Ice stratigraphy at the Pakitsoq ice margin, West Greenland, derived from gas records

Horizontal ice-core sites, where ancient ice is exposed at the glacier surface, offer unique opportunities for paleo-studies of trace components requiring large sample volumes. Following previous work at the Pâkitsoq ice margin in West Greenland, we use a combination of geochemical parameters measured in the ice matrix (δ¹⁸O[subscript ice]) and air occlusions (δ¹⁸O[subscript atm], δ¹⁵N of N₂ and methane concentration) to date ice layers from specific climatic intervals. The data presented here expand our understanding of the stratigraphy and three-dimensional structure of ice layers outcropping at Pâkitsoq. Sections containing ice from every distinct climatic interval during Termination I, including Last Glacial Maximum, Bølling/Allerød, Younger Dryas and the early Holocene, are identified. In the early Holocene, we find evidence for climatic fluctuations similar to signals found in deep ice cores from Greenland. A second glacial-interglacial transition exposed at the extreme margin of the ice is identified as another outcrop of Termination I (rather than the onset of the Eemian interglacial as postulated in earlier work). Consequently, the main structural feature at Pâkitsoq is a large-scale anticline with accordion-type folding in both exposed sequences of the glacial-Holocene transition, leading to multiple layer duplications and age reversals

In situ cosmogenic radiocarbon production and 2-D ice flow line modeling for an Antarctic blue ice area

Radiocarbon measurements at ice margin sites and blue ice areas can potentially be used for ice dating, ablation rate estimates and paleoclimatic reconstructions. Part of the measured signal comes from in situ cosmogenic ¹⁴C production in ice, and this component must be well understood before useful information can be extracted from ¹⁴C data. We combine cosmic ray scaling and production estimates with a two-dimensional ice flow line model to study cosmogenic ¹⁴C production at Taylor Glacier, Antarctica. We find (1) that ¹⁴C production through thermal neutron capture by nitrogen in air bubbles is negligible; (2) that including ice flow patterns caused by basal topography can lead to a surface ¹⁴C activity that differs by up to 25% from the activity calculated using an ablation-only approximation, which is used in all prior work; and (3) that at high ablation margin sites, solar modulation of the cosmic ray flux may change the strength of the dominant spallogenic production by up to 10%. As part of this effort we model two-dimensional ice flow along the central flow line of Taylor Glacier. We present two methods for parameterizing vertical strain rates, and assess which method is more reliable for Taylor Glacier. Finally, we present a sensitivity study from which we conclude that uncertainties in published cosmogenic production rates are the largest source of potential error. The results presented here can inform ongoing and future ¹⁴C and ice flow studies at ice margin sites, including important paleoclimatic applications such as the reconstruction of paleoatmospheric ¹⁴C content of methane

Multiple carbon cycle mechanisms associated with the glaciation of Marine Isotope Stage 4

Here we use high-precision carbon isotope data (δ13C-CO2) to show atmospheric CO2 during Marine Isotope Stage 4 (MIS 4, ~70.5-59 ka) was controlled by a succession of millennial-scale processes. Enriched δ13C-CO2 during peak glaciation suggests increased ocean carbon storage. Variations in δ13C-CO2 in early MIS 4 suggest multiple processes were active during CO2 drawdown, potentially including decreased land carbon and decreased Southern Ocean air-sea gas exchange superposed on increased ocean carbon storage. CO2 remained low during MIS 4 while δ13C-CO2 fluctuations suggest changes in Southern Ocean and North Atlantic air-sea gas exchange. A 7 ppm increase in CO2 at the onset of Dansgaard-Oeschger event 19 (72.1 ka) and 27 ppm increase in CO2 during late MIS 4 (Heinrich Stadial 6, ~63.5-60 ka) involved additions of isotopically light carbon to the atmosphere. The terrestrial biosphere and Southern Ocean air-sea gas exchange are possible sources, with the latter event also involving decreased ocean carbon storage

Radiometric ⁸¹Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica

We present the first successful ⁸¹Kr-Kr radiometric dating of ancient polar ice. Krypton was extracted from the air bubbles in four ~350 kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The ⁸¹Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean absolute age offset of 6 ± 2.5 ka. Our experimental methods and sampling strategy are validated by 1) ⁸⁵Kr and ³⁹Ar analyses that show the samples to be free of modern air contamination, and 2) air content measurements that show the ice did not experience gas loss. We estimate the error in the ⁸¹Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (MIS 5e, 130-115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA ⁸¹Kr analysis requires a 40-80 kg ice sample; as sample requirements continue to decrease ⁸¹Kr dating of ice cores is a future possibility.Keywords: paleoclimatology, glaciology, geochronolog

