An interlaboratory comparison of techniques for extracting and analyzing trapped gases in ice cores

We undertook an interlaboratory comparison of techniques used to extract and analyze trapped gases in ice cores. The intercomparison included analyses of standard reference gases and samples of ice from the Greenland Ice Sheet Project 2 (GISP2) site. Concentrations of CO₂, CH₄, the δ¹⁸O of O₂, the δ¹⁵N of N₂, and the O₂/N₂, and Ar/N₂ ratios were measured in air standards and ice core sampries. The standard reference scales for CO₂ and CH₄ were consistent at the ±2% level. The δᴼ²/N₂ and δ¹⁸O of O₂ measurements showed substantial deviations between the two laboratories able to measure these ratios. The deviations are probably related to errors associated with calibration of the working standards. The δᴬʳ/N₂ and δ¹⁵N of N₂ measurements were consistent. Five laboratories analyzed the CH₄ concentration in a 4.2-m section of the GISP2 ice core. The average of 20 discrete CH₄ measurements was 748±10 parts per billion by volume (ppbv). The standard deviation of these measurements was close to the total analytical uncertainty associated with the measurements. In all cases, those laboratories employing a dry extraction technique determined higher CH₄ values than laboratories using a wet extraction technique. The origin of this difference is unclear but may involve uncertainties associated with blank corrections. Analyses of the CO₂ concentration of trapped gases showed extreme variations which cannot be explained by analytical uncertainties alone. Three laboratories measured the [CO₂] on 21 discrete depths yielding an average value of 283±13 parts per million by volume (ppmv). In this case, the standard deviation was roughly a factor of 2 greater than the analytical uncertainties. We believe the variability in the measured [CO₂] results from impurities in the ice which may have compromised the [CO₂] of trapped gases in Greenland ice

Etude du methane atmospherique au cours du dernier cycle climatique a partir de l'analyse de l'air piege dans la glace antarctique

SIGLEINIST T 73284 / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Variations of air content in Dasuopu ice core from AD 1570-1927 and implications fore climate change

An ice core air content record that was recovered from the refrozen-recrystallization ice formation zone in the Dasuopu Glacier was investigated in this work, which showed that the air content in ice performed significant fluctuations both in the seasonal and long-time series. The air content was low in summer and high in winter, and fluctuated around the mean value of 5.025 cm3 per 100 g ice from AD 1571 to AD 1927. The correlation of the air content in ice with the climatic and environmental factors was discussed combining with the dating results, which showed that over about 400 yrs from AD 1570 to AD 1927 the air content in ice from the refrozen-recrystallization ice formation zone in the Dasuopu Glacier was mainly dominated by the insolation intensity rather than the temperature and other environmental factors in the Southern Tibetan Plateau. © 2010 Elsevier Ltd and INQUA

CH₄ and δ¹⁸O of O₂ records from Antarctic and Greenland ice: A clue for stratigraphic disturbance in the bottom part of the Greenland Ice Core Project and the Greenland Ice Sheet Project 2 ice cores

The suggestion of climatic instability during the last interglacial period (Eem), based on the bottom 10% of the Greenland Ice core Project (GRIP) isotopic profile, has been questioned because the bottom record from the neighboring Greenland Ice Sheet Project 2 (GISP2) core (28 km away) is strikingly different over the same interval and because records of the δ¹⁸O of atmospheric O₂ from both cores showed unexpected rapid fluctuations. Here we present detailed methane records from the Vostok (Antarctica), GRIP, and GISP2 cores over the relevant intervals. The GRIP and GISP2 data show rapid and large changes in methane concentration, which are correlative with variations of the δ¹⁸O of the ice, while the Vostok record shows no such variations. This discrepancy reinforces the suggestion that the bottom sections of the Greenland records are disturbed. By combining the methane data with measurements of δ¹⁸O of O₂ in the same samples, we attempt to constrain the nature of the stratigraphic disturbance and the age of the analyzed ice samples. Our results suggest that ice layers from part of the last interglacial period exist in the lower section of both ice cores and that some of the apparent climate instabilities in the GRIP core would be the result of a mixture of ice from the last interglacial with ice from the beginning of the last glaciation or from the penultimate glaciation

A 70 ka record of explosive eruptions from the TALDICE ice core (Talos Dome, East Antarctic plateau)

The new Antarctic TALDICE ice core (72° 49' S, 159° 11' E, 1620 m depth), containing abundant primary tephras, provides the opportunity to elucidate the late Quaternary volcanic history of the south polar region, as well as to broaden the East Antarctic tephrostratigraphic framework. Here grain size and glass compositional data for representative tephra layers from the last 70 ka core section are used for source identification. Results point to origin of layers from centres of the Melbourne Volcanic Province (McMurdo Volcanic Group), located ~250 km from the coring site. Occurrence of tephra layers within the ice core record suggests that explosive activity in the identified source was not constant over the considered period, with a minimum of activity between 20 and 35 ka, and increased activity back to 65 ka. In addition to palaeovolcanic implications, the TALDICE tephra layers offer prospects for firm correlations between diverse widely separated palaeoarchives and for accurate dating of the Antarctic climatic record. Copyright © 2010 John Wiley & Sons, Ltd

