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  • Adsorption  (1)
  • Reversible Exchange  (1)
  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Marine Chemistry 170 (2015): 49-60, doi:10.1016/j.marchem.2015.01.006.
    Description: The natural radionuclides 231Pa and 230Th are incorporated into the marine sediment record by scavenging, or adsorption to various particle types, via chemical reactions that are not fully understood. Because these isotopes have potential value in tracing several oceanographic processes, we investigate the nature of scavenging using trans-Atlantic measurements of dissolved (〈0.45 μm) and particulate (0.8-51 μm) 231Pa and 230Th, together with major particle composition. We find widespread impact of intense scavenging by authigenic Fe/Mn (hydr)oxides, in the form of hydrothermal particles emanating from the Mid-Atlantic ridge and particles resuspended from reducing conditions near the seafloor off the coast of West Africa. Biogenic opal was not found to be a significant scavenging phase for either element in this sample set, essentially because of its low abundance and small dynamic range at the studied sites. Distribution coefficients in shallow (〈 200 m) depths are anomalously low which suggests either the unexpected result of a low scavenging intensity for organic matter or that, in water masses containing abundant organic-rich particles, a greater percentage of radionuclides exist in the colloidal or complexed phase. In addition to particle concentration, the oceanic distribution of particle types likely plays a significant role in the ultimate distribution of sedimentary 230Th and 231Pa.
    Description: Cruise management for GA03 was funded by the U. S. National Science Foundation to W. Jenkins (OCE-0926423), E. Boyle (OCE-0926204), and G. Cutter (OCE-0926092). Radionuclide studies were supported by NSF (OCE-0927064 to LDEO, OCE-0926860 to WHOI, OCE- 0927757 to URI, and OCE-0927754 to UMN). Additional support came from the European Research Council (278705) to LFR and the Ford Foundation Predoctoral Fellowship to SMV. Particle studies were supported by NSF OCE-0963026 to PJL.
    Keywords: GEOTRACES ; Suspended particulate matter ; Adsorption ; Radioactive tracers ; Trace elements
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
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  • 2
    Publication Date: 2022-05-26
    Description: © The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Deep Sea Research Part I: Oceanographic Research Papers 113 (2016): 57-79, doi:10.1016/j.dsr.2016.03.008.
    Description: Thorium is a highly particle-reactive element that possesses different measurable radio-isotopes in seawater, with well-constrained production rates and very distinct half-lives. As a result, Th has emerged as a key tracer for the cycling of marine particles and of their chemical constituents, including particulate organic carbon. Here two different versions of a model of Th and particle cycling in the ocean are tested using an unprecedented data set from station GT11-22 of the U.S. GEOTRACES North Atlantic Section: (i) 21 228;230;234Th activities of dissolved and particulate fractions, (ii) 228Ra activities, (iii) 234;238U activities estimated from salinity data and an assumed 234U/238U ratio, and (iv) particle concentrations, below a depth of 125 m. The two model versions assume a single class of particles but rely on different assumptions about the rate parameters for sorption reactions and particle processes: a first version (V1) assumes vertically uniform parameters (a popular description), whereas the second (V2) does not. Both versions are tested by fitting to the GT11-22 data using generalized nonlinear least squares and by analyzing residuals normalized to the data errors. We find that model V2 displays a significantly better fit to the data than model V1. Thus, the mere allowance of vertical variations in the rate parameters can lead to a significantly better fit to the data, without the need to modify the structure or add any new processes to the model. To understand how the better fit is achieved we consider two parameters, K = k1=(k-1 + β-1) and K/P, where k1 is the adsorption rate constant, k-1 the desorption rate constant, β-1 the remineralization rate constant, and P the particle concentration. We find that the rate constant ratio K is large (≥0.2) in the upper 1000 m and decreases to a nearly uniform value of ca. 0.12 below 2000 m, implying that the specific rate at which Th attaches to particles relative to that at which it is released from particles is higher in the upper ocean than in the deep ocean. In contrast, K/P increases with depth below 500 m. The parameters K and K/P display significant positive and negative monotonic relationship with P, respectively, which is collectively consistent with a particle concentration effect.
    Description: We acknowledge the U.S. National Science Foundation for providing funding for this study (grant OCE-1232578) and for U.S. GEOTRACES North Atlantic section ship time, sampling, and data analysis.
    Description: 2017-03-31
    Keywords: GEOTRACES ; North Atlantic ; Thorium ; Particles ; Reversible Exchange ; Model ; Inverse Method
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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