79 research outputs found
Ion size effects at ionic exclusion from dielectric interfaces and slit nanopores
A previously developed field-theoretic model [R.D. Coalson et al., J. Chem.
Phys. 102, 4584 (1995)] that treats core collisions and Coulomb interactions on
the same footing is investigated in order to understand ion size effects on the
partition of neutral and charged particles at planar interfaces and the ionic
selectivity of slit nanopores. We introduce a variational scheme that can go
beyond the mean-field (MF) regime and couple in a consistent way pore modified
core interactions, steric effects, electrostatic solvation and image-charge
forces, and surface charge induced electrostatic potential. We show that in the
dilute limit, the MF and the variational theories agree well with MC simulation
results, in contrast to a recent RPA method. The partition of charged Yukawa
particles at a neutral dielectric interface (e.g air-water or protein-water
interface) is investigated. It is shown that as a result of the competition
between core collisions that push the ions towards the surface, and repulsive
solvation and image forces that exclude them from the interface, a
concentration peak of finite size ions sets in close to the dielectric
interface. We also characterize the role played by the ion size on the ionic
selectivity of neutral slit nanopores. We show that the complex interplay
between electrostatic forces, excluded volume effects induced by core
collisions and steric effects leads to an unexpected reversal in the ionic
selectivity of the pore with varying pore size: while large pores exhibits a
higher conductivity for large ions, narrow pores exclude large ions more
efficiently than small ones
Long-ranged attraction between disordered heterogeneous surfaces
Long-ranged attractions across water between two surfaces that are randomly
covered with (mobile) positive and negative charge domains have been attributed
to induced correlation of the charges (positive lining up with negative) as the
surfaces approach. Here we show, by directly measuring normal forces under a
rapid shear field, that these attractions may not in fact be due to such
correlations. It is rather the inherent interaction-asymmetry between equally-
and between oppositely-charged domains that results in the long-ranged
attraction even in the complete absence of any charge correlation
Changing atmospheric CO2 concentration was the primary driver of early Cenozoic climate
The Early Eocene Climate Optimum (EECO, which occurred about 51 to 53 million years ago)1, was the warmest interval of the past 65 million years, with mean annual surface air temperature over ten degrees Celsius warmer than during the pre-industrial period2–4. Subsequent global cooling in the middle and late Eocene epoch, especially at high latitudes, eventually led to continental ice sheet development in Antarctica in the early Oligocene epoch (about 33.6 million years ago). However, existing estimates place atmospheric carbon dioxide (CO2) levels during the Eocene at 500–3,000 parts per million5–7, and in the absence of tighter constraints carbon–climate interactions over this interval remain uncertain. Here we use recent analytical and methodological developments8–11 to generate a new high-fidelity record of CO2 concentrations using the boron isotope (δ11Β) composition of well preserved planktonic foraminifera from the Tanzania Drilling Project, revising previous estimates6. Although species-level uncertainties make absolute values difficult to constrain, CO2 concentrations during the EECO were around 1,400 parts per million. The relative decline in CO2 concentration through the Eocene is more robustly constrained at about fifty per cent, with a further decline into the Oligocene12. Provided the latitudinal dependency of sea surface temperature change for a given climate forcing in the Eocene was similar to that of the late Quaternary period13, this CO2 decline was sufficient to drive the well documented high- and low-latitude cooling that occurred through the Eocene14. Once the change in global temperature between the pre-industrial period and the Eocene caused by the action of all known slow feedbacks (apart from those associated with the carbon cycle) is removed2–4, both the EECO and the late Eocene exhibit an equilibrium climate sensitivity relative to the pre-industrial period of 2.1 to 4.6 degrees Celsius per CO2 doubling (66 per cent confidence), which is similar to the canonical range (1.5 to 4.5 degrees Celsius15), indicating that a large fraction of the warmth of the early Eocene greenhouse was driven by increased CO2 concentrations, and that climate sensitivity was relatively constant throughout this period
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