Estimates of anthropogenic halocarbon emissions based on its measured ratios relative to CO in the Pearl River Delta

Abstract

Abstract. Using a GC/FID/MS system, we analyzed the mixing ratio levels of 16 halocarbon species in more than 100 air samples collected in 2004 from the Pearl River Delta (PRD) region of southern China. The results revealed elevated regional mixing ratios for most halocarbons, especially for HClC = CCl2 (trichloroethylene, TCE), CH2Cl2 (dichloromethane, DCM), CH3Br (bromomethane), HCFC-22, CHCl3 (trichloromethane), CCl4 (tetrachloromethane), Cl2C = CCl2 (perchloroethylene, PCE), CH3CCl3 (methyl chloroform, MCF), and CFC-12. Comparisons were done with the data from TRACE-P and ALE/GAGE/AGAGE experiments, we found that the large variability in concentrations (relative standard deviation ranged from 9.31% to 96.55%) of the halocarbons suggested substantial local emissions from the PRD region in 2004. Correlations between the mixing ratio of each species and carbon monoxide (CO) were examined, and then each emission of halocarbon was quantified based on scaling the optimized CO emission inventory with the slope of the regression line fitted to each species relative to CO. The calculated results revealed that mass of CH2Cl2 (7.0 Gg), CH3CCl3 (6.7 Gg), and Cl2C = CCl2 (2.3 Gg) accounted for about 62.9% of total emissions, suggesting a significant contribution to halocarbon emissions from solvent use in the PRD region. Emissions of HCFC-22 (3.5 Gg), an alternative refrigerant to chlorofluorocarbons (CFCs), were about 2.3 times greater than those of CFC-12 (1.6 Gg). CFC-12 and HCFC-22 accounted for 21.5% of total emissions of halocarbons, so that the refrigerant would be the second largest source of halocarbons. However, the ratio approach found only minor emissions of other CFCs, such as CFC-11, and levels of CFC-114 and CFC-113 were close to zero. Emissions of other anthropogenic halocarbons, such as CCl4, CHCl3, CH3Br, and CH3Cl, were also estimated. Where possible, the emissions estimated from the measured ratios were compared with results from source inventory techniques, we found that both approaches gave emissions at similar magnitude for most of the halocarbons, except CFC-11. The comparison suggested that ratio method may be a useful tool for assessing regional halocarbon emissions, and emission uncertainty could be further reduced by incorporating both longer-term and higher-frequency observations, as well as improving the uncertainty of the CO inventory.