Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre,Brazil

For 41 days between 25 May 1996 and 27 March 1997, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured by electron capture gas chromatography at Santa Rita near Porto Alegre, RS, Brazil, where light-duty vehicles used either ethanol or a gasoline–MTBE blend. Daily maximum concentrations ranged from 0.19 to 6.67 ppb for PAN and 0.06 to 0.72 ppb for PPN. Linear regression of maximum PPN vs. maximum PAN yielded a slope of 0.105±0.004 (R²=0.974). Diurnal variations of ambient PAN often followed those of ozone with respect to time of day but not with respect to amplitude. This was reflected in the large relative standard deviations associated with the study-averaged PAN/ozone concentration ratio, 0.037±0.105 (ppb/ppb, n=789) and the maximum PAN/maximum ozone concentration ratio, 0.028±0.015 (ppb/ppb, range 0.005–0.078, n=41). On several days PAN accounted for large fractions of the total ambient NO_x in the late morning and afternoon hours, e.g., PAN/NO_x⩽0.58 and PAN/(NO_x–NO) ⩽0.76 on 27 March 1997. The amount of PAN lost by thermal decomposition (TPAN) was comparable in magnitude to that present in ambient air. The ratios TPAN/(PAN+TPAN) were up to 0.53, 0.67 and 0.64 during the warm afternoons of 25, 26 and 27 March 1997, respectively. The highest calculated value of TPAN was 5.6 ppb on 27 March 1997. On that day the 24 h-averaged value of TPAN (1.01 ppb) was nearly the same as that of PAN (1.09 ppb). Using computer kinetic modeling (SAPRC 97 chemical mechanism) and sensitivity analysis of VOC incremental reactivity, we ranked VOC present in Porto Alegre ambient air for their importance as precursors to PAN and to PPN. Using as input data the averages of VOC concentrations measured in downtown Porto Alegre during the ca. 1 yr period March 1996–April 1997, we calculated that the most important precursors to PAN and PPN were the SAPRC 97 model species ARO2 (which includes the aromatics xylenes, trimethylbenzenes, ethyltoluenes, etc.), which accounted for ca. 17% of the total PAN and total PPN formation potentials. Overall, the results indicate a major role for aromatics and alkenes and a minor role for acetaldehyde and ethanol as precursors to peroxyacyl nitrates in the Porto Alegre urban area.     

Urban and rural ozone concentrations in Alberta,Canada

Ozone concentrations in Alberta cities typically exhibit a maximum in May (up to 35 ppb) and a minimum in November (as low as 4 ppb). This behaviour is similar to that of rural Alberta O₃ concentrations. Annual O₃ concentrations at six urban monitoring stations vary from 11 ppb to 22 ppb and are about one-half the values at rural stations. In winter, urban O₃ concentrations are always smaller than rural concentrations and the cities act as sinks for O₃. Although urban stations do not exceed Canada's maximum acceptable levels of daily (25 ppb) and annual (15 ppb) O₃ concentrations as often as rural stations, the frequency is still quite large. Canada's hourly maximum desirable level (50 ppb) is exceeded 11 times more often at the remote (rural) station than at the downtown (urban) stations.     

Schedule of Technical Sessions

Peroxyacyl nitrates are a family of compounds which result from photochemical reactions between contaminants released to the atmosphere by combustion of organic fuels. Peroxyacetyl nitrate (PAN) is the most abundant member of this family and is responsible for serious plant injury in some polluted areas. Plant injury has been recognized in at least 19 states and several foreign countries but economic loss has caused greatest concern in California. Characteristically, injury from PAN appears as glazing or bronzing of the lower leaf surface but the symptom syndrome may also include tissue collapse, chlorosis, and leaf drop. PAN inhibits activity of several enzyme systems by attacking the sulfhydryl group when enzyme extracts are fumigated in vitro, PAN may produce visible symptoms when sensitive plants are exposed for 4 hours to about 14 ppb. Other chemical members of the family are more toxic than PAN. Concentrations of 20 to 30 ppb PAN occur frequently at Riverside, Calif, and a maximum peak of 58 ppb was measured for one 2-hour period. Peaks as high as 54 ppb were reported at Salt Lake City, and 210 ppb at Los Angeles, Calif.     

