Snowpack Chemistry Research Articles

Influence of Critical Zone Architecture and Snowpack on Streamflow Generation Processes: A Mountain‐Meadow Headwater System in a Mediterranean Climate

AbstractObservations from a granitic watershed within a Mediterranean climate reveal the hydrologic and critical zone functioning of a perennial stream headwater and its upslope contributing area within a meadow system in the Sierra Nevada, California. Chemical analysis (diagnostic tools of mixing models, end member mixing analysis, tritium, etc.) and physical data (stream stage, piezometers, soil water, snowpack, etc.) indicate there are two primary pathways of water input into a headwater stream sourced from a mountain meadow. One input is a shallower and younger subsurface pathway with water that resembles snowpack chemistry, and the other a deeper and older subsurface pathway with water that reflects the chemistry of the groundwater derived from the contributing hillslopes. Multi‐year observations reveal that regardless of snowpack amount, during the period of peak hillslope infiltration, shallow and deep pathways in the hillslope behave similarly to initiate headwater streams. However, during summer dry periods, similarities in active pathways within the meadow center are not maintained between high and low snowpack years. With less snow, perennial groundwater discharge within the meadow center is eliminated, becoming only a seasonal source at the meadow's outlet. At the meadow's edge, geophysically observed downslope thinning in saprolite thickness creates reduced lateral transmissivity and initiation points for headwater streams via enhanced groundwater discharge of upslope water. Combined, these findings suggest how loss of snowpack and critical zone structure can together mediate hydrologic function in a wet meadow system in a Mediterranean climate. Creating new understanding about the stability of hydraulic functioning in headwater wet‐meadow systems under a changing climate.

Source, timing and dynamics of ionic species mobility in the Svalbard annual snowpack

Nearly all ice core archives from the Arctic and middle latitudes (such as the Alps), apart from some very high elevation sites in Greenland and the North Pacific, are strongly influenced by melting processes. The increases in the average Arctic temperature has enhanced surface snow melting even of higher elevation ice caps, especially on the Svalbard Archipelago. The increase of the frequency and altitude of winter “rain on snow” events as well as the increase of the length of the melting season have had a direct impact on the chemical composition of the seasonal and permanent snow layers due to different migration processes of water-soluble species, such as inorganic ions. This re-allocation along the snowpack of ionic species could significantly modify the original chemical signal present in the annual snow. This paper aims to give a picture of the evolution of the seasonal snow strata with a daily time resolution to better understand: a) the processes that can influence deposition b) the distribution of ions in annual snow c) the impact of the presence of liquid water on chemical re-distribution within the annual snow pack. Specifically, the chemical composition of the first 100 cm of seasonal snow on the Austre Brøggerbreen Glacier (Spitsbergen, Svalbard Islands, Norway) was monitored daily from the 27th of March to the 31st of May 2015. The experimental period covered almost the entire Arctic spring until the melting season. This unique dataset gives us a daily picture of the snow pack composition, and helps us to understand the behaviour of cations (K+, Ca2+, Na+, Mg2+) and anions (Br−, I−, SO42−, NO3−, Cl−, MSA) in the Svalbard snow pack. We demonstrate that biologically related depositions occur only at the end of the snow season and that rain and melting events have different impacts on the snowpack chemistry.

Evaluating the impact of blowing-snow sea salt aerosol on springtime BrO and O<sub>3</sub> in the Arctic

Abstract. We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing-snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCDtropo) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well as against surface observations of O3. We conduct a simulation with blowing-snow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCDtropo to within 17 %, as well as their spatiotemporal variability (r=0.76–0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ∼5 in September–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCDtropo. We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40∘ N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %–40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %–75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry.

Preferential elution of ionic solutes in melting snowpacks: Improving process understanding through field observations and modeling in the Rocky Mountains

