The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

The possible influence of volcanic emissions on atmospheric aerosols in the city of Colima, Mexico

An elemental composition study of atmospheric aerosols from the City of Colima, in the Western Coast of Mexico, is presented. Samples of PM(15)-PM(2.5) and PM(2.5) were collected with Stacked Filter Units (SFU) of the Davis design, in urban and rural sites, the latter located between the City of Colima and the Volcán de Colima, an active volcano. Elemental analyses were carried out using Particle Induced X-ray Emission (PIXE). The gravimetric mass concentrations for the fine fraction were slightly higher in the urban site, while the mean concentrations in the coarse fraction were equal within the uncertainties. High Cl contents were determined in the coarse fraction, a fact also observed in emissions from the Volcán de Colima by other authors. In addition to average elemental concentrations, cluster analysis based on elemental contents was performed, with wind speed and direction data, showing that there is an industrial contributor to aerosols North of the urban area. Moreover, a contribution from the volcanic emissions was identified from the grouping of S, Cl, Cu, and Zn, elements associated to particles emitted by the Volcán de Colima.     

A mechanism describing the photochemical oxidation of toluene in smog

The photo-oxidation of toluene/NO_x exhibits several features that distinguish it from olefin and paraffin smog systems: highly photolytic products, a relatively low production rate of peroxy radicals, and strong sinks for NO_x. The underlying chemical behavior of the toluene smog system is discussed and a kinetic simulation mechanism is presented. The mechanism simulates toluene smog chamber experiments conducted at two facilities: the University of California at Riverside evacuable chamber, and the outdoor smog chamber at the University of North Carolina.     

Effects of photochemical smog and mineral nutrition on ponderosa pine seedlings

Two-year-old seedlings of ponderosa pine (Pinus ponderosa Dougl. ex Laws) were exposed to ambient concentrations of photochemical smog (AA) and clean air (CA) during a single field season at Tanbark Flat of the San Gabriel Mountains in the Los Angeles Basin. The seedlings were grown in a perlite-vermiculite medium with full supply of nutrients (based on modified Hoagland solution); reduced to 50% supply of N; reduced to 50% supply of Mg; and reduced to 50% supply of N+Mg. No significant effects of air pollution exposures on injury development, stem growth and concentrations of plant pigments were determined. The seedlings in the AA treatment had decreased N concentration in current year needles compared with CA seedlings; however, the needle concentrations of other elements did not change. Reduction of N supply in the growing medium caused decreased N, P, Ca, K and chlorophyll a concentrations in needles. Stem growth of the seedlings with reduced N supply was significantly decreased as well. No changes in stem growth or chemical composition of plants with reduced Mg supply were noted. Reduction of supply of nutrients did not change responses of trees to the air pollution exposures.     

Comparative analysis of chemical reaction mechanisms for photochemical smog

Six chemical reaction mechanisms for photochemical smog are analyzed to determine why, under identical conditions, they predict different maximum ozone concentrations. Answers to previously inaccessible questions such as the relative contributions of individual organic species to photochemical ozone formation are obtained. Based on the results of the analysis we have identified specific aspects of each mechanism that are responsible for the discrepancies with other mechanisms and with an explicit mechanism based on the latest understanding of atmospheric chemistry. For each mechanism critical areas are identified that when altered bring the predictions of the various mechanisms into much closer agreement. Thus, we identify why the predictions of the mechanisms are different, and have recommended research efforts that are needed to eliminate many of the discrepancies.     

Modeling inorganic aerosols and their response to changes in precursor concentration in Mexico City

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

Source apportionment of secondary organic aerosol during a severe photochemical smog episode

The UCD/CIT air quality model was modified to predict source contributions to secondary organic aerosol (SOA) by expanding the Caltech Atmospheric Chemistry Mechanism to separately track source apportionment information through the chemical reaction system as precursor species react to form condensable products. The model was used to predict source contributions to SOA in Los Angeles from catalyst-equipped gasoline vehicles, non-catalyst equipped gasoline vehicles, diesel vehicles, combustion of high sulfur fuel, other anthropogenic sources, biogenic sources, and initial/boundary conditions during the severe photochemical smog episode that occurred on 9 September 1993. Gasoline engines (catalyst+non-catalyst equipped) were found to be the single-largest anthropogenic source of SOA averaged over the entire model domain. The region-wide 24-h average concentration of SOA produced by gasoline engines was predicted to be 0.34 μg m⁻³ with a maximum 24-h average concentration of 1.81 μg m⁻³ downwind of central Los Angeles. The region-wide 24-h average concentration of SOA produced by diesel engines was predicted to be 0.02 μg m⁻³, with a maximum 24-h average concentration of 0.12 μg m⁻³ downwind of central Los Angeles. Biogenic sources are predicted to produce a region-wide 24-h average SOA value of 0.16 μg m⁻³, with a maximum 24-h average concentration of 1.37 μg m⁻³ in the less-heavily populated regions at the northern and southern edges of the air basin (close to the biogenic emissions sources). SOA concentrations associated with anthropogenic sources were weakly diurnal, with slightly lower concentrations during the day as mixing depth increased. SOA concentrations associated with biogenic sources were strongly diurnal, with higher concentrations of aqueous biogenic SOA at night when relative humidity (RH) peaked and little biogenic SOA formation during the day when RH decreased.     

