Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

Particulate size distributions and mass measured at a motorway during the BAB II campaign

From 1 May to 25 May 2001, the BAB II campaign was carried out at the motorway BAB (656) near Heidelberg. Atmospheric concentrations of particulate matter and gases were measured together with the meteorological conditions. This paper is focused on the particulate matter measured upwind and downwind from the motorway at ground level. In order to determine the source contribution from the motorway traffic, it was necessary to measure upwind and downwind simultaneously due to variations in background concentrations. The particle number contribution from the motorway was found to be 35,000 particles cm⁻³ for particles with diameters close to 20 nm and 5000 particles cm⁻³ for particles with diameters close to 70 nm. Bimodal size distributions were observed on the downwind side, whereas the upwind side showed unimodal size distributions. For particulate mass, it can be estimated that the contribution from the motorway to the PM₁ concentrations is in a range 0.6–1.3 μg m⁻³ for the chosen measurement sites approximately 60 m from the road at a height of 6 m. The soot measurements showed diurnal variation; however, the upwind downwind difference was not measured. Correlation factors showed good correlation between total particle number and number of particles with diameters below 80 nm, CO and NO. There was no correlation between particle number and PM₁₀, which is due to the observation that particle number was dominated by the 20 nm particles.     

Using a dispersion model to estimate emission rates of particulate matter from paved roads

From January 1996 to June 1997, we carried out a series of measurements to estimate emissions of PM₁₀ from paved roads in Riverside County, California. The program involved the measurement of upwind and downwind vertical profiles of PM₁₀, in addition to meteorological variables such as wind speed and vertical turbulent intensity. This information was analyzed using a new dispersion model that incorporates current understanding of micrometeorology and dispersion. The emission rate was inferred by fitting model predictions to measurements. The inferred emission factors ranged from 0.2 g VKT^-1 for freeways to about 3 g VKT^-1 for city roads. The uncertainty in these factors is estimated to be approximately a factor of two since the contributions of paved road PM₁₀ emissions to ambient concentrations were comparable to the uncertainty in the mean value of the measurement. At this stage, our best estimate of emission factor lies between 0.1 and 10 g VKT^-1; there is some indication that it is about 0.1 g VKT^-1 for heavily traveled freeways, and is an order of magnitude higher for older city roads. We found that measured silt loadings were poor predictors of emission factors.The measured emission factors imply that paved road emissions may contribute about 30% to the total PM₁₀ emissions from a high traffic area such as Los Angeles. This suggests that it is necessary to develop methods that are more reliable than the upwind–downwind concentration difference technique.     

Flow patterns influencing the seasonal behavior of surface ozone and carbon monoxide at a coastal site near Hong Kong

Surface O₃ and CO were measured at Cape D’Aguilar, Hong Kong during the period of January 1994 to December1996 in order to understand the temporal variations of surface O₃ and CO in East Asia–West Pacific region. The isentropic backward trajectories were used to isolate different air masses reaching the site and to analyze the long-range transport and photochemical buildup of O₃ on a regional scale. The results show that the diurnal variation of surface O₃ was significant in all seasons with daily O₃ production being about 20 ppbv in fall and 10 ppbv in winter, indicating more active photochemical processes in the subtropical region. The distinct seasonal cycles of O₃ and CO were found with a summer minimum (16 ppbv)–fall maximum (41 ppbv) for O₃ and a summer minimum (116 ppbv)–winter maximum (489 ppbv) for CO. The isentropic backward trajectory cluster analyses suggest that the air masses (associated with regional characteristics) to the site can be categorized into five groups, which are governed by the movement of synoptic weather systems under the influence of the Asian monsoon. For marine-originated air masses (M-SW, M-SE and M-E, standing for marine-southwest, marine-southeast and marine-east, respectively) which always appear in summer and spring, the surface O₃ and CO have relatively lower mixing ratios (18, 16 and 30 ppbv for O₃, 127, 134 and 213 ppbv for CO), while the continental air masses (C-E and C-N, standing for continent-east and continent-north, respectively) usually arrive at the site in winter and fall seasons with higher O₃ (43 and 48 ppbv) and CO (286 and 329 ppbv). The 43 ppbv O₃ and 286 ppbv CO are representative of the regionally polluted continental outflow air mass due to the anthropogenic activity in East Asia, while 17 ppbv O₃ and 131 ppbv CO can be considered as the signature of the approximately clean marine background of South China Sea. The very high CO values (461–508 ppbv) during winter indicate that the long-range transport of air pollutants from China continent is important at the monitoring site. The fall maximum (35–46 ppbv) of surface O₃ was believed to be caused by the effects of the weak slowly moving high-pressure systems which underlie favorable photochemical production conditions and the long-range transport of aged air masses with higher O₃ and its precursors.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Nitrogen oxide fluxes between corn (Zea mays L.) leaves and the atmosphere

