Stable isotopic signatures of methane from waste sources through atmospheric measurements

This study aimed to characterize the carbon isotopic signatures (δ13C-CH4) of several methane waste sources, predominantly in the UK, and during field campaigns in the Netherlands and Turkey. CH4 plumes emitted from waste sources were detected during mobile surveys using a cavity ring-down spectroscopy (CRDS) analyser. Air samples were collected in the plumes for subsequent isotope analysis by gas chromatography isotope ratio mass spectrometry (GC-IRMS) to characterize δ13C-CH4. The isotopic signatures were determined through a Keeling plot approach and the bivariate correlated errors and intrinsic scatter (BCES) fitting method. The δ13C-CH4 and δ2H-CH4 signatures were identified from biogas plants (−54.6 ± 5.6‰, n = 34; −314.4 ± 23‰ n = 3), landfills (−56.8 ± 2.3‰, n = 43; −268.2 ± 2.1‰, n = 2), sewage treatment plants (−51.6 ± 2.2‰, n = 15; −303.9 ± 22‰, n = 6), composting facilities (−54.7 ± 3.9‰, n = 6), a landfill leachate treatment plant (−57.1 ± 1.8‰, n = 2), one water treatment plant (−53.7 ± 0.1‰) and a waste recycling facility (−53.2 ± 0.2‰). The overall signature of 71 waste sources ranged from −64.4 to −44.3‰, with an average of −55.1 ± 4.1‰ (n = 102) for δ13C, −341 to −267‰, with an average of −300.3 ± 25‰ (n = 11) for δ2H, which can be distinguished from other source types in the UK such as gas leaks and ruminants. The study also demonstrates that δ2H-CH4 signatures, in addition to δ13C-CH4, can aid in better waste source apportionment and increase the granularity of isotope data required to improve regional modelling

Carbon isotopic signature of coal-derived methane emissions to the atmosphere: from coalification to alteration

Currently, the atmospheric methane burden is rising rapidly, but the extent to which shifts in coal production contribute to this rise is not known. Coalbed methane emissions into the atmosphere are poorly characterised, and this study provides representative δ13CCH4 signatures of methane emissions from specific coalfields. Integrated methane emissions from both underground and opencast coal mines in the UK, Australia and Poland were sampled and isotopically characterised. Progression in coal rank and secondary biogenic production of methane due to incursion of water are suggested as the processes affecting the isotopic composition of coal-derived methane. An averaged value of −65 ‰ has been assigned to bituminous coal exploited in open cast mines and of −55 ‰ in deep mines, whereas values of −40 and −30 ‰ can be allocated to anthracite opencast and deep mines respectively. However, the isotopic signatures that are included in global atmospheric modelling of coal emissions should be region- or nation-specific, as greater detail is needed, given the wide global variation in coal type

Diurnal, seasonal, and annual trends in tropospheric CO in Southwest London during 2000–2015: Wind sector analysis and comparisons with urban and remote sites

Ambient carbon monoxide (CO) and meteorological parameters measured at the Egham (EGH) semi-rural site in SW London during 2000–2015 have permitted wind sector analysis of diurnal and seasonal cycles, and interpretation of long-term trends. CO daily amplitudes are used as a proxy for anthropogenic emissions. At EGH, morning and evening peaks in CO arise from the dominant contribution of road transport sources. Smaller amplitudes are observed during weekends than weekdays due to lower combustion emissions, and for mornings compared to evenings due to the timing of the development and break-up of the nocturnal inversion layer or planetary boundary layer (PBL). A wavelet transform revealed that the dominant mode of CO variability is the annual cycle, with apparent winter maxima likely due to increased CO emissions from domestic heating with summer minima ascribed to enhanced dispersion and dilution during the annual maximum of PBL mixing heights. Over the last two decades, both mitigation measures to reduce CO emissions and also a major switch to diesel cars, have accompanied a change at EGH from the dominance of local diurnal sources to a site measuring close to Atlantic background levels in summer months. CO observed in the S and SW wind sectors has declined by 4.7 and 5.9 ppb yr−1 respectively. The EGH CO record shows the highest levels in the early 2000s, with levels in E and calm winds comparable to those recorded at background stations in Greater London. However, since 2012, levels in S-SW sector have become more comparable with Mace Head background except during rush-hour periods. Marked declines in CO are observed during 2000–2008 for the NE, E, SE (London) and calm wind sectors, with the smallest declines observed for the S, SW and W (background) sectors. For the majority of wind sectors, the decline in CO is less noticeable since 2008, with an apparent stabilisation for NE, E and SE after 2009. The EGH CO data record exhibits a similar but slower exponential decay, but from a much lower starting concentration, than do CO data recorded at selected monitoring sites in urban areas in SE England. CO/CO2 residuals determined using a 1 h window data in the diurnal cycle demonstrate a clear decline in CO from 2000 to 2015 during daily periods of increased vehicle traffic, which is consistent with a sustained reduction in CO emissions from the road transport sector

