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Sea ice is a defining feature of the polar marine environment. It is a critical domain for marine biota and it regulates ocean-atmosphere exchange, including the exchange of greenhouse gases such as CO2 and CH4. In this study, we determined the rates and pathways that govern gas transport through a mixed sea ice cover. N2O, SF6, 3He, 4He, and Ne were used as gas tracers of the exchange processes that take place at the ice-water and air-water interfaces in a laboratory sea ice experiment. Observation of the changes in gas concentrations during freezing revealed that He is indeed more soluble in ice than in water; Ne is less soluble in ice, and the larger gases (N2O and SF6) are mostly excluded during the freezing process. Model estimates of gas diffusion through ice were calibrated using measurements of bulk gas content in ice cores, yielding gas transfer velocity through ice (kice) of ∼5 × 10−4 m d−1. In comparison, the effective air-sea gas transfer velocities (keff) ranged up to 0.33 m d−1 providing further evidence that very little mixed-layer ventilation takes place via gas diffusion through columnar sea ice. However, this ventilation is distinct from air-ice gas fluxes driven by sea ice biogeochemistry. The magnitude of keff showed a clear increasing trend with wind speed and current velocity beneath the ice, as well as the combination of the two. This result indicates that gas transfer cannot be uniquely predicted by wind speed alone in the presence of sea ice.

Characterizing flow patterns and mixing of fossil fuel-derived CO2 is important for effectively using atmospheric measurements to constrain emissions inventories. Here we used measurements and a model of atmospheric radiocarbon (14C) to investigate the distribution and fluxes of atmospheric fossil fuel CO2 across the state of California. We sampled 14C in annual C3 grasses at 128 sites and used these measurements to test a regional model that simulated anthropogenic and ecosystem CO2 fluxes, transport in the atmosphere, and the resulting Δ14C of annual grasses (Δ g ). Average measured Δ g levels in Los Angeles, San Francisco, the Central Valley, and the North Coast were 27.7 ± 20.0, 44.0 ± 10.9, 48.7 ± 1.9, and 59.9 ± 2.5‰, respectively, during the 2004–2005 growing season. Model predictions reproduced regional patterns reasonably well, with estimates of 27.6 ± 2.4, 39.4 ± 3.9, 46.8 ± 3.0, and 59.3 ± 0.2‰ for these same regions and corresponding to fossil fuel CO2 mixing ratios (C f ) of 13.7, 6.1, 4.8, and 0.3 ppm. Δ g spatial heterogeneity in Los Angeles and San Francisco was higher in the measurements than in the predictions, probably from insufficient spatial resolution in the fossil fuel inventories (e.g., freeways are not explicitly included) and transport (e.g., within valleys). We used the model to predict monthly and annual transport patterns of fossil fuel-derived CO2 within and out of California. Fossil fuel CO2 emitted in Los Angeles and San Francisco was predicted to move into the Central Valley, raising C f above that expected from local emissions alone. Annually, about 21, 39, 35, and 5% of fossil fuel emissions leave the California airspace to the north, east, south, and west, respectively, with large seasonal variations in the proportions. Positive correlations between westward fluxes and Santa Ana wind conditions were observed. The southward fluxes over the Pacific Ocean were maintained in a relatively coherent flow within the marine boundary layer, while the eastward fluxes were more vertically dispersed. Our results indicate that state and continental scale atmospheric inversions need to consider areas where mixing ratio measurements are sparse (e.g., over the ocean to the south and west of California), transport within and across the marine boundary layer, and terrestrial boundary layer dynamics. Radiocarbon measurements can be very useful in constraining these estimates.