Black carbon footprint of human presence in Antarctica.

Black carbon (BC) from fossil fuel and biomass combustion darkens the snow and makes it melt sooner. The BC footprint of research activities and tourism in Antarctica has likely increased as human presence in the continent has surged in recent decades. Here, we report on measurements of the BC concentration in snow samples from 28 sites across a transect of about 2,000 km from the northern tip of Antarctica (62°S) to the southern Ellsworth Mountains (79°S). Our surveys show that BC content in snow surrounding research facilities and popular shore tourist-landing sites is considerably above background levels measured elsewhere in the continent. The resulting radiative forcing is accelerating snow melting and shrinking the snowpack on BC-impacted areas on the Antarctic Peninsula and associated archipelagos by up to 23 mm water equivalent (w.e.) every summer.

Contaminant emissions as indicators of chemical elements in the snow along a latitudinal gradient in southern Andes.

The chemical composition of snow provides insights on atmospheric transport of anthropogenic contaminants at different spatial scales. In this study, we assess how human activities influence the concentration of elements in the Andean mountain snow along a latitudinal transect throughout Chile. The concentration of seven elements (Al, Cu, Fe, Li, Mg, Mn and Zn) was associated to gaseous and particulate contaminants emitted at different spatial scales. Our results indicate carbon monoxide (CO) averaged at 20 km and nitrogen oxide (NOx) at 40 km as the main indicators of the chemical elements analyzed. CO was found to be a significant predictor of most element concentrations while concentrations of Cu, Mn, Mg and Zn were positively associated to emissions of NOx. Emission of 2.5 µm and 10 µm particulate matter averaged at different spatial scales was positively associated to concentration of Li. Finally, the concentration of Zn was positively associated to volatile organic compounds (VOC) averaged at 40 km around sampling sites. The association between air contaminants and chemical composition of snow suggests that regions with intensive anthropogenic pollution face reduced quality of freshwater originated from glacier and snow melting.

Elemental and Mineralogical Composition of the Western Andean Snow (18°S-41°S).

The snowpack is an important source of water for many Andean communities. Because of its importance, elemental and mineralogical composition analysis of the Andean snow is a worthwhile effort. In this study, we conducted a chemical composition analysis (major and trace elements, mineralogy, and chemical enrichment) of surface snow sampled at 21 sites across a transect of about 2,500 km in the Chilean Andes (18-41°S). Our results enabled us to identify five depositional environments: (i) sites 1-3 (in the Atacama Desert, 18-26°S) with relatively high concentrations of metals, high abundance of quartz and low presence of arsenates, (ii) sites 4-8 (in northern Chile, 29-32°S) with relatively high abundance of quartz and low presence of metals and arsenates, (iii) sites 9-12 (in central Chile, 33-35°S) with anthropogenic enrichment of metals, relatively high values of quartz and low abundance of arsenates, (iv) sites 13-14 (also in central Chile, 35-37°S) with relatively high values of quartz and low presence of metals and arsenates, and v) sites 15-21 (in southern Chile, 37-41°S) with relatively high abundance of arsenates and low presence of metals and quartz. We found significant anthropogenic enrichment at sites close to Santiago (a major city of 6 million inhabitants) and in the Atacama Desert (that hosts several major copper mines).

Black carbon and other light-absorbing impurities in snow in the Chilean Andes.

Vertical profiles of black carbon (BC) and other light-absorbing impurities were measured in seasonal snow and permanent snowfields in the Chilean Andes during Austral winters 2015 and 2016, at 22 sites between latitudes 18°S and 41°S. The samples were analyzed for spectrally-resolved visible light absorption. For surface snow, the average mass mixing ratio of BC was 15 ng/g in northern Chile (18-33°S), 28 ng/g near Santiago (a major city near latitude 33°S, where urban pollution plays a significant role), and 13 ng/g in southern Chile (33-41°S). The regional average vertically-integrated loading of BC was 207 µg/m2 in the north, 780 µg/m2 near Santiago, and 2500 µg/m2 in the south, where the snow season was longer and the snow was deeper. For samples collected at locations where there had been no new snowfall for a week or more, the BC concentration in surface snow was high (~10-100 ng/g) and the sub-surface snow was comparatively clean, indicating the dominance of dry deposition of BC. Mean albedo reductions due to light-absorbing impurities were 0.0150, 0.0160, and 0.0077 for snow grain radii of 100 µm for northern Chile, the region near Santiago, and southern Chile; respective mean radiative forcings for the winter months were 2.8, 1.4, and 0.6 W/m2. In northern Chile, our measurements indicate that light-absorption by impurities in snow was dominated by dust rather than BC.

