A new continuous high-resolution detection system for sulphate in ice cores

AbstractSulphate (SO42–) is a major ion found in polar ice cores and is related to different aerosol sources and processes. Explosive volcanic eruptions, even far away, can cause distinct sulphate peaks in ice core records. Thus, a robust sulphate detection system which is suitable for fieldwork and which enables the measurement of sulphate at high temporal resolution is of great interest. In this study, we present the adaptation of a new continuous flow analysis system for sulphate that is based on a spectrophotometric method using dimethylsulfonazo III and an inline reactor column containing barium sulphate particles. The method shows a detection limit of ∽70 ng g–1 and a linear range up to at least 3000 ng g–1. It is simple, robust and less prone to interferences compared to the previously used method.

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PANDA, the French analytical platform dedicated to ice core

10.5194/egusphere-egu21-13253 ◽

2021 ◽

Author(s):

Sophie Darfeuil ◽

Patrick Ginot ◽

Joel Savarino ◽

Nicolas Caillon ◽

Xavier Faïn ◽

...

Keyword(s):

Trace Metals ◽

Major Ions ◽

Ice Core ◽

Flow Analysis ◽

Common Interest ◽

Continuous Flow Analysis ◽

Laser Spectrometry ◽

O Isotopes ◽

And Performance ◽

Analysis System

Since 2018, under the impetus of the IGE (Grenoble) and the LSCE (Saclay) and the common interest of the "Carottes de Glace France" consortium, an analytical platform dedicated to glacier archives was created to meet the growing analytical needs requested by projects involving French partners (Ice Memory, EAIIST, BE-OI ...) and international collaborations with a ten-year vision. Within this framework 5 modules have been developed between the IGE and the LSCE. 3 modules are installed at the IGE, including a CHEMISTRY module which includes a large number of instruments coupled to the CFA (Continuous Flow Analysis) system, allowing high-resolution multi tracer analysis on a single ice stick (water isotopes, dust, conductivity, colorimetry, black carbon, trace metals and gas) as well as several auto-samplers for discrete analyses (major ions, organic species, trace metals, sugars ...). The GAS module is shared between continuous analyses on the CFA system (laser spectrometry CH4/CO) and discrete analyses (Gas chromatography CH4/CO2). The ISOTOPY module allows the analysis of nitrogen (N), sulfur (S) and oxygen (O) isotopes. At the LSCE, the WATER ISOTOPY module allows continuous (Picarro coupled to a CFA line equipped with conductivity cells and auto-sampler) or discrete (Picarro or mass spectrometer) analyses for &#948;D, &#948;18O and &#948;17O in water. The AIR ISOTOPY module completes the platform for analyses by mass spectrometry of &#948;15N of N2, the triple isotopic composition of O2 and noble gases isotopes (36/38/40 Ar; 82/84/86 Kr; 129-132 Xe). An overview of the capacity and performance of the platform will be presented.

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Improved methodologies for continuous-flow analysis of stable water isotopes in ice cores

Atmospheric Measurement Techniques ◽

10.5194/amt-10-617-2017 ◽

2017 ◽

Vol 10 (2) ◽

pp. 617-632 ◽

Cited By ~ 14

Author(s):

Tyler R. Jones ◽

James W. C. White ◽

Eric J. Steig ◽

Bruce H. Vaughn ◽

Valerie Morris ◽

...

Keyword(s):

