Air-ice Interface Research Articles

Multiscale modeling of heat and mass transfer in dry snow: influence of the condensation coefficient and comparison with experiments

Abstract. Temperature gradient metamorphism in dry snow is driven by heat and water vapor transfer through snow, which includes conduction/diffusion processes in both air and ice phases, as well as sublimation and deposition at the ice–air interface. The latter processes are driven by the condensation coefficient α, a poorly constrained parameter in the literature. In the present paper, we use an upscaling method to derive heat and mass transfer models at the snow layer scale for values of α in the range 10−10 to 1. A transition α value arises, of the order of 10−4, for typical snow microstructures (characteristic length ∼ 0.5 mm), such that the vapor transport is limited by sublimation–deposition below that value and by diffusion above it. Accordingly, different macroscopic models with specific domains of validity with respect to α values are derived. A comprehensive evaluation of the models is presented by comparison with three experimental datasets, as well as with pore-scale simulations using a simplified microstructure. The models reproduce the two main features of the experiments: the non-linear temperature profiles, with enhanced values in the center of the snow layer, and the mass transfer, with an abrupt basal mass loss. However, both features are underestimated overall by the models when compared to the experimental data. We investigate possible causes of these discrepancies and suggest potential improvements for the modeling of heat and mass transport in dry snow.

Analytical solutions for the advective–diffusive ice column in the presence of strain heating

Abstract. A thorough understanding of ice thermodynamics is essential for an accurate description of glaciers, ice sheets and ice shelves. Yet there exists a significant gap in our theoretical knowledge of the time-dependent behaviour of ice temperatures due to the inevitable compromise between mathematical tractability and the accurate description of physical phenomena. In order to bridge this shortfall, we have analytically solved the 1D time-dependent advective–diffusive heat problem including additional terms due to strain heating and depth-integrated horizontal advection. Newton's law of cooling is applied as a Robin-type top boundary condition to consider potential non-equilibrium temperature states across the ice–air interface. The solution is expressed in terms of confluent hypergeometric functions following a separation of variables approach. Non-dimensionalization reduces the parameter space to four numbers that fully determine the shape of the solution at equilibrium: surface insulation, effective geothermal heat flow, the Péclet number and the Brinkman number. The initial temperature distribution exponentially converges to the stationary solution. Transient decay timescales are only dependent on the Péclet number and the surface insulation, so higher advection rates and lower insulating values imply shorter equilibration timescales, respectively. In contrast, equilibrium temperature profiles are mostly independent of the surface insulation parameter. We have extended our study to a broader range of vertical velocities by using a general power-law dependence on depth, unlike prior studies limited to linear and quadratic velocity profiles. Lastly, we present a suite of benchmark experiments to test numerical solvers. Four experiments of gradually increasing complexity capture the main physical processes for heat propagation. Analytical solutions are then compared to their numerical counterparts upon discretization over unevenly spaced coordinate systems. We find that a symmetric scheme for the advective term and a three-point asymmetric scheme for the basal boundary condition best match our analytical solutions. A further convergence study shows that n≥15 vertical points are sufficient to accurately reproduce the temperature profile. The solutions presented herein are general and fully applicable to any problem with an equivalent set of boundary conditions and any given initial temperature distribution.