Determination of gas diffusivity in polar firn: Comparison between experimental measurements and inverse modeling, Geophys

Abstract. To study air diffusion in polar firns, and thus evaluate the mean age of air constituents as a function of depth, it is necessary to know the effective diffusivity profile for the studied gas and firn. In this work we compare effective diffusivity profiles obtained by two methods: first, by experimental measurements on firn samples, second, using an inverse gas diffusion model. Results are obtained for three gases, CO2, CH4 and SF6, in firns exposed to different climatic conditions. While measurements give similar results for the different sites, the inverse model shows variations depending on the climatic conditions. We therefore conclude that diffusivities measured on small firn samples cannot be directly used to determine the tortuosity profile of real firn and that diffusion models have to be used

Towards high-precision isotopic analysis of CO2 from ice-core gas bubbles using quantum cascade laser spectroscopy

International audienceThe paleo-climate archive provided by gas stored in bubbles in the ice provides a powerful means to study the ~40% increase in the atmospheric CO2 concentration between glacial and interglacial climates, in combination with numerical modeling studies, to elucidate the underlying physical mechanisms. Of particular interest is, considering the strong correlation between the carbon cycle and climate, and in light of the post-industrial revolution anthropogenic increase of the CO2 concentration. The source of the CO2 released into the atmosphere during previous deglaciations can be constrained from 13CO2 isotopic measurements on CO2 gas stored in bubbles in the ice-cores by the fact that the different CO2 reservoirs (terrestrial biosphere, oceans) and associated mechanisms (biological or physical) have different isotopic signatures. Unfortunately, conventional IRMS measurements on the small quantity of gas available are difficult, tedious, and time-consuming. We report here on the design of an alternative method based on Optical Feedback Cavity Enhanced Absorption Spectrometry (OF-CEAS) using a quantum cascade laser operating near 4.36 μm. The aim of this instrument design is to achieve the measurement of the 13C/12C isotopic ratio (δ13C) with a precision better than 0.05 ‰ on small quantities of the trapped atmospheric CO2. We describe the instrument and show preliminary results

Large Variations in Southern Hemisphere Biomass Burning During the Last 650 Years

International audienceWe present a 650-year Antarctic ice core record of concentration and isotopic ratios ([delta]13C and [delta]18O) of atmospheric carbon monoxide. Concentrations decreased by ~25% (14 parts per billion by volume) from the mid-1300s to the 1600s then recovered completely by the late 1800s. [delta]13C and [delta]18O decreased by about 2 and 4 per mil ([per mille sign]), respectively, from the mid-1300s to the 1600s then increased by about 2.5 and 4[per mille sign] by the late 1800s. These observations and isotope mass balance model results imply that large variations in the degree of biomass burning in the Southern Hemisphere occurred during the last 650 years, with a decrease by about 50% in the 1600s, an increase of about 100% by the late 1800s, and another decrease by about 70% from the late 1800s to present day

Simultaneous Detection of C<sub>2</sub>H<sub>6</sub>, CH<sub>4</sub> and δ<sup>13</sup>C-CH<sub>4</sub> Using Optical Feedback Cavity Enhanced Absorption Spectroscopy in the Mid-Infrared Region: Towards Application for Dissolved Gas Measurements

International audienc

Chemical and isotopic analysis of hydrocarbon gas at trace levels. Methodology and results

Isotopic mass spectrometry coupled online with gas chromatography (GC-C-IRMS) permits measurement of relative proportions of gaseous hydrocarbon (CH4 to C4H10) and CO2, and determination of carbon isotope ratio of hydrocarbon molecules. Access to these parameters provides valuable information about the source and the genesis of naturally-occurring gas, as well as on post-formation physico-chemical processes which might have taken place in the geological environment. In particular, it is possible to distinguish hydrocarbon gas of bacterial origin from that of thermogenic origin based on proportion and carbon isotope ratio of methane as measured by GC-C-IRMS. However, in samples containing very low amounts of hydrocarbons (from 1 ppm to 1000 ppm), accurate measurement of isotope ratios is often impossible due to the limitations of conventional GC-C-IRMS techniques using direct sample introduction. A technique was developed to overcome this limitation. It is based on a novel approach allowing pre-concentration of hydrocarbons prior to GC-C-IRMS analysis. The pre-concentration step consists in selective trapping of hydrocarbon molecules on a cold adsorbent phase, and removal of non-adsorbed gases (N2, O2, Ar,...). In a second step, pre-concentrated alkanes are desorbed, and released in an inert carrier gas, focused through a capillary and introduced into the GC-C-IRMS for chromatographic separation and measurement of concentration and carbon isotope composition of each individual carbon molecule. In order to achieve sufficient accuracy, several operating conditions are of prime importance, including sufficient signal intensity, well defined peak shape and low signal/noise ratio. Accurate measurements can be performed on samples as small as 10 cm3 of bulk gas in standard conditions, with concentrations as low as 1 ppm of methane, 0.5 ppm of ethane and 0.3 ppm of propane and butane. Total analytical uncertainty on δ13C measurements ranges from ± 0.2‰ to ± 1.5‰, depending on the hydrocarbon molecule. © 2009 Elsevier B.V. All rights reserved