Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and contributes significantly to the daily variation of surface maximum ozone concentrations (R2 = 0.19). However, the contribution of downward-mixing ozone to daily ozone variation is not included in most existing statistical models developed for predicting daily ozone variation. Finally, daily surface maximum ozone concentration is positively correlated with daily afternoon mixing depth, attributable to the downward-mixing ozone.     

Ozone and meteorological boundary-layer conditions at Summit,Greenland, during 3–21 June 2000

The temporal and spatial distributions of boundary-layer ozone were studied during June 2000 at Summit, Greenland, using surface-level measurements and vertical profiling from a tethered balloon platform. Three weeks of continuous ozone surface data, 133 meteorological vertical profile data and 82 ozone vertical profile data sets were collected from the surface to a maximum altitude of 1400 m above ground.The lower atmosphere at Summit was characterized by the prevalence of strong stable conditions with strong surface temperature inversions. These inversions reversed to neutral to slightly unstable conditions between ∼9.00 and 18.00 h local time with the formation of shallow mixing heights of ∼70–250 m above the surface.The surface ozone mixing ratio ranged from 39 to 68 ppbv and occasionally had rapid changes of up to 20 ppb in 12 h. The diurnal mean ozone mixing ratio showed diurnal trends indicating meteorological and photochemical controls of surface ozone. Vertical profiles were within the range of 37–76 ppb and showed strong stratification in the lower troposphere. A high correlation of high ozone/low water vapor air masses indicated the transport of high tropospheric/low stratospheric air into the lower boundary layer. A ∼0.1–3 ppb decline of the ozone mixing ratio towards the surface was frequently observed within the neutrally stable mixed layer during midday hours. These data suggest that the boundary-layer ozone mixing ratio and ozone depletion and deposition to the snowpack are influenced by photochemical processes and/or transport phenomena that follow diurnal dependencies. With 37 ppb of ozone being the lowest mixing ratio measured in all data no evidence was seen for the occurrence of ozone depletion episodes similar to those that have been reported within the boundary layer at coastal Arctic sites during springtime.     

Increase in springtime tropospheric ozone at a mountainous site in Japan for the period 1998–2006

The trend of tropospheric ozone from 1998 to 2006 was examined based on continuous measurements made at a site on Mt. Happo, Japan. We focused our study on springtime ozone, to coincide with the East Asian continental outflow that dominates the lower tropospheric ozone over Japan during this season. The observed increase of ～1 ppbv yr^?1 in the mean ozone level was statistically significant. We also found that the probability distribution of the springtime ozone mixing ratios was substantially modified, with the ozone mixing ratios greatly increasing at the upper end of the probability distribution. This increase has been particularly large since 2003, with larger increases occurring at the higher percentiles. The number of high-ozone days doubled during 2003–2006 compared to 1999–2002. One of the very likely explanations is the enhancement of regional ozone pollution due to rapidly increasing anthropogenic emissions from East Asia.     

Atmospheric conversion of sulfur dioxide to particulate sulfate and nitrogen dioxide to particulate nitrate and gaseous nitric acid in an urban area

Sulfur dioxide, nitrogen dioxide, particulate sulfate and nitrate, gaseous nitric acid, ozone and meteorological parameters (temperature and relative humidity) were measured during the winter season (1999-2000) and summer season (2000) in an urban area (Dokki, Giza, Egypt). The average particulate nitrate concentrations were 6.20 and 9.80 microg m(-3), while the average gaseous nitric acid concentrations were 1.14 and 6.70 microg m(-3) in the winter and summer seasons, respectively. The average sulfate concentrations were 15.32 microg m(-3) during the winter and 25.10 microg m(-3) during the summer season. The highest average concentration ratio of gaseous nitric acid to total nitrate was found during the summer season. Particulate sulfate and nitrate and gaseous nitric acid concentrations were relatively higher in the daytime than those in the nighttime. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) defined in the text were calculated from the field measurement data. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) in the summer were about 2.22 and 2.97 times higher than those in the winter season, respectively. Moreover, sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) were higher in the daytime than those in the nighttime during the both seasons. The sulfur conversion ratio (Fs) increases with increasing ozone concentration and relative humidity. This indicates that the droplet phase reactions and gas phase reactions are important for the oxidation of SO2 to sulfate. Moreover, the nitrogen conversion ratio (Fn) increases with increasing ozone concentration, and the gas phase reactions are important and predominant for the oxidation of NO2 to nitrate.     