Methane pumping by rapidly refreezing lead ice in the ice-covered Arctic Ocean

If and how the sea ice cycle drives the methane cycle in the high Arctic is an open question and crucial to improving source/sink balances. This study presents new insights into the effects of strong and fast freezing on the physical–chemical properties of ice and offers implications for methane fluxes into and out of newly formed lead ice. During the 2019–2020 transpolar drift of the Multidisciplinary Drifting Observatory for the Study of Arctic Climate (MOSAiC), we took weekly samples of growing lead ice and underlying seawater at the same site between January and March 2020. We analyzed concentrations and stable carbon isotopic signatures (δ13C–CH4) of methane and calculated methane solubility capacities (MSC) and saturation levels in both environments. During the first month, intense cooling resulted in the growth of two-thirds of the final ice thickness. In the second month, ice growth speed decreased by 50%. Both growth phases, disentangled, exposed different freeze impacts on methane pathways. The fast freeze caused strong brine entrapment, keeping the newly formed lead ice permeable for 2 weeks. These physical conditions activated a methane pump. An increased MSC induced methane uptake at the air–ice interface, and the still-open brine channels provided top-down transport to the ocean interface with brine drainage. When the subsurface layer became impermeable, the top-down pumping stopped, but the ongoing uptake induced a methane excess on top. During the second growth phase, methane exchange exclusively continued at the ice–ocean interface. The shift in the relative abundance of the 12C and 13C isotopes between lead ice and seawater toward a 13C-enrichment in seawater reveals brine drainage as the main pathway releasing methane from aging lead ice. We conclude that in winter, refrozen leads temporarily function as active sinks for atmospheric methane and postulate that the relevance of this process may even increase when the Arctic fully transitions into a seasonally ice-covered ocean when leads may be more abundant. To highlight the relevance of methane in-gassing at the air–ice interface as a potential but still unconsidered pathway, we include estimates of the occurrence and frequency of young lead ice from satellite observations of leads during MOSAiC.

Simulation Study on the Performance of Ultrasonic Pulse-Echo Detector for Ice Thickness Identification

In-flight icing detectors are important for the flight safety of aircraft. Detectors based on ultrasonic pulse-echo can be used for detecting ice thickness. To study the influencing factors of ultrasonic pulse-echo detection performance, a simulation model of elastic wave-piezoelectric coupling was established, which was used to analyze the influence of different types of piezoelectric ceramics, matching layers with different acoustic impedances, and different substrate materials on ultrasonic pulse-echo signals. It was found that when aluminum is used as the substrate material, the ultrasonic echo signal has a higher signal-to-noise ratio. Furthermore, the influence of aluminum substrate materials with different thicknesses on ultrasonic pulse-echo was analyzed. The ice thickness can be identified by measuring the time of flight between the aluminum-ice interface echo and the ice-air interface echo. The results indicate that when the thickness of the aluminum substrate is 25mm, the upper detection limit of ice layer thickness can reach about 10mm. Therefore, the detection upper limit of ice layer thickness can be extended by appropriately increasing the thickness of the aluminum substrate material.

Nitrate Photolysis at the Air–Ice Interface of Nature-Identical Snow

Nitrate Photolysis at the Air–Ice Interface of Nature-Identical Snow

Solvation Structure and UV–Visible Absorption Spectra of the Nitrate Anion at the Air–Ice Interface by First-Principles Molecular Simulations

Solvation Structure and UV–Visible Absorption Spectra of the Nitrate Anion at the Air–Ice Interface by First-Principles Molecular Simulations

Fast 3D ground penetrating radar simulations for glaciers

Modeling ground penetrating radar (GPR) reflection data on glaciers with methods that require the discretization of the full subsurface domain is extremely computationally expensive because of the combination of a large domain size and the comparatively short wavelength of the signal. To address this issue, we build on and extend a previously proposed approach based on the assumption of a homogeneous background medium (ice) in which various scattering objects (e.g., crevasses, channels, boulders) are embedded far from each other such that multiple scattering can be ignored. The glacier bed, below which no scatterers are assumed to exist, represents the lower limit of the modeling domain. With this method, the two-way propagation of the radar waves through the ice is simulated in a semi-analytical way, whereby scattering surfaces are represented with a set of planar elements of different electric and reflective properties, allowing a wide range of objects to be simulated. As we also take the antenna radiation pattern at the air-ice interface into account, this simple algorithm is able to produce realistic 3D GPR data in a fast and memory efficient way. In this study, we validate the presented algorithm with an analytical solution for a layered model, and we simulate radar data for a model of the Otemma glacier in Switzerland featuring a realistic topography of the glacier bed and a subglacial channel.

