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.     

The Impact of Stratospheric Ozone on Tropospheric Air Quality

A background of ozone (O₃), principally of stratospheric origin, is present in the lower free troposphere. Typical mean O₃ levels of 50 ppb, 40 ppb, and 30 ppb are encountered here in spring, summer, and fall, respectively. Maximum hourly O₃ concentrations which are twice these mean values can be expected. Ozone from the free troposphere is routinely brought down to ground level under turbulent atmospheric conditions. Deep and rapid Intrusions of stratospheric air into the lower troposphere are associated with low-pressure troughs and occur regularly. In the mid troposphere, O₃ levels as high as 300 ppb are found within these intrusions. Observational data showing these intrusions, containing high O₃ concentrations, to directly reach ground level are currently lacking. Over the United States, an intrusion was present aloft on 8 9% of the days in 1978. The frequency, however, is somewhat reduced in summer and a northward movement is evident. During 1978, no intrusion occurred south of 30°N between June and August and none south of 40 °N in August.

The hypothesis that low levels of stratospheric O₃ produce disproportionately large amounts of O₃ in the polluted atmosphere cannot be supported from currently known chemistry but should be studied further. The experimental technique involving a ⁷Be/O₃ ratio to estimate the daily stratospheric component of ground level O₃ is unverified and considered to be inadequate for air quality applications. Estimates resulting from such a technique are considered uncertain by a factor of more than three. Specially designed aircraft studies provide the best means to determine quantitatively the impact of stratospheric O₃ on ground level air quality.     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston, Texas

In Houston, some of the highest measured 8-hr ozone (O3) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O3 concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O3 changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O3 concentrations, the AQM predicted high O3 over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O3, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O3 concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O3 concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O3 standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O3, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.     

Defining the photochemical contribution to particulate matter in urban areas using time-series analysis

The objective of this project is to demonstrate how the ambient air measurement record can be used to define the relationship between O3 (as a surrogate for photochemistry) and secondary particulate matter (PM) in urban air. The approach used is to develop a time-series transfer-function model describing the daily PM10 (PM with less than 10 microm aerodynamic diameter) concentration as a function of lagged PM and current and lagged O3, NO or NO2, CO, and SO2. Approximately 3 years of daily average PM10, daily maximum 8-hr average O3 and CO, daily 24-hr average SO2 and NO2, and daily 6:00 a.m.-9:00 a.m. average NO from the Aerometric Information Retrieval System (AIRS) air quality subsystem are used for this analysis. Urban areas modeled are Chicago, IL; Los Angeles, CA; Phoenix, AZ; Philadelphia, PA; Sacramento, CA; and Detroit, MI. Time-series analysis identified significant autocorrelation in the O3, PM10, NO, NO2, CO, and SO2 series. Cross correlations between PM10 (dependent variable) and gaseous pollutants (independent variables) show that all of the gases are significantly correlated with PM10 and that O3 is also significantly correlated lagged up to two previous days. Once a transfer-function model of current PM10 is defined for an urban location, the effect of an O3-control strategy on PM concentrations is estimated by calculating daily PM10 concentrations with reduced O3 concentrations. Forecasted summertime PM10 reductions resulting from a 5 percent decrease in ambient O3 range from 1.2 microg/m3 (3.03%) in Chicago to 3.9 microg/m3 (7.65%) in Phoenix.     

Characteristics of urban ground-level ozone in Korea

This study considers the characteristics of ground-level ozone (O3) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8-hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologically equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.     

The Effect of NMOC and Ozone Aloft on Modeled Urban Ozone Production and Control Strategies

Carbon bond (CB-III) fractions for non-methane organic carbon compounds (NMOC) measured in the background alrmass adverted into several urban areas in the eastern and southern United States are reported. These, together with ozone measured aloft, were used In an Empirical Kinetic Modeling Approach (EKMA) to model urban ozone production and urban ozone control strategies.

