Atmospheric Environment (v.44, #33)

The TexAQS-II radical and aerosol measurement project (TRAMP) by Barry Lefer; Bernhard Rappenglück (3997-4004).

Photochemical and meteorological relationships during the Texas-II Radical and Aerosol Measurement Project (TRAMP) by Barry Lefer; Bernhard Rappenglück; James Flynn; Christine Haman (4005-4013).
The Moody Tower measurement site at the University of Houston experienced several large ozone events during the Texas-II Radical and Aerosol Measurement Project (TRAMP) campaign between 13 Aug–02 Oct, 2006. This rooftop site samples that atmosphere 70 m a.g.l. and consequently is less susceptible to local surface emissions. Several high-ozone episodes encountered at Moody Tower during the TRAMP campaign were preceded one to two days earlier by a cold front passage, creating a situation where polluted air is transported from the North interacts with local Houston emissions and with light local winds. High quality CO measurements were good indicators of long range transport of pollution and/or biomass burning. During TRAMP there were also 4 periods with low “background” CO characterized by southerly winds, overcast conditions and low NOx and O3 mixing ratios. The summer and fall of 2000 was an unusually hot period in Houston with considerably higher ozone levels than the 2000–2007 climatology. The 2006 TRAMP time period is more representative of the typical conditions for these 8 years. Over the time period from 1991 to 2009 the number of 8-h ozone episode days in Houston has decreased, as have the peak 1-h ozone mixing ratios. It is not possible from this analysis to demonstrate whether these improvements in Houston air quality are due to reductions in NOx levels, VOCs levels, and/or changes in meteorology.
Keywords: Ozone exceedance episodes; TexAQS-II; Post-frontal ozone events;

Nocturnal boundary layer characteristics and land breeze development in Houston, Texas during TexAQS II by Bridget M. Day; Bernhard Rappenglück; Craig B. Clements; Sara C. Tucker; W. Alan Brewer (4014-4023).
The nocturnal boundary layer in Houston, Texas was studied using a high temporal and vertical resolution tethersonde system on four nights during the Texas Air Quality Study II (TexAQS II) in August and September 2006. The launch site was on the University of Houston campus located approximately 4 km from downtown Houston. Of particular interest was the evolution of the nocturnal surface inversion and the wind flows within the boundary layer. The land–sea breeze oscillation in Houston has important implications for air quality as the cycle can impact ozone concentrations through pollutant advection and recirculation. The results showed that a weakly stable surface inversion averaging in depth between 145 and 200 m AGL formed on each of the experiment nights, typically within 2–3 h after sunset. Tethersonde vertical winds were compared with two other Houston data sets (High Resolution Doppler Lidar and radar wind profiler) from locations near the coastline and good agreement was found, albeit with a temporal lag at the tethersonde site. This comparison revealed development of a land breeze on three nights which began near the coastline and propagated inland both horizontally and vertically with time. The vertical temperature structure was significantly modified on one night at the tethersonde site after the land breeze wind shift, exhibiting near-adiabatic profiles below 100 m AGL.
Keywords: TexAQS II; Tethersonde; Urban nocturnal boundary layer; Inversion height; Land breeze;

An evaluation of the interaction of morning residual layer and afternoon mixed layer ozone in Houston using ozonesonde data by Gary A. Morris; Bonne Ford; Bernhard Rappenglück; Anne M. Thompson; Ashley Mefferd; Fong Ngan; Barry Lefer (4024-4034).
The Tropospheric Ozone Pollution Project (TOPP) launched >220 ozonesondes in Houston (July 2004–June 2008) providing examples of pollution transported into, re-circulated within, and exported from the Houston area. Fifty-one launches occurred during the Texas Air Quality Study (TexAQS) II and the summer portion of IONS-06 (INTEX [Intercontinental Transport Experiment] Ozonesonde Network Study). On 11 days during TexAQS II and on 8 other occasions, ozonesondes were launched both at dawn and in the afternoon. Analysis of these “intensive” launch sequences shows that morning residual layer (RL) ozone concentrations ([O3]) explained 60–70% of the variability found in the afternoon mixed layer (ML). Furthermore, maximum RL [O3] is nearly identical to the mean ML [O3] from the previous afternoon (morning minus afternoon = −1.6 ± 8.4 ppbv). During TexAQS II, mean [O3] below 1.3 km (the mean ML height from ozonesonde data) increased from 37 ± 22 ppbv in the morning to 74 ± 18 ppbv in the afternoon, suggesting an average net local daily O3 production of ∼500–900 tons over the metropolitan Houston area.
Keywords: Ozone; Pollution; Ozonesondes; Boundary layer; Residual layer; TexAQS II; Houston;

