The effects of ozone/limonene reactions on indoor secondary organic aerosols

An indoor air quality model was used to predict dynamic particle mass concentrations based on homogeneous chemical mechanisms and partitioning of semi-volatile products to particles. The ozone–limonene reaction mechanism was combined with gas-phase chemistry of common atmospheric organic and inorganic compounds and incorporated into the indoor air quality model. Experiments were conducted in an environmental chamber to investigate secondary particle formation resulting from ozone/limonene reactions. Experimental results indicate that significant fine particle growth occurs due to the interaction of ozone and limonene and subsequent intermediate by-products. Secondary particle mass concentrations were estimated from the measured particle size distribution. Predicted particle mass concentrations were in good agreement with experimental results—generally within ∼25% at steady-state conditions. Both experimental and predicted results suggest that air exchange rate plays a significant role in determining secondary fine particle levels in indoor environments. Secondary particle mass concentrations are predicted to increase substantially with lower air exchange rates, an interesting result given a continuing trend toward more energy efficient buildings. Lower air exchange rates also shifted the particle size distribution toward larger particle diameters. Secondary particle mass concentrations are also predicted to increase with higher outdoor ozone concentrations, higher outdoor particle concentrations, higher indoor limonene emission rates, and lower indoor temperatures.     

Modelling the formation and atmospheric transport of secondary inorganic aerosols with special attention to regions with high ammonia emissions

Regional simulations of sulfate, nitrate and ammonium aerosols were performed by a nested application of the online-coupled three-dimensional Eulerian model system COSMO-MUSCAT. This was done in a domain covering the northern part of Germany and surrounding regions for the full month of May and a 6-week period in August/September 2006 with the primary focus on secondary inorganic aerosol levels caused by ammonia emissions from domesticated animals and agricultural operations.The results show that in situations with westerly winds ammonium nitrate dominates with concentrations of about 5–10 μg m^?3 whereas the ammonium sulfate concentrations are about 5 μg m^?3. In situations with winds mainly from the East characterized by warmer and dryer air the ammonium sulfate concentrations have their maximum at about 10 μg m^?3 whereas at the same time no ammonium nitrate is present.A reduction of agricultural NH₃ emissions by 50% in a regional scale reduces the ammonium nitrate concentrations to a maximum of 30%, while the ammonium sulfate concentrations are unchanged. The reduction of NH₃ emissions in a more limited area (here in the Federal state of Germany Niedersachsen) does have no noticeable effect neither on ammonium sulfate nor on ammonium nitrate.     

Atmospheric ozone: formation and effects on vegetation

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.     

Influence of Saharan dust outbreaks and atmospheric stability upon vertical profiles of size-segregated aerosols and water vapor

Vertical profiles of aerosols and meteorological parameters were obtained using a hot air balloon and motorized paraglider. They were studied under anticyclonic conditions in four different contexts. Three flights occurred near sunrise, and one took place in the central hours of the day. The effects of North African dust intrusions were analyzed, whose entrance to the study area took place above the Stable Boundary Layer (SBL) in flight 1 and below it in flight 2. These flights have been compared with a non-intrusion situation (flight 3). A fourth flight characterized the profiles in the central hours of the day with a well-formed Convective Boundary Layer (CBL). With respect to the particle number distribution, the results show that not all sizes increase within the presence of an intrusion; during the first flight the smallest particles were not affected. The particle sizes affected in the second flight fell within the 0.35–2.5 μm interval. Under situations of convective dynamics, the reduction percentage of the particle number concentration reduces with increasing altitude, independently of their size, with respect to stability conditions. The negative vertical gradient for aerosols and water vapor, characteristic of a highly stable SBL (flight 3) becomes a constant profile within a CBL (flight 4). There are two situations that seem to alter the negative vertical gradient of the water vapor mixing ratio within the SBL: the presence of an intrusion and the possible stratification of the SBL based on different degrees of stability.     

Study of atmospheric ozone formation by means of a neural network-based model

The occurrence of high ozone levels in the atmosphere of urban areas has become a serious pollution problem in a number of large cities in the world. Although mathematical models have been proposed for predicting ozone concentrations as a function of a number of gas components, sometimes there are uncertainties due to lack of the combined effects of meteorological factors and the complex chemical reaction system involved. The application of neural network models, based on measured values of air pollutants and meteorological factors at different locations within the S?o Paulo Metropolitan Area, combine chemical and meteorological information. This has shown to be a promising tool for predicting ozone concentration. Simulations carried out with the model indicate the sensitivity of ozone in relation to different air pollution and weather conditions. Predictions using this model have shown good agreement with measured values of ozone concentrations.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Sensitivity of biogenic secondary organic aerosols to future climate change at regional scales: An online coupled simulation