Numerical simulation of photochemical smog formation in Athens, Greece—A case study

High emission levels and the unfavourable topography are the main reasons for the alarming photochemical air pollution levels in Athens. An analysis of available air quality data proves that air pollution levels in Athens are largely affected by local wind circulation systems. The most frequent of these systems is dominated by the phenomenon of the sea breeze. Severe air pollution episodes occur, however, primarily under synoptic situations leading to stagnant conditions in the atmosphere over Athens. Photosmog formation in the Athens Basin is studied with the photochemical dispersion model MARS. The implicit solution algorithm incorporated in MARS is characterized by a variable time increment and a variable order. This solver allows avoiding unnecessary operator splitting by a coupled treatment of vertical diffusion and chemical kinetics. In this paper, MARS is used to analyse the situation on 25 May 1990, a day for which very high air pollution levels were reported in Athens. The simulation results elucidate the characteristics of a photosmog episode under stagnant conditions in Athens. In general, the model results reproduce satisfactorily the observed air pollution patterns.     

Tethered balloon-based soundings of ozone,aerosols, and solar radiation near Mexico City during MIRAGE-MEX

A tethered balloon sampling system was used to measure vertical profiles of ozone, particles, and solar radiation in the atmospheric boundary layer on the northern edge of Mexico City, in March 2006 as part of the Megacity Impact on Regional and Global Environment-Mexico experiment. Several commercial sensors, designed for surface applications, were deployed on a tethered balloon platform.Profiles indicate that for these 3 scalars the boundary layer (surface up to 700 m) was well mixed in the period 10:00–16:00 LST. Good agreement was observed for median surface and balloon ozone and particle number concentrations. For most profiles, the surface deposition of ozone was not significant compared to median profile concentrations. Particle number concentration (0.3, 0.5, 1.0 and 5.0 μm) also showed little variation with attitude. Radiatprofiles showed a monotonic increase in diffuse radiation from the maximum altitude of profiles to the surface. Consequently, it was inferred that surface measurements of these likely were representative of lower boundary layer values during this time period.     

Absolute principal component analysis of atmospheric aerosols in Mexico city

A receptor model is presented based on absolute principal component analysis (APCA) of elemental concentrations in atmospheric aerosols from Mexico City during the Summer of 1995. Elemental contents on samples collected with a Stacking Filter Unit of the Davis design was carried out using Particle Induced X-ray Emission (PIXE). The sampling device allowed the separation of particles with mean aerodynamic diameters ranging from 2.5 μm to 15 μm (coarse fraction) and smaller than 2.5 μm (fine fraction). Sampling was divided into morning, afternoon and night periods, with higher concentrations being found during the morning. Seasonal variation is observed when comparisons with other studies are carried out. The application of APCA allowed identification of four sources for each fraction, with a soil-derived dust predominance in the coarse one. The influence of meteorological parameters is studied using cluster analysis, showing that during the morning there is a transport of pollutants from the west towards the sampling site, while the night transport corresponds to soil-derived dust from the north.     

Verification of a source-oriented externally mixed air quality model during a severe photochemical smog episode

The CIT/UCD three-dimensional source-oriented externally mixed air quality model is tested during a severe photochemical smog episode (Los Angeles, 7–9 September 1993) using two different chemical mechanisms that describe the formation of ozone and secondary reaction products. The first chemical mechanism is the secondary organic aerosol mechanism (SOAM) that is based on SAPRC90 with extensions to describe the formation of condensable organic products. The second chemical mechanism is the caltech atmospheric chemistry mechanism (CACM) that is based on SAPRC99 with more detailed treatment of organic oxidation products.The predicted ozone concentrations from the CIT/UCD/SOAM and the CIT/UCD/CACM models agree well with the observations made at most monitoring sites with a mean normalized error of approximately 0.4–0.5. Good agreement is generally found between the predicted and measured NO_x concentrations except during morning rush hours of 6–10 am when NO_x concentrations are under-predicted at most locations. Total VOC concentrations predicted by the two chemical mechanisms agree reasonably well with the observations at three of the four sites where measurements were made. Gas-phase concentrations of phenolic compounds and benzaldehyde predicted by the UCD/CIT/CACM model are higher than the measured concentrations whereas the predicted concentrations of other aromatic compounds approximately agree with the measured values.The fine airborne particulate matter mass concentrations (PM_2.5) predicted by the UCD/CIT/SOAM and UCD/CIT/CACM models are slightly greater than the observed values during evening hours and lower than observed values during morning rush hours. The evening over-predictions are driven by an excess of nitrate, ammonium ion and sulfate. The UCD/CIT/CACM model predicts higher nighttime concentrations of gaseous precursors leading to the formation of particulate nitrate than the UCD/CIT/SOAM model. Elemental carbon and total organic mass are under-predicted by both models during morning rush hour periods. When this latter finding is combined with the NO_x under-predictions that occur at the same time, it suggests a systematic bias in the diesel engine emissions inventory. The mass of particulate total organic carbon is under-predicted by both the UCD/CIT/SOAM and UCD/CIT/CACM models during afternoon hours. Elemental carbon concentrations generally agree with the observations at this time. Both the UCD/CIT/SOAM and UCD/CIT/CACM models predict low concentrations of secondary organic aerosol (SOA) (<3.5 μg m⁻³) indicating that both models could be missing SOA formation pathways. The representation of the aerosol as an internal mixture vs. a source-oriented external mixture did not significantly affect the predicted concentrations during the current study.     

