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Gregory, G. L.

Publications and source records attributed to Gregory, G. L..

At least 37 records · Page 2

Summertime distribution and relations of reactive odd nitrogen species and NO(y) in the troposphere over Canada

We report here large-scale features of the distribution of NO(x), HNO3, PAN, particle NO3, and NO(y) in the troposphere from 0.15 to 6 km altitude over central Canada. These measurements were conducted in July - August 1990 from the NASA Wallops Electra aircraft as part of the joint United States-Canadian Arctic Boundary Layer Expedition (ABLE) 3B-Northern Wetlands Study. Our findings show that this region is generally NO(x) limited, with NO(x) mixing ratios typically 20-30 parts per trillion by volume (pptv). We found little direct evidence for anthropogenic enhancement of mixing ratios of reactive odd nitrogen species and NO(y) above those in 'background' air. Instead, it appears that enhancements in the mixing ratios of these species were primarily due to emissions from several day old or CO-rich-NO(x)-poor smoldering local biomass-burning fires. NO(x) mixing ratios in biomass-burning impacted air masses were usually less than 50 pptv, but those of HNO3 and PAN were typically 100-300 pptv representing a twofold-threefold enhancement over 'background' air. During our study period, inputs of what appeared to be aged tropical air were a major factor influencing the distribution of reactive odd nitrogen in the midtroposphere over northeastern North America. These air masses were quite depleted in NO(y) (generally less than 150 pptv), and a frequent summertime occurrence of such air masses over this region would imply a significant influence on the reactive odd nitrogen budget. Our findings show that the chemical composition of aged air masses over subarctic Canada and those documented in the Arctic during ABLE 3A have strikingly similar chemistries, suggesting large-scale connection between the air masses influencing these regions.

Talbot, R. W.↗

Low Ozone in the Marine Boundary Layer of the Tropical Pacific Ocean

Aircraft measurements of ozone, its key precursors, and a variety of chemical tracers were made in the troposphere of the western and central Pacific in October 1991. These data are presented and analyzed to examine the occurrence of low ozone concentrations in the remote marine boundary layer of the tropical and equatorial Pacific Ocean. The data from these flights out of Guam, covering an area extending from the equator to 20 N and from south of the Philippines to Hawaii, show average O3 concentrations as low as 8-9 ppb (ppb=10(exp-9)v/v) at altitudes of 0.3-0.5 km in the boundary layer. Individual measurements as low as 2-5 ppb were recorded. Low O3 concentrations do not always persist in space and time. High O3, generally associated with the transport of upper tropospheric air, was also encountered in the boundary layer. In practically all cases, O3 increased to values as large as 25-30 ppb within 2 km above the boundary layer top. Steady state model computations are used to suggest that these low O3 concentrations are a result of net photochemical O3 destruction in a low NO environment, sea-surface deposition, and extremely low net entrainment rates (1-2 mm per second) from the free troposphere. Day/night measurements of ethane, propane, gaseous and aerosol Cl suggest that daytime (morning) Cl atom concentrations in the vicinity of 10(exp 5) molecules per cubic centimeter may be present in the marine boundary layer. This Cl atom abundance can be rationalized only if sea salt aerosols can release free chlorine (Cl2) to the gas phase in the presence of sun light (and possibly O3). These Cl atom concentrations, however, are still insufficient and Cl (or Br) chemistry is not likely to be an important cause of the observed low O3.

Singh, Hanwant B.↗

The impact of U.S. continental outflow on ozone and aerosol distributions over the western Atlantic

Aircraft measurements of selected trace gas species, aerosols, and meteorological parameters were performed in the lower troposphere off the U.S. east coast during August and September 1989 as part of the NASA Global Tropospheric Experiment (GTE) Chemical Instrumentation Test and Evaluation (CITE 3) expedition. In this paper, we examine these data to assess the impact of continental outflow on western Atlantic O3 and small aerosol budgets. Results show that mixed layer (ML) O3 concentrations and small aerosol number densities (Np) were enhanced by factors of 3 and 6, respectively, within air masses of predominantly continental origin compared with clean maritime background air. These enhancements exhibited a marked altitude dependence, declining rapidly above the ML to the point where only slight to moderate differences in O3 and Np, respectively, were notable above 2.4 km. Within continentally influenced ML's, both O3 and Np were correlated with CO, exhibiting linear regression slopes averaging 0.4 ppbv (O3)/ppbv(CO) for O3 and 7.7 (particles/cc)/ppbv(CO) for Np and indicating a primarily anthropogenic origin for the observed enhancement of these species. Comparisons between profiles in continental and background maritime air masses suggest that photochemical production below 1.4-km altitude adds over 10% to western Atlantic tropospheric column O3 abundance in continental outflow regimes. For aerosols, eastward advection of low-level continental air contributes an average net flux of 2.8 metric tons of submicron (accumulation mode) particles per kilometer of shoreline per day to the western Atlantic troposphere.