Instruments and Methods: A novel method for obtaining very large ancient air samples from ablating glacial ice for analyses of methane radiocarbon

We present techniques for obtaining large (∼100 L STP) samples of ancient air for analysis of ¹⁴C of methane (¹⁴CH₄) and other trace constituents. Paleoatmospheric ¹⁴CH₄ measurements should constrain the fossil fraction of past methane budgets, as well as provide a definitive test of methane clathrate involvement in large and rapid methane concentration ([CH₄]) increases that accompanied rapid warming events during the last deglaciation. Air dating to the Younger Dryas-Preboreal and Oldest Dryas-Bølling abrupt climatic transitions was obtained by melt extraction from old glacial ice outcropping at an ablation margin in West Greenland. The outcropping ice and occluded air were dated using a combination of δ¹⁵N of N₂, δ¹⁸O of O₂, δ¹⁸O[subscript ice] and [CH₄] measurements. The [CH₄] blank of the melt extractions was <4 ppb. Measurements of δ¹⁸O and δ¹⁵N indicated no significant gas isotopic fractionation from handling. Measured Ar/N₂, CFC-11 and CFC-12 in the samples indicated no significant contamination from ambient air. Ar/N₂, Kr/Ar and Xe/Ar ratios in the samples were used to quantify effects of gas dissolution during the melt extractions and correct the sample [CH₄]. Corrected [CH₄] is elevated over expected values by up to 132 ppb for most samples, suggesting some in situ CH₄ production in ice at this site.This is the publisher’s final pdf. The published article is copyrighted by the International Glaciological Society and can be found at: http://www.igsoc.org/journal

A New Method for Analyzing ¹⁴C of Methane in Ancient Air Extracted from Glacial Ice

We present a new method developed for measuring radiocarbon of methane (¹⁴CH₄) in ancient air samples extracted from glacial ice and dating 11,000–15,000 calendar years before present. The small size (~20 μg CH₄ carbon), low CH₄ concentrations ([CH₄], 400–800 parts per billion [ppb]), high carbon monoxide concentrations ([CO]), and low ¹⁴C activity of the samples created unusually high risks of contamination by extraneous carbon. Up to 2500 ppb CO in the air samples was quantitatively removed using the Sofnocat reagent. ¹⁴C procedural blanks were greatly reduced through the construction of a new CH₄ conversion line utilizing platinized quartz wool for CH₄ combustion and the use of an ultra-high-purity iron catalyst for graphitization. The amount and ¹⁴C activity of extraneous carbon added in the new CH₄ conversion line were determined to be 0.23 ± 0.16 μg and 23.57 ± 16.22 pMC, respectively. The amount of modern (100 pMC) carbon added during the graphitization step has been reduced to 0.03 μg. The overall procedural blank for all stages of sample handling was 0.75 ± 0.38 pMC for ~20-μg, ¹⁴C-free air samples with [CH₄] of 500 ppb. Duration of the graphitization reactions for small (<25 μg C) samples was greatly reduced and reaction yields improved through more efficient water vapor trapping and the use of a new iron catalyst with higher surface area. ¹⁴C corrections for each step of sample handling have been determined. The resulting overall ¹⁴CH₄ uncertainties for the ancient air samples are ~1.0 pMC.This is the publisher’s final pdf. The published article is copyrighted by the University of Arizona and can be found at: https://journals.uair.arizona.edu/index.php/radiocarbon/index

Using ice core measurements from Taylor Glacier, Antarctica, to calibrate in situ cosmogenic 14 C production rates by muons

Cosmic rays entering the Earth’s atmosphere produce showers of secondary particles such as protons, neutrons, and muons. The interaction of these particles with oxygen-16 (16O) in minerals such as ice and quartz can produce carbon-14 (14C). In glacial ice, 14C is also incorporated through trapping of 14C-containing atmospheric gases (14CO2, 14CO, and 14CH4). Understanding the production rates of in situ cosmogenic 14C is important to deconvolve the in situ cosmogenic and atmospheric 14C signals in ice, both of which contain valuable paleoenvironmental information. Unfortunately, the in situ 14C production rates by muons (which are the dominant production mechanism at depths of > 6m solid ice equivalent) are uncertain. In this study, we use measurements of in situ 14C in ancient ice (> 50 ka) from the Taylor Glacier, an ablation site in Antarctica, in combination with a 2D ice flow model to better constrain the compound-specific rates of 14C production by muons and the partitioning of in situ 14C between CO2, CO, and CH4. Our measurements show that 33.7% (11.4%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO and 66.1% (11.5%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO2. 14CH4 represents a very small fraction (< 0.3%) of the total. Assuming that the majority of in situ muogenic 14C in ice forms 14CO2, 14CO, and 14CH4, we also calculated muogenic 14C production rates that are lower by factors of 5.7 (3.6–13.9; 95% confidence interval) and 3.7 (2.0–11.9; 95% confidence interval) for negative muon capture and fast muon interactions, respectively, when compared to values determined in quartz from laboratory studies (Heisinger et al., 2002a, b) and in a natural setting (Lupker et al., 2015). This apparent discrepancy in muogenic 14C production rates in ice and quartz currently lacks a good explanation and requires further investigation