The preferential elution of ions from melting snowpacks is a complex problem that has been linked to temporary acidification of water bodies. However, the understanding of these processes in snowpacks around the world, including the polar regions that are experiencing unprecedented warming and melting, remains limited despite being instrumental in supporting climate change adaptation.In this study, data collected from a snowmelt lysimeter and snowpits at meadow and forest-gap sites in a high elevation watershed in Colorado were combined with the PULSE multi-phase snowpack chemistry model to investigate the controls of meltwater chemistry and preferential elution. The snowdepth at the meadow site was 64% of that at the forest-gap site, and the snowmelt rate was greater there (meadow snowpit) due to higher solar irradiance. Cations such as Ca2+ and NH4+ were deposited mostly within the upper layers of both the meadow and forest-gap snowpacks, and acid anions such as NO3− and SO42− were more evenly distributed. The snow ion concentrations were generally greater at the forest-gap snowpit, except for NH4+, which indicates that wind erosion of wet and dry deposited ions from the meadow may have reduced concentrations of residual snow. Furthermore, at the forest-gap site, snow interception and scavenging processes such as sublimation, ventilation, and throughfall led to particular ion enrichment of Ca2+, Mg2+, K+, Cl−, SO42− and NO3−. Model simulations and observations highlight that preferential elution is enhanced by low snowmelt rates, with the model indicating that this is due to lower dilution rates and increased contact time and area between the percolating meltwater and the snow. Results suggest that low snowmelt rates can cause multiple early meltwater ionic pulses for ions subject to lower ion exclusion. Ion exclusion rates at the grain-size level have been estimated for the first time.

Accumulating Mercury and Methylmercury Burdens in Watersheds Impacted by Oil Sands Pollution.

Bitumen mining and upgrading in northeastern Alberta, Canada, releases toxic pollutants into the atmosphere, including mercury (Hg) and methylmercury (MeHg). This Hg and MeHg is then deposited to the surrounding landscape; however, the fate of these contaminants remains unknown. Here, we compare snowpack chemistry to high-frequency measurements of river water quality across six watersheds (five impacted by oil sands development and one unimpacted). Catchment scale snowpack Hg and MeHg loads normalized to watershed area were highest near oil sands operations. River water Hg concentrations and loads tracked discharge and tended to be higher downstream of mining operations, while MeHg concentrations and loads increased through the summer, reflecting peak summer MeHg production rates. Except in the reference watershed, snowpack Hg and MeHg loads equaled or exceeded the amount of Hg and MeHg exported during freshet and, in some cases, the entire hydrologic year. This suggests landscapes across the oil sands region, which are dominated by low-relief wetlands and other shallow-water systems, are accumulating Hg and MeHg. Importantly, during years of high discharge, these low-relief systems appear to become better connected and flush MeHg (and Hg) from the watershed. Thus, these watersheds may act as temporary, rather than as permanent, natural repositories of oil sands contaminants.

Spatial variations in snowpack chemistry, isotopic composition of NO<sub>3</sub><sup>−</sup> and nitrogen deposition from the ice sheet margin to the coast of western Greenland

Abstract. The relative roles of anthropogenic nitrogen (N) deposition and climate change in causing ecological change in remote Arctic ecosystems, especially lakes, have been the subject of debate over the last decade. Some palaeoecological studies have cited isotopic signals (δ(15N)) preserved in lake sediments as evidence linking N deposition with ecological change, but a key limitation has been the lack of co-located data on both deposition input fluxes and isotopic composition of deposited nitrate (NO3−). In Arctic lakes, including those in western Greenland, previous palaeolimnological studies have indicated a spatial variation in δ(15N) trends in lake sediments but data are lacking for deposition chemistry, input fluxes and stable isotope composition of NO3−. In the present study, snowpack chemistry, NO3− stable isotopes and net deposition fluxes for the largest ice-free region in Greenland were investigated to determine whether there are spatial gradients from the ice sheet margin to the coast linked to a gradient in precipitation. Late-season snowpack was sampled in March 2011 at eight locations within three lake catchments in each of three regions (ice sheet margin in the east, the central area near Kelly Ville and the coastal zone to the west). At the coast, snowpack accumulation averaged 181 mm snow water equivalent (SWE) compared with 36 mm SWE by the ice sheet. Coastal snowpack showed significantly greater concentrations of marine salts (Na+, Cl−, other major cations), ammonium (NH4+; regional means 1.4–2.7 µmol L−1), total and non-sea-salt sulfate (SO42−; total 1.8–7.7, non-sea-salt 1.0–1.8 µmol L−1) than the two inland regions. Nitrate (1.5–2.4 µmol L−1) showed significantly lower concentrations at the coast. Despite lower concentrations, higher precipitation at the coast results in greater net deposition for NO3− as well as NH4+ and non-sea-salt sulfate (nss-SO42−) relative to the inland regions (lowest at Kelly Ville 6, 4 and 3; highest at coast 9, 17 and 11 mol ha−1 a−1 of NO3−, NH4+ and nss-SO42− respectively). The δ(15N) of snowpack NO3− shows a significant decrease from inland regions (−5.7 ‰ at Kelly Ville) to the coast (−11.3 ‰). We attribute the spatial patterns of δ(15N) in western Greenland to post-depositional processing rather than differing sources because of (1) spatial relationships with precipitation and sublimation, (2) within-catchment isotopic differences between terrestrial snowpack and lake ice snowpack, and (3) similarities between fresh snow (rather than accumulated snowpack) at Kelly Ville and the coast. Hence the δ(15N) of coastal snowpack is most representative of snowfall in western Greenland, but after deposition the effects of photolysis, volatilization and sublimation lead to enrichment of the remaining snowpack with the greatest effect in inland areas of low precipitation and high sublimation losses.

