Yin-Nan Lee

Ozone formation at a rural site in the southeastern United States

Trace gas measurements pertinent to understanding the transport and photochemical formation of O3 were made at a surface site in rural Georgia as part of the Southern Oxidant Study during the summer of 1991. It was found that there was a strong correlation between O3 and the oxidation products of NOx: O3(ppb) = 27 + 11.4 (NOy(ppb) − NOx(ppb)), r2 = 0.78. This fit is similar to that observed at other rural sites in eastern North America and indicates a nominal background O3 level of 27 ppb; values higher than 27 ppb are due to photochemical production in the recent past, which varied from near zero to ≈50 ppb. The origin of the O3 above background was investigated by using a free radical budget equation to calculate an in situ O3 production rate in terms of measured concentrations of NO and free radical precursors (O3, HCHO, peroxides, and other carbonyls). A comparison of observed and predicted diurnal trends in O3 indicates significant O3 production in the afternoon at a time when O3 concentration is either steady or decreasing. The afternoon near-surface layer is thereby a source region for O3 which can be exported. In situ production accounts for approximately one half of the morning increase in O3 concentration on days with high O3; the remainder is due to entrainment of dirty air aloft by the growing convective boundary layer. Additional evidence for the role of vertical transport in controlling the hour-to-hour changes in O3 is found in the diurnal cycles of SO2 and HNO3 which also have rapid increases in the morning. The day-to-day variability of O3 was investigated using a back trajectory model. NOy concentration at the measurement site could be reasonably accounted for by considering NOx emission sources located within 1-day transport distance. In as much as there is a strong correlation between O3 and NOy, the coincidence between trajectory location and NOx emission sources appears to be an important factor influencing midday O3 concentration. Hydrocarbon measurements are consistent with NOx being the limiting factor for formation of O3.

Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville/Middle Tennessee Ozone Study

Airborne measurements of formaldehyde (FA), glycolaldehyde (GA), glyoxal (GL), methylglyoxal (MG), and pyruvic acid (PD) were made on board instrumented aircraft platforms, the Department of Energy G1 and National Oceanic and Atmospheric Administration P3 (FA only), during the 1995 Nashville/Middle Tennessee Ozone Study. FA data determined on these two aircraft during three intercomparison flights agreed to within ∼10%. The mean and median (in parentheses) concentrations observed within the boundary layer ( 0.8) observed between FA and two other isoprene products, GA and MG. Further, the magnitudes of the nonzero FA intercept exhibited in these correlation plots are found to qualitatively agree with the fraction of precursors that did not concomitantly produce GA and MG. Inspection of specific flights showed direct evidence of the dominance of isoprene as a precursor for FA, appreciable contribution of FA to CO, and negligible decay of FA overnight. Because of the dominant role isoprene plays as a precursor of FA, FA could be used as a proxy of isoprene for assessing the applicability of various versions of biogenic emission inventory.

Dependence of ozone production on NO and hydrocarbons in the troposphere

An expression for the production rate of 03, P(O 3), is derived based on a radical budget equation applicable to low and high NOx conditions. Differentiation of this equation with respect to NO or hydrocarbons (HC) gives an approximate analytic formula in which the relative sensitivity of P(O3) to changes in NO or HC depends only on the fraction of radicals which are removed by reactions with NOx. This formula is tested by comparison with results from a photochemical calculation driven by trace gas observations from the 1995 Southern Oxidants Study (SOS) campaign in Nashville, Tennessee.

Ozone production in the New York City urban plume

In the summer of 1996 the Department of Energy G-1 aircraft was deployed in the New York City metropolitan area as part of the North American Research Strategy for Tropospheric Ozone-Northeast effort to determine the causes of elevated O3 levels in the northeastern United States. Measurements of O3, O3 precursors, and other photochemically active trace gases were made upwind and downwind of New York City with the objective of characterizing the O3 formation process and its dependence on ambient levels of NOx and volatile organic compounds (VOCs). Four flights are discussed in detail. On two of these flights, winds were from the W-SW, which is the typical direction for an O3 episode. On the other two flights, winds were from the NW, which puts a cleaner area upwind of the city. The data presented include plume and background values of O3, CO, NOx, and NOy concentration and VOC reactivity. On the W-SW flow days O3 reached 110 ppb. According to surface observations the G-1 intercepted the plume close to the region where maximum O3 occurred. At this point the ratio NOx/NOy was 20–30%, indicating an aged plume. Plume values of CO/NOy agree to within 20% with emission estimates from the core of the New York City metropolitan area. Steady state photochemical calculations were performed using observed or estimated trace gas concentrations as constraints. According to these calculations the local rate of O3 production P(O3) in all four plumes is VOC sensitive, sometimes strongly so. The local sensitivity calculations show that a specified fractional decrease in VOC concentration yields a similar magnitude fractional decrease in P(O3). Imposing a decrease in NOx, however, causes P(O3) to increase. The question of primary interest from a regulatory point of view is the sensitivity of O3 concentration to changes in emissions of NOx and VOCs. A qualitative argument is given that suggests that the total O3 formed in the plume, which depends on the entire time evolution of the plume, is also VOC sensitive. Indicator ratios O3/NOz and H2O2/NOz mainly support the conclusion that plume O3 is VOC sensitive.

