Abundances and variability of tropospheric volatile organic compounds at the South Pole and other Antarctic locations

Multiyear (2000–2006) seasonal measurements of carbon monoxide, hydrocarbons, halogenated species, dimethyl sulfide, carbonyl sulfide and C₁–C₄ alkyl nitrates at the South Pole are presented for the first time. At the South Pole, short-lived species (such as the alkenes) typically were not observed above their limits of detection because of long transit times from source regions. Peak mixing ratios of the longer lived species with anthropogenic sources were measured in late winter (August and September) with decreasing mixing ratios throughout the spring. In comparison, compounds with a strong oceanic source, such as bromoform and methyl iodide, had peak mixing ratios earlier in the winter (June and July) because of decreased oceanic production during the winter months. Dimethyl sulfide (DMS), which is also oceanically emitted but has a short lifetime, was rarely measured above 5 pptv. This is in contrast to high DMS mixing ratios at coastal locations and shows the importance of photochemical removal during transport to the pole. Alkyl nitrate mixing ratios peaked during April and then decreased throughout the winter. The dominant source of the alkyl nitrates in the region is believed to be oceanic emissions rather than photochemical production due to low alkane levels.Sampling of other tropospheric environments via a Twin Otter aircraft included the west coast of the Ross Sea and large stretches of the Antarctic Plateau. In the coastal atmosphere, a vertical gradient was found with the highest mixing ratios of marine emitted compounds at low altitudes. Conversely, for anthropogenically produced species the highest mixing ratios were measured at the highest altitudes, suggesting long-range transport to the continent. Flights flown through the plume of Mount Erebus, an active volcano, revealed that both carbon monoxide and carbonyl sulfide are emitted with an OCS/CO molar ratio of 3.3 × 10^?3 consistent with direct observations by other investigators within the crater rim.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin

For at least 30 years, ozone (O3) levels on weekends in parts of California's South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O3 precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NOx) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O3 formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NOx associated with black carbon (BC) to NOx associated with carbon monoxide (CO) were approximately 1.25 +/- 0.22 during weekdays and 0.76 +/- 0.07 and 0.52 +/- 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NOx emissions from diesel exhaust can be a major factor causing lower NOx mixing ratios and higher NMHC/NOx ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NOx ratios on weekend mornings.     

Source Resolution of Fine Particulate Polycyclic Aromatic Hydrocarbons Using a Receptor Model Modified for Reactivity

This paper provides source contribution estimates from vehicular and meat-cooking emissions to particulate polycyclic aromatic hydrocarbon (PAH) and elemental carbon (EC) concentrations measured at two Los Angeles sites during a field study in 1989. The source concentration matrix for PAH was based on new data for vehicular emissions and literature data for meat-cooking operations. The chemical mass balance (CMB 7.0) receptor model was used, and source profiles were modified to reflect reactive decay of PAH in the atmosphere. The calculations indicate that the Pico Rivera site was dominated by auto emissions, which account for more than 90 percent of all the PAH (except chrysene), carbon monoxide (CO), and 61 percent of the EC concentrations. In contrast, emissions from meat cooking contributed significantly (20 to 75 percent) to the concentrations of four-ring PAH measured at a residential site at Upland. The five-ring and larger PAH were attributed to auto emissions at Upland as well.     

The influence of south foehn on the ozone mixing ratios at the high alpine site Arosa

Within 2 years of trace gas measurements performed at Arosa (Switzerland, 2030 m above sea level), enhanced ozone mixing ratios were observed during south foehn events during summer and spring (5–10 ppb above the median value). The enhancements can be traced back to ozone produced in the strongly industrialized Po basin as confirmed by various analyses. Backward trajectories clearly show advection from this region during foehn. NO_y versus O₃ correlation and comparison of O₃ mixing ratios between Arosa and Mt. Cimone (Italy, 2165 m asl) suggest that ozone is the result of recent photochemical production (+5.6 ppb on average), either directly formed during the transport or via mixing of air processed in the Po basin boundary layer. The absence of a correlation between air parcel residence times over Europe and ozone mixing ratios at Arosa during foehn events is in contrast to a previous analysis, which suggested such correlation without reference to the origin of the air. In the case of south foehn, the continental scale influence of pollutants emission on ozone at Arosa appears to be far less important than the direct influence of the Po basin emissions. In contrast, winter time displays a different situation, with mean ozone reductions of about 4 ppb for air parcels passing the Po basin, probably caused by mixing with ozone-poor air from the Po basin boundary layer.     

