Methane emissions from floodplains in the Amazon Basin: challenges in developing a process-based model for global applications

Tropical wetlands are estimated to represent about 50% of the natural wetland methane (CH4) emissions and explain a large fraction of the observed CH4 variability on timescales ranging from glacial–interglacial cycles to the currently observed year-to-year variability. Despite their importance, however, tropical wetlands are poorly represented in global models aiming to predict global CH4 emissions. This publication documents a first step in the development of a process-based model of CH4 emissions from tropical floodplains for global applications. For this purpose, the LPX-Bern Dynamic Global Vegetation Model (LPX hereafter) was slightly modified to represent floodplain hydrology, vegetation and associated CH4 emissions. The extent of tropical floodplains was prescribed using output from the spatially explicit hydrology model PCR-GLOBWB. We introduced new plant functional types (PFTs) that explicitly represent floodplain vegetation. The PFT parameterizations were evaluated against available remote-sensing data sets (GLC2000 land cover and MODIS Net Primary Productivity). Simulated CH4 flux densities were evaluated against field observations and regional flux inventories. Simulated CH4 emissions at Amazon Basin scale were compared to model simulations performed in the WETCHIMP intercomparison project. We found that LPX reproduces the average magnitude of observed net CH4 flux densities for the Amazon Basin. However, the model does not reproduce the variability between sites or between years within a site. Unfortunately, site information is too limited to attest or disprove some model features. At the Amazon Basin scale, our results underline the large uncertainty in the magnitude of wetland CH4 emissions. Sensitivity analyses gave insights into the main drivers of floodplain CH4 emission and their associated uncertainties. In particular, uncertainties in floodplain extent (i.e., difference between GLC2000 and PCR-GLOBWB output) modulate the simulated emissions by a factor of about 2. Our best estimates, using PCR-GLOBWB in combination with GLC2000, lead to simulated Amazon-integrated emissions of 44.4 ± 4.8 Tg yr−1. Additionally, the LPX emissions are highly sensitive to vegetation distribution. Two simulations with the same mean PFT cover, but different spatial distributions of grasslands within the basin, modulated emissions by about 20%. Correcting the LPX-simulated NPP using MODIS reduces the Amazon emissions by 11.3%. Finally, due to an intrinsic limitation of LPX to account for seasonality in floodplain extent, the model failed to reproduce the full dynamics in CH4 emissions but we proposed solutions to this issue. The interannual variability (IAV) of the emissions increases by 90% if the IAV in floodplain extent is accounted for, but still remains lower than in most of the WETCHIMP models. While our model includes more mechanisms specific to tropical floodplains, we were unable to reduce the uncertainty in the magnitude of wetland CH4 emissions of the Amazon Basin. Our results helped identify and prioritize directions towards more accurate estimates of tropical CH4 emissions, and they stress the need for more research to constrain floodplain CH4 emissions and their temporal variability, even before including other fundamental mechanisms such as floating macrophytes or lateral water fluxes.

Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

Multiple inert gas elimination technique by micropore membrane inlet mass spectrometry--a comparison with reference gas chromatography.

The mismatching of alveolar ventilation and perfusion (VA/Q) is the major determinant of impaired gas exchange. The gold standard for measuring VA/Q distributions is based on measurements of the elimination and retention of infused inert gases. Conventional multiple inert gas elimination technique (MIGET) uses gas chromatography (GC) to measure the inert gas partial pressures, which requires tonometry of blood samples with a gas that can then be injected into the chromatograph. The method is laborious and requires meticulous care. A new technique based on micropore membrane inlet mass spectrometry (MMIMS) facilitates the handling of blood and gas samples and provides nearly real-time analysis. In this study we compared MIGET by GC and MMIMS in 10 piglets: 1) 3 with healthy lungs; 2) 4 with oleic acid injury; and 3) 3 with isolated left lower lobe ventilation. The different protocols ensured a large range of normal and abnormal VA/Q distributions. Eight inert gases (SF6, krypton, ethane, cyclopropane, desflurane, enflurane, diethyl ether, and acetone) were infused; six of these gases were measured with MMIMS, and six were measured with GC. We found close agreement of retention and excretion of the gases and the constructed VA/Q distributions between GC and MMIMS, and predicted PaO2 from both methods compared well with measured PaO2. VA/Q by GC produced more widely dispersed modes than MMIMS, explained in part by differences in the algorithms used to calculate VA/Q distributions. In conclusion, MMIMS enables faster measurement of VA/Q, is less demanding than GC, and produces comparable results.

Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

Stable carbon isotope analysis of methane (delta C-13 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 delta C-13 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 Kr-86 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 delta C-13. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

Mobilities, Entanglements and Transformations in Neolithic societies on the Swiss Plateau (3900-3500 BC)

The material culture of Neolithic settlements – especially pottery – was often taken as key argument to distinguish „Neolithic cultures“ like Cortaillod, Pfyn, Michelsberg, Munzingen, NMB, Altheim. „Foreign influences“ in these pottery styles point to complex entanglements between social groups and highly mobile people, bluring the supposed cultural boundaries. The two PhD-projects aim at a critical revision of former notions of „culture“ by focussion on similarities and differences in pottery practecies of dedrodated key sites on the Swiss Plateau (3900 -3500 BC).

