Lardie Gaylord Mary C.

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Lardie Gaylord
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Mary C.
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Now showing 1 - 6 of 6
  • Article
    Single Step Production of Graphite from Organic Samples [Poster]
    ( 2017) Elder, Kathryn L. ; Roberts, Mark L. ; Lardie Gaylord, Mary C.
    We present a low-cost, high-throughput method for converting many types of organic samples into graphite. The method combines sample combustion and graphitization in a single process. Using a modified sealed graphitization method, samples are placed in a Pyrex tube containing zinc, titanium hydride and iron catalyst. The tube is evacuated, flamed sealed, and placed in a muffle furnace for 7 hours. Graphite forms on the iron and is then analyzed for 14C content using either of NOSAMS’s two AMS systems. This method has been shown to work on a variety of organic samples including pure compounds, wood, peat, collagen and humics. This simplified procedure could be especially useful in reconnaissance studies in which it is desired to rapidly measure a large number of samples (untreated or pretreated), at low-cost with analytical precision and accuracy approaching that of traditional hydrogen reduction methods.
  • Article
    Advances in Sample Preparation at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS): Investigation of Carbonate Secondary Standards
    ( 2017) Cruz, Anne J. ; Childress, Laurel B. ; Gagnon, Alan R. ; McNichol, Ann P. ; Burton, Joshua R. ; Elder, Kathryn L. ; Lardie Gaylord, Mary C. ; Gospodinova, Kalina D. ; Hlavenka, Joshua ; Kurz, Mark D. ; Longworth, Brett E. ; Roberts, Mark L. ; Trowbridge, Nan Y. ; Walther, Tess ; Xu, Li
    The development of robust sample preparation techniques for ocean science research has been a hallmark of NOSAMS since its inception. Improvements to our standard methods include reducing the minimum size of the samples we can analyze, building modular graphite reactors of different sizes that we can swap in and out depending on our sample stream, and modifying our carbonate acidification methods to improve handling of the smaller samples we now receive. A relatively new instrument, the Ramped PyrOx, which allows the separation of organic matter into thermal fractions, has attracted much interest as a research and development tool. We will also discuss our progress on incorporating a Picarro isotope analyzer into our sample preparation options.
  • Article
    Ultra-small graphitization reactors for ultra-microscale 14C analysis at the National Ocean Sciences Accelerator Mass Spectrometry (NOSAMS) Facility
    (University of Arizona Libraries, 2015) Shah Walter, Sunita R. ; Gagnon, Alan R. ; Roberts, Mark L. ; McNichol, Ann P. ; Lardie Gaylord, Mary C. ; Klein, Elizabeth
    In response to the increasing demand for 14C analysis of samples containing less than 25 µg C, ultra-small graphitization reactors with an internal volume of ~0.8 mL were developed at NOSAMS. For samples containing 6 to 25 µg C, these reactors convert CO2 to graphitic carbon in approximately 30 min. Although we continue to refine reaction conditions to improve yield, the reactors produce graphite targets that are successfully measured by AMS. Graphite targets produced with the ultra-small reactors are measured by using the Cs sputter source on the CFAMS instrument at NOSAMS where beam current was proportional to sample mass. We investigated the contribution of blank carbon from the ultra-small reactors and estimate it to be 0.3 ± 0.1 µg C with an Fm value of 0.43 ± 0.3. We also describe equations for blank correction and propagation of error associated with this correction. With a few exceptions for samples in the range of 6 to 7 µg C, we show that corrected Fm values agree with expected Fm values within uncertainty for samples containing 6–100 µg C.
  • Article
    Petrocarbon evolution: Ramped pyrolysis/oxidation and isotopic studies of contaminated oil sediments from the Deepwater Horizon oil spill in the Gulf of Mexico.
    (Public Library of Science, 2019-02-28) Rogers, Kelsey L. ; Bosman, Samantha H. ; Lardie Gaylord, Mary C. ; McNichol, Ann P. ; Rosenheim, Brad E. ; Montoya, Joseph P. ; Chanton, Jeffrey P.
    Hydrocarbons released during the Deepwater Horizon (DWH) oil spill weathered due to exposure to oxygen, light, and microbes. During weathering, the hydrocarbons’ reactivity and lability was altered, but it remained identifiable as “petrocarbon” due to its retention of the distinctive isotope signatures (14C and 13C) of petroleum. Relative to the initial estimates of the quantity of oil-residue deposited in Gulf sediments based on 2010–2011 data, the overall coverage and quantity of the fossil carbon on the seafloor has been attenuated. To analyze recovery of oil contaminated deep-sea sediments in the northern Gulf of Mexico we tracked the carbon isotopic composition (13C and 14C, radiocarbon) of bulk sedimentary organic carbon through time at 4 sites. Using ramped pyrolysis/oxidation, we determined the thermochemical stability of sediment organic matter at 5 sites, two of these in time series. There were clear differences between crude oil (which decomposed at a lower temperature during ramped oxidation), natural hydrocarbon seep sediment (decomposing at a higher temperature; Δ14C = -912‰) and our control site (decomposing at a moderate temperature; Δ14C = -189‰), in both the stability (ability to withstand ramped temperatures in oxic conditions) and carbon isotope signatures. We observed recovery toward our control site bulk Δ14C composition at sites further from the wellhead in ~4 years, whereas sites in closer proximity had longer recovery times. The thermographs also indicated temporal changes in the composition of contaminated sediment, with shifts towards higher temperature CO2 evolution over time at a site near the wellhead, and loss of higher temperature CO2 peaks at a more distant site.