Global comparison of VOC and CO observations in urban areas

Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from ?3% to ?26% per year. Carbon monoxide decreased by ?12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from ?2% to ?13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C₅, alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.     

Simulation of the tropospheric distribution of carbon monoxide during the 1984 MAPS experiment

A global, three-dimensional tropospheric chemistry model was used to perform simulations of the tropospheric distribution of carbon monoxide (CO) coinciding with NASA's Measurement of Air Pollution from Satellites (MAPS) experiment which took place during 5–13 October 1984. Archived meteorological data for September and October, 1984, were obtained from the European Centre for Medium-Range Weather Forecasting and used to drive the offline chemical transport model simulations. Base-case CO emissions were generated by applying emission factors to compiled inventories for related or co-emitted trace species. Simulation results from September and October have been compared with a recent re-release of the 1984 MAPS data and with in situ correlative data taken during the MAPS mission. Because of unrealistically large spatial variability in N₂O mixing ratios measured concurrently by MAPS, model results were also compared with an adjusted CO data set generated by assuming that errors in N₂O measured mixing ratios were correlated with errors in the MAPS CO data. These comparisons, in conjunction with simulations probing model sensitivities, led to the conclusion that biomass burning CO emissions from central and southern Africa may have been larger during September and October, 1984, than our initial best estimate based on the CO₂ emissions data of Hao et al. (1990. Fire in the Tropical Biota; Ecosystem Processes and Global Challenges. Springer, Berlin, pp. 440–462; 1994. Global Biogeochemical Cycles 8, 495–503). This result is in disagreement with recent estimates of biomass burning emissions from Africa (Scholes et al., 1996, Journal of Geophysical Research 101, 23677–23682) which are smaller than previously thought for emissions from this region. Although unknown model deficiencies cannot be conclusively ruled out, model sensitivity studies indicate that increased CO emissions from central and southern Africa offer the best explanation for reducing observed differences between model results and MAPS data for this time period. Our results, in combination with a disparity in recent CO emission estimates from this region (Scholes et al., 1996; Hao et al., 1996, Journal of Geophysical Research 101, 23577–23584), and in light of recent indications of highly variable biomass burning activities from the tropical western Pacific (Folkins et al., 1997, Journal of Geophysical Research 102, 13291–13299), seem to suggest that biomass burning emissions exhibit significant year-to-year variability. This large variability of emissions sources makes the accurate simulation of specific time periods very difficult and suggests that biomass burning trace species inventories may have to be developed specifically for each simulated time period, employing satellite-derived information on fire coverage and flame intensity.     

Trends in Concentrations of Benzene Soluble Suspended Particulate Fraction and Benzo(a)pyrene

The bacterial mutagenicity of ambient particulate organic matter (POM) was measured for consecutive 3-hour time intervals over a 27-hour period in March 1983 at two sites on opposite sides of the heavily traveled San Diego Freeway (I-405) in West Los Angeles (WLA), California, the diurnal variations in the direct (not requiring S9 metabolic activation) mutagenic burden of airborne particulates and the magnitude of the mutagen doses observed at these sites were similar to those previously observed at a site just east of downtown Los Angeles (ELA). Highs (～150 rev m^?3) and lows (～35 rev m^?3) in mutagen densities occurred over short time intervals (a few hours) probably due to changes in emissions, mixing heights and wind speeds. Offshore air flows which drained the air basin between midnight and 0600 PST resulted in elevated mutagen density levels at the western edge of the Los Angeles Basjn. The incremental burden of direct mutagens in respirable POM attributable to freeway traffic reached 50 rev m^?3 during this study. Consistent with our results for ELA there was diminished response on the Salmonella typhimurium nitroreductase-deficient strain TA98NR vs. TA98 suggesting that nitroarenes contribute significantly to the direct mutagenicity of POM collected at the WLA sites.     

