B. Wert

Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide

During the fall 1997 North Atlantic Regional Experiment (NARE 97), two separate intercomparisons of aircraft-based carbon monoxide measurement instrumentation were conducted. On September 2, CO measurements were simultaneously made aboard the National Oceanic and Atmospheric Administration (NOAA) WP-3 by vacuum ultraviolet (VUV) fluorescence and by tunable diode laser absorption spectroscopy (TDLAS). On September 18, an intercomparison flight was conducted between two separate instruments, both employing the VUV fluorescence method, on the NOAA WP-3 and the U.K. Meteorological Office C-130 Hercules. The results indicate that both of the VUV fluorescence instruments and the TDLAS system are capable of measuring ambient CO accurately and precisely with no apparent interferences in 5 s. The accuracy of the measurements, based upon three independent calibration systems, is indicated by the agreement to within 11% with systematic offsets of less than 1 ppbv. In addition, one of the groups participated in the Measurement of Air Pollution From Satellite (MAPS) intercomparison [Novelli et al., 1998] with a different measurement technique but very similar calibration system, and agreed with the accepted analysis to within 5%. The precision of the measurements is indicated by the variability of the ratio of simultaneous measurements from the separate instruments. This variability is consistent with the estimated precisions of 1.5 ppbv and 2.2 ppbv for the 5 s average results of the C-130 and the WP-3 instruments, respectively, and indicates a precision of approximately 3.6% for the TDLAS instrument. The excellent agreement of the instruments in both intercomparisons demonstrates that significant interferences in the measurements are absent in air masses that ranged from 7 km in the midtroposphere to boundary layer conditions including subtropical marine air and continental outflow with embedded urban plumes. The intercomparison of the two VUV instruments that differed widely in their design indicates that the VUV fluorescence technique for CO measurements is not particularly sensitive to the details of its implementation. These intercomparisons help to establish the reliability of ambient CO measurements by the VUV fluorescence technique.

Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern United States

[1] We compare tropospheric measurements of nitrogen dioxide (NO2) and formaldehyde (HCHO) from the Global Ozone Monitoring Experiment (GOME) satellite instrument with in situ measurements over eastern Texas and the southeast United States. On average, the GOME and in situ measurements of tropospheric NO2 and HCHO columns are consistent despite pronounced sampling differences. The geometric mean in situ to GOME ratios over the campaign are 1.08 for NO2 and 0.84 for HCHO, with corresponding geometric standard deviations of 1.27 and 1.38. The correlation of the observed column spatial variability between the two NO2 measurement sets is encouraging before (r 2 = 0.54, n = 18) and after (r 2 = 0.67, n = 18) correcting for a sampling bias. Mean relative vertical profiles of HCHO and NO2 calculated with a global three-dimensional model (GEOS-CHEM) and used in the GOME retrieval are highly consistent with in situ measurements; differences would affect the retrieved NO2 and HCHO columns by a few percent. GOME HCHO columns over eastern Texas include contributions from anthropogenic volatile organic compound (VOC) emissions but are dominated by biogenic VOC emissions at the regional scale in August–September when HCHO columns are within 20% of those over the southeastern United States. In situ measurements show that during summer the lowest 1500 m (the lower mixed layer) contains 75% of the tropospheric NO2 column over Houston and Nashville, and 60% of the HCHO column over Houston. Future validation of space-based measurements of tropospheric NO2 and HCHO columns over polluted regions should include coincident in situ measurements that span the entire satellite footprint, especially in the heterogeneous mixed layer. INDEX TERMS: 0315 Atmospheric Composition and Structure: Biosphere/atmosphere interactions; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere— composition and chemistry; 0394 Atmospheric Composition and Structure: Instruments and techniques;

Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 Southern Oxidants Study

Isoprene (ISOP) and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK), were measured at an urban forested site in Nashville, Tennessee, as part of the 1999 Southern Oxidants Study (SOS). Hourly observations were performed at Cornelia Fort Airpark for a 4 week period between June 13 and July 14. At the midday photochemical peak (1200 local standard time, LST), average mixing ratios of isoprene, MACR, and MVK were 410 parts per trillion by volume (pptv), 240 pptv, and 430 pptv, respectively. Median isoprene, MACR, and MVK mixing ratios were 400 pptv, 200 pptv, and 360 pptv, respectively, at 1200 LST. An emissions inventory calculation for Davidson County, encompassing Nashville, suggests that MACR and MVK were produced predominately from isoprene oxidation rather than direct combustion emissions. The observations are compared with results from two chemical models: a simple sequential reaction scheme and a one-dimensional (1-D) numerical box model. The daytime ratios of MVK/ISOP and MACR/ISOP varied in a systematic manner and can be reproduced by the analytical solution of the sequential reaction scheme. Air masses with more photochemically aged isoprene were observed during SOS 1999 at Cornelia Fort (0.3-1.6 hours) compared to the SOS 1990 canopy study at Kinterbish (0.1-0.6 hours). This is consistent with the proximity of the tower inlets to the forest canopies during both campaigns. Isoprene had a chemical lifetime of 20 min at the average observed midday HO mixing ratio of 8 x 10 6 molecules/cm 3 . As a result, significant conversion of isoprene to its oxidation products was observed on the timescale of transport from the dense forest canopies surrounding Nashville. The systematic diurnal behavior in the MVK/MACR ratio can also be simulated with a 1-D photochemical box model. General agreement between the observations of MACR and MVK during SOS 1999 with the two chemical models suggests we have a comprehensive understanding of the first few stages of isoprene oxidation in this urban forested environment.

Direct measurements of urban OH reactivity during Nashville SOS in summer 1999

Emissions of volatile chemicals control the hydroxyl radical (OH), the atmospheres main cleansing agent, and thus the production of secondary pollutants. Accounting for all of these chemicals can be difficult, especially in environments with mixed urban and forest emissions. The first direct measurements of the atmospheric OH reactivity, the inverse of the OH lifetime, were made as part of the Southern Oxidant Study (SOS) at Cornelia Fort Airpark in Nashville, TN in summer 1999. Measured OH reactivity was typically 11 s(-1). Measured OH reactivity was 1.4 times larger than OH reactivity calculated from the sum of the products of measured chemical concentrations and their OH reaction rate coefficients. This difference is statistically significant at the 1sigma uncertainty level of both the measurements and the calculations but not the 2sigma uncertainty level. Measured OH reactivity was 1.3 times larger than the OH reactivity from a model that uses measured ambient concentrations of volatile organic compounds (VOCs), NO, NO2, SO2, and CO. However, it was within approximately 10% of the OH reactivity from a model that includes hydrocarbon measurements made in a Nashville tunnel and scaled to the ambient CO at Cornelia Fort Airpark. These comparisons indicate that 30% of the OH reactivity in Nashville may come from short-lived highly reactive VOCs that are not usually measured in field intensive studies or by US EPAs Photochemical Assessment Monitoring Stations.

Springtime photochemistry at northern mid and high latitudes

which increases rapidly during spring. Unlike in other tropospheric experiments, observed H2O2 concentrations are a factor of 2–10 lower than those simulated by the model. The required scavenging timescale to reconcile the model overestimates shows a rapid seasonal decrease down to 0.5–1 day in May, which cannot be explained by known mechanisms. This loss of H2O2 implies a large loss of HOx resulting in decreases in O3 production (10–20%) and OH concentrations (20–30%). Photolysis of CH2O, either transported into the region or produced by unknown chemical pathways, appears to provide a significant HOx source at 6–8 km at high latitudes. The rapid increase of in situ O3 production in spring is fueled by concurrent increases of the primary HOx production and NO concentrations. Long-lived reactive nitrogen species continue to accumulate at mid and high latitudes in spring. There is a net loss of NOx to HNO3 and PAN throughout the spring, suggesting that these long-term NOx reservoirs do not provide a net source for NOx in the region. In situ O3 chemical loss is dominated by the reaction of O3 and HO2, and not that of O( 1 D) and H2O. At midlatitudes, there is net in situ chemical production of O3 from February to May. The lower free troposphere (1–4 km) is a region of significant net O3 production. The net production peaks in April coinciding with the observed peak of column O3 (0–8 km). The net in situ O3 production at midlatitudes can explain much of the observed column O3 increase, although it alone cannot explain the observed April maximum. In contrast, there is a net in situ O3 loss from February to April at high latitudes. Only in May is the in situ O3 production larger than loss. The observed continuous increase of column O3 at high latitudes throughout the spring is due to transport from other tropospheric regions or the stratosphere not in situ photochemistry. INDEX TERMS: 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; KEYWORDS: springtime, ozone, HOx, oxidation, reactive nitrogen