The impact of day-old dilute smog on fresh smog systems: An outdoor chamber study

The effect of dilute day-old smog on fresh smog systems was studied in the UNC dual outdoor chamber. Smog systems which contained fresh smog precursors plus dilute residuals from the day before (0.04 ppm O₃, 0.1–0.3 ppm NMHC and 0.1 ppmC aldehydes) produced almost twice the ozone as fresh systems which had the same initial NMHC and NO_x injections. It is hypothesized that as much as 15–25% of this O₃ increase is due to residual first day aldehydes and that the remaining increase results from an increased morning percentage of NO₂ and the extra residual paraffinic hydrocarbons. The combined interactive effect of changes in initial aldehydes to NO₂ and aged paraffins appears to be greater than if each of these are considered separately.     

Intercontinental transport of aerosols and photochemical oxidants from Asia and its consequences

The intercontinental transport of aerosols and photochemical oxidants from Asia is a crucial issue for air quality concerns in countries downwind of the significant emissions and concentrations of pollutants occurring in this important region of the world. Since the lifetimes of some important pollutants are long enough to be transported over long distance in the troposphere, regional control strategies for air pollution in downwind countries might be ineffective without considering the effects of long-range transport of pollutants from Asia. Field campaigns provide strong evidence for the intercontinental transport of Asian pollutants. They, together with ground-based observations and model simulations, show that the air quality over parts of North America is being affected by the pollutants transported from Asia. This paper examines the current understanding of the intercontinental transport of gases and aerosols from Asia and resulting effects on air quality, and on the regional and global climate system.     

Heterogeneous photocatalytic effect of zinc oxide on photochemical smog formation reaction of C4H8-NO2-air

As a model of heterogeneous photochemical smog formation reaction, butene-NO₂-air systems in the presence of zinc oxide were experimentally studied using a flowing reaction system. Zinc oxide revealed a remarkable photocatalytic action which involved the production of hitherto unreported species such as cyano-compounds (HCN and CH₃CN) as well as a striking change in the distribution of the reaction products (aldehydes, ketones, epoxides, alkyl nitrates, HNO₃, CO, CO₂, etc.). It is confirmed that ZnO little affected the initial process of gas-phase photochemical reactions but interacted photocatalytically with the gas-phase reaction products.     

Public perception of smog: A case study in Ningbo City,China

Smog has become a public environmental crisis in most areas of China, and in response, research efforts have mainly focused on the chemical properties of smog and its impact on human health. However, in-depth research on the public’s perception of smog has not yet been conducted. A survey of residents living around eight state-controlled atmospheric environmental monitoring sites in Ningbo City was conducted using stratified sampling. The data was statistically analyzed to investigate people’s views and behavioral tendencies in smog weather, the influence of different media reports on public outlook, and public opinions on the local atmosphere and pollution management in different areas. The results showed that people’s perception of smog differs greatly from actual conditions, indicating that the public opinion tends to deviate when faced with a public crisis. Mainstream media (TV, newspaper, etc.), accounting for 67% of all media sources, are the main source for dissemination of smog information. The main sources of pollution, in order of decreasing contribution, according to residents of Ningbo City are as follows: motor vehicle exhaust, industrial coal combustion, large-scale construction, biomass burning, and kitchen fumes.

Implications: Since 2011, most areas of China have been affected by frequent smog. Most research on smog has been concentrated on its causes, alert systems, and prevention measures, whereas in-depth research on the public perception of smog has not yet been conducted. When a risky environmental event such as smog occurs, consequences may be more serious than the event itself will cause if people take irrational measures because of lacking relevant knowledge. Therefore, investigating people’s attitude and response to smog is both theoretically and practically significant.     

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.