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.     

A comparison of model photochemical ozone formation potential with observed regional scale ozone formation during a photochemical episode over the United Kingdom in April 1987

A photochemical trajectory model has been employed to calculate the maximum potential for ozone generation in air parcels passing over the U.K. during a photochemical pollution episode in April 1987. In all, 11 trajectories have been studied and the model results compared against an objective analysis of the integrated ozone generation based on the observations reported from the U.K. Department of the Environment ground level O₃network. There is apparently good correlation between the observed O₃formation and the model O₃formation potential although the latter overestimates the former by a factor of about 2.8. The solar illumination conditions employed in the photochemical trajectory model may have caused this overestimation, since the model is formulated for O₃control strategy assessment and simulates the ‘worst case’ situation likely to give the maximum potential for secondary pollutant formation. In addition to the model results for O₃, a wide range of primary and secondary pollutant concentrations from the model were examined, together with the influence of precursor pollutant emissions.     

Estimations of primary and secondary organic carbon formation in PM2.5 aerosols of Santiago City,Chile

High concentration of fine airborne particulates is considered one of the major environmental pollutants in Santiago, the Chilean Capital city, which in 1997 was declared a PM₁₀ saturated zone. To date there is no control of the amounts of fine and coarse aerosols concentrations and the source and chemical characterizations of the PM_2.5 particulates in the carbonaceous fractions are not well known even though this fraction could be represented almost the 50% in mass of the PM_2.5.In this work, we present for the first time determinations of primary organic aerosol (POA) and secondary organic aerosol composition (SOA) fractions of the total mass of PM_2.5 particulates collected in the urban atmosphere of Santiago City. Our purpose is to know the anthropogenic contributions to the formation of SOA. To accomplish this we used the elemental carbon (EC) and organic carbon (OC) determinations developed by automatic monitoring stations installed in the city during the period 2002–2005, with a particular analysis of the summer time occurred in February 2004. Based on the EC tracer method, we have estimated the POA and SOA fraction and our data permit us to estimate the SOA reaching up to 20% of total organic aerosol matter, in good agreement to other measurements observed in large cities of Europe and U.S.A.     

Nitrite in rain and dew in Santiago city,Chile. Its possible impact on the early morning start of the photochemical smog

Cations (pH, potassium, sodium, calcium, magnesium, and ammonium) and anions (sulfate, nitrate, nitrite, and chloride) concentrations were measured in Santiago city rain and dew waters collected during the 1995 to 1999. Concentrations measured in dews are considerably higher than those measured in rains. The high ionic concentration present in dew waters could contribute to their corrosion potential. Natural dust makes an important contribution to the ions present in dews, but the presence of rather high sulfate concentrations (up to 900 μeq/l) indicate a significant contribution of anthropogenic sources.A peculiar characteristic of dew waters is the relatively high nitrite concentrations (up to 180 μeq/l). This nitrite can be resuspended into the boundary layer after dew water evaporation, possibly due to the relatively high volatily of ammonium nitrite. This upward flux could constitute an important source of hydroxyl radicals in the early morning, contributing so to the initial steps of the observed photochemical smog.     

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.     

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.     

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.     

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.     

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%.     

The impact of motor vehicle control technologies on future photochemical ozone formation in the United Kingdom

Legislation to control motor vehicle exhaust emissions has been introduced in the United Kingdom in stages since the early 1970s. Recently, a further step has been taken towards reducing future exhaust emissions of carbon monoxide, unburnt hydrocarbons and oxides of nitrogen in the 'Luxembourg agreement' (Lubinska, 1985). In this paper, the possible impact of these proposed controls on photochemical air pollution formation in the United Kingdom is investigated, including an evaluation of the relative merits of the two principal emission control options for petrol-driven cars: 'Lean Burn' engines and 'Catalyst' exhaust gas treatment.     

