A determination of air-sea gas exchange and upper ocean biological production from five noble gases and tritiugenic helium-3

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 September 2007The five noble gases (helium, neon, argon, krypton, and xenon) are biologically and chemically inert, making them ideal oceanographic tracers. Additionally, the noble gases have a wide range of solubilities and molecular diffusivities, and thus respond differently to physical forcing. Tritium, an isotope of hydrogen, is useful in tandem with its daughter helium-3 as a tracer for water mass ages. In this thesis, a fourteen month time-series of the five noble gases, helium-3 and tritium was measured at the Bermuda Atlantic Time-series Study (BATS) site. The time-series of five noble gases was used to develop a parameterization of air-sea gas exchange for oligotrophic waters and wind speeds between 0 and 13 m s−1 that explicitly includes bubble processes and that constrains diffusive gas exchange to ± 6% and complete and partial air injection processes to ± 15%. Additionally, the parameterization is based on weeks to seasonal time scales, matching the time scales of many relevant biogeochemical cycles. The time-series of helium isotopes, tritium, argon, and oxygen was used to constrain upper ocean biological production. Specifically, the helium flux gauge technique was used to estimate new production, apparent oxygen utilization rates were used to quantify export production, and euphotic zone seasonal cycles of oxygen and argon were used to determine net community production. The concurrent use of these three methods allows examination of the relationship between the types of production and begins to address a number of apparent inconsistencies in the elemental budgets of carbon, oxygen, and nitrogen.I received funding towards my graduate research from the Department of Defense (NDSEG fellowship), the National Science Foundation (OCE-0221247), and the Scurlock Fund for research

Quantifying photosynthetic rates of microphytobenthos using the triple isotope composition of dissolved oxygen

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2013. 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: Methods 11 (2013): 360-373, doi:10.4319/lom.2013.11.360.Microphytobenthos are important mediators of nutrient and carbon fluxes in coastal environments. However, quantifying production rates by microphytobenthos is difficult, and existing methods necessitate perhaps erroneous assumptions that dark respiration equals light respiration. Here we present a new method for quantifying photosynthetic rates of microphytobenthos, i.e., gross primary production, by using the triple isotope composition of dissolved oxygen in benthic flux chambers. Because the triple oxygen isotope signature is sensitive to photosynthesis, but not to respiration, this method allows quantification of gross photosynthetic oxygen fluxes by microphytobenthos without assumptions about respiration. We present results from field experiments in Waquoit Bay, Massachusetts, that illustrate the method.We gratefully acknowledge funding for this work by the Coastal Ocean Institute of Woods Hole Oceanographic Institution and the National Science Foundation (OCE-82964400). EH was supported by a National Defense Science and Engineering Graduate Fellowship award

Rates of summertime biological productivity in the Beaufort Gyre : a comparison between the low and record-low ice conditions of August 2011 and 2012

