We have investigated the effects of organic matter (OM) that does not absorb sunlight ("nonchromophoric") on the reactive environment presented by bulk ice and ice surfaces. Fluorescence spectroscopy showed that the presence of as little as 2.5 × 10(-4) M octanol or decanol reduces the extent to which naphthalene self-associates at ice surfaces, which indicates that naphthalene partitions between ice and organic phases present there. We also measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene, pyrene, and phenanthrene in bulk ice and at ice surfaces containing 2.5 × 10(-5) M to 7.5 × 10(-3) M OM. In bulk ice, even the lowest concentrations of OM reduced photolysis kinetics to below our detection limits. Organic matter also reduced measured photolysis kinetics of PAHs at ice surfaces, but generally to a lesser extent than in bulk ice. Our results support previous reports that bulk ice and ice surfaces present distinct reaction environments, and show for the first time that OM can affect PAH photolysis kinetics by altering the physical environment within bulk ice and at ice surfaces.

Ice is an important but poorly understood atmospheric reaction medium. Reactions in ice and at air−ice interfaces are often modeled using rate constants measured in liquid aqueous solution, despite evidence that reactivity in these two media can be very different. This approach may be valid at high ionic strengths (e.g., in sea ice) as a result of the formation of liquid brine. However, recent experiments indicate uneven solute distribution at ice surfaces, suggesting that liquid water does not completely wet ice surfaces at environmentally relevant solute concentrations. We have investigated the distribution of liquid solution, solid ice, and solid salt (NaCl•2H 2 O, "hydrohalite") at the surface of frozen aqueous sodium chloride (NaCl) solutions and frozen seawater using Raman microscopy. At temperatures above the eutectic temperature (−21.1 °C), the ice surfaces were incompletely wetted, except occasionally at the highest temperatures (approximately −5 °C). Liquid water at the surface took the form of either isolated patches or channels, depending upon the salt concentration and sample temperature; liquid fractions ranged from approximately 11 to 85%. Three-dimensional ("volume") maps showed similar liquid fractions and channel widths at all depths investigated (up to 100 μm) as well as at the surface for each sample composition. Below −21.1 °C, no liquid was observed in any sample. Instead, hydrohalite was observed with surface coverages ranging from 13 to 100% depending upon the salt concentration; surface coverage was independent of temperature between −30 and −22 °C. Accounting for the presence of two distinct reaction environments at the surface of salty ice might improve predictions of physical and chemical processes in snow-covered regions.

We report cross-link-tunable, nonlinear optical pattern formation of transmitted light in a photopolymer undergoing free-radical polymerization. Photopolymerization induces microscale filamentation of a uniform, broad transmitted beam, which corresponds to a concurrent spatial evolution in cross-linked morphology in the photopolymer. Because the photopolymerization is permanent, the ensemble of filaments imprint a microstructure comprising a cross-link gradient pattern. Tuning the system's capability to cross-link and branch changes the magnitude of the refractive index change (Δn), which both induces nonlinear conditions and also changes the strength of the optical nonlinearity. Only a monomer with sufficient functionality shows stable optical pattern formation, and its nonlinear regime exists for a specific range of exposure intensities. A monomer of lower functionality can be pushed into the nonlinear regime by formulating it with higher functional monomers, whereby Δn is increased to provide a stronger response to light. In such formulations, the strength of the nonlinearity, as evidenced by changes in light confinement in the optical pattern, is tuned by varying this monomer's functionality or its relative weight fraction. The strong correlation among polymerization-induced refractive index change, optical pattern feature size, and cross-linked morphology demonstrates tunable optical nonlinearity through variations in the inherent polymer structure.

We measured photolysis kinetics of the PAH anthracene in aqueous solution, in bulk ice, and at ice surfaces in the presence and absence of chromophoric dissolved organic matter (CDOM). Self-association, which occurs readily at ice surfaces, may be responsible for the faster anthracene photolysis observed there. Photolysis rate constants in liquid water increased under conditions where anthracene self-association was observed. Concomitantly, kinetics changed from first-order to second-order, indicating that the photolysis mechanism at ice surfaces might be different than that in aqueous solution. Other factors that could lead to faster photolysis at ice surfaces were also investigated. Increased photon fluxes due to scattering in the ice samples can account for at most 20% of the observed rate increase, and other factors including singlet oxygen (O*) production and changes in pH and polarity were determined not to be responsible for the faster photolysis. CDOM (in the form of fulvic acid (FA)) did not affect anthracene photolysis kinetics in aqueous solution but suppressed photolysis in ice cubes and ice granules (by 30% and 56%, respectively). This was primarily due to competitive photon absorption (the inner filter effect). Freeze-concentration (or "salting out") appears to slightly increase the suppressing effects of FA on anthracene photolysis. This may be due to increased competitive photon absorption or to physical interactions between anthracene and FA.

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