[1] The chemical composition of the surface boundary layer over the Eurasian continent is still an area of high uncertainty. In the framework of the Trans-Siberian Observations Into the Chemistry of the Atmosphere (TROICA) project, measurements of O 3 , NO, NO 2 , CO, CO 2 , CH 4 , 222 Rn, J(NO 2 ), and black carbon aerosol were carried out on the TransSiberian railroad during June-July 1999. Boundary layer data over more than 16,000 km, from Kirov ($58°N, 49°E; 972 km east of Moscow) to Khabarovsk ($48°N, 135°E) and back to Moscow, were obtained without significant contamination, emphasizing the potential of using the Trans-Siberian railroad system for atmospheric measurements. The 222 Rn and CO 2 concentrations were determined for the first time using our laboratory wagon. The diurnal variations of these gases and of CH 4 due to micrometeorological conditions, as well as their dependence on various soil sources and vegetation types, were used to estimate ecosystem fluxes of CO 2 and CH 4 . The highest soil flux of CH 4 was 70 ± 35 m mol m À2 h À1 for the wet habitats of the West Siberian lowlands, and the lowest CH 4 flux was 3.2 ± 1.6 m mol m À2 h À1 for drier habitats of eastern Siberia. Although the wet tundra emissions found between 67°and 77°N are higher than in comparable environments at much lower latitudes [Christensen et al., 1995], boreal wetlands in Siberia at 50°-60°N represent a very important player in the global methane budget. The CO 2 density fluxes exhibited the opposite to CH 4 fluxes tendency. Ozone mixing ratios varied from a few nmol/mol during nighttime inversions to more than 60 nmol/mol during the day. These values were generally higher than during the 1996 summer campaign (TROICA 2). CH 4 and CO levels followed the pattern observed during TROICA 2; elevated levels of CH 4 with a mean mixing ratio of 1.97 ± 0.009 mmol/mol were found over the West Siberian lowlands, decreasing to 1.88 ± 0.13 mmol/mol toward East Siberia. Conversely, while background CO levels of the West Siberian wetlands were generally below 140 nmol/mol, high CO concentrations, once even exceeding 2 mmol/mol, were registered east of Chita ($52°N, 113°E), as a consequence of forest and other vegetation fires, which significantly affect the chemical composition of the air over parts of Russia.