Anderson, B. E.↗

Factors influencing dry season ozone distributions over the tropical South Atlantic

Airborne measurements of trace gas and aerosol species were obtained in the lower troposphere (less than 5 km) over the western Atlantic Ocean between 13 deg S and 40 deg N during the August/September 1990 NASA Chemical Instrument Test and Evaluation (CITE 3) experiment. The largest background O3 mixing ratios, averaging 35 and 70 ppbv within the mixed layer (ML) and free troposphere (FT; altitudes greater than 2.4 km), respectively, were found over the tropical South Atlantic. Several competing processes were observed to regulate O3 budgets in this region. Within the ML, rapid photochemical destruction produced a diurnal O3 variation of 8 ppbv and an O3/altitude gradient between the surface and 5 km of almost 10 ppbv (O3)/km. ML O3 concentrations were replenished by atmospheric downwelling which occurred at rates of up to and exceeding 1 cm/s. Ozone values within the subsiding FT air were enriched both by long-range transport of O3 produced photochemically within biomass combustion plumes and the downward propagation of dry, upper tropospheric air masses. Overall, the tropospheric O3 column below 3.3 km averaged 13.5 Dobson units (DU) over the South Atlantic region, which is 8-9 DU higher than observed during CITE 3 ferry flights over the northern tropical Atlantic Ocean or measured by ozonesondes over coastal Brazil during the wet season. An examination of simultaneous dew point and combustion tracer (e.g., CO) measurements suggests that the dry subsiding layers and biomass burning layers make approximately equal contributions to the observed O3 enhancement.

Anderson, B. E.↗

Large-scale variability of ozone and aerosols in the summertime Arctic and sub-Arctic troposphere

The results of mesoscale and large-scale studies of the distribution of aerosols and O3 using primarily an airborne DIAL system are reported. The tropospheric composition at high latitudes is found to be strongly influenced by stratospheric intrusions. Regions of low-aerosol scattering and enhanced O3 mixing ratios are correlated with descending air from the lower stratosphere. Over 37 percent of the troposphere along the flight track at latitudes higher than 57 deg N had significantly enhanced O3 levels due to stratospheric intrusions, and in the 4-6 km latitude range the tropospheric extent of the enhanced O3 exceeded 56 percent. Ozone mixing ratios of 80 ppbv at 6 km are common, with vertical O3 gradients of over 11 ppbv/km observed across the base of strong intrusions. In the mixed layer over the tundra, O3 was in the 25-35 ppbv range with a gradient of 5.5 ppbv/km, while in the continental polar air masses, the average gradient in the lower troposphere is 7.4 ppbv/km, indicating more downward transport of O3 at higher latitudes.

Browell, E. V.↗

Deposition of ozone to tundra

Eddy correlation measurements of O3 deposition fluxes to tundra during the Arctic Boundary Layer Expedition (ABLE 3A) are reported. The mean O3 deposition velocity was 0.24 cm/s in the daytime and 0.12 cm/s at night. The day-to-day difference in deposition velocity was driven by both atmospheric stability and surface reactivity. The mean surface resistance to O3 deposition was 2.6 s/cm in the daytime and 3.4 s/cm at night. The relatively low surface resistance at night is attributed to light-insensitive uptake of O3 at dry upland tundra surfaces. The small day-tonight difference in surface resistance is attributed to additional stomatal uptake by wet meadow tundra plants in the daytime. The mean O3 deposition flux to the world north of 60 deg N in July-August is estimated at 8.2 x 10 exp 10 molecules/sq cm/s. Suppression of photochemical loss by small anthropogenic inputs of nitrogen oxides could have a major effect on O3 concentrations in the summertime Arctic troposphere.

