Precise atmospheric oxygen measurements with a paramagnetic oxygen analyzer

A methodology has been developed for making continuous, high-precision measurements of atmospheric oxygen concentrations by modifying a commercially available paramagnetic oxygen analyzer. Incorporating several design improvements, an effective precision of 0.2 ppm O-2 from repeated measurements over a 1-hour interval was achieved. This is sufficient to detect background changes in atmospheric O-2 to a level that constrains various aspects of the global carbon cycle. The analyzer was used to measure atmospheric O-2 in a semicontinuous fashion from air sampled from the end of Scripps Pier, La Jolla, California, and data from a 1-week period in August 1996 are shown. The data exhibit strongly anticorrelated changes in O-2 and CO2 caused by local or regional combustion of fossil fuels. During periods of steady background CO2 concentrations, however, we see additional variability in O-2 concentrations, clearly not due to local combustion and presumably due to oceanic sources or sinks of O-2. This variability suggests that in contrast to CO2, higher O-2 sampling rates, such as those provided by continuous measurement programs, may be necessary to define an atmospheric O-2 background and thus aid in validating and interpreting other O-2 data from flask sampling programs. Our results have also demonstrated that this paramagnetic analyzer and gas handling design is well suited for making continuous measurements of atmospheric O-2 and is suitable for placement at remote background air monitoring sites

Thermal fractionation of air in polar firn by seasonal temperature gradients

Air withdrawn from the top 5-15 m of the polar snowpack (firn) shows anomalous enrichment of heavy gases during summer, including inert gases. Following earlier work, we ascribe this to thermal diffusion, the tendency of a gas mixture to separate in a temperature gradient, with heavier molecules migrating toward colder regions. Summer warmth creates a temperature gradient in the top few meters of the firn due to the thermal inertia of the underlying firn and causes gas fractionation by thermal diffusion. Here we explore and quantify this process further in order to (1) correct for bias caused by thermal diffusion in firn air and ice core air isotope records, (2) help calibrate a new technique for measuring temperature change in ice core gas records based on thermal diffusion [Severinghaus et al., 1998], and (3) address whether air in polar snow convects during winter and, if so, whether it creates a rectification of seasonality that could bias the ice core record. We sampled air at 2-m-depth intervals from the top 15 m of the firn at two Antarctic sites, Siple Dome and South Pole, including a winter sampling at the pole. We analyzed 15N/14N, 40Ar/36Ar, 40Ar/38Ar, 18O/16O of O2, O2/N2, 84Kr/36Ar, and 132Xe/36Ar. The results show the expected pattern of fractionation and match a gas diffusion model based on first principles to within 30%. Although absolute values of thermal diffusion sensitivities cannot be determined from the data with precision, relative values of different gas pairs may. At Siple Dome, δ40Ar/4 is 66 ± 2% as sensitive to thermal diffusion as δ15N, in agreement with laboratory calibration; δ18O/2 is 83 ± 3%, and δ84Kr/48 is 33 ± 3% as sensitive as δ15N. The corresponding figures for summer South Pole are 64 ± 2%, 81 ± 3%, and 34 ± 3%. Accounting for atmospheric change, the figure for δO2/N2/4 is 90 ± 3% at Siple Dome. Winter South Pole shows a strong depletion of heavy gases as expected. However, the data do not fit the model well in the deeper part of the profile and yield a systematic drift with depth in relative thermal diffusion sensitivities (except for Kr, constant at 34 ± 4%), suggesting the action of some other process that is not currently understood. No evidence for wintertime convection or a rectifier effect is seen

Abrupt changes in atmospheric methane at the MIS 5b–5a transition

New ice core analyses show that the prominent rise in atmospheric methane concentration at Dansgaard-Oeschger event 21 was interrupted by a century-long 20% decline, which was previously unrecognized. The reversal was found in a new ∼100-year resolution study of methane in the GISP2 ice core, encompassing the beginning of D-O event 21, which also corresponds to the transition from MIS 5b to 5a. Although a corresponding reversal (within age uncertainty) is observed in climate proxies measured in GISP2 ice, including δ¹⁸O[subscript ice], electrical conductivity, light scattering, and several ions, this feature has not been discussed previously. Abrupt changes in methane are paralleled by changes in δ¹⁵N of trapped air, a quantity that reflects local temperature change at Greenland summit. The reversal described here supports the hypothesis that climate can be unstable during major transitions, as was previously described for the last deglaciation.This is the publisher’s final pdf. The published article is copyrighted by the American Geophysical Union and can be found at: http://www.agu.org/journals/gl

In situ cosmogenic radiocarbon production and 2-D ice flow line modeling for an Antarctic blue ice area

Radiocarbon measurements at ice margin sites and blue ice areas can potentially be used for ice dating, ablation rate estimates and paleoclimatic reconstructions. Part of the measured signal comes from in situ cosmogenic ¹⁴C production in ice, and this component must be well understood before useful information can be extracted from ¹⁴C data. We combine cosmic ray scaling and production estimates with a two-dimensional ice flow line model to study cosmogenic ¹⁴C production at Taylor Glacier, Antarctica. We find (1) that ¹⁴C production through thermal neutron capture by nitrogen in air bubbles is negligible; (2) that including ice flow patterns caused by basal topography can lead to a surface ¹⁴C activity that differs by up to 25% from the activity calculated using an ablation-only approximation, which is used in all prior work; and (3) that at high ablation margin sites, solar modulation of the cosmic ray flux may change the strength of the dominant spallogenic production by up to 10%. As part of this effort we model two-dimensional ice flow along the central flow line of Taylor Glacier. We present two methods for parameterizing vertical strain rates, and assess which method is more reliable for Taylor Glacier. Finally, we present a sensitivity study from which we conclude that uncertainties in published cosmogenic production rates are the largest source of potential error. The results presented here can inform ongoing and future ¹⁴C and ice flow studies at ice margin sites, including important paleoclimatic applications such as the reconstruction of paleoatmospheric ¹⁴C content of methane

Does δ18O of O2 record meridional shifts in tropical rainfall?

