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To extract climatically relevant chemical signals from the deepest, oldest Antarctic ice, we must first investigate the degree to which chemical ions diffuse within solid ice. Volcanic sulfate peaks are an ideal target for such an investigation because they are high-amplitude, short-duration (∼3 years) events with a quasi-uniform structure. Here we present an analysis of the EPICA Dome C sulfate record over the last 450 kyr. We identify volcanic peaks and isolate them from the non-sea-salt sulfate background to reveal the effects of diffusion: amplitude damping and broadening of peaks in the time domain with increasing depth and age. Sulfate peak shape is also altered by the thinning of ice layers with depth that results from ice flow. Both processes must be simulated to derive effective diffusion rates. This is achieved by running a forward model to diffuse idealised sulfate peaks at different rates while also accounting for ice thinning. Our simulations suggest a median effective diffusion rate of sulfate ions of 2.4±1.7×10-7 m 2 yr -1 in Holocene ice, slightly faster than suggested by previous work. The effective diffusion rate observed in deeper ice is significantly lower, and Holocene ice shows the highest rate of the last 450 kyr. Beyond the Holocene, there is no systematic difference between the effective diffusion rates of glacial and interglacial periods despite variations in soluble ion concentrations, dust loading, and ice grain radii. Effective diffusion rates for 40 to 200 ka are relatively constant and of the order 1×10-8 m 2 yr -1. Our results suggest that the diffusion of sulfate ions within volcanic peaks is relatively fast initially, perhaps through an interconnected vein network, but slows significantly after 40 kyr. In the absence of clear evidence for a controlling influence of temperature on sulfate diffusivity with depth and age, we hypothesise that the rapid decrease in effective diffusion rate from the time of deposition to ice of 50 ka age may be due to a switch in the mechanism of diffusion resulting from the changing location of sulfate ions within the ice microstructure and/or interconnectedness of veins and grain boundaries. [ABSTRACT FROM AUTHOR]

Over the past two decades, with recognition that the ocean's sea-ice cover is neither insensitive to climate change nor a barrier to light and matter, research in sea-ice biogeochemistry has accelerated significantly, bringing together a multi-disciplinary community from a variety of fields. This disciplinary diversity has contributed a wide range of methodological techniques and approaches to sea-ice studies, complicating comparisons of the results and the development of conceptual and numerical models to describe the important biogeochemical processes occurring in sea ice. Almost all chemical elements, compounds, and biogeochemical processes relevant to Earth system science are measured in sea ice, with published methods available for determiningbiomass, pigments, net community production, primary production, bacterial activity, macronutrients, numerous natural and anthropogenic organic compounds, trace elements, reactive and inert gases, sulfur species, the carbon dioxide system parameters, stable isotopes, and water-ice-Atmosphere fluxes of gases, liquids, and solids. For most of these measurements, multiple sampling and processing techniques are available, but to date there has been little intercomparison or intercalibration between methods. In addition, researchers collect different types of ancillary data and document their samples differently, further confounding comparisons between studies. These problems are compounded by the heterogeneity of sea ice, in which even adjacent cores can have dramatically different biogeochemical compositions. We recommend that, in future investigations, researchers design their programs based on nested sampling patterns, collect a core suite of ancillary measurements, and employ a standard approach for sample identification and documentation. In addition, intercalibration exercises are most critically needed for measurements of biomass, primary production, nutrients, dissolved and particulate organic matter (including exopolymers), the CO2 system, air-ice gas fluxes, and aerosol production. We also encourage the development of in situ probes robust enough for long-Term deployment in sea ice, particularly for biological parameters, the CO2 system, and other gases.

Ice core records of carbon dioxide (CO2) throughout the last 2000 years provide context for the unprecedented anthropogenic rise in atmospheric CO2 and insights into global carbon cycle dynamics. Yet the atmospheric history of CO2 remains uncertain in some time intervals. Here we present measurements of CO2 and methane (CH4) in the Skytrain ice core from 1450 to 1700 CE. Results suggest a sudden decrease in CO2 around 1610 CE in one widely used record may be an artefact of a small number of anomalously low values. Our analysis supports a more gradual decrease in CO2 of 0.5 ppm per decade from 1516 to 1670 CE, with an inferred land carbon sink of 2.6 PgC per decade. This corroborates modelled scenarios of large-scale reorganisation of land use in the Americas following New World-Old World contact, whereas a rapid decrease in CO2 at 1610 CE is incompatible with even the most extreme land-use change scenarios. Ice core records of gradually declining atmospheric carbon dioxide (CO2) for the period 1450–1700 CE support modelled scenarios of large-scale reorganisation of land use in the Americas following New World-Old World contact. [ABSTRACT FROM AUTHOR]