Modeling pollutant penetration across building envelopes

As air infiltrates through unintentional openings in building envelopes, pollutants may interact with adjacent surfaces. Such interactions can alter human exposure to air pollutants of outdoor origin. We present modeling explorations of the proportion of particles and reactive gases (e.g., ozone) that penetrate building envelopes as air enters through cracks and wall cavities. Calculations were performed for idealized rectangular cracks, assuming regular geometry, smooth inner crack surface and steady airflow. Particles of 0.1–1.0 μm diameter are predicted to have the highest penetration efficiency, nearly unity for crack heights of 0.25 mm or larger, assuming a pressure difference of 4 Pa or greater and a flow path length of 3 cm or less. Supermicron and ultrafine particles are significantly removed by means of gravitational settling and Brownian diffusion, respectively. In addition to crack geometry, ozone penetration depends on its reactivity with crack surfaces, as parameterized by the reaction probability. For reaction probabilities less than ∼10⁻⁵, penetration is complete for cracks heights greater than ∼1 mm. However, penetration through mm scale cracks is small if the reaction probability is ∼10⁻⁴ or greater. For wall cavities, fiberglass insulation is an efficient particle filter, but particles would penetrate efficiently through uninsulated wall cavities or through insulated cavities with significant airflow bypass. The ozone reaction probability on fiberglass fibers was measured to be 10⁻⁷ for fibers previously exposed to high ozone levels and 6×10⁻⁶ for unexposed fibers. Over this range, ozone penetration through fiberglass insulation would vary from >90% to ∼10–40%. Thus, under many conditions penetration is high; however, there are realistic circumstances in which building envelopes can provide substantial pollutant removal. Not enough is yet known about the detailed nature of pollutant penetration leakage paths to reliably predict infiltration into real buildings.     

Measurements of fine and ultrafine particles formation in photocopy centers in Taiwan

This study investigates the levels of particulate matter smaller than 2.5 μm (PM_2.5) and some selected volatile organic compounds (VOCs) at 12 photocopy centers in Taiwan from November 2004 to June 2005. The results of BTEXS (benzene, toluene, ethylbenzene, xylenes and styrene) measurements indicated that toluene had the highest concentration in all photocopy centers, while the concentration of the other four compounds varied among the 12 photocopy centers. The average background-corrected eight-hour PM_2.5 in the 12 photocopy centers ranged from 10 to 83 μg m⁻³ with an average of 40 μg m⁻³. The 24-h indoor PM_2.5 at the photocopy centers was estimated and at two photocopy centers exceeded 100 μg m⁻³, the 24-h indoor PM_2.5 guideline recommended by the Taiwan EPA. The ozone level and particle size distribution at another photocopy center were monitored and indicated that the ozone level increased when the photocopying started and the average ozone level at some photocopy centers during business hour may exceed the value (50 ppb) recommended by the Taiwan EPA. The particle size distribution monitored during photocopying indicated that the emitted particles were much smaller than the original toner powders. Additionally, the number concentration of particles that were smaller than 0.5 μm was found to increase during the first hour of photocopying and it increased as the particle size decreased. The ultrafine particle (UFP, <100 nm) dominated the number concentration and the peak concentration appeared at sizes of under 50 nm. A high number concentration of UFP was found with a peak value of 1E+8 particles cm⁻³ during photocopying. The decline of UFP concentration was observed after the first hour and the decline is likely attributable to the surface deposition of charged particles, which are charged primarily by the diffusion charging of corona devices in the photocopier. This study concludes that ozone and UFP concentrations in photocopy centers should be concerned in view of indoor air quality and human health. The corona devices in photocopiers and photocopier-emitted VOCs have the potential to initiate indoor air chemistry during photocopying and result in the formation of UFP.     

