Prediction of sulfur dioxide concentrations at a site near downtown Santiago,Chile

We have analyzed the possibility to predict hourly averages of sulfur dioxide concentrations in the atmosphere at a site not far from the downtown area in the city of Santiago, Chile. We have compared the forecasts produced assuming persistence, linear regressions and feed forward neural networks. The effect of meteorological conditions is included by using forecasted values of temperature, relative humidity and wind speed at the time of the intended prediction as inputs to the different models. The best predictions for hourly averages are obtained with a three-layer neural network that has hourly averages of sulfur dioxide concentrations every 6 h on the previous day plus the actual values of the meteorological variables as input. Training the network with 1995 data, error in 8 h in advance prediction for 1996 data is of the order of 30%.     

Prediction of maximum of 24-h average of PM10 concentrations 30 h in advance in Santiago,Chile

We have developed a neural network based model that uses values of PM10 concentrations measured until 6 p.m. on the present day plus measured and forecasted values of meteorological variables as input in order to predict the level reached by the maximum of the 24-h moving average (24MA) of PM10 concentration on the next day. We have adjusted the parameters of the model using 1998 data to predict 1999 conditions and 1999 data to forecast 2000 maximum concentrations. We have found that among the relevant meteorological input variables, the forecasted difference between maximum and minimum temperature is the most important. Due to the fact that local authorities impose restrictions to emissions on days when the maximum of 24MA of PM10 concentration is expected to exceed 240 μg/m³, we have corrected the measured concentrations on these days before evaluating the efficacy of the forecasting model. Percent errors in forecasting the numerical value are of the order of 20%. The performance of the neural network is better than that of a linear model with the same inputs, but the difference being not great is an indication that the right choice of input variables may be more important than the decision to use a linear or a nonlinear model.     

Impacts of a strong cold front on concentrations of HONO,HCHO, O3, and NO2 in the heavy traffic urban area of Beijing

Much rain and strong winds caused by a cold front occurred in Beijing during the period of Sep. 27 to Oct. 4, 2004 and led to sharp drops in maximum and mean concentrations of HONO, HCHO, O₃, and NO₂, i.e., the maximum concentrations were reduced by 5.9, 21.3, 45.6, and 44.4 ppb, respectively, and the mean concentrations were decreased by 4.0, 5.5, 30.3, and 32.3 ppb, respectively. For daily HO_x production rates HONO photolysis was the largest contributor and over 90% contributions were from photolysis of HONO and HCHO. Large number and area percentages of soot aggregate from PM10, and high correlations between concentrations of PM10 and chemical formation of HONO suggested that heterogeneous reactions of NO₂ on surfaces of soot aggregate could be a key source of HONO in the heavy traffic areas of Beijing during the night and should be considered in air quality simulations for such areas.     

Carbon monoxide concentration forecasting in Santiago, Chile

In the city of Santiago, Chile, air quality is defined in terms of particulate matter with an aerodynamic diameter < or = 10 microm (PM10) concentrations. An air quality forecasting model based on past concentrations of PM10 and meteorological conditions currently is used by the metropolitan agency for the environment, which allows restrictions to emissions to be imposed in advance. This model, however, fails to forecast between 40 and 50% of the days considered to be harmful for the inhabitants every year. Given that a high correlation between particulate matter and carbon monoxide (CO) concentrations is observed at monitoring stations in the city, a model for CO concentration forecasting would be a useful tool to complement information about expected air quality in the city. Here, the results of a neural network-based model aimed to forecast maximum values of the 8-hr moving average of CO concentrations for the next day are presented. Forecasts from the neural network model are compared with those produced with linear regressions. The neural network model seems to leave more room to adjust free parameters with 1-yr data to predict the following year's values. We have worked with 3 yr of data measured at the monitoring station located in the zone with the worst air quality in the city of Santiago, Chile.     

