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  • 1
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    PANGAEA
    In:  Supplement to: Hermoso, Michael; Chan, I Z X; McClelland, H L O; Heureux, AMC; Rickaby, Rosalind E M (2016): Vanishing coccolith vital effects with alleviated carbon limitation. Biogeosciences, 13(1), 301-312, https://doi.org/10.5194/bg-13-301-2016
    Publication Date: 2024-03-15
    Description: By recreating a range of geologically relevant concentrations of dissolved inorganic carbon (DIC) in the laboratory, we demonstrate that the magnitude of the vital effects in both carbon and oxygen isotopes of coccolith calcite of multiple species relates to ambient DIC concentration. Under high DIC levels, all the examined coccoliths exhibit significantly reduced isotopic offsets from inorganic calcite compared to the substantial vital effects expressed at low (preindustrial and present-day) DIC concentrations. The supply of carbon to the cell exerts a primary control on biological fractionation in coccolith calcite via the modulation of coccolithophore growth rate, cell size and carbon utilisation by photosynthesis and calcification, altogether accounting for the observed interspecific differences between coccolith species. These laboratory observations support the recent hypothesis from field observations that the appearance of interspecific vital effect in coccolithophores coincides with the long-term Neogene decline of atmospheric CO2 concentrations and bring further valuable constraints by demonstrating a convergence of all examined species towards inorganic values at high pCO2 regimes. This study provides palaeoceanographers with a biogeochemical framework that can be utilised to further develop the use of calcareous nannofossils in palaeoceanography to derive sea surface temperature and pCO2 levels, especially during periods of relatively elevated pCO2 concentrations, as they prevailed during most of the Meso-Cenozoic.
    Keywords: Alkalinity, total; Aragonite saturation state; Bicarbonate ion; Biomass/Abundance/Elemental composition; Bottles or small containers/Aquaria (〈20 L); Calcidiscus leptoporus; Calcite saturation state; Calculated using seacarb after Nisumaa et al. (2010); Carbon, inorganic, dissolved; Carbonate ion; Carbonate system computation flag; Carbon dioxide; Chromista; Coccolithus pelagicus; Coccosphere, diameter; Emiliania huxleyi; Fugacity of carbon dioxide (water) at sea surface temperature (wet air); Growth/Morphology; Growth rate; Haptophyta; Laboratory experiment; Laboratory strains; North Atlantic; OA-ICC; Ocean Acidification International Coordination Centre; Partial pressure of carbon dioxide (water) at sea surface temperature (wet air); Pelagos; pH; Phytoplankton; Pleurochrysis placolithoides; Potentiometric titration; Registration number of species; Salinity; Single species; Species; Temperature, water; Type; Uniform resource locator/link to reference; Δδ13C; Δδ18O; δ13C; δ13C, calcite; δ18O, calcite; δ18O, water
    Type: Dataset
    Format: text/tab-separated-values, 1479 data points
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 89 (1985), S. 463-465 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 86 (1982), S. 2428-2431 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 74 (1993), S. 4259-4261 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Superconducting TlSr2(Ca,Cr)Cu2O7 thin films with zero resistance temperature Tc up to 102 K and critical current density Jc as high as 106 A/cm2 at 77.7 K have been successfully prepared via laser ablation and thallium diffusion. Prolonged low temperature annealing in air was used for film processing. X-ray diffraction patterns indicated that the films were highly oriented 1212 phase with c axes normal to the LaAlO3(100) or MgO(100) substrates.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 929-936 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have conducted optically detected magnetic resonance (ODMR) experiments at pressure up to 40 kbar for neat biactyl (BA), neat benzil (BZ), and acetophenone (AP) doped in dibromobenzene (DBB). The pressure dependences of their zero-field splitting (ZFS) parameters D and E are reported. For BA and BZ systems, the ||D|| value decreases greatly with increasing pressure. This behavior is in contrast with that of benzophenone (BP), whose ||D|| value increases sigmoidally 13% over the same pressure range. These results may be rationalized in a qualitative theory based on pressure modulation of the spin-orbit coupling (SOC) contribution to the ZFS. ln aromatic ketones, lattice compression modifies the twist angle of the phenyl ring(s) relative to the carbonyl frame, thus changing the energy of the 3ππ* state relative to that of the 3nπ* state. This variation of the energy denominator in a second order perturbation enhances the SOC contribution to the ZFS. In comparison, the increase of spin–spin (SS) dipolar interaction by isotropic compression is relatively unimportant. Consistent with this picture, the very small 3ππ*–3nπ* energy gap produces an enormous pressure sensitivity of D and E in AP/DBB. The behavior of the ZFS in this case may be interpreted as a consequence of pressure tuning of the 3ππ* state through an anticrossing region. In addition, a new set of high frequency ODMR signals appears under pressure. This is attributed to a new site of AP having the 3nπ* as the phosphorescent triplet state. The pressure dependence of ZFS for benzil shows complicated fine structure. This is a testimony to the flexible nature of benzil in both the dihedral angle of the dicarbonyl fragment and the phenyl twist angle.