Field performance of dichotomous sequential PM air samplers

For over one year, the Environmental Protection Commission of Hillsborough County (EPCHC) in Tampa, Florida, operated two dichotomous sequential particulate matter air samplers collocated with a manual Federal Reference Method (FRM) air sampler at a waterfront site on Tampa Bay. The FRM was alternately configured as a PM_2.5, then as a PM₁₀ sampler. For the dichotomous sampler measurements, daily 24-h integrated PM_2.5 and PM_10–2.5 ambient air samples were collected at a total flow rate of 16.7 l min⁻¹. A virtual impactor split the air into flow rates of 1.67 and 15.0 l min⁻¹ onto PM_10–2.5 and PM_2.5 47-mm diameter PTFE^® filters, respectively. Between the two dichotomous air samplers, the average concentration, relative bias and relative precision were 13.3 μg m⁻³, 0.02% and 5.2% for PM_2.5 concentrations (n=282), and 12.3 μg m⁻³, 3.9% and 7.7% for PM_10–2.5 concentrations (n=282). FRM measurements were alternate day 24-h integrated PM_2.5 or PM₁₀ ambient air samples collected onto 47-mm diameter PTFE^® filters at a flow rate of 16.7 l min⁻¹. Between a dichotomous and a PM_2.5 FRM air sampler, the average concentration, relative bias and relative precision were 12.4 μg m⁻³, −5.6% and 8.2% (n=43); and between a dichotomous and a PM₁₀ FRM air sampler, the average concentration, relative bias and relative precision were 25.7 μg m⁻³, −4.0% and 5.8% (n=102). The PM_2.5 concentration measurement standard errors were 0.95, 0.79 and 1.02 μg m⁻³; for PM₁₀ the standard errors were 1.06, 1.59, and 1.70 μg m⁻³ for two dichotomous and one FRM samplers, respectively, which indicate the dichotomous samplers have superior technical merit. These results reveal the potential for the dichotomous sequential air sampler to replace the combination of the PM_2.5 and PM₁₀ FRM air samplers, offering the capability of making simultaneous, self-consistent determinations of these particulate matter fractions in a routine ambient monitoring mode.     

Aerosol mass-size distributions at a tropical coastal environment: response to mesoscale and synoptic processes

Regular measurements of total mass concentration and mass-size distribution of near-surface aerosols, made using a ten-channel Quartz Crystal Microbalance (qcm) Impactor for the period October 1998–December 1999 at the tropical coastal station Trivandrum (8.5°N, 77°E), are used to study the response of aerosol characteristics to regional mesoscale and synoptic processes. Results reveal that aerosol mass concentrations are generally higher under land breeze conditions. The sea breeze generally has a cleansing effect, depleting the aerosol loading. The continental air (LB regime) is richer in accumulation mode (submicron) aerosols than the marine air. On a synoptic scale, aerosol mass concentration in the submicron mode decreased from an average high value of ∼86 μg m⁻³ during the dry months (January–March) to ∼11 μg m⁻³ during the monsoon season (June–September). On the contrary mass concentration in the supermicron mode increased from a low value of ∼15 μg m⁻³ during the dry months to reach a comparatively high value of ∼35 μg m⁻³ during April, May. Correspondingly, the effective radius (R_eff) increased from a low value of 0.15–0.17 μm to ∼0.3 μm indicating a seasonal change in the size distribution. The mass-size distribution shows mainly three modes, a fine mode (∼0.1 μm); a large mode (∼0.5 μm) and a coarse mode (∼3 μm). The fine mode dominates in winter. In summer the large mode becomes more conspicuous and the coarse mode builds up. The fine mode is highly reduced in monsoon and the large and coarse modes continue to remain high (replenished) so that their relative dominance increases. The size distribution tends to revert to the winter pattern in the post-monsoon season. Accumulation (submicron) aerosols account for ∼98% of the total surface area and ∼70% of the total volume of aerosols during winter. During monsoon, even though they still account for ∼90% of the area, their contribution to the volume is reduced to ∼50%; the coarse aerosols account for the rest.     