Volatile carbonylic compounds in downtown Santiago, Chile

Formaldehyde, acetaldehyde, acetone, propanal, butanal, 2-butenal, 3-methylbutanal, hexanal, benzaldehyde, 2-methylbenzaldehyde, and 2,5-dimethylbenzaldehyde were measured during six spring days at downtown Santiago de Chile. Measurements were performed 24h/day and averaged over three hour periods. The averages of the maxima (ppbv) were, formaldehyde: 3.9+/-1.4; butanal: 3.3+/-3.4; acetaldehyde: 3.0+/-0.9; acetone: 2.4+/-1.0; 2-butenal: 0.56+/-0.52; propanal: 0.46+/-0.21; benzaldehyde: 0.34+/-0.3; 3-butanal: 0.11+/-0.05; hexanal: 0.11+/-0.08; 2-methylbenzaldehyde: 0.08+/-0.05; 2,5-dimethylbenzaldehyde: 0.05+/-0.03. Aliphatic aldehydes (C1-C3) are strongly correlated among them and weakly with primary (toluene) and secondary (ozone plus nitrogen dioxide or PAN) pollutants. In particular, the correlation between acetaldehyde and propanal values remains even if diurnal and nocturnal data are considered separately, indicating similar sources. All these aldehydes present maxima values in the morning (9-12h) and minima at night (0-3h). The best correlation is observed when butanal and 2-butenal data are considered (r=0.99, butanal/2-butenal=6.2). These compounds present maxima values during the 3-6h period, with minima values in the 0-3h period. These data imply a strong pre-dawn emission. Other aldehydes show different daily profiles, suggesting unrelated origins. Formaldehyde is the aldehyde whose concentration values best correlate with the levels of oxidants. The contribution of primary emissions and photochemical processes to formaldehyde concentrations were estimated by using a multiple regression. This treatment indicates that (32+/-16)% of measured values arise from direct emissions, while (79+/-23)% is attributable to secondary formation.     

Soil and street dust heavy metal concentrations in and around Cuenca, Ecuador

Lead, cadmium and zinc concentrations have been obtained in a total of 83 soil and dust samples in and around the city of Cuenca, Ecuador. Elevated heavy metal concentrations were observed in the city, with comparable Pb concentrations to those commonly found in European and North American cities. Lead concentrations were also elevated above the estimated regional background (less than 9 microg g(-1)) along a rural track used by about 100 vehicles per day. The extent of the contamination by Cd and Zn was restricted to the urban area.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

Analysis of PM10, PM2.5, and PM2 5-10 concentrations in Santiago, Chile, from 1989 to 2001

Daily particle samples were collected in Santiago, Chile, at four urban locations from January 1, 1989, through December 31, 2001. Both fine PM with da < 2.5 microm (PM2.5) and coarse PM with 2.5 < da < 10 microm (PM2.5-10) were collected using dichotomous samplers. The inhalable particle fraction, PM10, was determined as the sum of fine and coarse concentrations. Wind speed, temperature and relative humidity (RH) were also measured continuously. Average concentrations of PM2.5 for the 1989-2001 period ranged from 38.5 microg/m3 to 53 microg/m3. For PM2.5-10 levels ranged from 35.8-48.2 microg/m3 and for PM10 results were 74.4-101.2 microg/m3 across the four sites. Both annual and daily PM2.5 and PM10 concentration levels exceeded the U.S. National Ambient Air Quality Standards and the European Union concentration limits. Mean PM2.5 levels during the cold season (April through September) were more than twice as high as those observed in the warm season (October through March); whereas coarse particle levels were similar in both seasons. PM concentration trends were investigated using regression models, controlling for site, weekday, month, wind speed, temperature, and RH. Results showed that PM2.5 concentrations decreased substantially, 52% over the 12-year period (1989-2000), whereas PM2.5-10 concentrations increased by approximately 50% in the first 5 years and then decreased by a similar percentage over the following 7 years. These decreases were evident even after controlling for significant climatic effects. These results suggest that the pollution reduction programs developed and implemented by the Comisión Nacional del Medio Ambiente (CONAMA) have been effective in reducing particle levels in the Santiago Metropolitan region. However, particle levels remain high and it is thus imperative that efforts to improve air quality continue.     

Rapid urban growth,land-use changes and air pollution in Santiago,Chile

This paper is a contribution to the understanding of the topoclimatic and environmental geography of the basin where Santiago — one of the most polluted Latin American city – is located. In the first part, land-use change is analysed looking at the climatic transformation caused by the rapid transit from natural semiarid surface to urban areas. In the second part, seasonal weather and daily cycles of slope winds and the available ventilation are described trying to relate those patterns with the spatial distribution of air pollution. A combination of meteorological, geographical and cultural factors explain extreme air pollution events: meteorologically, Santiago is under permanent subsidence inversion layers. Geographically, the city is located in a closed basin surrounded by mountains. Culturally, the urban area has the highest population concentration (40% of the national total), industries (near 70% of the total) and vehicles, which are the main sources of smog. The urban and suburban transport system is based on a large number of buses (diesel) and private cars, both experiencing a rapid growth from the past few years. The city and specially the transport system generates high emissions of pollutant, but the natural semiarid deforested soils and slopes are also important sources. The local wind system can explain the differential spatial distribution on the concentration of air pollutants in the city and its periphery. In winter (rain season) concentrations of particulate matter are higher at the centre and the SW part of the city. The andean piedmont area (E part of the city) shows minimum values, suggesting major ventilation effects of slope and valley winds. Ozone exceeds air quality standards in summer (dry season) at all sites in the centre and periphery. However, the O₃-concentrations are higher on preferred residential areas located at the piedmont area (E part of the city), suggesting air pollution transport effects. Currently, there is no consideration of these local climatic features in the process of urban planning.     

