Search

Wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been conducted, coupling between interconnected chemical and meteorological processes remains an insufficiently studied research area. Gaps in understanding the coupled chemical–meteorological interactions that drive high-pollution events make identification of the most effective air-basin specific emission control strategies challenging. To address this, a September 2019 workshop occurred with the goal of planning a future research campaign to investigate air quality in western U.S. basins. Approximately 120 people participated, representing 50 institutions and five countries. Workshop participants outlined the rationale and design for a comprehensive wintertime study that would couple atmospheric chemistry and boundary layer and complex-terrain meteorology within western U.S. basins. Participants concluded the study should focus on two regions with contrasting aerosol chemistry: three populated valleys within Utah (Salt Lake, Utah, and Cache Valleys) and the San Joaquin Valley in California. This paper describes the scientific rationale for a campaign that will acquire chemical and meteorological datasets using airborne platforms with extensive range, coupled to surface-based measurements focusing on sampling within the near-surface boundary layer, and transport and mixing processes within this layer, with high vertical resolution at a number of representative sites. No prior wintertime basin-focused campaign has provided the breadth of observations necessary to characterize the meteorological–chemical linkages outlined here, nor to validate complex processes within coupled atmosphere–chemistry models.

During the Benzene and other Toxics Exposure (BEE-TEX) study, a remote sensing network based on long path Differential Optical Absorption Spectroscopy (DOAS) was set up in the Manchester neighborhood beside the Ship Channel of Houston, Texas in order to perform Computer Aided Tomography (CAT) scans of hazardous air pollutants. On 18–19 February 2015, the CAT scan network detected large nocturnal plumes of toluene and xylenes most likely associated with railcar loading and unloading operations at Ship Channel petrochemical facilities. The presence of such plumes during railcar operations was confirmed by a mobile laboratory equipped with a Proton Transfer Reaction—Mass Spectrometer (PTR-MS), which measured transient peaks of toluene and C 2 -benzenes of 50 ppb and 57 ppb respectively around 4 a.m. LST on 19 February 2015. Plume reconstruction and source attribution were performed using the 4D variational data assimilation technique and a 3D micro-scale forward and adjoint air quality model based on both tomographic and PTR-MS data. Inverse model estimates of fugitive emissions associated with railcar transfer emissions ranged from 2.0 to 8.2 kg/hr for toluene and from 2.2 to 3.5 kg/hr for xylenes in the early morning of 19 February 2015.

The February–March 2014 deployment of the National Aeronautics and Space Administration (NASA) Airborne Tropical Tropopause Experiment (ATTREX) provided unique in situ measurements in the western Pacific tropical tropopause layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the Convective Transport of Active Species in the Tropics (CONTRAST) and the Coordinated Airborne Studies in the Tropics (CAST) airborne campaigns based in Guam using lower-altitude aircraft (see companion articles in this issue). The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes, as well as for evaluation and improvement of global-model representations of TTL processes. The ATTREX data are publicly available online (at https://espoarchive.nasa.gov/).

Aromatic hydrocarbons are well known air toxics which are regulated by the US EPA and other air quality agencies. Accurate, long-term monitoring of these compounds at low part-per-billion levels, as well as identifying emission point sources is therefore crucial to protect human health in neighborhoods near large emission sources. Here we present a new long-path differential optical absorption spectroscopy (LP-DOAS) instrument specifically designed to monitor aromatic hydrocarbons. The system is based on a novel dual - light emitting diode (LED) light source, which eliminates the requirement to suppress spectrometer stray light. This light source, together with a high stability fiber-based sending/receiving telescope, allows the measurement of aromatic hydrocarbons on once-folded absorptions paths of 200–1200 m length. The new instrument shows very good agreement with simultaneous in-situ measurements if inhomogeneities of the trace gas spatial distributions are considered. The new instrument performed well during a three-month field test as an automated fence-line monitor at a refinery, successfully distinguishing upwind background levels of ∼1 ppb from emissions reflected in elevated mixing ratios of 3–4 ppb. A two-dimensional measurement network based on two identical LP-DOAS instruments operating on seven crossed light paths was operated successfully in Houston, TX. Qualitative and quantitative analysis of two events with toluene and xylene plumes demonstrate how this setup can be used to derive the spatial distribution of aromatic hydrocarbons, and identify point sources.

Nighttime chemistry in the troposphere is closely tied to the dinitrogen pentoxide (N2O5) budget, but high uncertainties remain regarding the model representation of the heterogeneous hydrolysis of N2O5 on aerosol particles. In this study we used the community model WRF-Chem to simulate a 3-day period during the California Nexus (CalNex) Campaign in 2010. We extended WRF-Chem to include the heterogeneous hydrolysis of N2O5 and contrasted the impact of different published parameterizations of N2O5 heterogeneous hydrolysis on the spatial distribution of uptake coefficients and the resulting N2O5 concentrations. For all the cases, modeled N2O5 uptake coefficients showed strong spatial variability, with higher values in the nocturnal boundary layer compared to the residual layer, especially in environments with high relative humidities, such as over the ocean and along the coast. The best agreement of modeled and observed uptake coefficients was obtained using the parameterization by Davis et al. (2008) combined with the treatment of organic coating by Riemer et al. (2009). For this case the temporal evolution of lower boundary layer N2O5 mixing ratios was reproduced well, and the predictions of surface mixing ratios of ozone and NOx were improved. However, the model still overpredicted the uptake coefficients in the residual layer and consequently underpredicted N2O5 concentrations in the residual layer. This study also highlights that environments with low relative humidities pose a challenge for aerosol thermodynamic models in calculating aerosol water uptake, and this impacts N2O5 heterogeneous hydrolysis parameterizations.