A new insight into the interaction of hydroxyl radical with supercooled nanodroplet in the atmosphere

• The interaction between OH* and supercooled nanodroplet led to delocalized states caused by surface effects. • The OH* shows a high tendency for accepting H-bond from neighboring water molecules around (1.77 Å, 122°). • RDF and ring analysis results confirmed the LDA ice for OH*-supercooled nanodroplet. • The preference of six-membered rings in supercooled nanodroplet based on ring analysis. • The 3-fold and 4-fold coordination were revealed as dominant structures. Fallstreak clouds are types of clouds with supercooled water droplets, meaning that they are still liquid at sub-freezing temperatures. In the atmosphere, hydroxyl radicals serve as an important source of oxidants. The reactivity of the hydroxyl radicals in ice environments is significant, affecting other atmospheric reactions. However, the interaction between OH radical with supercooled water nanodroplet remains unknown. This work presents a comprehensive computational study of OH radicals at the air-ice interface. Ab initio molecular dynamics simulation showed that despite previous assumptions, the hemibond could also exist in large OH*-nanodroplet systems under supercooling process. Two hydrogen-bonded water molecules along with the hemibond have been found to be the reason for OH* stability. There is a significant correlation between our RDF and ring analysis results and the structural information from X-ray crystallography, confirming LDA ice for supercooled nanodroplets. The hydrogen bond analysis revealed that there is no radical effect on the hydrogen bond formation of water nanodroplets at 250 K. Moreover, the time evolution of critical bonds based on distances revealed that the OH* could be a movable and reactive radical during the supercooling process. Results from this research contribute to a better understanding of natural phenomena and rational design of anti-icing systems for aviation, wind energy, and infrastructures along with cryopreservation.

Enhanced photodegradation of dimethoxybenzene isomers in/on ice compared to in aqueous solution

Abstract. Photochemical reactions of contaminants in snow and ice can be important sinks for organic and inorganic compounds deposited onto snow from the atmosphere and sources for photoproducts released from snowpacks into the atmosphere. Snow contaminants can be found in the bulk ice matrix, in internal liquid-like regions (LLRs), or in quasi-liquid layers (QLLs) at the air–ice interface, where they can readily exchange with the firn air. Some studies have reported that direct photochemical reactions occur faster in LLRs and QLLs than in aqueous solution, while others have found similar rates. Here, we measure the photodegradation rate constants for loss of the three dimethoxybenzene isomers under varying experimental conditions, including in aqueous solution, in LLRs, and at the air–ice interface of nature-identical snow. Relative to aqueous solution, we find modest photodegradation enhancements (3- and 6-fold) in LLRs for two of the isomers and larger enhancements (15- to 30-fold) at the air–ice interface for all three isomers. We use computational modeling to assess the impact of light absorbance changes on photodegradation rate enhancements at the interface. We find small (2–5 nm) bathochromic (red) absorbance shifts at the interface relative to in solution, which increases light absorption, but this factor only accounts for less than 50 % of the measured rate constant enhancements. The major factor responsible for photodegradation rate enhancements at the air–ice interface appears to be more efficient photodecay: estimated dimethoxybenzene quantum yields are 6- to 24-fold larger at the interface compared to in aqueous solution and account for the majority (51 %–96 %) of the observed enhancements. Using a hypothetical model compound with an assumed Gaussian-shaped absorbance peak, we find that a shift in the peak to higher or lower wavelengths can have a minor to substantial impact on photodecay rate constants, depending on the original location of the peak and the magnitude of the shift. Changes in other peak properties at the air–ice interface, such as peak width and height (i.e., molar absorption coefficient), can also impact rates of light absorption and direct photodecay. Our results suggest our current understanding of photodegradation processes underestimates the rate at which some compounds are broken down, as well as the release of photoproducts into the atmosphere.

