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Rhodes, RH, Brook EJ, Chiang JCH, Blunier T, Maselli OJ, McConnell JR, Romanini D, Severinghaus JP.  2015.  Enhanced tropical methane production in response to iceberg discharge in the North Atlantic. Science. 348:1016-1019.   10.1126/science.1262005   AbstractWebsite

The causal mechanisms responsible for the abrupt climate changes of the Last Glacial Period remain unclear. One major difficulty is dating ice-rafted debris deposits associated with Heinrich events: Extensive iceberg influxes into the North Atlantic Ocean linked to global impacts on climate and biogeochemistry. In a new ice core record of atmospheric methane with ultrahigh temporal resolution, we find abrupt methane increases within Heinrich stadials 1, 2, 4, and 5 that, uniquely, have no counterparts in Greenland temperature proxies. Using a heuristic model of tropical rainfall distribution, we propose that Hudson Strait Heinrich events caused rainfall intensification over Southern Hemisphere land areas, thereby producing excess methane in tropical wetlands. Our findings suggest that the climatic impacts of Heinrich events persisted for 740 to 1520 years.

Buizert, C, Cuffey KM, Severinghaus JP, Baggenstos D, Fudge TJ, Steig EJ, Markle BR, Winstrup M, Rhodes RH, Brook EJ, Sowers TA, Clow GD, Cheng H, Edwards RL, Sigl M, McConnell JR, Taylor KC.  2015.  The WAIS Divide deep ice core WD2014 chronology - Part 1: Methane synchronization (68-31 kaBP) and the gas age-ice age difference. Climate of the Past. 11:153-173.   10.5194/cp-11-153-2015   AbstractWebsite

The West Antarctic Ice Sheet Divide (WAIS Divide, WD) ice core is a newly drilled, high-accumulation deep ice core that provides Antarctic climate records of the past similar to 68 ka at unprecedented temporal resolution. The upper 2850m (back to 31.2 ka BP) have been dated using annual-layer counting. Here we present a chronology for the deep part of the core (67.8-31.2 ka BP), which is based on stratigraphic matching to annual-layer-counted Greenland ice cores using globally well-mixed atmospheric methane. We calculate the WD gas age-ice age difference (Delta age) using a combination of firn densification modeling, ice-flow modeling, and a data set of delta N-15-N-2, a proxy for past firn column thickness. The largest Delta age at WD occurs during the Last Glacial Maximum, and is 525 +/- 120 years. Internally consistent solutions can be found only when assuming little to no influence of impurity content on densification rates, contrary to a recently proposed hypothesis. We synchronize the WD chronology to a linearly scaled version of the layer-counted Greenland Ice Core Chronology (GICC05), which brings the age of Dansgaard-Oeschger (DO) events into agreement with the U = Th absolutely dated Hulu Cave speleothem record. The small Delta age at WD provides valuable opportunities to investigate the timing of atmospheric greenhouse gas variations relative to Antarctic climate, as well as the interhemispheric phasing of the "bipolar seesaw".

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.

Petrenko, VV, Smith AM, Brook EJ, Lowe D, Riedel K, Brailsford G, Hua Q, Schaefer H, Reeh N, Weiss RF, Etheridge D, Severinghaus JP.  2009.  14C-CH4 Measurements in Greenland Ice: Investigating Last Glacial Termination CH4 Sources. Science. 324:506-508.   10.1126/science.1168909   AbstractWebsite

The cause of a large increase of atmospheric methane concentration during the Younger Dryas-Preboreal abrupt climatic transition (similar to 11,600 years ago) has been the subject of much debate. The carbon-14 (C-14) content of methane ((CH4)-C-14) should distinguish between wetland and clathrate contributions to this increase. We present measurements of (CH4)-C-14 in glacial ice, targeting this transition, performed by using ice samples obtained from an ablation site in west Greenland. Measured (CH4)-C-14 values were higher than predicted under any scenario. Sample (CH4)-C-14 appears to be elevated by direct cosmogenic C-14 production in ice. C-14 of CO was measured to better understand this process and correct the sample (CH4)-C-14. Corrected results suggest that wetland sources were likely responsible for the majority of the Younger Dryas-Preboreal CH4 rise.

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.

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.

