Quantification of carbon dioxide, methane, nitrous oxide and chloroform emissions over ireland from atmospheric observations at mace head

Flux estimates Of CO2, CH4, N2O and CHCl3 over Ireland are inferred frorn continuous atmospheric records of these species. We use radon-222 (Rn-222) as a reference compound to estimate unknown sources of other species. The correlation between each species and 222Rn is calculated for a suite of diurnal events that have been selected in the Mace Head record over the period 1995 1997 to represent air masses exposed to sources over Ireland. We established data selection criteria based on Rn-222 and Pb-212 concentrations, We estimated flux densities of 12 x 10(3) kg CH4 km(-2) yr(-1), 680 kg N2O km(-2) yr(-1) and 20 kg CHCl3 km(-2) yr(-1) for CH4, N2O and CHCl3, respectively. We also inferred flux densities of 250 x 10(3) kg C km(-2) yr(-1) for CO2 during wintertime, and of 760 x 10(3) kg C km(-2) yr(-1) for CO2 during summer night-time. Our CH4 inferred flux compare well with the CORINAIR90 and CORNAIR94 inventories for Ireland. The N2O emission flux we inferred is close to the inventory value by CORINAIR90, but twice the inventory value by CORINAIR94 and EDGAR 2.0. This discrepancy may have been caused by the use of the revised 1996 IPCC guidelines for national greenhouse gas inventories in 1994, which include a new methodology for N2O emissions from agriculture. We carried out the first estimation of CHCl3 emission fluxes over Ireland. This estimation is 4 times larger than the CHCl3 emission fluxes measured close to the Mace Head station over peatlands. Our CHCl3 emission fluxes estimate is consistent with the interpretation of the same data by Ryall (personal communication, 2000), who obtained, using a Lagrangian atmospheric transport model, CHCl3 fluxes of 24 +/- 7 kg CHCl3 km(-2) yr(-1). Our estimates of CO2 emission fluxes during summer night-time and wintertime are close to those estimated from inventories and to one biogeochemical model of heterotrophic respiration