Where does the methane entrapped in Antarctic sea ice come from?

info:eu-repo/semantics/publishe

Changes in the Isotopic Signature of Atmospheric Nitrous Oxide and Its Global Average Source During the Last Three Millennia

Nitrous oxide (N2O) is a strong greenhouse gas whose mole fraction in the atmosphere has increased over the industrial period. We present a new set of isotope measurements of N2O in air extracted from ice cores covering the last 3,000 years. For the preindustrial (PI) atmosphere, we find an average N2O mole fraction of (267 ± 1) nmol/mol and average tropospheric N2O isotopic values of δ15Nav PI = (9.5 ± 0.1)‰, δ18OPI = (47.1 ± 0.2)‰, δ15Nα PI = (17.8 ± 0.4)‰, and δ15Νβ PI = (1.2 ± 0.4)‰. From PI to modern times all isotope signatures decreased with a total change of δ15Nav = (−2.7 ± 0.2)‰, δ18O = (−2.5 ± 0.4)‰, δ15Nα = (−2.0 ± 0.7)‰, and δ15Νβ (−3.5 ± 0.7)‰. Interestingly, the temporal evolution is not the same for δ15Nav and δ18O. δ18O trends are relatively larger during the early part, and δ15Nav trends are larger during the late part of the industrial period, implying a decoupling of sources over the industrial period. Using a mass balance model, we determined the isotopic composition of the total average N2O source. Assuming that the total present source is the sum of a constant natural source and an increasing anthropogenic source, this anthropogenic source has an isotopic signature of δ15Nav source,anthrop = (−15.0 ± 2.6)‰, δ18Osource,anthrop = (30.0 ± 2.6)‰, δ15Nα source,anthrop = (−4.5 ± 1.7)‰, and δ15Nβ source,anthrop = (−24.0 ± 8.4)‰. The 15N site preference of the source has increased since PI times, which is indicative of a relative shift from denitrification to nitrification sources, consistent with agricultural emissions playing a major role in the N2O increase.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1)nmolmol-1 in 1940 to (322±1)nmolmol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2±0.2)% for δ15Nav, (-1.0±0.3)% for δ18O, (-1.3±0.6)% for δ15Nα, and (-2.8±0.6)% for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav Combining double low line (-7.6±0.8)% (vs. air-N2), δ18O Combining double low line (32.2±0.2)% (vs. Vienna Standard Mean Ocean Water-VSMOW) for δ18O, δ15Nα Combining double low line (-3.0±1.9)% and δ15Nβ Combining double low line (-11.7±2.3)%. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference (Combining double low line δ15Nα-δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large

Understanding the glacial methane cycle.

Atmospheric methane (CH4) varied with climate during the Quaternary, rising from a concentration of 375 p.p.b.v. during the last glacial maximum (LGM) 21,000 years ago, to 680 p.p.b.v. at the beginning of the industrial revolution. However, the causes of this increase remain unclear; proposed hypotheses rely on fluctuations in either the magnitude of CH4 sources or CH4 atmospheric lifetime, or both. Here we use an Earth System model to provide a comprehensive assessment of these competing hypotheses, including estimates of uncertainty. We show that in this model, the global LGM CH4 source was reduced by 28-46%, and the lifetime increased by 2-8%, with a best-estimate LGM CH4 concentration of 463-480 p.p.b.v. Simulating the observed LGM concentration requires a 46-49% reduction in sources, indicating that we cannot reconcile the observed amplitude. This highlights the need for better understanding of the effects of low CO2 and cooler climate on wetlands and other natural CH4 sources

The origin of methane in the East Siberian Arctic Shelf unraveled with triple isotope analysis

The Arctic Ocean, especially the East Siberian Arctic Shelf (ESAS), has been proposed as a significant source of methane that might play an increasingly important role in the future. However, the underlying processes of formation, removal and transport associated with such emissions are to date strongly debated. CH4 concentration and triple isotope composition were analyzed on gas extracted from sediment and water sampled at numerous locations on the shallow ESAS from 2007 to 2013. We find high concentrations (up to 500 µM) of CH4 in the pore water of the partially thawed subsea permafrost of this region. For all sediment cores, both hydrogen and carbon isotope data reveal the predominant occurrence of CH4 that is not of thermogenic origin as it has long been thought, but resultant from microbial CH4 formation. At some locations, meltwater from buried meteoric ice and/or old organic matter preserved in the subsea permafrost were used as substrates. Radiocarbon data demonstrate that the CH4 present in the ESAS sediment is of Pleistocene age or older, but a small contribution of highly 14C-enriched CH4, from unknown origin, prohibits precise age determination for one sediment core and in the water column. Our sediment data suggest that at locations where bubble plumes have been observed, CH4 can escape anaerobic oxidation in the surface sediment

Simultaneous stable isotope analysis of methane and nitrous oxide on ice core samples

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 CH4 and N2O stable isotope analysis from ice core air, using an ice grating device. The system allows simultaneous analysis of δD(CH4) or δ13C(CH4), together with δ15N(N2O), δ18O(N2O) and δ15N(NO+fragment) on a single ice core sample, using two isotope mass spectrometry systems. The optimum quantity of ice for analysis is about 600g with typical "Holocene" mixing ratios for CH4 and N2O. In this case, the reproducibility (1σ) is 2.1 ‰ for δD(CH4), 0.18 ‰ for δ13C(CH4), 0.51 ‰ for δ15N(N2O), 0.69 ‰ for δ18O(N2O) and 1.12 ‰ for δ15N(NO+fragment). For smaller amounts of ice the standard deviation increases, particularly for N2O isotopologues. For both gases, small-scale intercalibrations using air and/or ice samples have been carried out 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 be corrected for