T. Röckmann

Methane emissions from terrestrial plants under aerobic conditions

Methane is an important greenhouse gas and its atmospheric concentration has almost tripled since pre-industrial times. It plays a central role in atmospheric oxidation chemistry and affects stratospheric ozone and water vapour levels. Most of the methane from natural sources in Earths atmosphere is thought to originate from biological processes in anoxic environments. Here we demonstrate using stable carbon isotopes that methane is readily formed in situ in terrestrial plants under oxic conditions by a hitherto unrecognized process. Significant methane emissions from both intact plants and detached leaves were observed during incubation experiments in the laboratory and in the field. If our measurements are typical for short-lived biomass and scaled on a global basis, we estimate a methane source strength of 62–236 Tg yr-1 for living plants and 1–7 Tg yr-1 for plant litter (1 Tg = 1012 g). We suggest that this newly identified source may have important implications for the global methane budget and may call for a reconsideration of the role of natural methane sources in past climate change.

Dynamic Processes Governing Lower-Tropospheric HDO/H2O Ratios as Observed from Space and Ground

Cycling Around Water vapor is the most important greenhouse gas, and clouds are one of the most important components of climate, but the global hydrological cycle is still poorly-enough understood that the atmospheric cycling of water and cloud formation are inadequately represented in global climate models. As the transformation from liquid into vapor tends to deplete water of the isotope deuterium, Frankenburg et al. (p. 1374) were able to use satellite measurements of global “heavy” water abundances to provide a deeper understanding of atmospheric water dynamics. Tropospheric distributions of light and heavy water reveal previously unrecognized features of atmospheric circulation. The hydrological cycle and its response to environmental variability such as temperature changes is of prime importance for climate reconstruction and prediction. We retrieved deuterated water/water (HDO/H2O) abundances using spaceborne absorption spectroscopy, providing an almost global perspective on the near-surface distribution of water vapor isotopologs. We observed an unexpectedly high HDO/H2O seasonality in the inner Sahel region, pointing to a strong isotopic depletion in the subsiding branch of the Hadley circulation and its misrepresentation in general circulation models. An extension of the analysis at high latitudes using ground-based observations of δD¯ and a model study shows that dynamic processes can entirely compensate for temperature effects on the isotopic composition of precipitation.

Methoxyl groups of plant pectin as a precursor of atmospheric methane: evidence from deuterium labelling studies

* The observation that plants produce methane (CH4) under aerobic conditions has caused considerable controversy among the scientific community and the general public. It led to much discussion and debate not only about its contribution to the global CH4 budget but also about the authenticity of the observation itself. Previous results suggested that methoxyl groups of the abundant plant structural component pectin might play a key role in the in situ formation process of CH4. Here, this effect is investigated using an isotope labelling study. * Polysaccharides, pectin and polygalacturonic acid, with varying degrees of trideuterium-labelled methyl groups in the methoxyl moieties, were investigated for CH4 formation under UV irradiation and heating. * A strong deuterium signal in the emitted CH4 was observed from these labelled polysaccharides. * Results clearly demonstrate that ester methyl groups of pectin can serve as a precursor of CH4, supporting the idea of a novel chemical route of CH4 formation in plants under oxic environmental conditions.

Mass Spectrometry of the Intramolecular Nitrogen Isotope Distribution of Environmental Nitrous Oxide Using Fragment-ion Analysis

Mass spectrometry is applied to measure the intramolecular distribution of (15)N in N(2)O samples of near natural isotopic composition. The method is relatively straightforward and based on the analysis of the (14)NO and (15)NO fragment ion beams at mass 30 and 31, respectively, in combination with the standard analysis of the masses 44, 45, and 46 of the non-fragmented N(2)O. Various complications in the application, not all of which are resolved at present, are discussed. Copyright 1999 John Wiley & Sons, Ltd.

Atmospheric constraints on global emissions of methane from plants

We investigate whether a recently proposed large source of CH_4 from vegetation can be reconciled with atmospheric measurements. Atmospheric transport model simulations with and without vegetation emissions are compared with background CH_4, δ^(13)C-CH_4 and satellite measurements. For present–day CH_4 we derive an upper limit to the newly discovered source of 125 Tg CH_4 yr^(−1). Analysis of preindustrial CH_4, however, points to 85 Tg CH_4 yr^(−1) as a more plausible limit. Model calculations with and without vegetation emissions show strikingly similar results at background surface monitoring sites, indicating that these measurements are rather insensitive to CH_4 from plants. Simulations with 125 Tg CH_4 yr^(−1) vegetation emissions can explain up to 50% of the previously reported unexpectedly high CH_4 column abundances over tropical forests observed by SCIAMACHY. Our results confirm the potential importance of vegetation emissions, and call for further research.

