regions (e.g., WSS: Western Scotian Shelf, CSS: Central Scotian Shelf, ESS: Eastern Scotian Shelf) as defined in Lehmann et al (2023).

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2013

Description: The stable isotopes, δ15N and δ18O, of nitrite and nitrate can be powerful tools used to interpret nitrogen cycling in the ocean. In order to interpret isotope profiles, the isotope systematics of each process involved must be known. This thesis describes numerous experiments using both cultures of nitrifying organisms as well as natural seawater samples to determine the oxygen isotope systematics of nitrification. These experiments show that the accumulation of nitrite has a large effect on the resulting δ18ONO3. Also, the δ18ONO2 was developed as a unique tracer because it undergoes abiotic equilibration with water δ18O at a predictable rate based on pH, temperature and salinity. This rate, its dependencies, and how the δ18ONO2 values can be used as not only biological source indicators but also indicators of age are described. Finally, using the isotope systematics of nitrification as well as the properties of nitrite oxygen isotope exchange described in this thesis, the final chapter interprets multi-isotope nitrate and nitrite profiles in the Costa Rica Upwelling Dome using a simple 1D model. Overall, this thesis describes new nitrogen and oxygen isotopic tracers and uses them to elucidate the complicated nitrogen biogeochemistry in oxygen deficient zones.

Description: The work described in this thesis was funded by the National Science Foundation grants OCE 05-26277 and OCE 09-610998 to KLC, the MIT Presidential Fellowship, the WHOI Coastal Ocean Institute, the WHOI Academic Programs Office, and the MIT Houghton fund.

Description: © The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 12 (2015): 7483-7502, doi:10.5194/bg-12-7483-2015.

Description: Nitrogen (N) is a key component of fundamental biomolecules. Hence, its cycling and availability are central factors governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO3−) from a site in the oligotrophic North Atlantic (Integrated Ocean Drilling Program – IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO3- accumulates far above bottom seawater concentrations (~ 21 μM) throughout the sediment column (up to ~ 50 μM) down to the oceanic basement as deep as 90 m b.s.f. (below sea floor), reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ15N and δ18O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion–reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO3- isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide stable isotopic evidence for expanded zones of co-occurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ15N and δ18O of newly produced nitrate (δ15NNTR (NTR, referring to nitrification) and δ18ONTR), as well as the isotope effect for denitrification (15ϵDNF) (DNF, referring to denitrification), parameters with high relevance to global ocean models of N cycling. Estimated values of δ15NNTR were generally lower than previously reported δ15N values for sinking particulate organic nitrogen in this region. We suggest that these values may be, in part, related to sedimentary N2 fixation and remineralization of the newly fixed organic N. Values of δ18ONTR generally ranged between −2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ18ONTR values were elevated, suggesting incorporation of 18O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH4+ and NO2− oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supplies a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic-matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.

Description: Funding for this work was provided in part by the International Ocean Drilling Program, Woods Hole Oceanographic Institution and a grant from the Center for Dark Energy Biosphere Investigations (C-DEBI) to SW and WZ and a postdoc fellowship to CB from C-DEBI. WZ was supported in part by NSF grant OCE-1131671.

Description: Author Posting. © American Geophysical Union, 2015. 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 29 (2015): 2061–2081, doi:10.1002/2015GB005187.