Chemical Morphology Controls Reactivity of OH Radicals at the Air-Ice Interface.

At the air-ice interface, some aromatic compounds such as benzene and anthracene are surprisingly unreactive toward OH. This may be a consequence of the poor solvation of these compounds at the interface, resulting in clustering there. We test this hypothesis by comparing the reaction of OH with pyrene, a 4-ring polyaromatic hydrocarbon (PAH), to reactions of OH with the more water-soluble compounds coumarin and 7-hydroxycoumarin (7OHC). We observe that OH reacts readily with coumarin and 7OHC at both liquid and frozen air-water interfaces. Pyrene, a much less soluble compound, reacts with OH at the liquid surface but not at the air-ice interface. We report evidence of pyrene aggregation at the ice surface based on its broadened and red-shifted emission spectrum alongside fluorescence mapping of anthracene, a closely related 3-ring PAH, which shows bunching at the ice surface. By contrast, fluorescence mapping shows that coumarin is fairly homogeneously distributed at the air-ice interface. Together, these results suggest that the limited reactivity of some compounds toward OH at the ice surface may be a consequence of their propensity to self-aggregate, demonstrating that chemical morphology can play an important role in reactions at the ice surface.

Identification of Stability Constraints in the Particle Engineering of an Inhaled Monoclonal Antibody Dried Powder

Monoclonal antibody (mAb) based therapies may provide a valuable new treatment modality for acute and chronic lung diseases, including asthma, respiratory infections, and lung cancer. Currently mAbs are delivered via systemic administration routes, but direct delivery to the lungs via the inhaled route could provide higher concentrations at the site of disease and reduced off-target effects. Though lyophilized mAbs may be reconstituted and delivered to the lungs using nebulizers, dry powder inhalers provide a more patient-friendly delivery method based upon their fast administration time and portability. However, particle engineering processes required to prepare respirable dried powders for DPI delivery involve multiple potential stressors for mAbs, which have not been fully explored. In this study, a systematic examination of various aspects of the particle engineering process (atomization, freezing, drying, and storage) was performed to further understand their impact on mAb structure and aggregation. Using anti-streptavidin IgG1 as a model mAb, atomization settings were optimized using a design of experiments approach to elucidate the relationship between feed flow rate, formulation solid content, and atomization airflow rate and protein structural changes and aggregation. The optimized atomization conditions were then applied to spray drying and spray freezing drying particle engineering processes to determine the effects of freezing and drying on IgG1 stability and aerosol performance of the powders. IgG1 was found to be particularly susceptible to degradation induced by the expansive air-ice interface generated by spray freeze drying and this process also produced powders that exhibited decreased storage stability. This study further delineates the design space for manufacturing of respirable biologic therapies and is intended to serve as a roadmap for future development work.

Bathochromic Shift in the UV-Visible Absorption Spectra of Phenols at Ice Surfaces: Insights from First-Principles Calculations.

Some organic pollutants in snowpacks undergo faster photodegradation than in solution. One possible explanation for such effect is that their UV-visible absorption spectra are shifted toward lower energy when the molecules are adsorbed at the air-ice interface. However, such bathochromic shift is difficult to measure experimentally. Here, we employ a multiscale/multimodel approach that combines classical and first-principles molecular dynamics, quantum chemical methods, and statistical learning to compute the light absorption spectra of two phenolic molecules in different solvation environments at the relevant thermodynamic conditions. Our calculations provide an accurate estimate of the bathochromic shift of the lowest-energy UV-visible absorption band when these molecules are adsorbed at the air-ice interface, and they shed light into its molecular origin.