Continuous Flow ◽

Ice Core ◽

Flow Analysis ◽

Ice Cores ◽

Isotope Ratio Mass Spectrometry ◽

Absorption Spectrometry ◽

Isotopic Analysis ◽

Water Isotopes ◽

Stable Water Isotopes ◽

Continuous Flow Analysis

Abstract. Water isotopes in ice cores are used as a climate proxy for local temperature and regional atmospheric circulation as well as evaporative conditions in moisture source regions. Traditional measurements of water isotopes have been achieved using magnetic sector isotope ratio mass spectrometry (IRMS). However, a number of recent studies have shown that laser absorption spectrometry (LAS) performs as well or better than IRMS. The new LAS technology has been combined with continuous-flow analysis (CFA) to improve data density and sample throughput in numerous prior ice coring projects. Here, we present a comparable semi-automated LAS-CFA system for measuring high-resolution water isotopes of ice cores. We outline new methods for partitioning both system precision and mixing length into liquid and vapor components – useful measures for defining and improving the overall performance of the system. Critically, these methods take into account the uncertainty of depth registration that is not present in IRMS nor fully accounted for in other CFA studies. These analyses are achieved using samples from a South Pole firn core, a Greenland ice core, and the West Antarctic Ice Sheet (WAIS) Divide ice core. The measurement system utilizes a 16-position carousel contained in a freezer to consecutively deliver ∼  1 m  ×  1.3 cm2 ice sticks to a temperature-controlled melt head, where the ice is converted to a continuous liquid stream and eventually vaporized using a concentric nebulizer for isotopic analysis. An integrated delivery system for water isotope standards is used for calibration to the Vienna Standard Mean Ocean Water (VSMOW) scale, and depth registration is achieved using a precise overhead laser distance device with an uncertainty of ±0.2  mm. As an added check on the system, we perform inter-lab LAS comparisons using WAIS Divide ice samples, a corroboratory step not taken in prior CFA studies. The overall results are important for substantiating data obtained from LAS-CFA systems, including optimizing liquid and vapor mixing lengths, determining melt rates for ice cores with different accumulation and thinning histories, and removing system-wide mixing effects that are convolved with the natural diffusional signal that results primarily from water molecule diffusion in the firn column.

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Improved Methodologies for Continuous Flow Analysis of Stable Water Isotopes in Ice Cores

10.5194/amt-2016-118 ◽

2016 ◽

Cited By ~ 2

Author(s):

Tyler R. Jones ◽

James W. C. White ◽

Eric J. Steig ◽

Bruce H. Vaughn ◽

Valerie Morris ◽

...

Keyword(s):

Continuous Flow ◽

Ice Core ◽

Flow Analysis ◽

Ice Cores ◽

Isotope Ratio Mass Spectrometry ◽

Isotopic Analysis ◽

Water Isotopes ◽

Mixing Length ◽

Stable Water Isotopes ◽

Continuous Flow Analysis

Abstract. Water isotopes in ice cores are used as a climate proxy for local temperature and regional atmospheric circulation as well as evaporative conditions in moisture source regions. Traditional measurements of water isotopes have been achieved using magnetic sector isotope ratio mass spectrometry (IRMS). However, a number of recent studies have shown that laser absorption spectrometers (LAS) perform as well or better than IRMS. The new LAS technology has been combined with continuous flow analysis (CFA) to improve data density and sample throughput in numerous prior ice coring projects. Here, we present a comparable semi-automated LAS-CFA system for measuring high-resolution water isotopes of ice cores. We outline new methods for partitioning both system uncertainty and system mixing length into liquid and vapor components – useful measures for defining and improving the overall performance of the system. Critically, our methods take into account the uncertainty of depth registration that is not present in IRMS nor fully accounted for in other CFA studies. We also explain a method for introducing consecutive sections of isotopically distinct ice at the melt head to define the system-wide mixing length. These analyses are achieved using samples from a South Pole firn core, a Greenland ice core, and the WAIS Divide ice core. The measurement system utilizes a 16-position carousel contained in a freezer to consecutively deliver ~ 1 m × 1.3 cm2 ice sticks to a temperature controlled melt head, where the ice is converted to a continuous liquid stream, and eventually vaporized using a concentric nebulizer for isotopic analysis. An integrated delivery system for water isotope standards is used for calibration to the VSMOW-SLAP scale and depth registration is achieved using a precise overhead laser distance device with an uncertainty of ±0.2 mm. As an added check on our system, we perform inter-lab LAS comparisons using WAIS Divide ice samples, a corroboratory step not taken in prior CFA studies. The overall results are important for substantiating data obtained from LAS-CFA systems, including optimizing liquid and vapor mixing lengths, determining melt rates for ice cores with different accumulation and thinning histories, and removing system-wide mixing effects that are convolved with the natural diffusional signal that results primarily from water molecule diffusion in the firn column.

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On the occurrence of annual layers in Dome Fuji ice core early Holocene ice

Climate of the Past ◽

10.5194/cp-11-1127-2015 ◽

2015 ◽

Vol 11 (9) ◽

pp. 1127-1137 ◽

Cited By ~ 5

Author(s):

A. Svensson ◽

S. Fujita ◽

M. Bigler ◽

M. Braun ◽

R. Dallmayr ◽

...

