Geochemistry, isotopic ratios and aldehyde concentrations of frost flowers, snow and ice near Barrow, Alaska

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 (NO3- and H2O2) 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, doi:10.1029/2011JD016186)) 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.

(Table 1) Characteristics of marine snow and ice samples at Barrow, Alaska

We measured light absorption in 42 marine snow, sea ice, seawater, brine, and frost flower samples collected during the OASIS field campaign between February 27 and April 15, 2009. Samples represented multiple sites between landfast ice and open pack ice in coastal areas approximately 5 km west of Barrow, Alaska. The chromophores that are most commonly measured in snow, H2O2, NO3-, and NO2-, on average account for less than 1% of sunlight absorption in our samples. Instead, light absorption is dominated by unidentified "residual" species, likely organic compounds. Light absorption coefficients for the frost flowers on first-year sea ice are, on average, 40 times larger than values for terrestrial snow samples at Barrow, suggesting very large rates of photochemical reactions in frost flowers. For our marine samples the calculated rates of sunlight absorption and OH production from known chromophores are (0.1-1.4) x 10**14 (photons/cm**3/s) and (5-70) x 10**-12 (mol/L/s), respectively. Our residual spectra are similar to spectra of marine chromophoric dissolved organic matter (CDOM), suggesting that CDOM is the dominant chromophore in our samples. Based on our light absorption measurements we estimate dissolved organic carbon (DOC) concentrations in Barrow seawater and frost flowers as approximately 130 and 360 µM C, respectively. We expect that CDOM is a major source of OH in our marine samples, and it is likely to have other significant photochemistry as well.