Atmospheric characteristics conducive to high-ozone days in the Atlanta metropolitan area

The purpose of this paper is to identify the atmospheric conditions associated with elevated ground-level ozone concentrations during June–August of 2000–2007 at 11 ozone-monitoring stations in the Atlanta, GA, USA metropolitan statistical area (MSA). Analyses were confined to high-ozone days (HODs), which had a daily maximum 8-h average ozone concentration in the 95th percentile of all June–August values. Therefore, each station had 36 HODs. The southeastern and far northern portions of the MSA had HODs with the highest and lowest ozone concentrations, respectively. HODs at nearly all Atlanta MSA ozone-monitoring stations were enabled by migratory anticyclones. HODs for most stations were hot, dry, and calm with low morning mixing heights and high afternoon mixing heights. All sets of HODs had daily mean relative humidities and afternoon mixing heights that, respectively, were significantly less than and significantly greater than mean values for the remaining days. Urbanized Atlanta typically was upwind of an ozone-monitoring station on its HODs; therefore, wind direction on HODs varied considerably among the stations. HODs may have been caused partially by NO_x emissions from electric-utility power plants: HODs in the southern portion of the MSA were linked to air-parcel trajectories intersecting a power plant slightly northwest of Atlanta and plants in the Ohio River Valley, while HODs in the northern portion of the MSA were linked to air-parcel trajectories intersecting two large power plants slightly southeast of the Atlanta MSA. Results from this study suggest that future research in the Atlanta MSA should focus on power-plant contributions to ground-level ozone concentrations as well as the identification of non-monitored locations with potentially high ozone concentrations.     

Evaluation of air quality models for the simulation of a high ozone episode in the Houston metropolitan area

A high ozone event in the Houston–Galveston–Brazoria area was utilized to study the shortcomings of the current air quality models. To improve the baseline simulations with the Comprehensive Air quality Model with Extensions (CAMx) for developing the state implementation plan, the Texas Commission on Environmental Quality (TCEQ) imputed emissions of highly reactive volatile organic compounds (HRVOCs) by scaling the amount of fugitive emissions of olefins to co-emitted NO_x from selected point sources, effectively multiplying by 3–12 times over the regular inventory values. In this paper, CAMx and the Community Multiscale Air Quality (CMAQ) model were used to determine if the imputed HRVOC emissions were consistent with the observed atmospheric conditions. With the base emissions, CMAQ and CAMx both with the Carbon-Bond 4 (CB-4) mechanism simulated similar ozone concentrations. But with the imputed HRVOC emissions, CMAQ predicted lower ozone peaks than CAMx in the vicinity and downwind of the Ship Channel and other highly HRVOC-rich areas. Based on analyses of sensitivity simulations of CMAQ with different emission inputs and vertical diffusion algorithms in the model, we found that the modeled atmosphere lacked reactivity to produce the observed high ozone event. Although the imputed HRVOC emissions improved ozone prediction at the surface sites, but the ethylene concentrations were not consistent with the measurements at the super sites (La Porte and Clinton) and by NOAA aircraft. Several sensitivity tests designed to provide additional radicals into the system and other research results suggested that the lack of reactivity may need to be corrected by targeted, and probably of episodic, increase of HRVOC emissions, from the sources in the Houston Ship Channel. Additional investigation of the ozone production efficiency for different chemical mechanisms is necessary to pinpoint the emissions uncertainty issues.     

Beryllium-7 Measurements in the Houston and Phoenix Urban Areas: An Estimation of Upper Atmospheric Ozone Contributions

Abstract

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O₃) and aerosols in the troposphere. Beryllium-7 (⁷Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. ⁷Be has a 53.29-day half-life (478 keV γ) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O₃ from aloft can be transported into rural and urban regions during stratospheric–tropospheric folding events leading to increased background levels of O₃ at the surface. ⁷Be can be used as a tracer of upper atmospheric air parcels and the O₃ associated with them. Aerosol samples with a 2.5-µm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August– September of 2000, and at Waddell, AZ, near Phoenix, in June–July of 2001. A comparison of ⁷Be levels with 12-hr O₃ averages and maxima shows little correlation. Comparison of nighttime and daytime O₃ levels indicate that during the day, when mixing is anticipated to be higher, the correlation of ⁷Be with O₃ in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O₃ by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O₃ variance can be explained by the correlation with ⁷Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for ⁷Be correlations with either O₃ 24-hr averages or O₃ 12-hr maxima and is also in the range of the low O₃ levels (25 ppb) observed at Deer Park during a tropical storm event where the O₃ is attributable primarily to background air masses. That is, maximum background O₃ level contributions from stratospheric sources aloft are estimated to be in the range of 15–30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

