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

2014 ◽  
Vol 7 (12) ◽  
pp. 12081-12124 ◽  
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.

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

2015 ◽  
Vol 8 (7) ◽  
pp. 2869-2883 ◽  
Author(s):  
B. D. Emanuelsson ◽  
W. T. Baisden ◽  
N. A. N. Bertler ◽  
E. D. Keller ◽  
V. Gkinis
Keyword(s):  
Response Time ◽  
Laser Spectroscopy ◽  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Stability Tests ◽  
Analytical Instruments ◽  
Continuous Flow Analysis ◽  
Δ18o And Δd

Abstract. Here we present an experimental setup for water stable isotope (δ18O and δD) continuous-flow measurements and provide metrics defining the performance of the setup during a major ice core measurement campaign (Roosevelt Island Climate Evolution; RICE). We also use the metrics to compare alternate systems. Our setup 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 water samples from an ice core. A Water Vapor Isotope Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to (1) enable measurements on several water standards, (2) increase the temporal resolution by reducing the response time and (3) 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 custom setups provide 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 custom setups have a reduced memory effect. Stability tests comparing the custom and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the custom 2013 setup the precision after integration times of 103 s is 0.060 and 0.070 ‰ for δ18O and δD, respectively. The corresponding σAllan values for the custom 2014 setup 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 custom setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O are 0.30 and 0.18 ‰ for the custom 2013 and WVISS setup, respectively, after averaging times of 104 s (2.78 h). Using response time tests and stability tests, we show that the custom setups are more responsive (shorter response time), whereas the University of Copenhagen (UC) setup is more stable. More broadly, comparisons of different setups address the challenge of integrating vaporizer/spectrometer isotope measurement systems into a CFA campaign with many other analytical instruments.

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

2017 ◽  
Vol 10 (2) ◽  
pp. 617-632 ◽  
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.

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

2016 ◽  
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.

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 Continuous-Flow Analysis of δ17O, δ18O, and δD of H2O on an Ice Core from the South Pole

2021 ◽  
Vol 9 ◽  
Author(s):  
Eric J. Steig ◽  
Tyler R. Jones ◽  
Andrew J. Schauer ◽  
Emma C. Kahle ◽  
Valerie A. Morris ◽  
...  
Keyword(s):  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
South Pole ◽  
Deuterium Excess ◽  
The South ◽  
Continuous Flow Analysis ◽  
Hydrogen Isotope Ratios ◽  
Δ18o And Δd ◽  
Replicate Measurements

The δD and δ18O values of water are key measurements in polar ice-core research, owing to their strong and well-understood relationship with local temperature. Deuterium excess, d, the deviation from the average linear relationship between δD and δ18O, is also commonly used to provide information about the oceanic moisture sources where polar precipitation originates. Measurements of δ17O and “17O excess” (Δ17O) are also of interest because of their potential to provide information complementary to d. Such measurements are challenging because of the greater precision required, particularly for Δ17O. Here, high-precision measurements are reported for δ17O, δ18O, and δD on a new ice core from the South Pole, using a continuous-flow measurement system coupled to two cavity ring-down laser spectroscopy instruments. Replicate measurements show that at 0.5 cm resolution, external precision is ∼0.2‰ for δ17O and δ18O, and ∼1‰ for δD. For Δ17O, achieving external precision of <0.01‰ requires depth averages of ∼50 cm. The resulting ∼54,000-year record of the complete oxygen and hydrogen isotope ratios from the South Pole ice core is discussed. The time series of Δ17O variations from the South Pole shows significant millennial-scale variability, and is correlated with the logarithmic formulation of deuterium excess (dln), but not the traditional linear formulation (d).

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 A novel approach to process brittle ice for continuous flow analysis of stable water isotopes

2018 ◽  
Vol 64 (244) ◽  
pp. 289-299 ◽  
Author(s):  
REBECCA L. PYNE ◽  
ELIZABETH D. KELLER ◽  
SILVIA CANESSA ◽  
NANCY A. N. BERTLER ◽  
ALEX R. PYNE ◽  
...  
Keyword(s):  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
Ice Cores ◽  
Water Isotopes ◽  
Stable Water Isotopes ◽  
Climate History ◽  
Continuous Flow Analysis ◽  
Isotope Measurements ◽  
Water Isotope

