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Buizert, C, Martinerie P, Petrenko VV, Severinghaus JP, Trudinger CM, Witrant E, Rosen JL, Orsi AJ, Rubino M, Etheridge DM, Steele LP, Hogan C, Laube JC, Sturges WT, Levchenko VA, Smith AM, Levin I, Conway TJ, Dlugokencky EJ, Lang PM, Kawamura K, Jenk TM, White JWC, Sowers T, Schwander J, Blunier T.  2012.  Gas transport in firn: multiple-tracer characterisation and model intercomparison for NEEM, Northern Greenland. Atmospheric Chemistry and Physics. 12:4259-4277.   10.5194/acp-12-4259-2012   AbstractWebsite

Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1 sigma Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Delta age) at the firn-ice transition is calculated to be 182(-9)(+3) yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

Buizert, C, Gkinis V, Severinghaus JP, He F, Lecavalier BS, Kindler P, Leuenberger M, Carlson AE, Vinther B, Masson-Delmotte V, White JWC, Liu ZY, Otto-Bliesner B, Brook EJ.  2014.  Greenland temperature response to climate forcing during the last deglaciation. Science. 345:1177-1180.   10.1126/science.1254961   AbstractWebsite

Greenland ice core water isotopic composition (delta O-18) provides detailed evidence for abrupt climate changes but is by itself insufficient for quantitative reconstruction of past temperatures and their spatial patterns. We investigate Greenland temperature evolution during the last deglaciation using independent reconstructions from three ice cores and simulations with a coupled ocean-atmosphere climate model. Contrary to the traditional delta O-18 interpretation, the Younger Dryas period was 4.5 degrees +/- 2 degrees C warmer than the Oldest Dryas, due to increased carbon dioxide forcing and summer insolation. The magnitude of abrupt temperature changes is larger in central Greenland (9 degrees to 14 degrees C) than in the northwest (5 degrees to 9 degrees C), fingerprinting a North Atlantic origin. Simulated changes in temperature seasonality closely track changes in the Atlantic overturning strength and support the hypothesis that abrupt climate change is mostly a winter phenomenon.

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Kobashi, T, Kawamura K, Severinghaus JP, Barnola JM, Nakaegawa T, Vinther BM, Johnsen SJ, Box JE.  2011.  High variability of Greenland surface temperature over the past 4000 years estimated from trapped air in an ice core. Geophysical Research Letters. 38   10.1029/2011gl049444   AbstractWebsite

Greenland recently incurred record high temperatures and ice loss by melting, adding to concerns that anthropogenic warming is impacting the Greenland ice sheet and in turn accelerating global sea-level rise. Yet, it remains imprecisely known for Greenland how much warming is caused by increasing atmospheric greenhouse gases versus natural variability. To address this need, we reconstruct Greenland surface snow temperature variability over the past 4000 years at the GISP2 site (near the Summit of the Greenland ice sheet; hereafter referred to as Greenland temperature) with a new method that utilises argon and nitrogen isotopic ratios from occluded air bubbles. The estimated average Greenland snow temperature over the past 4000 years was -30.7 degrees C with a standard deviation of 1.0 degrees C and exhibited a long-term decrease of roughly 1.5 degrees C, which is consistent with earlier studies. The current decadal average surface temperature (2001-2010) at the GISP2 site is -29.9 degrees C. The record indicates that warmer temperatures were the norm in the earlier part of the past 4000 years, including century-long intervals nearly 1 C warmer than the present decade (20012010). Therefore, we conclude that the current decadal mean temperature in Greenland has not exceeded the envelope of natural variability over the past 4000 years, a period that seems to include part of the Holocene Thermal Maximum. Notwithstanding this conclusion, climate models project that if anthropogenic greenhouse gas emissions continue, the Greenland temperature would exceed the natural variability of the past 4000 years sometime before the year 2100. Citation: Kobashi, T., K. Kawamura, J. P. Severinghaus, J.-M. Barnola, T. Nakaegawa, B. M. Vinther, S. J. Johnsen, and J. E. Box (2011), High variability of Greenland surface temperature over the past 4000 years estimated from trapped air in an ice core, Geophys. Res. Lett., 38, L21501, doi:10.1029/2011GL049444.

