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  • fluoride complexation  (2)
  • Calcium carbonate  (1)
  • 1
    Publication Date: 2022-11-06
    Description: Author Posting. © American Geophysical Union, 2022. 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 36(5), (2022): e2022GB007388, https://doi.org/10.1029/2022gb007388.
    Description: The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situ coccolith and foraminiferal calcite dissolution rates. We combine these rates with solid phase fluxes, dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean. The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution rates of all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods) are too slow to explain the patterns of both CaCO3 sinking flux and alkalinity regeneration in the North Pacific. Using a combination of dissolved and solid-phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3 dissolution with a combination of ambient saturation state and oxygen consumption simultaneously explains solid-phase CaCO3 flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. We do not need to invoke the presence of carbonate phases with higher solubilities. Instead, biomineralization and metabolic processes intimately associate the acid (CO2) and the base (CaCO3) in the same particles, driving the coupled shallow remineralization of organic carbon and CaCO3. The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration within degrading particle aggregates. The coupling of these cycles acts as a major filter on the export of both organic and inorganic carbon to the deep ocean.
    Description: This work was funded by NSF OCE-1220301 to W.B., NSF OCE-1220600 to J.F.A., and startup funding for A.V.S.
    Description: 2022-11-06
    Keywords: Calcium carbonate ; Dissolution ; Carbon cycle
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 29 (2000), S. 1089-1099 
    ISSN: 1572-8927
    Keywords: Rare earth elements ; fluoride complexation ; stability constants ; sodium perchlorate ; ionic strength ; lanthanide ; yttrium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Formation constants for the complexation of yttrium and rare earth elements(YREE) by fluoride ions have been measured at 25°C. The ionic strength (μ)dependence of YREE formation constants in perchlorate solution for ionicstrengths between 0 and 6 molar can be expressed aslogFβ1 (M, μ) =logFβ1 o (M) −3.066 μ0.5/(1 + 1.769 μ0.5)+ 0.1645 μwhere logFβ1 o(M) represents MF2+formation constants at zero ionic strength.The logFβ1 o(M) results obtained inthis work are: Y(4.46), La(3.62), Ce(3.86),Pr(3.84), Nd(3.82), Sm(4.15), Eu(4.27), Gd(4.24), Tb(4.37), Dy(4.39), Ho(4.28),Er(4.27), Tm(4.29), Yb(4.39), and Lu(4.25). The relative magnitudes of YREEformation constants are independent of ionic strength. The pattern oflogFβ1(M,μ),formation constants obtained in this work [relative magnitudes oflogFβ1 o (M)],exhibits a shallow minimum between Dy and Yb. In contrast to the smoothpattern of stability constants expected if fluoride were to interact with bare ions(with monotonically decreasing crystal radii between La and Lu), theinteractionof F− with YREEs, which have extensive hydration spheres[M(H2O)8–9 3+] resultsin a relatively complex pattern of lanthanide stability constants. The fluoridecomplexation behavior of yttrium differs distinctly from the behavior of any rareearth. Although the crystal radius of Y3;pl is approximately equalto that of Ho3+,differences in the covalence/ionicity of Y3+ relative to therare earths leads to aYF2+ stability constant that exceeds that of any rare earthelement (REE).
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 22 (1993), S. 751-766 
    ISSN: 1572-8927
    Keywords: Rare earth elements ; fluoride complexation ; stability constant ; solvent exchange ; tributyl phosphate ; sodium perchlorate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Rare earth fluoride stability constants for Ce, Eu, Gd, Tb and Yb at 25°C have been determined by examining the influence of fluoride ions on the distribution of rare earths between tributyl phosphate (TBP) and 0.68M NaClO4. Our results indicate that rare earth mono and difluoro complexation constants show a steady increase as a function of atomic number from La to Tb but remain relatively constant after Dy. This behavior is similar to that which has been observed for dicarboxylic acids. Stepwise stability constant ratios, K2/K1, obtained in our work (where K1=[MF2+][M3+]−1[F−]−1 and K2=[MF 2 + ]−1[MF2+]−1[F−]−1) indicated that, for all rare earths, K2/K1=0.09±0.03.
    Type of Medium: Electronic Resource
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