Smog Chamber Simulation of Los Angeles Pollutant Transport

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. In the absence of any evidence, it has been widely assumed that increasing NO _x emissions have caused oxidant levels to increase downwind of Los Angeles, i.e., Riverside and San Bernardino. This smog chamber study simulated pollutant transport from Los Angeles to the downwind areas by irradiating a typical Los Angeles hydrocarbon/NO _x mixture for extended periods of time. The smog chamber experiments were extended to 22 hours to obtain an integrated light intensity equal to that which occurs in the Los Angeles area. The effects of variations of nitrogen oxide emissions on an aged air mass were examined. The results show that downwind oxidant levels are only slightly affected by large changes in NO _x emissions. However, it is clear that reduced nitrogen oxide emissions will lead to an increase in oxidant in downtown Los Angeles.     

Variability in ultraviolet total optical depth during the Southern California Ozone Study (SCOS97)

Formation of photochemical air pollution is governed in part by the solar ultraviolet actinic radiation flux, but wavelength-resolved measurements of UV radiation in polluted urban atmospheres are rarely available. As part of the 1997 Southern California Ozone Study, cosine weighted solar irradiance was measured continuously at seven UV wavelengths (300, 306, 312, 318, 326, 333 and 368 nm) at two sites during the period 1 July to 1 November 1997. The first site was at Riverside (260 m a.s.l.) in the Los Angeles metropolitan area, which frequently experiences severe air pollution episodes. The second site was at Mt Wilson (1725 m a.s.l.), approximately 70 km northwest of Riverside, and located above much of the urban haze layer. Measurements of direct (i.e., total minus diffuse) solar irradiance were used to compute total atmospheric optical depths. At 300 nm, optical depths (mean±1 S.D.) measured over the entire study period were 4.3±0.3 at Riverside and 3.7±0.2 at Mt Wilson. Optical depth decreased with increasing wavelength, falling at 368 nm to values of 0.8±0.2 at Riverside and 0.5±0.1 at Mt Wilson. At all wavelengths, both the mean and the relative standard deviation of optical depths were larger at Riverside than at Mt Wilson. At 300 nm, the difference between the smallest and largest observed optical depths corresponds to over a factor 2 increase in the direct beam irradiance for overhead sun, and over a factor 7 increase for a solar zenith angle of 60°. Principal component analysis was used to reveal underlying factors contributing to variability in optical depths. PCA showed that a single factor (component) was responsible for the major part of the variability. At Riverside, the first component was responsible for 97% of the variability and the second component for 2%. At Mt Wilson, 89% of the variability could be attributed to the first component and 10% to the second. Dependence of the component contributions on wavelength allowed identification of probable physical causes: the first component is linked to light scattering and absorption by atmospheric aerosols, and the second component is linked to light absorption by ozone. These factors are expected to contribute to temporal and spatial variability in solar actinic flux and photodissociation rates of species including ozone, nitrogen dioxide, and formaldehyde.     

Lead Concentrations in Detroit,New York,and Los Angeles Air

Lead concentrations in air were measured at 12 sites in Detroit, New York and Los Angeles as part of a program to relate automobile emissions and polynuclear aromatic hydrocarbons in air. The information on lead is reported separately because of the current interest in lead as an air pollutant. Sampling was conducted by means of a large “absolute” filter and equipment contained in a step-van truck. A portion of the filter was macerated in nitric acid and the lead determined spectrographically. The combined annual average lead concentration for four sites in metropolitan Los Angeles was approximately 40% higher than the combined averages of either the five sites in metropolitan New York or the three sites in metropolitan Detroit. Concentrations ranged from 0.4 ug/M³ at Santa Monica, to 18.4 ug/M³ at a Los Angeles Freeway Interchange. Concentrations were generally highest in freeway areas, intermediate in commercial areas, and lowest in residential areas. They were about 40% higher in daytime than at night. Average lead concentrations were highest during autumn in New York and winter in Los Angeles reflecting an inverse relationship with wind speed. Correlation coefficients between lead and carbon monoxide, at all sites, were statistically non-zero with 99% confidence and varied from 0.75 to 0.96. Lead concentrations in this study were higher than concentrations reported by others for Detroit, New York, and Los Angeles, presumably because sampling in this study was closer to traffic. However, concentrations in this study were lower than in-traffic concentrations given in the literature.     

