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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]

We present an age model for the 651 m deep Skytrain Ice Rise ice core. The top 2000 years have previously been dated using age markers interpolated through annual layer counting. Below this, we align the Skytrain core to the AICC2012 age model using tie points in the ice and air phase, and apply the Paleochrono program to obtain the best fit to the tie points and glaciological constraints. In the gas phase, ties are made using methane and, in critical sections, d18Oair; in the ice phase ties are through 10Be across the Laschamps Event, and through ice chemistry related to long-range dust transport and deposition. This strategy provides a good outcome to about 108 ka (~605 m). Beyond that there are signs of flow disturbance, with a section of ice probably repeated. Nonetheless values of CH4 and d18Oair confirm that part of the last interglacial (LIG), from about 117-126 ka (617-628 m), is present and in chronological order. Below this there are clear signs of stratigraphic disturbance, with rapid oscillation of values in both the ice and gas phase at the base of the LIG section. Based on methane values, the warmest part of the LIG and the coldest part of the penultimate glacial are missing from our record. Ice below 631 m appears to be of age >150 ka. [ABSTRACT FROM AUTHOR]

Volcanic eruptions are the dominant cause of natural variability in climate forcing on timescales up to multidecadal. Large volcanic eruptions lead to global-scale climate effects and influence the carbon cycle on long timescales. However, estimating the frequency of eruptions is challenging. Here we assess the frequency at which eruptions with particular deposition fluxes are observed in the EPICA Dome C ice core over the last 200 kyr. Using S isotope analysis we confirm that most of the largest peaks recorded at Dome C are from stratospheric eruptions. The cumulative frequency through 200 kyr is close to linear suggesting an approximately constant rate of eruptions. There is no evidence for an increase in the rate of events recorded in Antarctica at either of the last two deglaciations. Millennial variability is at the level expected from recording small numbers of eruptions, while multimillennial variability may be partly due to changes in transport efficiency through the Brewer-Dobson circulation. Our record of events with sulfate deposition rates > 20 mg m-2 and >50 mg m-2 contains 678 and 75 eruptions respectively over the last 200 kyr. Calibration with data on historic eruptions and analysis of a global Quaternary dataset of terrestrial eruptions indicates that sulfate peaks with deposition rates > 20 mg m-2 and >50 mg m-2 correspond to explosive eruptions of magnitude ≥ 6.5 and ≥ 7 respectively. The largest recorded eruption deposited just over 300 mg m-2. [ABSTRACT FROM AUTHOR]

The resemblance of the orbitally filtered isotope signal from the past 340 kyr in Antarctic ice cores to Northern Hemisphere summer insolation intensity has been used to suggest that the northern hemisphere may drive orbital-scale global climate changes (1).A recent Letter (2) by Laepple et al. suggests that, contrary to this interpretation, this semblance may instead be explained by weighting the orbitally controlled Antarctic seasonal insolation cycle with a static (present-day) estimate of the seasonal cycle of accumulation. We suggest, however, that both time variability in accumulation seasonality and alternative stable seasonality can markedly alter the weighted insolation signal. This indicates that, if the last 340 kyr of Antarctic accumulation has not always looked like the estimate of precipitation and accumulation seasonality made by Laepple et al. (2), this particular accumulation weighting explanation of the Antarctic orbital-scale isotopic signal might not be robust., ARISING FROM T. Laepple, M. Werner & G. Lohmann Nature 471, 91-94 (2011) Laepple et al. (2) present a range of present-day accumulation and precipitation estimates from a variety of [...]

