scholarly journals High precision dual-inlet IRMS measurements of the stable isotopes of CO<sub>2</sub> and the N<sub>2</sub>O/CO<sub>2</sub> ratio from polar ice core samples

2014 ◽  
Vol 7 (7) ◽  
pp. 6529-6564 ◽  
Author(s):  
T. K. Bauska ◽  
E. J. Brook ◽  
A. C. Mix ◽  
A. Ross
Keyword(s):  
Isotopic Composition ◽  
Water Vapor Pressure ◽  
Ice Core ◽  
Ice Cores ◽  
Spectrometric Method ◽  
Mass Spectrometric Method ◽  
Polar Ice ◽  
Mixing Ratios ◽  
Core Samples ◽  
Oxygen Isotopic

Abstract. An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ13C-CO2) trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ13C of CO2 at exceptional precision, as well as measuring the CO2 and N2O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~ 400 grams) with a dry-extraction "ice-grater" device. The liberated air is cryogenically purified to a CO2 and N2O mixture and analyzed with a micro-volume equipped dual-inlet IRMS (Thermo MAT 253). The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02‰ for δ13C-CO2 and 2 ppm and 4 ppb for the CO2 and N2O mixing ratios, respectively (1-sigma pooled standard deviation). Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultra-low temperature freezer (−60 °C) improves the precision and decreases the experimental blank of the method. We describe techniques for accurate calibration of small samples and the application of a mass spectrometric method based on source fragmentation for reconstructing the N2O history of the atmosphere. The oxygen isotopic composition of CO2 is also investigated, confirming previous observations of oxygen exchange between gaseous CO2 and solid H2O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H2O and CO2 exchange below the H2O bulk melting temperature.

scholarly journals High-precision dual-inlet IRMS measurements of the stable isotopes of CO<sub>2</sub> and the N<sub>2</sub>O / CO<sub>2</sub> ratio from polar ice core samples

2014 ◽  
Vol 7 (11) ◽  
pp. 3825-3837 ◽  
Author(s):  
T. K. Bauska ◽  
E. J. Brook ◽  
A. C. Mix ◽  
A. Ross
Keyword(s):  
Isotopic Composition ◽  
High Precision ◽  
Water Vapor Pressure ◽  
Ice Core ◽  
Ice Cores ◽  
Mass Spectrometric Method ◽  
Polar Ice ◽  
Mixing Ratios ◽  
Core Samples ◽  
Oxygen Isotopic

Abstract. An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ13C-CO2) trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ13C of CO2 at very high precision, as well as measuring the CO2 and N2O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~400 g) with a dry-extraction "ice grater" device. The liberated air is cryogenically purified to a CO2 and N2O mixture and analyzed with a microvolume-equipped dual-inlet IRMS (Thermo MAT 253). The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02‰ for δ13C-CO2 and 2 ppm and 4 ppb for the CO2 and N2O mixing ratios, respectively (1σ pooled standard deviation). Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultralow-temperature freezer (−60 °C) improves the precision and decreases the experimental blank of the method to −0.07 ± 0.04‰. We describe techniques for accurate calibration of small samples and the application of a mass-spectrometric method based on source fragmentation for reconstructing the N2O history of the atmosphere. The oxygen isotopic composition of CO2 is also investigated, confirming previous observations of oxygen exchange between gaseous CO2 and solid H2O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H2O and CO2 exchange below the H2O bulk melting temperature.

scholarly journals Post-coring entrapment of modern air in polar ice cores collected near the firn-ice transition: evidence from CFC-12 measurements in Antarctic firn air and shallow ice cores

2010 ◽  
Vol 10 (1) ◽  
pp. 1631-1657 ◽  
Author(s):  
M. Aydin ◽  
S. A. Montzka ◽  
M. O. Battle ◽  
M. B. Williams ◽  
W. De Bruyn ◽  
...  
Keyword(s):  
Ice Core ◽  
Ice Cores ◽  
Trace Gas ◽  
Gas Composition ◽  
Physical Processes ◽  
Polar Ice ◽  
Air Samples ◽  
Mixing Ratios ◽  
Core Samples ◽  
History Of

Abstract. In this study, we report the first measurements of CFC-12 (CCl2F2) in air extracted from shallow ice cores along with firn air CFC-12 measurements from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for presence of modern air entrapped in shallow ice core samples. We propose that this is due to closure of open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our measurements reveal the presence of open porosity below the depth at which firn air samples can be collected and demonstrate how the composition of bubble air in shallow ice cores can be altered during the post-drilling period through purely physical processes. These results have implications for investigations involving trace gas composition of bubbles in shallow ice cores.