In the United States, fertilized corn fields, which make up approximately 5% of the total land area, account for approximately 45% of total soil NO_x emissions. Leaf chamber measurements were conducted of NO and NO₂ fluxes between individual corn leaves and the atmosphere in (1) field-grown plants near Champaign, IL (USA) in order to assess the potential role of corn canopies in mitigating soil–NO_x emissions to the atmosphere, and (2) greenhouse-grown plants in order to study the influence of various environmental variables and physiological factors on the dynamics of NO₂ flux. In field-grown plants, fluxes of NO were small and inconsistent from plant to plant. At ambient NO concentrations between 0.1 and 0.3 ppbv, average fluxes were zero. At ambient NO concentrations above 1 ppbv, NO uptake occurred, but fluxes were so small (14.3±0.0 pmol m⁻² s⁻¹) as to be insignificant in the NO_x inventory for this site. In field-grown plants, NO₂ was emitted to the atmosphere at ambient NO₂ concentrations below 0.9 ppbv (the NO₂ compensation point), with the highest rate of emission being 50 pmol m⁻² s⁻¹ at 0.2 ppbv. NO₂ was assimilated by corn leaves at ambient NO₂ concentrations above 0.9 ppbv, with the maximum observed uptake rate being 643 pmol m⁻² s⁻¹ at 6 ppbv. When fluxes above 0.9 ppbv are standardized for ambient NO₂ concentration, the resultant deposition velocity was 1.2±0.1 mm s⁻¹. When scaled to the entire corn canopy, NO₂ uptake rates can be estimated to be as much as 27% of the soil-emitted NO_x. In greenhouse-grown and field-grown leaves, NO₂ deposition velocity was dependent on incident photosynthetic photon flux density (PPFD; 400–700 nm), whether measured above or below the NO₂ compensation point. The shape of the PPFD dependence, and its response to ambient humidity in an experiment with greenhouse-grown plants, led to the conclusion that stomatal conductance is a primary determinant of the PPFD response. However, in field-grown leaves, measured NO₂ deposition velocities were always lower than those predicted by a model solely dependent on stomatal conductance. It is concluded that NO₂ uptake rate is highest when N availability is highest, not when the leaf deficit for N is highest. It is also concluded that the primary limitations to leaf-level NO₂ uptake concern both stomatal and mesophyll components.     

Shouldn’t snowpacks be sources of monocarboxylic acids?

We report the first measurements of the mixing ratios of acetic (CH₃COOH) and formic (HCOOH) acids in the air filling the pore spaces of the snowpacks (firn air) at Summit, Greenland and South Pole. Both monocarboxylic acids were present at levels well above 1 ppbv throughout the upper 35 cm of the snowpack at Summit. Maximum mixing ratios in Summit firn air reached nearly 8 ppbv CH₃COOH and 6 ppbv HCOOH. At South Pole the mixing ratios of these acids in the top 35 cm of firn air were also generally >1 ppbv, though their maximums barely exceeded 2.5 ppbv of CH₃COOH and 2.0 ppbv of HCOOH. Mixing ratios of the monocarboxylic acids in firn air did not consistently respond to diel and experimental (fast) variations in light intensity, unlike the case for N oxides in the same experiments. Air-to-snow fluxes of CH₃COOH and HCOOH apparently support high mixing ratios (means of (CH₃COOH/HCOOH) 445/460 and 310/159 pptv at Summit and South Pole, respectively) in air just above the snow during the summer sampling seasons at these sites. We hypothesize that oxidation of carbonyls and alkenes (that are produced by photo- and OH-oxidation of ubiquitous organic compounds) within the snowpack is the source of the monocarboxylic acids.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