Petrenko, VV, Severinghaus JP, Smith AM, Riedel K, Baggenstos D, Harth C, Orsi A, Hua Q, Franz P, Takeshita Y, Brailsford GW, Weiss RF, Buizert C, Dickson A, Schaefer H.  2013.  High-precision C-14 measurements demonstrate production of in situ cosmogenic (CH4)-C-14 and rapid loss of in situ cosmogenic (CO)-C-14 in shallow Greenland firn. Earth and Planetary Science Letters. 365:190-197.   10.1016/j.epsl.2013.01.032   AbstractWebsite

Measurements of radiocarbon (C-14) in carbon dioxide (CO2), methane (CH4) and carbon monoxide (CO) from glacial ice are potentially useful for absolute dating of ice cores, studies of the past atmospheric CH4 budget and for reconstructing the past cosmic ray flux and solar activity. Interpretation of C-14 signals in ice is complicated by the fact that the two major C-14 components-trapped atmospheric and in situ cosmogenic-are present in a combined form, as well as by a very limited understanding of the in situ component. This study measured (CH4)-C-14 and (CO)-C-14 content in glacial firn with unprecedented precision to advance understanding of the in situ C-14 component. (CH4)-C-14 and (CO)-C-14 were melt-extracted on site at Summit, Greenland from three very large (similar to 1000 kg each) replicate samples of firn that spanned a depth range of 3.6-5.6 m. Non-cosmogenic C-14 contributions were carefully characterized through simulated extractions and a suite of supporting measurements. In situ cosmogenic (CO)-C-14 was quantified to better than +/- 0.6 molecules g(-1) ice, improving on the precision of the best prior ice (CO)-C-14 measurements by an order of magnitude. The (CO)-C-14 measurements indicate that most (>99%) of the in situ cosmogenic C-14 is rapidly lost from shallow Summit firn to the atmosphere. Despite this rapid C-14 loss, our measurements successfully quantified (CH4)-C-14 in the retained fraction of cosmogenic C-14 (to +/- 0.01 molecules g(-1) ice or better), and demonstrate for the first time that a significant amount of (CH4)-C-14 is produced by cosmic rays in natural ice. This conclusion increases the confidence in the results of an earlier study that used measurements of (CH4)-C-14 in glacial ice to show that wetlands were the likely main driver of the large and rapid atmospheric CH4 increase approximately 1 1.6 kyr ago. (C) 2013 Elsevier B.V. All rights reserved.

Taylor, KC, Mayewski PA, Alley RB, Brook EJ, Gow AJ, Grootes PM, Meese DA, Saltzman ES, Severinghaus JP, Twickler MS, White JWC, Whitlow S, Zielinski GA.  1997.  The Holocene Younger Dryas transition recorded at Summit, Greenland. Science. 278:825-827.   10.1126/science.278.5339.825   AbstractWebsite

Analysis of ice from Dye-3, Greenland, has demonstrated that the transition between the Younger Dryas and Holocene climate periods occurred over a 40-year period. A near annually resolved, multiparameter record of the transition recorded in the GISP2 core from Summit, Greenland, shows that most of the transition occurred in a series of steps with durations of about 5 years. Some climate proxies associated with more northern regions. Changes in atmospheric water vapor are likely to have played a large role in the climate transition.