Biogenic emissions and secondary organic aerosols (SOA) are strongly dependent on climatic conditions. To understand the SOA levels and their sensitivity to future climate change in the United States (U.S.), we present a modeling work with the consideration of SOA formation from the oxidation of biogenic emissions with atmospheric oxidants (e.g., OH, O₃, and NO₃). The model simulation for the present-day climate is evaluated against satellite and ground-based aerosol measurements. Although the model underestimates aerosol concentrations over the northwestern U.S. due to the lack of fire emissions in the model simulations, overall, the SOA results agree well with previous studies. Comparing with the available measurements of organic carbon (OC) concentrations, we found that the amount of SOA in OC is significant, with the ratio ranging from 0.1 to 0.5/0.6. The enhanced modeling system driven by global climate model output was also applied for two three-year one-month simulations (July, 2001–2003 and 2051–2053) to examine the sensitivity of SOA to future climate change. Under the future two emissions scenarios (A1B and A2), future temperature changes are predicted to increase everywhere in the U.S., but with different degrees of increase in different regions. As a result of climate change in the future, biogenic emissions are predicted to increase everywhere, with the largest increase (～20%) found in the southeastern and northwestern U.S. under the A1B scenario. Changes in SOA are not identical with those in biogenic emissions. Under the A1B scenario, the biggest increase in SOA is found over Texas, with isoprene emissions being the major contributor to SOA formation. The range of change varies from 5% over the southeast region to 26% over Texas. The changes in either biogenic emissions or SOA under the two climate scenarios are different due to the differences in climatic conditions. Our results also suggest that future SOA concentrations are also influenced by several other factors such as the partitioning coefficients, the atmospheric oxidative capability, primary organic carbon aerosols and anthropogenic emissions.     

Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels

The impact of biogenic volatile organic compound (BVOC) emissions on European ozone distributions has not yet been evaluated in a comprehensive way. Using the CHIMERE chemistry-transport model the variability of surface ozone levels from April to September for 4 years (1997, 2000, 2001, 2003) resulting from biogenic emissions is investigated. It is shown that BVOC emissions increased on average summer daily ozone maxima over Europe by 2.5 ppbv (5%). The impact is most significant in Portugal (up to 15 ppbv) and in the Mediterranean region (about 5 ppbv), being smaller in the northern part of Europe (1.3 ppbv north of 47.5°N). The average impact is rather similar for the three summers (1997, 2000, 2001), but is much larger during the extraordinarily hot summer of 2003. Here, the biogenic contribution to surface ozone doubles compared to other years at some locations. Interaction with anthropogenic NO_x emissions is found to be a key process for ozone production of biogenic precursors. Comparing the impact of the state-of-the-art BVOC emission inventory compiled within the NatAir project and an earlier, widely used BVOC inventory derived from Simpson et al. [1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research 104(D7), 8113–8152] on surface ozone shows that ozone produced from biogenic precursors is less in central and northern Europe but in certain southern areas much higher e.g. Iberian Peninsula and the Mediterranean Sea. The uncertainty in the regionally averaged impact of BVOC on ozone build-up in Europe is estimated to be ±50%.     

The ozone formation potential of 1-bromo-propane

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

Within season and carry-over effects following exposure of grassland species mixtures to increasing background ozone

Few studies have investigated effects of increased background ozone in the absence of episodic peaks, despite a predicted increase throughout the northern hemisphere over the coming decades. In this study Leontodon hispidus was grown with Anthoxanthum odoratum or Dactylis glomerata and exposed in the UK to one of eight background ozone concentrations for 20 weeks in solardomes. Seasonal mean ozone concentrations ranged from 21.4 to 102.5 ppb. Ozone-induced senescence of L. hispidus was enhanced when grown with the more open canopy of A. odoratum compared to the denser growing D. glomerata. There was increased cover with increasing ozone exposure for both A. odoratum and D. glomerata, which resulted in an increase in the grass:Leontodon cover ratio in both community types. Carry-over effects of the ozone exposure were observed, including delayed winter die-back of L. hispidus and acceleration in the progression from flowers to seed-heads in the year following ozone exposure.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

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.     

The effect of temperature on the gas–particle partitioning of reactive mercury in atmospheric aerosols

Measurements of gas–particle-partitioning coefficients for reactive mercury in dry urban and laboratory aerosol were found to strongly depend on ambient temperature. Samples of atmospheric and laboratory aerosols (defined as both the gas and particle phases) were collected using filter and absorbent methods and analyzed for reactive mercury using thermal desorption combined with cold vapor atomic fluorescence spectroscopy. Synthetic ambient aerosols were generated in the laboratory from ammonium sulfate and adipic acid mixed with mercuric chloride in a purpose-built aerosol reactor. The aerosol reactor was operated in a temperature-controlled laboratory. Linear relationships between the logarithm of inverse gas–particle partitioning and inverse temperature were observed and parameterized for use in the atmospheric modeling of reactive mercury. Reactive mercury was observed to partition from the particle to the gas phase as ambient temperature increased. Good agreement between measurements made using urban and laboratory aerosols was seen after gas–particle-partitioning coefficients were normalized for surface area instead of mass. Thermodynamic analyses of the urban and laboratory gas–particle-partitioning measurements revealed that the strength of interaction between reactive mercury and particle surfaces was suggestive of chemisorption. Gas–particle-partitioning coefficients made with the Tekran ambient mercury analyzer (AMA) also showed a dependence on temperature. However, the Tekran AMA partitioning coefficients did not agree well with partitioning coefficients measured using the filter-based methods. The disagreement is consistent with the 50 °C operational temperature of the Tekran AMA.     