A Theoretical Model of Wind-Wave Growth Over an Ice-Covered Sea

A wind-wave generation model over an ice-covered sea is proposed. The wind velocity over the ice upper surface is decomposed into the mean velocity profile of the boundary-layer flow and small perturbations, while the ice cover is modelled as a viscoelastic layer, with the water part modelled as an inviscid fluid. The present model is based on two-dimensional linear flow-instability theory, with no-slip boundary conditions at the air–ice interface, and both normal and shear stress boundary conditions matched on the air–ice interface. It is shown that the model converges to the field and experimental data for open-water cases. The ice elasticity is found to be the critical factor for generating wind waves, and the generation of flexural-gravity waves and elastic waves in ice is analyzed.

Solar radiative transfer in Antarctic blue ice: spectral considerations, subsurface enhancement, inclusions, and meteorites

Abstract. We describe and validate a Monte Carlo model to track photons over the full range of solar wavelengths as they travel into optically thick Antarctic blue ice. The model considers both reflection and transmission of radiation at the surface of blue ice, scattering by air bubbles within it, and spectral absorption due to the ice. The ice surface is treated as planar whilst bubbles are considered to be spherical scattering centres using the Henyey–Greenstein approximation. Using bubble radii and number concentrations that are representative of Antarctic blue ice, we calculate spectral albedos and spectrally integrated downwelling and upwelling radiative fluxes as functions of depth and find that, relative to the incident irradiance, there is a marked subsurface enhancement in the downwelling flux and accordingly also in the mean irradiance. This is due to the interaction between the refractive air–ice interface and the scattering interior and is particularly notable at blue and UV wavelengths which correspond to the minimum of the absorption spectrum of ice. In contrast the absorption path length at IR wavelengths is short and consequently the attenuation is more complex than can be described by a simple Lambert–Beer style exponential decay law – instead we present a triple-exponential fit to the net irradiance against depth. We find that there is a moderate dependence on the solar zenith angle and surface conditions such as altitude and cloud optical depth. Representative broadband albedos for blue ice are calculated in the range from 0.585 to 0.621. For macroscopic absorbing inclusions we observe both geometry- and size-dependent self-shadowing that reduces the fractional irradiance incident on an inclusion's surface. Despite this, the inclusions act as local photon sinks and are subject to fluxes that are several times the magnitude of the single-scattering contribution. Such enhancement may have consequences for the energy budget in regions of the cryosphere where particulates are present near the surface. These results also have particular relevance to measurements of the internal radiation field: account must be taken of both self-shadowing and the optical effect of introducing the detector. Turning to the particular example of englacial meteorites, our modelling predicts iron meteorites to reside at much reduced depths than previously suggested in the literature (< 10 cm vs. ∼ 40 cm) and further shows a size dependency that may explain the observed bias in their Antarctic size distribution.

Photodecay of guaiacol is faster in ice, and even more rapid on ice, than in aqueous solution.

Snowpacks contain a wide variety of inorganic and organic compounds, including some that absorb sunlight and undergo direct photoreactions. How the rates of these reactions in, and on, ice compare to rates in water is unclear: some studies report similar rates, while others find faster rates in/on ice. Further complicating our understanding, there is conflicting evidence whether chemicals react more quickly at the air-ice interface compared to in liquid-like regions (LLRs) within the ice. To address these questions, we measured the photodegradation rate of guaiacol (2-methoxyphenol) in various sample types, including in solution, in ice, and at the air-ice interface of nature-identical snow. Compared to aqueous solution, we find modest rate constant enhancements (increases of 3- to 6-fold) in ice LLRs, and much larger enhancements (of 17- to 77-fold) at the air-ice interface of nature-identical snow. Our computational modeling suggests the absorption spectrum for guaiacol red-shifts and increases on ice surfaces, leading to more light absorption, but these changes explain only a small portion (roughly 2 to 9%) of the observed rate constant enhancements in/on ice. This indicates that increases in the quantum yield are primarily responsible for the increased photoreactivity of guaiacol on ice; relative to solution, our results suggest that the quantum yield is larger by a factor of roughly 3-6 in liquid-like regions and 12-40 at the air-ice interface.

