Tai-Yih Chen

Biomass burning emissions and vertical distribution of atmospheric methyl halides and other reduced carbon gases in the South Atlantic region

The NASA TRACE A experiment (September – October 1992) investigated effects of dry season biomass burning emissions from both South America and southern Africa on the tropical South Atlantic troposphere. Whole air canister samples were collected aboard the NASA DC-8 aircraft and analyzed for a wide range of nonmethane hydrocarbons (NMHCs) and halocarbons. Fast response in situ quantification of CH4, CO, and CO2 were also performed on the DC-8. Sampling took place over Brazilian agricultural areas and southern African savanna where there was active biomass burning. The vertical distribution of the measured gases revealed that the concentrations of most hydrocarbons, methyl halides, CH4, CO, and CO2, were enhanced in the boundary layer of these regions principally as a result of biomass fires. Brazilian and African biomass burning emission ratios were calculated for CH3Br, CH3Cl, CH3I, and NMHCs relative to CO and CO2. Although both fire regions were dominated by efficient (flaming) combustion (CO/CO2 ratios <0.1), the Brazilian samples exhibited the lower (more flaming) CO/CO2 ratio of 0.037 compared with the African savanna value of 0.062. This difference in combustion efficiency was reflected in lower ratios versus CO2 for all correlated gases. However, the gases more closely associated with smoldering combustion (e.g., C3H8 and CH3Cl) exhibited significantly higher ratios relative to CO for the Brazilian fires, while the African samples exhibited higher values versus CO for compounds associated more closely with flaming combustion (e.g., C2H2). This variation in the trace gas ratios versus CO is most likely caused by different fuel characteristics. On the basis of the emission ratios obtained, the total biomass burning emission rates for savannas and worldwide were calculated for the hydrocarbons and methyl halides. From these it was estimated that roughly 25% and 20% of global CH3Cl and CH3Br emissions, respectively, derive from biomass burning but that the contribution of biomass burning to total CH3I emissions was not significant.

Three-dimensional distribution of nonmenthane hydrocarbons and halocarbons over the northwestern Pacific during the 1991 Pacific Exploratory Mission (PEM-West A)

A total of 1667 whole air samples were collected onboard the NASA DC-8 aircraft during the 6-week Pacific Exploratory Mission over the western Pacific (PEM-West A) in September and October 1991. The samples were assayed for 15 C2-C7 hydrocarbons and six halocarbons. Latitudinal (0.5°S to 59.5°N) and longitudinal (114°E to 122°W) profiles were obtained from samples collected between ground level and 12.7 km. Thirteen of the 18 missions exhibited at least one vertical profile where the hydrocarbon mixing ratios increased with altitude. Longitude-latitude color patch plots at three altitude levels and three-dimensional color latitude-altitude and longitude-altitude contour plots exhibit a significant number of middle-upper tropospheric pollution events. These and several lower tropospheric pollution plumes were characterized by comparison with urban data from Tokyo and Hong Kong, as well as with natural gas and the products from incomplete combustion. Elevated levels of nonmethane hydrocarbons (NMHC) and other trace gases in the upper-middle free troposphere were attributed to deep convection over the Asian continent and to typhoon-driven convection near the western Pacific coast of Asia. In addition, NMHCs and CH3CCl3 were found to be useful tracers with which to distinguish hydrocarbon and halocarbon augmented plumes emitted from coastal Asian cities into the northwestern Pacific.

Distribution and seasonality of selected hydrocarbons and halocarbons over the western Pacific basin during PEM‐West A and PEM‐West B

