Quantification of carbon dioxide and methane emissions in urban areas: source apportionment based on atmospheric observations

Anthropogenic emissions of carbon dioxide (CO 2 ) and methane (CH 4 ) in the atmosphere constitute an important component of the related carbon budget. The main source of anthropogenic CO 2 is burning of fossil fuels, especially in densely populated areas. Similar emissions of CH 4 are associated with the agricultural sector, coal mining, and other human activities, such as waste management and storage and natural gas networks supplying methane to large urban, industrial centers. We discuss several methods aimed at characterizing and quantifying atmospheric loads and fluxes of CO 2 and CH 4 in Krakow, the second largest city in Poland. The methods are based on atmospheric observations of mixing ratios as well as isotopic composition of the investigated gases. Atmospheric mixing ratios of CO 2 and CH 4 were measured using gas chromatography (GC) and cavity ring-down spectroscopy (CRDS). The isotopic composition of CO 2 and CH 4 was analyzed using isotope ratio mass spectrometry (IRMS), accelerator mass spectrometry (AMS), and CRDS techniques. These data, combined with auxiliary information characterizing the intensity of vertical mixing in the lower atmosphere (height of the nocturnal boundary layer [NBL] and atmospheric 222 Rn concentration), were further used to quantify emission rates of CO 2 and CH 4 in the urban atmosphere of Krakow. These methods provide an efficient way of quantifying surface emissions of major greenhouse gases originating from distributed sources, thus complementing the widely used bottom-up methodology based on emission statistics.