Observation of an Excited B±c Meson State with the ATLAS Detector

A search for excited states of the B ± c meson is performed using 4.9  fb −1 of 7 TeV and 19.2  fb −1 of 8 TeV pp collision data collected by the ATLAS experiment at the LHC. A new state is observed through its hadronic transition to the ground state, with the latter detected in the decay B ± c →J/ψπ ± . The state appears in the m(B ± c π + π − )−m(B ± c )−2m(π ± ) mass difference distribution with a significance of 5.2 standard deviations. The mass of the observed state is 6842±4±5  MeV , where the first error is statistical and the second is systematic. The mass and decay of this state are consistent with expectations for the second S -wave state of the B ± c meson, B ± c (2S) .

The stable carbon isotopic composition of Daphnia ephippia in small, temperate lakes reflects in-lake methane availability

Daphnia can ingest methane-oxidizing bacteria and incorporate methanogenic carbon into their biomass, leading to low stable carbon isotope ratios (expressed as δ13C values) of their tissue. Therefore, δ13C analysis of Daphnia resting eggs (ephippia) in lake sediment records can potentially be used to reconstruct past in-lake availability of methane (CH4). However, detailed multilake studies demonstrating that δ13C values of recently deposited Daphnia ephippia (δ13Cephippia) are systematically related to in-lake CH4 concentrations (CH4aq) are still missing. We measured δ13Cephippia from surface sediments of 15 small lakes in Europe, and compared these values with late-summer CH4aq. δ13Cephippia ranged from −51.6‰ to −25.9‰, and was strongly correlated with CH4aq in the surface water and above the sediment (r −0.73 and −0.77, respectively), whereas a negative rather than the expected positive correlation was found with δ13C values of carbon dioxide (CO2) (r −0.54), and no correlation was observed with CO2aq. At eight sites, offsets between δ13 CCO2 and δ13Cephippia exceeded offsets between δ13 CCO2 and δ13Calgae reported in literature. δ13Cephippia was positively correlated with δ13C values of sedimentary organic matter (r 0.54), but up to 20.7‰ lower in all except one of the lakes (average −6.1‰). We conclude that incorporation of methanogenic carbon prior to ephippia formation must have been widespread by Daphnia in our study lakes, especially those with high CH4aq. Our results suggest a systematic relationship between δ13Cephippia values and CH4aq in small temperate lakes, and that δ13Cephippia analysis on sediment records may provide insights into past changes in in-lake CH4aq.

An inter-regional assessment of concentrations and δ13C values of methane and dissolved inorganic carbon in small European lakes

Methane (CH4) and carbon dioxide emissions from lakes are relevant for assessing the greenhouse gas output of wetlands. However, only few standardized datasets describe concentrations of these gases in lakes across different geographical regions. We studied concentrations and stable carbon isotopic composition (δ13C) of CH4 and dissolved inorganic carbon (DIC) in 32 small lakes from Finland, Sweden, Germany, the Netherlands, and Switzerland in late summer. Higher concentrations and δ13C values of DIC were observed in calcareous lakes than in lakes on non-calcareous areas. In stratified lakes, δ13C values of DIC were generally lower in the hypolimnion due to the degradation of organic matter (OM). Unexpectedly, increased δ13C values of DIC were registered above the sediment in several lakes. This may reflect carbonate dissolution in calcareous lakes or methanogenesis in deepwater layers or in the sediments. Surface water CH4 concentrations were generally higher in western and central European lakes than in Fennoscandian lakes, possibly due to higher CH4 production in the littoral sediments and lateral transport, whereas CH4 concentrations in the hypolimnion did not differ significantly between the regions. The δ13C values of CH4 in the sediment suggest that δ13C values of biogenic CH4 are not necessarily linked to δ13C values of sedimentary OM but may be strongly influenced by OM quality and methanogenic pathway. Our study suggests that CH4 and DIC cycling in small lakes differ between geographical regions and that this should be taken into account when regional studies on greenhouse gas emissions are upscaled to inter-regional scales.

Material culture entanglements of early wetland sites in central Switzerland (4300-3850 BC)

In central Switzerland, the earliest wetland settlements with definitely attested finds and features date into the second half of the 5th millennium BC. Combining the information they have yielded with that from dryland sites, we can construct a detailed picture of material culture at the turn of the 5th to the 4th millennium. On this basis, the definition of clearly delimited archaeological cultures seems questionable, not only from a theoretical point of view. Similiarities and differences in the pottery show small-scale regional units defined via vessel forms as well as stylistic and technological aspects. Yet there are also inter-regional connections: roundbased vessels with opposing handles are typical for Lake Zurich, central and western Switzerland, the Valais and the central Rhône valley. In turn, ‘foreign‘ types such as shoulder-band beakers indicate regular connections between groups living in central Switzerland and those in Alsace and southern Germany. Are these beakers ‘imports‘ or locally produced items (‘imitations‘) indicating the adoption of ‘foreign‘ vessel types and concepts? This and similar material culture phenomena result in a picture of many material entanglements and problematise the kinds of relationships and mobility which might have existed. Our paper addresses these questions and discusses how and whether these interwoven connections changed in the early 4th millennium.