Over a range of zero to double the mean of the measured NMOC concentrations aloft (0 to 70 ppbC) and zero to the highest ozone levels recorded aloft (0 to 65 ppb), it was found that urban ozone production and control strategies were relatively insensitive to NMOC from aloft. However, urban ozone production was sensitive to ozone from aloft, while ozone control strategies were insensitive to ozone from aloft.     

Spatial heterogeneity of PM10 and O3 in São Paulo, Brazil, and implications for human health studies

Developing exposure estimates is a challenging aspect of investigating the health effects of air pollution. Pollutant levels recorded at centrally located ambient air quality monitors in a community are commonly used as proxies for population exposures. However, if ample intraurban spatial variation in pollutants exists, city-wide averages of concentrations may introduce exposure misclassification. We assessed spatial heterogeneity of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) and ozone (O3) and evaluated implications for epidemiological studies in S?o Paulo, Brazil, using daily (24-hr) and daytime (12-hr) averages and 1-hr daily maximums of pollutant levels recorded at the regulatory monitoring network. Monitor locations were also analyzed with respect to a socioeconomic status index developed by the municipal government. Hourly PM10 and O3 data for the Sāo Paulo Municipality and Metropolitan Region (1999-2006) were used to evaluate heterogeneity by comparing distance between monitors with pollutants' correlations and coefficients of divergence (CODs). Both pollutants showed high correlations across monitoring sites (median = 0.8 for daily averages). CODs across sites averaged 0.20. Distance was a good predictor of CODs for PM10 (p < 0.01) but not O3, whereas distance was a good predictor of correlations for O3 (p < 0.01) but not PM10. High COD values and low temporal correlation indicate a spatially heterogeneous distribution of PM10. Ozone levels were highly correlated (r > or = 0.75), but high CODs suggest that averaging over O3 levels may obscure important spatial variations. Of municipal districts in the highest of five socioeconomic groups, 40% have > or = 1 monitor, whereas districts in the lowest two groups, representing half the population, have no monitors. Results suggest that there is a potential for exposure misclassification based on the available monitoring network and that spatial heterogeneity depends on pollutant metric (e.g., daily average vs. daily 1-hr maximum). A denser monitoring network or alternative exposure methods may be needed for epidemiological research. Findings demonstrate the importance of considering spatial heterogeneity and differential exposure misclassification by subpopulation.     

Rural southeast Texas air quality measurements during the 2006 Texas Air Quality Study

The authors conducted air quality measurements of the criteria pollutants carbon monoxide, nitrogen oxides, and ozone together with meteorological measurements at a park site southeast of College Station, TX, during the 2006 Texas Air Quality Study II (TexAQS). Ozone, a primary focus of the measurements, was above 80 ppb during 3 days and above 75 ppb during additional 8 days in summer 2006, suggestive of possible violations of the ozone National Ambient Air Quality Standard (NAAQS) in this area. In concordance with other air quality measurements during the TexAQS II, elevated ozone mixing ratios coincided with northerly flows during days after cold front passages. Ozone background during these days was as high as 80 ppb, whereas southerly air flows generally provided for an ozone background lower than 40 ppb. Back trajectory analysis shows that local ozone mixing ratios can also be strongly affected by the Houston urban pollution plume, leading to late afternoon ozone increases of as high as 50 ppb above background under favorable transport conditions. The trajectory analysis also shows that ozone background increases steadily the longer a southern air mass resides over Texas after entering from the Gulf of Mexico. In light of these and other TexAQS findings, it appears that ozone air quality is affected throughout east Texas by both long-range and regional ozone transport, and that improvements therefore will require at least a regionally oriented instead of the current locally oriented ozone precursor reduction policies.     