Baggenstos, D, Severinghaus JP, Mulvaney R, McConnell JR, Sigl M, Maselli O, Petit JR, Grente B, Steig EJ.  2018.  A horizontal ice core from Taylor Glacier, its implications for Antarctic climate history, and an improved Taylor Dome ice core time scale. Paleoceanography and Paleoclimatology. 33:778-794.   10.1029/2017pa003297   AbstractWebsite

Ice core records from Antarctica show mostly synchronous temperature variations during the last deglacial transition, an indication that the climate of the entire continent reacted as one unit to the global changes. However, a record from the Taylor Dome ice core in the Ross Sea sector of East Antarctica has been suggested to show a rapid warming, similar in style and synchronous with the Oldest Dryas-Bolling warming in Greenland. Since publication of the Taylor Dome record, a number of lines of evidence have suggested that this interpretation is incorrect and reflects errors in the underlying time scale. The issues raised regarding the dating of Taylor Dome currently linger unresolved, and the original time scale remains the de facto chronology. We present new water isotope and chemistry data from nearby Taylor Glacier to resolve the confusion surrounding the Taylor Dome time scale. We find that the Taylor Glacier record is incompatible with the original interpretation of the Taylor Dome ice core, showing that the warming in the area was gradual and started at similar to 18 ka BP (before 1950) as seen in other East Antarctic ice cores. We build a consistent, up-to-date Taylor Dome chronology from 0 to 60 ka BP by combining new and old age markers based on synchronization to other ice core records. The most notable feature of the new TD2015 time scale is a gas age-ice age difference of up to 12,000 years during the Last Glacial Maximum, by far the largest ever observed.

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Rosen, JL, Brook EJ, Severinghaus JP, Blunier T, Mitchell LE, Lee JE, Edwards JS, Gkinis V.  2014.  An ice core record of near-synchronous global climate changes at the Bolling transition. Nature Geoscience. 7:459-463.   10.1038/ngeo2147   AbstractWebsite

The abrupt warming that initiated the Bolling-Allerod interstadial was the penultimate warming in a series of climate variations known as Dansgaard-Oeschger events. Despite the clear expression of this transition in numerous palaeoclimate records, the relative timing of climate shifts in different regions of the world and their causes are subject to debate. Here we explore the phasing of global climate change at the onset of the Bolling-Allerod using air preserved in bubbles in the North Greenland Eemian ice core. Specifically, we measured methane concentrations, which act as a proxy for low-latitude climate, and the N-15/N-14 ratio of N-2, which reflects Greenland surface temperature, over the same interval of time. We use an atmospheric box model and a firn air model to account for potential uncertainties in the data, and find that changes in Greenland temperature and atmospheric methane emissions at the Bolling onset occurred essentially synchronously, with temperature leading by 4.5(-24)(+21) years. We cannot exclude the possibility that tropical climate could iag changing methane concentrations by up to several decades, if the initial methane rise came from boreal sources alone. However, because even boreal methane-producing regions lie far from Greenland, we conclude that the mechanism that drove abrupt change at this time must be capable of rapidly transmitting climate changes across the globe.

Schaefer, H, Whiticar MJ, Brook EJ, Petrenko VV, Ferretti DF, Severinghaus JP.  2006.  Ice record of delta C-13 for atmospheric CH4 across the Younger Dryas-Preboreal transition. Science. 313:1109-1112.   10.1126/science.1126562   AbstractWebsite

We report atmospheric methane carbon isotope ratios (delta(CH4)-C-13) from the Western Greenland ice margin spanning the Younger Dryas - to - Preboreal (YD-PB) transition. Over the recorded similar to 800 years, delta(CH4)-C-13 was around - 46 per mil (parts per thousand); that is, similar to 1 parts per thousand higher than in the modern atmosphere and similar to 5.5 parts per thousand higher than would be expected from budgets without C-13-rich anthropogenic emissions. This requires higher natural C-13-rich emissions or stronger sink fractionation than conventionally assumed. Constant delta(CH4)-C-13 during the rise in methane concentration at the YD-PB transition is consistent with additional emissions from tropical wetlands, or aerobic plant CH4 production, or with a multisource scenario. A marine clathrate source is unlikely.