Keyword(s):

Ice Core ◽

Flow Analysis ◽

Ice Cores ◽

Snow Accumulation ◽

Early Holocene ◽

High Temporal Resolution ◽

High Accumulation ◽

Data Set ◽

Antarctic Plateau ◽

Annual Layer

Abstract. Whereas ice cores from high-accumulation sites in coastal Antarctica clearly demonstrate annual layering, it is debated whether a seasonal signal is also preserved in ice cores from lower-accumulation sites further inland and particularly on the East Antarctic Plateau. In this study, we examine 5 m of early Holocene ice from the Dome Fuji (DF) ice core at a high temporal resolution by continuous flow analysis. The ice was continuously analysed for concentrations of dust, sodium, ammonium, liquid conductivity, and water isotopic composition. Furthermore, a dielectric profiling was performed on the solid ice. In most of the analysed ice, the multi-parameter impurity data set appears to resolve the seasonal variability although the identification of annual layers is not always unambiguous. The study thus provides information on the snow accumulation process in central East Antarctica. A layer counting based on the same principles as those previously applied to the NGRIP (North Greenland Ice core Project) and the Antarctic EPICA (European Project for Ice Coring in Antarctica) Dronning Maud Land (EDML) ice cores leads to a mean annual layer thickness for the DF ice of 3.0 ± 0.3 cm that compares well to existing estimates. The measured DF section is linked to the EDML ice core through a characteristic pattern of three significant acidity peaks that are present in both cores. The corresponding section of the EDML ice core has recently been dated by annual layer counting and the number of years identified independently in the two cores agree within error estimates. We therefore conclude that, to first order, the annual signal is preserved in this section of the DF core. This case study demonstrates the feasibility of determining annually deposited strata on the central East Antarctic Plateau. It also opens the possibility of resolving annual layers in the Eemian section of Antarctic ice cores where the accumulation is estimated to have been greater than in the Holocene.

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

10.5194/egusphere-egu21-11820 ◽

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>The Dye-3 ice core was drilled to bedrock at the Southern part of the central Greenland ice sheet (65&#176;11'N, 43&#176;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.</div><div>In October and November 2019, the remaining ice, two mostly complete sections covering the depths of 1753&#8211;1820m and 1865&#8211;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).</div><div>&#160;</div><div>The measured data consist chemistry and impurities contained in the ice, isotopes, as well as analysis of methane and other atmospheric gases.&#160;</div><div>The chemistry measurements include NH4+, Ca2+, and Na+&#160;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.</div><div>&#160;</div><div>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.</div>

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Variability of sulfate signal in ice core records based on five replicate cores

Climate of the Past ◽

10.5194/cp-12-103-2016 ◽

2016 ◽

Vol 12 (1) ◽

pp. 103-113 ◽

Cited By ~ 19

Author(s):

E. Gautier ◽

J. Savarino ◽

J. Erbland ◽

A. Lanciki ◽

P. Possenti

Keyword(s):

Ice Core ◽

Ice Cores ◽

Flux Measurement ◽

Volcanic Eruptions ◽

Local Scale ◽

High Temporal Resolution ◽

Polar Regions ◽

Regional Patterns ◽

Snow Drift ◽

Volcanic Events

Abstract. Current volcanic reconstructions based on ice core analysis have significantly improved over the past few decades by incorporating multiple-core analyses with a high temporal resolution from different parts of the polar regions into a composite common volcanic eruption record. Regional patterns of volcanic deposition are based on composite records, built from cores taken at both poles. However, in many cases only a single record at a given site is used for these reconstructions. This assumes that transport and regional meteorological patterns are the only source of the dispersion of the volcanic products. Here we evaluate the local-scale variability of a sulfate profile in a low-accumulation site (Dome C, Antarctica), in order to assess the representativeness of one core for such a reconstruction. We evaluate the variability with depth, statistical occurrence, and sulfate flux deposition variability of volcanic eruptions detected in five ice cores, drilled 1 m apart from each other. Local-scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events when a single core is used as the site reference, with a bulk probability of 30 % of missing volcanic events and close to 65 % uncertainty on one volcanic flux measurement (based on the standard deviation obtained from a five-core comparison). Averaging n records reduces the uncertainty of the deposited flux mean significantly (by a factor 1∕ √ n); in the case of five cores, the uncertainty of the mean flux can therefore be reduced to 29 %.