Large eddy simulation of shading effects on NO2 and O3 concentrations within an idealised street canyon

A large eddy simulation (LES) model that accounts for chemical reactions between oxides of nitrogen and ozone has been used to investigate the effect of local shading within an idealised street canyon on pollutant concentrations. It has shown that local shading can have a substantial impact on kerbside concentrations (>6 ppb difference for some situations presented) and that this may need to be taken into account to set up numerical model runs as well as sampling sites. A sensitivity study has been performed to investigate the effect of various governing parameters. A strong influence was found for the actual reduction of the photolytic rate constant within the shaded areas. A near linear relationship appeared between the reduction and the effect on pollutant concentrations. The chemical regime above and within the street canyon (determined by background concentrations aloft and emission rates at the ground) was also shown to be of high importance. The geometrical layout of the shading within the canyon and the wind speed in the canyon was shown to affect the spatial distribution of the shading effect rather than its overall magnitude.     

A study of the relationship of street level carbon monoxide concentrations to traffic parameters

The concentration of carbon monoxide at different locations was measured concurrently with traffic flow and vehicle speeds for a period of 6 months from September 1976 to March 1977. This experiment was carried out in eight streets during different hours of the day. These streets had uniform building density and were all shallow canyons with a height-to-width ratio of about 0.5. Climatic conditions were also recorded.This study was conducted to establish relationships between the CO content of the atmosphere and street and traffic parameters. The measurements were taken at the height of 1.5m from the ground. The CO concentration at the pavement was found, in most cases, to be slightly lower than that at street centerline.The level of carbon monoxide concentration generally decreased as the average vehicle speed increased. In the case of moderate vehicle speeds and high traffic flow, the CO concentration reached values as high as 150 ppm. The variation of CO content of atmosphere with vehicle speed showed a peak indicating that for a certain range of traffic flow, the number of vehicles is more important than the vehicle speed in generating the vehicular pollution.     

Emission factors for gasoline light-duty vehicles: experimental program in Santiago, Chile

The emission inventory of the city of Santiago, Chile, related to mobile sources was built up using constant emission factors extracted from international literature. To improve the estimate of mobile source emissions, an experimental program was designed, consisting of transient tests on a chassis dynamometer over a sample of about 166 vehicles, applying 9 local driving cycles with average speeds of 3-80 km/hr, and experimentally determined in previous research carried out by the authors. An analysis of the influence of fuel inlet technology, and a year time-length model over emissions, was undertaken. We proposed emission factors as a function of average speed and of CO, THC, and NOx for catalytic and noncatalytic light-duty gasoline vehicles, disaggregated on commercial and private cars. A comparative analysis with emission factors obtained for the application of the COPERT II and AP-42 models was also presented. Our current analysis gives solid evidence indicating that to obtain a reasonable accuracy on emission estimates and calculations, local emission factors must be used.     

Total element concentration and chemical fractionation in airborne particulate matter from Santiago,Chile

Total element determination and chemical fractionation were carried out in airborne particulate matter (PM₁₀) from the Cerrillos monitoring station in Santiago, Chile, sampled in July (winter), 1997–2003.Element concentration in the period under study (1997–2003) was statistically analyzed through cluster analysis in order to identify groups of elements having similar behavior along time. Elements such as Cd, Cu, Pb, Ni, As and Mg show a clear decrease in concentration with time. On the contrary, chromium increases its concentration almost linearly during the period.In order to estimate whether the presence of a certain element in PM₁₀ matrix is mainly due to anthropogenic or natural processes, the enrichment factor of each element was determined.According to their behavior in the sequential extraction procedure, the elements were grouped by multivariate analysis in three clusters: (a) those mobile elements (Pb, Cd, Zn, Mn, Cu and As) which are weakly bound to the matrix (fractions 1 and 2) (b) those elements (V, Ti, and Cr) mainly bound to carbonates and oxides (fraction 3) and (c) the most immobile elements (Ni, Mo, Ca, Mg, Ba and Al), mainly bound to silicates and organic matter (fraction 4). A source of great concern is the fact that elements of such high toxicity as Pb, Cd and As are highly concentrated in both mobile fractions, indicating that these elements have a direct impact on the environment and on the health of the exposed population.     

Atmospheric BTEX-concentrations in an area with intensive street traffic

The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 μg/m³, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 μg/m³, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.     

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.     