Microscale Rearrangement of Ammonium Induced by Snow Metamorphism

Earth’s snowpack hosts chemical impurities that exchange with the overlying air, strongly impacting atmospheric chemistry. Being embedded in firn and glacier ice formed from surface snow, impurities provide the basis for reconstructing past atmospheric composition from ice core records. The location of these impurity compounds within the snow critically controls their reactivity and preservation. Ammonium (NH4+) determines acid-base equilibria and buffer capacity within the snow and is a fundamental ice-core proxy, especially for biogenic, forest fire, and anthropogenic emissions. However, the redistribution during snow metamorphism affecting snow chemical reactivity and potential post-depositional relocation is not understood so far. Here, we study the rearrangement of NH4+ and five other major ions (Ca2+, Cl–, F–, Na+ and SO42–) during dry snow metamorphism using a series of elution experiments. Artificial and natural snow samples were stored for up to three months at a controlled temperature gradient of 40 K/m and isothermal conditions. The different types of snow increase complexity as natural and artificial snow have a different history that impacts their physical properties and the initial distribution of impurities. Further, we test our findings using natural snow samples taken from different depths of a natural snowpack at the Weissfluhjoch (Swiss Alps) to confirm the impact of our laboratory results to the cryosphere. With progressing temperature gradient metamorphism, snow structures in natural and artificial snow converged and ions with high solubility in ice (NH4+, F- and Cl-) were incorporated into the less accessible ice interior. In contrast, ions with lower solubility (Ca2+, SO42- and Na+) became better accessible for the eluent. Our results show that the redistribution during snow metamorphism is strongly dependent on the temperature gradient, exposure time and chemical composition. This study allowed for the first time to explicitly relate the general low relocation proneness of NH4+ during post-depositional processes such as meltwater percolation to the preferred incorporation of this ion into the less accessible ice interior during snow metamorphism. Furthermore, our results imply that with ongoing aging of a snowpack, NH4+, independent of its primary location, is less available for chemical reactions at the air-ice interface.

The Surface of Ice under Equilibrium and Nonequilibrium Conditions.

ConspectusThe ice premelt, often called the quasi-liquid layer (QLL), is key for the lubrication of ice, gas uptake by ice, and growth of aerosols. Despite its apparent importance, in-depth understanding of the ice premelt from the microscopic to the macroscopic scale has not been gained. By reviewing data obtained using molecular dynamics (MD) simulations, sum-frequency generation (SFG) spectroscopy, and laser confocal differential interference contrast microscopy (LCM-DIM), we provide a unified view of the experimentally observed variation in quasi-liquid (QL) states. In particular, we disentangle three distinct types of QL states of disordered layers, QL-droplet, and QL-film and discuss their nature.The topmost ice layer is energetically unstable, as the topmost interfacial H2O molecules lose a hydrogen bonding partner, generating a disordered layer at the ice–air interface. This disordered layer is homogeneously distributed over the ice surface. The nature of the disordered layer changes over a wide temperature range from −90 °C to the bulk melting point. Combined MD simulations and SFG measurements reveal that the topmost ice surface starts to be disordered around −90 °C through a process that the topmost water molecules with three hydrogen bonds convert to a doubly hydrogen-bonded species. When the temperature is further increased, the second layer starts to become disordered at around −16 °C. This disordering occurs not in a gradual manner, but in a bilayer-by-bilayer manner.When the temperature reaches −2 °C, more complicated structures, QL-droplet and QL-film, emerge on the top of the ice surface. These QL-droplets and QL-films are inhomogeneously distributed, in contrast to the disordered layer. We show that these QL-droplet and QL-film emerge only under supersaturated/undersaturated vapor pressure conditions, as partial and pseudopartial wetting states, respectively. Experiments with precisely controlled pressure show that, near the water vapor pressure at the vapor-ice equilibrium condition, no QL-droplet and QL-film can be observed, implying that the QL-droplet and QL-film emerge exclusively under nonequilibrium conditions, as opposed to the disordered layers formed under equilibrium conditions.These findings are connected with many phenomena related to the ice surface. For example, we explain how the disordering of the topmost ice surface governs the slipperiness of the ice surface, allowing for ice skating. Further focus is on the gas uptake mechanism on the ice surface. Finally, we note the unresolved questions and future challenges regarding the ice premelt.