Nonmethane hydrocarbons (NMHCs) and halocarbons were measured in the troposphere over the northwestern Pacific as part of the airborne component of NASAs Pacific Exploratory Mission-West Phase B (PEM-West B). This study took place in late winter of 1994, a period characterized by maximum outflow from the Asian continent. The results are compared to those from Pacific Exploratory Mission-West Phase A (PEM-West A), which was flown in the same region during late summer of 1991, when flow from the subtropical western Pacific dominated the lower troposphere. Mixing ratios of NMHCs, tetrachloroethene (C2Cl4), and methyl bromide (CH3Br) were significantly higher during PEM-West B than during PEM-West A, particularly at latitudes north of 25°N and altitudes lower than 6 km. The primary reasons for these higher ambient concentrations were the seasonal increase in the atmospheric lifetimes of trace gases controlled by HO radical reactions, and the more frequent input of continental air masses. During PEM-West B, air masses of continental origin observed north of 25°N latitude were augmented with urban signature gases such as C2Cl4. By contrast, more southerly continental outflow had characteristics associated with combustion sources such as biomass burning, including wood fuel burning. During the summer PEM-West A period, the spatial distribution of methyl iodide (CH3I) was consistent with effective oceanic sources at all latitudes, being especially strong in tropical and subtropical regions. At low latitudes, PEM-West B CH3I mixing ratios in the lower troposphere were similar to PEM-West A, but at latitudes greater than about 25°N PEM-West B concentrations were significantly reduced. Equatorial regions exhibited enhanced CH3I mixing ratios extending into the upper tropical troposphere, consistent with fast vertical transport of air from the tropical marine boundary layer.

Effects of biomass burning on summertime nonmethane hydrocarbon concentrations in the Canadian wetlands

Approximately 900 whole air samples were collected and assayed for selected C2-C10 hydrocarbons and seven halocarbons during the 5-week Arctic Boundary Layer Expedition (ABLE) 3B conducted in eastern Canadian wetland areas. In more than half of the 46 vertical profiles flown, enhanced nonmethane hydrocarbon (NMHC) concentrations attributable to plumes from Canadian forest fires were observed. Urban plumes, also enhanced in many NMHCs, were separately identified by their high correlation with elevated levels of perchloroethene. Emission factors relative to ethane were determined for 21 hydrocarbons released from Canadian biomass burning. Using these data for ethane, ethyne, propane, n-butane, and carbon monoxide enhancements from the literature, global emissions of these four NMHCs were estimated. Because of its very short atmospheric lifetime and its below detection limit background mixing ratio, 1,3-butadiene is an excellent indicator of recent combustion. No statistically significant emissions of nitrous oxide, isoprene, or CFC 12 were observed in the biomass-burning plumes encountered during ABLE 3B. The presence of the short-lived biogenically emitted isoprene at altitudes as high as 3000 m implies that mixing within the planetary boundary layer (PBL) was rapid. Although background levels of the longer-lived NMHCs in this Canadian region increase during the fire season, isoprene still dominated local hydroxyl radical photochemistry within the PBL except in the immediate vicinity of active fires. The average biomass-burning emission ratios for hydrocarbons from an active fire sampled within minutes of combustion were, relative to ethane, ethene, 2.45; ethyne 0.57; propane, 0.25; propene, 0.73; propyne, 0.06; n-butane, 0.09; i;-butane, 0.01; 1-butene, 0.14; cis-2-butene, 0.02; trans-2-butene, 0.03; i-butylene, 0.07; 1,3-butadiene, 0.12; n-pentane, 0.05; i-pentane, 0.03; 1-pentene, 0.06; n-hexane, 0.05; 1-hexene, 0.07; benzene, 0.37; toluene, 0.16.

Summertime measurements of selected nonmethane hydrocarbons in the Arctic and Subarctic during the 1988 Arctic Boundary Layer Expedition (ABLE 3A)

Approximately 1000 whole air samples were collected and assayed for selected C2-C5 hydrocarbons during the 6-week Arctic Boundary Layer Expedition (ABLE 3A). Transit flights enabled latitudinal (40°N to 83°N) and longitudinal (70°W to 155°W) profiles to be obtained for altitudes between 4000 and 6000 m yielding summertime background mixing ratios for ethane, ethyne, propane and n-butane of 1050±200, 100±40, 120±80 and 10±8 pptv, respectively. Drilling associated with oil exploration in the Alaskan North Slope area is suggested to be a probable source of the enhanced levels of alkanes observed in the Arctic region within a radius in excess of 300 km from Prudhoe Bay, Alaska. A significant number of pollution plumes were encountered which could be attributed to wildfires. Factors describing the emissions caused by biomass burning relative to ethane for ethyne (0.40) and propane (0.08) were determined. An increase of hydrocarbon mixing ratios with altitude was observed during all but two of the missions. Therefore, the Arctic and sub-Arctic are significantly influenced by the long-range transport of pollutants from nonlocal sources. A single vertical profile made in the vicinity of Wallops Island, Virginia, revealed elevated levels of isoprene, numerous hydrocarbons of the types associated with the leakage of natural gas and fossil fuel combustion, and substantial concentrations of nitrogen oxides and ozone. This implies that long-range transport of various gases from urban areas, combined with local biogenic emissions of isoprene, are significant sources of regional tropospheric ozone.