Seasonal Variability and Evolution of Glaciochemistry at An Alpine Temperate Glacier on the Southeastern Tibetan Plateau

Temperate glaciers are highly sensitive to climatic and environmental changes. Studying the chemical composition of snow, firn, and ice on temperate glaciers is important for understanding the variations in atmospheric circulation patterns, deposition conditions, and melting processes. To define snowpack chemistry and environmental significance, seven snowpacks (one snowpack in late autumn, two in winter, two in spring, and two in summer) were sampled in 2008/2009 on Baishui Glacier No. 1 in Mt. Yulong. Soluble ions in the winter snowpacks showed low values in the middle part but high values in the lower and upper parts, influenced by the atmospheric deposition of snow accumulation. The larger variations of ionic concentrations in the spring snowpacks were associated with the variable atmospheric patterns with high dust content in spring, leading to high ionic concentrations in the upper snowpack. Strong meltwater percolation resulted in quick migration and redistribution of ions for the profiles during the monsoon period. The ion elution sequence was Ca2+ > SO42− > NH4+ > K+ > NO3− > Na+ > Cl− > Mg2+. Factor analysis showed that NO3−, SO42−, NH4+ were mainly supplied by wet deposition-plus-anthropogenic input, while Cl− and Na+ originated from marine sources. Ca2+ and Mg2+ had multiple sources and the local terrestrial source was important because of locally exposed carbonate. The results suggest that chemical concentrations reflect mainly impurities supplied by atmospheric circulation and precipitation during periods of snow accumulation, as well as during the melting process.

Surface ozone and its precursors at Summit, Greenland: comparison between observations and model simulations

Abstract. Recent studies have shown significant challenges for atmospheric models to simulate tropospheric ozone (O3) and its precursors in the Arctic. In this study, ground-based data were combined with a global 3-D chemical transport model (GEOS-Chem) to examine the abundance and seasonal variations of O3 and its precursors at Summit, Greenland (72.34° N, 38.29° W; 3212 m a.s.l.). Model simulations for atmospheric nitrogen oxides (NOx), peroxyacetyl nitrate (PAN), ethane (C2H6), propane (C3H8), carbon monoxide (CO), and O3 for the period July 2008–June 2010 were compared with observations. The model performed well in simulating certain species (such as CO and C3H8), but some significant discrepancies were identified for other species and further investigated. The model generally underestimated NOx and PAN (by ∼ 50 and 30 %, respectively) for March–June. Likely contributing factors to the low bias include missing NOx and PAN emissions from snowpack chemistry in the model. At the same time, the model overestimated NOx mixing ratios by more than a factor of 2 in wintertime, with episodic NOx mixing ratios up to 15 times higher than the typical NOx levels at Summit. Further investigation showed that these simulated episodic NOx spikes were always associated with transport events from Europe, but the exact cause remained unclear. The model systematically overestimated C2H6 mixing ratios by approximately 20 % relative to observations. This discrepancy can be resolved by decreasing anthropogenic C2H6 emissions over Asia and the US by ∼ 20 %, from 5.4 to 4.4 Tg year−1. GEOS-Chem was able to reproduce the seasonal variability of O3 and its spring maximum. However, compared with observations, it underestimated surface O3 by approximately 13 % (6.5 ppbv) from April to July. This low bias appeared to be driven by several factors including missing snowpack emissions of NOx and nitrous acid in the model, the weak simulated stratosphere-to-troposphere exchange flux of O3 over the summit, and the coarse model resolution.