Ground-based remote sensing measurements of aerosol and ozone in an urban area: A case study of mixing height evolution and its effect on ground-level ozone concentrations

We have estimated the mixing height (MH) and investigated the relationship between vertical mixing and ground-level ozone concentrations in Seoul, Korea, by using three ground-based active remote sensing instruments operating side by side: micro-pulse lidar (MPL), differential absorption lidar (DIAL), and differential optical absorption spectroscopy (DOAS). The MH is estimated from MPL measurements of aerosol extinction profiles by the gradient method under convective conditions. Comparisons of the MHs estimated from MPL and radiosonde measurements show a good agreement (r²=0.99). Continuous MPL measurements with high temporal and vertical resolution reveal the diurnal variations of the MH under convective conditions and the presence of a residual layer during the nighttime. Comprehensive measurements of ozone and aerosol by MPL, DIAL and DOAS during an high ozone episode (24–26 May 2000) in Seoul, Korea, reveal that (1) photochemical ozone production and advection from upwind regions (the western part of Seoul) contribute two peaks of ozone concentrations at the ground around 14:00 and 18:00 local time on 25 May 2000, respectively, and (2) the entrainment and the fumigation processes of ozone aloft in the nighttime residual layer into the ground is a major contributor of high concentrations of ground-level ozone observed on the following day (26 May 2000).     

Characteristic Study of Ambient Air Total Gaseous Mercury (TGM) Concentrations During Rainy and Non-Rainy Periods at a Traffic Site in Taiwan

This investigation studied the concentrations of ambient air total gaseous mercury (TGM) during the rainy periods at the Hung-Kuang traffic sampling site in central Taiwan from May 26 to June 16, 2014. The results were compared with those of a previous study for ambient air TGM during non-rainy daytime and nighttime periods at the Hung-Kuang traffic sampling site, which was conducted during March 21 to July 20, 2012. The observed mean concentration of ambient air TGM was 1.16 ng/m³ during the rainy periods at the Hung-Kuang traffic sampling site. The mean ambient air TGM concentrations were higher in the non-rainy sampling period in daytime than in the rainy sampling period from this study. The mean ratio of non-rainy sampling period in daytime to that of rainy sampling period for ambient air TGM were 3.15. Furthermore, the mean ambient air TGM concentrations were higher in the non-rainy sampling period in nighttime in than in the rainy sampling period for this study. The mean rations for non-rainy sampling period in nighttime to that of the rainy sampling period for ambient air TGM were 2.70. The results obtained in this study also revealed that the ambient air TGM concentrations during the rainy period had the lowest concentrations when compared with the other sampling sites in other world regions.     

Some insights into short-term variability of total gaseous mercury in urban air

The concentrations of total gaseous mercury (Hg) were determined at hourly intervals along with relevant environmental parameters that include both meteorological plus criteria pollutant data during two field campaigns (September 1997 and May/June 1998). The mean concentrations of Hg for the two study periods were computed as 3.94 and 3.43 ng m⁻³, respectively. By separating the data into daytime and nighttime periods, we further analyzed diurnal variation patterns for both seasons. Using our Hg data sets, we were able to recognize two contrasting diurnal variation patterns of Hg between two different seasons that can be characterized as: (1) the occurrences of peak Hg concentration during daytime (fall) and (2) slight reductions in daytime Hg concentration relative to nighttime (summer). To study the systematic differences in diurnal patterns between two different seasons, we analyzed Hg data in terms of different statistical approaches such as correlation (and linear regression) and factor analysis. Results of these analyses consistently indicated that different mechanisms were responsible for controlling the daytime distribution patterns of Hg. When the relationship between Hg and concurrently determined O₃ is considered, its reaction with ozone is unlikely to limit Hg levels as the dominant sink mechanism (within the ranges of ozone concentrations found during this study, regardless of season). It is on the other hand suspected that the variation of boundary layer conditions between day/night periods may have been important in introducing the relative reduction in daytime Hg levels during summer. To further provide a general account of short-term variations in Hg distribution data, it is desirable to describe other unknown sink mechanisms.     

Structural analysis and flux associations of CO2, H2O,heat and ozone over cotton and grape canopies

Micrometeorological tower data, collected over grape and cotton canopies as part of the California ozone deposition experiment (CODE) during the summer of 1991, are used to examine the temporal association between fluxes, and the physical characteristics of the coherent structures which dominate transport for both stable nighttime and unstable daytime conditions. Flux was calculated using the eddy covariance technique and the dominant modes of flux transport determined by quadrant analysis. The mean flux densities for both the cotton and grape site showed the surface acting as a sink for CO₂ and ozone and a source of heat and H₂O during the day, as would be expected, while during the night it became a source for CO₂ and a sink for heat, but remained a sink for ozone and a source of H₂O. The flux association results indicated a single vegetated ozone sink for the grape site, but a vegetated as well as a non-vegetated sink for the cotton site. For both sites, structures simultaneously transporting significant flux contributions of CO₂, H₂O, heat and ozone dominate during unstable conditions, but differed during stable conditions, where unmixed single flux structures dominated over cotton but not over grape. Structure sizes were less than 10 m during nighttime conditions and ranged from 3 to 69 m during the day. The results of this study contribute empirical evidence about the relationship between ozone uptake and the physical and physiological state of vegetation, as well as the limitations placed on eddy scales in simulation models.     