Extensive aerosol optical properties and aerosol mass related measurements during TRAMP/TexAQS 2006 – Implications for PM compliance and planning by Monica E. Wright; Dean B. Atkinson; Luke Ziemba; Robert Griffin; Naruki Hiranuma; Sarah Brooks; Barry Lefer; James Flynn; Ryan Perna; Bernhard Rappenglück; Winston Luke; Paul Kelley (4035-4044).
Extensive aerosol optical properties, particle size distributions, and Aerodyne quadrupole aerosol mass spectrometer measurements collected during TRAMP/TexAQS 2006 were examined in light of collocated meteorological and chemical measurements. Much of the evident variability in the observed aerosol-related air quality is due to changing synoptic meteorological situations that direct emissions from various sources to the TRAMP site near the center of the Houston-Galveston-Brazoria (HGB) metropolitan area. In this study, five distinct long-term periods have been identified. During each of these periods, observed aerosol properties have implications that are of interest to environmental quality management agencies. During three of the periods, long range transport (LRT), both intra-continental and intercontinental, appears to have played an important role in producing the observed aerosol. During late August 2006, southerly winds brought super-micron Saharan dust and sea salt to the HGB area, adding mass to fine particulate matter (PM2.5) measurements, but apparently not affecting secondary particle growth or gas-phase air pollution. A second type of LRT was associated with northerly winds in early September 2006 and with increased ozone and sub-micron particulate matter in the HGB area. Later in the study, LRT of emissions from wildfires appeared to increase the abundance of absorbing aerosols (and carbon monoxide and other chemical tracers) in the HGB area. However, the greatest impacts on Houston PM2.5 air quality are caused by periods with low-wind-speed sea breeze circulation or winds that directly transport pollutants from major industrial areas, i.e., the Houston Ship Channel, into the city center.
Keywords: Urban air quality; PM; Aerosol optical properties; AMS; Particle size distribution;

Mercury species measured atop the Moody Tower TRAMP site, Houston, Texas by Steven Brooks; Winston Luke; Mark Cohen; Paul Kelly; Barry Lefer; Bernhard Rappenglück (4045-4055).
Atmospheric mercury speciation was monitored within Houston, Texas, USA, August 6–October 14, 2006 as part of the TexAQS Radical and Aerosol Measurement Program (TRAMP). On average, all mercury levels were significantly elevated compared to a rural Gulf of Mexico coastal site. Concentrations varied from very clean to very dirty. Multi-day periods of stagnant or low-wind conditions brought elevated concentrations of all mercury species, whereas multi-day periods of strong winds, particularly southerly winds off the Gulf of Mexico, brought very low values of mercury species. Over the entire mercury measurement period, the daily averages of mercury species showed distinct and consistent relationships with the average planetary boundary layer dynamics, with gaseous elemental and particulate-bound mercury near-surface concentrations enhanced by a shallow nocturnal boundary layer, and reactive gaseous mercury concentration enhanced by midday convective boundary layer air entrainment transporting air aloft to the surface. Mercury concentrations were not significantly correlated with known products of combustion, likely indicating non-combustion mercury sources from the Houston area petrochemical complexes. On the morning of August 31, 2006 an observed emission event at a refinery complex on the Houston Ship Channel resulted in extremely high concentrations of aerosol mass and particulate-bound mercury at the TRAMP measurement site 20 km downwind.
Keywords: Houston; TexAQS-II; Mercury; GEM; RGM; FPM;