Schaefer, H, Petrenko VV, Brook EJ, Severinghaus JP, Reeh N, Melton JR, Mitchell L.  2009.  Ice stratigraphy at the Pakitsoq ice margin, West Greenland, derived from gas records. Journal of Glaciology. 55:411-421.   10.3189/002214309788816704   AbstractWebsite

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 Pakitsoq ice margin in West Greenland, we use a combination of geochemical parameters measured in the ice matrix (delta(18)O(ice)) and air occlusions (delta(18)O(atm), delta(15)N of N(2) 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 Pakitsoq. Sections containing ice from every distinct climatic interval during Termination I, including Last Glacial Maximum, Bolling/Allerod, 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 Pakitsoq 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.

Buerki, PR, Jackson BC, Schilling T, Rufer T, Severinghaus JP.  2006.  Improved helium exchange gas cryostat and sample tube designs for automated gas sampling and cryopumping. Geochemistry Geophysics Geosystems. 7   10.1029/2006gc001341   AbstractWebsite

[ 1] In order to eliminate the use of liquid helium for the extraction of atmospheric gases from polar ice cores, two units of a redesigned top load helium exchange gas cryostat were built and tested. The cryostats feature the shortest and largest diameter sample wells built to date, a base temperature below 7 Kelvin, and a sample well without baffles. The cryostats allowed shortening the length and thus increasing the gas pressure inside our sample tubes by 58% and increasing the amount of sample ending up in the mass spectrometer by 4.4%. The cryostats can either be used as mobile stand-alone units for manual gas processing lines or integrated into a fully automated vacuum extraction and gas analysis line. For the latter application the cryostat was equipped with a custom-designed automated changeover system.

Buizert, C, Petrenko VV, Kavanaugh JL, Cuffey KM, Lifton NA, Brook EJ, Severinghaus JP.  2012.  In situ cosmogenic radiocarbon production and 2-D ice flow line modeling for an Antarctic blue ice area. Journal of Geophysical Research-Earth Surface. 117   10.1029/2011jf002086   AbstractWebsite

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 C-14 production in ice, and this component must be well understood before useful information can be extracted from C-14 data. We combine cosmic ray scaling and production estimates with a two-dimensional ice flow line model to study cosmogenic C-14 production at Taylor Glacier, Antarctica. We find (1) that C-14 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 C-14 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 C-14 and ice flow studies at ice margin sites, including important paleoclimatic applications such as the reconstruction of paleoatmospheric C-14 content of methane.

Birner, B, Buizert C, Wagner TJW, Severinghaus JP.  2018.  The influence of layering and barometric pumping on firn air transport in a 2-D model. Cryosphere. 12:2021-2037.   10.5194/tc-12-2021-2018   AbstractWebsite

Ancient air trapped in ice core bubbles has been paramount to developing our understanding of past climate and atmospheric composition. Before air bubbles become isolated in ice, the atmospheric signal is altered in the firn column by transport processes such as advection and diffusion. However, the influence of low-permeability layers and barometric pumping (driven by surface pressure variability) on firn air transport is not well understood and is not readily captured in conventional one-dimensional (1-D) firn air models. Here we present a two-dimensional (2-D) trace gas advection-diffusion-dispersion model that accounts for discontinuous horizontal layers of reduced permeability. We find that layering or barometric pumping individually yields too small a reduction in gravitational settling to match observations. In contrast, when both effects are active, the model's gravitational fractionation is suppressed as observed. Layering focuses airflows in certain regions in the 2-D model, which acts to amplify the dispersive mixing resulting from barometric pumping. Hence, the representation of both factors is needed to obtain a realistic emergence of the lock-in zone. In contrast to expectations, we find that the addition of barometric pumping in the layered 2-D model does not substantially change the differential kinetic fractionation of fast-and slow-diffusing trace gases. Like 1-D models, the 2-D model substantially underestimates the amount of differential kinetic fractionation seen in actual observations, suggesting that further subgrid-scale processes may be missing in the current generation of firn air transport models. However, we find robust scaling relationships between kinetic isotope fractionation of different noble gas isotope and elemental ratios. These relationships may be used to correct for kinetic fractionation in future high-precision ice core studies and can amount to a bias of up to 0.45 degrees C in noble-gas-based mean ocean temperature reconstructions at WAIS Divide, Antarctica.