Ozone distribution and phytotoxic potential in mixed conifer forests of the San Bernardino Mountains, southern California

In the San Bernardino Mountains of southern California, ozone (O(3)) concentrations have been elevated since the 1950s with peaks reaching 600ppb and summer seasonal averages >100ppb in the 1970s. During that period increased mortality of ponderosa and Jeffrey pines occurred. Between the late 1970s and late1990s, O(3) concentrations decreased with peaks approximately 180ppb and approximately 60ppb seasonal averages. However, since the late 1990s concentrations have not changed. Monitoring during summers of 2002-2006 showed that O(3) concentrations (2-week averages) for individual years were much higher in western sites (58-69ppb) than eastern sites (44-50ppb). Potential O(3) phytotoxicity measured as various exposure indices was very high, reaching SUM00 - 173.5ppmh, SUM60 - 112.7ppmh, W126 - 98.3ppmh, and AOT40 - 75ppmh, representing the highest values reported for mountain areas in North America and Europe.     

A climatology of 7Be at four high-altitude stations at the Alps and the Northern Apennines

The ⁷Be activity concentrations measured from 1996 to 1998 at four high-altitude stations, Jungfraujoch—Switzerland, Zugspitze—Germany, Sonnblick—Austria and Mt. Cimone—Italy, were analyzed in combination with a set of, meteorological and atmospheric parameters such as the tropopause height, relative and specific humidity and also in conjunction with 3D back-trajectories in order to investigate the climatological features of ⁷Be. A frequency distribution analysis on ⁷Be activity concentrations revealed the existence of two concentration classes around 1.5 and 6 mBq m⁻³ and a transition class between the two modes of the distribution at 3–4 mBq m⁻³. Cross-correlation analysis performed between ⁷Be and a number of meteorological and atmospheric parameters at the first three stations showed a strong negative correlation with relative humidity (−0.56, −0.51, −0.41) indicating the importance of wet scavenging as a controlling mechanism. Also, the positive correlation with the height of 3-days back-trajectories and tropopause height (+0.49/+0.43, +0.59/+0.36, +0.44/+0.38) shows that downward transport from the upper or middle to lower troposphere within anticyclonic conditions plays also an important role. Trajectory statistics showed that low ⁷Be concentrations typically originate from lower-altitude subtropical ocean areas, while high concentrations arrive from the north and high altitudes, as is characteristic for stratospheric intrusions. Although the ⁷Be activity concentrations are highly episodic, the monthly means indicate an annual cycle with a late-summer maximum at all stations. The correlation coefficients calculated for monthly means of the ⁷Be and atmospheric data suggest that the main predictor controlling the seasonality of the ⁷Be concentrations is tropopause height (+0.76, +0.56, +0.60), reflecting more vertical transport from upper tropospheric levels into the lower troposphere during the warm season than during the cold season.     

A climatology of Be at four high-altitude stations at the Alps and the Northern Apennines

The ⁷Be activity concentrations measured from 1996 to 1998 at four high-altitude stations, Jungfraujoch—Switzerland, Zugspitze—Germany, Sonnblick—Austria and Mt. Cimone—Italy, were analyzed in combination with a set of, meteorological and atmospheric parameters such as the tropopause height, relative and specific humidity and also in conjunction with 3D back-trajectories in order to investigate the climatological features of ⁷Be. A frequency distribution analysis on ⁷Be activity concentrations revealed the existence of two concentration classes around 1.5 and 6 mBq m⁻³ and a transition class between the two modes of the distribution at 3–4 mBq m⁻³. Cross-correlation analysis performed between ⁷Be and a number of meteorological and atmospheric parameters at the first three stations showed a strong negative correlation with relative humidity (−0.56, −0.51, −0.41) indicating the importance of wet scavenging as a controlling mechanism. Also, the positive correlation with the height of 3-days back-trajectories and tropopause height (+0.49/+0.43, +0.59/+0.36, +0.44/+0.38) shows that downward transport from the upper or middle to lower troposphere within anticyclonic conditions plays also an important role. Trajectory statistics showed that low ⁷Be concentrations typically originate from lower-altitude subtropical ocean areas, while high concentrations arrive from the north and high altitudes, as is characteristic for stratospheric intrusions. Although the ⁷Be activity concentrations are highly episodic, the monthly means indicate an annual cycle with a late-summer maximum at all stations. The correlation coefficients calculated for monthly means of the ⁷Be and atmospheric data suggest that the main predictor controlling the seasonality of the ⁷Be concentrations is tropopause height (+0.76, +0.56, +0.60), reflecting more vertical transport from upper tropospheric levels into the lower troposphere during the warm season than during the cold season.     

