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Abstract Measuring, reporting, and verification (MRV) of ocean-based carbon dioxide removal (CDR) presents challenges due to the dynamic nature of the ocean and the complex processes influencing marine carbonate chemistry. Given these challenges, finding the optimal sampling strategies and suite of parameters to be measured is a timely research question. While traditional carbonate parameters such as total alkalinity (TA), dissolved inorganic carbon (DIC), pH, and seawater pCO2 are commonly considered, exploring the potential of carbon isotopes for quantifying additional CO2 uptake remains a relatively unexplored research avenue. In this study, we use a coupled physical-biogeochemical model of the California Current System (CCS) to run a suite of Ocean Alkalinity Enhancement (OAE) simulations. The physical circulation for the CCS is generated using a nested implementation of the Regional Ocean Modeling System (ROMS) with an outer domain of 1/10 ̊ (~10 km) and an inner domain of 1/30 ̊ (~3 km) resolution. The biogeochemical model, NEMUCSC, is a customized version of the North Pacific Ecosystem Model for Understanding Regional Oceanography (NEMURO) that includes carbon cycling and carbon isotopes. The CCS is one of four global eastern boundary upwelling systems characterized by high biological activity and CO2 concentrations. Consequently, the CCS represents an essential test case for investigating the efficacy and potential side effects of OAE deployments. The study aims to address two key questions: (1) the relative merit of OAE to counter ocean acidification versus the additional sequestration of CO2 from the atmosphere, and (2) the footprint of potentially harmful seawater chemistry adjacent to OAE deployments. We plan to leverage these high-resolution model results to competitively evaluate different MRV strategies, with a specific focus on analyzing the spatiotemporal distribution of carbon isotopic signatures following OAE. In this talk, we will showcase our initial results and discuss challenges in integrating high-resolution regional modeling into models of the global carbon cycle. More broadly, this work aims to provide insights into the plausibility of OAE as a climate solution that maintains ocean health and to inform accurate quantification of carbon uptake for MRV purposes. https://agu.confex.com/agu/OSM24/prelim.cgi/Paper/1491096 

Abstract In this work, we utilize a transect of core top, mid- to late Holocene, sediments from the Eastern Siberian Sea to the central Arctic Ocean, spanning gradients in upper-ocean water column properties, to examine regional planktic foraminiferal species abundances and geochemistry. We present species- and morphotype-specific foraminiferal assemblages at these sites and stable isotope analyses of neogloboquadrinids. We find little variation in planktic species populations, and only small variations in N. pachyderma morphotype distributions, between sites. Spatial averages of N. pachyderma morphotype and N. incompta δ18O values show no significant differences, suggesting a similar calcification depth for all morphotypes of N. pachyderma and N. incompta across our sites, which we estimate to be between ∼ 50–150 m. Values of δ18O of a group of unencrusted specimens delineate a shallower calcification habitat. Neogloboquadrina pachyderma-2 Mg/Ca values yield temperatures outside the range of observations using available calibration equations, pointing toward the need for more Arctic-specific Mg/Ca-temperature calibrations. 

The observation of extremely low radiocarbon content / old radiocarbon ages (>4000 years old) in the intermediate-depth ocean during the last ice age draws attention to our incomplete understanding of ocean carbon cycling. For example, glacial-interglacial seawater 14C anomalies near the Gulf of California have been explained by both the advection from a 14C-depleted abyssal source and local geologic carbon flux. To provide insight to this the origin of the seawater 14C anomalies, we have produced several new records of glacial-interglacial intermediate water (i.e., 14C, δ11B, δ18O, and δ13C) in waters that are “upstream” and “downstream” of the Gulf of California. These observations plus geochemical modeling allow us to: (1) Answer whether the old seawater 14C ages are advected or produced locally; (2) Identify the approximate chemical make-up of this carbon; and (3) Consider the role of known sedimentary processes in this carbon flux to the ocean. (Note that several sites have age model controls based on terrestrial plant 14C ages, providing more confidence in our results.) Our new measurements and modeling indicate that the well-established >4000-year-old seawater 14C anomalies observed near known seafloor volcanism in the Gulf of California are not present “upstream,” indicating that this carbon flux results from a “local” geologic carbon. Furthermore, based on our new benthic foraminifera δ11B measurements, this local carbon Blux does not appear to affect seawater pH. Finally, we suggest several potential geologic carbon source(s) that could explain the anomalously old seawater 14C ages, the relatively unremarkable changes in seawater δ13C, and the essentially negligible change in seawater pH. 