Photochemical formation and transport of ozone in Athens,Greece

An evaluation of the diurnal variation of the hourly ozone concentrations measured at five sites in Greater Athens from June until early September 1984 indicates that photosmog episodes in Greater Athens are associated with the sea breeze circulation. Due to local air circulation in the Athens basin, precursors of O₃ are transported to and accumulated in the Saronikos Bay during the morning hours while the land breeze is blowing. At noon, when the sea breeze sets in, the O₃ formed over the sea is brought back to the coast and to central Athens where it increases the local O₃ concentration by a factor of 3–5 within a few hours. The O₃ levels often remain high throughout the night. During the photochemical smog episodes, all of them accompanied by well-developed sea breezes, the U.S. Air Quality Standard of 120 ppb O₃ was exceeded for 4–7 h day⁻¹. Peak O₃ concentrations up to nearly 200 ppb were recorded in the smog episodes.Relatively high O₃ concentrations were measured on the island of Aegina. They tend to remain high during the night and can be attributed only to primary pollutant transport from Greater Athens advected by the land breeze. The O₃ values obtained at Mount Immitos (1000 m above MSL) suggest that, first, the sea breeze inhibits the influence of vertical thermal convection up to heights above 600 m, and second, no O₃ is noticeable from above the tropopause to ground level or from long-range transport.     

Vertical Ozone Profile in the Lower Troposphere over Chicago

ABSTRACT

A 15-year (1981-95) climatology for the diurnal maximum ozone concentration (DMOC) was developed using 1-hr average ozone concentrations in the Baltimore-Washington area, which was made up of four regions: Baltimore, Washington, non-urban Maryland, and non-urban northern Virginia. The DMOC time series for each of these regions were divided into four terms representing different behavioral time scales: the long-term mean; the mean in-tra-annual perturbation; the interannual perturbation; and the synoptic perturbation. The urban regions had smaller values of the long-term mean ozone, but the annual range was larger. The values of the interannual perturbation were largest in the summer, when ozone production is significant, and smallest in the late winter and early spring. The interannual perturbation in the summer in the four regions consistently had positive departures in 1983, 1988, and 1991, and it had negative departures in 1981, 1984, 1985, 1989, 1990, and 1992. Summers with large positive interannual departures experienced a large number of ozone exceedances (i.e., relative to the 1-hr National Ambient Air Quality Standard of 125 parts per billion [ppb]), and summers with large negative departures experienced few or no exceedances. About 50% of the exceedances had concentrations ranging in value from 125-135 ppb, and about 75% had concentrations from 125-145 ppb.     

Peroxyacetyl nitrate (PAN) in the urban atmosphere

Peroxyacetyl nitrate (PAN) in air has been well known as the indicator of photochemical smog due to its frequent occurrences in Seoul metropolitan area. This study was implemented to assess the distribution characteristics of atmospheric PAN in association with relevant parameters measured concurrently. During a full year period in 2011, PAN was continuously measured at hourly intervals at two monitoring sites, Gwang Jin (GJ) and Gang Seo (GS) in the megacity of Seoul, South Korea. The annual mean concentrations of PAN during the study period were 0.64 ± 0.49 and 0.57 ± 0.46 ppb, respectively. The seasonal trends of PAN generally exhibited dual peaks in both early spring and fall, regardless of sites. Their diurnal trends were fairly comparable to each other. There was a slight time lag (e.g., 1 h) in the peak occurrence pattern between O₃ and PAN, as the latter trended to peak after the maximum UV irradiance period (16:00 (GJ) and 17:00 (GS)). The concentrations of PAN generally exhibited strong correlations with particulates. The results of this study suggest that PAN concentrations were affected sensitively by atmospheric stability, the wet deposition of NO₂, wind direction, and other factors.     

