Novel analytical strategies for tracing the organic carbon cycle in marine and riverine particles

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 2017Particulate organic carbon (POC) in the ocean and mobilized by rivers on land transfers ~0.1% of global primary productivity to the deep ocean sediments. This small fraction regulates the long-term carbon cycle by removing carbon dioxide from the atmosphere for centuries to millennia. This thesis investigates mechanisms of POC transfer to the deep ocean by analyzing particles collected in transit through two globally significant carbon reservoirs: the Southern Ocean and the Amazon River Basin. These endeavors test the hypothesis that organic matter composition controls the recycling and transfer efficiency of POC to the deep ocean, and illustrate new applications for ramped pyrolysis/oxidation (RPO), a growing method of POC characterization by thermal stability. By coupling RPO to stable and radiocarbon isotope analyses of riverine POC, I quantify three thermally distinct soil organic carbon pools mobilized by the Amazon River, and evaluate the degradability and fate of these different pools during transport to the coastal Atlantic Ocean. More directly, RPO analyses of marine samples suggest that POC transfer in the water column is in fact selective. Observations of consistent biomolecular changes that accompany transport of phytoplankton-derived organic matter to depth across the Southern Ocean support the argument for preferential degradation of specific POC pools in the water column. Combining discussions of POC recycling and transfer across both marine and terrestrial systems offer new perspectives of thermal stability as a proxy for diagenetic stability and POC degradation state. The challenges of interpreting RPO data in these two environments set the stage for applying the technique to more controlled experiments that trace POC from source to long-term sink.The research in this dissertation was funded by the National Science Foundation Graduate Research Fellowship Program, the Woods Hole Research Center Board of Trustees, the WHOI Ocean Exploration Institute Student Fellowship, WHOI Ocean Ventures Fund, the WHOI Coastal Ocean Institute Grant, the National Ocean Sciences Accelerator Mass Spectrometry student research and development support, the WHOI Academic Programs Office, the PAOC Houghton Fund, WHOI start up funds, and several NSF and NASA awards: NSF OCE-090880, NSF OCE-0961660, NSF OCE- 1443577, NSF OCE-1333387, NSF OCE-1233272, NASA NNX11A072G, and NASA NNX11AL93G

Technical note : an inverse method to relate organic carbon reactivity to isotope composition from serial oxidation

© The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 14 (2017): 5099-5114, doi:10.5194/bg-14-5099-2017.Serial oxidation coupled with stable carbon and radiocarbon analysis of sequentially evolved CO2 is a promising method to characterize the relationship between organic carbon (OC) chemical composition, source, and residence time in the environment. However, observed decay profiles depend on experimental conditions and oxidation pathway. It is therefore necessary to properly assess serial oxidation kinetics before utilizing decay profiles as a measure of OC reactivity. We present a regularized inverse method to estimate the distribution of OC activation energy (E), a proxy for bond strength, using serial oxidation. Here, we apply this method to ramped temperature pyrolysis or oxidation (RPO) analysis but note that this approach is broadly applicable to any serial oxidation technique. RPO analysis directly compares thermal reactivity to isotope composition by determining the E range for OC decaying within each temperature interval over which CO2 is collected. By analyzing a decarbonated test sample at multiple masses and oven ramp rates, we show that OC decay during RPO analysis follows a superposition of parallel first-order kinetics and that resulting E distributions are independent of experimental conditions. We therefore propose the E distribution as a novel proxy to describe OC thermal reactivity and suggest that E vs. isotope relationships can provide new insight into the compositional controls on OC source and residence time.This research was supported by the NSF Graduate Research Fellowship Program grant no. 2012126152 (Jordon D. Hemingway), NASA Astrobiology grant no. NNA13AA90A and NSF grant no. EAR-1338810 (Daniel H. Rothman), and the WHOI Independent Study Award (Valier V. Galy)

The effect of sample drying temperature on marine particulate organic carbon composition

Author Posting. © The Author(s), 2018. 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 Limnology and Oceanography Methods 16 (2018): 286-298, doi:10.1002/lom3.10245.Compositional changes in marine particulate organic carbon (POC) throughout the water column trace important processes that underlie the biological pump’s efficiency. While labor-intensive, particle sampling efforts offer potential to expand the empirical POC archive at different stages in the water column, provided that organic composition is sufficiently preserved between sampling and analysis. The standard procedure for preserving organic matter composition in marine samples is to immediately store particles at -80°C to -20°C until they can be freeze-dried for analysis. This report investigates the effect of warmer drying and storage temperatures on POC composition, which applies to the majority of POC samples collected in the field without intention for organic analysis. Particle samples collected off Woods Hole, MA were immediately dried at 56°C, at room temperature, or stored at -80°C until being freeze-dried. Results show that oven- and air-drying did not shift the bulk composition (i.e., carbon and nitrogen content and stable isotope composition) of POC in the samples relative to freeze-drying. Similarly, warmer drying temperatures did not affect POC thermal stability, as inferred by ramped pyrolysis/oxidation (RPO), a growing technique that uses a continuous temperature ramp to differentiate components of organic carbon by their decomposition temperature. Oven- and air-drying did depress lipid abundances relative to freeze-drying, the extent of which depended on compound size and structure. The data suggest that field samples dried at room temperatures and 56°C are appropriate for assessing bulk POC composition and thermal stability, but physical mechanisms such as molecular volatilization bias their lipid composition.This research was funded by the National Science Foundation (NSF) Graduate Research Fellowship program and the NSF Cooperative Agreement for the Operation of a National Ocean Sciences Accelerator Mass Spectrometry Facility (OCE-0753487)