Gas exchange between the atmosphere and ocean interior profoundly impacts global climate and biogeochemistry. However, our understanding of the relevant physical processes remains limited by a scarcity of direct observations. Dissolved noble gases in the deep ocean are powerful tracers of physical air-sea interaction due to their chemical and biological inertness, yet their isotope ratios have remained underexplored. Here, we present high-precision noble gas isotope and elemental ratios from the deep North Atlantic (~32°N, 64°W) to evaluate gas exchange parameterizations using an ocean circulation model. The unprecedented precision of these data reveal deep-ocean undersaturation of heavy noble gases and isotopes resulting from cooling-driven air-to-sea gas transport associated with deep convection in the northern high latitudes. Our data also imply an underappreciated and large role for bubble-mediated gas exchange in the global air-sea transfer of sparingly soluble gases, including O 2 , N 2 , and SF 6 . Using noble gases to validate the physical representation of air-sea gas exchange in a model also provides a unique opportunity to distinguish physical from biogeochemical signals. As a case study, we compare dissolved N 2 /Ar measurements in the deep North Atlantic to physics-only model predictions, revealing excess N 2 from benthic denitrification in older deep waters (below 2.9 km). These data indicate that the rate of fixed N removal in the deep Northeastern Atlantic is at least three times higher than the global deep-ocean mean, suggesting tight coupling with organic carbon export and raising potential future implications for the marine N cycle. 

A compilation of radiocarbon measurements is used to characterize deep-sea overturning since the last ice age. 

Abstract 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 Southern Ocean surface into the global pycnocline (roughly the upper 1.2 km), as opposed to directly from the deep ocean. We estimate that 62 ± 5% of the pycnocline nitrate and phosphate originate from the Southern Ocean. Mixing, as opposed to advection, accounts for most of the gross nutrient input to the pycnocline. However, in net, mixing carries nutrients away from the pycnocline. Despite the quantitative dominance of mixing in the gross nutrient transport, the nutrient richness of the pycnocline relies on the large-scale advective flow, through which nutrient-rich water is converted to nutrient-poor surface water that eventually flows to the North Atlantic. 

Abstract. Nitrate is a critical ingredient for life in the ocean because, as the mostabundant form of fixed nitrogen in the ocean, it is an essential nutrientfor primary production. The availability of marine nitrate is principallydetermined by biological processes, each having a distinct influence on theN isotopic composition of nitrate (nitrate δ15N) – a propertythat informs much of our understanding of the marine N cycle as well asmarine ecology, fisheries, and past ocean conditions. However, the sparsespatial distribution of nitrate δ15N observations makes itdifficult to apply this useful property in global studies or to facilitaterobust model–data comparisons. Here, we use a compilation of publishednitrate δ15N measurements (n=12 277) and climatological mapsof physical and biogeochemical tracers to create a surface-to-seafloor,1∘ resolution map of nitrate δ15N using an ensembleof artificial neural networks (EANN). The strong correlation (R2>0.87) and small mean difference (<0.05 ‰) between EANN-estimated and observed nitrateδ15N indicate that the EANN provides a good estimate ofclimatological nitrate δ15N without a significant bias. Themagnitude of observation-model residuals is consistent with the magnitude of seasonal to interannual changes in observed nitrate δ15N that are notcaptured by our climatological model. The EANN provides a globally resolved map of mean nitrate δ15Nfor observational and modeling studies of marine biogeochemistry,paleoceanography, and marine ecology. 

Abstract In eastern boundary current systems, strong coastal upwelling brings deep, nutrient‐rich waters to the surface ocean, supporting a productive food web. The nitrate load in water masses that supply the region can be impacted by a variety of climate‐related processes that subsequently modulate primary productivity. In this study, two coastal upwelling regimes along central and southern California were sampled seasonally for nitrogen and oxygen stable isotopes of nitrate (i.e., nitrate isotopes) over several years (2010–2016) on 14 California Cooperative Oceanic Fisheries Investigations (CalCOFI) cruises. Seasonal, interannual, and spatial variations in euphotic zone nitrate isotopes were largely driven by the extent of nitrate utilization, sometimes linked to iron limitation of diatom productivity. Pronounced isotopic enrichment developed with the El Niño conditions in late 2015 and early 2016 which likely resulted from increased nitrate utilization linked to reduced nitrate supply to the euphotic zone. Differential enrichment of nitrogen and oxygen isotopes was observed in the surface ocean, suggesting that phytoplankton increased their reliance on locally nitrified (recycled) nitrate during warmer and more stratified periods. Overall, nitrate isotopes effectively differentiated important euphotic zone processes such as nitrate assimilation and nitrification, while archiving the influence of disparate controls such as iron limitation and climatic events through their effects on nitrate utilization and isotopic fractionation.