Industrial sources influence air concentrations of hydrogen sulfide and sulfur dioxide in rural areas of western Canada

A survey of monthly average concentrations of sulfur dioxide (SO2) and hydrogen sulfide (H2S) at rural locations in western Canada (provinces of Alberta, British Columbia, and Saskatchewan) was conducted in 2001-2002, as part of an epidemiological study of the effects of oil and gas industry emissions on the health of cattle. Repeated measurements were obtained at some months and locations. We aimed to develop statistical models of the effect of oil and gas infrastructure on air concentrations. The regulatory authorities supplied the information on location of the different oil and gas facilities during the study period and, for Alberta, provided data on H2S content of wells and flaring volumes. Linear mixed effects models were used to relate observed concentrations to proximity and type of oil and gas infrastructure. Low concentrations were recorded; the monthly geometric mean was 0.1-0.2 ppb for H2S, and 0.3-1.3 ppb for SO2. Substantial variability between repeated measurements was observed. The precision of the measurement method was 0.005 ppb for both contaminants. There were seasonal trends in the concentrations, but the spatial variability was greater. This was explained, in part, by proximity to oil/gas/bitumen wells and (for SO2) gas plants. Wells within 2 km of monitoring stations had the greatest impact on measured concentrations. For H2S, 8% of between-location variability was explained by proximity to industrial sources of emissions; for SO2 this proportion was 18%. In Alberta, proximity to sour gas wells and flares was associated with elevated H2S concentrations; however, the estimate of the effect of sour gas wells in the immediate vicinity of monitoring stations was unstable. Our study was unable to control for all possible sources of the contaminants. However, the results suggest that oil and gas extraction activities contribute to air pollution in rural areas of western Canada.     

Modelling local and synoptic scale influences on ozone concentrations in a topographically complex region of Southern Italy

A modelling study with the on-line coupled Eulerian chemical-weather model WRF/Chem for the Southern Italian region around Cosenza (Calabria) was conducted to identify the influences of synoptic scale meteorology, local scale wind systems and local emissions on ozone concentrations in this orographically complex region. Four periods of 5–7 days were chosen, one from each season, which had wind pattern characteristics representative of typical local climatological conditions, in order to study the local versus non-local impacts on ozone transport and formation. To account for the complex terrain, the horizontal resolution of the smallest modelling domain was 3 km. Model results were compared with measurements to demonstrate the capability of the model to reproduce ozone concentrations in the region. The comparison was favourable with a mean bias of ?1.1 ppb. The importance of local emissions on ozone formation and destruction was identified with the use of three different emission scenarios. Generally the influence of regional emissions on the average ozone concentration was small. However during periods when mountain-sea wind systems were well developed and synoptic scale winds were weak, the influence of local emissions from the urban area was at its greatest. The maximum influence of local emissions on ozone concentrations was 18 ppb.     

A synoptic climatology for surface ozone concentrations in Southern Ontario, 1976–1981

The synoptic climatology of ozone (O₃) for S Ontario has shown that, over the 1976–1981 period, average summer O₃ concentrations follow a relationship similar to that reported for event analysis during periods of high O₃ concentration. Highest average concentrations, 36 parts per billion (ppb), occur with ‘back of the high’ situations while lowest average concentrations (20 ppb) occur with ‘front of the high’ situations.With similar weather events in the winter, the pattern is reversed with highest average O₃ concentrations on the ‘front of the high’ (19 ppb) and lowest average concentrations on the ‘back of the high’ (13 ppb). Concentration of O₃ in the ‘front of the high’ sector is due in part to the intrusion of O₃ in the vicinity of storms from the stratosphere. The seasonal variation of average concentrations in these situations is low, ranging from 14 to 26 ppb.The very low average concentration during the winter and fall for the ‘back of the high’ situation may be the result of scavenging by NO_x from the urban/industrial areas around the Great Lakes. During the spring and summer, solar energy and warm temperatures cause the photochemical production of O₃ from NO_x and HCs precursors. In the fall and winter, photochemical production of O₃ is either very low or absent, and the NO_x consume O₃ rather than produce it. Thus, average O₃ concentrations for winter ‘back of the high’ situations are one-third of those in the summer months.The synoptic climatology of events during the months from May to September with maximum O₃ concentrations in excess of 80 ppb indicates that 78 % of these events occur under synoptic weather classes generally indicative of back or centre of the high situations.     