Four-dimensional variational data assimilation for inverse modeling of atmospheric methane emissions: Analysis of SCIAMACHY observations

Recent observations from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instrument aboard ENVISAT have brought new insights in the global distribution of atmospheric methane. In particular, the observations showed higher methane concentrations in the tropics than previously assumed. Here, we analyze the SCIAMACHY observations and their implications for emission estimates in detail using a four-dimensional variational (4D-Var) data assimilation system. We focus on the period September to November 2003 and on the South American continent, for which the satellite observations showed the largest deviations from model simulations. In this set-up the advantages of the 4D-Var approach and the zooming capability of the underlying TM5 atmospheric transport model are fully exploited. After application of a latitude-dependent bias correction to the SCIAMACHY observations, the assimilation system is able to accurately fit those observations, while retaining consistency with a network of surface methane measurements. The main emission increments resulting from the inversion are an increase in the tropics, a decrease in South Asia, and a decrease at northern hemispheric high latitudes. The SCIAMACHY observations yield considerable additional emission uncertainty reduction, particularly in the (sub-)tropical regions, which are poorly constrained by the surface network. For tropical South America, the inversion suggests more than a doubling of emissions compared to the a priori during the 3 months considered. Extensive sensitivity experiments, in which key assumptions of the inversion set-up are varied, show that this finding is robust. Independent airborne observations in the Amazon basin support the presence of considerable local methane sources. However, these observations also indicate that emissions from eastern South America may be smaller than estimated from SCIAMACHY observations. In this respect it must be realized that the bias correction applied to the satellite observations does not take into account potential regional systematic errors, which - if identified in the future - will lead to shifts in the overall distribution of emission estimates.

Isotope analysis based source identification for atmospheric CH4 and CO sampled across Russia using the Trans‐Siberian railroad

The isotopic composition of carbon monoxide (13C, 14C, 18O) and methane (13C, D) was measured on air samples collected between Vladivostok and Moscow using the Trans-Siberian railroad during August 1996. Apart from short term fluctuations in the direct vicinity of sources, continuous measurements of CO and CH4 showed sustained, elevated mixing ratios over several hundreds of kilometers indicating the large scale influencing of traversed air masses by significant sources. Persistent, enhanced CH4 levels were found over the west Siberian lowlands concurrent with significantly depleted δ13C and δD values. The derived isotopic signature of the CH4 source (δ13C = −62.5±4.7‰ V-PDB; δD = −311±14‰ V-SMOW) clearly indicates the dominance of biogenic CH4, with the west Siberian wetlands being the most likely candidate. A second major feature in the data set is the enormous enhancement of CO (up to 1500 nmol/mol) east of Chita, extending over a 2000 km section along the river Amur. The 14CO measurements and back trajectory analyses identify biomass burning as the origin of the highly elevated CO. This is further supported by the δ18O(CO) and the δ13C/δD signature of the accompanying moderate CH4 enhancement.

Natural and anthropogenic variations in methane sources during the past two millennia

Methane is an important greenhouse gas that is emitted from multiple natural and anthropogenic sources. Atmospheric methane concentrations have varied on a number of timescales in the past, but what has caused these variations is not always well understood. The different sources and sinks of methane have specific isotopic signatures, and the isotopic composition of methane can therefore help to identify the environmental drivers of variations in atmospheric methane concentrations. Here we present high-resolution carbon isotope data (δ13C content) for methane from two ice cores from Greenland for the past two millennia. We find that the δ13C content underwent pronounced centennial-scale variations between 100 bc and ad 1600. With the help of two-box model calculations, we show that the centennial-scale variations in isotope ratios can be attributed to changes in pyrogenic and biogenic sources. We find correlations between these source changes and both natural climate variability—such as the Medieval Climate Anomaly and the Little Ice Age—and changes in human population and land use, such as the decline of the Roman empire and the Han dynasty, and the population expansion during the medieval period.

Methane formation in aerobic environments

Methane (CH_4), the second principal anthropogenic greenhouse gas after CO_2, is the most abundant reduced organic compound in the atmosphere and plays a central role in atmospheric chemistry. Therefore a comprehensive understanding of its sources and sinks and the parameters that control emissions is prerequisite to simulate past, present and future atmospheric conditions. Until recently biological CH_4 formation has been associated exclusively with anoxic environments and methanogenic activity. However, there is growing and convincing evidence of alternative pathways in the aerobic biosphere including terrestrial plants, soils, marine algae and animals. Identifying and describing these sources is essential to complete our understanding of the biogeochemical cycles that control CH_4 in the atmospheric environment and its influence as a greenhouse gas.

Isotopic enrichment of nitrous oxide (15N14NO, 14N15NO, 14N14N18O) in the stratosphere and in the laboratory

Nitrous oxide (N2O) extracted from stratospheric whole air samples has been analyzed for its 15N and 18O isotopic composition, and strong enrichments in the heavy isotopes are observed concomitant with decreasing N2O mixing ratio. Notably, the N enrichment is strongly different at the two nonequivalent positions in the molecule. Laboratory broadband photolysis experiments at wavelengths representative for the stratosphere confirm that photolysis is the prime cause for the observed fractionation in the stratosphere. However, the in situ stratospheric fractionation constants are significantly reduced compared to the laboratory data, reflecting the importance of dynamic processes. In addition, small but significant variations in the ratio of the two 15N fractionation constants indicate the influence of additional chemical processes like the oxidation of N2O by O(1 D).