© The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Journal of Marine Systems 147 (2015): 29-44, doi:10.1016/j.jmarsys.2014.04.006.The Arctic Ocean is changing rapidly as the global climate warms but it is not well known how these changes are affecting biological productivity and the carbon cycle. Here we study the Beaufort Gyre region of the Canada Basin in August and use the large reduction in summertime sea ice extent from 2011 to 2012 to investigate potential impacts of climate warming on biological productivity. We use the gas tracers O2/Ar and triple oxygen isotopes to quantify rates of net community production (NCP) and gross oxygen production (GOP) in the gyre. Comparison of the summer of 2011 with the summer of 2012, the latter of which had record low sea ice coverage, is relevant to how biological productivity might change in a seasonally ice-free Arctic Ocean. We find that, in the surface waters measured here, GOP in 2012 is significantly greater than in 2011, with the mean basin-wide 2012 GOP = 38 ± 3 mmol O2 m− 2 d− 1 whereas in 2011, mean basin GOP = 16 ± 5 mmol O2 m− 2 d− 1. We hypothesize that this is because the lack of sea ice and consequent increase in light penetration allows photosynthesis to increase in 2012. However, despite the increase in GOP, NCP is the same in the two years; mean NCP in 2012 is 3.0 ± 0.2 mmol O2 m− 2 y− 1 and in 2011 is 3.1 ± 0.2 mmol O2 m− 2 y− 1. This suggests that the heterotrophic community (zooplankton and/or bacteria) increased its activity as well and thus respired the additional carbon produced by the increased photosynthetic production. In both years, stations on the shelf had GOP 3 to 5 times and NCP 2 to 10 times larger than the basin stations. Additionally, we show that in 2011, the NCP/GOP ratio is smallest in regions with highest ice cover, suggesting that the microbial loop was more efficient at recycling carbon in regions where the ice was just starting to melt. These results highlight that although satellite chlorophyll records show, and many models predict, an increase in summertime primary production in the Arctic Basin as it warms, the net amount of carbon processed by the biological pump during summer may not change as a function of ice cover. Thus, a rapid reduction in summertime ice extent may not change the net community productivity or carbon balance in the Beaufort Gyre.We thank our funding sources: the National Science Foundation (PLR 1304406, PLR-0856531) and the support of Fisheries and Oceans Canada

The triple oxygen isotope tracer of primary productivity in a dynamic ocean model

Author Posting. © American Geophysical Union, 2014. 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 Cycle 28 (2014): 538–552, doi:10.1002/2013GB004704.The triple oxygen isotopic composition of dissolved oxygen (17Δdis) was added to the ocean ecosystem and biogeochemistry component of the Community Earth System Model, version 1.1.1. Model simulations were used to investigate the biological and physical dynamics of 17Δdis and assess its application as a tracer of gross photosynthetic production (gross oxygen production (GOP)) of O2 in the ocean mixed layer. The model reproduced large-scale patterns of 17Δdis found in observational data across diverse biogeographical provinces. Mixed layer model performance was best in the Pacific and had a negative bias in the North Atlantic and a positive bias in the Southern Ocean. Based on model results, the steady state equation commonly used to calculate GOP from tracer values overestimated the globally averaged model GOP by 29%. Vertical entrainment/mixing and the time rate of change of 17Δdis were the two largest sources of bias when applying the steady state method to calculate GOP. Entrainment/mixing resulted in the largest overestimation in midlatitudes and during summer and fall and almost never caused an underestimation of GOP. The tracer time rate of change bias resulted both in underestimation of GOP (e.g., during spring blooms at high latitudes) and overestimation (e.g., during the summer following a bloom). Seasonally, bias was highest in the fall (September-October-November in the Northern Hemisphere, March-April-May in the Southern), overestimating GOP by 62%, globally averaged. Overall, the steady state method was most accurate in equatorial and low-latitude regions where it estimated GOP to within ±10%. Field applicable correction terms are derived for entrainment and mixing that capture 86% of model vertical bias and require only mixed layer depth history and triple oxygen isotope measurements from two depths.We acknowledge support from Center for Microbial Oceanography Research and Education (CMORE) (NSF EF-0424599) and NOAA Climate Program Office (NA 100AR4310093).2014-11-2

Quantifying seasonal air-sea gas exchange processes using noble gas time-series : a design experiment