Schilt, A, Brook EJ, Bauska TK, Baggenstos D, Fischer H, Joos F, Petrenko VV, Schaefer H, Schmitt J, Severinghaus JP, Spahni R, Stocker TF.  2014.  Isotopic constraints on marine and terrestrial N2O emissions during the last deglaciation. Nature. 516:234-+.   10.1038/nature13971   AbstractWebsite

Nitrous oxide (N2O) is an important greenhouse gas and ozone-depleting substance that has anthropogenic as well as natural marine and terrestrial sources(1). The tropospheric N2O concentrations have varied substantially in the past in concert with changing climate on glacial-interglacial and millennial timescales(2-8). It is not well understood, however, how N2O emissions from marine and terrestrial sources change in response to varying environmental conditions. The distinct isotopic compositions of marine and terrestrial N2O sources can help disentangle the relative changes in marine and terrestrial N2O emissions during past climate variations(4,9,10). Here we present N2O concentration and isotopic data for the last deglaciation, from 16,000 to 10,000 years before present, retrieved from air bubbles trapped in polar ice at Taylor Glacier, Antarctica. With the help of our data and a box model of the N2O cycle, we find a 30 per cent increase in total N2O emissions from the late glacial to the interglacial, with terrestrial and marine emissions contributing equally to the overall increase and generally evolving in parallel over the last deglaciation, even though there is no a priori connection between the drivers of the two sources. However, we find that terrestrial emissions dominated on centennial timescales, consistent with a state-of-the-art dynamic global vegetation and land surface process model that suggests that during the last deglaciation emission changes were strongly influenced by temperature and precipitation patterns over land surfaces. The results improve our understanding of the drivers of natural N2O emissions and are consistent with the idea that natural N2O emissions will probably increase in response to anthropogenic warming(11).

Landais, A, Caillon N, Severinghaus J, Barnola JM, Goujon C, Jouzel J, Masson-Delmotte V.  2004.  Isotopic measurements of air trapped in ice to quantify temperature changes. Comptes Rendus Geoscience. 336:963-970.   10.1016/j.crte.2004.03.013   AbstractWebsite

Isotopic measurements of air trapped in ice to quantify temperature changes. Isotopic measurements in polar ice core have shown a succession of rapid warming periods during the last glacial period over Greenland. However, this method underestimates the surface temperature variations. A new method based on gas thermal diffusion in the firn manages to quantify surface temperature variations through associated isotopic fractionations. We developed a method to extract air from the ice and to perform isotopic measurements to reduce analytical uncertainties to 0.006 and 0.020parts per thousand for delta(15)N and delta(40)Ar. It led to a 16 +/- 1.5degreesC surface temperature variation during a rapid warming (-70000 yr). (C) 2004 Academie des sciences. Publie par Elsevier SAS. Tous droits reserves.

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Bereiter, B, Shackleton S, Baggenstos D, Kawamura K, Severinghaus J.  2018.  Mean global ocean temperatures during the last glacial transition. Nature. 553:39-+.   10.1038/nature25152   AbstractWebsite

Little is known about the ocean temperature's long-term response to climate perturbations owing to limited observations and a lack of robust reconstructions. Although most of the anthropogenic heat added to the climate system has been taken up by the ocean up until now, its role in a century and beyond is uncertain. Here, using noble gases trapped in ice cores, we show that the mean global ocean temperature increased by 2.57 +/- 0.24 degrees Celsius over the last glacial transition (20,000 to 10,000 years ago). Our reconstruction provides unprecedented precision and temporal resolution for the integrated global ocean, in contrast to the depth-, region-, organism-and season-specific estimates provided by other methods. We find that the mean global ocean temperature is closely correlated with Antarctic temperature and has no lead or lag with atmospheric CO2, thereby confirming the important role of Southern Hemisphere climate in global climate trends. We also reveal an enigmatic 700-year warming during the early Younger Dryas period (about 12,000 years ago) that surpasses estimates of modern ocean heat uptake.