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 7067-7073 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Optically detected two-pulse and three-pulse echo experiments have been performed under pressure to 50 kbar using a diamond anvil cell. In this paper we report the results on excited triplet neat biacetyl (BA) and BA-d6. Three-pulse echoes are easier to perform, and coherence has been maintained for durations longer than one triplet lifetime. In contrast, the two-pulse echo technique is prone to have spurious contributions, and it is besieged by the envelope modulation effect for BA-d6. Our data point to the importance of spectral diffusion caused by the bulk nuclei. Their flip–flop motion creates a fluctuating magnetic field on the triplet spin, destroying its coherence. As pressure increases, an increase in number density of such nuclei shortens the phase memory time (TM). A plot of TM vs relative volume produces a linear correlation. Our three-pulse echo lifetime shows a 40% increase from BA-h6 to BA-d6. This very small deuteration effect might suggest that electronic flip–flop, rather than nuclear spin flip–flop, is the dominant relaxing mode. However, a study of TM on different exciting light levels disproves this mechanism.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5591-5599 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report optically detected magnetic resonance (ODMR) experiments at pressures up to 40 kbar for p-benzoquinone (BQ) in dibromobenzene (DBB) and for a deep x-trap in a BQ-d4 neat crystal. It is known from previous works that the phosphorescent triplet state (3B1g) of these systems is vibronically coupled to a nearby 3Au state, such that the former exhibits a double-minimum potential well. The zero-field splitting (ZFS) parameter D of both systems changes by several gigahertz over our pressure range. The greatest slope occurs at zero pressure, and the rate of change slows down exponentially at higher pressure. In addition, we observed a phase transition in BQ-d4 crystals at 6 kbar, which causes a huge step-discontinuity in both D and E. In contrast to the enormous change in D, the E-value is not sensitive to pressure except for the step-change during the phase transition. Triplet state kinetics and phosphorescence spectra are used to establish the existence of an in-plane distortion at least in the high-pressure phase. A model is proposed to interpret these results based on the pressure-dependent vibronic interaction, leading to a reduction of the spin–orbit coupling contribution to the ZFS.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5852-5853 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3877-3883 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Optically detected magnetic resonance experiments have been conducted at pressure up to 45 kbar for p-dichlorobenzene (DCB), s-tetrachlorobenzene (TCB) and quinoxaline (Q). The pressure dependence of their zero-field splitting parameters and, for DCB, the quadrupolar splitting are reported. For all three systems the D value decreases moderately with increasing pressure. The slope for TCB is approximately twice that for DCB. These results are interpreted in terms of pressure dependence of the mesomeric effect and the inductive effect of the substituents on the aromatic triplet state. For Q, the influence of pressure on spin-orbit interaction is also suggested.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 6284-6290 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the effect of pressure on the photoinitiated hydrogen transfer reaction in a mixed crystal of acridine in fluorene. Upon excitation to its triplet state, the aza-atom of acridine abstracts a hydrogen atom from the methylene bridge of fluorene. The reaction rate constant for both the hydro- and deutero- (methylenic) species has been measured as a function of pressure. For both species, the room temperature transfer rate increases exponentially with increasing pressure. Furthermore, the rate of change is the same for the two isotopic species. At 77 K, the H-transfer rate again increases exponentially, but with a smaller slope. In contrast, the D-transfer rate remains too small to affect the precursor triplet lifetime which hardly changes over a pressure range of 36 kbar. The H-transfer rate was also measured as a function of temperature for a few higher pressures. A temperature independent regime is observed at low temperature. This limiting low temperature rate increases with pressure and reflects the tunneling rate from the vibrational ground state. At ambient pressure it was too small to be accessible to measurements. High pressure allows the direct determination of this ground state tunneling rate. The implications of our observations in the tunneling mechanism are discussed.
    Type of Medium: Electronic Resource
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