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Because of the importance of HONO as a radical reservoir, consistent and accurate measurements of its concentration are needed. As part of SHARP (Study of Houston Atmospheric Radical Precursors), time series of HONO were obtained by six different measurement techniques on the roof of the Moody Tower at the University of Houston. Techniques used were long path differential optical absorption spectroscopy (DOAS), stripping coil-visible absorption photometry (SC-AP), long path absorption photometry (LOPAP®), mist chamber/ion chromatography (MC-IC), quantum cascade-tunable infrared laser differential absorption spectroscopy (QC-TILDAS), and ion drift-chemical ionization mass spectrometry (ID-CIMS). Various combinations of techniques were in operation from 15 April through 31 May 2009. All instruments recorded a similar diurnal pattern of HONO concentrations with higher median and mean values during the night than during the day. Highest values were observed in the final 2 weeks of the campaign. Inlets for the MC-IC, SC-AP, and QC-TILDAS were collocated and agreed most closely with each other based on several measures. Largest differences between pairs of measurements were evident during the day for concentrations

The California Research at the Nexus of Air Quality and Climate Change (CalNex) field study was conducted throughout California in May, June, and July of 2010. The study was organized to address issues simultaneously relevant to atmospheric pollution and climate change, including (1) emission inventory assessment, (2) atmospheric transport and dispersion, (3) atmospheric chemical processing, and (4) cloud-aerosol interactions and aerosol radiative effects. Measurements from networks of ground sites, a research ship, tall towers, balloon-borne ozonesondes, multiple aircraft, and satellites provided in situ and remotely sensed data on trace pollutant and greenhouse gas concentrations, aerosol chemical composition and microphysical properties, cloud microphysics, and meteorological parameters. This overview report provides operational information for the variety of sites, platforms, and measurements, their joint deployment strategy, and summarizes findings that have resulted from the collaborative analyses of the CalNex field study. Climate-relevant findings from CalNex include that leakage from natural gas infrastructure may account for the excess of observed methane over emission estimates in Los Angeles. Air-quality relevant findings include the following: mobile fleet VOC significantly declines, and NO_x emissions continue to have an impact on ozone in the Los Angeles basin; the relative contributions of diesel and gasoline emission to secondary organic aerosol are not fully understood; and nighttime NO_3 chemistry contributes significantly to secondary organic aerosol mass in the San Joaquin Valley. Findings simultaneously relevant to climate and air quality include the following: marine vessel emissions changes due to fuel sulfur and speed controls result in a net warming effect but have substantial positive impacts on local air quality.

[1] Ozone (O3) and secondary fine particles come from the atmospheric oxidation chemistry that involves the hydroxyl radical (OH) and hydroperoxyl radical (HO2), which are together called HOx. Radical precursors such as nitrous acid (HONO) and formaldehyde (HCHO) significantly affect the HOx budget in urban environments. These chemical processes connect surface anthropogenic and natural emissions to local and regional air pollution. Using the data collected during the Study of Houston Atmospheric Radical Precursors (SHARP) in spring 2009, we examine atmospheric oxidation chemistry and O3 production in this polluted urban environment. A numerical box model with five different chemical mechanisms was used to simulate the oxidation processes and thus OH and HO2 in this study. In general, the model reproduced the measured OH and HO2 with all five chemical mechanisms producing similar levels of OH and HO2, although midday OH was overpredicted and nighttime OH and HO2 were underpredicted. The calculated HOx production was dominated by HONO photolysis in the early morning and by the photolysis of O3 and oxygenated volatile organic compounds (OVOCs) in the midday. On average, the daily HOx production rate was 24.6 ppbv d−1, of which 30% was from O3 photolysis, 22% from HONO photolysis, 15% from the photolysis of OVOCs (other than HCHO), 14% from HCHO photolysis, and 13% from O3 reactions with alkenes. The O3 production was sensitive to volatile organic compounds (VOCs) in the early morning but was sensitive to NOx for most of afternoon. This is similar to the behavior observed in two previous summertime studies in Houston: the Texas Air Quality Study in 2000 (TexAQS 2000) and the TexAQS II Radical and Aerosol Measurement Project in 2006 (TRAMP 2006). Ozone production in SHARP exhibits a longer NOx-sensitive period than TexAQS 2000 and TRAMP 2006, indicating that NOx control may be an efficient approach for the O3 control in springtime for Houston. Results from this study provide additional support for regulatory actions to reduce NOx and reactive VOCs in Houston in order to reduce O3 and other secondary pollutants.

We evaluate predictions from the Community Multiscale Air Quality (CMAQ version 4.7.1) model against a suite of airborne and ground-based meteorological measurements, gas- and aerosol-phase inorganic measurements, and black carbon (BC) measurements over Southern California during the CalNex field campaign in May/June 2010. Ground-based measurements are from the CalNex Pasadena ground site, and airborne measurements took place onboard the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Navy Twin Otter and the NOAA WP-3D aircraft. BC predictions are in general agreement with observations at the Pasadena ground site and onboard the WP-3D, but are consistently overpredicted when compared to Twin Otter measurements. Adjustments to predicted inorganic mass concentrations, based on predicted aerosol size distributions and the AMS transmission efficiency, are shown to be significant. Owing to recent shipping emission reductions, the dominant source of sulfate in the L.A. Basin may now be long-range transport. Sensitivity studies suggest that severely underestimated ammonia emissions, and not the exclusion of crustal species (Ca^(2 +), K^+, and Mg^(2 +)), are the single largest contributor to measurement/model disagreement in the eastern part of the L.A. Basin. Despite overstated NO_x emissions, total nitrate concentrations are underpredicted, which suggests a missing source of HNO_3 and/or overprediction of deposition rates. Adding gas-phase NH_3 measurements and size-resolved measurements, up to 10 μm, of nitrate and various cations (e.g. Na^+, Ca^(2 +), K^+) to routine monitoring stations in the L.A. Basin would greatly facilitate interpreting day-to-day fluctuations in fine and coarse inorganic aerosol.

Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14–18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301–387 nm), visible (410–525 nm), and near infrared (900–1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O3, O4, NO2, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O4 observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O4 SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O3 observations overcomes this issue. Extensive sensitivity calculations show that the novel O3-scaling technique allows the retrieval of BrO and NO2 mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO2 mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS.

We reanalyze a data set of hydrocarbons in ambient air obtained by gas chromatography-mass spectrometry at a surface site in Pasadena in the Los Angeles basin during the NOAA California Nexus study in 2010. The number of hydrocarbon compounds quantified from the chromatograms is expanded through the use of new peak-fitting data analysis software. We also reexamine hydrocarbon removal processes. For alkanes, small alkenes, and aromatics, the removal is determined by the reaction with hydroxyl (OH) radicals. For several highly reactive alkenes, the nighttime removal by ozone and nitrate (NO3) radicals is also significant. We discuss how this nighttime removal affects the determination of emission ratios versus carbon monoxide (CO) and show that previous estimates based on nighttime correlations with CO were too low. We analyze model output from the Weather Research and Forecasting-Chemistry model for hydrocarbons and radicals at the Pasadena location to evaluate our methods for determining emission ratios from the measurements. We find that our methods agree with the modeled emission ratios for the domain centered on Pasadena and that the modeled emission ratios vary by 23% across the wider South Coast basin. We compare the alkene emission ratios with published results from ambient measurements and from tunnel and dynamometer studies of motor vehicle emissions. We find that with few exceptions the composition of alkene emissions determined from the measurements in Pasadena closely resembles that of motor vehicle emissions.

We present quantitative, fast time response measurements of formaldehyde (HCHO) onboard an aircraft using a Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) instrument. The HCHO measurement by PTR-MS is strongly humidity dependent and therefore airborne measurements are difficult and have not been reported. The PTR-MS instrument was run in the standard PTR-MS operating mode (de Gouw and Warneke, 2007), where about 15 volatile organic compounds (VOCs) are measured together with HCHO onboard the NOAA WP-3 aircraft during the CalNex 2010 campaign in California. We compare the humidity dependence determined in the laboratory with in-flight calibrations of HCHO and calculate the HCHO mixing ratio during all flights using the results from both. The detection limit (S/N = 1) for HCHO was between 100 pptv in the dry free troposphere and 300 pptv in the humid marine boundary layer for a one second acquisition time every 17 s. The PTR-MS measurements are compared with HCHO measurements using a DOAS instrument and a Hantzsch monitor at a ground site in Pasadena. The PTR-MS agreed with the DOAS within the stated uncertainties and was just outside the uncertainties with the Hantzsch. We also compare HCHO enhancement ratios in the Los Angeles basin and in the free troposphere with literature values and find good agreement. The usefulness of the PTR-MS HCHO measurements in atmospheric observations is demonstrated by following an isolated anthropogenic plume. The photochemical production of HCHO can be observed simultaneously with production of acetaldehyde and the photochemical degradation of aromatic compounds using the PTR-MS. The results show that PTR-MS seems a useful instrument to measure HCHO, but more inter-comparisons are needed.

For several decades, dinitrogen pentoxide (N2O5) has been recognized as an important reactive intermediate in the atmospheric chemistry of nitrogen oxides and nitrate aerosol, especially during nighttime. However, due to the lack of ambient observations of N2O5, the nocturnal nitrogen oxide chemistry could not be quantified until recent years. The objective of the present article is to assess the current state-of-the-art knowledge of N2O5 dynamics within the tropospheric aerosol. An up-to-date summary of N2O5 chemistry and major loss mechanisms are provided. Furthermore, techniques for measuring ambient N2O5 and an overview of typical N2O5 levels in the troposphere are described. In addition, model representations of N2O5 chemistry are reviewed along with key features of N2O5 vertical profiles based on numerical simulations. Lastly, the article provides the outstanding uncertainties and needs for further research into the atmospheric chemistry of N2O5. These include the need for better characterization of...

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j (NO 2 ) photolysis frequencies by nominally 17%, while aerosols reduced j (NO 2 ) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h −1 .

Nocturnal chemistry can play an important role in determining the initial morning conditions for daytime chemistry in urban areas. However, the impact on daytime O3 levels is difficult to assess as the suppression of vertical trace gas transport leads to highly altitude dependent nocturnal chemistry, in particular with respect to the removal and conversion of nitrogen oxides (NOx) and volatile organic compounds (VOC). One-dimensional (1-D) chemical transport model calculations for different nighttime vertical stabilities and different ozone formation regimes (i.e. NOx- vs. VOC-sensitive) were performed assuming a 1000 m high daytime boundary layer and a growing nocturnal boundary layer reaching 200 m height at the end of the night. Exclusion of NO3 chemistry from the model leads to daytime O3 concentration changes from −4% to +16% for different O3 sensitivities. In all cases strong nocturnal vertical concentration profiles of NOx, O3, NO3 and N2O5 and a dependence of these profiles on vertical stability were found at night. The nocturnal NOx loss averaged over the lowest 1000 m changes by 9–24% for different vertical stabilities and ozone sensitivities. The impact of nocturnal vertical stability leads to 7–12% difference in O3 concentration in the morning and ∼0–2.5% in the afternoon.

Nitrous acid is an important component of nighttime N-oxide chemistry, and provides a significant source of both OH and NO in polluted urban air masses shortly after sunrise. Several recent studies have called for new sources of HONO to account for daytime levels much higher than are consistent with current understanding. However, measurement of HONO is problematic, with most in-situ techniques reporting higher values than simultaneous optical measurements by long-path DOAS, especially during daytime. The discrepancy has been attributed to positive interference in the in-situ techniques, negative interference in DOAS retrievals, the difficulty of comparing the different air masses sampled by the methods, or combinations of these. During August and September 2006, HONO mixing ratios from collocated long-path DOAS and auto- mated mist-chamber/ion chromatograph (MC/IC) systems ranged from several ppbv during morning rush hour to daytime minima near 100 pptv. Agreement between the two techniques was excellent across this entire range during many days, showing that both instruments accurately measured HONO during this campaign. A small bias towards higher LP-DOAS observations at night can be attributed to slow vertical mixing leading to pronounced HONO profiles. A positive daytime bias of the MC/IC instrument during several days in late August/early September was correlated with photochemically produced compounds such as ozone, HNO 3 and HCHO, but not with NO2 ,N O x ,H O 2NO2, or the NO2 photolysis rate. While an interferant could not be identified organic nitrites appear a possible expla- nation for our observations.