VOC source–receptor relationships in Houston during TexAQS-II by Michael Leuchner; Bernhard Rappenglück (4056-4067).
During the TRAMP field campaign in August–September 2006, C2–C10 volatile organic compounds (VOCs) were measured continuously and online at the urban Moody Tower (MT) site. This dataset was compared to corresponding VOC data sets obtained at six sites located in the highly industrialized Houston Ship Channel area (HSC). Receptor modeling was performed by positive matrix factorization (PMF) at all sites. Conditional probability functions (CPF) were used to determine the origin of the polluted air masses in the Houston area. A subdivision into daytime and nighttime was carried out to discriminate photochemical influences. Eight main source categories of industrial, mobile, and biogenic emissions were identified at the urban receptor site, seven and six, respectively, at the different HSC sites. At MT natural gas/crude oil contributed most to the VOC mass (27.4%), followed by liquefied petroleum gas (16.7%), vehicular exhaust (15.3%), fuel evaporation (14.3%), and aromatics (13.4%). Also petrochemical sources from ethylene (4.7%) and propylene (3.6%) play an important role. A minor fraction of the VOC mass can be attributed to biogenic sources mainly from isoprene (4.4%). Based on PMF analyses of different wind sectors, the total VOC mass was estimated to be twofold at MT with wind directions from HSC compared to air from a typical urban sector, for petrochemical compounds more than threefold. Despite the strong impact of air masses influenced by industrial sources at HSC, still about a third of the total mass contributions at MT can be apportioned to other sources, mainly motor vehicles and aromatic solvents. The investigation of diurnal variation in combination with wind directional frequencies revealed the greatest HSC impact at the urban site during the morning, and the least during the evening.
Keywords: Volatile organic compounds (VOC); Receptor modeling; Positive matrix factorization (PMF); Source apportionment; Conditional probability function (CPF); Air quality; Houston;

Measurements of primary trace gases and NOY composition in Houston, Texas by Winston T. Luke; Paul Kelley; Barry L. Lefer; James Flynn; Bernhard Rappenglück; Michael Leuchner; Jack E. Dibb; Luke D. Ziemba; Casey H. Anderson; Martin Buhr (4068-4080).
Concentrations of CO, SO2, NO, NO2, and NOY were measured atop the University of Houston's Moody Tower supersite during the 2006 TexAQS-II Radical and Aerosol Measurement Project (TRAMP). The lowest concentrations of all primary and secondary species were observed in clean marine air in southerly flow. SO2 concentrations were usually low, but increased dramatically in sporadic midday plumes advected from sources in the Houston Ship Channel (HSC), located NE of the site. Concentrations of CO and NOx displayed large diurnal variations in keeping with their co-emission by mobile sources in the Houston Metropolitan Area (HMA). CO/NOx emission ratios of 5.81 ± 0.94 were observed in the morning rush hour. Nighttime concentrations of NOx (NOx = NO + NO2) and NOY (NOY = NO + NO2 + NO3 + HNO3 + HONO + 2∗N2O5 + HO2NO2 + PANs + RONO2 + p-NO3  + …) were highest in winds from the NNW-NE due to emission from mobile sources. Median ratios of NOx/NOY were approximately 0.9 overnight, reflecting the persistence and/or generation of NOZ (NOZ = NOY − NOx) species in the nighttime Houston boundary layer, and approached unity in the morning rush hour. Daytime concentrations of NOx and NOY were highest in winds from the HSC. NOx/NOY ratios reached their minimum values (median ca 0.63) from 1300 to 1500 CST, near local solar noon, and air masses often retained enough NOx to sustain additional O3 formation farther downwind. HNO3 and PANs comprised the dominant NOZ species in the HMA, and on a median basis represented 17–20% and 12–15% of NOY, respectively, at midday. Concentrations of HNO3, PANs, and NOZ, and fractional contributions of these species to NOY, were at a maximum in NE flow, reflecting the source strength and reactivity of precursor emissions in the HSC. As a result, daytime O3 concentrations were highest in air masses with HSC influence. Overall, our findings confirm the impact of the HSC as a dominant source region within the HMA. A comparison of total NOY measurements with the sum of measured NOY species (NOYi = NOx + HNO3 + PANs + HONO + p-NO3 ) yielded excellent overall agreement during both day ([NOY](ppb) = ([NOYi](ppb)∗1.03 ± 0.16) − 0.42; r 2 = 0.9933) and night ([NOY](ppb) = ([NOYi](ppb)∗1.01 ± 0.16) + 0.18; r 2 = 0.9975). A similar comparison between NOY–NOx concentrations and the sum of NOZi (NOZi = HNO3 + PANs + HONO + p-NO3 ) yielded good overall agreement during the day ([NOZ](ppb) = ([NOZi](ppb)∗1.01 ± 0.30) + 0.044 ppb; r 2 = 0.8527) and at night ([NOZ](ppb) = ([NOZi](ppb)∗1.12 ± 0.69) + 0.16 ppb; r 2 = 0.6899). Median ratios of NOZ/NOZi were near unity during daylight hours but increased to approximately 1.2 overnight, a difference of 0.15–0.50 ppb. Differences between NOZ and NOZi rarely exceeded combined measurement uncertainties, and variations in NOZ/NOZi ratios may have resulted solely from errors in conversion efficiencies of NOY species and changes in NOY composition. However, nighttime NOZ/NOZi ratios and the magnitude of NOZ − NOZi differences were generally consistent with recent observations of ClNO2 in the nocturnal Houston boundary layer.
Keywords: NOY budget; Ozone photochemistry; Air quality; Sulfur dioxide; Carbon monoxide; Houston; TEXAQS-II;

Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere by Luke D. Ziemba; Jack E. Dibb; Robert J. Griffin; Casey H. Anderson; Sallie I. Whitlow; Barry L. Lefer; Bernhard Rappenglück; James Flynn (4081-4089).
Nitrous acid (HONO), nitric acid (HNO3), and organic aerosol were measured simultaneously atop an 18-story tower in Houston, TX during August and September of 2006. HONO and HNO3 were measured using a mist chamber/ion chromatographic technique, and aerosol size and chemical composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Observations indicate the potential for a new HONO formation pathway: heterogeneous conversion of HNO3 on the surface of primary organic aerosol (POA). Significant HONO production was observed, with an average of 0.97 ppbv event−1 and a maximum increase of 2.2 ppb in 4 h. Nine identified events showed clear HNO3 depletion and well-correlated increases in both HONO concentration and POA-dominated aerosol surface area (SA). Linear regression analysis results in correlation coefficients (r 2) of 0.82 for HONO/SA and 0.92 for HONO/HNO3. After correction for established HONO formation pathways, molar increases in excess HONO (HONOexcess) and decreases in HNO3 were nearly balanced, with an average HONOexcess/HNO3 value of 0.97. Deviations from this mole balance indicate that the residual HNO3 formed aerosol-phase nitrate. Aerosol mass spectral analysis suggests that the composition of POA could influence HONO production. Several previously identified aerosol-phase PAH compounds were enriched during events, suggesting their potential importance for heterogeneous HONO formation.
Keywords: HONO; HNO3; Primary organic aerosol; AMS; Heterogeneous reaction;

Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston, TX by Jochen Stutz; Hoon-Ju Oh; Sallie I. Whitlow; Casey Anderson; Jack E. Dibb; James H. Flynn; B. Rappenglück; B. Lefer (4090-4098).
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 automated 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, HNO3 and HCHO, but not with NO2, NO x , HO2NO2, or the NO2 photolysis rate. While an interferant could not be identified organic nitrites appear a possible explanation for our observations.
Keywords: Nitrous acid; HONO; Measurement techniques;

Nocturnal NO3 radical chemistry in Houston, TX by Jochen Stutz; Kam Weng Wong; Laura Lawrence; Luke Ziemba; James H. Flynn; Bernhard Rappenglück; Barry Lefer (4099-4106).
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 ∼0.9 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 + isoprene/1,3-butadiene reactions implies the efficient formation of organic nitrates and secondary organic aerosol at night in Houston.
Keywords: NO3 radical; Nitrate radical; Nocturnal chemistry; Air pollution;

Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies by Jingqiu Mao; Xinrong Ren; Shuang Chen; William H. Brune; Zhong Chen; Monica Martinez; Hartwig Harder; Barry Lefer; Bernhard Rappenglück; James Flynn; Michael Leuchner (4107-4115).
Both similarities and differences in summertime atmospheric photochemical oxidation appear in the comparison of four field studies: TEXAQS2000 (Houston, 2000), NYC2001 (New York City, 2001), MCMA2003 (Mexico City, 2003), and TRAMP2006 (Houston, 2006). The compared photochemical indicators are OH and HO2 abundances, OH reactivity (the inverse of the OH lifetime), HO x budget, OH chain length (ratio of OH cycling to OH loss), calculated ozone production, and ozone sensitivity. In terms of photochemical activity, Houston is much more like Mexico City than New York City. These relationships result from the ratio of volatile organic compounds (VOCs) to nitrogen oxides (NO x ), which are comparable in Houston and Mexico City, but much lower in New York City. Compared to New York City, Houston and Mexico City also have higher levels of OH and HO2, longer OH chain lengths, a smaller contribution of reactions with NO x to the OH reactivity, and NO x -sensitivity for ozone production during the day. In all four studies, the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) are significant, if not dominant, HO x sources. A problematic result in all four studies is the greater OH production than OH loss during morning rush hour, even though OH production and loss are expected to always be in balance because of the short OH lifetime. The cause of this discrepancy is not understood, but may be related to the under-predicted HO2 in high NO x conditions, which could have implications for ozone production. Three photochemical indicators show particularly high photochemical activity in Houston during the TRAMP2006 study: the long portion of the day for which ozone production was NO x -sensitive, the calculated ozone production rate that was second only to Mexico City's, and the OH chain length that was twice that of any other location. These results on photochemical activity provide additional support for regulatory actions to reduce reactive VOCs in Houston in order to reduce ozone and other pollutants.
Keywords: OH; HO2; OH reactivity; OH chainlength; HO x budget; Ozone production rate; Ozone production sensitivity;

A comparison of chemical mechanisms based on TRAMP-2006 field data by Shuang Chen; Xinrong Ren; Jingqiu Mao; Zhong Chen; William H. Brune; Barry Lefer; Bernhard Rappenglück; James Flynn; Jennifer Olson; James H. Crawford (4116-4125).
A comparison of a model using five widely known mechanisms (RACM, CB05, LaRC, SAPRC-99, SAPRC-07, and MCMv3.1) has been conducted based on the TexAQS II Radical and Aerosol Measurement Project (TRAMP-2006) field data in 2006. The concentrations of hydroxyl (OH) and hydroperoxy (HO2) radicals were calculated by a zero-dimensional box model with each mechanism and then compared with the OH and HO2 measurements. The OH and HO2 calculated by the model with different mechanisms show similarities and differences with each other and with the measurements. First, measured OH and HO2 are generally greater than modeled for all mechanisms, with the median modeled-to-measured ratios ranging from about 0.8 (CB05) to about 0.6 (SAPRC-99). These differences indicate that either measurement errors, the effects of unmeasured species or chemistry errors in the model or the mechanisms, with some errors being independent of the mechanism used. Second, the modeled and measured ratios of HO2/OH agree when NO is about 1 ppbv, but the modeled ratio is too high when NO was less and too low when NO is more, as seen in previous studies. Third, mechanism–mechanism HO x differences are sensitive to the environmental conditions – in more polluted conditions, the mechanism–mechanism differences are less. This result suggests that, in polluted conditions, the mechanistic details are less important than in cleaner conditions, probably because of the dominance of reactive nitrogen chemistry under polluted conditions.
Keywords: Hydroxyl radical; Hydroperoxy radical; Model intercomparison; Chemical mechanisms; Atmospheric chemistry;

Impact of clouds and aerosols on ozone production in Southeast Texas by James Flynn; Barry Lefer; Bernhard Rappenglück; Michael Leuchner; Ryan Perna; Jack Dibb; Luke Ziemba; Casey Anderson; Jochen Stutz; William Brune; Xinrong Ren; Jingqiu Mao; Winston Luke; Jennifer Olson; Gao Chen; James Crawford (4126-4133).
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(NO2) photolysis frequencies by nominally 17%, while aerosols reduced j(NO2) 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.
Keywords: TexAQS-II; TRAMP; Photolysis rates; Ozone production; Radiative transfer model; Photochemical box model;