Seasonal characteristics of water-soluble organic carbon in atmospheric particles in the inland Kanto plain,Japan

An investigation of water-soluble organic carbon (WSOC) in atmospheric particles was conducted as an index of the formation of secondary organic aerosol (SOA) from April 2005 to March 2006 at Maebashi and Akagi located in the inland Kanto plain in Japan. Fine (<2.1 μm) and coarse (2.1–11 μm) particles were collected by using an Andersen low-volume air sampler, and WSOC, organic carbon (OC), elemental carbon (EC), and ionic components were measured. The mean mass concentrations of the fine particles were 22.2 and 10.5 μg m^?3 at Maebashi and Akagi, respectively. The WSOC in fine particles accounted for a large proportion (83%) of total WSOC. The concentration of fine WSOC ranged from 1.2 to 3.5 μg-C m^?3 at Maebashi, rising from summer to fall. At Akagi, it rose from spring to summer, associated with the southerly wind from urban areas. The WSOC/OC ratio increased in summer at both sites, but the ratio at Akagi was higher, which we attributed to differences in primary emissions and secondary formation between the sites. The fine WSOC concentration was significantly positively correlated with concentrations of SO₄^2?, EC, and K⁺, and we inferred that WSOC was produced by photochemical reaction and caused by the combustion of both fuel and biomass. We estimated that SOA accounted for 11–30% of the fine particle mass concentration in this study, suggesting that SOA is a significant year-round component in fine particles.     

The continuous analysis of nitrate and ammonium in aerosols by the steam jet aerosol collector (SJAC): extension and validation of the methodology

Classical methodology based on the application of filters for sampling, followed by extraction and analysis, introduces severe artifacts for semi-volatile compounds like ammonium nitrate. These filter methods do not meet the requirements for the assessment of the impact of aerosols on acidification, air quality and especially on the radiative balance, in terms of required speed, detection limits and selectivity. These artifacts are avoided by using a steam jet aerosol collector sampler, based on scavenging of aerosols by droplet formation, in combination with on-line analytical techniques such as ion-chromatography for nitrate and membrane separation followed by conductivity detection for ammonium. The SJAC sampler combines very low blanks with high efficiency of collection of particles. The ammonium detector and the IC system, based on 1-point internal standard calibration in combination with correction for curved calibration graphs, enables detection of ammonium and nitrate at background conditions, the detection limit is about 0.02 μg m⁻³ of ammonium and nitrate. Accuracy is, depending on ambient concentration, in the order of 5–10% relative, at a range of 0.05–50 μg m⁻³. The time resolution is 15–120 min, depending on required detection limit, and is short enough for continuously monitoring the chemical composition of aerosols. Quality assurance and quality control experiments and intercomparison experiments with classical filter methods, thermo-denuder systems, denuder difference methods and other continuous monitoring techniques have shown that the results are reliable. The instrument has successfully been employed in field campaigns in Europe and the US.     

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.     

Experimental studies on particle impaction and bounce: effects of substrate design and material

This paper presents an experimental investigation of the effects of impaction substrate designs and material in reducing particle bounce and reentrainment. Particle collection without coating by using combinations of different impaction substrate designs and surface materials was conducted using a personal particle sampler (PPS) developed by the University of Southern California. The PPS operates at flow rate of 4 l min^-1 with a 50% cutpoint of approximately 0.9 μm in aerodynamic diameter. The laboratory results showed that the PPS collection efficiency for particles larger than 50% cutpoint is strikingly low (e.g., less than 50%) when an uncoated open cavity made of aluminum was used as an impaction substrate. The collection efficiency gradually increased when Teflon tape, Nuclepore, and glass fiber filters were used as impaction surfaces, respectively. Conical or partially enclosed cavity substrate designs increased collection efficiency of particles of 9 μm up to 80–90%. A conical cavity with glass fiber filter used as impaction surface was identified as the optimum configuration, resulting in a collection efficiency of 92% at Stokes numbers as high as 15.4 (corresponding to 9 μm in aerodynamic diameter). Particle losses were low (less than 10%) and relatively independent of particle size in any design with glass fiber filter. Losses seemed to increase slightly with particle size in all other configurations. Finally, outdoor PM₁ concentrations obtained with the PPS (in its optimum configuration) and a modified micro-orifice uniform deposit impactor (MOUDI) with coated impaction stages were in excellent agreement. The mean ratio of the PPS-to-MOUDI concentration was 1.13(±0.17) with a correlation coefficient R²=0.95. Results from this investigation can be readily applied to design particle bounce-free impaction substrates without the use of coating. This is a very important feature of impactors, especially when chemical analysis of the collected particulate matter is desirable.     

Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China

Carbonyl compounds in urban ambient air and street canyons were measured from December 2008 to August 2009 in a mountainous city in southwest China (Guiyang). The formaldehyde yield from the photo-oxidation of isoprene emitted by vegetation was estimated to be in the range of 0.63–3.62 μg m^?3 from May to August, which accounted for 28.8–33.4% of ambient formaldehyde. Based on the calculation of photolysis rates and rates of reaction with the OH radical, it was found that photolysis was the predominant sink for formaldehyde and acetone in both summer and winter. For acetaldehyde, photo-oxidation by OH radicals and photolysis were the major sinks in summer while photo-oxidation by OH radicals was the dominant sink in winter. Wet precipitation was found to be an important removal process for the atmospheric carbonyls. In the urban ambient air, the average concentrations of formaldehyde, acetaldehyde, acetone and all carbonyls were 4.8 ± 2.1, 5.7 ± 3.3, 5.1 ± 2.5, and 25.1 ± 9.2 μg m^?3 (n = 139), respectively. The average concentrations of these species in street canyons were 18.8 ± 6.5, 9.4 ± 3.2, 10.9 ± 2.1, and 64.1 ± 16.3 μg m^?3 (n = 62), respectively. The significantly higher carbonyl levels on weekdays (compared to weekends) highlight the contribution of vehicle emissions to carbonyls in the street canyons.     

Evaluating urban PM10 pollution benefit induced by street cleaning activities

Despite their burden in urban particulate air pollution, road traffic non-exhaust emissions are often uncontrolled and information about the effectiveness of mitigation measures on paved roads is still scarce. The present study is aimed to evaluate the effectiveness of mechanical sweeping/water flushing treatments in mitigating urban road dust resuspension and to quantify the real benefit in terms of ambient PM₁₀ concentrations. To this aim a specific campaign was carried out in a heavily trafficked central road of Barcelona (Spain), a Mediterranean city suffering from a traffic-related pollution, both for a high car density and a frequent lack of precipitation. Several street washings were performed by means of mechanical sweepers and pressure water during night in all traffic lanes and sidewalks. PM₁₀ levels were simultaneously compared with four reference urban background air quality stations to interpret any meteorological variability. At the downwind measurement site, PM₁₀ concentrations registered a mean daily decrease of 8.8 μg m^?3 during the 24 h after street washing treatments. However 3.7–4.9 μg m^?3 of such decrease were due to the meteorological variability detected at the upwind site, as well as at two of the reference sites. This reveals that an effective decrease of 4–5 μg m^?3 (7–10%) can be related to street washing efficiency. Mitigation of road dust resuspension was confirmed by investigating the chemical composition of airborne-PM₁₀ filters. Concentrations of Cu, Sb, Fe and mineral matter decrease significantly with respect to concentrations of elemental carbon, used as tracer for exhaust diesel emissions. High efficiency of street washing in reducing road dust loads was found by performing periodic samplings both on the treated and the untreated areas.     