Radical chemistry in the nocturnal urban boundary layer is dominated by the nitrate radical, NO3, which oxidizes hydrocarbons and, through the aerosol uptake of N2O5, indirectly influences the nitrogen budget. The impact of NO3 chemistry on polluted atmospheres and urban air quality is, however, not well understood, due to a lack of observations and the strong impact of vertical stability of the boundary layer, which makes nocturnal chemistry highly altitude dependent. Here we present long-path DOAS observations of the vertical distribution of the key nocturnal species O3, NO2, and NO3 during the TRAMP experiment in Summer 2006 in Houston, TX. Our observations confirm the altitude dependence of nocturnal chemistry, which is reflected in the concentration profiles of all trace gases at night. In contrast to other study locations, NO3 chemistry in Houston is dominated by industrial emissions of alkenes, in particular of isoprene, isobutene, and sporadically 1,3-butadiene, which are responsible for more than 70% of the nocturnal NO3 loss. The nocturnally averaged loss of NOx in the lowest 300 m of the Houston atmosphere is w0.9 ppb h �1 , with little day-to-day variability. A comparison with the daytime NOx loss shows that NO3 chemistry is responsible for 16–50% of the NOx loss in a 24-h period in the lowest 300 m of the atmosphere. The importance of the NO3 þ isoprene/1,3butadiene reactions implies the efficient formation of organic nitrates and secondary organic aerosol at night in Houston.

Atmospheric measurements were performed during a 1 month period in early summer of 1997 at the Dead Sea in Israel in an attempt to identify bromine monoxide BrO, and evaluate its effect on ozone chemistry. The differential optical absorption spectroscopy (DOAS) technique was utilized to identify and measure BrO present in the air masses. Concurrent to the DOAS measurements, continuous monitoring of SO2, NO/NOx, O3, and CO was performed. Filter samples for aerosol analysis and whole air canister samples for bromocarbon analysis were also collected. The present paper reports the complete comprehensive data set of the measurements at the Dead Sea site and is a continuation to our preliminary communication [Heberstreit et al., 1999]. The more complete data now available enable a more detailed examination of the sources and mechanisms of the reactive halogen species and the presentation of new conclusions. The results showed a diurnal repeating cycle of O3 and BrO variations, correlated with solar radiation and wind direction. During the elevated BrO events, where bromine oxide rose to daily maximum values often exceeding 100 ppt, a clear negative correlation with O3 was observed. During these episodes, the O3 regularly decreased from noontime levels of 50–80 ppb or higher down to 10–30 ppb and occasionally to levels below the detection limit of 2 ppb. The enhanced BrO levels were associated with southerly winds that are typical for the location during midday hours. This suggests that a possible source for the reactive bromine species is the interaction of atmospheric oxidants with bromide at the surface of the large salt pans located at the southern end of the Dead Sea. Research flights flown over the area showed that ozone destruction to levels well below the background values were observed over large areas of the Dead Sea Valley.

Recently, the influence of tropospheric clouds on zenith sky observations of atmospheric gases (O3, NO2, O4, H2O, and others) has been reported [Van Roozendael et al., 1994; Erle et al., 1995]. For measurements under heavy cloud cover, Erle et al. [1995] determined from simultaneously measured absorptions of different tropospheric species an average optical path for photons reaching the instrument of >100 km. This path length was much larger than expected from previous reports [Feigelson, 1981]. Thus an important question was whether the magnitude of the observation was a typical situation rather than a rare exception. Here we add a large set of new “cloud event” observations evaluated from data which were recorded in the Arctic, at midlatitudes, and the tropics. It is shown that the observed absorption enhancements of O3, H2O, and O4 perfectly coincide with indirect cloud indicators, i.e., changes in the average intensity and the color index as well as direct observations of cloud passages detected by satellite. In particular, we demonstrate that the observed optical paths have the same magnitude as the path lengths reported by Erle et al [1995], and thus optical paths under cloudy skies may indeed become much larger than previously reported. Besides these observations made during specific meteorological conditions we also studied optical paths continuously for several weeks in Arctic winter/spring conditions. We derived a frequency distribution of path lengths for cloudy skies with an average mean optical path of 29 km.

The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring 2007 and summer 2008 to investigate the impact of halogens on HOx (= OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + RO2), ozone (O3), nitrogen oxide (NO), nitric acid (HNO3), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer 2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly improve the ratio of OH to HO2 + RO2 and the correlation between predictions and observations. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2 + RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.

The Texas Environmental Research Consortium (TERC) funded significant components of the Second Texas Air Quality Study (TexAQS II), including the TexAQS II Radical and Aerosol Measurement Project (TRAMP) and instrumented flights by a Piper Aztec aircraft. These experiments called attention to the role of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. TRAMP instruments recorded daytime HCHO pulses as large as 32 parts per billion (ppb) originating from upwind industrial activities in the Houston Ship Channel, where in situ surface monitors detected HCHO peaks as large as 52 ppb. Moreover, Ship Channel petrochemical flares were observed to produce plumes of apparent primary HCHO. In one such combustion plume that was depleted of ozone by large emissions of oxides of nitrogen (NOx), the Piper Aztec measured a ratio of HCHO to carbon monoxide (CO) 3 times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares or mobile sources can increase peak ozone in Houston by up to 30 ppb. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of nighttime radicals (approximately30 parts per trillion [ppt] HO2). HONO may be formed heterogeneously on urban canopy or particulate matter surfaces and may be enhanced by organic aerosol of industrial or motor vehicular origin, such as through conversion of nitric acid (HNO3). Additional HONO sources may increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality models could enhance the simulated effectiveness of control strategies.