scholarly journals EBSD analysis of subgrain boundaries and dislocation slip systems in Antarctic and Greenland ice

Solid Earth ◽  
2017 ◽  
Vol 8 (5) ◽  
pp. 883-898 ◽  
Author(s):  
Ilka Weikusat ◽  
Ernst-Jan N. Kuiper ◽  
Gill M. Pennock ◽  
Sepp Kipfstuhl ◽  
Martyn R. Drury
Keyword(s):  
Basal Slip ◽  
Plastic Anisotropy ◽  
Ice Core ◽  
Ice Cores ◽  
Dislocation Slip ◽  
Slip Systems ◽  
Polar Ice ◽  
Electron Backscattered Diffraction ◽  
Depth Level ◽  
Core Samples

Abstract. Ice has a very high plastic anisotropy with easy dislocation glide on basal planes, while glide on non-basal planes is much harder. Basal glide involves dislocations with the Burgers vector b = 〈a〉, while glide on non-basal planes can involve dislocations with b = 〈a〉, b = [c], and b = 〈c + a〉. During the natural ductile flow of polar ice sheets, most of the deformation is expected to occur by basal slip accommodated by other processes, including non-basal slip and grain boundary processes. However, the importance of different accommodating processes is controversial. The recent application of micro-diffraction analysis methods to ice, such as X-ray Laue diffraction and electron backscattered diffraction (EBSD), has demonstrated that subgrain boundaries indicative of non-basal slip are present in naturally deformed ice, although so far the available data sets are limited. In this study we present an analysis of a large number of subgrain boundaries in ice core samples from one depth level from two deep ice cores from Antarctica (EPICA-DML deep ice core at 656 m of depth) and Greenland (NEEM deep ice core at 719 m of depth). EBSD provides information for the characterization of subgrain boundary types and on the dislocations that are likely to be present along the boundary. EBSD analyses, in combination with light microscopy measurements, are presented and interpreted in terms of the dislocation slip systems. The most common subgrain boundaries are indicative of basal 〈a〉 slip with an almost equal occurrence of subgrain boundaries indicative of prism [c] or 〈c + a〉 slip on prism and/or pyramidal planes. A few subgrain boundaries are indicative of prism 〈a〉 slip or slip of 〈a〉 screw dislocations on the basal plane. In addition to these classical polygonization processes that involve the recovery of dislocations into boundaries, alternative mechanisms are discussed for the formation of subgrain boundaries that are not related to the crystallography of the host grain.The finding that subgrain boundaries indicative of non-basal slip are as frequent as those indicating basal slip is surprising. Our evidence of frequent non-basal slip in naturally deformed polar ice core samples has important implications for discussions on ice about plasticity descriptions, rate-controlling processes which accommodate basal glide, and anisotropic ice flow descriptions of large ice masses with the wider perspective of sea level evolution.

scholarly journals A method for analysis of vanillic acid in polar ice cores

2015 ◽  
Vol 11 (2) ◽  
pp. 227-232 ◽  
Author(s):  
M. M. Grieman ◽  
J. Greaves ◽  
E. S. Saltzman
Keyword(s):  
Biomass Burning ◽  
Vanillic Acid ◽  
Ice Core ◽  
Ice Cores ◽  
Reversed Phase ◽  
Polar Ice ◽  
Core Samples ◽  
Wide Range ◽  
Polar Ice Sheets ◽  
Arctic Ice

Abstract. Biomass burning generates a wide range of organic compounds that are transported via aerosols to the polar ice sheets. Vanillic acid is a product of conifer lignin combustion, which has previously been observed in laboratory and ambient biomass burning aerosols. In this study a method was developed for analysis of vanillic acid in melted polar ice core samples. Vanillic acid was chromatographically separated using reversed-phase liquid chromatography (HPLC) and detected using electrospray ionization–triple quadrupole mass spectrometry (ESI-MS/MS). Using a 100 μL injection loop and analysis time of 4 min, we obtained a detection limit of 77 ppt (parts per trillion by mass) and an analytical precision of ±10%. Measurements of vanillic acid in Arctic ice core samples from the Siberian Akademii Nauk core are shown as an example application of the method.

scholarly journals Post-coring entrapment of modern air in some shallow ice cores collected near the firn-ice transition: evidence from CFC-12 measurements in Antarctic firn air and ice cores

2010 ◽  
Vol 10 (11) ◽  
pp. 5135-5144 ◽  
Author(s):  
M. Aydin ◽  
S. A. Montzka ◽  
M. O. Battle ◽  
M. B. Williams ◽  
W. J. De Bruyn ◽  
...  
Keyword(s):  
Ice Core ◽  
Ice Cores ◽  
Trace Gas ◽  
Gas Composition ◽  
Accumulation Rates ◽  
Physical Processes ◽  
Air Samples ◽  
Mixing Ratios ◽  
Core Samples ◽  
History Of