Peroxy radical concentration and ozone formation rate at a rural site in the southeastern United States

As part of the Southern Oxidants Study, Brookhaven National Laboratory operated an intensive measurement site near Metter, Georgia, during parts of the summers of 1991 and 1992. Measurements were made of photochemically active trace gases and meteorological parameters relevant to determining causes for elevated ambient ozone concentration. The 1992 data set was used to calculate peroxy radical concentration and ozone formation rate based on determining the departure from the photostationary state (PSS) and based on a radical budget equation, such as applied previously to the 1991 data set. Averaged over the 28-day experimental period, we find maximum radical production occurring near noon at 2.5 ppb h−1, maximum peroxy radical concentration also occurring near noon at 80 ppt, and maximum ozone production of 8 ppb h−1 occurring near 1000 EST. Ozone photolysis accounts for 55% of radical production, HCHO and other carbonyl compounds about 40%. The radical budget and PSS methods depend in different ways on atmospheric photochemistry and a comparison between them affords a test of our understanding of the photochemical production of O3. We find that these methods agree to the extent expected based on uncertainty estimates. For the data set as a whole, the median estimate for fractional error in hourly average peroxy radical concentration determined from the radical budget method is approximately 30% and from the PSS method, 50%. Error estimates for the PSS method are highly variable, becoming infinite as peroxy radical concentration approaches zero. This behavior can be traced back to the difference form of the PSS equations. To conduct a meaningful comparison between the methods, the data set was segregated into subsets based on PSS uncertainty estimates. For the low-uncertainty subset, consisting of a third of the whole data set, we find that the ratio of peroxy radical concentration predicted from the PSS method to that predicted from the radical budget method to be 1.22±32%.

Atmospheric carbonyl compounds at a rural southeastern United States site

Atmospheric concentrations of a series of carbonyl compounds known as formaldehyde (FA), acetaldehyde (AC), acetone (AN), glycolaldehyde (GA), glyoxal (GL), methylglyoxal (MG), glyoxylic acid (GD), and pyruvic acid (PD) were measured at a rural site in Georgia in summers of 1991 and 1992. The midafternoon median concentrations, in parts per billion, determined for 1991–1992 were FA, 3.6/3.1; AC, 0.58/0.74; AN, 1.7/1.8; GA, 0.21/0.26; GL, 0.02/0.09; MG, 0.03/0.08; GD, 0.46; and PD, 0.11, the latter two for 1992 only. All of the carbonyls except AC and AN exhibited a strong diurnal dependence, with maxima in the midafternoon and minima during the night, consistent with a rapid in situ photochemical production in the daytime and a loss by dry deposition in a shallow inversion during the night. FA correlated well with O3, GA and MG, consistent with their photochemical production near the surface at the measurement site. GL and MG showed the strongest correlation among all species, suggesting common origins as well as similar atmospheric lifetimes. The presence of GA, MG, and GL along with FA at the observed relative concentrations are consistent with laboratory developed isoprene oxidation mechanism and the expectation that isoprene represents a major reactive hydrocarbon in this rural region. At the concentrations observed, these carbonyls serve as important radical sources. The contribution of FA accounts for half of that by O3 and the higher carbonyls approximates half of that by FA. With respect to production of peroxyacetyl nitrate, isoprene contributes as much as acetaldehyde. These results lend further credence to the notion that isoprene plays a pivotal role in photochemical processes, especially in rural environments.

Intercomparison of near real time monitors of PM2.5 nitrate and sulfate at the U.S. Environmental Protection Agency Atlanta Supersite

[1] Five new instruments for semicontinuous measurements of fine particle (PM2.5) nitrate and sulfate were deployed in the Atlanta Supersite Experiment during an intensive study in August 1999. The instruments measured bulk aerosol chemical composition at rates ranging from every 5 min to once per hour. The techniques included a filter sampling system with automated water extraction and online ion chromatographic (IC) analysis, two systems that directly collected particles into water for IC analysis, and two techniques that converted aerosol nitrate or sulfate either catalytically or by flash vaporization to gaseous products that were measured with gas analyzers. During the one-month study, 15-min integrated nitrate concentrations were low, ranging from about 0.1 to 3.5 μg m -3 with a mean value of 0.5 μg m -3 . Ten-minute integrated sulfate concentrations varied between 0.3 and 40 μg m -3 with a mean of 14 μg m -3 . By the end of the one-month study most instruments were in close agreement, with r-squared values between instrument pairs typically ranging from 0.7 to 0.94. Based on comparison between individual semicontinuous devices and 24-hour integrated filter measurements, most instruments were within 20-30% for nitrate (∼0.1-0.2 μg m -3 ) and 10-15% for sulfate (1-2 leg m -3 ). Within 95% confidence intervals, linear regression fits suggest that no biases existed between the semicontinuous techniques and the 24-hour integrated filter measurements of nitrate and sulfate;, however, for nitrate, the semicontinuous intercomparisons showed significantly less variability than intercomparisons amongst the 24-hour integrated filters.