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.     

Background ozone levels of air entering the west coast of the US and assessment of longer-term changes

An analysis of surface ozone measurements at a west coast site in northern California (Trinidad Head) demonstrates that this location is well situated to sample air entering the west coast of the US from the Pacific Ocean. During the seasonal maximum in the spring, this location regularly observes hourly average ozone mixing ratios 50 ppbv in air that is uninfluenced by the North American continent. Mean daytime values in the spring exceed 40 ppbv. A location in southern California (Channel Islands National Park) demonstrates many of the characteristics during the spring as Trinidad Head in terms of air flow patterns and ozone amounts suggesting that background levels of ozone entering southern California from the Pacific Ocean are similar to those in northern California. Two inland locations (Yreka and Lassen Volcanic National Park) in northern California with surface ozone data records of 20 years or more are more difficult to interpret because of possible influences of local or regional changes. They show differing results for the long-term trend during the spring. The 10-year ozone vertical profile measurements obtained with weekly ozonesondes at Trinidad Head show no significant longer-term change in tropospheric ozone.     

Carbonyl sulfide exchange on an ecosystem scale: soil represents a dominant sink for atmospheric COS

The soil/plant/atmosphere exchange of carbonyl sulfide (COS) was investigated in an open oak woodland ecosystem at a rural site in northern California. Measurements of atmospheric concentrations of COS were made in June and in December 1994. We found a significant diel cycle with a drop of COS levels by approximately 150 ppt during the night in both seasons. The mean COS daytime background mixing ratios showed a distinct seasonal difference with 465±77 ppt in summer and 375±56 ppt in winter. The nighttime bulk COS flux into the ecosystem was estimated using a micrometeorological model. To address the observed depletion of COS during stable nocturnal boundary layer conditions, the potential of various ecosystem compartments to act as a sink for COS was investigated. Studies using dynamic enclosures flushed with ambient air excluded vegetation as an important sink during nighttime due to high stomatal resistance. Results from soil chamber measurements indicate that the soil can act as a dominant sink for atmospheric COS.     

Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

Trends over a 20-year period from 1987 to 2007 in surface ozone at the atmospheric research station,Mace Head,Ireland

Hourly measurements of baseline ozone at the Mace Head Atmospheric Research Station on the Atlantic Ocean coast of Ireland are observed when unpolluted air masses are advected to the station from across the North Atlantic Ocean. Monthly mean ozone mixing ratios in baseline air masses have risen steadily during the 1980s and 1990s reaching unprecedented levels during the early months of 1999. During the 2000s, baseline ozone mixing ratios have shown evidence of decline and stabilisation. Over the entire 20-year 1987–2007 period, the trend in annual baseline ozone has been +0.31±0.12(2−σ) ppb year⁻¹ and is highly statistically significant. Trends have been highest in the spring months and lowest in the summer months, producing a significant increase in the amplitude of the seasonal cycle. Over the shorter 1995–2007 period, we demonstrate how the growth to peak in 1999 and the subsequent decline have been driven by boreal biomass burning events during 1998/1999 and 2002/2003. The 2000s have been characterised by relatively constant baseline ozone and CH₄ levels and these may be a reasonable guide to future prospects, at least in the short term.     

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.     

A study on nighttime–daytime PM10 concentration and elemental composition in relation to atmospheric dispersion in the urban area of Milan (Italy)

In this paper, results on a PM10 daytime–nighttime measurement campaign carried out in Milan to study the evolution of PM10 concentration and composition in relation to atmospheric dispersion conditions are shown. To account for the evolution of atmospheric dispersion conditions, Radon hourly concentration measurements were performed. The significant correlation between PM10 and ²²²Rn daytime concentrations evidences the dominant role of atmospheric dispersion in determining the temporal variation of PM10 levels. Whenever ²²²Rn concentrations accumulate during the night (indicating the formation of nocturnal atmospheric stability conditions), PM10 concentrations are higher than those registered during the daytime before, despite a decrease in emissions from active sources. On the contrary, when ²²²Rn concentrations do not accumulate during night hours, PM10 levels are lower than those measured during the daytime before.As concerns the average elemental concentrations (in ng m⁻³), the nighttime–daytime variations are in the range −17% to +37%; during the night, soil-related elements (Al, Si, Ca, Ti) decrease while anthropogenic elements (Zn, Cu, Fe, Pb) increase.A case study concerning a ‘green’ Sunday (when traffic was forbidden from 8 a.m. to 8 p.m.) is also discussed. The difference of PM10 concentration and elemental composition registered during the ‘green’ Sunday daytime and the following nighttime, together with the information on atmospheric dilution power obtained by Radon measurements, allowed the characterisation of the traffic source elemental profile and increased the comprehension of the low effectiveness of some PM10 reduction strategies.     