Dynamics of ozone and nitrogen oxides at Summit, Greenland. II. Simulating snowpack chemistry during a spring high ozone event with a 1-D process-scale model

Observed depth profiles of nitric oxide (NO), nitrogen dioxide (NO2), and ozone (O3) in snowpack interstitial air at Summit, Greenland were best replicated by a 1-D process-scale model, which included (1) geometrical representation of snow grains as spheres, (2) aqueous-phase chemistry confined to a quasi-liquid layer (QLL) on the surface of snow grains, and (3) initialization of the species concentrations in the QLL through equilibrium partitioning with mixing ratios in snowpack interstitial air. A comprehensive suite of measurements in and above snowpack during a high O3 event facilitated analysis of the relationship between the chemistry of snowpack and the overlying atmosphere. The model successfully reproduced 2 maxima (i.e., a peak near the surface of the snowpack at solar noon and a larger peak occurring in the evening that extended down from 0.5 to 2 m) in the diurnal profile of NO2 within snowpack interstitial air. The maximum production rate of NO2 by photolysis of nitrate (NO3−) was approximately 108 molec cm−3 s−1, which explained daily observations of maxima in NO2 mixing ratios near solar noon. Mixing ratios of NO2 in snowpack interstitial air were greatest in the deepest layers of the snowpack at night and were attributed to thermal decomposition of peroxynitric acid, which produced up to 106 molec NO2 cm−3 s−1. Highest levels of NO in snowpack interstitial air were confined to upper layers of the snowpack and observed profiles were consistent with photolysis of NO2. Production of nitrogen oxides (NOx) from NO3− photolysis was estimated to be two orders of magnitude larger than NO production and supports the hypothesis that NO3− photolysis is the primary source of NOx within sunlit snowpack in the Arctic. Aqueous-phase oxidation of formic acid by O3 resulted in a maximum consumption rate of ∼106–107 molec cm−3 s−1 and was the primary removal mechanism for O3.

The transport of chemical components in homogeneous snowpacks on Urumqi Glacier No. 1, eastern Tianshan Mountains, Central Asia

Chemical records from alpine ice cores provide an invaluable source of paleoclimatic and environmental information. Not only the atmospheric chemical composition but also depositional and post-depositional processes are recorded within snow/firn strata. To interpret the environmental and climatic significance of ice core records, we studied the variability of glacier snowpack chemistry by investigating homogeneous snowpacks from October 2003 to September 2006 on Urumqi Glacier No. 1 in eastern Tianshan Mountains, Central Asia. Principle Component Analysis of ionic species in dry and wet seasons revealed the impact of meltwater in redistributing ions in the snowpacks. The 1st, 2nd and 3rd principle components for dry seasons differ significantly, reflecting complex associations between depositional or/and post-depositional processes. The variability trend of ionic concentrations during the wet seasons was found to fit a Gauss Function with significant parameters. The elution factor revealed that more than half of ions are leached out during the wet seasons. Differences with respect to ion snowpack mobility were found. Of the ions studied SO4 2− was the most mobile and Mg2+ the least mobile. A threshold relationship between air temperatures and the elution process was investigated over the study period. The results indicate that the strong melt /ablation processes and iconic redistribution occur at a threshold air temperature of 0°C. The study found that surface melt on the snowpacks is the main factor causing the alteration of the snowpack chemistry. Rainfall also has an impact on the chemistry but plays a less significant role than the surface melt.

Acidity decline in Antarctic ice cores during the Little Ice Age linked to changes in atmospheric nitrate and sea salt concentrations

AbstractAcidity is an important chemical variable that impacts atmospheric and snowpack chemistry. Here we describe composite time series and the spatial pattern of acidity concentration (Acy = H+ − HCO3−) during the last 2000 years across the Dronning Maud Land region of the East Antarctic Plateau using measurements in seven ice cores. Coregistered measurements of the major ion species show that sulfuric acid (H2SO4), nitric acid (HNO3), and hydrochloric acid (HCl) determine greater than 98% of the acidity value. The latter, also described as excess chloride (ExCl−), is shown mostly to be derived from postdepositional diffusion of chloride with little net gain or loss from the snowpack. A strong inverse linear relationship between nitrate concentration and inverse accumulation rate provides evidence of spatially homogenous fresh snow concentrations and reemission rates of nitrate from the snowpack across the study area. A decline in acidity during the Little Ice Age (LIA, 1500–1900 Common Era) is observed and is linked to declines in HNO3 and ExCl− during that time. The nitrate decline is found to correlate well with published methane isotope data from Antarctica (δ13CH4), indicating that it is caused by a decline in biomass burning. The decrease in ExCl− concentration during the LIA is well correlated to published sea surface temperature reconstructions in the Atlantic Ocean, which suggests increased sea salt aerosol production associated with greater sea ice extent.