Climate during the last glacial period was marked by abrupt instability on millennial time scales that included large swings of temperature in and around Greenland (Daansgard-Oeschger events) and smaller, more gradual changes in Antarctica (AIM events). Less is known about the existence and nature of similar variability during older glacial periods, especially during the early Pleistocene when glacial cycles were dominantly occurring at 41-kyr intervals compared to the much longer and deeper glaciations of the more recent period. Here we report a continuous millennially-resolved record of stable isotopes of planktic and benthic foraminifera at IODP Site U1385 (the "Shackleton Site") from the southwestern Iberian margin for the last 1.5 million years, which includes the Middle Pleistocene Transition (MPT). Our results demonstrate that millennial climate variability (MCV) was a persistent feature of glacial climate, both before and after the MPT. Prior to 1.2 Ma in the early Pleistocene, the amplitude of MCV was modulated by the 41-kyr obliquity cycle and increased when axial tilt dropped below 23.5o and benthic δ18O exceeded ~3.8? (corrected to Uvigerina), indicating a threshold response to orbital forcing. Afterwards, MCV became focused mainly on the transitions into and out of glacial states (i.e., inceptions and terminations) and during times of intermediate ice volume. During the MPT (1.2-0.65 Ma), obliquity continues to modulate the amplitude of MCV but in a more non-linear fashion as evidenced by the appearance of multiples (82, 123 kyrs) and combination tones (28 kyrs) of the 41-kyr cycle. At the end of the MPT (~0.65 Ma), obliquity modulation of MCV amplitude wanes as quasi-periodic 100-kyr and precession power increase, coinciding with growth of oversized ice sheets on North America and the appearance of Heinrich layers in North Atlantic sediments. Whereas the planktic δ18O of Site U1385 shows a strong resemblance to Greenland temperature and atmospheric methane (i.e., northern hemisphere climate), millennial changes in benthic δ18O closely follow the temperature history of Antarctica for the past 800 ka. The phasing of planktic and benthic δ18O throughout much of the record is similar to that observed for MIS 3, which has been suggested to mimic the signature of the bipolar seesaw -- i.e., an interhemispheric asymmetry between the timing of cooling in Antarctica and warming in Greenland. The Iberian margin isotopic record suggests bipolar asymmetry was a robust feature of interhemispheric glacial climate variations for at least the past 1.5 Ma despite changing glacial boundary conditions. A strong correlation exists between millennial increases in planktic δ18O (cooling) and decreases in benthic δ13C, indicating millennial variations in North Atlantic surface temperature are mirrored by changes in deep-water circulation and remineralization of carbon in the abyssal ocean. We find strong evidence that climate variability on millennial and orbital scales are coupled across different time scales and interact, in both directions, which may be important for linking internal climate dynamics and external astronomical forcing. [ABSTRACT FROM AUTHOR]

We determine the physicochemical habitat for microorganisms in subsurface terrestrial ice by quantitatively constraining the partitioning of bacteria and fluorescent beads (1-10 [micro]m) between the solid ice crystals and the water-filled veins and boundaries around individual ice crystals. We demonstrate experimentally that the partitioning of spherical particles within subsurface ice depends strongly on size but is largely independent of source particle concentration. Although bacteria are shown consistently to partition to the veins, larger particles, which would include eukaryotic cells, become trapped in the crystals with little potential for continued metabolism. We also calculate the expected concentrations of soluble impurities in the veins for typical bulk concentrations found in natural ice. These calculations and scanning electron microscope observations demonstrate a concentrated chemical environment (3.5 M total ions at -10 [degrees]C) in the veins, where bacteria were found to reside, with a mixture of impurities that could sustain metabolism. Our calculations show that typical bacterial cells in glacial ice would fit within the narrow veins, which are a few micrometers across. These calculations are confirmed by microscopic images of spherical, 1.9-[micro]m-diameter, fluorescent beads and stained bacteria in subsurface veins. Typical bacterial concentrations in clean ice ([10.sup.2]-[10.sup.3] cells/mL) would result in concentrations of [10.sup.6]-[10.sup.8] cells/mL of vein fluid, but occupy only a small fraction of the total available vein volume ( Keywords: ice, glacier, water veins, bacteria, eukaryote, bacterial habitat.

Interglacials and glacials represent low and high ice volume end-members of ice age cycles. While progress has been made in our understanding of how and when transitions between these states occur, their relative intensity has been lacking an explanatory framework. With a simple quantitative model, we show that over the last 800,000 years interglacial intensity can be described as a function of the strength of the previous glacial and the summer insolation at high latitudes in both hemispheres during the deglaciation. Since the precession components in the boreal and austral insolation counteract each other, the amplitude increase in obliquity cycles after 430,000 years ago is imprinted in interglacial intensities, contributing to the manifestation of the so-called Mid-Brunhes Event. Glacial intensity is also linked with the strength of the previous interglacial, the time elapsed from it, and the evolution of boreal summer insolation. Our results suggest that the memory of previous climate states and the time course of the insolation are crucial for understanding interglacial and glacial intensities. [ABSTRACT FROM AUTHOR]