Wintertime size distribution of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the urban environment: Street- vs rooftop-level measurements

The size distribution of ambient air particles and associated organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) including hexachlorocyclohexanes (HCHs), DDT and metabolites, etc., was investigated at a traffic-impacted site of Thessaloniki, Greece. Investigation took place during wintertime of 2006 at two heights above ground: at the street level (1.5 m) and at the rooftop level (15 m). Size-resolved samples (<0.95 μm, 0.95–1.5 μm, 1.5–3 μm, 3–7.5 μm and >7.5 μm) were concurrently collected from the two height levels using five-stage high volume cascade impactors. At both heights, particle mass exhibited bimodal distribution with peaks in the 0.95–1.5 μm and the 3–7.5 μm size fractions, whereas most organic pollutants exhibited one peak at 0.95–1.5 μm. Apart from the 0.95–1.5 μm fraction, particle concentrations of all size ranges were significantly higher at the street level than at the rooftop as a result of more intensive vehicular emissions and road dust resuspension. On the contrary, the concentrations of most organic pollutants did not differentiate significantly between the two elevations.     

Assessment of environmental tobacco smoke and respirable suspended particle exposures for nonsmokers in Basel by personal monitoring

One hundred and ninety-six randomly selected nonsmoking subjects collected air samples close to their breathing zone by wearing personal monitors for 24 h. The study was centred in Basel, Switzerland, and comprised housewives in one group, primarily for assessing exposures in the home, and office workers in a second group to assess the contribution of the workplace to overall exposure. Samples collected were analysed for respirable suspended particles (RSP), nicotine, 3-ethenylpyridine and environmental tobacco smoke (ETS) particles by using ultraviolet absorbance, fluorescence and solanesol measurements. Saliva cotinine analyses were also undertaken to confirm the nonsmoking status of the subjects. Based upon median 24 h time weighted average concentrations, office workers who live and work with smokers were exposed to 39 μg m^-3 RSP, 6.6 μg m^-3 ETS particles and 0.90 μg m^-3 nicotine. Housewives living with smokers were exposed to median concentrations of 34 μg m^-3 RSP, 1.4 μg m^-3 ETS particles and 0.60 μg m^-3 nicotine. Workplaces where smoking occurred were estimated, on average, to contribute between 34 and 46% to annual exposure of ETS particles and nicotine. Based upon 90th percentile values the most highly exposed housewives, those living with smokers, would potentially inhale 18 cigarette equivalents per year whilst the most highly exposed office workers, both living and working with smokers, might inhale 61 cigarette equivalents. The rate at which subjects misreported their nonsmoking status varied between 9.7 and 12.2%.     

Properties of organic matter in PM2.5 at Changdao Island,China—A rural site in the transport path of the Asian continental outflow

Fifty-five seasonal PM_2.5 samples were collected March 2003–January 2004 at Changdao, a resort island located at the demarcation line between Bohai Sea and Yellow Sea in Northern China. Changdao is in the transport path of the continental aerosols heading toward the Pacific Ocean in winter and spring due to the East Asia Monsoon. Solvent-extractable organic compounds (SEOC), organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) were analyzed for source identification based on molecular markers. This data set provides useful information for the downstream site researchers of the Asian continental outflow. Total carbon (TC, OC+EC) was ∼18 μg m⁻³ in winter, ∼9 μg m⁻³ in spring and autumn and a large part of the TC was WSOC (33% in winter, >45% in the other seasons). Winter and spring were the high SEOC seasons with n-fatty acids the highest at ∼290 and ∼170 ng m⁻³, respectively, followed by n-alkanes at ∼210 and ∼90 ng m⁻³, and polycyclic aromatic hydrocarbons (PAHs) were also at high at ∼120 and ∼30 ng m⁻³. High WSOC/TC, low C_18:1/C₁₈ of fatty acids, and low concentrations of labile PAHs such as benzo(a)pyrene, together with back trajectory analysis suggested that the aerosols were aged and transported. PAHs, triterpane and sterane distributions provided evidence that coal burning was the main source of the continental outflow. The detection of levoglucosan and β-sitosterol in nearly all the samples showed the impact of biomass burning.     