Impact of the leakage of liquefied petroleum gas (LPG) on Santiago Air Quality

The leakage of unburned liquefied petroleum gas (LPG) is a major source of urban nonmethane hydrocarbons (NMHCs) in the air of Santiago, Chile. Roughly 5% of the LPG that is sold in Santiago leaks in its unburned form to the atmosphere. Because of the leakage, propane is the most abundant NMHC in Santiagos air, even under heavy traffic conditions. NMHCs are an important precursor to the formation of ground-level ozone, and the LPG leakage may contribute as much as 15% to the excess ozone levels in Santiago. Improvement to the local air quality may be obtained by lowering the rates of LPG leakage, and by minimizing the use of alkene-rich LPG formulations.

Estimation of global vehicular methyl bromide emissions: Extrapolation from a case study in Santiago, Chile

Between June 1 and June 8, 1996, 144 whole air samples were collected in Santiago, Chile. The temporal and geographical enhancement of CH3Br correlated with incomplete combustion tracers emitted from vehicles during the morning commute. From these, a city-wide CH3Br/CO volume emission ratio of 2.2 × 10−6 was measured in ambient air. Without using the CO measurements, we estimate an annual release of 8.9 tons of CH3Br in Santiago based solely upon enhanced concentrations observed throughout the study area during the morning traffic period. This enhancement corresponds to 8.0 × 10−6 kg CH3Br emitted for each liter of gasoline used (leaded and unleaded). By scaling the annual gasoline usage in Santiago to countries still using leaded gasoline, and assuming the above 8.0 × 10−6 kg/L value holds true, a global vehicular CH3Br emission of 4 ± 3 Gg/year is calculated. This small vehicular CH3Br emission source strength will not improve the current CH3Br budget imbalance.

Influence of convection and biomass burning outflow on tropospheric chemistry over the tropical Pacific

Observations over the tropics from the Pacific Exploratory Mission-Tropics A Experiment are analyzed using a one-dimensional model with an explicit formulation for convective transport. Adopting tropical convective mass fluxes from a general circulation model (GCM) yields a large discrepancy between observed and simulated CH3I concentrations. Observations of CH3I imply the convective mass outflux to be more evenly distributed with altitude over the tropical ocean than suggested by the GCM. We find that using a uniform convective turnover lifetime of 20 days in the upper and middle troposphere enables the model to reproduce CH3I observations. The model reproduces observed concentrations of H2O2 and CH3OOH. Convective transport of CH3OOH from the lower troposphere is estimated to account for 40–80% of CH3OOH concentrations in the upper troposphere. Photolysis of CH3OOH transported by convection more than doubles the primary HOx source and increases OH concentrations and O3 production by 10–50% and 0.4 ppbv d−1, respectively, above 11 km. Its effect on the OH concentration and O3 production integrated over the tropospheric column is, however, small. The effects of pollutant import from biomass burning regions are much more dominant. Using C2H2 as a tracer, we estimate that biomass burning outflow enhances O3 concentrations, O3 production, and concentrations of NOx and OH by 60%, 45%, 75%, and 7%, respectively. The model overestimates HNO3 concentrations by about a factor of 2 above 4 km for the upper one-third quantile of C2H2 data while it generally reproduces HNO3 concentrations for the lower and middle one-third quantiles of C2H2 data.

Nonmethane hydrocarbon measurements in the North Atlantic Flight Corridor during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment

Mixing ratios of nonmethane hydrocarbons (NMHCs) were not enhanced in whole air samples collected within the North Atlantic Flight Corridor (NAFC) during the fall of 1997. The investigation was conducted aboard NASAs DC-8 research aircraft, as part of the Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX). NMHC enhancements were not detected within the general organized tracking system of the NAFC, nor during two tail chases of the DC-8s own exhaust. Because positive evidence of aircraft emissions was demonstrated by enhancements in both nitrogen oxides and condensation nuclei during SONEX, the NMHC results suggest that the commercial air traffic fleet operating in the North Atlantic region does not contribute at all or contributes negligibly to NMHCs in the NAFC.