Influence of secondary formation on atmospheric occurrences of oxygenated polycyclic aromatic hydrocarbons in airborne particles

Temporal and spatial variations in concentrations of particle-associated polycyclic aromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives (nitro-PAHs and oxy-PAHs) were investigated to assess the influence of secondary formation on atmospheric occurrences of oxy-PAHs associated with particulate matter in downtown Tokyo, Japan. The daily variation in concentration of 1,8-naphthalic anhydride (1,8-NA) in summer 2007 was similar to that for 2-nitrofluoranthene (2-NF), a representative secondary formed nitro-PAH, while the variation for benzanthrone (BA) was similar to PAHs. In addition, the concentrations of polycyclic aromatic compounds (PACs) associated with airborne particulate matter decreased in the order of PAHs > BA > 9-fluorenone (9-FO) or 9,10-anthraquinone (9,10-AQ) > 1,8-NA with an increase in distance from the roadside, whereas 2-NF was constant. These results suggest that a considerable fraction of some oxy-PAHs such as 1,8-NA associated with airborne particulate matter in downtown Tokyo originates from atmospheric secondary formation.     

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.     

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NOx photooxidation system

High concentrations (>15 μm³ cm^?3) of CaSO₄, Ca(NO₃)₂ and (NH₄)₂SO₄ were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO_x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO₄ and aqueous Ca(NO₃)₂), even at elevated concentrations. The presence of high concentrations of (NH₄)₂SO₄ aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH₄)₂SO₄ on SOA yield is found to be positively correlated with the (NH₄)₂SO₄ surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH₄)₂SO₄ seed aerosols.     

The effects of meteorology on ozone in urban areas and their use in assessing ozone trends

The United States Environmental Protection Agency issues periodic reports that describe air quality trends in the US. For some pollutants, such as ozone, both observed and meteorologically adjusted trends are displayed. This paper describes an improved statistical methodology for meteorologically adjusting ozone trends as well as characterizes the relationships between individual meteorological parameters and ozone. A generalized linear model that accommodates the nonlinear effects of the meteorological variables was fit to data collected for 39 major eastern US urban areas. Overall, the model performs very well, yielding R² statistics as high as 0.80. The analysis confirms that ozone is generally increasing with increasing temperature and decreasing with increasing relative humidity. Examination of the spatial gradients of these responses show that the effect of temperature on ozone is most pronounced in the north while the opposite is true of relative humidity. By including HYSPLIT-derived transport wind direction and distance in the model, it is shown that the largest incremental impact of wind direction on ozone occurs along the periphery of the study domain, which encompasses major NO_x emission sources.     

Evidence of impact of aerosols on surface ozone concentration in Tianjin,China

In this study, we will present evidence that aerosol particles have strong effects on the surface ozone concentration in a highly polluted city in China. The measured aerosol (PM10), UV flux, and O₃ concentrations were analyzed from 1 November (1 Nov) to 7 November (7 Nov) 2005 in Tianjin, China. During this period, the aerosol concentration had a strong day-by-day variation, ranging from 0.2 to 0.6 mg m⁻³. The ozone concentration also shows a strong variability in correlation with the aerosol concentration. During 1 Nov, 2 Nov, 6 Nov, and 7 Nov, the ozone concentration was relatively high (about 30–35 ppbv; defined as a high-ozone period), and during 3 Nov to 5 Nov, the ozone concentration was relatively low (about 5–20 ppbv; defined as a low-ozone period). The analysis of the measurement shows that the ozone concentration is strongly correlated to the measured UV flux. Because there were near cloud-free conditions between 1 Nov and 7 Nov, the variation of the UV flux mainly resulted from the variation of aerosol concentration. The result shows that higher aerosol concentrations produce a lower UV flux and lower ozone concentrations. By contrast, the lower aerosol concentration leads to a higher UV flux and higher ozone concentrations. A chemical mechanism model (NCAR MM) is applied to interpret the measurement. The model result shows that the extremely high aerosol concentration in this polluted city has a very strong impact on photochemical activities and ozone formation. The correlation between aerosol and ozone concentrations appears in a non-linear feature. The O₃ concentration is very sensitive to aerosol loading when aerosol loading is high, and this sensitivity is reduced when aerosol loading is low. For example, the ratio of Δ[O₃]/Δ[AOD] is about −16 ppbv AOD⁻¹ when AOD is less than 2, and is only −4 ppbv AOD⁻¹ when AOD is between 2 and 5. This result implies that a future decrease in aerosol loading could lead to a rapid increase in the O₃ concentration in this region.