Methane Source Attribution in the UK Using Multi‐Year Records of CH4 and δ13C

Isotopic measurements of atmospheric methane are valuable for the verification of bottom-up atmospheric emissions inventories. The balance of sources in emissions inventories must be consistent with the δ13C-CH4 isotopic record in the air. Long-term records of both methane mole fraction and δ13C from five sites across the UK are presented, showing post-2007 growth in CH4 and negative trend in δ13C, consistent with global background sites. Miller-Tans analyses of atmospheric measurements identified that the δ13C signature of the methane source mix varied between −50.1 and −56.1‰, with less depleted δ13C signatures at sites receiving air from urban areas, consistent with an increased proportion of thermogenic sources. Isotopic signatures calculated for all sites are more enriched than those expected from the bottom-up emissions inventory, suggesting that inventories for the UK either underestimate contributions of thermogenic/pyrogenic emissions or overestimate biogenic sources

First validation of high-resolution satellite-derived methane emissions from an active gas leak in the UK

Atmospheric methane (CH4) is the second-most-important anthropogenic greenhouse gas and has a 20-year global warming potential 82 times greater than carbon dioxide (CO2). Anthropogenic sources account for ∼ 60 % of global CH4 emissions, of which 20 % come from oil and gas exploration, production and distribution. High-resolution satellite-based imaging spectrometers are becoming important tools for detecting and monitoring CH4 point source emissions, aiding mitigation. However, validation of these satellite measurements, such as those from the commercial GHGSat satellite constellation, has so far not been documented for active leaks. Here we present the monitoring and quantification, by GHGSat's satellites, of the CH4 emissions from an active gas leak from a downstream natural gas distribution pipeline near Cheltenham, UK, in the spring and summer of 2023 and provide the first validation of the satellite-derived emission estimates using surface-based mobile greenhouse gas surveys. We also use a Lagrangian transport model, the UK Met Office's Numerical Atmospheric-dispersion Modelling Environment (NAME), to estimate the flux from both satellite- and ground-based observation methods and assess the leak's contribution to observed concentrations at a local tall tower site (30 km away). We find GHGSat's emission estimates to be in broad agreement with those made from the in situ measurements. During the study period (March–June 2023) GHGSat's emission estimates are 236–1357 kg CH4 h−1, whereas the mobile surface measurements are 634–846 kg CH4 h−1. The large variability is likely down to variations in flow through the pipe and engineering works across the 11-week period. Modelled flux estimates in NAME are 181–1243 kg CH4 h−1, which are lower than the satellite- and mobile-survey-derived fluxes but are within the uncertainty. After detecting the leak in March 2023, the local utility company was contacted, and the leak was fixed by mid-June 2023. Our results demonstrate that GHGSat's observations can produce flux estimates that broadly agree with surface-based mobile measurements. Validating the accuracy of the information provided by targeted, high-resolution satellite monitoring shows how it can play an important role in identifying emission sources, including unplanned fugitive releases that are inherently challenging to identify, track, and estimate their impact and duration. Rapid, widespread access to such data to inform local action to address fugitive emission sources across the oil and gas supply chain could play a significant role in reducing anthropogenic contributions to climate change