Airborne particle PM2.5/PM10 mass distribution and particle-bound PAH concentrations near a medical waste incinerator

This study attempts to determine the influence of air quality in a residential area near a medical waste incineration plant. Ambient air concentrations of polycyclic aromatic hydrocarbons (PAHs), PM₁₀ and PM_2.5 (PM—particulate matter) were determined by collecting air samples in areas both upwind and downwind of the plant. The differences in air pollutant levels between the study area and a reference area 11 km away from the plant were evaluated.Dichotomous samplers were used for sampling PM_2.5 and PM₁₀ from ambient air. Two hundred and twenty samples were obtained from the study area, and 100 samples were taken from a reference area. Samples were weighed by an electronic microbalance and concentrations of PM_2.5 and PM₁₀ were determined. A HPLC equipped with a fluorescence detector was employed to analyze the concentrations of 15 PAHs compounds adsorbed into PM_2.5 and PM₁₀.The experimental results indicated that the average concentrations of PM_2.5 and PM₁₀ were 30.34±17.95 and 36.81±20.45 μg m⁻³, respectively, in the study area, while the average ratio of PM_2.5/PM₁₀ was 0.82±0.01. The concentrations of PM_2.5 and PM₁₀ of the study area located downwind of the incinerator were significantly higher than the study area upwind of the incinerator (P<0.05).The concentration of PAHs in PM_2.5 in the study area was 2.2 times higher than in the reference area (P<0.05). Furthermore, the benzo(a)pyrene concentrations in PM_2.5 and PM₁₀ were 0.11±0.05 ng m⁻³ and 0.12±0.06 ng m⁻³ in the study area, respectively. The benzo(a)pyrene concentrations of PM_2.5 and PM₁₀ in the study area were 7 and 5.3 times higher than in the reference area (P<0.05), respectively.The study indicated that the air quality of PM_2.5, PM₁₀ and PAHs had significant contamination by air pollutants emitted from a medical waste incineration factory, representing a public health problem for nearby residences, despite the factory being equipped with a modern air pollution control system.     

Aircraft measurements of O3, NOx,CO, VOCs,and SO2 in the Yangtze River Delta region

In this study, air pollutants, including ozone (O₃), nitrogen oxides (NO_x = NO + NO₂), carbon monoxides (CO), sulfur dioxide (SO₂), and volatile organic compounds (VOCs) measured in the Yangtze River Delta (YRD) region during several air flights between September/30 and October/11 are analyzed. This measurement provides horizontal and vertical distributions of air pollutants in the YRD region. The analysis of the result shows that the measured O₃ concentrations range from 20 to 60 ppbv. These values are generally below the US national standard (84 ppbv), suggesting that at the present, the O₃ pollutions are modest in this region. The NO_x concentrations have strong spatial and temporal variations, ranging from 3 to 40 ppbv. The SO₂ concentrations also have large spatial and temporal variations, ranging from 1 to 35 ppbv. The high concentrations of CO are measured with small variations, ranging from 3 to 7 ppmv. The concentrations of VOCs are relatively low, with the total VOC concentrations of less than 6 ppbv. The relative small VOC concentrations and the relative large NO_x concentrations suggest that the O₃ chemical formation is under a strong VOC-limited regime in the YRD region. The measured O₃ and NO_x concentrations are strongly anti-correlated, indicating that enhancement in NO_x concentrations leads to decrease in O₃ concentrations. Moreover, the O₃ concentrations are more sensitive to NO_x concentrations in the rural region than in the city region. The ratios of Δ[O₃]/Δ[NO_x] are ?2.3 and ?0.25 in the rural and in the city region, respectively. In addition, the measured NO_x and SO₂ concentrations are strongly correlated, highlighting that the NO_x and SO₂ are probably originated from same emission sources. Because SO₂ emissions are significantly originated from coal burnings, the strong correlation between SO₂ and NO_x concentrations suggests that the NO_x emission sources are mostly from coal burned sources. As a result, the future automobile increases could lead to rapid enhancements in O₃ concentrations in the YRD region.     