Aromatic hydrocarbons in the atmospheric environment. Part III: personal monitoring

As part of a larger study, personal sampling of the aromatic hydrocarbons benzene, toluene, ethylbenzene and the isomeric xylenes (BTEX) was carried out by 55 nonsmoking volunteers for a period of 14 days. Thirty-nine persons lived in a rural area near Hannover (Germany) with hardly any traffic at all, while 16 persons lived in a high-traffic city street in Hannover. The personal exposure level of the persons in the rural area (some commuting to Hannover) was: 2.9, 24.8, 2.4 and 7.7 μg m⁻³ for benzene, toluene, ethylbenzene and the sum of xylenes, respectively, while the corresponding data for the high traffic city streets were 4.0, 22.2, 2.8 and 9.7 μg m⁻³ (geometric means). Four microenvironments have been monitored which contribute to the total exposure to BTEX, i.e. the home, the outdoor air, the workplace and the car cabin. The most important microenvironment for non-working persons is the private home. The concentration of most BTEX in the private home is almost equal to the personal exposure level, demonstrating that the indoor pollution in the home makes by far the highest contribution to the total exposure. For working people (mostly office workers), the workplace is the second most important microenvironment contributing to the total BTEX exposure. Taking all working persons into consideration (independent of the location of their private home) the personal exposure level is higher by a factor of 1.2–1.4 than that of the workplace (for toluene this factor is 2.2). As already found by others, very high BTEX concentrations may be found in car cabins, in particular, if the engine is gasoline-driven. In the cabin of 44 cars in the rural/urban area average benzene concentrations (geometric mean) of 12/14 μg m⁻³ and a maximum value of ∼550 μg m⁻³ were found. On average, the participating volunteers drove their car for 45 min day⁻¹ (i.e. 3% of the day). Nevertheless, the car cabin constitutes about 10% of the total benzene exposure. Refueling of the car during the 14-day sampling period has only a small effect on the personal exposure level.     

The composition of individual aerosol particle in the troposphere and stratosphere over Xianghe (39.45°N, 117.0°E), China

A balloon observation was carried out on 22 August in 1993 from Xianghe Scientific Balloon Base (39.75°N, 117.0°E) near Beijing in China. Individual aerosol particles in the five samples collected in the troposphere and lower stratosphere were analyzed by using a transmission electron microscope equipped with an energy-dispersive X-ray (EDX) analyzer. Types of particles were classified by the quantitative EDX analysis and particle morphology. Following results were obtained by the analyses of aerosol particles in the radius range of 0.1–0.5 μm: (1) Sulfate particles were dominant (80%) in aerosol particles collected between 4 and 6 km altitude. (2) Sulfuric acid particles were present in 74% of particles at ∼8 km altitude, 91% at 11 km, 95% at 17 km and 88% at 21.2 km. (3) “S-rich” particles with K were collected both in the troposphere and lower stratosphere. It was considered that the particles containing K found at ∼5, ∼8 km altitude could originate from burning processes in the continent including the Tibetan plateau and be transported to the middle troposphere. (4) Sulfuric acid particles with Fe were present in 20–30% of sulfuric acid particles in the lower stratosphere. (5) Particles mainly composed of minerals were present in 6, 11% of particles at ∼5, ∼8 km, indicating the vertical transport to the upper troposphere. (6) Mineral particles which contain sulfuric acid and sulfate suggest the formation of sulfuric acid and sulfate on mineral particles by heterogeneous processes in the troposphere. (7) Sea-salt particles with and without minerals were collected in the troposphere and lower stratosphere, suggesting the vertical transport by convective clouds.     

Benzene,toluene, ozone,NO2 and SO2 measurements in an urban street canyon in Thessaloniki,Greece