Jacob, D. J.↗

Summertime tropospheric observations related to N(x)O(y) distributions and partitioning over Alaska - Arctic Boundary Layer Expedition 3A

Measurements of NO, NO2, PAN and NO(y) are presented for the summertime middle/lower troposphere over northern high latitudes. Chemical signatures from concurrent measurements of O3, CO, C2H2, C2H6, C3H8, C2Cl4, and H2O are used to characterize factors affecting the budget and distribution of N(x)O(y) in the Arctic and Sub-Arctic tropospheric air masses sampled over Alaska during the NASA Arctic Boundary Layer Expedition (ABLE 3A). The results implicate biomass burning in Siberia as the probable source of about one-third of the NO(y) abundance within the middle lower troposphere over Alaska and the downward transport of air from altitude in the vicinity of the tropopause as a major contributor to the abundance of NO(y) within the lower 6 km column over Alaska.

Sandholm, S. T.↗

Atmospheric measurements of peroxyacetyl nitrate and other organic nitrates at high latitudes - Possible sources and sinks

Measurements of PAN and other reactive nitrogen species during the NASA Arctic Boundary Layer Expedition (ABLE 3A) are described, their north-south and east-west gradients in the free troposphere are characterized, and the sources and sinks of PAN and NO(y) are assessed. Large concentrations of PAN and NO(y) are present in the Arctic/sub-Arctic troposphere of the Northern Hemisphere during the summer. Mixing ratios of PAN and a variety of other molecules are more abundant in the free troposphere compared to the boundary layer. Coincident PAN and O3 atmospheric structures suggest that phenomena that define PAN also define the corresponding O3 behavior. Model calculations, correlations between NO(y) and anthropogenic tracers, and the compositions of NO(y) itself suggest that the Arctic/sub-Arctic reactive nitrogen measured during ABLE 3A is predominantly of anthropogenic origin with a minor component from the stratosphere.

Singh, H. B.↗

Atmospheric chemistry in the Arctic and subarctic - Influence of natural fires, industrial emissions, and stratospheric inputs

Layers with enhanced concentrations of trace gases intercepted by the NASA Electra aircraft over Alaska during the Arctic Boundary Layer Expedition (ABLE 3A) in July-August 1988 are discussed. Haze layers apparently associated with boreal fires were enriched in hydrocarbons and NO(y), with emission factors corresponding closely to laboratory data for smoldering combustion. It is argued that atmospheric composition was strongly modified by wildfires during several periods of the ABLE 3A mission. The associated enhancement of NO(y) was smaller than observed for most other combustion processes but was nonetheless significant in the context of very low background concentrations. Ozone production in fire plumes was negligible. Ambient O3 was supplied by the stratosphere, with little direct input from midlatitude source during summer. It is argued that NO(y) was supplied about equally by the stratosphere and by wildfires. Hydrocarbons and CO appear to derive from biomass fires and from human activities.

Wofsy, S. C.↗

Airborne measurements of total reactive odd nitrogen (NO(y))

Airborne total reactive odd nitrogen measurements were made during August and September 1986 over the continental United States and off the west coast over the Pacific Ocean during NASA's Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation 2 program. Measurements were made in the marine and continental boundary layer and the free troposphere up to 6.1 km altitude. NO(y) mixing ratios between 24 pptv and more than 1 ppbv were found, with median values of 101 pptv in the marine boundary layer, 298 pptv in the marine free troposphere, and 288 pptv in the continental free troposphere, respectively. The marine troposphere exhibited layered structure which was also seen in the simultaneously measured ozone mixing ratio and dew point temperature. The averaged vertical NO(y) profile over the ocean does not show a distinct gradient. The NO(y) mixing ratio over the continent decreases with increasing altitude. The latter is consistent with our understanding that the continents are the major source region for these gases.

Huebler, G.↗

Ozone and aerosol distributions over the Amazon Basin during the wet season

Results are presented of O3 and aerosol measurements made in the lower troposphere from April 13 through May 10, 1987, as part of the wet season field experiment. Aircraft flights on the NASA Electra were conducted in the vicinity of Manaus, Brazil and between Manaus and the mouth of the Amazon River. Airborne O3 measurements were made in situ and with a lidar system pointed below the aircraft in nadir mode of operation. Data collection and results concerning the distributions of O3 and aerosols observed during the wet season from within the mixed layer to the middle troposphere over the central Amazon basin and between Manaus and Belem are discussed, and these observations are compared to the measurements obtained in the 1985 dry season. Ozone mixing ratio values are found to be lower than those of the 1985 dry season by 6-8 ppbv, indicating a strong removal process near the surface during wet season. It is also found that within the mixed layer O3 levels appeared to be lower over the forest compared to over the ocean.