Assessing the blank carbon contribution, isotope mass balance, and kinetic isotope fractionation of the Ramped Pyrolysis/Oxidation instrument at NOSAMS

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 Radiocarbon 59 (2017): 179-193, doi:10.1017/RDC.2017.3.We estimate the blank carbon mass over the course of a typical Ramped PyrOx (RPO) analysis (150 to 1000 °C; 5 °C×min-1) to be (3.7 ± 0.6) μg C with an Fm value of 0.555 ± 0.042 and a δ13C value of (-29.0 ± 0.1) ‰ VPDB. Additionally, we provide equations for RPO Fm and δ13C blank corrections, including associated error propagation. By comparing RPO mass-weighted mean and independently measured bulk δ13C values for a compilation of environmental samples and standard reference materials (SRMs), we observe a small yet consistent 13C depletion within the RPO instrument (mean – bulk: μ = -0.8 ‰; ±1σ = 0.9 ‰; n = 66). In contrast, because they are fractionation-corrected by definition, mass-weighted mean Fm values accurately match bulk measurements (mean – bulk: μ = 0.005; ±1σ = 0.014; n = 36). Lastly, we show there exists no significant intra-sample δ13C variability across carbonate SRM peaks, indicating minimal mass-dependent kinetic isotope fractionation during RPO analysis. These data are best explained by a difference in activation energy between 13C- and 12C-containing compounds (13–12ΔE) of 0.3 to 1.8 J×mol-1, indicating that blank and mass-balance corrected RPO δ13C values accurately retain carbon source isotope signals to within 1 to 2‰.J.D.H. was partly supported by the NSF Graduate Research Fellowship Program under grant number 2012126152; V.V.G. was partly supported by the US National Science Foundation (grants OCE- 0851015 and OCE-0928582), the WHOI Coastal Ocean Institute (grant 27040213) and an Independent Study Award (grant 27005306) from WHOI; G.S. and P.K.Z. were supported by the WHOI Postdoctoral Scholar Program with funding provided by NOSAMS (OCE-1239667)

Sixty years of Sverdrup : a retrospective of progress in the study of phytoplankton blooms

Author Posting. © The Oceanography Society, 2014. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 27, no. 1 (2014): 222–235, doi:10.5670/oceanog.2014.26.One of the most dramatic large-scale features in the ocean is the seasonal greening of the North Atlantic in spring and summer due to the accumulation of phytoplankton biomass in the surface layer. In 1953, Harald Ulrik Sverdrup hypothesized a now canonical mechanism for the development and timing of phytoplankton blooms in the North Atlantic. Over the next 60 years, Sverdrup's Critical Depth Hypothesis spurred progress in understanding of bloom dynamics and offered a valuable theoretical framework on which to build. In reviewing 60 years of literature, the authors trace the development of modern bloom initiation hypotheses, highlighting three case studies that illuminate the complexity, including both catalysts and impediments, of scientific progress in the wake of Sverdrup's hypothesis. Most notably, these cases demonstrate that the evolution of our understanding of phytoplankton blooms was paced by access not only to technology but also to concurrent insights from several disciplines. This exploration of the trajectories and successes in bloom studies highlights the need for expanding interdisciplinary collaborations to address the complexity of phytoplankton bloom dynamics

Exploring ethos? Discourses of 'charity' in the provision of emergency services for homeless people

This paper examines the ethos of organisations providing emergency services for homeless people in Britain. Drawing on extensive surveys of nonstatutory organisations we present a discourse analysis of statements of 'mission', 'values', and 'ethics', arguing that, although care needs to be exercised in translating organisational ethos into likely practices of care, these overarching messages of ethos are significant waymarkers in the moral landscapes of caring for homeless people. Using Coles's rethinking of the politics of generosity, we interrogate ethos in terms of three ideal types -- Christian caritas, secular humanism, and postsecular charity -- concluding that the principal fault-line in current services divides organisations which expect particular behavioural outcomes from homeless people (including Christian 'conversion' and more secular assumptions of self-responsibility), and those which provide care regardless of individual response