Kobashi, T, Severinghaus JP, Brook EJ, Barnola JM, Grachev AM.  2007.  Precise timing and characterization of abrupt climate change 8200 years ago from air trapped in polar ice. Quaternary Science Reviews. 26:1212-1222.   10.1016/j.quascirev.2007.01.009   AbstractWebsite

How fast and how much climate can change has significant implications for concerns about future climate changes and their potential impacts on society. An abrupt climate change 8200 years ago (8.2 ka event) provides a test case to understand possible future climatic variability. Here, methane concentration (taken as an indicator for terrestrial hydrology) and nitrogen isotopes (Greenland temperature) in trapped air in a Greenland ice core (GISP2) are employed to scrutinize the evolution of the 8.2 ka event. The synchronous change in methane and nitrogen implies that the 8.2 ka event was a synchronous event (within +/- 4 years) at a hemispheric scale, as indicated by recent climate model results [Legrande, A. N., Schmidt, G. A., Shindell, D. T., Field, C. V., Miller, R. L., Koch, D. M., Faluvegi, G., Hoffmann, G., 2006. Consistent simulations of multiple proxy responses to an abrupt climate change event. Proceedings of the National Academy of Sciences 103, 837-842]. The event began with a large-scale general cooling and drying around similar to 8175 +/- 30 years BP (Before Present, where Present is 1950 AD). Greenland temperature cooled by 3.3 +/- 1.1 degrees C (decadal average) in less than similar to 20 years, and atmospheric methane concentration decreased by similar to 80 +/- 25 ppb over similar to 40 years, corresponding to a 15 +/- 5% emission reduction. Hemispheric scale cooling and drying.. inferred from many paleoclimate proxies, likely contributed to this emission reduction. In central Greenland, the coldest period lasted for similar to 60 years, interrupted by a milder interval of a few decades, and temperature subsequently warmed in several steps over similar to 70 years. The total duration of the 8.2 ka event was roughly 150 years. (c) 2007 Elsevier Ltd. All rights reserved.

Petrenko, VV, Severinghaus JP, Brook EJ, Reeh N, Schaefer H.  2006.  Gas records from the West Greenland ice margin covering the Last Glacial Termination: a horizontal ice core. Quaternary Science Reviews. 25:865-875.   10.1016/j.quascirev.2005.09.005   AbstractWebsite

Certain sites along ice sheet margins provide an easily accessible and almost unlimited supply of ancient ice at the surface. Measurements of gases in trapped air from ice outcropping at Pakitsoq, West Greenland, demonstrate that ancient air is mostly well preserved. No alterations in delta O-18(atm) and delta N-15 of N-2 are apparent, and alterations in methane are found in only a few ice sections. Using measurements of these gases, we have unambiguously identified a stratigraphic section containing ice from the end of last glacial period as well as Bolling-Allerod, Younger Dryas and Preboreal intervals. Extensive sections of ice from the Holocene and most ages within the last glacial period are probably also present. Very accurate dating has been possible in the ice section containing the Younger Dryas-Preboreal abrupt climate transition signal. The ice at Pakitsoq is folded and non-uniformly thinned, with many cross-cutting bands of bubble-free ice and dust. The cross-cutting features are associated with anomalies in both the gas and the ice records. With careful sampling to avoid these, the ice at Pakitsoq is suitable for recovery of large-volume samples of the ancient atmosphere for analysis of trace constituents such as (CH4)-C-14. (c) 2005 Elsevier Ltd. All rights reserved.

Huber, C, Beyerle U, Leuenberger M, Schwander J, Kipfer R, Spahni R, Severinghaus JP, Weiler K.  2006.  Evidence for molecular size dependent gas fractionation in firn air derived from noble gases, oxygen, and nitrogen measurements. Earth and Planetary Science Letters. 243:61-73.   10.1016/j.epsl.2005.12.036   AbstractWebsite

We present elemental and isotopic measurements of noble gases (He, Ne, Ar, Kr, and Xe), oxygen and nitrogen of firn air from two sites. The first set of samples was taken in 1998 at the summit of the Devon Ice Cap in the eastern part of Devon Island. The second set was taken in 2001 at NGRIP location (North Greenland). He and Ne are heavily enriched relative to Ar with respect to the atmosphere in the air near the close-off depth at around 50-70 in. The enrichment increases with depth and reaches the maximum value in the deepest samples just above the zone of impermeable ice where no free air could be extracted anymore. Similarly, elemental ratios of O(2)/N(2), O(2)/Ar and Ar/N(2) are increasing with depth. In contrast but in line with expectations, isotopic ratios of (15)N/(14)N, (18)O/(16)O, and (36)Ar/(40)Ar show no significant enrichment near the close-off depth. The observed isotopic ratios in the firn air column can be explained within the uncertainty ranges by the well-known processes of gravitational enrichment and thermal diffusion. To explain the elemental ratios, however, an additional fractionation process during bubble inclusion has to be considered. We implemented this additional process into our firn air model. The fractionation factors were found by fitting model profiles to the data. We found a very similar close-off fractionation behavior for the different molecules at both sites. For smaller gas species (mainly He and Ne) the fractionation factors are linearly correlated to the molecule size, whereas for diameters greater than about 3.6 A the fractionation seems to be significantly smaller or even negligible. An explanation for this size dependent fractionation process could be gas diffusion through the ice lattice. At Devon Island the enrichment at the bottom of the firn air column is about four times higher compared to NGRIP. We explain this by lower firn diffusivity at Devon Island, most probably due to melt layers, resulting in significantly reduced back diffusion of the excess gas near the close-off depth. The results of this study considerably increase the understanding of the processes occurring during air bubble inclusion near the close-off depth in firn and can help to improve the interpretation of direct firn air measurements, as well as air bubble measurements in ice cores, which are used in numerous studies as paleo proxies. (c) 2006 Elsevier B.V. All rights reserved.