Synoptic weather patterns and their relationship to high ozone concentrations in the Taichung Basin

Frequent high ozone days (defined as daily maximum ozone concentration ⩾80 ppb) during recent years in the Taichung Basin have caused much concern. High ozone days occur mainly during autumn and spring. Statistically, there is no clear linear relationship between a single meteorological variable and ozone concentration. In this study, data from 1996–2000 has shown that high ozone concentrations occur during two types of synoptic weather patterns. The first type is a continental cyclone emanating from mainland China, the southern part of it swept towards Taiwan by easterly winds. The second pattern is a tropical depression moving northwards toward the region, the northern part of it affecting Taiwan via easterly winds. Both types cover Taiwan with easterly winds, which are blocked by the Central Mountain Ranges (altitude of 2000–3000 m). The ranges create lee cyclogenesis to the west, which is unfavorable for pollutant dispersion and leads to serious air pollution episodes.The statistical results of the synoptic weather patterns in relation to ozone concentrations are based on the 5 yr data (1996–2000). This was obtained from a network of air-pollution monitoring sites in the study area, while the vertical data come from two 3-day tethersonde experimental campaigns conducted during March and October 2000, measuring air pressure, air temperature, relative humidity, wind speed and direction, non-methane hydrocarbons, NO_x and O₃.     

Photochemical Pollution at Two Southern California Smog Receptor Sites

A one-year survey of air quality has been carried out at two southern California inland locations, Perris and Palm Springs (90 km E-SE and 120 km E of Los Angeles) to evaluate transport of photochemical smog from the Los Angeles area and to assess population exposure to toxic air pollutants in the Coachella Valley and eastern Riverside County. Air pollutants measured included formaldehyde, acetaldehyde, nitric acid, and peroxyacetyl nitrate (PAN). Acetic acid was also measured as part of the time-integrated method employed to measure PAN. In addition, intensive studies were carried out at both locations and included measurements of aldehydes, nitric acid, PAN, peroxypropionyl nitrate (PPN), methylchloroform and tetrachloroethylene.

Maximum concentrations of HCHO, CH₃CHO, HNO₃, PAN, PPN, CH₃COOH and C₂CI₄ were 26, 21, 4.5, 7.6, 0.42, 6.6 and 0.29 ppb in Palm Springs and 15, 30, 6.3, 9.1, 0.73, 7.8 and 0.43 ppb in Perris. Pollutant concentrations measured in Palm Springs and Perris are compared to those measured in the Los Angeles area, and are discussed in terms of formation and removal during transport.     

Evaluation of the Community Multiscale Air Quality (CMAQ) model version 4.5: Sensitivities impacting model performance: Part I—Ozone

This study examines ozone (O₃) predictions from the Community Multiscale Air Quality (CMAQ) model version 4.5 and discusses potential factors influencing the model results. Daily maximum 8-h average O₃ levels are largely underpredicted when observed O₃ levels are above 85 ppb and overpredicted when they are below 35 ppb. Using a clustering approach, model performance was examined separately for several different synoptic regimes. Under the most common synoptic conditions of a typical summertime Bermuda High setup, the model showed good overall performance for O₃, while associations have been identified here between other, less frequent, synoptic regimes and the O₃ overprediction and underprediction biases. A sensitivity test between the CB-IV and CB05 chemical mechanisms showed that predictions of daily maximum 8-h average O₃ using CB05 were on average 7.3% higher than those using CB-IV. Boundary condition (BC) sensitivity tests show that the overprediction biases at low O₃ levels are more sensitive to the BC O₃ levels near the surface than BC concentrations aloft. These sensitivity tests also show the model performance for O₃ improved when using the global GEOS-CHEM BCs instead of default profiles. Simulations using the newest version of the CMAQ model (v4.6) showed a small improvement in O₃ predictions, particularly when vertical layers were not collapsed. Collectively, the results suggest that key synoptic weather patterns play a leading role in the prediction biases, and more detailed study of these episodes are needed to identify further modeling improvements.     