Interactions between snow chemistry, mercury inputs and microbial population dynamics in an Arctic snowpack.

We investigated the interactions between snowpack chemistry, mercury (Hg) contamination and microbial community structure and function in Arctic snow. Snowpack chemistry (inorganic and organic ions) including mercury (Hg) speciation was studied in samples collected during a two-month field study in a high Arctic site, Svalbard, Norway (79°N). Shifts in microbial community structure were determined by using a 16S rRNA gene phylogenetic microarray. We linked snowpack and meltwater chemistry to changes in microbial community structure by using co-inertia analyses (CIA) and explored changes in community function due to Hg contamination by q-PCR quantification of Hg-resistance genes in metagenomic samples. Based on the CIA, chemical and microbial data were linked (p = 0.006) with bioavailable Hg (BioHg) and methylmercury (MeHg) contributing significantly to the ordination of samples. Mercury was shown to influence community function with increases in merA gene copy numbers at low BioHg levels. Our results show that snowpacks can be considered as dynamic habitats with microbial and chemical components responding rapidly to environmental changes.

Atmospheric deposition as a source of carbon and nutrients to an alpine catchment of the Colorado Rocky Mountains

Abstract. Many alpine areas are experiencing deglaciation, biogeochemical changes driven by temperature rise, and changes in atmospheric deposition. There is mounting evidence that the water quality of alpine streams may be related to these changes, including rising atmospheric deposition of carbon (C) and nutrients. Given that barren alpine soils can be severely C limited, atmospheric deposition sources may be an important source of C and nutrients for these environments. We evaluated the magnitude of atmospheric deposition of C and nutrients to an alpine site, the Green Lake 4 catchment in the Colorado Rocky Mountains. Using a long-term dataset (2002–2010) of weekly atmospheric wet deposition and snowpack chemistry, we found that volume weighted mean dissolved organic carbon (DOC) concentrations were 1.12 ± 0.19 mg l−1, and weekly concentrations reached peaks as high at 6–10 mg l−1 every summer. Total dissolved nitrogen concentration also peaked in the summer, whereas total dissolved phosphorus and calcium concentrations were highest in the spring. To investigate potential sources of C in atmospheric deposition, we evaluated the chemical quality of dissolved organic matter (DOM) and relationships between DOM and other solutes in wet deposition. Relationships between DOC concentration, fluorescence, and nitrate and sulfate concentrations suggest that pollutants from nearby urban and agricultural sources and organic aerosols derived from sub-alpine vegetation may influence high summer DOC wet deposition concentrations. Interestingly, high DOC concentrations were also recorded during "dust-in-snow" events in the spring, which may reflect an association of DOM with dust. Detailed chemical and spectroscopic analyses conducted for samples collected in 2010 revealed that the DOM in many late spring and summer samples was less aromatic and polydisperse and of lower molecular weight than that of winter and fall samples. Our C budget estimates for the Green Lake 4 catchment illustrated that wet deposition (9.9 kg C ha−1 yr−1) and dry deposition (6.9 kg C ha−1 yr−1) were a combined input of approximately 17 kg C ha−1 yr−1, which could be as high as 24 kg C ha−1 yr−1 in high dust years. This atmospheric C input approached the C input from microbial autotrophic production in barren soils. Atmospheric wet and dry deposition also contributed 4.3 kg N ha−1 yr−1, 0.15 kg P ha−1 yr−1, and 2.7 kg Ca2+ ha−1 yr−1 to this alpine catchment.

Modeling chemistry in and above snow at Summit, Greenland – Part 2: Impact of snowpack chemistry on the oxidation capacity of the boundary layer

Abstract. The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the mid-day OH concentrations. Bromine chemistry increases the OH concentration by 10–18% (10% at noon LT), while snow sourced NOx increases OH concentrations by 20–50% (27% at noon LT). We show for the first time, using a coupled one-dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss.

