No abstract

Atmospheric methane (CH 4 ) records reconstructed from polar ice cores represent an integrated view on processes predominantly taking place in the terrestrial biogeosphere. Here, we present dual stable isotopic methane records [δ 13 CH 4 and δD(CH 4 )] from four Antarctic ice cores, which provide improved constraints on past changes in natural methane sources. Our isotope data show that tropical wetlands and seasonally inundated floodplains are most likely the controlling sources of atmospheric methane variations for the current and two older interglacials and their preceding glacial maxima. The changes in these sources are steered by variations in temperature, precipitation, and the water table as modulated by insolation, (local) sea level, and monsoon intensity. Based on our δD(CH 4 ) constraint, it seems that geologic emissions of methane may play a steady but only minor role in atmospheric CH 4 changes and that the glacial budget is not dominated by these sources. Superimposed on the glacial/interglacial variations is a marked difference in both isotope records, with systematically higher values during the last 25,000 y compared with older time periods. This shift cannot be explained by climatic changes. Rather, our isotopic methane budget points to a marked increase in fire activity, possibly caused by biome changes and accumulation of fuel related to the late Pleistocene megafauna extinction, which took place in the course of the last glacial.atmosphere | methane | megafauna | ice core | stable isotopes

Abstract. The temperature sensitivity of soil organic carbon decomposition is critical for predicting future climate change because soils store 2-3 times the amount of atmospheric carbon. Of particular controversy is the question, whether temperature sensitivity differs between young or labile and old or more stable carbon pools. Ambiguities in experimental methodology have so far limited corroboration of any particular hypothesis. Here, we show in a clear-cut approach that differences in temperature sensitivity between young and old carbon are negligible. Using the change in stable isotope composition in transitional systems from C3 to C4 vegetation, we were able to directly distinguish the temperature sensitivity of carbon differing several decades in age. This method had several advantages over previously followed approaches. It allowed to identify release of much older carbon, avoided un-natural conditions of long-term incubations and did not require arguable curve-fitting. Our results demonstrate that feedbacks of the carbon cycle on climate change are driven equally by young and old soil organic carbon.

Abstract. Methane and nitrous oxide are important greenhouse gases which show a strong increase in atmospheric mixing ratios since pre-industrial time as well as large variations during past climate changes. The understanding of their biogeochemical cycles can be improved using stable isotope analysis. However, high-precision isotope measurements on air trapped in ice cores are challenging because of the high susceptibility to contamination and fractionation.Here, we present a dry extraction system for combined CH 4 and N 2 O stable isotope analysis from ice core air, using an ice grating device. The system allows simultaneous analysis of δD(CH 4 ) or δ 13 C(CH 4 ), together with δ 15 N(N 2 O), δ 18 O(N 2 O) and δ 15 N(NO + fragment) on a single ice core sample, using two isotope mass spectrometry systems. The optimum quantity of ice for analysis is about 600 g with typical "Holocene" mixing ratios for CH 4 and N 2 O. In this case, the reproducibility (1σ ) is 2.1 ‰ for δD(CH 4 ), 0.18 ‰ for δ 13 C(CH 4 ), 0.51 ‰ for δ 15 N(N 2 O), 0.69 ‰ for δ 18 O(N 2 O) and 1.12 ‰ for δ 15 N(NO + fragment). For smaller amounts of ice the standard deviation increases, particularly for N 2 O isotopologues. For both gases, small-scale intercalibrations using air and/or ice samples have been carried out in collaboration with other institutes that are currently involved in isotope measurements of ice core air. Significant differences are shown between the calibration scales, but those offsets are consistent and can therefore be corrected for.

Abstract. Using high-precision and centennial-resolution ice core information on atmospheric nitrous oxide concentrations and its stable nitrogen and oxygen isotopic composition, we quantitatively reconstruct changes in the terrestrial and marine N2O emissions over the last 21 000 years. Our reconstruction indicates that N2O emissions from land and ocean increased over the deglaciation largely in parallel by 1.7±0.3 and 0.7±0.3 TgN yr−1, respectively, relative to the Last Glacial Maximum level. However, during the abrupt Northern Hemisphere warmings at the onset of the Bølling–Allerød warming and the end of the Younger Dryas, terrestrial emissions respond more rapidly to the northward shift in the Intertropical Convergence Zone connected to the resumption of the Atlantic Meridional Overturning Circulation. About 90 % of these large step increases were realized within 2 centuries at maximum. In contrast, marine emissions start to slowly increase already many centuries before the rapid warmings, possibly connected to a re-equilibration of subsurface oxygen in response to previous changes. Marine emissions decreased, concomitantly with changes in atmospheric CO2 and δ13C(CO2), at the onset of the termination and remained minimal during the early phase of Heinrich Stadial 1. During the early Holocene a slow decline in marine N2O emission of 0.4 TgN yr−1 is reconstructed, which suggests an improvement of subsurface water ventilation in line with slowly increasing Atlantic overturning circulation. In the second half of the Holocene total emissions remain on a relatively constant level, but with significant millennial variability. The latter is still difficult to attribute to marine or terrestrial sources. Our N2O emission records provide important quantitative benchmarks for ocean and terrestrial nitrogen cycle models to study the influence of climate on nitrogen turnover on timescales from several decades to glacial–interglacial changes.

Stable carbon isotope analysis of methane (δ¹³C of CH₄) on atmospheric samples is one key method to constrain the current and past atmospheric CH₄ budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in δ¹³C of CH₄, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged ⁸⁶Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH₄ mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in δ¹³C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias

Permafrost and methane hydrates are large, climate-sensitive old carbon reservoirs that have the potential to emit large quantities of methane, a potent greenhouse gas, as the Earth continues to warm. We present ice core isotopic measurements of methane (Δ14C, δ13C, and δD) from the last deglaciation, which is a partial analog for modern warming. Our results show that methane emissions from old carbon reservoirs in response to deglacial warming were small (<19 teragrams of methane per year, 95% confidence interval) and argue against similar methane emissions in response to future warming. Our results also indicate that methane emissions from biomass burning in the pre-Industrial Holocene were 22 to 56 teragrams of methane per year (95% confidence interval), which is comparable to today.

Abstract. Life on earth drives a continuous exchange of carbon between soils and the atmosphere. Some forms of soil carbon, or organic matter, are more stable and have a longer residence time in soil than others. Relative differences in stability have often been derived from shifts in δ 13 C (which is bound to a vegetation change from C3 to C4 type) or through 14 C-dating (which is bound to small sample numbers because of high measurement costs). Here, we propose a new concept based on the increase in δ 15 N and the decrease in C:N ratio with increasing stability. We tested the concept on grasslands at different elevations in the Swiss Alps. Depending on elevation and soil depth, it predicted mineral-associated organic carbon to be 3 to 73 times more stable than particulate organic carbon. Analysis of 14 C-ages generally endorsed these predictions.