[1] Volatile organic compound (VOC) measurements were made during the summer 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) at Thompson Farm (TF), a continental site 25 km from the New Hampshire coast, and Appledore Island (AI), a marine site 10 km off the Maine coast. The 24 h mean total hydroxyl radical (OH) reactivity (±1σ) for the suite of VOCs was 4.15 (±2.64) s−1 at TF and 2.57 (±1.10) s−1 at AI. The larger range of reactivity at TF was dominated by isoprene and the monoterpenes (mean combined reactivity = 2.01 (±2.57) s−1). The impact of local anthropogenic hydrocarbon sources such as liquefied petroleum gas (LPG) leakage and fossil fuel evaporation was evident at both sites. During the campaign, a propane flux of 9 (±2) × 109 molecules cm−2 s−1 was calculated from the linear regression of the mean 0100–0400 local time mixing ratios at TF. This is consistent with fluxes observed in 2003 at sites spread throughout the coastal area of New Hampshire indicating that LPG tank leakage is a major hydrocarbon source throughout the region. Net monoterpene fluxes during ICARTT at TF were 6 (±2), 1.8 (±0.4), 1.2 (±0.6), and 0.4 (±0.5) × 109 molecules cm−2 s−1 for α-pinene, β-pinene, camphene, and limonene, respectively. Comparison to estimated NO3 and O3 loss rates indicate that gross monoterpene emission rates were approximately double the observed net fluxes at TF and comparable to current monoterpene nighttime emission inventory estimates for the northeast.

[1] The nocturnal nitrogen oxides, NO3 and N2O5, are important to the chemical transformation and transport of NOx, O3 and VOC. Their concentrations, sources and sinks are known to be vertically stratified in the nighttime atmosphere. In this paper, we report vertical profiles for NO3 and N2O5 measured from an aircraft (the NOAA P-3) as part of the New England Air Quality Study in July and August 2004. The aircraft data are compared to surface measurements made in situ from a ship and by long-path DOAS. Consistent with previous, vertically resolved studies of NO3 and N2O5, the aircraft measurements show that these species occur at larger concentrations and are longer lived aloft than they are at the surface. The array of in situ measurements available on the P-3 allows for investigation of the mechanisms that give rise to the observed vertical gradients. Selected vertical profiles from this campaign illustrate the role of biogenic VOC, particularly isoprene and dimethyl sulfide, both within and above the nocturnal and/or marine boundary layer. Gradients in relative humidity and aerosol surface may also create a vertical gradient in the rate of N2O5 hydrolysis. Low-altitude intercepts of power plant plumes showed strong vertical stratification, with plume depths of 80 m. The efficiency of N2O5 hydrolysis within these plumes was an important factor determining the low-level NOx and O3 transport or loss at night. Averages of nocturnal O3, NO2, NO3 and N2O5 binned according to altitude were consistent with the trends from individual profiles. While production rates of NO3 peaked near the surface, lifetimes of NO3 and N2O5 were maximum aloft, particularly in the free troposphere. Variability in NO3 and N2O5 was large and exceeded that of NO2 or O3 because of inhomogeneous distribution of NOx emissions and NO3 and N2O5 sinks.

Received 5 April 2007; revised 22 June 2007; accepted 7 August 2007; published 2 November 2007. [1] Trace gases including nitrogen dioxide (NO2), nitrate radical (NO3), ozone (O3), and a suite of volatile organic compounds (VOCs) were measured within the New England coastal marine boundary layer on Appledore Island (AI), Maine, USA as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) field campaign. These measurements, together with local meteorological records and published kinetic data were used to investigate nighttime NO3 chemistry at AI during the period of 8–28 July 2004. Among the VOCs, isoprene, monoterpenes and dimethylsulfide (DMS) were the dominant NO3 reactants; on average, DMS accounted for 51 ± 34% of the total reactivity. For three case studies, NO3 mixing ratios were calculated from measured parameters with resultant uncertainties of � 30%. Discrepancies with measured NO3 appeared to result primarily from input parameter variability and exclusion of heterogeneous dinitrogen pentoxide (N2O5) chemistry. We indirectly determined that nighttime NO3 and NOx (=NO + NO2) removal via N2O5 chemistry (gas-phase + heterogeneous) was on average 51–54% and 63–66% of the total respectively. Our analysis suggested that the minimum average NO3 and NOx removal via heterogeneous N2O5 chemistry was � 10% of the total. Reducing gas-phase N2O5 reactivity in accord with Brown et al. (2006a) increased the importance of heterogeneous N2O5 chemistry substantially. It is plausible that the latter pathway was often comparable to gas-phase removal of NO3 and NOx. Overall, 24 h-averaged NOx removal was � 11 ppbv, with nighttime chemical pathways contributing � 50%.

Li et al . (Reports, 18 April 2014, p. 292) proposed a unity nitrous acid (HONO) yield for reaction between nitrogen dioxide and the hydroperoxyl-water complex and suggested a substantial overestimation in HONO photolysis contribution to hydroxyl radical budget. Based on airborne observations of all parameters in this chemical system, we have determined an upper-limit HONO yield of 0.03 for the reaction.