Variations of surface O3 in August at a rural site near Shanghai: influences from the West Pacific subtropical high and anthropogenic emissions

Large day-to-day variability in O₃ and CO was observed at Chongming, a remote rural site east of Shanghai, in August 2010. High ozone periods (HOPs) that typically lasted for 3?C5?days with daily maximum ozone exceeding 102?ppb were intermittent with low ozone periods (LOPs) with daily maximum ozone less than 20?ppb. The correlation analysis of ozone with meteorological factors suggests that the large variations of surface ozone are driven by meteorological conditions correlated with the changes in the location and intensity of the west Pacific subtropical high (WPSH) associated with the East Asian summer monsoon (EASM). When the center of WPSH with weaker intensity is to the southeast of Chongming site, the mixing ratios and variability of surface ozone are higher. When the center of WPSH with stronger intensity is to the northeast of Chongming site, the mixing ratios and variability of surface ozone are lower. Sensitivity simulations using the GEOS-Chem chemical transport model indicate that meteorological condition associated with WPSH is the primary factor controlling surface ozone at Chongming in August, while local anthropogenic emissions make significant contributions to surface ozone concentrations only during HOP.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.     

The influence of sampling protocol on nonmethane hydrocarbon mixing ratios

The effect of sampling protocol on ambient air hydrocarbon mixing ratios was examined on eight sampling days in Los Angeles during 2007 and 2008. Four protocols, which were based on previously published multi-city urban hydrocarbon studies in the United States, were compared and differences were quantified. Whole air canister samples were collected and analyzed for nonmethane hydrocarbons (NMHCs). Differing sampling protocols resulted in large differences in mixing ratios, up to an order of magnitude, for certain NMHCs on the same sampling day. However, the magnitude of the variability between NMHC levels obtained by the four protocols was not consistent throughout the eight sampling days. It was found that sampling time, followed by sampling location, had the greatest influence on the magnitude of the mixing ratio. Ratios between hydrocarbons, often used in urban studies to gain information on emission sources, also varied depending on the protocol used. Comparison of absolute NMHC mixing ratios collected in urban environments using differing sampling protocols should be made with care.     

Emissions from lit-use Motor Vehicles in Los Angeles: A Pilot Study of Remote Sensing and the Inspection and Maintenance Program

As part of a major field study to understand the causes of persistent, elevated carbon monoxide pollution episodes in Los Angeles, we performed a project to understand the emissions of vehicles in use. In this experiment, we assessed the accuracy of a remote sensing instrument designed to measure CO concentrations from vehicles as they were driven on the road. The remote sensor was shown to be accurate within ten percent of the directly measured tailpipe value. We performed a roadside inspection on 60 vehicles and demonstrated that the remote sensor could be used as an effective surveillance tool to identify high CO-emitting vehicles. We also compared the roadside data set to the biennial Smog Check (I/M) tests for the same vehicles, and observed that carbon monoxide and exhaust hydrocarbons from high emitters were much higher than when the vehicles received their routine inspection. Furthermore, for the high-emitting vehicles in this data set, the length of time since the biennial Smog Check had little influence on the cars’ emissions in the roadside inspection.     

Effects of meteorology on diurnal and nocturnal levels of priority polycyclic aromatic hydrocarbons and elemental and organic carbon in PM10 at a source and a receptor area in Mexico City

PM₁₀ levels of the 16 US-EPA Priority Pollutant polycyclic aromatic hydrocarbons (PAHs) were measured from March 17 to 31, 2003, in 8-h time bins (morning, afternoon and nighttime) at Merced, a source site dominated by vehicular traffic emissions near the center of Mexico City, and at Pedregal, a receptor area located downwind in a residential area of low traffic. Along with PAH, elemental (EC) and organic carbon (OC), mass, and prevailing meteorological parameters were measured. At the source location, measured concentrations of benzo[a]pyrene (BAP), an agent suspected of being carcinogenic to humans and of causing oxidative DNA damage, reached concentrations as high as 2.04 and 2.11 ng m^?3 during the morning of a weekday and the night period of a holiday. Compared with source dominated areas in Central Los Angeles, the BAP levels found in Central Mexico City are approximately 6 times higher. Benzo[ghi]perylene (BGP) levels were, in general, the highest among the target PAH, both at the source (7.2 ng m^?3) and the receptor site (2.8 ng m^?3), suggesting that, at both locations, exhaust emission by light-duty (LD) vehicles is an important contributor to the atmospheric PAH burden. Higher PAH concentrations were observed during the morning period (5:00–13:00 h) at the source and the receptor site. The concentrations of PAHs found predominantly in the particle-phase (MW > 202) correlated well (r = 0.57–0.71) with the occurrence of surface thermal inversions and with mixing heights (r = ?0.57 to ?0.72). Organic and elemental carbon ratios also indicated that Pedregal is impacted by secondary aerosols during the afternoon hours.     

