Plume mapping and isotopic characterisation of anthropogenic methane sources

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for delta C-13-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining delta C-13-CH4 to +/- 0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a delta C-13 -CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged delta C-13-CH4 for landfill sites is -58 +/- 3%o. The delta C-13-CH4 signature for gas leaks is also fairly constant around -36 +/- 2 parts per thousand, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 +/- 0.3 parts per thousand to 30.9 +/- 1.4 parts per thousand, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that iiotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution. (C) 2015 Elsevier Ltd. All rights reserved.