Hinrich Schaefer

14CH4 measurements in Greenland ice: investigating last glacial termination CH4 sources.

Radiocarbon measurements show that wetlands were responsible for the rapid increase of atmospheric methane concentration during the last deglaciation. Methane from Wetlands At the end of the cold climate interval called the Younger Dryas, approximately 11,600 years ago, global temperatures began their final ascent to the warmth of the Holocene, and the concentration of methane in the atmosphere increased rapidly and substantially. There has been much speculation about the cause of that increase, with most recent evidence pointing to wetlands as the source. The most direct proof of that explanation requires the measurement of the radiocarbon content of that methane. Petrenko et al. (p. 506; see the Perspective by Nisbet and Chappellaz) analyzed 1000 kilogramsized samples of Greenland ice, which have sufficient methane to allow measurement of its 14C content. They show that wetland sources indeed must have been responsible for the majority of the rise in atmospheric methane levels at the end of the Younger Dryas. The cause of a large increase of atmospheric methane concentration during the Younger Dryas–Preboreal abrupt climatic transition (~11,600 years ago) has been the subject of much debate. The carbon-14 (14C) content of methane (14CH4) should distinguish between wetland and clathrate contributions to this increase. We present measurements of 14CH4 in glacial ice, targeting this transition, performed by using ice samples obtained from an ablation site in west Greenland. Measured 14CH4 values were higher than predicted under any scenario. Sample 14CH4 appears to be elevated by direct cosmogenic 14C production in ice. 14C of CO was measured to better understand this process and correct the sample 14CH4. Corrected results suggest that wetland sources were likely responsible for the majority of the Younger Dryas–Preboreal CH4 rise.

Ice Record of δ13C for Atmospheric CH4 Across the Younger Dryas-Preboreal Transition

We report atmospheric methane carbon isotope ratios (δ13CH4) from the Western Greenland ice margin spanning the Younger Dryas–to–Preboreal (YD-PB) transition. Over the recorded ∼800 years, δ13CH4 was around –46 per mil (‰); that is, ∼1‰ higher than in the modern atmosphere and ∼5.5‰ higher than would be expected from budgets without 13C-rich anthropogenic emissions. This requires higher natural 13C-rich emissions or stronger sink fractionation than conventionally assumed. Constant δ13CH4 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.

Carbon isotopes characterize rapid changes in atmospheric carbon dioxide during the last deglaciation

Significance Antarctic ice cores provide a precise, well-dated history of increasing atmospheric CO2 during the last glacial to interglacial transition. However, the mechanisms that drive the increase remain unclear. Here we reconstruct a key indicator of the sources of atmospheric CO2 by measuring the stable isotopic composition of CO2 in samples spanning the period from 22,000 to 11,000 years ago from Taylor Glacier, Antarctica. Improvements in precision and resolution allow us to fingerprint CO2 sources on the centennial scale. The data reveal two intervals of rapid CO2 rise that are plausibly driven by sources from land carbon (at 16.3 and 12.9 ka) and two others that appear fundamentally different and likely reflect a combination of sources (at 14.6 and 11.5 ka). An understanding of the mechanisms that control CO2 change during glacial–interglacial cycles remains elusive. Here we help to constrain changing sources with a high-precision, high-resolution deglacial record of the stable isotopic composition of carbon in CO2 (δ13C-CO2) in air extracted from ice samples from Taylor Glacier, Antarctica. During the initial rise in atmospheric CO2 from 17.6 to 15.5 ka, these data demarcate a decrease in δ13C-CO2, likely due to a weakened oceanic biological pump. From 15.5 to 11.5 ka, the continued atmospheric CO2 rise of 40 ppm is associated with small changes in δ13C-CO2, consistent with a nearly equal contribution from a further weakening of the biological pump and rising ocean temperature. These two trends, related to marine sources, are punctuated at 16.3 and 12.9 ka with abrupt, century-scale perturbations in δ13C-CO2 that suggest rapid oxidation of organic land carbon or enhanced air–sea gas exchange in the Southern Ocean. Additional century-scale increases in atmospheric CO2 coincident with increases in atmospheric CH4 and Northern Hemisphere temperature at the onset of the Bølling (14.6–14.3 ka) and Holocene (11.6–11.4 ka) intervals are associated with small changes in δ13C-CO2, suggesting a combination of sources that included rising surface ocean temperature.

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 14 C of methane ( 14 CH4) and other trace constituents. Paleoatmospheric 14 CH4 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-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 d 15 No f N 2, d 18 Oo f O 2, d 18 Oice and (CH4) measurements. The (CH4) blank of the melt extractions was <4 ppb. Measurements of d 18 O and d 15 N 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.

Minimal geological methane emissions during the Younger Dryas–Preboreal abrupt warming event

Methane (CH4) is a powerful greenhouse gas and plays a key part in global atmospheric chemistry. Natural geological emissions (fossil methane vented naturally from marine and terrestrial seeps and mud volcanoes) are thought to contribute around 52 teragrams of methane per year to the global methane source, about 10 per cent of the total, but both bottom-up methods (measuring emissions) and top-down approaches (measuring atmospheric mole fractions and isotopes) for constraining these geological emissions have been associated with large uncertainties. Here we use ice core measurements to quantify the absolute amount of radiocarbon-containing methane (14CH4) in the past atmosphere and show that geological methane emissions were no higher than 15.4 teragrams per year (95 per cent confidence), averaged over the abrupt warming event that occurred between the Younger Dryas and Preboreal intervals, approximately 11,600 years ago. Assuming that past geological methane emissions were no lower than today, our results indicate that current estimates of today’s natural geological methane emissions (about 52 teragrams per year) are too high and, by extension, that current estimates of anthropogenic fossil methane emissions are too low. Our results also improve on and confirm earlier findings that the rapid increase of about 50 per cent in mole fraction of atmospheric methane at the Younger Dryas–Preboreal event was driven by contemporaneous methane from sources such as wetlands; our findings constrain the contribution from old carbon reservoirs (marine methane hydrates, permafrost and methane trapped under ice) to 19 per cent or less (95 per cent confidence). To the extent that the characteristics of the most recent deglaciation and the Younger Dryas–Preboreal warming are comparable to those of the current anthropogenic warming, our measurements suggest that large future atmospheric releases of methane from old carbon sources are unlikely to occur.

Carbon isotope ratios suggest no additional methane from boreal wetlands during the rapid Greenland Interstadial 21.2

Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (δ13C-CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (∼25%). Our new measurements disclose a concomitant shift in δ13C-CH4 of 1‰. Keeling plot analyses reveal the δ13C of the additional CH4 source constituting the CH4 anomaly as -56.8 ± 2.8‰, which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI-21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI-21.2.

Methane from the East Siberian Arctic Shelf

In their Report “Extensive methane venting to the atmosphere from sediments of the East Siberian Arctic Shelf” (5 March, p. [1246][1]), N. Shakhova et al. write that methane (CH4) release resulting from thawing Arctic permafrost “is a likely positive feedback to climate warming.” They add

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 Pakitsoq ice margin in West Greenland, we use a combination of geochemical parameters measured in the ice matrix (d 18 Oice) and air occlusions (d 18 Oatm, d 15 No f 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.