  • Preprint
    Quantifying bamboo coral growth rate nonlinearity with the radiocarbon bomb spike : a new model for paleoceanographic chronology development
    ( 2017-04) Frenkel, Megan M. ; LaVigne, Michèle ; Miller, H. R. ; Hill, Tessa M. ; McNichol, Ann P. ; Lardie Gaylord, Mary C.
    Bamboo corals, long-lived cold water gorgonin octocorals, offer unique paleoceanographic archives of the intermediate ocean. These Isididae corals are characterized by alternating gorgonin nodes and high Mg-calcite internodes, which synchronously extend radially. Bamboo coral calcite internodes have been utilized to obtain geochemical proxy data, however, growth rate uncertainty has made it difficult to construct precise chronologies for these corals. Previous studies have relied upon a tie point from records of the anthropogenic Δ14C bomb spike preserved in the gorgonin nodes of live-collected corals to calculate a mean radial extension rate for the outer ~50 years of skeletal growth. Bamboo coral chronologies are typically constructed by applying this mean extension rate to the entire coral record, assuming constant radial extension with coral age. In this study, we aim to test this underlying assumption by analyzing the organic nodes of six California margin bamboo corals at high enough resolution (<0.5 mm) to identify the Δ14C bomb spike, including two tie points at 1957 and 1970, plus coral collection date (2007.5) for four samples. Radial extension rates between tie points ranged from 10 to 204 μm/year, with a decrease in growth rate evident between the 1957-1970 and 1970- 2007.5 periods for all four corals. A negative correlation between growth rate and coral radius (r = -0.7; p = 0.03) was determined for multiple bamboo coral taxa and individuals from the California margin, demonstrating a decline in radial extension rate with specimen age and size. To provide a mechanistic basis for these observations, a simple mathematical model was developed based on the assumption of a constant increase in circular cross sectional area with time to quantify this decline in radial extension rate with coral size between chronological tie points. Applying the area-based model to our Δ14C bomb spike time series from individual corals improves chronology accuracy for all live-collected corals with complete Δ14C bomb spikes. Hence, this study provides paleoceanographers utilizing bamboo corals with a method for reducing age model uncertainty within the anthropogenic bomb spike era (~1957-present). Chronological uncertainty is larger for the earliest portion of coral growth, particularly for skeleton precipitated prior to bomb spike tie points, meaning age estimations for samples living before 1957 remain uncertain. Combining this technique with additional chronological markers could improve age models for an entire bamboo coral. Finally, the relative consistency in growth rate in similarly-aged corals of the same depth and location supports the hypothesis that skeletal growth may be limited by local environmental conditions.
  • Article
    Refractory dissolved organic matter has similar chemical characteristics but different radiocarbon signatures with depth in the marine water column
    (American Geophysical Union, 2023-04-04) White, Margot E. ; Nguyen, Tran B. ; Koester, Irina ; Lardie Gaylord, Mary C. ; Beman, J. Michael ; Smith, Kenneth L. ; McNichol, Ann P. ; Beaupré, Steven R. ; Aluwihare, Lihini I.
    The >5,000‐year radiocarbon age (14C‐age) of much of the 630 ± 30 Pg C oceanic dissolved organic carbon (DOC) reservoir remains an enigma in the marine carbon cycle. The fact that DOC is significantly older than dissolved inorganic carbon at every depth in the ocean forms the basis of our current framing of the marine DOC cycle, where some component persists over multiple cycles of ocean mixing. As a result, 14C‐depleted, aged DOC is hypothesized to be present as a uniform reservoir with a constant 14C signature and concentration throughout the water column. However, key requirements of this model, including direct observations of DOC with similar 14C signatures in the surface and deep ocean, have never been met. Despite decades of research, the distribution of Δ14C values in marine DOC remains a mystery. Here, we applied a thermal fractionation method to compare operationally defined refractory DOC (RDOC) from different depths in the North Pacific Ocean. We found that RDOC shares chemical characteristics (as recorded by OC bond strength) throughout the water column but does not share the same 14C signature. Our results support one part of the current paradigm—that RDOC is comprised of structurally related components throughout the ocean that form a “background” reservoir. However, in contrast to the current paradigm, our results are consistent with a vertical concentration gradient and a vertical and inter‐ocean Δ14C gradient for RDOC. The observed Δ14C gradient is compatible with the potential addition of pre‐aged DOC to the upper ocean.