Influence of a planar boundary on the electric field emitted by a particle shower

The radio detection of cosmic rays consists in the estimation of the properties of a primary cosmic ray by observing the electric field emitted by the extensive air shower (EAS) created when the primary cosmic ray enters the atmosphere. This technique is fully operative nowadays and presents a good degree of maturity. In addition, several projects intend to employ this technique for the detection of neutrinos. In order for the technique to be useful, accurate methods for computing the electric field created by a particle shower in the context of a particular experiment must exist. Although current ground-based radio experiments lie on the air-soil interface and some planned experiments on the South Pole envision antennas near the air-ice interface, most of the analytical approaches and Monte Carlo codes used for calculating the electric field either do not take into account the effect of the boundary or calculate the radiation fields only (direct, reflected and transmitted radiation fields). When the particle shower and the antenna are close to the boundary, compared to the observation wavelength, the far-field approximation breaks down, which is the case for the low-frequency EXTASIS experiment, for instance. We present in this work a new formula for calculating the exact field emitted by a particle track in two semi-infinite media separated by a planar boundary. We also explore the validity of the far-field approximation and make some predictions for EAS using a simple shower model.

The quasi-liquid layer of ice revisited: the role of temperature gradients and tip chemistry in AFM studies

Abstract. In this work, we present new results of atomic force microscopy (AFM) force curves over pure ice at different temperatures, performed with two different environmental chambers and different kinds of AFM tips. Our results provide insight to resolve the controversy on the interpretation of experimental AFM curves on the ice–air interface for determining the thickness of the quasi-liquid layer (QLL). The use of a Mini Environmental Chamber (mEC) that provides an accurate control of the temperature and humidity of the gases in contact with the sample allowed us for the first time to get force curves over the ice–air interface without jump-in (jump of the tip onto the ice surface, widely observed in previous studies). These results suggest a QLL thickness below 1 nm within the explored temperature range (−7 to −2 ∘C). This upper bound is significantly lower than most of the previous AFM results, which suggests that previous authors overestimate the equilibrium QLL thickness, due to temperature gradients, or indentation of ice during the jump-in. Additionally, we proved that the hydrophobicity of AFM tips affects significantly the results of the experiments. Overall, this work shows that, if one chooses the experimental conditions properly, the QLL thicknesses obtained by AFM lie over the lower bound of the highly disperse results reported in the literature. This allows estimating upper boundaries for the QLL thicknesses, which is relevant to validate QLL theories and to improve multiphase atmospheric chemistry models.

Photodegradation Rate Constants for Anthracene and Pyrene Are Similar in/on Ice and in Aqueous Solution.

Snowpacks contain a variety of chemicals, including organic pollutants such as toxic polycyclic aromatic hydrocarbons (PAHs). While PAHs undergo photodegradation in snow and ice, the rates of these reactions remain in debate. Some studies report that photochemical reactions in snow proceed at rates similar to those expected in a supercooled aqueous solution, but other studies report faster reaction rates, particularly at the air-ice interface (i.e., the quasi-liquid layer, or QLL). In addition, one study reported a surprising nonlinear dependence on photon flux. Here we examine the photodegradation of two common PAHs, anthracene and pyrene, in/on ice and in solution. For a given PAH, rate constants are similar in aqueous solution, in internal liquid-like regions of ice, and at the air-ice interface. In addition, we find the expected linear relationship between reaction rate constant and photon flux. Our results indicate that rate constants for the photochemical loss of PAHs in, and on, snow and ice are very similar to those in aqueous solution, with no enhancement at the air-ice interface.