Emission Factors for Gasoline Light-Duty Vehicles: Experimental Program in Santiago,Chile

ABSTRACT

The emission inventory of the city of Santiago, Chile, related to mobile sources was built up using constant emission factors extracted from international literature. To improve the estimate of mobile source emissions, an experimental program was designed, consisting of transient tests on a chassis dynamometer over a sample of about 166 vehicles, applying 9 local driving cycles with average speeds of 3-80 km/hr, and experimentally determined in previous research carried out by the authors. An analysis of the influence of fuel inlet technology, and a year time-length model over emissions, was undertaken. We proposed emission factors as a function of average speed and of CO, THC, and NO_x for catalytic and noncatalytic light-duty gasoline vehicles, disaggregated on commercial and private cars. A comparative analysis with emission factors obtained for the application of the COPERT II and AP-42 models was also presented. Our current analysis gives solid evidence indicating that to obtain a reasonable accuracy on emission estimates and calculations, local emission factors must be used.     

The change in O3, SO2 and NO2 concentrations in Lithuania

Due to the dynamic nature of the atmosphere, substantial amounts of gaseous and particulate pollutants are transported to the areas distant from their sources. In order to determine the regional concentration levels of atmospheric pollutants in Lithuania, concentrations of gaseous O₃, SO₂, NO₂ and other pollutants have been measured at the Preila background station (55°20′ N and 21°00′ E, 5 m a.s.l.) since 1981. The long-term concentration data set enabled us to get temporal trends, both on a seasonal and longer time scale, to identify source areas of pollutants and to relate them to the emission data. Based on the data obtained, the different tendencies in the pollutant concentration changes were revealed. Positive trends for ozone (of 2.9% per year during 1983–2000) and a distinct negative trend for both sulphur dioxide (of 3.8% per year during 1981–2000) and nitrogen dioxide (of 3.8% per year during 1983–2000) were found. The air mass back-trajectory analysis was used to assess the source region of air pollutants transported to Lithuania. The pollutant concentration levels were compared with their emission changes in Europe and Lithuania. The general trends in SO₂ as well as in NO₂ concentrations observed are consistent with changes in SO₂ and NO₂ emissions in Europe and Lithuania.     

Modeling the impacts of traffic emissions on air toxics concentrations near roadways

The dispersion formulation incorporated in the U.S. Environmental Protection Agency's AERMOD regulatory dispersion model is used to estimate the contribution of traffic-generated emissions of select VOCs – benzene, 1,3-butadiene, toluene – to ambient air concentrations at downwind receptors ranging from 10-m to 100-m from the edge of a major highway in Raleigh, North Carolina. The contributions are computed using the following steps: 1) Evaluate dispersion model estimates with 10-min averaged NO data measured at 7 m and 17 m from the edge of the road during a field study conducted in August, 2006; this step determines the uncertainty in model estimates. 2) Use dispersion model estimates and their uncertainties, determined in step 1, to construct pseudo-observations. 3) Fit pseudo-observations to actual observations of VOC concentrations measured during five periods of the field study. This provides estimates of the contributions of traffic emissions to the VOC concentrations at the receptors located from 10 m to 100 m from the road. In addition, it provides estimates of emission factors and background concentrations of the VOCs, which are supported by independent estimates from motor vehicle emissions models and regional air quality measurements. The results presented in the paper demonstrate the suitability of the formulation in AERMOD for estimating concentrations associated with mobile source emissions near roadways. This paper also presents an evaluation of the key emissions and dispersion modeling inputs necessary for conducting assessments of local-scale impacts from traffic emissions.     

Correlations among atmospheric elements,airborne particulate matter,benzene extracts,benzo(a)pyrene,NO, NO2 and so2 concentrations in Japan

Concentration levels of elements, airborne particulate matter, benzene extracts, benzo(a)pyrene B(a)P, NO, NO₂ and SO₂ in five residential areas were seasonally determined from May 1979 to January 1980. These air pollutants exhibited higher concentration in autumn and winter than in spring and summer. These were correlations among Pb, Cu, Ni, V and Se, among Si, Fe, Al and Ti and among NO, NO₂, B(a)P, benzene extracts and airborne particulate matter. NO, NO₂, B(a)P, benzene extracts and airborne particulate matter were correlated with Pb, Cu, Ni, V and Se, but not appreciably with Si, Fe, Al and Ti. On the basis of correlations between various air pollutants, the emitting source of the air pollutants and the health hazard by combined air pollution were discussed.     

Phenol and nitrophenols in the air and dew waters of Santiago de Chile

Phenol, nitrophenols and dinitrophenols were measured in air and dews in downtown Santiago de Chile. In both systems, phenol, 2-nitrophenol (2-NP), and 4-nitrophenol (4-NP) were the compounds found in higher concentrations and with major frequency. Temporal profiles in air were compatible with a significant direct incorporation from mobile sources. The data can be explained in terms of a faster removal of 2-NP than 4-NP, with the former predominating in fresh air masses and 4-NP in more aged samples. All these compounds, as well as dinitrophenols, were found in dew waters. Simultaneous measurements in air and dew indicate that phenol present in dew exceeds that expected in equilibrated samples, while the opposite occurs with 4-NP. This last result is associated to mass transfer limitations for the highly water soluble nitroderivative.