Analysis of ozone and VOCs measured in Shanghai: A case study

Shanghai Meteorological Administration has established a volatile organic compounds (VOCs) laboratory and an observational network for VOCs and ozone (O₃) measurements in the city of Shanghai. In this study, the measured VOCs and O₃ concentrations from 15 November (15-Nov) to 26 November (26-Nov) of 2005 in Shanghai show that there are strong day-to-day and diurnal variations. The measured O₃ and VOCs concentrations have very different characterizations between the two periods. During 15-Nov to 21-Nov (defined as the first period), VOCs and O₃ concentrations are lower than the values during 22-Nov to 28-Nov (defined as the second period). There is a strong diurnal variation of O₃ during the second period with maximum concentrations of 40–80 ppbv at noontime, and minimum concentrations at nighttime. By contrast, during the first period, the diurnal variation of O₃ is in an irregular pattern with maximum concentrations of only 20–30 ppbv. The VOC concentrations change rapidly from 30–50 ppbv during the first period to 80–100 ppbv during the second period. Two chemical models are applied to interpret the measurements. One model is a regional chemical/dynamical model (WRF-Chem) and another is a detailed chemical mechanism model (NCAR MM). Model analysis shows that the meteorological conditions are very different between the two periods, and are mainly responsible for the different chemical characterizations of O₃ and VOCs between the two periods. During the first period, meteorological conditions are characterized by cloudy sky and high-surface winds in Shanghai, resulting in a higher nighttime planetary boundary layer (PBL) and faster transport of air pollutants. By contrast, during the second period, the meteorological conditions are characterized by clear sky and weak surface winds, resulting in a lower nighttime PBL and slower transport of air pollutants. The chemical mechanism model calculation shows that different VOC species has very different contributions to the high-ozone concentrations during the second period. Alkane (40 ppbv) and aromatic (30 ppbv) are among the highest VOC concentrations observed in Shanghai. The analysis suggests that the aromatic is a main contributor for the O₃ chemical production in Shanghai, with approximately 79% of the O₃ being produced by aromatic. This analysis implies that future increase in VOC (especially aromatic) emissions could lead to significant increase in O₃ concentrations in Shanghai.     

Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Characteristics of the major chemical constituents of PM2.5 and smog events in Seoul,Korea in 2003 and 2004

One hundred ninety-five chemically speciated samples were collected from March 2003 to February 2005 in the Seoul Metropolitan area to investigate the characteristics of the major components in PM_2.5 and to characterize the chemical variations between smog and non-smog events. The annual average PM_2.5 concentration was 43 μg m⁻³ that is almost three times higher than the US NAAQS annual PM_2.5 standard of 15 μg m⁻³. During this sampling period, smog and yellow sand events were observed on 27 and 10 days, respectively. The PM_2.5 concentrations and its constituents during smog events were about two–three times higher than those during non-smog and yellow sand events. In particular, the mass fractions of secondary aerosols such as sulfate, nitrate, and ammonium during the smog events were higher than those of the other constituents. The mean concentration and mass fraction of secondary organic carbon (SOC) were highest during the winter smog events. Sulfate, nitrate and SOC that can have long residence times were important species during the smog events suggesting that regional scale sources rather than local sources were important. Five-day backward air trajectory analysis showed that the air parcels during smog events passed through the major industrial areas in China more often than those during non-smog events.     

