Seasonal and diurnal variations of greenhouse gases in Florence (Italy): inferring sources and sinks from carbon isotopic ratios

In this study, the results of a continuous monitoring of (i) CO2 fluxes, and (ii) CO2 and CH4 concentrations and carbon isotopic ratios (δ13C-CO2 and δ13C-CH4) in air, carried out from 7 to 21 July 2017 and from October 10 to December 15, 2017 in the city centre of Florence, are presented. The measurements were performed from the roof of the historical building of the Ximenes Observatory. CO2 flux data revealed that the metropolitan area acted as a net source of CO2 during thewhole observation period. According to the Keeling plot analysis, anthropogenic contributions to atmospheric CO2 were mainly represented by vehicular traffic (about 30%) andnatural gas combustion (about 70%), the latter contributing 7 times more in December than in July. Moreover, the measured CO2 fluxes were about 80% higher in fall than in summer, confirming that domestic heating based on natural gas is the dominant CO2 emitting source in themunicipality of Florence. Even though the continuous monitoring revealed a shift in the δ13C-CO2 values related to photosynthetic uptake of atmospheric CO2, the isotopic effect induced by plant activity was restricted to few hours in October and, to a lesser extent, in November. This suggests that urban planning policies should be devoted to massively increase green infrastructures in the metropolitan area in order to counterbalance anthropogenic emissions. During fall, the atmospheric CH4 concentrations were sensibly higher with respect to those recorded in summer, whilst the δ13C-CH4 values shifted towards heavier values. The Keeling plot analysis suggested that urban CH4 emissions were largely related to fugitive emissions from the natural gas distribution pipeline network. On the other hand, δ13C-CH4 monitoring allowed to recognize vehicular traffic as a minor CH4 emitting source.