Predominance of soot-mode ultrafine particles in Santiago de Chile: Possible sources

A monitoring campaign was performed in Santiago de Chile during a winter month of 2003 and 2006 (July) using several instruments to measure the size distribution of particulate material. For the first time, the size distribution of ultrafine particles was measured in Santiago, and an estimation of its sources was done by analyzing its temporal variation. The study was performed in three sites; one of them is located in the eastern part of Santiago, a sector with low particle concentration and about 100 m from a busy street. The other site is located in the western part, which is the sector that has the highest concentration of fine and coarse particle matter during winter, also located far from a street. The third site is located within 5 m from the busiest street in Santiago. In all stations traffic is the dominating source for fine and ultrafine particles and the size distribution is peaked towards 60–100 nm (soot mode). Only in the site near the street, it is possible to see a clear peak towards smaller sizes (10–30 nm). The size distribution measurements presented here indicate that aerosol dynamics play a more important role for the Santiago case as compared to cleaner cities in Europe. Changes in the particle size during different hours of the day reflect both variations in meteorological mixing conditions as well as effects of aerosol dynamic processes such as coagulation, condensation and dry deposition. A relative increase in the number of the larger ultrafine particles (d ≥ 70 nm), as compared to the number of smaller particles (d < 70 nm) correlated with wind speed is an indication of pollution transport with aged particles from other parts of the city.     

Trends in the elemental composition of fine particulate matter in Santiago, Chile, from 1998 to 2003

Santiago, Chile, is one of the most polluted cities in South America. As a response, over the past 15 yr, numerous pollution reduction programs have been implemented by the environmental authority, Comisión Nacional del Medio Ambiente. This paper assesses the effectiveness of these interventions by examining the trends of fine particulate matter (PM(2.5)) and its associated elements. Daily fine particle filter samples were collected in Santiago at a downtown location from April 1998 through March 2003. Additionally, meteorological variables were measured continuously. Annual average concentrations of PM(2.5) decreased only marginally, from 41.8 microg/m3 for the 1998-1999 period to 35.4 microg/m3 for the 2002-2003 period. PM(2.5) concentrations exceeded the annual U.S. Environmental Protection Agency standard of 15 microg/m3. Also, approximately 20% of the daily samples exceeded the old standard of 65 microg/m3, whereas approximately half of the samples exceeded the new standard of 35 microg/m3 (effective in 2006). Mean PM(2.5) levels measured during the cold season (April through September) were three times higher than those measured in the warm season (October through March). Particulate mass and elemental concentration trends were investigated using regression models, controlling for year, month, weekday, wind speed, temperature, and relative humidity. The results showed significant decreases for Pb, Br, and S concentrations and minor but still significant decreases for Ni, Al, Si, Ca, and Fe. The larger decreases were associated with specific remediation policies implemented, including the removal of lead from gasoline, the reduction of sulfur levels in diesel fuel, and the introduction of natural gas. These results suggest that the pollution reduction programs, especially the ones related to transport, have been effective in reducing various important components of PM(2.5). However, particle mass and other associated element levels remain high, and it is thus imperative to continue the efforts to improve air quality, particularly focusing on industrial sources.     

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.     

Prediction of NO and NO2 concentrations near a street with heavy traffic in Santiago,Chile

Based on NO concentrations and meteorological variables recorded hourly at a point close to an avenue with heavy traffic in the city of Santiago, we are able to build a simple model that allows prediction of NO concentrations several hours in advance. Predicted NO concentrations in conjunction with forecasted meteorological data may be used to predict NO₂ concentrations with reasonable accuracy. We compare predictions generated using persistence, linear regressions and multi layer neural networks.     