Author Posting. © Sears Foundation for Marine Research, 2006. This article is posted here by permission of Sears Foundation for Marine Research for personal use, not for redistribution. The definitive version was published in Journal of Marine Research 64 (2006): 267-295, doi:10.1357/002224006777606452.A multi-year time-series of measurements of five noble gases (He, Ne, Ar, Kr, and Xe) at a subtropical ocean location may allow quantification of air-sea gas exchange parameters with tighter constraints than is currently available by other methods. We have demonstrated this using a one-dimensional upper ocean model forced by 6-hourly NCEP reanalysis winds and heat flux for the Sargasso Sea near Bermuda. We performed ensemble model runs to characterize the response of the modeled noble gas saturation anomalies to a range of air-sea gas exchange parameters. We then used inverse calculations to quantify the sensitivity of the parameters to hypothetical observations. These calculations show that with currently achievable measurement accuracies, noble gas concentrations in the Sargasso Sea could be used to constrain the magnitude of equilibrium gas exchange to ±11%, the magnitude of the total air injection flux to ±14%, and the magnitude of net photosynthetic oxygen production to ±1.5 mol O2 m−2 y−1. Additionally, we can use noble gases to quantify the relative contributions of bubbles that are partially dissolved to bubbles that are completely dissolved. These constraints are based on idealized assumptions and may not fully account for some of the uncertainties in the meteorological data, in lateral transport processes, and in the solubilities of the noble gases. As a limited demonstration, we applied this approach to a time series of He, Ne, Ar, and O2 measurements from the Sargasso Sea from 1985 to 1988 (data from Spitzer, 1989). Due to the limited number of gases measured and the lower accuracy of those measurements, the constraints in this example application are weaker than could be achieved with current capabilities.This work was supported by the National Science Foundation Chemical Oceanography program (OCE-0221247) and by the Department of Defense (graduate fellowship to RHRS)

A phytoplankton model for the allocation of gross photosynthetic energy including the trade‐offs of diazotrophy

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 123 (2018): 1796-1816, doi:10.1029/2017JG004263.Gross photosynthetic activity by phytoplankton is directed to linear and alternative electron pathways that generate ATP, reductant, and fix carbon. Ultimately less than half is directed to net growth. Here we present a phytoplankton cell allocation model that explicitly represents a number of cell metabolic processes and functional pools with the goal of evaluating ATP and reductant demands as a function of light, nitrate, iron, oxygen, and temperature for diazotrophic versus nondiazotrophic growth. We employ model analogues of Synechoccocus and Crocosphaera watsonii, to explore the trade‐offs of diazotrophy over a range of environmental conditions. Model analogues are identical in construction, except for an iron quota associated with nitrogenase, an additional respiratory demand to remove oxygen in order to protect nitrogenase and an additional ATP demand to split dinitrogen. We find that these changes explain observed differences in growth rate and iron limitation between diazotrophs and nondiazotrophs. Oxygen removal imparted a significantly larger metabolic cost to diazotrophs than ATP demand for fixing nitrogen. Results suggest that diazotrophs devote a much smaller fraction of gross photosynthetic energy to growth than nondiazotrophs. The phytoplankton cell allocation model model provides a predictive framework for how photosynthate allocation varies with environmental conditions in order to balance cellular demands for ATP and reductant across phytoplankton functional groups.DOC | NOAA | Climate Program Office (CPO) Grant Number: NA100AR4310093; National Science Foundation (NSF) Grant Number: EF‐0424599; Center for Microbial Oceanography Research and Education (CMORE) Grant Number: NSF EF‐0424599; NOAA Global Carbon Program Grant Number: NA100AR43100932018-11-0

Nitrogen cycling in the secondary nitrite maximum of the eastern tropical North Pacific off Costa Rica

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.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.National Science Foundation. Grant Numbers OCE 05-26277, OCE 09-610998; WHOI Coastal Ocean Institute2016-06-1

A new automated method for measuring noble gases and their isotopic ratios in water samples

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 10 (2009): Q05008, doi:10.1029/2009GC002429.A method is presented for precisely measuring all five noble gases and their isotopic ratios in water samples using multiple programmed multistage cryogenic traps in conjunction with quadrupole mass spectrometry and magnetic sector mass spectrometry. Multiple automated cryogenic traps, including a two-stage cryotrap used for removal of water vapor, an activated charcoal cryotrap used for helium separation, and a stainless steel cryotrap used for neon, argon, krypton, and xenon separation, allow reproducible gas purification and separation. The precision of this method for gas standards is ±0.10% for He, ±0.14% for Ne, ±0.10% for Ar, ±0.14% for Kr, and ±0.17% for Xe. The precision of the isotopic ratios of the noble gases in gas standards are ±1.9‰ for 20Ne/22Ne, ±2.0‰ for 84Kr/86Kr, ±2.5‰ for 84Kr/82Kr, ±0.9‰ for 132Xe/129Xe, and ±1.3‰ for 132Xe/136Xe. The precision of this method for water samples, determined by measurement of duplicate pairs, is ±1% for He, ±0.9% for Ne, ±0.3% for Ar, ±0.3% for Kr, and ±0.2% for Xe. An attached magnetic sector mass spectrometer measures 3He/4He with precisions of ±0.1% for air standards and ±0.14% for water samples.We are grateful for support by the National Science Foundation Chemical Oceanography program (OCE-0221247), by the Department of Defense (graduate fellowship to RHRS), and by the Woods Hole Oceanographic Institution (postdoctoral fellowship for B.B.)

