[1] The fluid permeability k of sea ice constrains a broad range of processes, such as the growth and decay of seasonal ice, the evolution of summer ice albedo, and biomass build-up. Such processes are critical to how sea ice and associated ecosystems respond to climate change. However, studies of k and its dependence on brine porosity f and microstructure are sparse. Here we present a multifaceted theory for k(f) which closely captures laboratory and field data. X-ray computed tomography provides an unprecedented look at the brine phase and its connectivity. We find that sea ice displays universal transport properties remarkably similar to crustal rocks, yet over a much narrower temperature range. Our results yield simple parameterizations for fluid transport in terms of temperature and salinity, and permit more realistic representations of sea ice in global climate and biological models. Citation:

The binding of Na+ to aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), and glutamine (Gln) is examined in detail by studying the collision-induced dissociation (CID) of the four sodiated amino acid complexes with Xe using a guided ion beam tandem mass spectrometer (GIBMS). Analysis of the energy-dependent CID cross sections provides 0 K sodium cation affinities for the complexes after accounting for unimolecular decay rates, internal energy of the reactant ions, and multiple ion-molecule collisions. Quantum chemical calculations for a number of geometric conformations of each Na+(L) complex are determined at the B3LYP/6-311+G(d,p) level with single-point energies calculated at MP2(full), B3LYP, and B3P86 levels using a 6-311+G(2d,2p) basis set. This coordinated examination of both experimental work and quantum chemical calculations allows the energetic contributions of individual functionalities as well as steric influences of relative chain lengths to be thoroughly explored. Na+ binding affinities for the amide complexes are systematically stronger than those for the acid complexes by 14 +/- 1 kJ/mol, which is attributed to an inductive effect of the OH group in the carboxylic acid side chain. Additionally, the Na+ binding affinity for the longer-chain amino acids (Glx) is enhanced by 4 +/- 1 kJ/mol compared to the shorter-chain Asx because steric effects are reduced.

The binding of K(+) to aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), and glutamine (Gln) is examined in detail by studying the collision-induced dissociation (CID) of the four potassium cation-bound amino acid complexes with Xe using a guided ion beam tandem mass spectrometer (GIBMS). Formed by electrospray ionization, these complexes have energy-dependent CID cross sections that are analyzed to provide 0 K bond energies after accounting for unimolecular decay rates, internal energy of reactant ions, and multiple ion-molecule collisions. Quantum chemical calculations for a number of geometric conformations of each K(+)(L) complex are determined at the B3LYP/6-311+G(d,p) level with single-point energies calculated at B3LYP, B3P86, and MP2(full) levels using a 6-311+G(2d,2p) basis set. Theoretical bond dissociation energies are in good agreement with the experimental values. This coordinated examination of both experimental work and quantum chemical calculations allows for a comprehensive understanding of the molecular interactions of K(+) with the Asx and Glx amino acids. K(+) binding affinities for the amide complexes are systematically stronger than those for the acid complexes by 9+/-1 kJ/mol, which is attributed to an inductive effect of the OH group in the carboxylic acid side chain. Additionally, the K(+) binding affinity for the longer-chain amino acids (Glx) is enhanced by 5+/-1 kJ/mol compared to the shorter-chain Asx because steric effects are reduced. Further, a detailed comparison between experimental and theoretical results reveals interesting differences in the binding of K(+) and Na(+) to these amino acids.

The interactions of rubidium cations with the four amino acids (AA), glycine (Gly), serine (Ser), threonine (Thr), and proline (Pro), are examined in detail. Experimentally, the bond energies are determined using threshold collision-induced dissociation of the Rb(+)(AA) complexes with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy dependent cross sections include consideration of unimolecular decay rates, internal energy of reactant ions, and multiple ion-molecule collisions. 0 K bond energies of 108.9 +/- 7.0, 115.7 +/- 4.9, 122.1 +/- 4.6, and 125.2 +/- 4.5 kJ/mol are determined for complexes of Rb(+) with Gly, Ser, Thr, and Pro, respectively. Quantum chemical calculations are conducted at the B3LYP, B3P86, and MP2(full) levels of theory with geometries and zero point energies calculated at the B3LYP level using both HW*/6-311+G(2d,2p) and Def2TZVP basis sets. Results obtained using the former basis sets are systematically low compared to the experimental bond energies, whereas the latter basis sets show good agreement. For Rb(+)(Gly), the ground state conformer has the rubidium ion binding to the carbonyl group of the carboxylic acid, and a similar geometry is found for Rb(+)(Pro) except the secondary nitrogen accepts the carboxylic acid hydrogen to form the zwitterionic structure. Both Rb(+)(Ser) and Rb(+)(Thr) are found to have tridentate binding at the B3LYP and MP2(full) levels, whereas the B3P86 slightly prefers binding Rb(+) at the carboxylic acid. Comparison of these results to those for the lighter alkali ions provides insight into the trends in binding affinities and structures associated with metal cation variations.

Gas-phase structures of cationized asparagine (Asn) including complexes with Li(+), Na(+), K(+), Rb(+), Cs(+), and Ba(2+), as well as protonated Asn, are examined by infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light generated by a free electron laser. Experimental spectra for the alkali metal cation complexes exhibit systematic trends, whereas spectra for Ba(2+)(Asn) and H(+)(Asn) are more distinct. To identify the structures formed experimentally, measured IRMPD spectra are compared to spectra calculated at a B3LYP/6-311+G(d,p) level with several effective core potentials and basis sets evaluated for the heavy metal systems. The dominant conformation ascertained for complexes with the smaller metal cations, Li(+)(Asn) and Na(+)(Asn), is a charge-solvated, tridentate [N,CO,CO] structure that binds the metal cation with the amine group of the amino acid backbone and to the carbonyl oxygen atoms of the backbone and amino acid side chain. For the larger alkali metal cation complexes, K(+)(Asn), Rb(+)(Asn), and Cs(+)(Asn), an additional charge-solvated, tridentate [COOH,CO] structure that binds the metal cation with the two oxygen atoms of the backbone carboxylic acid group and the carbonyl oxygen atom of the Asn side chain may also be present. The Ba(2+)(Asn) spectrum is characteristic of a single charge-solvated [N,CO,CO] conformation, in contrast to Gly, Trp, Arg, Gln, Pro, Ser, Val, and Glu, which all take on a zwitterionic structure when complexed to Ba(2+). In no case do the cationized Asn complexes show definitive evidence of forming a zwitterionic structure in the complexes studied here. For H(+)(Asn), a mixture of two [N,CO] structures, which differ only in the orientation the side chain and are calculated to be nearly identical in energy, explains the experimental spectrum well.