Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H 2O2 and CH3OOH (from here on MHP) with average (±1) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H2O2 and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night timemaxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1-5×1011 moleculesm-3 s-1 equivalent to 24-96 pptv h-1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summerlevels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H 2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.

Annually resolved ice core records from different regions over the Greenland ice sheet (GrIS) are used to investigate the spatial and temporal variability of calcium (Ca2+, mainly from mineral dust) and sodium (Na+, mainly from sea salt) deposition. Cores of high common inter-annual variability are grouped with an EOF analysis, resulting in regionally representative Ca2+ and Na+ records for northeastern and central Greenland. Utilizing a regression and validation method with ERA-40 reanalysis data, these common records are associated with distinct regional atmospheric circulation patterns over the North American Arctic, Greenland, and Central to Northern Europe. These patterns are interpreted in terms of transport and deposition of the impurities. In the northeastern part of the GrIS sea salt records reflect the intrusion of marine air masses from southeasterly flow. A large fraction of the Ca2+ variability in this region is connected to a circulation pattern suggesting transport from the west and dry deposition. This pattern is consistent with the current understanding of a predominantly Asian source of the dust deposited over the GrIS. However, our results also indicate that a significant fraction of the inter-annual dust variability in NE and Central Greenland is determined by the frequency and intensity of wet deposition during the season of high atmospheric dust loading, rather than representing the variability of the Asian dust source and/or long-range transport to Greenland. The variances in the regional proxy records explained by the streamfunction patterns are high enough to permit reconstructions of the corresponding regional deposition regimes and the associated circulation patterns. © Springer-Verlag 2006.

The first measurements of peroxy (HO2+RO2) and hydroxyl (OH) radicals above the arctic snowpack were collected during the summer 2003 campaign at Summit, Greenland. The median measured number densities for peroxy and hydroxyl radicals were 2.2×108 mol cm-3 and 6.4×106 mol cm-3, respectively. The observed peroxy radical values are in excellent agreement (R2 = 0.83, M / O = 1.06) with highly constrained model predictions. However, calculated hydroxyl number densities are consistently more than a factor of 2 lower than the observed values. These results indicate that our current understanding of radical sources and sinks is in accord with our observations in this environment but that there may be a mechanism that is perturbing the (HO2+RO2)/OH ratio. This observed ratio was also found to depend on meteorological conditions especially during periods of high winds accompanied by blowing snow. Backward transport model simulations indicate that these periods of high winds were characterized by rapid transport (1-2 days) of marine boundary layer air to Summit. These data suggest that the boundary layer photochemistry at Summit may be periodically impacted by halogens. © 2007.