Estimates of community exposure and health risk to sulfur dioxide from power plant emissions using short-term mobile and stationary ambient air monitoring

To estimate plausible health effects associated with peak sulfur dioxide (SO₂) levels from three coal-fired power plants in the Baltimore, Maryland, area, air monitoring was conducted between June and September 2013. Historically, the summer months are periods when emissions are highest. Monitoring included a 5-day mobile and a subsequent 61-day stationary monitoring study. In the stationary monitoring study, equipment was set up at four sites where models predicted and mobile monitoring data measured the highest average concentrations of SO₂. Continuous monitors recorded ambient concentrations each minute. The 1-min data were used to calculate 5-min and 1-hr moving averages for comparison with concentrations from clinical studies that elicited lung function decrement and respiratory symptoms among asthmatics. Maximum daily 5-min moving average concentrations from the mobile monitoring study ranged from 70 to 84 ppb (183–220 µg/m³), and maximum daily 1-hr moving average concentrations from the mobile monitoring study ranged from 15 to 24 ppb (39–63 µg/m³). Maximum 5-min moving average concentrations from stationary monitoring ranged from 39 to 229 ppb (102–600 µg/m³), and maximum daily 1-hr average concentrations ranged from 15 to 134 ppb (40–351 µg/m³). Estimated exposure concentrations measured in the vicinity of monitors were below the lowest levels that have demonstrated respiratory symptoms in human clinical studies for healthy exercising asthmatics. Based on 5-min and 1-hr monitoring, the exposure levels of SO₂ in the vicinity of the C.P. Crane, Brandon Shores, and H.A. Wagner power plants were not likely to elicit respiratory symptoms in healthy asthmatics.

Implications: Mobile and stationary air monitoring for SO₂ were conducted to quantify short-term exposure risk, to the surrounding community, from peak emissions of three coal-fired power plants in the Baltimore area. Concentrations were typically low, with only a few 5-min averages higher than levels indicated during clinical trials to induce changes in lung capacity for healthy asthmatics engaged in exercise outdoors.     

Meteorological factors of ozone predictability at Houston, Texas

Several ozone modeling approaches were investigated to determine if uncertainties in the meteorological data would be sufficiently large to limit the application of physically realistic ozone (O3) forecast models. Three diagnostic schemes were evaluated for the period of May through September 1997 for Houston, TX. Correlations between measured daily maximum and model calculated O3 air concentrations were found to be 0.70 using a linear regression model, 0.65 using a non-advective box model, and 0.49 using a three-dimensional (3-D) transport and dispersion model. Although the regression model had the highest correlation, it showed substantial underestimates of the highest concentrations. The box model results were the most similar to the regression model and did not show as much underestimation. The more complex 3-D modeling approach yielded the worst results, likely resulting from O3 maxima that were driven by local factors rather than by the transport of pollutants from outside of the Houston domain. The highest O3 concentrations at Houston were associated with light winds and meandering trajectories. A comparison of the gridded meteorological data used by the 3-D model to the observations showed that the wind direction and speed values at Houston differed most on those days on which the O3 underestimations were the greatest. These periods also tended to correspond with poor precipitation and temperature estimates. It is concluded that better results are not just obtained through additional modeling complexity, but there needs to be a comparable increase in the accuracy of the meteorological data.     