Brook, EJ, White JWC, Schilla ASM, Bender ML, Barnett B, Severinghaus JP, Taylor KC, Alley RB, Steig EJ.  2005.  Timing of millennial-scale climate change at Siple Dome, West Antarctica, during the last glacial period. Quaternary Science Reviews. 24:1333-1343.   10.1016/j.quascirev.2005.02.002   AbstractWebsite

Using atmospheric methane and the isotopic composition of O-2 as correlation tools, we place the 6D record of ice from the Siple Dome (West Antarctica) ice core on a precise common chronology with the GISP2 (Greenland) ice core for the period from 9 to 57 ka. The onset of major millennial warming events in Siple Dome preceded major abrupt warmings in Greenland, and the pattern of millennial change at Siple Dome was broadly similar, though not identical, to that previously observed for the Byrd ice core (also in West Antarctica). The addition of Siple Dome to the database of well-dated Antarctic paleoclimate records supports the case for a coherent regional pattern of millennial-scale climate change in Antarctica during much of the last ice age and glacial-interglacial transition.

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].

Severinghaus, JP, Sowers T, Brook EJ, Alley RB, Bender ML.  1998.  Timing of abrupt climate change at the end of the Younger Dryas interval from thermally fractionated gases in polar ice. Nature. 391:141-146.   10.1038/34346   AbstractWebsite

Rapid temperature change fractionates gas Isotopes in unconsolidated snow, producing a signal that is preserved in trapped air bubbles as the snow forms ice, The fractionation of nitrogen and argon isotopes at the end of the Younger Dryas cold interval, recorded in Greenland ice, demonstrates that warming at this time was abrupt. This warming coincides with the onset of a prominent rise in atmospheric methane concentration, indicating that the climate change was synchronous (within a few decades) over a region of at least hemispheric extent, and providing constraints on previously proposed mechanisms of climate change at this time, The depth of the nitrogen-isotope signal relative to the depth of the climate change recorded in the Ice matrix indicates that, during the Younger Dryas, the summit of Greenland was 15 +/- 3 degrees C colder than today.

Severinghaus, JP, Keeling RF, Miller BR, Weiss RF, Deck B, Broecker WS.  1997.  Feasibility of using sand dunes as archives of old air. Journal of Geophysical Research-Atmospheres. 102:16783-16792.   10.1029/97jd00525   AbstractWebsite

Large unaltered samples of the atmosphere covering the past century would complement the history of atmospheric gases obtained from bubbles in ice cores, enabling measurement of geochemically important species such as O-2, (CH4)-C-14, and (CO)-C-14. Sand dunes are a porous media with interstitial air in diffusive contact with the atmosphere, somewhat analogous to the unconsolidated layer of firn atop glaciers. Recent studies have demonstrated the value of firn as an archive of old air [Battle et al., 1996; Bender et al., 1994a]. Unlike firn, sand dunes are incompressible and so remain permeable to greater depths and may extend the firn record into the past century. To evaluate the feasibility of using sand dunes as archives of old air, we drilled 60 m deep test holes in the Algodones Dunes, Imperial Valley, California. The main objective was to see if the air in a sand dune is as old as predicted by a diffusion model, or if the dune is rapidly flushed by advective pumping during windstorms and barometric pressure changes. We dated the air with chlorofluorocarbons and krypton-85, anthropogenic tracers whose atmospheric concentrations are known and have been increasing rapidly in the past half century. These tracer data match the pure diffusion model well, showing that advection in this dune is negligible compared to diffusion as a transport mechanism and that the mean age of the air at 61 m depth is similar to 10 years. Dunes therefore do contain old air. However, dunes appear to suffer from two serious drawbacks as archives. Microbial metabolism is evident in elevated CO2 and N2O and depressed CH4 and O-2 concentrations in this dune, corrupting the signals of interest in this and probably most dunes. Second, isotopic analyses of N-2 and O-2 from the dune show that fractionation of the gases occurs due to diffusion of water vapor, complicating the interpretation of the O-2 signal beyond the point of viability for an air archive. Sand dunes may be useful for relatively inert gases with large atmospheric concentration changes such as chlorofluorocarbons.