Petrenko, VV, Severinghaus JP, Schaefer H, Smith AM, Kuhl T, Baggenstos D, Hua Q, Brook EJ, Rose P, Kulin R, Bauska T, Harth C, Buizert C, Orsi A, Emanuele G, Lee JE, Brailsford G, Keeling R, Weiss RF.  2016.  Measurements of 14C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14CH4 and 14CO production rates. Geochimica et Cosmochimica Acta. 177:62-77.   10.1016/j.gca.2016.01.004   Abstract

Carbon-14 (14C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14C of trapped methane (14CH4) is a powerful tracer for past CH4 emissions from “old” carbon sources such as permafrost and marine CH4 clathrates. 14C in trapped carbon dioxide (14CO2) can be used for absolute dating of ice cores. In situ produced cosmogenic 14C in carbon monoxide (14CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14C. We analyzed very large (≈1000 kg) ice samples in the 2.26–19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14CH4 and 14CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14CH4 production rates and improve on prior estimates of 14CO production rates in ice. We find a constant 14CH4/14CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14CO for correcting the 14CH4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14C production by fast muons in a natural setting (ice or rock) and suggest that the 14C production rates in ice commonly used in the literature may be too high.

Brook, EJ, Severinghaus JP.  2011.  Methane and megafauna. Nature Geoscience. 4:271-272.   10.1038/ngeo1140   AbstractWebsite
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Petrenko, VV, Etheridge DM, Weiss RF, Brook EJ, Schaefer H, Severinghaus JP, Smith AM, Lowe D, Hua QA, Riedel K.  2010.  Methane from the East Siberian Arctic Shelf. Science. 329:1146-1147.   10.1126/science.329.5996.1146-b   AbstractWebsite
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Petrenko, VV, Smith AM, Brailsford G, Riedel K, Hua Q, Lowe D, Severinghaus JP, Levchenko V, Bromley T, Moss R, Muhle J, Brook EJ.  2008.  A new method for analyzing (14)C of methane in ancient air extracted from glacial ice. Radiocarbon. 50:53-73. AbstractWebsite

We present a new method developed for measuring radiocarbon of methane ((14)CH(4)) in ancient air samples extracted from glacial ice and dating 11,000-15,000 calendar years before present. The small size (similar to 20 mu g CH(4) carbon), low CH(4) concentrations ([CH(4)], 400-800 parts per billion [ppb]), high carbon monoxide concentrations ([CO]), and low (14)C 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. (14)C procedural blanks were greatly reduced through the construction of a new CH(4) conversion line utilizing platinized quartz wool for CH(4) combustion and the use of an ultra-high-purity iron catalyst for graphitization. The amount and (14)C activity of extraneous carbon added in the new CH(4) conversion line were determined to be 0.23 +/- 0.16 pg 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 mu g. The overall procedural blank for all stages of sample handling was 0.75 0.38 pMC for similar to 20-mu g, (14)C-free air samples with [CH(4)] of 500 ppb. Duration of the graphitization reactions for small (<25 mu g 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. (14)C corrections for each step of sample handling have been determined. The resulting overall (14)CH(4) uncertainties for the ancient air samples are similar to 1.0 pMC.

Bereiter, B, Kawamura K, Severinghaus JP.  2018.  New methods for measuring atmospheric heavy noble gas isotope and elemental ratios in ice core samples. Rapid Communications in Mass Spectrometry. 32:801-814.   10.1002/rcm.8099   AbstractWebsite