Comments on 'Possible contribution of triboelectricity to snow - air interactions'

There have been numerous new discoveries of chemical activity at the snow–atmosphere interface over the last 20 years. These observations have stimulated an increasing body of research on snow chemical systems. The findings from this research have led to a general consensus that photochemical processes are the determining control of this snow chemistry. Traditional gasphase chemical reactions have fallen short of fully explaining observed behaviour. Heterogeneous and quasi-liquid layer chemistry has been postulated to play a role in accounting for the discrepancies. The Tkachenko and Kozachkov article is therefore a timely presentation of new ideas for further elucidating snowpack chemical mechanisms. In the following discussion we present recent data relevant to testing hypothesis proposed by Tkachenko and Kozachkov. Some of the hypotheses presented in this paper build upon data from measurements of ozone (O3) in interstitial air of the deep, glacial snowpack at Summit, Greenland, that were presented in our previous work. These experiments reported on positive O3 atmosphere–snowpack gradients, i.e. depleted O3 within the snowpack, and their dynamical behaviour dependent on environmental conditions. We have since taken this research to other locations and further investigated the dependencies of O3 within snow on a variety of parameters. A particular interest of this new research was to further investigate snowpack chemistry in environments with different snowpack conditions (year-round dry, polar snow; seasonal mid-latitude snowpack; snow over permafrost; snow over frozen freshwater lakes). We have also conducted a further 2 years of experiments at Summit, where the measurement depth in the snowpack was increased to 2.5m and experiments were extended year round to include winter observations. Another environment with polar year-round snowpack over glacial ice was investigated at South Pole, Antarctica. From the comparison with these other sites it has become obvious that the Summit snowpack is somewhat unique in that (1) O3 levels within the snowpack are generally higher than observed at other locations, and (2) interstitial air O3 shows a muchmore dynamic dependence on time of day and season than at the other locations that we have investigated. This behaviour might be in agreement with some hypotheses presented by Tkachenko and Kozachkov as they propose that O3 production by the triboelectrical effect would be most pronounced at sites characterised by a thick, glacial snowpack, low humidity, periodic high wind speeds, and low temperatures; all conditions that are typical for Summit. Our series of experiments have shown that different processes dominate snowpack chemistry in non-glacial snowpack. For example, one definite influence on O3 reactions in seasonal, midlatitude snowpack is the role of NO emitted from microbial processes in the subniveal soil. These influences were evident at a high alpine site at Niwot Ridge, CO, in the RockyMountains; snowpack under a canopy at the University of Michigan Biological Station (B. Seok, D. Helmig, M. W. Williams, C. Vogel, P. Curtis, unpubl. data); and snowpack over permafrost at Toolik Field Station, AK (B. Van Dam, D. Helmig, R. Honrath, L. Kramer, C. Toro, unpubl. data). For the Summit snowpack, Helmig et al. noted that O3 atmosphere–snowpack concentration gradients show three

Major element chemistry in inner alpine snowpacks (Aosta Valley Region, NW Italy)

Major element chemistry of the snow cover was investigated at 15 sampling sites at about 2000 m a.s.l. in the Aosta Valley Region (North Western Italy), an inner alpine region characterized by a continental climate, during late winter 2005–2006. Snowfall in winter 2005–2006 was primarily due to westerly, Atlantic air flows, while southerly flows were not a significant source of precipitation. These two factors (i.e. the inner alpine topography and the peculiar air flow patterns) determined a unique ion distribution compared to rest of the Alps. Calcium and magnesium concentrations in snowpacks were low, consistent with the absence of Saharan dust events and local geological sources. Sodium and chloride concentrations were higher than the average for the Alps, supporting the influence of the Atlantic air masses on the ionic composition of snowfall. Sulfate concentrations were in the range of background concentrations reported for high altitude and latitude sites, indicating that industrial emissions were not a main source of chemicals in Aosta Valley snowpacks for winter 2005–2006. Ammonium and nitrate values were comparable to concentrations found in other sites of the Alps for low-emission winters. We estimated dissolved inorganic nitrogen stored in snow to range between 0.25 and 0.75 kg N ha− 1, corresponding to about 2–6% of the over-winter-N mineralization in Alpine soils in the Western Alps. In the Aosta Valley, local biogenic pollution rather than long-range transport may contribute substantially to the ionic load in the snowpack when westerly air masses are the main source of precipitation. Although conducted over only one winter season, this study suggests a peculiar and previously unreported pattern of snowpack chemistry, that may be representative of the inner alpine, continental valleys in the absence of strong anthropogenic pollution or dust deposition. Due to the fact that inner alpine valleys cover a non-negligible surface of the Alps, we suggest these patterns to be taken into account while modeling ion depositions at a global scale.