Abstract. In this study, we report measurements of CFC-12 (CCl2F2) in firn air and in air extracted from shallow ice cores from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, some of the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for the presence of modern air entrapped in the shallow ice core samples that likely contained open pores at the time of collection. We propose that this is due to closure of the open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our results reveal that open porosity can exist below the maximum depth at which firn air samples can be collected, particularly at sites with lower accumulation rates. CFC-12 measurements demonstrate that post-drilling closure of open pores can lead to a change in the composition of bubble air in shallow ice cores through purely physical processes. The results have implications for investigations involving trace gas composition of bubbles in shallow ice cores collected near the firn-ice transition.

scholarly journals A method for analysis of vanillic acid in polar ice cores

2014 ◽  
Vol 10 (4) ◽  
pp. 2805-2820 ◽  
Author(s):  
M. M. Grieman ◽  
J. Greaves ◽  
E. S. Saltzman
Keyword(s):  
Biomass Burning ◽  
Vanillic Acid ◽  
Ice Core ◽  
Ice Cores ◽  
Reversed Phase ◽  
Polar Ice ◽  
Core Samples ◽  
Wide Range ◽  
Polar Ice Sheets ◽  
Arctic Ice

Abstract. Biomass burning generates a wide range of organic compounds that are transported via aerosols to the polar ice sheets. Vanillic acid is a product of conifer lignin combustion, which has previously been observed in laboratory and ambient biomass burning aerosols. In this study a method was developed for analysis of vanillic acid in melted polar ice core samples. Vanillic acid was chromatographically separated using reversed phase LC and detected using electrospray triple quadrupole mass spectrometry (ESI-MS/MS). Using a 100 μL injection loop and analysis time of 4 min, we obtained a detection limit (S : N = 2) of 58 ppt (parts per trillion by mass) and an analytical precision of ±10 %. Measurements of vanillic acid in Arctic ice core samples from the Siberian Akademii Nauk core are shown as an example application of the method.

scholarly journals A new CF-IRMS system for quantifying stable isotopes of carbon monoxide from ice cores and small air samples

2010 ◽  
Vol 3 (5) ◽  
pp. 1307-1317 ◽  
Author(s):  
Z. Wang ◽  
J. E. Mak
Keyword(s):  
Carbon Monoxide ◽  
Stable Isotopes ◽  
Ice Core ◽  
Isotope Analysis ◽  
Ice Cores ◽  
Isotope Ratio Mass Spectrometry ◽  
Vacuum Extraction ◽  
Air Samples ◽  
Mixing Ratios ◽  
Core Samples

Abstract. We present a new analysis technique for stable isotope ratios (δ13C and δ18O) of atmospheric carbon monoxide (CO) from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS); it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO2, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ) for δ13C and 0.6‰ (±1δ) for δ18O can be obtained for 100 mL (STP) air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO). Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.

scholarly journals Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate and ozone at Dumont d'Urville, coastal Antarctica

2016 ◽  
Author(s):  
Sakiko Ishino ◽  
Shohei Hattori ◽  
Joel Savarino ◽  
Bruno Jourdain ◽  
Susanne Preunkert ◽  
...  
Keyword(s):  
Seasonal Variation ◽  
Ice Cores ◽  
Oxidative Capacity ◽  
So2 Oxidation ◽  
Mixing Ratios ◽  
Isotopic Compositions ◽  
Oxygen Isotopic ◽  
Low Sensitivity ◽  
Complex Chemistry ◽  
Oxidation Chemistry

Abstract. Reconstruction of the oxidative capacity of the atmosphere is of great importance to understanding climate change, because of its key role in determining the life times of trace gases. Triple oxygen isotopic compositions (Δ17O = δ17O − 0.52 × δ18O) of atmospheric sulfate (SO42−) and nitrate (NO3−) in the Antarctic ice cores have shown potential as stable proxies, because they reflect the oxidation chemistry involved in their formation processes. However, observations of Δ17O values of SO42−, NO3− and ozone in the present-day Antarctic atmosphere are very limited, and their complex chemistry is not fully understood in this region. We present the first simultaneous measurement of Δ17O values of atmospheric sulfate, nitrate, and ozone collected at Dumont d'Urville station (66°40' S, 140°01' E) throughout 2011. Δ17O values of sulfate and nitrate exhibited seasonal variation characterized by summer minima and winter maxima, within the ranges of 0.9–3.4 ‰ and 23.0–41.9 ‰, respectively. In contrast, Δ17O values of ozone showed no significant seasonal variation, with values of 26 ± 1 ‰ through the year. These contrasting seasonal trends suggest that Δ17O(O3) is not the major factor determining seasonal changes in Δ17O(SO42−) and Δ17O(NO3−) values. The summer/winter trends for Δ17O(SO42−) and Δ17O(NO3−) values are caused by sunlight-driven changes in O3/ROX ratios, which decrease in summer through ozone destruction and photo-oxidants production, resulting in co-variation between ozone mixing ratios and Δ17O(SO42−) and Δ17O(NO3−) values. However, despite similar ranges of ozone mixing ratios in spring (September to November) and fall (March to May), Δ17O(SO42−) values observed in spring were lower than in fall. The relatively low sensitivity of Δ17O(SO42−) values to the ozone mixing ratio in spring is possibly explained by (i) lower O3/ROX ratios caused by NOX emission from snowpack and/or (ii) SO2 oxidation by hypohalous acids (HOX = HOCl + HOBr) in the aqueous phase.