Benzene, toluene, sulphur dioxide, ozone and nitrogen dioxide were measured at a mean level of 13.5 m above ground in a narrow, four-lane street canyon (height 30 m, width 20 m) in Thessaloniki, Greece during the period January–July 1997 by means of a commercial differential optical absorption spectrometer (OPSIS DOAS). Primary pollutant levels were found to be 2.5–4.4 times higher during the cold part of the year than during the warm part of the year, the winter/summer ratio increasing with the reaction rate constant with OH for each of the measured species. Ozone, on the other hand, exhibited a winter/summer ratio of 0.36. NO₂ originates from both primary and secondary sources; its winter/summer concentration ratio of 1.4 lies, therefore, between those of primary pollutants and ozone. Pollution levels were influenced considerably by wind speed, while for the street canyon under study wind direction did not influence pollutant levels considerably. While primary pollution was found to decrease with increasing wind speed, ozone increased. Benzene mean levels during the study period were around 6 ppb and hence much higher than the EU annual limit value of 5 μg m⁻³ (1.44 ppb at STP). Toluene mean levels were around 14 ppb and hence also several times above the WHO recommendation of 2 ppb for 24 h. The apportionment of traffic emissions in four time zones used in most inventories in urban airshed models was tested using benzene and toluene measurements at low (<1 m s⁻¹) wind speeds. The agreement between model emissions and calculated emissions apportionment into the four time zones was good, except for Zone D (23:00–1:59), where model inventory emissions were somewhat too low.     

A review of surface ozone in the polar regions

Surface ozone records from ten polar research stations were investigated for the dependencies of ozone on radiative processes, snow-photochemisty, and synoptic and stratospheric transport. A total of 146 annual data records for the Arctic sites Barrow, Alaska; Summit, Greenland; Alert, Canada; Zeppelinfjellet, Norway; and the Antarctic stations Halley, McMurdo, Neumayer, Sanae, Syowa, and South Pole were analyzed. Mean ozone at the Northern Hemisphere (NH) stations (excluding Summit) is ∼5 ppbv higher than in Antarctica. Statistical analysis yielded best estimates for the projected year 2005 median annual ozone mixing ratios, which for the Arctic stations were 33.5 ppbv at Alert, 28.6 ppbv at Barrow, 46.3 ppbv ppb at Summit and 33.7 ppbv at Zeppelinfjellet. For the Antarctic stations the corresponding ozone mixing ratios were 21.6 ppbv at Halley, 27.0 ppbv at McMurdo, 24.9 ppbv at Neumayer, 27.2 ppbv at Sanae, 29.4 ppbv at South Pole, and 25.8 ppbv at Syowa. At both Summit (3212 m asl) and South Pole (2830 m asl), annual mean ozone is higher than at the lower elevation and coastal stations. A trend analysis revealed that all sites in recent years have experienced low to moderate increases in surface ozone ranging from 0.02 to 0.26 ppbv yr⁻¹, albeit none of these changes were found to be statistically significant trends. A seasonal trend analysis showed above-average increases in ozone during the spring and early summer periods for both Arctic (Alert, Zeppelinfjellet) and Antarctic (McMurdo, Neumayer, South Pole) sites. In contrast, at Barrow, springtime ozone has been declining. All coastal stations experience springtime episodes with rapid depletion of ozone in the boundary layer, attributable to photochemically catalyzed ozone depletion from halogen chemistry. This effect is most obvious at Barrow, followed by Alert. Springtime depletion episodes are less pronounced at Antarctic stations. At South Pole, during the Antarctic spring and summer, photochemical ozone production yields frequent episodes with enhanced surface ozone. Other Antarctic stations show similar, though less frequent spring and summertime periods with enhanced ozone. The Antarctic data provide evidence that austral spring and summertime ozone production in Antarctica is widespread, respectively, affects all stations at least through transport events. This ozone production contributes to a several ppbv enhancement in the annual mean ozone over the Antarctic plateau; however, it is not the determining process in the Antarctic seasonal ozone cycle. Although Summit and South Pole have many similarities in their environmental conditions, this ozone production does not appear to be of equal importance at Summit. Amplitudes of diurnal, summertime ozone cycles at these polar sites are weaker than at lower latitude locations. Amplitudes of seasonal ozone changes are larger in the Southern Hemisphere (by ∼5 ppbv), most likely due to less summertime photochemical ozone loss and more transport of ozone-rich air to the Arctic during the NH spring and summer months.     

