Setup and first testing of Laser Ablation - ICP-MS measurements for high resolution chemical ice core analyses at University of Cambridge

2020 ◽  
Author(s):  
Helene Hoffmann ◽  
Eric Wolff ◽  
Jason Day ◽  
Mackenzie Grieman ◽  
Jack Humby ◽  
...  
Keyword(s):  
Laser Ablation ◽  
High Resolution ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Depth Resolution ◽  
Calibration Method ◽  
Last Interglacial ◽  
Measurement Sensitivity ◽  
Icp Ms

<p>The ice in the deepest and therefore oldest parts of polar ice cores is highly compressed and therefore annual layers, although potentially preserved, can be thinned to a millimeter level or even below. However, for many palaeoclimate studies these are the most interesting sections. Within the WACSWAIN project we aim to investigate the basal part of an ice core recently drilled to bedrock at the Skytrain ice rise in West Antarctica to obtain unique information on the state of the Filchner-Ronne ice shelf during the last interglacial. To achieve this we have set up a system to perform high resolution laser-ablation ICP-MS measurements using a cryocell stage on selected segments of the deepest parts of the ice cores.</p><p>Here we present first results of system performance including assessment of measurement sensitivity and precision with respect to analyses of the most relevant components, namely sodium, calcium and aluminium. We also report on the development and the performance of a matrix matched calibration method using flash-freezed water samples of known composition to convert relative signal intensities into concentrations. This especially focuses on homogeneity and reproducibility of the in-house produced standard. Finally, the results of laser ablation ICP-MS results are compared to parallel low resolution data from continuous flow analysis of the Skytrain core to evaluate the capabilities of the method in terms of improving depth resolution.</p>

Towards an improved understanding of high-resolution impurity signals in deep Antarctic ice cores

2020 ◽  
Author(s):  
Pascal Bohleber ◽  
Marco Roman ◽  
Carlo Barbante ◽  
Barbara Stenni ◽  
Barbara Delmonte
Keyword(s):  
Laser Ablation ◽  
High Resolution ◽  
Inductively Coupled Plasma ◽  
Ice Core ◽  
Ice Cores ◽  
Inductively Coupled ◽  
Icp Ms ◽  
First Results ◽  
Plasma Mass Spectrometry ◽  
Fine Resolution

<p>Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) offers minimally destructive ice core impurity analysis at micron-scale resolution. This technique is especially suited for exploring closely spaced layers of ice within samples collected at low accumulation sites or in regions of highly compressed and thinned ice. Accordingly, LA-ICP-MS promises invaluable insights in the analysis of a future “Oldest ice core” from Antarctica. However, in contrast to ice core melting techniques, taking into account the location of impurities is crucial to avoid misinterpretation of ultra-fine resolution signals obtained from newly emerging laser ablation technologies. Here we present first results from a new LA-ICP-MS setup developed at the University of Venice, based on a customized two-volume cryogenic ablation chamber optimized for fast wash-out times. We apply our method for high-resolution chemical imagining analysis of impurities in samples from intermediate and deep sections of the Talos Dome and EPICA Dome C ice cores. We discuss the localization of both soluble and insoluble impurities within the ice matrix and evaluate the spatial significance of a single profile along the main core axis. With this, we aim at establishing a firm basis for a future deployment of the LA-ICP-MS in an “Oldest Ice Core”. Moreover, our work illustrates how LA-ICP-MS may offer new means to study the impurity-microstructure interplay in deep polar ice, thereby promising to advance our understanding of these fundamental processes.</p>

Forty years later: High resolution continuous flow analysis of the Dye3 ice core

2021 ◽  
Author(s):  
Helle Astrid Kjær ◽  
Margaret Harlan ◽  
Paul Vallelonga ◽  
Anders Svensson ◽  
Thomas Blunier ◽  
...  
Keyword(s):  
High Resolution ◽  
Forest Fires ◽  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Sheet ◽  
Greenland Ice Sheet ◽  
Ice Cores ◽  
The Core ◽  
Continuous Flow Analysis