Measurement of Organic Acids,Aldehydes, and Ketones in Residential Environments and Their Relation to Ozone

Abstract

Ozone and several polar volatile organic compounds (VOCs) including organic acids and carbonyls (aldehydes and ketones) were measured over an approximately 24 hour period in four residences during the winter of 1993 and in nine residences during the summer of 1993. All residences were in the greater Boston, Massachusetts area. The relation of the polar VOCs to the ozone concentration was examined. Indoor carbonyl concentrations were similar between the summer and winter, with the total mean winter concentration being 31.7 ppb and the total mean summer concentration being 36.6 ppb. However, the average air exchange rate was 0.9 hr^?1 during the winter and 2.6 hr^?1 during the summer. Therefore, the estimated carbonyl emission rates were significantly higher during the summer. Indoor organic acid concentrations were about twice as high during the summer as during the winter. For formic acid, the indoor winter mean was 9.8 ppb, and the summer indoor mean was 17.8 ppb. For acetic acid, the indoor winter mean was 15.5 ppb, and the summer indoor mean was 28.7 ppb. The concentrations of the polar VOCs were found to be significantly correlated with one another. Also, the emission rates of the polar VOCs were found to be correlated with both the environmental variables such as temperature and relative humidity and the ozone removal rate; however, it was difficult to apportion the relative effects of the environmental variables and the ozone removal.     

Wet deposition mercury fluxes in the Canadian sub-Arctic and southern Alberta,measured using an automated precipitation collector adapted to cold regions

This paper reports mercury (Hg) concentrations and fluxes in precipitation that was collected from 2006 to 2008 at three sites in Canada: sub-Arctic boreal forest, sub-Arctic coast, and southern Alberta, using cold-adapted precipitation collectors which operated reliably at temperatures below ?30 °C during the study. The southern Alberta site (Crossfield) may be influenced by Calgary urban air, whereas the sub-Arctic coastal (Churchill, Manitoba) and boreal forest (Fort Vermilion, Alberta) sites are in more remote northern areas. Annual mean Hg concentrations in precipitation (5.0–9.2 ng L^?1) at the study sites were in the lower half of the range reported for southern Canada and the USA by the Mercury Deposition Network (MDN). But owing to typically low precipitation rates, gross wet Hg fluxes (0.54–2.0 μg m^?2 yr^?1) were among the lowest reported by MDN, with Crossfield having about twice the flux in 2007 of the other two sites. Flux was significantly correlated with precipitation, and thus was highest in summer (June–August) and lowest during winter, a pattern typical of other temperate continental locations. There was no evidence of higher wet Hg fluxes or concentrations in springtime at Churchill where atmospheric mercury depletion events (AMDEs) occur. Measured gross deposition fluxes at the study locations were ～2–8 times lower than estimated by GEOS-Chem and GRAHM atmospheric models. The largest discrepancy occurred for Churchill, which raises the question of how well Hg deposition from AMDEs is described by current models. Better agreement between measurements and models was obtained from MDN stations in Alberta and Alaska, where wet Hg fluxes were 2–10 times higher than the study sites either because of power plant emissions (Alberta), or because of high precipitation rates (Alaska).     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Serum concentrations of perfluorooctanesulfonate and other fluorochemicals in an elderly population from Seattle, Washington