Atmospheric oxidation of sulfur dioxide: A review as viewed from power plant and smelter plume studies

An overview is presented of significant historical, recent, and new power plant and smelter plume studies which have been directed at understanding the atmospheric oxidation of sulfur dioxide. It can be concluded that the average rate of oxidation of sulfur dioxide in plumes entering into and mixing with clean air is generally less than 1 %h⁻¹ but with polluted urban air the rate can be at least twice as fast. In addition, a diurnal variation in the rate is sometimes observed that is near zero at night and approx. 3% during mid-day. Although there is a tendency for some scientific observers to select the homogenous over the hetrogenous mechanism as the dominant pathway for the oxidation, the basis for choice is not definitive and most likely both mechanisms are at times operative. Suggestions are advanced for new and important studies that can be performed with technologies just becoming available.     

Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston,TX

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.     

Beryllium-7 measurements in the Houston and Phoenix urban areas: an estimation of upper atmospheric ozone contributions

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O3) and aerosols in the troposphere. Beryllium-7 (7Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. 7Be has a 53.29-day half-life (478 keV gamma) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O3 from aloft can be transported into rural and urban regions during stratospheric-tropospheric folding events leading to increased background levels of O3 at the surface. 7Be can be used as a tracer of upper atmospheric air parcels and the O3 associated with them. Aerosol samples with a 2.5-microm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August-September of 2000, and at Waddell, AZ, near Phoenix, in June-July of 2001. A comparison of 7Be levels with 12-hr O3 averages and maxima shows little correlation. Comparison of nighttime and daytime O3 levels indicate that during the day, when mixing is anticipated to be higher, the correlation of 7Be with O3 in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O3 by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O3 variance can be explained by the correlation with 7Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for 7Be correlations with either O3 24-hr averages or O3 12-hr maxima and is also in the range of the low O3 levels (25 ppb) observed at Deer Park during a tropical storm event where the O3 is attributable primarily to background air masses. That is, maximum background O3 level contributions from stratospheric sources aloft are estimated to be in the range of 15-30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

Size-resolved,real-time measurement of water-insoluble aerosols in metropolitan Atlanta during the summer of 2004

During the month of August 2004, the size-resolved number concentration of water-insoluble aerosols (WIA) from 0.25 to 2.0 μm was measured in real-time in the urban center of Atlanta, GA. Simultaneous measurements were performed for the total aerosol size distribution from 0.1 to 2.0 μm, the elemental and organic carbon mass concentration, the aerosol absorption coefficient, and the aerosol scattering coefficient at a dry (RH=30%) humidity. The mean aerosol number concentration in the size range 0.1–2.0 μm was found to be 360±175 cm⁻³, but this quantity fluctuated significantly on time scales of less than one hour and ranged from 25 to 1400 cm⁻³ during the sample period. The mean WIA concentration (0.25–2.0 μm) was 13±7 cm⁻³ and ranged from 1 to 60 cm⁻³. The average insoluble fraction in the size range 0.25–2.0 μm was found to be 4±2.5% with a range of 0.3–38%. The WIA population was found to follow a consistent diurnal pattern throughout the month with concentration maxima concurring with peaks in vehicular traffic flow. WIA concentration also responded to changes in meteorological conditions such as boundary layer depth and precipitation events. The temporal variability of the absorption coefficient followed an identical pattern to that of WIA and ranged from below the detection limit to 55 Mm⁻¹ with a mean of 8±6 Mm⁻¹. The WIA concentration was highly correlated with both the absorption coefficient and the elemental carbon mass concentration, suggesting that WIA measurements are dominated by fresh emissions of elemental carbon. For both the total aerosol and the WIA size distributions, the maximum number concentration was observed at the smallest sizes; however the WIA size distribution also exhibited a peak at 0.45 μm which was not observed in the total population. Over 60% of the particles greater than 1.0 μm were observed to be insoluble in the water sampling stream used by this instrumentation. Due to the refractive properties of black carbon, it is highly unlikely that these particles could be composed of elemental carbon, suggesting a crustal source for super-micron WIA.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