<div><span><span>The Dye-3 ice core was drilled to bedrock at the Southern part of the central Greenland ice sheet (65°11'N, 43°50'W) in 1979-1981. The southern location is characterized by high accumulation rates compared to more central locations of the ice sheet. Since its drilling, numerous analyses of the core have been performed, and the ice has since been in freezer storage both in the USA and in Denmark.</span></span></div><div><span>In October and November 2019, the remaining ice, two mostly complete sections covering the depths of 1753–1820m and 1865–1918m of the Dye-3 core, were melted during a continuous flow analysis (CFA) campaign at the Physics of Ice, Climate, and Earth (PICE) group at the University of Copenhagen. The data represents both Holocene, Younger Dryas and Glacial sections (GS 5 to 12).</span></div><div> </div><div><span><span>The measured data consist chemistry and impurities contained in the ice, isotopes, as well as analysis of methane and other atmospheric gases. </span></span></div><div><span><span>The chemistry measurements include NH</span></span><span><span><sub>4</sub></span></span><span><span><sup>+</sup></span></span><span><span>, Ca</span></span><span><span><sup>2+</sup></span></span><span><span>, and Na</span></span><span><span><sup>+</sup></span></span><span><span> ions, which besides being influenced by transport, provide information about forest fires, wind-blown dust, and sea ice, respectively, as well as acidity, which aids in the identification of volcanic events contained in the core. The quantity and grain size distribution of insoluble particles was analyzed by means of an Abakus laser particle counter.</span></span></div><div> </div><div><span>We compare the new high-resolution CFA record of dye3 with previous analysis and thus evaluate the progress made over 40 years. Further we compare overlapping time periods with other central Greenland ice cores and discuss spatial patterns in relation to the presented climate proxies.</span></div>

scholarly journals New LA-ICP-MS cryocell and calibration technique for sub-millimeter analysis of ice cores

2015 ◽  
Vol 61 (226) ◽  
pp. 233-242 ◽  
Author(s):  
Sharon B. Sneed ◽  
Paul A. Mayewski ◽  
W.G. Sayre ◽  
Michael J. Handley ◽  
Andrei V. Kurbatov ◽  
...  
Keyword(s):  
Inductively Coupled Plasma ◽  
Chemical Constituents ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Calibration Technique ◽  
Inductively Coupled ◽  
Annual Layer ◽  
Icp Ms ◽  
Plasma Mass Spectrometry

AbstractIce cores provide a robust reconstruction of past climate. However, development of timescales by annual-layer counting, essential to detailed climate reconstruction and interpretation, on ice cores collected at low-accumulation sites or in regions of compressed ice, is problematic due to closely spaced layers. Ice-core analysis by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) provides sub-millimeter-scale sampling resolution (on the order of 100 μm in this study) and the low detection limits (ng L−1) necessary to measure the chemical constituents preserved in ice cores. We present a newly developed cryocell that can hold a 1 m long section of ice core, and an alternative strategy for calibration. Using ice-core samples from central Greenland, we demonstrate the repeatability of multiple ablation passes, highlight the improved sampling resolution, verify the calibration technique and identify annual layers in the chemical profile in a deep section of an ice core where annual layers have not previously been identified using chemistry. In addition, using sections of cores from the Swiss/Italian Alps we illustrate the relationship between Ca, Na and Fe and particle concentration and conductivity, and validate the LA-ICP-MS Ca profile through a direct comparison with continuous flow analysis results.

scholarly journals Comparison of analytical methods used for measuring major ions in the EPICA Dome C (Antarctica) ice core

2002 ◽  
Vol 35 ◽  
pp. 299-305 ◽  
Author(s):  
Geneviève C. Littot ◽  
Robert Mulvaney ◽  
Regine Röthlisberger ◽  
Roberto Udisti ◽  
Eric W. Wolff ◽  
...  
Keyword(s):  
High Resolution ◽  
Ion Chromatography ◽  
Major Ions ◽  
Full Range ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
High Resolution Data ◽  
Wide Range