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A High-Resolution Continuous Flow Analysis System for Polar Ice Cores

Bulletin of Glaciological Research ◽

10.5331/bgr.16r03 ◽

2016 ◽

Vol 34 (0) ◽

pp. 11-20 ◽

Cited By ~ 1

Author(s):

Rémi DALLMAYR ◽

Kumiko GOTO-AZUMA ◽

Helle ASTRID KJÆR ◽

Nobuhiko AZUMA ◽

Morimasa TAKATA ◽

...

Keyword(s):

High Resolution ◽

Continuous Flow ◽

Flow Analysis ◽

Ice Cores ◽

Polar Ice ◽

Continuous Flow Analysis ◽

Analysis System

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High-resolution continuous flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

Atmospheric Measurement Techniques Discussions ◽

10.5194/amtd-7-12081-2014 ◽

2014 ◽

Vol 7 (12) ◽

pp. 12081-12124 ◽

Cited By ~ 1

Author(s):

B. D. Emanuelsson ◽

W. T. Baisden ◽

N. A. N. Bertler ◽

E. D. Keller ◽

V. Gkinis

Keyword(s):

Response Time ◽

Laser Spectroscopy ◽

Temporal Resolution ◽

Continuous Flow ◽

Ice Core ◽

Flow Analysis ◽

Ice Cores ◽

Flow Measurements ◽

Continuous Flow Analysis ◽

Δ18o And Δd

Abstract. Here we present an experimental setup for water stable isotopes (δ18O and δD) continuous flow measurements. It is the first continuous flow laser spectroscopy system that is using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research – LGR) in combination with an evaporation unit to continuously analyze sample from an ice core. A Water Vapor Isotopic Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to: (1) increase the temporal resolution by reducing the response time (2) enable measurements on several water standards, and (3) to reduce the influence from memory effects. While this setup was designed for the Continuous Flow Analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The modified setup provides a shorter response time (~54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the modified setup has a reduced memory effect. Stability tests comparing the modified WVISS and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the 2013 modified setup the precision after integration times of 103 s are 0.060 and 0.070‰ for δ18O and δD, respectively. For the WVISS setup the corresponding σAllan values are 0.030, 0.060 and 0.043‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042‰ after 103 s for δ18O, δD and δ17O, respectively. Both the modified setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O of 0.30 and 0.18‰ for the modified (2013) and WVISS setup, respectively after averaging times of 104 s (2.78 h). The Isotopic Water Analyzer (IWA)-modified WVISS setup used during the 2013 Roosevelt Island Climate Evolution (RICE) ice core processing campaign achieved high precision measurements, in particular for δD, with high temporal resolution for the upper part of the core, where a seasonally resolved isotopic signal is preserved.

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Continuous measurements of methane mixing ratios from ice cores

Atmospheric Measurement Techniques ◽

10.5194/amt-5-999-2012 ◽

2012 ◽

Vol 5 (5) ◽

pp. 999-1013 ◽

Cited By ~ 37

Author(s):

C. Stowasser ◽

C. Buizert ◽

V. Gkinis ◽

J. Chappellaz ◽

S. Schüpbach ◽

...

Keyword(s):

Measurement Technique ◽

Transport Model ◽

Ice Core ◽

Flow Analysis ◽

Ice Cores ◽

Atmospheric Methane ◽

Water Stream ◽

Mixing Ratios ◽

The North ◽

Analysis System

Abstract. This work presents a new, field-deployable technique for continuous, high-resolution measurements of methane mixing ratios from ice cores. The technique is based on a continuous flow analysis system, where ice core samples cut along the long axis of an ice core are melted continuously. The past atmospheric air contained in the ice is separated from the melt water stream via a system for continuous gas extraction. The extracted gas is dehumidified and then analyzed by a Wavelength Scanned-Cavity Ring Down Spectrometer for methane mixing ratios. We assess the performance of the new measurement technique in terms of precision (±0.8 ppbv, 1σ), accuracy (±8 ppbv), temporal (ca. 100 s), and spatial resolution (ca. 5 cm). Using a firn air transport model, we compare the resolution of the measurement technique to the resolution of the atmospheric methane signal as preserved in ice cores in Greenland. We conclude that our measurement technique can resolve all climatically relevant variations as preserved in the ice down to an ice depth of at least 1980 m (66 000 yr before present) in the North Greenland Eemian Ice Drilling ice core. Furthermore, we describe the modifications, which are necessary to make a commercially available spectrometer suitable for continuous methane mixing ratio measurements from ice cores.

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

Journal of Glaciology ◽

10.1017/jog.2021.75 ◽

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).

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