Source apportionment of methane emissions from the Upper Silesian Coal Basin using isotopic signatures

Anthropogenic emissions are the primary source of the increase in atmospheric methane ( CH 4 ) levels. However, estimates of anthropogenic CH 4 emissions still show large uncertainties at global and regional scales. Differences in CH 4 isotopic source signatures delta 13 C and delta 2 H can help to constrain different source contributions (e.g., fossil, waste, agriculture). The Upper Silesian Coal Basin (USCB) represents one of the largest European CH 4 emission regions, with more than 500 Gg CH 4 yr - 1 released from more than 50 coal mine ventilation shafts, landfills, and wastewater treatment plants. During the CoMet (Carbon Dioxide and Methane Mission) campaign in June 2018 methane observations were conducted from a variety of platforms including aircraft and cars to quantify these emissions. Besides the continuous sampling of atmospheric methane concentration, numerous air samples were taken from inside and around the ventilation shafts (1-2 km distance) and aboard the High Altitude and Long Range Research Aircraft (HALO) and DLR Cessna Caravan aircraft, and they were analyzed in the laboratory for the isotopic composition of CH 4 .The airborne samples downwind of the USCB contained methane from the entire region and thus enabled determining the mean signature of the USCB accurately. This mean isotopic signature of methane emissions was - 50.9 +/- 0.7 parts per thousand for delta 13 C and - 226 +/- 9 parts per thousand for delta 2 H . This is in the range of previous USCB studies based on samples taken within the mines for delta 13 C but more depleted in delta 2 H than reported before. Signatures of methane enhancements sampled upwind of the mines and in the free troposphere clearly showed the influence of biogenic sources. We determined the source signatures of individual coal mine ventilation shafts using ground-based samples. These signatures displayed a considerable range between different mines and also varied for individual shafts from day to day. Different layers of the USCB coal contain thermogenic methane, isotopically similar to natural gas, and methane formed through biogenic carbonate reduction. The signatures vary depending on what layer of coal is mined at the time of sampling. Mean shaft signatures range from - 60 parts per thousand to - 42 parts per thousand for delta 13 C and from - 200 parts per thousand to - 160 parts per thousand for delta 2 H . A gradient in the signatures of subregions of the USCB is reflected both in the aircraft data and in the ground samples, with emissions from the southwest being most depleted in delta 2 H and emissions from the south being most depleted in delta 13 C , which is probably associated with the structural and lithostratigraphic history of the USCB and generation and migration processes of methane in the coal. The average signature of - 49.8 +/- 5.7 parts per thousand in delta 13 C and - 184 +/- 32 parts per thousand in delta 2 H from the ventilation shafts clearly differs from the USCB regional signature in delta 2 H . This makes a source attribution using delta 2 H signatures possible, which would not be possible with only the delta 13 C isotopic signatures. We assume that the USCB plume mainly contains fossil coal mine methane and biogenic methane from waste treatment, because the USCB is a highly industrialized region with few other possible methane sources. Assuming a biogenic methane signature between and - 320 parts per thousand and - 280 parts per thousand for delta 2 H , the biogenic methane emissions from the USCB account for 15 %-50 % of total emissions. The uncertainty range shows the need of comprehensive and extensive sampling from all possible source sectors for source apportionment. The share of anthropogenic-biogenic emissions of 0.4 %-14 % from this densely populated industrial region is underestimated in commonly used emission inventories. Generally, this study demonstrates the importance of delta 2 H - CH 4 observations for methane source apportionment in regions with a mix of thermogenic and biogenic sources and, especially in our case, where the delta 13 C signature of the coal mine gas has a large variability.