Mathematical Modeling of Photochemical Smog Using the PICK Method

A new method for solving the turbulent atmospheric diffusion equation has been developed based on Lagrangian mass points, or particles moving through an Eulerian grid. The method is one of a family of Particle-/n-Cell techniques but is a unique extension to incorporate the effects of turbulent diffusion based on K-theory; thus the acronym PICK.

In the three-dimensional computer-aided model, NEXUS (Numerical EXamination of Urban Smog), this method has been applied to simulation of carbon monoxide (CO) in Los Angeles. For CO the NEXUS simulation was within 20% of observed day-averaged concentrations at 12 stations and the hour-averages were also in good agreement. This model was extended to include the effects of photochemical smog in Los Angeles. The results of the photochemical simulation were also qualitatively correct due to rapid NO to NO₂ conversion in the simulation.     

Size distribution and diurnal characteristics of particle-bound metals in source and receptor sites of the Los Angeles Basin

Measurement of daily size-fractionated ambient PM₁₀ mass, metals, inorganic ions (nitrate and sulfate) and elemental and organic carbon were conducted at source (Downey) and receptor (Riverside) sites within the Los Angeles Basin. In addition to 24-h concentration measurements, the diurnal patterns of the trace element and metal content of fine (0–2.5 μm) and coarse (2.5–10 μm) PM were studied by determining coarse and fine PM metal concentrations during four time intervals of the day.The main source of crustal metals (e.g., Al, Si, K, Ca, Fe and Ti) can be attributed to the re-suspension of dust at both source and receptor sites. All the crustals are predominantly present in supermicron particles. At Downey, potentially toxic metals (e.g., Pb, Sn, Ni, Cr, V, and Ba) are predominantly partitioned (70–85%, by mass) in the submicron particles. Pb, Sn and Ba have been traced to vehicular emissions from nearby freeways, whereas Ni and Cr have been attributed to emissions from powerplants and oil refineries upwind in Long Beach. Riverside, adjacent to Southern California deserts, exhibits coarser distributions for almost all particle-bound metals as compared to Downey. Fine PM metal concentrations in Riverside seem to be a combination of few local emissions and those transported from urban Los Angeles. The majority of metals associated with fine particles are in much lower concentrations at Riverside compared to Downey. Diurnal patterns of metals are different in coarse and fine PM modes in each location. Coarse PM metal concentration trends are governed by variations in the wind speeds in each location, whereas the diurnal trends in the fine PM metal concentrations are found to be a function both of the prevailing meteorological conditions and their upwind sources.     

Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

Alkyl nitrates (C₁–C₅) were measured at two sites (near urban and rural) in southeast England during the Tropospheric Organic Chemistry Experiment (TORCH). Methyl nitrate was the dominant species during both campaigns accounting for on average about one third of the total measured alkyl nitrates. High mixing ratios (>50 pptv) and variability of methyl nitrate were observed at the near urban site (TORCH1) that were not seen at the rural site (TORCH2) and which could not be explained by local photochemical production or direct emissions. The diurnal variation of methyl nitrate during TORCH1 showed a morning maximum that would be consistent with nighttime chemistry followed by transport to the surface by boundary layer dynamics. Similarly, elevated morning mixing ratios were also observed during TORCH2 although the magnitudes were much smaller. As a result, methyl nitrate could represent a tracer for nighttime chemistry seen at the ground the following day. At both campaigns, the dominant source of short chain alkyl nitrates and carbonyl precursor radicals (≤C₄) were from decomposition of larger compounds. The magnitude of the source increased with decreasing carbon number consistent with increasing total precursor abundance. Non-photochemical emissions of acetaldehyde and acetone could not be accounted for by automobile exhaust emissions alone and indicated that other direct sources are likely important in this environment.