scholarly journals Concept and Testing of a Remotely Operated Vehicle-Mountable Inductive Electrothermal Polar Under-Ice Corer

2017 ◽  
Vol 51 (6) ◽  
pp. 33-43 ◽  
Author(s):  
Narayanaswamy Vedachalam ◽  
Arumugam Vadivelan ◽  
Arunachalam Umapathy ◽  
Munusamy Murugesan ◽  
Gopal Durai ◽  
...  
Keyword(s):  
Ice Core ◽  
Input Power ◽  
Design Development ◽  
Polar Ice ◽  
Remotely Operated Vehicle ◽  
Element Analysis ◽  
Ice Shelves ◽  
Core Samples ◽  
Inner Diameter ◽  
Aided Design

AbstractIce core samples from the polar ice shelves contain valuable paleo-climatic records and information for understanding the unique polar under-ice ecosystem. This paper describes the finite element analysis-aided design, development, and qualification of a 63-mm-inner diameter, 250-mm-long variable power underwater remotely operated vehicle-mountable inductive ice corer (IIC) for collecting ice core samples beneath the polar ice shelves. It is determined that, with the IIC operating with an input power of 1,000 W at 30 kHz, it is possible to have an ice penetration rate of 14 mm/min and obtain an ice core of 51 mm in diameter. The experimental results are found to comply with the numerical model with an accuracy of 95%.

On the relationship between stable isotopes and major impurity species as inferred from a two-dimensional firn sampling approach at EDML, East Antarctica

2021 ◽  
Author(s):  
Thomas Münch ◽  
Maria Hörhold ◽  
Johannes Freitag ◽  
Melanie Behrens ◽  
Thomas Laepple
Keyword(s):  
Isotopic Composition ◽  
Interannual Variability ◽  
Ice Core ◽  
Ice Cores ◽  
Temperature Changes ◽  
Impurity Species ◽  
Intermittent Precipitation ◽  
Ice Core Record ◽  
Stable Oxygen ◽  
Atmospheric Variations

&lt;p&gt;Ice cores constitute a major palaeoclimate archive by recording, among many others, the atmospheric variations of stable oxygen and hydrogen isotopic composition of water and of soluble ionic impurities. While impurities are used as proxies for, e.g., variations in sea ice, marine biological activity and volcanism, stable isotope records are the main source of information for the reconstruction of polar temperature changes.&lt;/p&gt;&lt;p&gt;However, such reconstruction efforts are complicated by the fact that temperature is by far not the only driver of isotopic composition changes. A single isotopic ice-core record will comprise variations caused by a multitude of processes, from variable atmospheric circulation and moisture pathways to the intermittency of precipitation and finally to the mixing and re-location of surface snow by wind drift (stratigraphic noise). Under the assumption that specific trace components are originally deposited with the precipitated snow and its isotopic composition, the retrieved impurity records should display a similar spatial and seasonal to interannual variability as the isotope records, caused by local stratigraphic noise as well as the time-variable and intermittent precipitation patterns, respectively.&lt;/p&gt;&lt;p&gt;In this contribution, we investigate the possible relationship between isotope and impurity data at the East Antarctic low-accumulation site EDML. We sampled and analysed isotopic composition and major impurity species on a four metre deep and 50&amp;#160;metre long trench. This enables us (1) to study the spatial (horizontal times vertical) relationship in the data, and (2) to analyse and compare the seasonal and interannual variability after removing the strong contribution of local stratigraphic noise. By this, the study improves our understanding of the depositional mechanisms that play an important role for the formation of ice-core records, and it offers to investigate the potential of using impurities to correct isotopic variability in order to improve temperature reconstructions.&lt;/p&gt;

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