Perfluorocyclobutane (PFC-318, &lt;i&gt;c&lt;/i&gt;-C&lt;sub&gt;4&lt;/sub&gt;F&lt;sub&gt;8&lt;/sub&gt;) in the global atmosphere

We reconstruct atmospheric abundances of the potent greenhouse gas span classCombining double low line inline-formula span classCombining double low line inline-formula perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of span classCombining double low line inline-formula reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66ppt (parts per trillion dry-air mole fraction) in 2017. Global span classCombining double low line inline-formula span classCombining double low line inline-formula emissions rose from near zero in the 1960s to span classCombining double low line inline-formula (1span classCombining double low line inline-formula gyrspan classCombining double low line inline-formula in the late 1970s to late 1980s, then declined to span classCombining double low line inline-formula classCombining double low line inline-formula in the mid-1990s to early 2000s, followed by a rise since the early 2000s to span classCombining double low line inline-formula 2.20±0.05 Ggyrspan classCombining double low line inline-formula in 2017. These emissions are significantly larger than inventory-based emission estimates. Estimated emissions from eastern Asia rose from 0.36Ggyrspan classCombining double low line inline-formula in 2010 to 0.73Ggyrspan classCombining double low line inline-formula in 2016 and 2017, 31% of global emissions, mostly from eastern China. We estimate emissions of 0.14Ggyrspan classCombining double low line inline-formula from northern and central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from northwestern Europe and Australia are estimated to be small (span classCombining double low line inline-formula % each). We suggest that emissions from China, India, andspan idCombining double low line page10336 Russia are likely related to production of polytetrafluoroethylene (PTFE, Teflon ) and other fluoropolymers and fluorochemicals that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (span classCombining double low line inline-formula) in which span classCombining double low line inline-formula classCombining double low line inline-formula is a known by-product. The semiconductor sector, where span classCombining double low line inline-formula span classCombining double low line inline-formula is used, is estimated to be a small source, at least in South Korea, Japan, Taiwan, and Europe. Without an obvious correlation with population density, incineration of waste-containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of span classCombining double low line inline-formula span classCombining double low line inline-formula are known and though we cannot categorically exclude unknown sources, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce the span classCombining double low line inline-formula span classCombining double low line inline-formula by-product were probably not in place in the early decades, explaining the increase in emissions in the 1960s and 1970s. With the advent of by-product reporting requirements to the United Nations Framework Convention on Climate Change (UNFCCC) in the 1990s, concern about climate change and product stewardship, abatement, and perhaps the collection of span classCombining double low line inline-formula span classCombining double low line inline-formula by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries. We predict that span classCombining double low line inline-formula span classCombining double low line inline-formula emissions will continue to rise and that span classCombining double low line inline-formula span classCombining double low line inline-formula will become the second most important emitted PFC in terms of span classCombining double low line inline-formula equivalent emissions within a year or two. The 2017 radiative forcing of span classCombining double low line inline-formula span classCombining double low line inline-formula 0.52mWmspan classCombining double low line inline-formula) is small but emissions of span classCombining double low line inline-formula span classCombining double low line inline-formula and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions inferred outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country-scale emissions of PFCs and other synthetic greenhouse gases and ozone-depleting substances.United States. National Aeronautics and Space Administration (Grant NNX07AE89G)United States. National Aeronautics and Space Administration (Grant NNX07AF09G)United States. National Aeronautics and Space Administration (Grant NNX07AE87G)Great Britain. Department for Business, Energy & Industrial Strategy (Grant 1028/06/2015)United States. National Oceanic and Atmospheric Administration (Grant RA-133-R15-CN-0008)National Natural Science Foundation of China (Grant 41575114)National Science Foundation (U.S.) (Grant ARC-1203779)National Science Foundation (U.S.) (Grant ARC-1204084)Natural Environment Research Council (Great Britain) (Grant NE/I027282/1