RationaleThe global ocean constitutes the largest heat buffer in the global climate system, but little is known about its past changes. The isotopic and elemental ratios of heavy noble gases (krypton and xenon), together with argon and nitrogen in trapped air from ice cores, can be used to reconstruct past mean ocean temperatures (MOTs). Here we introduce two successively developed methods to measure these parameters with a sufficient precision to provide new constraints on past changes in MOT. MethodsThe air from an 800-g ice sample - containing roughly 80mL STP air - is extracted and processed to be analyzed on two independent dual-inlet isotope ratio mass spectrometers. The primary isotope ratios (N-15, Ar-40 and Kr-86 values) are obtained with precisions in the range of 1 per meg (0.001) per mass unit. The three elemental ratio values Kr/N-2, Xe/N-2 and Xe/Kr are obtained using sequential (non-simultaneous) peak-jumping, reaching precisions in the range of 0.1-0.3. ResultsThe latest version of the method achieves a 30% to 50% better precision on the elemental ratios and a twofold better sample throughput than the previous one. The method development uncovered an unexpected source of artefactual gas fractionation in a closed system that is caused by adiabatic cooling and warming of gases (termed adiabatic fractionation) - a potential source of measurement artifacts in other methods. ConclusionsThe precisions of the three elemental ratios Kr/N-2, Xe/N-2 and Xe/Kr - which all contain the same MOT information - suggest smaller uncertainties for reconstructed MOTs (+/- 0.3-0.1 degrees C) than previous studies have attained. Due to different sensitivities of the noble gases to changes in MOT, Xe/N-2 provides the best constraints on the MOT under the given precisions followed by Xe/Kr, and Kr/N-2; however, using all of them helps to detect methodological artifacts and issues with ice quality.

Arnold, T, Harth CM, Mühle J, Manning AJ, Salameh PK, Kim J, Ivy DJ, Steele PL, Petrenko VV, Severinghaus JP, Baggenstos D, Weiss RF.  2013.  Nitrogen trifluoride global emissions estimated from updated atmospheric measurements. Proceedings of the National Academy of Sciences.   10.1073/pnas.1212346110   AbstractWebsite

Nitrogen trifluoride (NF3) has potential to make a growing contribution to the Earth’s radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF3 in 2011 were 1.18 ± 0.21 Gg⋅y−1, or ∼20 Tg CO2-eq⋅y−1 (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF3). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y−2 over the prior decade. In terms of CO2 equivalents, current NF3 emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF3 over hexafluoroethane (C2F6) in electronics manufacture is significant—emissions of between 53 and 220 Tg CO2-eq⋅y−1 were avoided during 2011. Despite these savings, total NF3 emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF3 emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing.

Petrenko, VV, Severinghaus JP, Brook EJ, Muhle J, Headly M, Harth CM, Schaefer H, Reeh N, Weiss RF, Lowe D, Smith AM.  2008.  A novel method for obtaining very large ancient air samples from ablating glacial ice for analyses of methane radiocarbon. Journal of Glaciology. 54:233-244.   10.3189/002214308784886135   AbstractWebsite

We present techniques for obtaining large (similar to 100 L STP) samples of ancient air for analysis of (14)C of methane ((14)CH(4)) and other trace constituents. Paleoatmospheric (14)CH(4) 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 ([CH(4)]) increases that accompanied rapid warming events during the last deglaciation. Air dating to the Younger Dryas-Preboreal and Oldest Dryas-Bolling 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 delta(15)N of N(2), delta(18)O of O(2), delta(18)O(ice) and [CH(4)] measurements. The [CH(4)] blank of the melt extractions was <4 ppb. Measurements of delta(18)O and delta(15)N indicated no significant gas isotopic fractionation from handling. Measured Ar/N(2), CFC-11 and CFC-12 in the samples indicated no significant contamination from ambient air. Ar/N(2), 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 [CH(4)]. Corrected [CH(4)] is elevated over expected values by up to 132 ppb for most samples, suggesting some in situ CH(4) production in ice at this site.