This paper evaluates the accuracy of ozone measurements made by monitors that determine ozone concentrations in ambient air by UV absorption. These monitors are typically used to measure ozone for the purpose of establishing local compliance to air-quality standards. The study was predicated by the concern that commercially available UV absorbance O3 monitors may be subject to interference from volatile organic carbon (VOC) species that absorb light at 254 nm. To test for these and other effects, we compared simultaneous O3 measurements made by a commercial UV O3 monitor with an O3-NO chemiluminescence instrument, which is not subject to interference by VOC compounds. The comparisons were carried out in the summers of 1999 and 2000 at urban/industrial sites in Nashville and Houston, and in 2004 aboard a ship in the Gulf of Maine. In the two urban areas, we also compared the 03 measurements from these two methods with O3 measurements made by a long-path differential optical absorption spectrometer (DOAS). Our tests indicate that, with well-maintained monitors, there are no significant interferences even in areas with significant ambient concentrations of potentially interfering VOCs.

First, we briefly review the atmospheric chemistry and previous intercomparison measurements for HCHO, with special reference to the diffusion scrubber Hantzsch reaction based fluorescence instrument used in the field studies reported herein. Then we discuss summertime HCHO levels in five major U.S. cities measured over 1999-2002, primarily from ground-based measurements. Land-sea breeze circulations play a major role in observed concentrations in coastal cities. Very high HCHO peak mixing ratios were observed in Houston (47 ppb) where the overall median mixing ratio was 3.3 ppb; the corresponding values in Atlanta were approximately18 and 7.9 ppb, respectively. The peak and median mixing ratios (9.3 and 2.3 ppb) were the lowest for Tampa, where the land-sea breeze also played an important role. In several cities, replicate HCHO measurements were made by direct spectroscopic instruments; the instruments were located kilometers from each other and addressed very different heights (e.g., 106 vs 10 m). Even under these conditions, there was remarkable qualitative and often quantitative agreement between the different instruments, when they were all sampling the same air mass within a short period of each other. Local chemistry dominates how HCHO is formed and dissipated. The high concentrations in Houston resulted from emissions near the ship channel; the same formaldehyde plume was measured at two sites and clearly ranged over tens of kilometers. Local micrometeorology is another factor. HCHO patterns measured at a high-rise site in downtown Nashville were very much in synchrony with other ground sites 12 km away until July 4 celebrations whence HCHO concentrations at the downtown site remained elevated for several days and nights. The formation and dissipation of HCHO in the different cities are discussed in terms of other concurrently measured species and meteorological vectors. The vertical profiles of HCHO in and around Tampa under several different atmospheric conditions are presented. The extensive data set represented in this paper underscores that urban HCHO measurements can now be made easily; the agreement between disparate instruments (that are independently calibrated or rely on the absolute absorption cross section) further indicates that such measurements can be done reliably and accurately for this very important atmospheric species. The data set presented here can be used as a benchmark for future measurements if the use of formaldehyde precursors such as methanol or methyl tert-butyl ether (MTBE) as oxygenated fuel additives increases in the future.

[1] The role of nitrous acid, HONO, as a precursor for hydroxyl radicals in polluted urban air has been recognized for many years. The chemical processes leading to the formation of HONO are, however, still not well understood. Laboratory studies show that HONO formation occurs primarily on surfaces and is first order in NO2. Water also plays an important role in the conversion process. While the latter has been shown in the laboratory, little information is available regarding the influence of water on the NO2 and HONO chemistry in the real atmosphere. Here we present nocturnal DOAS measurements of HONO and NO2 from three field experiments. The observations show that [HONO]/[NO2] ratios between 10 and 30% relative humidity (RH) do not exceed 0.04, while values of up to 0.09 were observed at higher RH. These results are analyzed by interpreting the observed maximum [HONO]/[NO2] ratio at a given relative humidity as the pseudo steady state (PSS) between the heterogeneous NO2 to HONO conversion and the HONO loss on surfaces. Theoretical considerations show that the [HONO]/[NO2] ratio at the PSS is equal to the ratio of the heterogeneous NO2 to HONO conversion coefficient and the reactive HONO uptake coefficient, thus showing that these processes depend on the RH. This result implies that RH has to be considered in the parameterization of HONO formation in air pollution models.

[1] Recent field observations in urban areas have shown that trace gases, such as O3, NO2, and NO3, develop distinct vertical concentration profiles at night. Because nocturnal chemistry can change the gas-phase and particulate composition in the urban boundary layer considerably, it is important to understand the mechanisms that lead to the change of trace gas levels with altitude. The quantification of the altitude dependence of chemical processes leading to the removal of volatile organic carbons (VOC) and NOx are crucial to assess the influence of nocturnal chemistry on ozone formation during the following day. We present a one-dimensional chemical transport model developed to study the interaction between chemistry and vertical transport in the nocturnal boundary layer. The model reproduces the general features found in field observations, such as positive O3 and NO3 gradients. The slow upward transport of NO and VOC emitted near the ground and the simultaneously occurring chemistry, in particular the reactions of NO with O3 and NO3, are found to control the vertical structure of the chemistry of NOx, NO3, N2O5, and VOC. In the case of NO2 and O3, dry deposition is also significant. The model results show that vertical transport of N2O5 plays an important role, and is often the main source of NO3 radicals near the ground. Chemical steady state calculations of the concentrations of NO3 and N2O5, as they have been used in the past, are therefore not representative in cases with significant vertical fluxes of N2O5. The vertical gradient of the oxidation rate of NO2 implies that the removal of NOx occurs predominately in the upper nocturnal boundary layer (NBL). Our study shows that observations at one altitude and chemical box models are often insufficient to accurately describe the chemistry in NBL.