Detecting improvement in ambient air toxics: An application to ambient benzene measurements in Houston,Texas

Traditional regulatory methods for evaluating air toxics have several limitations. Two common methods rely either on self-reported industrial emissions from the Toxics Release Inventory or a single summary statistic such as the average or arithmetic mean. A novel statistical approach for detecting overall long term improvement in ambient air quality is demonstrated using measurements of the air toxic benzene evaluated over five years in Houston, Texas. Through trends of seven key statistical measures, long term improvements were detected at more monitors than would have been found using traditional methods while lack of improvement is highlighted at other monitors. This new approach includes analysis of high and low end concentrations, as well as central tendency, evaluated at specific air toxic human health risk thresholds.     

Atmospheric oxidation of elemental mercury by ozone in the aqueous phase

The aqueous phase oxidation of elemental mercury by ozone has been investigated in the laboratory using a quartz glass reactor with gas phase concentrations of 400–1800ng m⁻³ and 70–200 ppb for Hg(0) and O₃, respectively. The absorption of Hg in the water phase was increased by three orders of magnitude with O₃ present. If the oxidation were to proceed with the same speed in liquid water in contact with the atmosphere,conversion rales of 1–4% h⁻¹ would be implied. Experiments using ambient urban air with 2–6 ng Hg m⁻³ confirm the process at elevated O₃ concentrations. At ambient O₃ concentrations competitive reactions become important, e.g. O₃ consumption by SO₂, hydrocarbons etc., and even some reduction of Hg²⁺ could occur. The atmospheric oxidation of Hg(0) by O₃ in water is thus considered important at high O₃ levels in regionally polluted or remote areas.     

Atmospheric measurements of the halogenated hydrocarbons involved in global change phenomena

Chlorofluorocarbons and their replacement compounds are anthropogenic compounds of great environmental concern. For this reason monitoring their atmospheric mixing ratios on a worldwide scale is recommended. An analytical methodology for the simultaneous determination of selected chlorofluorocarbons and their replacement compounds has recently been developed. This methodology was applied in the analysis of actual air samples collected in remote and semi-remote areas located in the Northern and Southern Hemispheres. The concentration levels measured in the air samples collected in the two hemispheres are reported.     

Nitric acid measurements in connection with corrosion studies

Atmospheric nitric acid does not only contribute to acidification and eutrophication but causes also deterioration of many materials. Material belonging to our cultural heritage is irreplaceable and its lifetime can depend on the corrosion rate. Nowadays, only very few long-term measurements of nitric acid concentration in Europe and elsewhere have been published so far. Due to the fact that atmospheric corrosion is a long-term effect, the relevant research does not necessarily require monitoring of nitric acid on a daily basis. Moreover, power supply is often not available at sites where it is of interest to study the corrosion rate of objects belonging to our cultural heritage. Besides, such measurements must not disturb the impression of the objects. In this context, the diffusive sampling technique provides average concentrations over long-term periods at a low cost. In addition, the samplers used are noiseless, comparatively small in size, and thus, their ambient exposure can be made inconspicuously and with discretion. The present paper is focussed on an intensive corrosion study, which was performed at 11 rural and 23 urban sites in Europe and one rural site in Canada during 2002/2003. For the above-mentioned reasons, the diffusive sampler's technique was employed for the nitric acid monitoring, where the diffusive samplers were first tested against the denuder technique and bi-monthly measurements of nitric acid were thus obtained. The bi-monthly concentrations varied from 0.05 to 4.3 μg m⁻³ and the annual averages from 0.16 to 2.0 μg m⁻³. The observations collected, depicted a summertime maximum and a wintertime minimum in the nitric acid concentrations, except at the northern rural sites, where a maximum in the winter was observed. Furthermore, the observed nitric acid concentrations in Southern Europe were higher than in Northern Europe. In a few places, close to the sites of urban measurements, rural measurements of nitric acid were also performed. The obtained nitric acid concentrations were higher in the cities, especially during the period of maximum concentrations.     

复合陶粒基质甲烷氧化能力评价

以陶粒为载体,利用甲烷、氧气和养分制备出新型甲烷氧化基质--复合陶粒基质.以水分、孔隙度、碳氮比、NO3-浓度为影响因素,以复合陶粒基质的最大甲烷氧化速率(Vmax)为目标函数,进行L16(45)正交试验.以正交试验单因子方差分析结果(F值)为权重分配依据,应用层次分析法建立复合陶粒基质的甲烷氧化能力评分机制.评价结果...     