Caillon, N, Jouzel J, Severinghaus JP, Chappellaz J, Blunier T.  2003.  A novel method to study the phase relationship between Antarctic and Greenland climate. Geophysical Research Letters. 30   10.1029/2003gl017838   AbstractWebsite

A classical method for understanding the coupling between northern and southern hemispheres during millennial-scale climate events is based on the correlation between Greenland and Antarctic ice core records of atmospheric composition. Here we present a new approach based on the use of a single Antarctic ice core in which measurements of methane concentration and inert gas isotopes place constraints on the timing of a rapid climate change in the North and of its Antarctic counterpart. We applied it to the Marine Isotope Stage (MIS) 5d/c transition early in the last glaciation similar to108 ky BP. Our results indicate that the Antarctic temperature increase occurred 2 ky before the methane increase, which is used as a time marker of the warming in the Northern Hemisphere. This result is in agreement with the "bipolar seesaw'' mechanism used to explain the phase relationships documented between 23 and 90 ky BP [Blunier and Brook, 2001].

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Seibt, U, Brand WA, Heimann M, Lloyd J, Severinghaus JP, Wingate L.  2004.  Observations of O-2 : CO2 exchange ratios during ecosystem gas exchange. Global Biogeochemical Cycles. 18   10.1029/2004gb002242   AbstractWebsite

We determined O-2:CO2 exchange ratios of ecosystem fluxes during field campaigns in different forest ecosystems (Harvard Forest/United States, Griffin Forest/United Kingdom, Hainich/Germany). The exchange ratios of net assimilation observed in chamber experiments varied between 0.7 and 1.6, with averages of 1.1 to 1.2. A measurement of soil gas exchange yielded an exchange ratio of 0.94. On the other hand, the observed canopy air O-2:CO2 ratios, derived from the concurrent variations of O-2 and CO2 abundances in canopy air, were virtually indistinguishable from 1.0 over the full diurnal cycle. Simulations with a simple one-box model imply that the combined processes of assimilation, respiration, and turbulent exchange yield canopy air O-2:CO2 ratios that differ from the exchange ratios of the separate fluxes. In particular, the simulated canopy air O-2:CO2 ratios (1.01 to 1.12) were clearly lower than the exchange ratios of net turbulent fluxes between the ecosystem and the atmosphere (1.26 to 1.38). The simulated canopy air ratios were also sensitive to changes in the regional O-2:CO2 ratio of air above the canopy. Offsets between the various exchange ratios could thus arise if the component ecosystem fluxes have different diurnal cycles and distinct exchange ratios. Our results indicate that measurements of O-2 and CO2 abundances in canopy air may not be the appropriate method to determine O-2:CO2 exchange ratios of net ecosystem fluxes.

Mitchell, LE, Buizert C, Brook EJ, Breton DJ, Fegyveresi J, Baggenstos D, Orsi A, Severinghaus J, Alley RB, Albert M, Rhodes RH, McConnell JR, Sigl M, Maselli O, Gregory S, Ahn J.  2015.  Observing and modeling the influence of layering on bubble trapping in polar firn. Journal of Geophysical Research-Atmospheres. 120:2558-2574.   10.1002/2014jd022766   AbstractWebsite

Interpretation of ice core trace gas records depends on an accurate understanding of the processes that smooth the atmospheric signal in the firn. Much work has been done to understand the processes affecting air transport in the open pores of the firn, but a paucity of data from air trapped in bubbles in the firn-ice transition region has limited the ability to constrain the effect of bubble closure processes. Here we present high-resolution measurements of firn density, methane concentrations, nitrogen isotopes, and total air content that show layering in the firn-ice transition region at the West Antarctic Ice Sheet (WAIS) Divide ice core site. Using the notion that bubble trapping is a stochastic process, we derive a new parameterization for closed porosity that incorporates the effects of layering in a steady state firn modeling approach. We include the process of bubble trapping into an open-porosity firn air transport model and obtain a good fit to the firn core data. We find that layering broadens the depth range over which bubbles are trapped, widens the modeled gas age distribution of air in closed bubbles, reduces the mean gas age of air in closed bubbles, and introduces stratigraphic irregularities in the gas age scale that have a peak-to-peak variability of 10 years at WAIS Divide. For a more complete understanding of gas occlusion and its impact on ice core records, we suggest that this experiment be repeated at sites climatically different from WAIS Divide, for example, on the East Antarctic plateau.