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

AbstractDissolved 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).European Research Counci

A method for analysis of vanillic acid in polar ice cores

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 I1/4L 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

A method for analysis of vanillic acid in polar ice cores

© Author(s) 2015. CC Attribution 3.0 License. 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 I1/4L 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

Burning-derived vanillic acid in an Arctic ice core from Tunu, northeastern Greenland

In this study, vanillic acid was measured in the Tunu ice core from northeastern Greenland in samples covering the past 1700 years. Vanillic acid is an aerosol-borne aromatic methoxy acid, produced by the combustion of lignin during biomass burning. Air mass trajectory analysis indicates that North American boreal forests are likely the major source region for biomass burning aerosols deposited to the ice core site. Vanillic acid levels in the Tunu ice core range from < 0.005 to 0.08 ppb. Tunu vanillic acid exhibits centennial-scale variability in pre-industrial ice, with elevated levels during the warm climates of the Roman Warm Period and Medieval Climate Anomaly, and lower levels during the cooler climates of the Late Antique Little Ice Age and the Little Ice Age. Analysis using a peak detection method revealed a positive correlation between vanillic acid in the Tunu ice core and both ammonium and black carbon in the North Greenland Eemian Ice Drilling (NEEM) project ice core from 600 to 1200 CE. The data provide multiproxy evidence of centennial-scale variability in North American high-latitude fire during this time period

Burning-derived vanillic acid in an Arctic ice core from Tunu, northeastern Greenland

In this study, vanillic acid was measured in the Tunu ice core from northeastern Greenland in samples covering the past 1700 years. Vanillic acid is an aerosol-borne aromatic methoxy acid, produced by the combustion of lignin during biomass burning. Air mass trajectory analysis indicates that North American boreal forests are likely the major source region for biomass burning aerosols deposited to the ice core site. Vanillic acid levels in the Tunu ice core range from < 0.005 to 0.08 ppb. Tunu vanillic acid exhibits centennial-scale variability in pre-industrial ice, with elevated levels during the warm climates of the Roman Warm Period and Medieval Climate Anomaly, and lower levels during the cooler climates of the Late Antique Little Ice Age and the Little Ice Age. Analysis using a peak detection method revealed a positive correlation between vanillic acid in the Tunu ice core and both ammonium and black carbon in the North Greenland Eemian Ice Drilling (NEEM) project ice core from 600 to 1200 CE. The data provide multiproxy evidence of centennial-scale variability in North American high-latitude fire during this time period

Aromatic acids in an Arctic ice core from Svalbard: A proxy record of biomass burning

This study presents vanillic acid and parahydroxybenzoic acid levels in an Arctic ice core from Lomonosovfonna, Svalbard covering the past 800 years. These aromatic acids are likely derived from lignin combustion in wildfires and long-range aerosol transport. Vanillic and para-hydroxybenzoic acid are present throughout the ice core, confirming that these compounds are preserved on millennial timescales. Vanillic and para-hydroxybenzoic acid concentrations in the Lomonosovfonna ice core ranged from below the limits of detection to 0.2 and 0.07 ppb, respectively (1 ppb =1000 ng L-1). Vanillic acid levels are high (maximum of 0.1 ppb) from 1200 to 1400 CE, then gradually decline into the twentieth century. The largest peak in the vanillic acid in the record occurs from 2000 to 2008 CE. In the para-hydrobenzoic acid record, there are three centennialscale peaks around 1300, 1550, and 1650 CE superimposed on a long-term decline in the baseline levels throughout the record. Ten-day air mass back trajectories for a decade of fire seasons (March-November, 2006-2015) indicate that Siberia and Europe are the principle modern source regions for wildfire emissions reaching the Lomonosovfonna site. The Lomonosovfonna data are similar to those from the Eurasian Arctic Akademii Nauk ice core during the early part of the record (1220-1400 CE), but the two ice cores diverge markedly after 1400 CE. This coincides with a shift in North Atlantic climate marked by a change of the North Atlantic Oscillation from a positive to a more negative state

Aromatic acids in a Eurasian Arctic ice core: A 2600-year proxy record of biomass burning

Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb = 1000 ng L-1) to about 1 ppb, with roughly 30% of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650-300 BCE, 340-660 CE, and 1460-1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning

The ST22 chronology for the Skytrain Ice Rise ice core - Part 1: A stratigraphic chronology of the last 2000 years

Abstract. A new ice core was drilled in West Antarctica on Skytrain Ice Rise in field season 2018/2019. This 651 m ice core is one of the main targets of the WACSWAIN (WArm Climate Stability of the West Antarctic ice sheet in the last INterglacial) project. A present-day accumulation rate of 13.5 cm w.e. yr−1 was derived. Although the project mainly aims to investigate the last interglacial (115–130 ka), a robust chronology period covering the recent past is needed to constrain the age models for the deepest ice. Additionally, this time period is important for understanding current climatic changes in the West Antarctic region. Here, we present a stratigraphic chronology for the top 184.14 m of the Skytrain ice core based on absolute age tie points interpolated using annual layer counting encompassing the last 2000 years of climate history. Together with a model-based depth–age relationship of the deeper part of the ice core, this will form the ST22 chronology. The chemical composition, dust content, liquid conductivity, water isotope concentration and methane content of the whole core was analysed via continuous flow analysis (CFA) at the British Antarctic Survey. Annual layer counting was performed by manual counting of seasonal variations in mainly the sodium and calcium records. This counted chronology was informed and anchored by absolute age tie points, namely, the tritium peak (1965 CE) and six volcanic eruptions. Methane concentration variations were used to further constrain the counting error. A minimal error of ±1 year at the tie points was derived, accumulating to ± 5 %–10 % of the age in the unconstrained sections between tie points. This level of accuracy enables data interpretation on at least decadal timescales and provides a solid base for the dating of deeper ice, which is the second part of the chronology. </jats:p