Vertical mixing above Summit,Greenland: Insights into seasonal and high frequency variability from the radionuclide tracers 7Be and 210Pb

The activity of the natural radionuclide tracers ⁷Be and ²¹⁰Pb has been determined in bulk aerosol samples collected over 2-day intervals for nearly five full years at Summit, Greenland. Year-round sampling was conducted in three campaigns; summer 1997 to summer 1998, summer 2000 to summer 2002, and summer 2003 to present. As in previous summer campaigns at Summit, and a year-round investigation at Dye 3, variations in the activities of the tracers on short time scales were strongly correlated despite the upper troposphere/lower stratosphere source of ⁷Be and the continental surface source of ²²²Rn (precursor of ²¹⁰Pb). This behavior is attributed to boundary layer dynamics exerting the dominant control on activities in air just above the ice sheet. Aerosols and associated species are depleted from the boundary layer above the snow when a strong inversion limits exchange with the free troposphere. Episodic weakening of the inversion allows ventilation of the boundary layer. This cycle drives simultaneous decreases and increases in the radionuclide tracers. The correlation between ⁷Be and ²¹⁰Pb on seasonal and annual bases was found to be stronger than at Dye 3, and the average activity of ⁷Be was lower at Summit despite the higher elevation (3.0 versus 2.5 km). These observations indicate that the boundary layer at Summit is more effectively isolated than at Dye 3. The activity of ⁷Be at Summit peaked in June or July all 5 years, closely following the seasonality of stratospheric injection of ⁷Be into the Arctic troposphere (based on seasonality of the ¹⁰Be/⁷Be ratio previously measured at Alert, NWT). This suggests that when the boundary layer at Summit is replenished by ventilation, it receives air reflecting the composition of the mid and upper troposphere.     

Application of artificial neural networks to modeling and prediction of ambient ozone concentrations

The deterministic modeling of ambient O3 concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O3 concentrations based on a limited number of measured hydrocarbon species, NOx compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O3, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O3 concentrations from measured VOC and NOx concentrations. To predict the future concentrations of O3, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species. The steady-state model produced an approximation of O3 data and demonstrated the functional relationship between O3 and VOC-NOx concentrations. The dynamic models were able to the adequately predict the O3 concentration and behavior of VOC-NOx-O3 system a number of hourly intervals into the future. For 3 hr into the future, O3 concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

Mercury species measured atop the Moody Tower TRAMP site,Houston, Texas

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.     

Molecular composition of organic fine particulate matter in Houston,TX

Organic fine particulate matter collected in Houston, TX between March 1997 and March 1998 was analyzed to determine the concentration of individual organic compounds. Samples from four sites were analyzed including two industrial locations (Houston Regional Monitoring Corporation (HRM-3) site in Channelview and Clinton Drive site near the Ship Channel Turning Basin), one suburban location (Bingle Drive site in Northwest Houston) and one background site (Galveston Island). At the three urban locations, samples were divided into three seasonal sample aggregates (spring, summer and winter), while at the background site a single annual average sample pool was used. Between 10 and 16 individual samples were pooled to get aggregate samples with enough organic carbon mass for analysis. Overall, 82 individual organic compounds were quantified. These include molecular markers which are compounds unique to specific fine particle sources and can be used to track the relative contribution of source emissions to ambient fine particle levels. The differences both spatially and temporally in these tracers can be used to evaluate the variability in emission source strengths.     

Consultant Guide/1987

ABSTRACT

This study considers the characteristics of ground-level ozone (O₃) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologi-cally equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.     

Method comparisons for particulate nitrate, elemental carbon, and PM2.5 mass in seven U.S. cities

Methods that measure PM2.5 mass, total particulate NO3-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r2 = 0.99) with the PM2.5 Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies. The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r2 = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Particulate NO3- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO3- measured from the HI Teflon (DuPont) filter to assess NO3- artifacts. Significant NO3- losses (approximately 50% of total NO3-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na2CO3-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO3- from the Teflon filter. The HEADS with the Na2CO3-coated filter consistently underestimated the total particulate NO3- by approximately 20% compared to the nylon HEADS.