The ∼74 ka Toba eruption was one of the largest volcanic events of the Quaternary. There is much interest in determining the impact of such a large event, particularly on the climate and hominid populations at the time. Although the Toba eruption has been identified in both land and marine archives as the Youngest Toba Tuff, its precise place in the ice core record is ambiguous. Several volcanic sulfate signals have been identified in both Antarctic and Greenland ice cores and span the Toba eruption 40Ar/39Ar age uncertainty. Here, we measure sulfur isotope compositions in Antarctic ice samples from the Dome C (EDC) and Dronning Maud Land (EDML) ice cores at high temporal resolution across 11 of these potential Toba sulfate peaks to identify candidates with sulfur mass-independent fractionation (S-MIF), indicative of an eruption whose plume reached altitudes at or above the stratospheric ozone layer. Using this method, we identify several candidate sulfate peaks that contain stratospheric sulfur. We further narrow down potential candidates based on the isotope signatures by identifying sulfate peaks that are due to a volcanic event at tropical latitudes. In one of these sulfate peaks at 73.67 ka, we find the largest ever reported magnitude of S-MIF in volcanic sulfate in polar ice, with a Δ 33S value of -4.75 ‰. As there is a positive correlation between the magnitude of the S-MIF signal recorded in ice cores and eruptive plume height, this could be a likely candidate for the Toba super-eruption, with a plume top height in excess of 45 km. These results support the 73.7±0.3 ka (1 σ) 40Ar/39Ar age estimate for the eruption, with ice core ages of our candidates with the largest magnitude S-MIF at 73.67 and 73.74 ka. Finally, since these candidate eruptions occurred on the transition into Greenland Stadial 20, the relative timing suggests that Toba was not the trigger for the large Northern Hemisphere cooling at this time although we cannot rule out an amplifying effect. [ABSTRACT FROM AUTHOR]

The ~74 ka Toba eruption was one of the largest volcanic events of the Quaternary. There is much interest in determining the impact of such a huge event, particularly on the climate and hominid populations at the time. Although the Toba eruption has been identified in both land and marine archives as the Youngest Toba Tuff, its precise place in the ice core record is ambiguous. Multiple volcanic sulfate signals have been identified in both Antarctic and Greenland ice cores within the uncertainty of age estimates as possible events for the Toba eruption. We measure sulfur isotope compositions in Antarctic ice samples at high temporal resolution across 11 of these potential Toba sulfate peaks in two cores to identify candidates with sulfur mass-independent fractionation (S-MIF), indicative of an eruption whose plume reached altitudes at or above the ozone layer in the stratosphere. Using this method, we identify several candidate sulfate peaks that contain stratospheric sulfur. We further narrow down potential candidates based on the isotope signatures by identifying sulfate peaks that are due to a volcanic event at tropical latitudes. In one of these sulfate peaks at 73.67 ka, we find the largest ever reported magnitude of S-MIF in volcanic sulfate in polar ice, with a Δ33S value of −4.75 ‰. As there is a positive correlation between the magnitude of the S-MIF signal recorded in ice cores and eruptive plume height, this could be a likely candidate for the Toba supereruption, with a plume height in excess of 45 km. These results support the 73.7 ± 0.3 ka (1σ) ka Ar/Ar age estimate for the eruption, with ice core ages of our candidates with the largest magnitude S-MIF at 73.67 and 73.74 ka. Finally, since these candidate eruptions occurred on the transition into Greenland Stadial 20, the relative timing suggests that Toba was not the trigger for the large Northern Hemisphere cooling at this time although we cannot rule out an amplifying effect. [ABSTRACT FROM AUTHOR]

Two consecutive cruises in the Weddell Sea, Antarctica, in winter 2013 provided the first direct observations of sea salt aerosol (SSA) production from blowing snow above sea ice, thereby validating a model hypothesis to account for winter time SSA maxima in polar regions not explained otherwise. Blowing or drifting snow always lead to increases in SSA during and after storms. Observed aerosol gradients suggest that net production of SSA takes place near the top of the blowing or drifting snow layer. The observed relative increase of SSA concentrations with wind speed suggests that on average the corresponding aerosol mass flux during storms was equal or larger above sea ice than above the open ocean, demonstrating the importance of the blowing snow source for SSA in winter and early spring. For the first time it is shown that snow on sea ice is depleted in sulphate relative to sodium with respect to sea water. Similar depletion observed in the aerosol suggests that most sea salt originated from snow on sea ice and not the open ocean or leads, e.g. on average 93% during the 8 June and 12 August 2013 period. A mass budget calculation shows that sublimation of snow even with low salinity (<1psu) can account for observed increases of atmospheric sea salt from blowing snow. Furthermore, snow on sea ice and blowing snow showed no or small depletion of bromide relative to sodium with respect to sea water, whereas aerosol at 29m was enriched suggesting that SSA from blowing snow is a source of atmospheric reactive bromine, an important ozone sink, with bromine loss taking place preferentially in the aerosol phase between 2 and 29m above the sea ice surface. Evaluation of the current model for SSA production from blowing snow showed that the parameterisations used can generally be applied to snow on sea ice. Snow salinity, a sensitive model parameter, depends to a first order on snowpack depth and therefore is higher above first-year than above multi-year sea ice. Shifts in the ratio of FYI and MYI over time are therefore expected to change the seasonal SSA source flux and contribute to the variability of SSA in ice cores, which both represents an opportunity and a challenge for the quantitative interpretation of the sea salt sea ice proxy. It is expected that similar processes take place in the Arctic regions. [ABSTRACT FROM AUTHOR]