[1] Elevated OH and peroxy radical levels have recently been observed in the nocturnal boundary layer (NBL). Despite the possible importance of OH for the gas phase and particulate composition, the source of these ROx radicals at night is currently unclear. To investigate the influence of vertical mixing on nocturnal ROx chemistry, calculations with a one-dimensional chemical transport model were performed. The model predicts distinct vertical profiles for all ROx radical species during the night, with a pronounced RO2 maximum aloft and maxima of HO2 and OH closer to the ground. We conceptualize our results by distinguishing three chemical regimes in the NBL: (1) In the unreactive ground layer, which only forms at high NO emissions and strong vertical stabilities, OH chemistry is suppressed by high NO levels. (2) The upper layer, located in the upper NBL, is decoupled from the NO emissions at the ground. Ozonolysis of volatile organic compounds (VOCs) leads to the formation of ∼105 molecules cm−3 of OH. The RO2 maximum develops in the lower part of the upper layer by the elevated O3/NO3 + VOC reaction rates. (3) In the reactive mixing layer, in the height interval between the upper layer and the ground layer, RO2 and HNO4 (as HO2 reservoir) from the upper layer are mixed with NO from the ground layer. The active radical propagation chain leads to distinctive maxima of HO2 and OH (up to several 106 molecules cm−3) in this layer. The OH radicals in the reactive mixing layer can contribute up to 43% to the nocturnal VOC oxidation, illustrating that OH chemistry can be important even at night. Our model simulations show that vertical transport can redistribute ROx radicals in the NBL, acting as an important radical source in the lowest few meters of the atmosphere.

[1] OH and HO2 mixing ratios and total OH reactivity were measured together with photolysis frequencies, NOx, O3, many VOCs, and other trace gases during the midsummer 1999 SOS campaign in Nashville, Tennessee. These measurements provided an excellent opportunity to study OH and HO2 (collectively called HOx), and their sources and sinks in a polluted metropolitan environment. HOx generally showed the expected diurnal evolution, with maxima around noon of up to about 0.8 pptv of OH and 80 pptv of HO2 during sunny days. Overall, daytime observed OH and HO2 were a factor of 1.33 and 1.56 times modeled values, within the combined 2σ instrument and model uncertainties. The chain length of HOx, which is determined from the ratio of the measured total OH reactivity that cycles OH to the total HOx loss, was on average 3–8 during daytime and up to 3 during nighttime, in general agreement with expectations. However, differences occurred between observed HOx behavior and expectations from theory and models. First, HO2 was greater than expected during daytime when NO mixing ratios were high; ozone production did not decrease as expected when NO was greater than 2 ppbv. Ozone production determined by the imbalance of the NOx photostationary state, which was almost twice that from HO2, also shows this dependence on NO. Second, the calculated OH production rate, which should equal the measured OH loss rate because OH is in steady state, is instead less than the measured OH loss rate by (1–2) × 107 molecules cm-3 s-1, with low statistical significance during the day and high statistical significance at night. Third, surprisingly high OH and HO2 mixing ratios were often observed during nighttime. The nighttime OH mixing ratio and the HO2/OH ratio cannot be explained by known reaction mechanisms, even those involving O3 and alkenes. Because instrument tests have failed to reveal any instrument artifacts, more exotic chemicals or chemistry, such as OH adducts or other radicals that fall apart into OH inside the instrument, are suspected.

[1] Measurements of isoprene and its oxidation products, methacrolein, methyl vinyl ketone and peroxymethacrylic nitric anhydride, were conducted between 13 June and 14 July 1999, at the Cornelia Fort Airpark during the Nashville intensive of the Southern Oxidant Study. Trends in isoprene and its oxidation products showed marked variability from night-to-night. The reaction between isoprene and the nitrate radical was shown to be important to the chemical budget of isoprene and often caused rapid decay of isoprene mixing ratios in the evening. Trends in methacrolein, methyl vinyl ketone, and peroxymethacrylic nitric anhydride were steady during the evening isoprene decay period, consistent with their slow reaction rate with the nitrate radical. For cases when isoprene sustained and even increased in mixing ratio throughout the night, the observed isoprene oxidation rates via the hydroxyl radical, ozone, and the nitrate radical were all small. Sustained isoprene mixing ratios within the nocturnal boundary layer give a unique opportunity to capture hydroxyl radical photochemistry at sunrise as isoprene was observed to rapidly convert to its first stage oxidation products before vertical mixing significantly redistributed chemical species. The observed nighttime isoprene variability at urban, forested sites is related to a complex coupling between nighttime boundary layer dynamics and chemistry.

[1] The photolysis of nitrous acid (HONO) in the early morning hours is believed to be a significant source of hydroxyl radicals (OH), the most important daytime oxidizing species. Although the importance of this mechanism has been recognized for many years, no accurate experimental quantification is available. Here we present measurements of HONO, NO2, SO2, O3 and HCHO by Differential Optical Absorption Spectroscopy (DOAS) during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono (LOOP/PIPAPO) study in May–June 1998 in Milan, Italy. The concentration of NO and J(NO2)/J(HONO) were simultaneously monitored by in situ monitors. The photolysis frequencies of HCHO and O3 were determined with a radiative transfer model. High nocturnal HONO mixing ratios of up to 4.4 ppb were regularly observed. Elevated daytime HONO levels during cloudy periods show that the formation of HONO proceeds after sunrise and therefore also represents a source of hydroxyl radicals throughout the day. Averaged over 24 hours, HCHO photolysis is the most important source of OH in Milan, followed by either ozone or HONO photolysis. Our observations indicate that on certain days the OH production from HONO can be even more important than that from ozone photolysis. The diurnal variation of the different OH formation mechanisms shows that HONO photolysis is by far the most important source in the early hours of the morning, and can be as large as and even surpass the total OH production at noon.