Rainwater formaldehyde: concentration,deposition and photochemical formation

Formaldehyde (HCHO) concentrations were measured in 116 rain samples in Wilmington, NC from June 1996 to February 1998. Concentrations ranged from below the detection limit of 10 nM, to 13 μM, in the range of HCHO levels reported at other locations worldwide. The volume-weighted annual average rainwater formaldehyde concentration was 3.3±0.3 μM and comprised approximately 3% of the measured dissolved organic carbon. Using the volume weighted average HCHO concentration and annual precipitation of 1.4 m, an annual formaldehyde deposition of 4.6 mmol m⁻² yr⁻¹ was determined. Rainwater is a significant source of formaldehyde to surface waters and may contribute as much as 30 times the resident amount found in natural waters of southeastern North Carolina during the summer. Formaldehyde concentrations did not correlate with precipitation volume suggesting continuous supply during rain events. Evidence is presented which indicates part of this supply may be from direct photochemical production in the aqueous phase. Formaldehyde levels exhibited a distinct seasonal oscillation, with higher concentrations during the summer. This pattern is similar to that observed with other rainwater parameters at this site including pH, nitrate, and ammonium, and is most likely the result of increased photochemical production, as well as biogenic and anthropogenic emissions during summer months. The concentration of formaldehyde in both winter El Nino rains and summer tropical rains was less than half its concentration in non-El Nino or non-tropical events, suggesting significant terrestrial input. Formaldehyde was correlated with hydrogen peroxide and non-sea-salt sulfate deposition suggesting a relationship between HCHO, H₂O₂, S(VI) within the troposphere.     

Nocturnal depletion of photochemical ozone at a rural site

Nocturnal depletion of ozone during a period of photochemical pollution has been observed at a rural site by continuous ground-level measurements and the determination of vertical profiles of ozone concentration. An acoustic sounder was used to provide continuous information upon the vertical temperature structure of the atmosphere. The results are interpreted in terms of recent theories of long-range transport of photochemical ozone and the chemical and physical processes causing ozone depletion.     

Simultaneous measurements of formaldehyde and nitrous acid in dews and gas phase in the atmosphere of Santiago,Chile

The amounts of formaldehyde and nitrous acid (HONO) in gas phase and dews of Santiago de Chile were simultaneously measured. Formaldehyde concentrations values in the liquid phase (dews) correlate fairly well with those in the gaseous phase and are even higher than those expected from gas–dew equilibrium. On the other hand, nitrite concentrations in dews were considerably smaller (ca. 15 times) than those expected from the gas-phase concentrations. This under-saturation is attributed to diffusion limitations due to the relatively large HONO solubility. In agreement with this, under-saturation increases with the rate of dew formation and the pH of the collected waters, factors that should increase the rate of gas to liquid HONO transfer required to reach equilibrium.     

Seasonal dependence of the oxidation capacity of the city of Santiago de Chile

The oxidation capacity of the highly polluted urban area of Santiago de Chile has been evaluated during a winter measurement campaign from May 25 to June 07, 2005, with the results compared and contrasted with those previously evaluated during a summer campaign from March 8 to 20, 2005. The OH radical budget was evaluated in both campaigns employing a simple quasi-photostationary state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O₃, NO, NO₂, j(O¹D), j(NO₂), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used for the analysis of the radical budgets and concentrations of OH, HO₂ and RO₂. Besides the above parameters, the MCM model has been constrained by the measured CO and other volatile organic compounds (VOCs) including alkanes and aromatics. Total production and destruction rates of OH and HO₂ in winter are about two times lower than that during summer. Simulated OH levels by both PSS and MCM models are similar during the daytime for both winter and summer indicating that the primary OH sources and sinks included in the simple PSS model are predominant. On a 24 h basis, HONO photolysis was shown to be the most important primary OH radical source comprising 81% and 52% of the OH initiation rate during winter and summer, respectively followed by alkene ozonolysis (12.5% and 29%), photolysis of HCHO (6.1% and 15%), and photolysis of O₃ (<1% and 4%), respectively. During both winter and summer, there was a balance between the OH secondary production (HO₂ + NO) and destruction (OH + VOCs) showing that initiation sources of RO₂ and HO₂ are no net OH initiation sources. This result was found to be fulfilled also for all other studies investigated. Seasonal impacts on the radical budgets are also discussed.