The Influence of an Extensive Dust Event on Snow Chemistry in the Southern Rocky Mountains

In mid-February 2006, windstorms in Arizona, Utah, and western Colorado generated a dust cloud that distributed a layer of dust across the surface of the snowpack throughout much of the Colorado Rockies; it remained visible throughout the winter. We compared the chemical composition of snowfall and snowpack collected during and after the dust deposition event with pre-event snow at 17 sites extending from central Colorado into southern Wyoming. The chemistry of dust-event snowfall and the post-event snowpack were compared to long-term wetfall precipitation and snowpack chemistry at the Fraser Experimental Forest (FEF). The pH of the snowpack formed during the dust event was 1.5 units higher, calcium was 10-fold higher, and acid neutralizing capacity (ANC) was 100-fold higher than levels measured in either early or late-season snow. Elevated ANC was attributable to dust-derived increase in carbonate/bicarbonate ions, likely from soluble calcium carbonate inclusions in dust material. The single dust event contributed carbonate/bicarbonate-derived ANC equivalent to the sum of strong acids deposited during the entire winter at FEF. Effects appeared more pronounced at upper elevations and in the sparse forest near treeline, compared to densely forested lower elevation sites. Monthly snowpack solute analysis at FEF has not documented an event of similar magnitude during its 17-year period of record. The solute composition of post-event snow is similar to average Fraser streamwater, however. To assess the effect of dust on the timing and composition of water exported from high-elevation ecosystems, future work should consider both the contributions of eolian deposition on soil development, plant communities, and nutrient and water relations plus the impact of individual deposition events on snowpack chemistry and duration.

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites. Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant ( p<0.11) in constrast to highly significant increases in snowpack ( p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions ( p<0.03), while no trends were noted for the Northern Rockies subregion.

Release of Nitric Oxide and Iodine to the Atmosphere from the Freezing of Sea-Salt Aerosol Components

The known room-temperature, solution-phase reaction between nitrite ions and iodide ions, which occurs in acidic conditions (pH < 5.5), is shown to be accelerated when neutral aqueous solutions are frozen. The reaction is proposed to occur in liquid "micropockets" within the ice structure at temperatures between the freezing point and the eutectic temperature. The products, nitric oxide and molecular iodine, are known to play significant roles in atmospheric compositional change, and therefore, the results obtained here, which are not dependent on acidification, may impact on observed snowpack chemistry. Investigation of the effect of oxygen on the chemical processing indicates that a chain reaction mechanism is operative.

Micro-Raman Investigations of the Formaldehyde−Ice System

Rapidly frozen aqueous solutions containing variable amounts of dissolved formaldehyde (0.1, 5, 7, 10, 15, and 20 mol %) have been analyzed by micro-Raman spectroscopy at ambient pressure and low temperature. The importance of the formladehyde-ice system has been repeatedly quoted in various contexts, such as atmospheric and snowpack chemistry and interstellar and cometary ices. Understanding and characterizing the effects of freezing and the interactions of formaldehyde with ice are therefore of relevant interest. In this study, the distinct vibrational signatures of the oligomers present in the solution and in the frozen ice mixtures have been identified in the 120-4000 cm(-1) spectral range. From the subtle changes of the bands assigned to the CO and CH group frequencies, at least two distinct crystalline phases (pI and pII) are found to coexist with ice at different temperatures. Depending on the cooling-rewarming protocol, pI is found to crystallize in the 163-213 K temperature range. Above approximately 213 K, pI gets transformed irreversibly into pII which is stable up to approximately 234 K. pII is found to interact more strongly with ice than pI, as revealed, for example, by the drop in frequency of the bands assigned to the O-H stretching as pI transforms into pII. It is suggested that pII consists of a hydrogen-bonded network of oligomers and water molecules. On the other hand, it is suggested that the oligomers mainly present in pI interact through weak forces with the surrounding water molecules.