Description: Nitrite is a central intermediate in the marine nitrogen cycle and represents a critical juncture where nitrogen can be reduced to the less bioavailable N2 gas or oxidized to nitrate and retained in a more bioavailable form. We present an analysis of rates of microbial nitrogen transformations in the oxygen deficient zone (ODZ) within the eastern tropical North Pacific Ocean (ETNP). We determined rates using a novel one-dimensional model using the distribution of nitrite and nitrate concentrations, along with their natural abundance nitrogen (N) and oxygen (O) isotope profiles. We predict rate profiles for nitrate reduction, nitrite reduction, and nitrite oxidation throughout the ODZ, as well as the contributions of anammox to nitrite reduction and nitrite oxidation. Nitrate reduction occurs at a maximum rate of 25 nM d−1 at the top of the ODZ, at the same depth as the maximum rate of nitrite reduction, 15 nM d−1. Nitrite oxidation occurs at maximum rates of 10 nM d−1 above the secondary nitrite maximum, but also in the secondary nitrite maximum, within the ODZ. Anammox contributes to nitrite oxidation within the ODZ but cannot account for all of it. Nitrite oxidation within the ODZ that is not through anammox is also supported by microbial gene abundance profiles. Our results suggest the presence of nitrite oxidation within the ETNP ODZ, with implications for the distribution and physiology of marine nitrite-oxidizing bacteria, and for total nitrogen loss in the largest marine ODZ.

Description: National Science Foundation. Grant Numbers OCE 05-26277, OCE 09-610998; WHOI Coastal Ocean Institute

Description: 2016-06-15

Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nature Communications 8 (2017): 15595, doi:10.1038/ncomms15595.

Description: Although increasing atmospheric nitrous oxide (N2O) has been linked to nitrogen loading, predicting emissions remains difficult, in part due to challenges in disentangling diverse N2O production pathways. As coastal ecosystems are especially impacted by elevated nitrogen, we investigated controls on N2O production mechanisms in intertidal sediments using novel isotopic approaches and microsensors in flow-through incubations. Here we show that during incubations with elevated nitrate, increased N2O fluxes are not mediated by direct bacterial activity, but instead are largely catalysed by fungal denitrification and/or abiotic reactions (e.g., chemodenitrification). Results of these incubations shed new light on nitrogen cycling complexity and possible factors underlying variability of N2O fluxes, driven in part by fungal respiration and/or iron redox cycling. As both processes exhibit N2O yields typically far greater than direct bacterial production, these results emphasize their possibly substantial, yet widely overlooked, role in N2O fluxes, especially in redox-dynamic sediments of coastal ecosystems.

Description: D.D.B. acknowledges support from the Max Planck Institute for Marine Microbiology. This work was supported by the National Science Foundation grants to W.Z. and S.D.W. (OCE-1260373) and to S.D.W. (EAR-1252161).

Description: Author Posting. © Association for the Sciences of Limnology and Oceanography, 2016. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 61 (2016): 1188–1200, doi:10.1002/lno.10266.

Description: Reactive oxygen species (ROS) are key players in the health and biogeochemistry of the ocean and its inhabitants. The vital contribution of microorganisms to marine ROS levels, particularly superoxide, has only recently come to light, and thus the specific biological sources and pathways involved in ROS production are largely unknown. To better understand the biogenic controls on ROS levels in tropical oligotrophic systems, we determined rates of superoxide production under various conditions by natural populations of the nitrogen-fixing diazotroph Trichodesmium obtained from various surface waters in the Sargasso Sea. Trichodesmium colonies collected from eight different stations all produced extracellular superoxide at high rates in both the dark and light. Colony density and light had a variable impact on extracellular superoxide production depending on the morphology of the Trichodesmium colonies. Raft morphotypes showed a rapid increase in superoxide production in response to even low levels of light, which was not observed for puff colonies. In contrast, superoxide production rates per colony decreased with increasing colony density for puff morphotypes but not for rafts. These findings point to Trichodesmium as a likely key source of ROS to the surface oligotrophic ocean. The physiological and/or ecological factors underpinning morphology-dependent controls on superoxide production need to be unveiled to better understand and predict superoxide production by Trichodesmium and ROS dynamics within marine systems.

Description: Major support for this work was provided by NSF OCE- 1246174 to CMH, NSF OCE-1332912 to STD and NSF OCE-13329898 to BASVM.

Description: © The Author(s), 2013. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in PLoS ONE 8 (2013): e78275, doi:10.1371/journal.pone.0078275.