AbstractIn the past, ionic analyses of deep ice cores tended to consist of a few widely spaced measurements that indicated general trends in concentration. the ion-chromatographic methods widely used provide well-validated individual data, but are time-consuming. the development of continuous flow analysis (CFA) methods has allowed very rapid, high-resolution data to be collected in the field for a wide range of ions. In the European Project for Ice Coring in Antarctica (EPICA) deep ice-core drilling at Dome C, many ions have been measured at high resolution, and several have been analyzed by more than one method. the full range of ions has been measured in five different laboratories by ion chromatography (IC), at resolutions of 2.5–10 cm. In the field, CFA was used to measure the ions Na+, Ca2+, nitrate and ammonium. Additionally, a new semi-continuous in situ IC method, fast ion chromatography (FIC), was used to analyze sulphate, nitrate and chloride. Some data are now available to 788 m depth. In this paper we compare the data obtained by the three methods, and show that the rapid methods (CFA and FIC) give an excellent indication of trends in ionic data. Differences between the data from the different methods do occur, and in some cases these are genuine, being due to differences in speciation in the methods. We conclude that the best system for most deep ice-core analysis is a rapid system of CFA and FIC, along with in situ meltwater collection for analysis of other ions by IC, but that material should be kept aside for a regular check on analytical quality and for more detailed analysis of some sections.

scholarly journals A refined TALDICE-1a age scale from 55 to 112 ka before present for the Talos Dome ice core based on high-resolution methane measurements

2011 ◽  
Vol 7 (2) ◽  
pp. 1175-1193 ◽  
Author(s):  
S. Schüpbach ◽  
U. Federer ◽  
M. Bigler ◽  
H. Fischer ◽  
T. F. Stocker
Keyword(s):  
High Resolution ◽  
Ross Sea ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Ice Age ◽  
Before Present ◽  
Bottom Part ◽  
Analysis Technique ◽  
The Impact

Abstract. A precise synchronization of different climate records is indispensable for a correct dynamical interpretation of paleoclimatic data. A chronology for the TALDICE ice core from the Ross Sea sector of East Antarctica has recently been presented based on methane synchronization with Greenland and the EDC ice cores and δ18Oice synchronization with EDC in the bottom part (TALDICE-1). By the use of new high-resolution methane data, obtained with a continuous flow analysis technique, we present a refined age scale for the age interval from 55–112 ka before present where TALDICE is synchronized with EDC. New and more precise tie points reduce the uncertainties of the age scale from up to 2000 yr in TALDICE-1 to below 1000 yr over most of the refined interval. Thus, discussions of climate dynamics at sub-millennial time scales are now possible back to 110 ka, in particular during the inception of the last ice age. Calcium data of EDC and TALDICE are compared to show the impact of the refinement to the synchronization of the two ice cores not only for the gas but also for the ice age scale.

scholarly journals A refined TALDICE-1a age scale from 55 to 112 ka before present for the Talos Dome ice core based on high-resolution methane measurements

2011 ◽  
Vol 7 (3) ◽  
pp. 1001-1009 ◽  
Author(s):  
S. Schüpbach ◽  
U. Federer ◽  
M. Bigler ◽  
H. Fischer ◽  
T. F. Stocker
Keyword(s):  
High Resolution ◽  
Ross Sea ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Ice Age ◽  
Before Present ◽  
Bottom Part ◽  
Analysis Technique ◽  
The Impact