Validation of a hybrid forecasting system for the ozone concentrations over the Paris area

A simplified hybrid statistical-deterministic chemistry-transport model, is used in real time for the prediction of ozone in the area of Paris during Summer 1999. We present here a statistical validation of this experiment. We distinguish the forecasts in the urban area from forecasts in the pollution plume downwind of the city. The validation of model forecasts, up to 3 days ahead, is performed against ground based observations within and up to 50 km outside of Paris. In the urban area, ozone levels are fairly well forecast, with correlation coefficients between forecast and observations ranging between 0.7 and 0.8 and root mean square errors in the range 15–20 μg m⁻³ at short lead times. While the bias of urban forecast is very low, the largest peaks are somehow underestimated. The ozone plume amplitude is generally well reproduced, even at long lead times (root mean square errors of about 20–30 μg m⁻³), while the direction of the plume is only captured at short lead times (about 70% of the time). The model has difficulties in forecasting the direction of the plume under stagnant weather conditions. We estimate the model ability to forecast concentrations above 180 μg m⁻³, which are of practical relevance to air quality managers. It is found that about 60% of these events are well forecast, even at long lead times, while the exact monitoring station where the exceedance is observed can only be forecast at short lead times. Finally, we found that about half of the forecast error is due to the error in the estimation of the boundary conditions, which are forecast by a simple linear regression model here.     

Measurement of the vapor phase deposition of polychlorinated bipheyls (PCBs) using a water surface sampler

A water surface sampler (WSS) was employed in combination with greased knife-edge surface deposition plates (KSSs) to measure the vapor phase deposition rates of PCBs to the sampler at an urban site, Chicago, IL. This sampler employed a water circulation system that continuously removed deposited PCBs. Total (gas+particle) and particulate PCB fluxes were collected with the WSS and KSSs, respectively. Gas phase PCB fluxes were then calculated by subtracting the KSS fluxes (particulate) from the WSS fluxes (gas+particle). The calculated gas phase PCB fluxes averaged 830±910 ng m⁻²d⁻¹. This flux value is, in general, higher than the fluxes determined using simultaneously measured air–water concentrations in natural waters and is in the absorption direction. This difference is primarily because the PCBs were continuously removed from the WSS water keeping the water PCB concentration near zero.Concurrently, ambient air samples were collected using a modified high volume air sampler. The gas phase PCB concentrations ranged between 1.10 and 4.46 ng m⁻³ (average±SD, 2.29±1.28 ng m⁻³). The gas phase fluxes were divided by the simultaneously measured gas phase ambient concentrations to determine the overall gas phase mass transfer coefficients (MTCs) for PCBs. The average gas phase overall MTCs (K_g) for each homolog group ranged between 0.22 and 1.32 cm s⁻¹ (0.54±0.47 cm s⁻¹). The average MTC was in good agreement with those determined using similar techniques.     

Resuspension of coarse particles in the region of Chernobyl

Measurements of resuspension into air in the coarse particle range (>10 μm in aerodynamic diameter) were performed as part of a field measurement experiment at four sites around Chernobyl during wind-driven and anthropogenic enhanced resuspension (agricultural activities). Caesium-137 was used to quantify the magnitude of resuspension. The mean resuspension factor of coarse particles was between 1×10^-10 and 6×10^-10 m^-1 for wind-driven resuspension. During agricultural activities, the resuspension increased by up to three orders of magnitude. Coarse particles comprised about one-third of the total amount of resuspended Caesium-137. The activity size distribution of Caesium-137 was not uniform in the coarse particle range: approximately 44% of the activity was found in the range 10–20 μm aerodynamic diameter. The determination of the number concentration of particles >20 μm aerodynamic diameter showed a linear relation between particle number and activity: the mean activity per particle was 0.75±0.15 μBq at the site Novozybkov, Russia. The resuspension factor was found to decrease exponentially with increasing relative soil moisture content. At higher soil humidity, the portion of coarse particles of the total resuspended activity was larger.