Submesoscale hotspots of productivity and respiration : insights from high-resolution oxygen and fluorescence sections

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part I: Oceanographic Research Papers 130 (2017): 1-11, doi:10.1016/j.dsr.2017.10.005.Modeling studies have shown that mesoscale and submesoscale processes can stimulate phytoplankton productivity and export production. Here, we present observations from an undulating, towed Video Plankton Recorder (VPR-II) in the tropical Atlantic. The VPR-II collected profiles of oxygen, fluorescence, temperature and salinity in the upper 140 m of the water column at a spatial resolution of 1 m in the vertical and <2 km in the horizontal. The data reveal remarkable "hotspots", i.e. locations 5 to 10 km wide which have elevated fluorescence and decreased oxygen, both of which are likely the result of intense submesoscale upwelling. Based on estimates of source water, estimated from identical temperature and salinity surfaces, hotspots are more often areas of net respiration than areas of net production — although the inferred changes in oxygen are subject to uncertainty in the determination of the source of the upwelled waters since the true source water may not have been sampled. We discuss the spatial distribution of these hotspots and present a conceptual model outlining their possible generation and decline. Simultaneous measurements of O2/Ar in the mixed layer from a shipboard mass spectrometer provide estimates of rates of surface net community production. We find that the subsurface biological hotspots are often expressed as an increase in mixed layer rates of net community production. Overall, the large number of these hotspots support the growing evidence that submesoscale processes are important drivers in upper ocean biological production.Funding for this work came from the National Science Foundation (R.H.R.S. and D.J.M) (OCE-0925284, OCE-1048897, and OCE- 1029676) and the National Aeronautics and Space Administration (D.J.M.) (NNX08AL71G and NNX13AE47G)

Quantifying air-sea gas exchange using noble gases in a coastal upwelling zone

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in IOP Conference. Series: Earth and Environmental Science 35 (2016): 012017, doi:10.1088/1755-1315/35/1/012017.The diffusive and bubble-mediated components of air-sea gas exchange can be quantified separately using time-series measurements of a suite of dissolved inert gases. We have evaluated the performance of four published air-sea gas exchange parameterizations using a five-day time-series of dissolved He, Ne, Ar, Kr, and Xe concentration in Monterey Bay, CA. We constructed a vertical model including surface air-sea gas exchange and vertical diffusion. Diffusivity was measured throughout the cruise from profiles of turbulent microstructure. We corrected the mixed layer gas concentrations for an upwelling event that occurred partway through the cruise. All tested parameterizations gave similar results for Ar, Kr, and Xe; their air-sea fluxes were dominated by diffusive gas exchange during our study. For He and Ne, which are less soluble, and therefore more sensitive to differences in the treatment of bubble-mediated exchange, the parameterizations gave widely different results with respect to the net gas exchange flux and the bubble flux. This study demonstrates the value of using a suite of inert gases, especially the lower solubility ones, to parameterize air-sea gas exchange.Funding for this work was provided by NSF award OCE-1060840 to RHR Stanley, NSF award OCE-1129644 to DP Nicholson, an Ocean Ventures Fund award from the WHOI Academic Programs Office to CC Manning, and graduate scholarships from NSERC and CMOS to CC Manning