ABSTRACTBrittle ice, which occurs in all intermediate-depth and deep ice cores retrieved from high-latitude regions, presents a challenge for high-resolution measurements of water isotopes, gases, ions and other quantities conducted with continuous flow analysis (CFA). We present a novel method of preserving brittle ice for CFA stable water isotope measurements using data from a new ice core recovered by the Roosevelt Island Climate Evolution (RICE) project. Modest modification of the drilling technique and the accommodation of non-horizontal fractures (‘slanted breaks’) in processing led to a substantial improvement in the percentage of brittle ice analyzed with CFA (87.8%). Whereas traditional processing methods remove entire fragmented pieces of ice, our method allowed the incorporation of a total of 3 m of ice (1% of the 261 m of brittle ice and ~1300 years of climate history) that otherwise would not have been available for CFA. Using the RICE stable water isotope CFA dataset, we demonstrate the effect of slanted breaks and analyze the resulting smoothing of the data with real and simulated examples. Our results suggest that retaining slanted breaks are a promising technique for preserving brittle ice material for CFA stable water isotope measurements.

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.

Continuous flow analysis of the Mount Brown South ice core

2021 ◽  
Author(s):  
Margaret Harlan ◽  
Helle Astrid Kjær ◽  
Tessa Vance ◽  
Paul Vallelonga ◽  
Vasileios Gkinis ◽  
...  
Keyword(s):  
Indian Ocean ◽  
Size Distribution ◽  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
East Antarctica ◽  
Southern Indian Ocean ◽  
Indian Ocean Region ◽  
Continuous Flow Analysis ◽  
Ocean Region

<p>The Mount Brown South (MBS) ice core is an approximately 300-meter-long ice core, drilled in 2016-2017 to the south of Mount Brown, Wilhelm II Land, East Antarctica. This location in East Antarctica was chosen as it produces an ice core with well-preserved sub-annual records of both chemistry and isotope concentrations, spanning back over 1000 years. MBS is particularly well suited to represent climate variations of the Indian Ocean sector of Antarctica, and to provide information about regional volcanism in the Southern Indian Ocean region.</p><p>A section of ice spanning the length of the MBS core was melted as part of the autumn 2019 continuous flow analysis (CFA) campaign at the Physics of Ice, Climate, and Earth (PICE) group at the University of Copenhagen. During this campaign, measurements were conducted for chemistry and impurities contained in the ice, in addition to water isotopes. The data measured in Copenhagen include measurements of H<sub>2</sub>O<sub>2,</sub> pH, electrolytic conductivity, and NH<sub>4</sub><sup>+</sup>, Ca<sup>2+</sup>, and Na<sup>+</sup> ions, in addition to insoluble particulate concentrations and size distribution measured using an Abakus laser particle counter.</p><p>Here, we present an overview of the CFA chemistry and impurity data, as well as preliminary investigations into the size distribution of insoluble particles and the presence of volcanic material within the ice. These initial chemistry and particulate size distribution data sets are useful in order to identify sections of the MBS core to subject to further analysis to increase our understanding of volcanic activity in the Southern Indian Ocean region.</p>

scholarly journals Calculating uncertainty for the RICE ice core continuous flow analysis water isotope record

2018 ◽  
Vol 11 (8) ◽  
pp. 4725-4736 ◽  
Author(s):  
Elizabeth D. Keller ◽  
W. Troy Baisden ◽  
Nancy A. N. Bertler ◽  
B. Daniel Emanuelsson ◽  
Silvia Canessa ◽  
...  
Keyword(s):  
High Resolution ◽  
Continuous Flow ◽  
Ice Core ◽  
Flow Analysis ◽  
Calibration Error ◽  
Data Set ◽  
Total Uncertainty ◽  
Continuous Flow Analysis ◽  
Uncertainty Estimates ◽  
Water Isotope

Abstract. We describe a systematic approach to the calibration and uncertainty estimation of a high-resolution continuous flow analysis (CFA) water isotope (δ2H, δ18O) record from the Roosevelt Island Climate Evolution (RICE) Antarctic ice core. Our method establishes robust uncertainty estimates for CFA δ2H and δ18O measurements, comparable to those reported for discrete sample δ2H and δ18O analysis. Data were calibrated using a time-weighted two-point linear calibration with two standards measured both before and after continuously melting 3 or 4 m of ice core. The error at each data point was calculated as the quadrature sum of three factors: Allan variance error, scatter over our averaging interval (error of the variance) and calibration error (error of the mean). Final mean total uncertainty for the entire record is δ2H=0.74 ‰ and δ18O=0.21 ‰. Uncertainties vary through the data set and were exacerbated by a range of factors, which typically could not be isolated due to the requirements of the multi-instrument CFA campaign. These factors likely occurred in combination and included ice quality, ice breaks, upstream equipment failure, contamination with drill fluid and leaks or valve degradation. We demonstrate that our methodology for documenting uncertainty was effective across periods of uneven system performance and delivered a significant achievement in the precision of high-resolution CFA water isotope measurements.

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