Description: Anaerobic ammonia oxidation (anammox) as an important nitrogen loss pathway has been reported in marine oxygen minimum zones (OMZs), but the community composition and spatial distribution of anammox bacteria in the eastern tropical North Pacific (ETNP) OMZ are poorly determined. In this study, anammox bacterial communities in the OMZ off Costa Rica (CRD-OMZ) were analyzed based on both hydrazine oxidoreductase (hzo) genes and their transcripts assigned to cluster 1 and 2. The anammox communities revealed by hzo genes and proteins in CRD-OMZ showed a low diversity. Gene quantification results showed that hzo gene abundances peaked in the upper OMZs, associated with the peaks of nitrite concentration. Nitrite and oxygen concentrations may therefore colimit the distribution of anammox bacteria in this area. Furthermore, transcriptional activity of anammox bacteria was confirmed by obtaining abundant hzo mRNA transcripts through qRT-PCR. A novel hzo cluster 2x clade was identified by the phylogenetic analysis and these novel sequences were abundant and widely distributed in this environment. Our study demonstrated that both cluster 1 and 2 anammox bacteria play an active role in the CRD-OMZ, and the cluster 1 abundance and transcriptional activity were higher than cluster 2 in both free-living and particle-attached fractions at both gene and transcriptional levels.

Description: National Science Foundation (OCE #0961098) Hong Kong Research Grants Council (661911 and 661912) Chinese Academy of Science (SIDSSE-BR-201301).

Description: Dataset: Porewater Nitrogen

Description: Porewater measurements of nitrate and nitrite concentration and N and O isotopic ratios (d15N and d18O) collected from sites 3 and 10 on the North Atlantic Long Core Cruise R/V Knorr KN223 from October to December 2014. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/748792

Description: NSF Division of Ocean Sciences (NSF OCE) OCE-0939564, NSF Division of Ocean Sciences (NSF OCE) OCE-1433150, NSF Division of Ocean Sciences (NSF OCE) OCE-1537485

Description: Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 57 (2012): 1361-1375, doi:10.4319/lo.2012.57.5.1361.

Description: The δ18O value of nitrate produced during nitrification (δ18ONO3,nit) was measured in experiments designed to mimic oceanic conditions, involving cocultures of ammonia-oxidizing bacteria or ammonia-oxidizing archaea and nitrite-oxidizing bacteria, as well as natural marine assemblages. The estimates of ranged from −1.5‰ ± 0.1‰ to +1.3‰ ± 1.4‰ at δ18O values of water (H2O) and dissolved oxygen (O2) of 0‰ and 24.2‰ vs. Vienna Standard Mean Ocean Water, respectively. Additions of 18O-enriched H2O allowed us to evaluate the effects of oxygen (O) isotope fractionation and exchange on . Kinetic isotope effects for the incorporation of O atoms were the most important factors for setting overall values relative to the substrates (O2 and H2O). These isotope effects ranged from +10‰ to +22‰ for ammonia oxidation (O2 plus H2O incorporation) and from +1‰ to +27‰ for incorporation of H2O during nitrite oxidation. values were also affected by the amount and duration of nitrite accumulation, which permitted abiotic O atom exchange between nitrite and H2O. Coculture incubations where ammonia oxidation and nitrite oxidation were tightly coupled showed low levels of nitrite accumulation and exchange (3% ± 4%). These experiments had values of −1.5‰ to +0.7‰. Field experiments had greater accumulation of nitrite and a higher amount of exchange (22% to 100%), yielding an average value of +1.9‰ ± 3.0‰. Low levels of biologically catalyzed exchange in coculture experiments may be representative of nitrification in much of the ocean where nitrite accumulation is low. Abiotic oxygen isotope exchange may be important where nitrite does accumulate, such as oceanic primary and secondary nitrite maxima.

Description: This research was funded by the National Science Foundation Chemical Oceanography grants 05-26277 and 09- 610998 to K.L.C.