Monitoring of ozone in a marine environment in Tenerife (Canary Islands)

In the Aguere Valley (in the oceanic boundary layer at Tenerife, 28°N, 16°W, 580 m a.s.l.) the ozone levels were monitored for ambient air quality assessment. Although precursors are emitted in this area, the strong correlation between ozone levels and wind velocity indicates that ozone is transported into the valley from the ocean. The inland ozone supply along the valley is induced by an orographic channelling effect of the northern oceanic air masses. The highest ozone concentrations are mostly recorded during the nocturnal stage under the influence of fresh oceanic air masses, and during high wind speed events. The seasonal cycle is characterised by elevated ozone mixing ratios in the spring (nighttime levels >45 ppbv) and low mixing ratios in the summer (nighttime levels in the range 20–35 ppbv). Back-trajectory analysis shows that the ozone monitored in the Aguere Valley is associated with long-range transport processes. High ozone events in the spring are associated with transport from upper tropospheric levels, both over the North Atlantic-high latitudes (>45°N) and Europe. This downward transport was observed in the western edge of upper tropospheric cyclones, which suggests that the upper tropospheric/low stratospheric ozone sources play a significant role. In summer, ozone is mainly transported from the North Atlantic-high latitudes (>45°N) and from mid- to low-tropospheric levels. In autumn and winter, the high ozone concentrations are transported from sources located a few km above the North Atlantic-high latitudes (>45°N) and over Europe. The Central-North Atlantic (<45°N) and North Africa are not significant sources of ozone. The high spring and lower summer ozone events in the Aguere Valley agree with other North Atlantic ozone observation in the oceanic boundary layer. However, this behaviour contrasts with the high ozone events frequently recorded at Izaña BAPMoN station (located in the free troposphere in Tenerife) during the summer, which have been attributed in the literature to downward transport from upper levels. An intensification of the inversion layer that separates the oceanic boundary layer of the free troposphere during the summer in Canary Islands is interpreted as the cause of this different behaviour between ozone in the Aguere Valley and Izaña BAPMoN station.     

Ozone Levels in the Vicinity of 33 Cities

Hourly concentrations of ozone were measured by the chemiluminescence method during the summer of 1971 in the vicinity of 33 cities. A listing was made of the percent of time the National Air Quality Standard for photochemical oxidants was violated. At 4 selected cities the daytime and nighttime average concentrations were related to wind directions showing the direction to source areas. Another set of tables and graphs was used to show the source directions for high concentrations (equal to or above 120 µg/m³) and disregarding the times of more usual or background concentrations. Numerous occasions of high ozone concentrations occurred when wind directions were apparently from areas with low concentrations of the known precursors. Because of this, other sources of ozone were considered such as thunderstorms and the transport of ozone for long distances. Examples of ozone concentrations during thunderstorms or related to long distance transport are cited.     

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

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

Fine organic aerosols collected in a humid,rural location (Great Smoky Mountains,Tennessee, USA): Chemical and temporal characteristics

Fine organic aerosols collected at the Great Smoky Mountain National Park, Tennessee (USA) during 15 July –25 August 1995 as part of the Southeastern Aerosol and Visibility Study (SEAVS) were chemically characterized. The water-soluble organic species (WSOS) often dominated over the solvent-soluble organic species (SSOS) at this remote, humid sampling site, contributing 76–98% of the total identified organic mass in 17 out of the 21 daytime samples analyzed. Nighttime samples tended to have slightly larger concentrations of total SSOS than the daytime, with nocturnal/diurnal organic mass ratios greater than 1.0 in 7 out of the 10 paired samples. However, for total WSOS mass, the nocturnal-to-diurnal ratios were less than 0.3 in 7 out of the 10 paired samples, reflecting much more substantial depletion and/or less production of the more polar organics during nighttime. Based on identified species, the organic-mass-to-organic-carbon (OM–OC) ratios at the SEAVS site are estimated as 2.0, 2.2, and 1.3 for the daytime total organics, WSOS, and SSOS, respectively. For the nighttime samples, the OM–OC ratio for total identified organics is estimated to be 1.8, slightly lower than the daytime ratio due to the smaller mass fraction of WSOS present at night.