Ozone production efficiency in an urban area

Ozone production efficiency can be defined as the number of molecules of oxidant (O 3 + NO 2 ) produced photochemically when a molecule of NO X (NO + NO 2 ) is oxidized. It conveys information about the conditions under which O 3 is formed and is an important parameter to consider when evaluating impacts from NO x emission sources. We present calculational and observational results on ozone production efficiency based on measurements made from aircraft flights in the Phoenix metropolitan area in May and June of 1998. Constrained steady state box model calculations are used to relate a ratio of O 3 production rate to NO x consumption rate (i.e., P(0 3 )/P(NO z )) to a VOC to NO 2 ratio of OH reactivity. Lagrangian calculations show how this ratio generally increases with time due to oxidation chemistry and plume dilution. City to city differences in ozone production efficiency can be attributed to corresponding differences in VOC to NO 2 reactivity ratio which in turn reflect emission patterns. Ozone production efficiencies derived from aircraft measurements in 20 plumes show a dependence on NO x concentration similar to that calculated for P(0 3 )/P(NO z ). Calculations are based on data from a single location but are believed to be applicable to a wide range of plumes from different areas.

Tropospheric formaldehyde concentration at the Mauna Loa Observatory during the Mauna Loa Observatory Photochemistry Experiment 2

The concentration of formaldehyde at Mauna Loa Observatory, Hawaii, was determined during four Mauna Loa Observatory Photochemistry Experiment 2 (MLOPEX 2) measurement intensives between September 1991 and August 1992. The observed diurnal variations, 200–900 parts per trillion by volume (pptv) during daytime and 60–200 pptv during nighttime, resulted mainly from the local air circulation pattern whereby island modified marine boundary layer air prevailed during the day and free tropospheric air dominated during the night. A seasonal variation was also observed; the median/mean values of all data points are: 149/196, 129/149, 143/178, and 181/211 pptv for autumn, winter, spring, and summer intensives, respectively. During nighttime downslope flow periods which brought in free tropospheric air to the measurement site, the formaldehyde concentrations (median/mean) were 122/123, 110/112, 120/125, and 140/137 pptv for autumn, winter, spring, and summer, respectively. This seasonal dependence may be attributable to changes in solar insolation and NO concentrations. A simple box model calculation constrained by the experimentally determined concentrations of CH3OOH yielded a formaldehyde concentration (without/with heterogeneous removal) for free tropospheric air, at 7°C, of 155/140, 125/115, 210/195, and 220/205 pptv for autumn, winter, spring and summer, respectively. The calculated values are in good agreement with the measured concentrations for winter (within 27/15%, without/with heterogeneous removal) and fall (within 14/5%), but are significantly higher for spring (75/63%) and summer (57/46%).

NO y lifetimes and O3 production efficiencies in urban and power plant plumes: Analysis of field data

In an effort to describe and characterize power plant plumes in the Nashville region, emissions from a small power plant (Gallatin) and a large power plant (Paradise) were examined using data obtained on the Department of Energy G-1 airborne sampling platform. Observations made on July 3, 7, 15, 17, and 18, 1995, were compiled, and a kinetic analysis of the chemical evolution of the power plant plumes was performed. Analysis of the power plant plume data revealed a very active photochemistry, as had been determined previously for the urban plume. Ozone production efficiencies (OPE), defined as the number of molecules of O3 formed per NOx molecule consumed, were found to be 3 for Gallatin and 2 for Paradise. Lifetimes for NOx (2.8 and 4.2 hours) and NOy (7.0 and 7.7 hours) were determined for Gallatin and Paradise, respectively. These NOx and NOy lifetimes imply rapid loss of NOz (NOz is assumed to be primarily HNO3). Lifetimes for NOz are calculated to be 3 and 2.5 hours for Gallatin and Paradise, respectively. A sensitivity analysis indicates that the Gallatin NOz lifetime could be as long as 5 hours, bringing it into agreement with the value determined for the Nashville urban plume. It is unlikely that the Paradise NOz lifetime is as long as 4 hours. If NOz loss is attributed to dry deposition, a 3 hour lifetime implies a deposition velocity greater than 10 cm s−1, which is much faster than expected based on accepted theory. Possible reasons for this discrepancy are discussed.