Mechanism of anisotropic surface self-diffusivity at the prismatic ice-vapor interface.

Predictive theoretical models for mesoscopic roughening of ice require improved understanding of attachment kinetics occurring at the ice-vapor interface. Here, we use classical molecular dynamics to explore the generality and mechanics of a transition from anisotropic to isotropic self-diffusivity on exposed prismatic surfaces. We find that self-diffusion parallel to the crystallographic a-axis is favored over the c-axis at sub-melt temperatures below about -35 °C, for three different representations of the water-water intermolecular potential. In the low-temperature anisotropic regime, diffusion results from interstitial admolecules encountering entropically distinct barriers to diffusion in the two in-plane directions. At higher temperatures, isotropic self-diffusion occurring deeper within the quasi-liquid layer becomes the dominant mechanism, owing to its larger energy of activation.

Arrhenius analysis of anisotropic surface self-diffusion on the prismatic facet of ice.

We present an Arrhenius analysis of self-diffusion on the prismatic surface of ice calculated from molecular dynamics simulations. The six-site water model of Nada and van der Eerden was used in combination with a structure-based criterion for determining the number of liquid-like molecules in the quasi-liquid layer. Simulated temperatures range from 230 K-287 K, the latter being just below the melting temperature of the model, 289 K. Calculated surface diffusion coefficients agree with available experimental data to within quoted precision. Our results indicate a positive Arrhenius curvature, implying a change in the mechanism of self-diffusion from low to high temperature, with a concomitant increase in energy of activation from 29.1 kJ mol(-1) at low temperature to 53.8 kJ mol(-1) close to the melting point. In addition, we find that the surface self-diffusion is anisotropic at lower temperatures, transitioning to isotropic in the temperature range of 240-250 K. We also present a framework for self-diffusion in the quasi-liquid layer on ice that aims to explain these observations.

A responsivity-based criterion for accurate calibration of FTIR emission spectra: identification of in-band low-responsivity wavenumbers.

Spectra measured by remote-sensing Fourier transform infrared spectrometers are often calibrated using two calibration sources. At wavenumbers where the absorption coefficient is large, air within the optical path of the instrument can absorb most calibration-source signal, resulting in extreme errors. In this paper, a criterion in terms of the instrument responsivity is used to identify such wavenumbers within the instrument bandwidth of two remote-sensing Fourier transform infrared spectrometers. Wavenumbers identified by the criterion are found to be correlated with strong absorption line-centers of water vapor. Advantages of using a responsivity-based criterion are demonstrated.

Comparative molecular dynamics study of vapor-exposed basal, prismatic, and pyramidal surfaces of ice.

We present the results of molecular dynamics simulations in which ice I(h) slabs with free basal, prismatic, 28° pyramidal, and 14° pyramidal facets are exposed to vapor. All simulations were carried out at 250 K using a six-site intermolecular potential. Characteristics common to all facets include spontaneous development of a quasi-liquid layer (QLL) within ∼10 ns and QLL stratification into outer (ε(1)) and inner (ε(2)) sublayers having on average two and three hydrogen bonds, respectively. Vapor pressure, based on the rate of escape of molecules from the QLL to the vapor phase, is found to be greatest for the 14° pyramidal and basal facets (∼230 Pa), while significantly lower values are obtained for the prismatic and 28° pyramidal facets (∼200 Pa). The geometric thickness of the QLL also varies between facets, with the 14° pyramidal having the greatest thickness. The free prismatic and pyramidal facets exhibit significant anisotropic diffusivity, in-plane motion being faster in the trans-prismatic direction than in the basal-to-basal direction. The in-plane diffusion length is greatest for the 28° pyramidal facet and smallest for the prismatic facet. This diversity of facet-specific properties provides a rich set of possibilities for mechanisms of ice crystal growth and ablation.

Responsivity-based criterion for accurate calibration of FTIR emission spectra: theoretical development and bandwidth estimation.

An analytical expression for the variance of the radiance measured by Fourier-transform infrared (FTIR) emission spectrometers exists only in the limit of low noise. Outside this limit, the variance needs to be calculated numerically. In addition, a criterion for low noise is needed to identify properly calibrated radiances and optimize the instrument bandwidth. In this work, the variance and the magnitude of a noise-dependent spectral bias are calculated as a function of the system responsivity (r) and the noise level in its estimate (σr). The criterion σr/r<0.3, applied to downwelling and upwelling FTIR emission spectra, shows that the instrument bandwidth is specified properly for one instrument but needs to be restricted for another.