Ions in motor vehicle exhaust and their dispersion near busy roads

Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm^?3) was about one-half of that near motorways (1211 cm^?3) and about twice as high as that in the urban background (269 cm^?3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density (R² = 0.3 at p < 0.05) and correlated well with each other in real time (R² = 0.87 at p < 0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120–150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2 m to 5 m of the kerb. Measured concentrations decreased to background at about 15 m from the kerb when the wind speed was 1.3 m s^?1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.     

A simple technique for measuring power station SO2 and NO2 emissions

Emissions of SO₂ and NO₂ from fossil fuel power stations can have serious environmental consequences via conversion to sulphuric and nitric acids and subsequent deposition. Consequently, there is considerable interest in techniques capable of monitoring these emissions, in order to ensure compliance with environmental legislation. Here we present a novel approach to measuring power station SO₂ and NO₂ emissions by traversing underneath the plume by car or on-foot or scanning the power station's plume from a fixed position with a compact and lightweight UV spectrometer. This work was performed at a power station in eastern England during January, February and June 2003, resulting in a SO₂ flux of 5.2 kg s⁻¹, which is in close correspondence with the in-stack measured value of 5.3 kg s⁻¹. This technique is considerably simpler and cheaper than other remote sensing approaches to monitoring these emissions.     

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.     

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.     

Pollution events over the East Mediterranean: Synergistic use of GOME,ground-based and sonde observations and models

The behaviour of ozone (O₃) and two important precursors, nitrogen dioxide (NO₂) and formaldehyde (HCHO), over the East Mediterranean in spring from 1996 to 2002 is studied in order to characterise the buildup of tropospheric O₃. The vertical distribution of O₃ observed over Crete during the Photochemical Activity and Solar Ultraviolet Radiation (PAUR II) campaign in May 1999 has been used for validation of satellite-derived data. Retrievals of O₃ columns from measurements of backscattered radiation by Global Ozone Monitoring Experiment (GOME) are compared with Total Ozone Mapping Spectrometer (TOMS), balloon, Systeme d’Analyse par Observation Zenithale (SAOZ) and LIDAR observations. The total O₃ vertical columns vary between 270 and 402 DU and correlate well with changes in air circulation patterns. The total observed variability in tropospheric O₃ is about 25 DU. Chemical box model calculations associate the GOME-observed NO₂ and HCHO tropospheric columns with a potential of daily photochemical enhancement in the tropospheric O₃ columns of about 0.8–1 DU over Crete and estimate the daily potential of regional photochemical buildup within upwind polluted air masses at about 2–8 DU. A Langrangian analysis attributes at most 10–20 DU of tropospheric O₃ to stratosphere–troposphere exchange (STE). The remainder is attributed to long-range transport of O₃ from industrial regions in Central Europe. From 1996 to 2002, in May no significant inter-annual variation in the tropospheric NO₂ and HCHO columns over Crete has been observed by GOME suggesting no detectable increase in regionally produced tropospheric O₃.     

Sources and concentration of nanoparticles (<10 nm diameter) in the urban atmosphere

Whilst limited information on particle size distributions and number concentrations in cities is available, very few data on the very smallest of particles, nanoparticles, have been recorded. Measurements in this study show that road traffic and stationary combustion sources generate a significant number of nanoparticles of diameter <10 nm. Measurements at the roadside (4 m from the kerb) and downwind from the traffic (more than 25 m from the kerb) show that nanoparticles (<10 nm diameter) accounted for more than 36–44% of the total particle number concentrations. Measurements designed to sample the plume of individual vehicles showed that both a diesel- and a petrol-fuelled vehicle generated nanoparticles (<10 nm diameter). The fraction of nanoparticles was even greater in a plume 350 m downwind of a stationary combustion source. On a few occasions, a temporal association between nanoparticles in the size range 3–7 nm and solar radiation was observed in urban background air at times when no other local sources were influential, which suggests that homogeneous nucleation can also be an important source of particles in the urban atmosphere.