Perfluorooctanesulfonyl fluoride (POSF, C₈F₁₇SO₂F) related-materials have been used as surfactants, paper and packaging treatments, and surface (e.g., carpet, textile, upholstery) protectants. A metabolite, perfluorooctanesulfonate (PFOS, C₈F₁₇SO₃⁻), has been identified in the serum and liver of non-occupationally exposed humans and wildlife. Because of its persistence, an important question was whether elderly humans might have higher PFOS concentrations. From a prospective study designed to examine cognitive function in the Seattle (WA) metropolitan area, blood samples were collected from 238 dementia-free subjects (ages 65–96). High-pressure liquid chromatography-electrospray tandem mass spectrometry determined seven fluorochemicals: PFOS; N-ethyl perfluorooctanesulfonamidoacetate; N-methyl perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamide; perfluorooctanoate; and perfluorohexanesulfonate. Serum PFOS concentrations ranged from less than the lower limit of quantitation (3.4 ppb) to 175.0 ppb (geometric mean 31.0 ppb; 95% CI 28.8–33.4). An estimate of the 95% tolerance limit was 84.1 ppb (upper 95% confidence limit 104.0 ppb). Serum PFOS concentrations were slightly lower among the most elderly. There were no significant differences by sex or years residence in Seattle. The distributions of the other fluorochemicals were approximately an order of magnitude lower. Similar to other reported findings of younger adults, the geometric mean serum PFOS concentration in non-occupational adult populations likely approximates 30–40 ppb with 95% of the population’s serum PFOS concentrations below 100 ppb.     

Characterization of Ozone During Consecutive Drought and Wet Years at a Rural West Virginia Site

Ozone concentrations at a rural-remote site in a forested region of north-central West Virginia were monitored during 1988 and 1989, a drought and wet year, respectively. During 1988, the absolute maximum average concentration for a single hour was 156 ppb, while it was only 107 ppb in 1989. Overall, the frequency of high concentrations was greater during 1988; the 120 ppb National Ambient Air Quality Standard was exceeded 17 times. The 7-h period encompassing the highest growing season concentrations for this site over the 2-yr period is 1100- 1759 h EST, rather than the period 0900-1559 h originally used by the National Crop Loss Assessment Network. The 7-h growing season means (0900-1559 h) of 52.6 ppb and 47.1 ppb for 1988 and 1989, respectively, compare well to those reported for the Piedmont/Mountain/Ridge-Valley area, but are higher than those for other surrounding areas. The diurnal ozone patterns, as well as the distribution of concentration ranges and timing of seasonal maxima, suggest that long-range transport of ozone and its precursors probably is an important factor at this site, given its remote and rural character.     

Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): analysis of short-term and episodic variations in PM2.5 concentrations using hourly air monitoring data

One-hour average ambient concentrations of particulate matter (PM) with an aerodynamic diameter < 2.5 microm (PM2.5) were determined in Steubenville, OH, between June 2000 and May 2002 with a tapered element oscillating microbalance (TEOM). Hourly average gaseous copollutant [carbon monoxide (CO), sulfur dioxide (SO2), nitrogen oxide (NOx), and ozone (O3)] concentrations and meteorological conditions also were measured. Although 75% of the 14,682 hourly PM2.5 concentrations measured during this period were < or = 17 microg/m3, concentrations > 65 microg/m3 were observed 76 times. On average, PM2.5 concentrations at Steubenville exhibited a diurnal pattern of higher early morning concentrations and lower afternoon concentrations, similar to the diurnal profiles of CO and NO(x). This pattern was highly variable; however, PM2.5 concentrations > 65 microg/m3 were never observed during the mid-afternoon between 1:00 p.m. and 5:00 p.m. EST. Twenty-two episodes centered on one or more of these elevated concentrations were identified. Five episodes occurred during the months June through August; the maximum PM2.5 concentration during these episodes was 76.6 microg/m3. Episodes occurring during climatologically cooler months often featured higher peak concentrations (five had maximum concentrations between 95.0 and 139.6 microg/m3), and many exhibited strong covariation between PM2.5 and CO, NO(x), or SO2. Case studies suggested that nocturnal surface-based temperature inversions were influential in driving high nighttime concentrations of these species during several cool season episodes, which typically had dramatically lower afternoon concentrations. These findings provide insights that may be useful in the development of PM2.5 reduction strategies for Steubenville, and suggest that studies assessing possible health effects of PM2.5 should carefully consider exposure issues related to the intraday timing of PM2.5 episodes, as well as the potential for toxicological interactions among PM2.5, and primary gaseous pollutants.