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[1] Frost flowers, intricate featherlike crystals that grow on refreezing sea ice leads, have been implicated in lower atmospheric chemical reactions. Few studies have presented chemical composition information for frost flowers over time and many of the chemical species commonly associated with Polar tropospheric reactions have never been reported for frost flowers. We undertook this study on the sea ice north of Barrow, Alaska to quantify the major ion, stable oxygen and hydrogen isotope, alkalinity, light absorbance by soluble species, organochlorine, and aldehyde composition of seawater, brine, and frost flowers. For many of these chemical species we present the first measurements from brine or frost flowers. Results show that major ion and alkalinity concentrations, stable isotope values, and major chromophore (NO 3 À and H 2 O 2 ) concentrations are controlled by fractionation from seawater and brine. The presence of these chemical species in present and future sea ice scenarios is somewhat predictable. However, aldehydes, organochlorine compounds, light absorbing species, and mercury (part 2 of this research and Sherman et al. (2012)) are deposited to frost flowers through less predictable processes that probably involve the atmosphere as a source. The present and future concentrations of these constituents in frost flowers may not be easily incorporated into future sea ice or lower atmospheric chemistry scenarios. Thinning of Arctic sea ice will likely present more open sea ice leads where young ice, brine, and frost flowers form. How these changing ice conditions will affect the interactions between ice, brine, frost flowers and the lower atmosphere is unknown.

Abstract. Following polar sunrise in the Arctic springtime, tropospheric ozone episodically decreases rapidly to near-zero levels during ozone depletion events (ODEs). Many uncertainties remain in our understanding of ODE characteristics, including the temporal and spatial scales, as well as environmental drivers. Measurements of ozone, bromine monoxide (BrO), and meteorology were obtained during several deployments of autonomous, ice-tethered buoys (O-Buoys) from both coastal sites and over the Arctic Ocean; these data were used to characterize observed ODEs. Detected decreases in surface ozone levels during the onset of ODEs corresponded to a median estimated apparent ozone depletion timescale (based on both chemistry and the advection of O3-depleted air) of 11 h. If assumed to be dominated by chemical mechanisms, these timescales would correspond to larger-than-observed BrO mole fractions based on known chemistry and assumed other radical levels. Using backward air mass trajectories and an assumption that transport mechanisms dominate observations, the spatial scales for ODEs (defined by time periods in which ozone levels ≤15 nmol mol−1) were estimated to be 877 km (median), while areas estimated to represent major ozone depletions (<10 nmol mol−1) had dimensions of 282 km (median). These observations point to a heterogeneous boundary layer with localized regions of active, ozone-destroying halogen chemistry, interspersed among larger regions of previously depleted air that retain reduced ozone levels through hindered atmospheric mixing. Based on the estimated size distribution, Monte Carlo simulations showed it was statistically possible that all ODEs observed could have originated upwind, followed by transport to the measurement site. Local wind speed averages were low during most ODEs (median of ~3.6 m s−1), and there was no apparent dependence on local temperature.

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected on the Beaufort Sea ice near Barrow, Alaska, in March 2009 as part of the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) and OASIS-Canada International Polar Year programmes. These results represent the first atmospheric mercury speciation measurements collected on the sea ice. Concentrations of PHg averaged 393.5 pg m⁻³ (range 47.1–900.1 pg m⁻³) and RGM concentrations averaged 30.1 pg m⁻³ (range 3.5–105.4 pg m⁻³) during the two-week-long study. The mean concentration of GEM during the study was 0.59 ng m⁻³ (range 0.01–1.51 ng m⁻³) and was depleted compared to annual Arctic ambient boundary layer concentrations. It is shown that when ozone (O₃) and bromine oxide (BrO) chemistry were active there is a positive linear relationship between GEM and O₃, a negative one between PHg and O₃, a positive correlation between RGM and BrO, and none between RGM and O₃. For the first time, GEM was measured simultaneously over the tundra and the sea ice. The results show a significant difference in the magnitude of the emission of GEM from the two locations, with significantly higher emission over the tundra. Elevated chloride levels in snow over sea ice are proposed to be the cause of lower GEM emissions over the sea ice because chloride has been shown to suppress photoreduction processes of RGM to GEM in snow. Since the snowpack on sea ice retains more mercury than inland snow, current models of the Arctic mercury cycle may greatly underestimate atmospheric deposition fluxes because they are based predominantly on land-based measurements. Land-based measurements of atmospheric mercury deposition may also underestimate the impacts of sea ice changes on the mercury cycle in the Arctic. The predicted changes in sea ice conditions and a more saline future snowpack in the Arctic could enhance retention of atmospherically deposited mercury and increase the amount of mercury entering the Arctic Ocean and coastal ecosystems

Abstract. A buoy based instrument platform (the "O-buoy") was designed, constructed, and field tested for year-round measurement of ozone, bromine monoxide, carbon dioxide, and meteorological variables over Arctic sea ice. The O-buoy operated in an autonomous manner with daily, bi-directional data transmissions using Iridium satellite communication. The O-buoy was equipped with three power sources: primary lithium-ion battery packs, rechargeable lead acid packs, and solar panels that recharge the lead acid packs, and can fully power the O-buoy during summer operation. This system was designed to operate under the harsh conditions present in the Arctic, with minimal direct human interaction, to aid in our understanding of the atmospheric chemistry that occurs in this remote region of the world. The current design requires approximately yearly maintenance limited by the lifetime of the primary power supply. The O-buoy system was field tested in Elson Lagoon, Barrow, Alaska from February to May 2009, and deployed in the Beaufort Sea in October 2009. Here, we describe the design and present preliminary data.