Separating contributions from natural and anthropogenic sources in atmospheric methane from the Black Sea region,Romania

The Danube Delta-Black Sea region of Romania is an important wetland, and this preliminary study evaluates the significance of this region as a source of atmospheric CH₄. Measurements of the mixing ratio and δ¹³C in CH₄ are reported from air and water samples collected at eight sites in the Danube Delta. High mixing ratios of CH₄ were found in air (2500–14,000 ppb) and dissolved in water samples (∼1–10 μmol L⁻¹), demonstrating that the Danube Delta is an important natural source of CH₄. The intercepts on Keeling plots of about −62‰ show that the main source of CH₄ in this region is microbial, probably resulting primarily from acetate fermentation. Atmospheric CH₄ and CO data from the NOAA/ESRL (National Oceanic and Atmospheric Administration/Earth System Research Laboratory) were used to make a preliminary estimate of biogenic CH₄ at the Black Sea sampling site at Constanta (BSC). These data were used to calculate ratios of CH₄/CO in air samples, and using an assumed CH₄/CO anthropogenic emissions ratio of 0.6, fossil fuel emissions at BSC were estimated. Biogenic CH₄ emissions were then estimated by a simple mass balance approach. Keeling plots of well-mixed air from the BSC site suggested a stronger wetland source in summer and a stronger fossil fuel source in winter.