[1] The international field experiment Pianura Padana Produzione di Ozono (PIPAPO) studying the volatile organic compounds (VOC)/NOx ozone production sensitivity took place in May and June 1998 downwind of the metropolitan area of Milan. The project was embedded in the framework of the EUROTRAC-2 Limitation of Oxidant Production (LOOP) subproject. Several ground stations between the city of Milan and the Alps north of Milan combined with airborne measurements delivered a comprehensive data set suitable for observation-based analysis and validation of chemical transport models. The special section devoted to the PIPAPO project contains 10 contributions on the characterization of secondary aerosol formation, and radical precursors, and the characterization of ozone production sensitivity based on field measurements and numerical model simulations. In this paper the scientific background and the major objectives of PIPAPO are described. An overview of the field measurement program, the study site, and the meteorological conditions prevailing during the experiment are given. A general conclusion of the combined results is that under typical summer conditions in the Milan area with clear skies, low wind speeds and high temperatures, the transition from VOC- to NOx-sensitive ozone production occurs a few tens of kilometers downwind of the strongest emission sources in the city of Milan.

[1] The source of nitrous acid, HONO, in the troposphere remains uncertain, even after two decades of research. It is currently believed that HONO is formed by heterogeneous conversion of NO2 on either the ground or the aerosol surface. While this conversion has been studied in the laboratory, few atmospheric studies have been reported. Here we present the first simultaneous determination of the vertical gradients and fluxes of HONO, its precursor NO2, and SO2 over a flat grass surface in the polluted atmosphere. The measurements were performed in Milan, Italy, during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono (LOOP/PIPAPO) study in summer 1998, using differential optical absorption spectroscopy. While deposition of NO2 onto the ground was frequently observed, heterogeneous HONO formation was much smaller than expected. We can explain our observation by a mechanism that consists of a combination of NO2 and HONO deposition, and a heterogeneous conversion of NO2 to HONO on the ground. The compensation point for deposition and formation of HONO is characterized by a HONO/NO2 ratio of ∼0.03, indicating that only one HONO molecule is released into the gas phase for every 33 NO2 molecules deposited. Our measurements also show that direct emission of HONO is an important source in strongly polluted areas.

During two field campaigns in spring 1995 and 1996, boundary layer concentration levels of BrO, ClO, IO, SO 2 , NO 2 , HNO 2 , CH 2 O and O 3 , were observed at a time resolution of better than 1.5 h by Differential Optical Absorption Spectroscopy (DOAS). Up to 30 ppt of both, BrO and ClO, were found to coincide with low ozone events (LOE). During periods of normal ozone, average levels of BrO and ClO were close to zero. Average ClO levels during LOE were considerably higher in 1995 (21 ppt) than in 1996 (3.3 ppt). Generally, only upper limits for NO 2 and SO 2 of 50 ppt can be given, however, a series of concentration spikes (up to a few ppb) observed are in the case of NO 2 most likely due to local pollution, while the origin of the SO 2 spikes remains unclear. Analysis of the data suggests that the ozone loss is most likely caused by a combination of BrO x (= Br + BrO)- and BrO x + ClO x − catalysed ozone destruction (with the BrO self reaction and ClO + BrO reaction being the rate limiting steps, respectively). The presence of IO at levels exceeding 1–2 ppt and thus its contribution to ozone destruction is unlikely, but cannot be completely excluded. The observed levels of BrO and ClO are sufficiently high to destroy 1–2 ppb O 3 per hour, thus completely eliminating 40 ppb of initial O 3 within 1–2 days. However airmass dynamics is also likely to be important, in particular observed O 3 decrease rates of up to 7 ppb/h can only be attributed to advection of air already depleted in ozone. The Cl-atom and Br-atom concentrations deduced from ClO and BrO measurements and estimates of ClO/CL and BrO/Br ratios, are compared with data derived from “hydrocarbon clock” observations in the arctic. While both sets of data are compatible for BrO and 1996 ClO data, in 1995 the DOAS ClO data indicate much higher Cl-atom levels than seen by hydrocarbon clock observations. DOI: 10.1034/j.1600-0889.49.issue5.9.x

During the period May 12–23, 1992, seven groups from seven countries met in Lauder, New Zealand, to intercompare their remote sensing instruments for the measurement of atmospheric column NO2 from the surface. The purpose of the intercomparison was to determine the degree of intercomparability and to qualify instruments for use in the Network for the Detection of Stratospheric Change (NDSC). Three of the instruments which took part in the intercomparison are slated for deployment at primary NDSC sites. All instruments were successful in obtaining slant column NO2 amounts at sunrise and sunset on most of the 12 days of the intercomparison. The group as a whole was able to make measurements of the 90° solar zenith angle slant path NO2 column amount that agreed to about ±10% most of the time; however, the sensitivity of the individual measurements varied considerably. Part of the sensitivity problem for these measurements is the result of instrumentation, and part is related to the data analysis algorithms used. All groups learned a great deal from the intercomparison and improved their results considerably as a result of this exercise.

[1] The nitrate radical (NO3) is the dominant atmospheric oxidant during the night in most environments. During the day, however, NO3 has thus far been considered insignificant. Here we present daytime measurements of NO3 by Differential Optical Absorption Spectroscopy near Houston, Texas, during the Texas Air Quality Study 2000. On 3 consecutive days in August/September 2000, NO3 reached levels from ∼5 ppt 3 hours before sunset to 31 ppt around sunset. Daytime NO3 had a negligible effect on the photostationary state (PSS) between O3 and NOx, with the exception of the last hour before sunset, when it significantly accelerated NO-to-NO2 conversion. On August 31, chemical reactions involving NO3 destroyed 8 (±4) ppb Ox (= O3 + NO2) during the day and 27 (±6) ppb at night. NO3 chemistry contributed 10 (±7)% to the total Ox loss during the daytime, and 28% (±18%) integrated over a 24-hour period. It therefore played an important role in the Ox budget. NO3 also contributed significantly to the daytime oxidation of hydrocarbons such as monoterpenes and phenol in Houston. The observed daytime NO3 mixing ratios can be described as a function of O3 and NOx. Above [NOx]/[O3] ratios of 3%, daytime NO3 becomes independent of NOx and proportional to the square of O3. Our calculations indicate that elevated (>1 ppt) NO3 levels can be present whenever ozone mixing ratios exceed typical urban smog levels of 100 ppb.