Abstract. A precise synchronization of different climate records is indispensable for a correct dynamical interpretation of paleoclimatic data. A chronology for the TALDICE ice core from the Ross Sea sector of East Antarctica has recently been presented based on methane synchronization with Greenland and the EDC ice cores and δ18Oice synchronization with EDC in the bottom part (TALDICE-1). Using new high-resolution methane data obtained with a continuous flow analysis technique, we present a refined age scale for the age interval from 55–112 thousand years (ka) before present, where TALDICE is synchronized with EDC. New and more precise tie points reduce the uncertainties of the age scale from up to 1900 yr in TALDICE-1 to below 1100 yr over most of the refined interval and shift the Talos Dome dating to significantly younger ages during the onset of Marine Isotope Stage 3. Thus, discussions of climate dynamics at sub-millennial time scales are now possible back to 110 ka, in particular during the inception of the last ice age. Calcium data of EDC and TALDICE are compared to show the impact of the refinement to the synchronization of the two ice cores not only for the gas but also for the ice age scale.

scholarly journals Continuous flow analysis methods for sodium, magnesium and calcium detection in the Skytrain ice core

2021 ◽  
pp. 1-11
Author(s):  
Mackenzie M. Grieman ◽  
Helene M. Hoffmann ◽  
Jack D. Humby ◽  
Robert Mulvaney ◽  
Christoph Nehrbass-Ahles ◽  
...  
Keyword(s):  
Continuous Flow ◽  
Inductively Coupled Plasma ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Sea Ice Extent ◽  
Icp Ms ◽  
Continuous Flow Analysis ◽  
Relative Standard ◽  
Sodium Magnesium

Abstract Dissolved and particulate sodium, magnesium and calcium are analyzed in ice cores to determine past changes in sea ice extent, terrestrial dust variability and atmospheric aerosol transport efficiency. They are also used to date ice cores if annual layers are visible. Multiple methods have been developed to analyze these important compounds in ice cores. Continuous flow analysis (CFA) is implemented with instruments that sample the meltstream continuously. In this study, CFA with ICP-MS (inductively coupled-plasma mass spectrometry) and fast ion chromatography (FIC) methods are compared for analysis of sodium and magnesium. ICP-MS, FIC and fluorescence methods are compared for analysis of calcium. Respective analysis of a 10 m section of the Antarctic WACSWAIN Skytrain Ice Rise ice core shows that all of the methods result in similar levels of the compounds. The ICP-MS method is the most suitable for analysis of the Skytrain ice core due to its superior precision (relative standard deviation: 1.6% for Na, 1.3% for Mg and 1.2% for Ca) and sampling frequency compared to the FIC method. The fluorescence detection method may be preferred for calcium analysis due to its higher depth resolution (1.4 cm) relative to the ICP-MS and FIC methods (~4 cm).

scholarly journals High resolution aerosol concentration data from the Greenland NorthGRIP and NEEM deep ice cores

2021 ◽  
Author(s):  
Tobias Erhardt ◽  
Matthias Bigler ◽  
Urs Federer ◽  
Gideo Gfeller ◽  
Daiana Leuenberger ◽  
...  
Keyword(s):  
High Resolution ◽  
Continuous Flow ◽  
Ice Core ◽  
Historical Context ◽  
Flow Analysis ◽  
Ice Cores ◽  
Deposition Flux ◽  
Concentration Data ◽  
Continuous Flow Analysis ◽  
North Greenland

Abstract. Records of chemical impurities from ice cores enable us to reconstruct the past deposition of aerosols onto the polar ice sheets and alpine glaciers. Through that, they allow us to gain insight into changes of the source, transport and deposition processes that ultimately determine the deposition flux at the coreing location. However, the low concentrations of the aerosol species in the ice and the resulting high risk of contamination poses a formidable analytical challenge, especially if long, continuous and highly resolved records are needed. Continuous Flow Analysis, CFA, the continuous melting, decontamination and analysis of ice-core samples has mostly overcome this issue and has quickly become the de-facto standard to obtain high-resolution aerosol records from ice cores after its inception at the University of Bern in the mid 90s. Here we present continuous records of calcium (Ca2+), sodium (Na+), ammonium (NH4+), nitrate (NO3−1) and electrolytic conductivity at 1 mm depth resolution from the NGRIP (North Greenland Ice Core Project) and NEEM (North Greenland Eemian Ice Drilling) ice cores produced by the Bern Continuous Flow Analysis group in the years 2000 to 2011. Both of the records have previously been used in a number of studies but have never been published in the full 1 mm resolution. Alongside the 1 mm datasets we provide decadal averages, a detailed description of the methods, relevant references, an assessment of the quality of the data and its usable resolution. Along the way we will also give some historical context on the development of the Bern CFA system.