Rising atmospheric methane: 2007-2014 growth and isotopic shift

From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7±1.2ppb yr$^{-1}$. Simultaneously, $\delta^{13}$C$_\text{CH4}$ (a measure of the $^{13}$C/$^{12}$C isotope ratio in methane) has shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5±0.4ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short-term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more $^{13}$C-depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post-2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.This work was supported by the UK Natural Environment Research Council projects NE/N016211/1 The Global Methane Budget, NE/M005836/1 Methane at the edge, NE/K006045/1 The Southern Methane Anomaly and NE/I028874/1 MAMM. We thank the UK Meteorological Office for flask collection and hosting the continuous measurement at Ascension, the Ascension Island Government for essential support, and Thumeka Mkololo for flask collection in Cape Tow

Measurement of the 13 C isotopic signature of methane emissions from Northern European wetlands

Isotopic data provide powerful constraints on regional and global methane emissions and their source profiles. However, inverse modeling of spatially-resolved methane flux is currently constrained by a lack of information on the variability of source isotopic signatures. In this study, isotopic signatures of emissions in the Fennoscandian Arctic have been determined in chambers over wetland, in the air 0.3 to 3 m above the wetland surface and by aircraft sampling from 100 m above wetlands up to the stratosphere. Overall the methane flux to atmosphere has a coherent δ13C isotopic signature of -71 ± 1‰, measured in situ on the ground in wetlands. This is in close agreement with δ13C isotopic signatures of local and regional methane increments measured by aircraft campaigns flying through air masses containing elevated methane mole fractions. In contrast results from wetlands in Canadian boreal forest further south gave isotopic signatures of -67 ± 1 ‰. Wetland emissions dominate the local methane source measured over the European Arctic in summer. Chamber measurements demonstrate a highly variably methane flux and isotopic signature, but the results from air sampling within wetland areas show that emissions mix rapidly immediately above the wetland surface and methane emissions reaching the wider atmosphere do indeed have strongly coherent C isotope signatures. The study suggests that for boreal wetlands (>60°N) global and regional modeling can use an isotopic signature of -71‰ to apportion sources more accurately, but there is much need for further measurements over other wetlands regions to verify this.UK Natural Environment Research Council (NERC). Grant Numbers: NE/I028874/1, NE/I014683/1, NE/F020937/1 European Community's Seventh Framework Programme. Grant Number: FP7/2007‐2013 InGOS. Grant Number: 28427

δ13C methane source signatures from tropical wetland and rice field emissions

The atmospheric methane (CH4) burden is rising sharply, but the causes are still not well understood. One factor of uncertainty is the importance of tropical CH4 emissions into the global mix. Isotopic signatures of major sources remain poorly constrained, despite their usefulness in constraining the global methane budget. Here, a collection of new δ13CCH4 signatures is presented for a range of tropical wetlands and rice fields determined from air samples collected during campaigns from 2016 to 2020. Long-term monitoring of δ13CCH4 in ambient air has been conducted at the Chacaltaya observatory, Bolivia and Southern Botswana. Both long-term records are dominated by biogenic CH4 sources, with isotopic signatures expected from wetland sources. From the longer-term Bolivian record, a seasonal isotopic shift is observed corresponding to wetland extent suggesting that there is input of relatively isotopically light CH4 to the atmosphere during periods of reduced wetland extent. This new data expands the geographical extent and range of measurements of tropical wetland and rice δ13CCH4 sources and hints at significant seasonal variation in tropical wetland δ13CCH4 signatures which may be important to capture in future global and regional models. This article is part of a discussion meeting issue ‘Rising methane: is warming feeding warming? (part 2)’

Isotopic Ratios of Tropical Methane Emissions by Atmospheric Measurement

Tropical methane sources are an important part of the global methane budget and include natural wetlands, rice agriculture, biomass burning, ruminants, fossil fuels, and waste. δ13CCH4 can provide strong constraints on methane source apportionment. For example, tropical wetlands in this study give δ13CCH4 values between −61.5 ± 2.9‰ and −53.0 ± 0.4‰ and in general are more enriched in 13C than temperate and boreal wetlands. However, thus far, relatively few measurements of δ13CCH4 in methane-enriched air have been made in the tropics. In this study samples have been collected from tropical wetland, rice, ruminant, and biomass burning emissions to the atmosphere. Regional isotopic signatures vary greatly as different processes and source material affect methane signatures. Measurements were made to determine bulk source inputs to the atmosphere, rather than to study individual processes. These measurements provide inputs for regional methane budget models, to constrain emissions with better source apportionment