Snowpack-stored atmospheric surface-active contaminants traced with snowmelt water surface film rheology

The aim of the study was to quantify the adsorptive and thermo-elastic properties of snowmelt water surface films and their spatial-temporal evolution with snowpack structure characteristics and the entrapped surface-active organic composition. Surface pressure–area (π-A)(T) isotherms, surface pressure-temperature (π-T)(A) isochors, and stress–relaxation (π-t) measurements were performed using a Langmuir trough system on snowmelt water samples collected in a large-scale field studies performed at several industrialized and rural Tricity (Gdansk, Poland) areas at various environmental conditions and subsequent stages of the snowpack melting progress. Since the snow-melted water composition and concentrations of surface active organic matter fractions therein are largely undetermined, the force-area isotherm scaling formalisms (2D virial equation and 2D film scaling theory of polymeric films) were adapted to the complex mixture of surfactants. The surface film parameters and their spatial and temporal evolution turned out to be unequivocally related to principal signatures of the film-forming materials: surfactant concentrations (π, A(lim)), surface activity (E(isoth), |E|), film material solubility (R), surface material miscibility and 2D architecture complexity (y, β(s)), molecular thermal mobility (π(k)), and a timescale of the relaxation processes within the film (τ(i), |E|). Moreover, the parameters appeared to be correlated with snowpack structure characteristics (snow density ρ, specific snow area SSA, snow cover thickness), sample age time, and anthropogenic atmospheric contamination pressure source locations. In particular, E(isoth) was found to be related to ρ and SSA, while R correlated with the solubility of film-forming organics which turned out to be long-chain fatty acids; similarly, spatial profiles of E(isoth) revealed the peak values next to the areas being under a severe anthropogenic air pollution pressure. Snowmelt water films stand for a structurally heterogeneous (y > 10) interfacial system where several transition processes of differentiated time-scales (relaxation times from 7 to 63 s) took place leading to the apparent surface viscoelasticity. To sum up, the established surface rheological parameters could serve as novel indicators, based solely on physical attributes, allowing to follow the snowpack evolution, and its melting polymorphism in order to test or improve the existing snow-entrapped organics release models based on chemical analyses. The cross-correlation functional dependences of practical value remain to be established on the larger data set.