Marine sediments, speleothems, paleo-lake elevations, and ice core methane and δ¹⁸O of O₂ (δ¹⁸Oatm) records provide ample evidence for repeated abrupt meridional shifts in tropical rainfall belts throughout the last glacial cycle. To improve understanding of the impact of abrupt events on the global terrestrial biosphere, we present composite records of δ¹⁸Oatm and inferred changes in fractionation by the global terrestrial biosphere (ΔεLAND) from discrete gas measurements in the WAIS Divide (WD) and Siple Dome (SD) Antarctic ice cores. On the common WD timescale, it is evident that maxima in ΔεLAND are synchronous with or shortly follow small-amplitude WD CH₄ peaks that occur within Heinrich stadials 1, 2, 4, and 5 – periods of low atmospheric CH₄ concentrations. These local CH₄ maxima have been suggested as markers of abrupt climate responses to Heinrich events. Based on our analysis of the modern seasonal cycle of gross primary productivity (GPP)-weighted δ¹⁸O of terrestrial precipitation (the source water for atmospheric O₂ production), we propose a simple mechanism by which ΔεLAND tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, ΔεLAND should decrease due to the underlying meridional gradient in rainfall δ¹⁸O. A southward shift should increase ΔεLAND. Monsoon intensity also influences δ¹⁸O of precipitation, and although we cannot determine the relative contributions of the two mechanisms, both act in the same direction. Therefore, we suggest that abrupt increases in ΔεLAND unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by ΔεLAND

Ice stratigraphy at the Pakitsoq ice margin, West Greenland, derived from gas records

Horizontal ice-core sites, where ancient ice is exposed at the glacier surface, offer unique opportunities for paleo-studies of trace components requiring large sample volumes. Following previous work at the Pâkitsoq ice margin in West Greenland, we use a combination of geochemical parameters measured in the ice matrix (δ¹⁸O[subscript ice]) and air occlusions (δ¹⁸O[subscript atm], δ¹⁵N of N₂ and methane concentration) to date ice layers from specific climatic intervals. The data presented here expand our understanding of the stratigraphy and three-dimensional structure of ice layers outcropping at Pâkitsoq. Sections containing ice from every distinct climatic interval during Termination I, including Last Glacial Maximum, Bølling/Allerød, Younger Dryas and the early Holocene, are identified. In the early Holocene, we find evidence for climatic fluctuations similar to signals found in deep ice cores from Greenland. A second glacial-interglacial transition exposed at the extreme margin of the ice is identified as another outcrop of Termination I (rather than the onset of the Eemian interglacial as postulated in earlier work). Consequently, the main structural feature at Pâkitsoq is a large-scale anticline with accordion-type folding in both exposed sequences of the glacial-Holocene transition, leading to multiple layer duplications and age reversals

A horizontal ice core from Taylor Glacier, its implications for Antarctic climate history, and an improved Taylor Dome ice core time scale

Ice core records from Antarctica show mostly synchronous temperature variations during the last deglacial transition, an indication that the climate of the entire continent reacted as one unit to the global changes. However, a record from the Taylor Dome ice core in the Ross Sea sector of East Antarctica has been suggested to show a rapid warming, similar in style and synchronous with the Oldest Dryas—Bølling warming in Greenland. Since publication of the Taylor Dome record, a number of lines of evidence have suggested that this interpretation is incorrect and reflects errors in the underlying time scale. The issues raised regarding the dating of Taylor Dome currently linger unresolved, and the original time scale remains the de facto chronology. We present new water isotope and chemistry data from nearby Taylor Glacier to resolve the confusion surrounding the Taylor Dome time scale. We find that the Taylor Glacier record is incompatible with the original interpretation of the Taylor Dome ice core, showing that the warming in the area was gradual and started at ∼18 ka BP (before 1950) as seen in other East Antarctic ice cores. We build a consistent, up‐to‐date Taylor Dome chronology from 0 to 60 ka BP by combining new and old age markers based on synchronization to other ice core records. The most notable feature of the new TD2015 time scale is a gas age—ice age difference of up to 12,000 years during the Last Glacial Maximum, by far the largest ever observed

High variablity of Greenland surface temperature over the past 4000 years estimated from trapped air in ice core

第2回極域科学シンポジウム　氷床コアセッション 11月16日（水） 国立極地研究所 2階大会議

Multiple carbon cycle mechanisms associated with the glaciation of Marine Isotope Stage 4

Here we use high-precision carbon isotope data (δ13C-CO2) to show atmospheric CO2 during Marine Isotope Stage 4 (MIS 4, ~70.5-59 ka) was controlled by a succession of millennial-scale processes. Enriched δ13C-CO2 during peak glaciation suggests increased ocean carbon storage. Variations in δ13C-CO2 in early MIS 4 suggest multiple processes were active during CO2 drawdown, potentially including decreased land carbon and decreased Southern Ocean air-sea gas exchange superposed on increased ocean carbon storage. CO2 remained low during MIS 4 while δ13C-CO2 fluctuations suggest changes in Southern Ocean and North Atlantic air-sea gas exchange. A 7 ppm increase in CO2 at the onset of Dansgaard-Oeschger event 19 (72.1 ka) and 27 ppm increase in CO2 during late MIS 4 (Heinrich Stadial 6, ~63.5-60 ka) involved additions of isotopically light carbon to the atmosphere. The terrestrial biosphere and Southern Ocean air-sea gas exchange are possible sources, with the latter event also involving decreased ocean carbon storage