臭氧氧化及其他强化技术协同降解聚乙烯醇

采用O₃氧化降解水中聚乙烯醇（PVA）,考察了O₃氧化的影响因素及与其他强化技术协同下的降解效果。结果表明,经12 min处理,O₃/超声波、O₃/紫外光协同作用下PVA降解率较直接O₃氧化的63.2%有显著提高,表现出了良好的协同效应。通过比较酸性条件下添加不同量Fenton试剂的作用效果可知,·OH的氧化作用是PVA降解的重要原因。     

Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).     

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston,TX

The sources of submicrometer particulate matter (PM₁) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM₁ composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM₁ and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM₁ levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM₁ mass concentrations (average 11.6 ± 5.7 µg/m³) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM₁ (average 4.4 ± 3.3 µg/m³), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA.

Implications: This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM₁) in greater Houston. The data set indicates substantial spatial variations in PM₁ sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM₁. These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM₁ from automobiles and industry but also to reduce the emissions of important secondary PM₁ precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.     

Further studies of oxidation processes on filter surfaces: Evidence for oxidation products and the influence of time in service

The sensory pollutants emitted by loaded ventilation filters are assumed to include products formed via oxidation of organics associated with captured particles. In this study, experiments were performed that used either particle production or ozone removal as probes to further improve our understanding of such processes. The measured ratio of downstream to upstream submicron particle concentrations increased when ozone was added to air passing through samples from loaded particle filters. Such an observation is consistent with low volatility oxidation products desorbing from the filter and subsequently partitioning between the gas phase and the surface of particles that have passed through the filter, including particles that were previously too small (<20 nm) to be detected by the instrument used in these studies. A related set of experiments conducted with unused filters and filters that had been in service from 2 to 16 weeks found that ozone removal efficiencies changed in a manner that indicated at least two different removal mechanisms—reactions with compounds present on the filter media following manufacturing and reactions with compounds associated with captured particles. The contribution from the former varies with the type and manufacturer of the filter, while that of the latter varies with the duration of service and nature of the captured particles. In complimentary experiments, a filter sample protected from ozone during its 9 weeks of service had higher ozone removal efficiencies than an identical filter not protected from ozone during the same 9 weeks of service filtering the same air. This result indicates that a filter's exposure history subsequently influences the quantity of oxidation products generated when ozone-containing air flows through it.     

Comparison of life-cycle energy and emissions footprints of passenger transportation in metropolitan regions

A comparative life-cycle energy and emissions (greenhouse gas, CO, NO_X, SO₂, PM₁₀, and VOCs) inventory is created for three U.S. metropolitan regions (San Francisco, Chicago, and New York City). The inventory captures both vehicle operation (direct fuel or electricity consumption) and non-operation components (e.g., vehicle manufacturing, roadway maintenance, infrastructure operation, and material production among others). While urban transportation inventories have been continually improved, little information exists identifying the particular characteristics of metropolitan passenger transportation and why one region may differ from the next. Using travel surveys and recently developed transportation life-cycle inventories, metropolitan inventories are constructed and compared. Automobiles dominate total regional performance accounting for 86–96% of energy consumption and emissions. Comparing system-wide averages, New York City shows the lowest end-use energy and greenhouse gas footprint compared to San Francisco and Chicago and is influenced by the larger share of transit ridership. While automobile fuel combustion is a large component of emissions, diesel rail, electric rail, and ferry service can also have strong contributions. Additionally, the inclusion of life-cycle processes necessary for any transportation mode results in significant increases (as large as 20 times that of vehicle operation) for the region. In particular, emissions of CO₂ from cement production used in concrete throughout infrastructure, SO₂ from electricity generation in non-operational components (vehicle manufacturing, electricity for infrastructure materials, and fuel refining), PM₁₀ in fugitive dust releases in roadway construction, and VOCs from asphalt result in significant additional inventory. Private and public transportation are disaggregated as well as off-peak and peak travel times. Furthermore, emissions are joined with healthcare and greenhouse gas monetized externalities to evaluate the societal costs of passenger transportation in each region. Results are validated against existing studies. The dominating contribution of automobile end-use energy consumption and emissions is discussed and strategies for improving regional performance given private travel's disproportionate share are identified.