scholarly journals A comparison of annual layer thickness model estimates with observational measurements using the Berkner Island ice core, Antarctica

2017 ◽  
Vol 29 (4) ◽  
pp. 382-393
Author(s):  
A. Massam ◽  
S.B. Sneed ◽  
G.P. Lee ◽  
R.R. Tuckwell ◽  
R. Mulvaney ◽  
...  
Keyword(s):  
High Resolution ◽  
Layer Thickness ◽  
Inductively Coupled Plasma ◽  
Ice Core ◽  
Ultra Violet ◽  
Analytical Techniques ◽  
Inductively Coupled ◽  
Annual Layer ◽  
Icp Ms ◽  
Chemical Profiles

AbstractA model to estimate the annual layer thickness of deposited snowfall at a deep ice core site, compacted by vertical strain with respect to depth, is assessed using ultra-high-resolution laboratory analytical techniques. A recently established technique of high-resolution direct chemical analysis of ice using ultra-violet laser ablation inductively-coupled plasma mass spectrometry (LA ICP-MS) has been applied to ice from the Berkner Island ice core, and compared with results from lower resolution techniques conducted on parallel sections of ice. The results from both techniques have been analysed in order to assess the capability of each technique to recover seasonal cycles from deep Antarctic ice. Results do not agree with the annual layer thickness estimates from the age–depth model for individual samples <1 m long as the model cannot reconstruct the natural variability present in annual accumulation. However, when compared with sections >4 m long, the deviation between the modelled and observational layer thicknesses is minimized to within two standard deviations. This confirms that the model is capable of successfully estimating mean annual layer thicknesses around analysed sections. Furthermore, our results confirm that the LA ICP-MS technique can reliably recover seasonal chemical profiles beyond standard analytical resolution.

A novel high-resolution laser-melting sampler for discrete analyses of ion concentrations and stable water isotopic compositions in firn and ice cores

2021 ◽  
Author(s):  
Yuko Motizuki ◽  
Yoichi Nakai ◽  
Kazuya Takahashi ◽  
Junya Hirose ◽  
Yu Vin Sahoo ◽  
...  
Keyword(s):  
Ice Core ◽  
Ice Cores ◽  
Depth Resolution ◽  
Climatic Changes ◽  
Accumulation Rates ◽  
Laser Melting ◽  
Ion Concentrations ◽  
Annual Layer ◽  
Annual Resolution ◽  
High Depth

&lt;p&gt;Ice cores preserve past climatic changes and, in some cases, astronomical signals. Here we present a newly developed automated ice-core sampler that employs laser melting. A hole in an ice core approximately 3 mm in diameter is melted and heated well below the boiling point by laser irradiation, and the meltwater is simultaneously siphoned by a 2 mm diameter movable evacuation nozzle that also holds the laser fiber. The advantage of sampling by laser melting is that molecular ion concentrations and stable water isotope compositions in ice cores can be measured at high depth resolution, which is advantageous for ice cores with low accumulation rates. This device takes highly discrete samples from ice cores, attaining depth resolution as small as ~3 mm with negligible cross contamination; the resolution can also be set at longer lengths suitable for validating longer-term profiles of various ionic and water isotopic constituents in ice cores. This technique allows the detailed reconstruction of past climatic changes at annual resolution and the investigation of transient ionic and isotopic signals within single annual layers in low-accumulation cores, potentially by annual layer counting.&lt;/p&gt;

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