Browell, Edward V.↗

Carbon monoxide over the Amazon Basin during the wet season

Measurements of the distribution of carbon monoxide in the lower atmosphere (150-5000 m) over the Amazon region of Brazil during the wet season, taken in conjunction with the 1987 NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment (ABLE 2B), are analyzed. About 100 hr of airborne, in situ CO measurements were obtained using a tunable diode laser system, providing insights into factors influencing the basin-scale distribution of CO in the Amazonian troposphere during wet season conditions. Distribution of CO over the altitudes 0.15-4.5 km was influenced by such factors as surface emissions from biological sources and long-range transport of pollutants from Northern Hemisphere sources. It is noted that the disruption of mixed layer growth and decay processes has a particularly important influence on CO concentration in the daytime lower troposphere and that the correlation of CO with O3 was positive under conditions influenced by Northern Hemisphere air and negative under all other conditions observed.

Harriss, R. C.↗

Atmospheric peroxyacetyl nitrate measurements over the Brazilian Amazon Basin during the wet season - Relationships with nitrogen oxides and ozone

An analysis is presented on the distribution and variability of PAN as well as its relationship with measured chemical and meteorological parameters. The chemicals of most interest for which measurements were available are PAN, NO(x), O3, CO, and C2Cl4. PAN was measured by the electron capture gas chromatographic technique, and the technique for calibrations and measurements are detailed. Data show that significant concentrations of PAN (5-125 ppt) are present during the wet season and this PAN is 1-5 times more abundant than NO(x). PAN levels at different atmospheric locations are discussed, and it is noted that PAN shows evidence of a possible latitudinal gradient in the free troposphere, with values falling rapidly from the northern midlatitudes toward the equator. High correlations between O3 and PAN levels suggest that nonmethane hydrocarbons may contribute significantly to high O3 in the free troposphere. Evidence indicates that virtually all of the NO(x) above 4 km could result from PAN decomposition.

Singh, H. B.↗

An intercomparison of airborne nitric acid measurements

Results are reported on the performance of (1) denuder-tube/chemiluminescent, (2) nylon-filter/ion-chromatography, and (3) tunable-diode-laser/multipath-absorption HNO3 measurement instruments during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instrument designs, test protocols, and CITE 2 flights are described, and the results are presented in extensive graphs and discussed in detail. The data obtained with the three instruments are shown to be in very poor agreement at mixing ratios below 150 parts per trillion by volume (pptv), with significant discrepancies even at higher levels. Instrument (3) gave systematically higher values than (1) and (2). It is concluded that none of the instruments is accurate enough for reliable use at normal atmospheric HNO3 levels (around 100 pptv).

Gregory, G. L.↗

An intercomparison of airborne nitrogen dioxide instruments

Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).

Gregory, G. L.↗

Peroxyacetyl nitrate measurements during CITE 2 - Atmospheric distribution and precursor relationships

Results are reported from airborne PAN measurements obtained at altitudes 0-6 km over the continental U.S. and the eastern Pacific during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The CITE 2 flights and instrumentation are described, and the results are presented in extensive graphs and characterized in detail. It is shown that PAN is an important reactive N-containing species in the troposphere. Although the PAN mixing ratios were highly variable, in general high mixing ratios of 100-300 parts per trillion by volume (pptv) were found at 4-6 km, and very low ratios (5-20 pptv) were detected in the marine boundary layer. Good correlation was seen between the CITE 2 PAN values and those for O3, NO(y), NO(x), HNO3, C2H6, CO, and CFCl3.

Singh, H. B.↗

Aircraft measurements of NO(x) over the eastern Pacific and continental United States and implications for ozone production

Results are reported from airborne measurements of NO, NO2, O3, and CO obtained in the free troposphere (FT) and boundary layer (BL) over the western U.S. and eastern Pacific during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The aircraft instrumentation and the CITE 2 flight protocols are described, and the results are presented in extensive tables and graphs. Over the ocean the median mixing ratios for NO and NO2 were found to be 4.0 and 10.4 parts per trillion by volume (pptv), respectively, in the BL and 12.4 and 18.0 pptv in the FT; the corresponding values over land were 34.5 and 75.0 pptv in the BL and 13.0 and 36.0 pptv in the FT. in continental air masses. NO(x) is shown to be positively correlated with O3 and CO and negatively correlated with dewpoint over the ocean, whereas over land NO(x) was positively correlated with O3, CO, and dewpoint.

Carroll, M. A.↗