Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

Comparative evaluation of nitrogen oxides and ozone passive diffusion tubes for exposure studies

Passive diffusion tubes are recognised as a cost-effective sampling method for characterising the spatial variability, as well as the seasonal and annual trends, of NO₂ concentrations in urban areas. In addition, NO_X and O₃ passive diffusion tubes have been developed and deployed in urban and rural areas. Despite their many advantages (e.g. low operational and analysis cost, small size and no need for power supply), they have certain limitations mainly related to their accuracy and precision. In particular, the absorbent solution used, the length of the exposure period, the exact location and use of protective devices, and other environmental conditions (e.g. wind, ambient temperature and relative humidity) may have a significant impact on the performance of passive diffusion tubes. The aim of this study is to evaluate the performance of co-located NO₂, NO_X and O₃ diffusion tubes in an urban environment.A one-year passive sampling campaign was carried out in Birmingham (UK) for this purpose. NO₂, NO_X and O₃ diffusion tubes (including triplicate sets of each) were co-located at one urban background and two roadside permanent air quality monitoring stations equipped with standard gas analysers. In addition, meteorological data, such as wind speed and direction, ambient temperature and relative humidity, were obtained during the same period of time. A thorough QA/QC procedure, including storage and laboratory blanks was followed throughout the campaign. The analysis of results showed a very good agreement of NO₂ passive samplers with co-located chemiluminescence analysers, but substantial underestimations of total NO_X levels by the diffusion tubes. The O₃ diffusion sampler appeared to marginally overestimate the automatic UV analyser results, especially during warm weather periods.     

Kinetics of IO radicals with C1, C2 aliphatic alcohols in tropospherically relevant conditions

Environmental Science and Pollution Research - Kinetics of the reaction of IO radicals with methanol (MeOH) and ethanol (EtOH) were experimentally studied in the gas phase using pulsed laser...     

Measurements and analyses of nitrogen oxides and ozone in the yard and on the roof of a street-canyon in Suzhou

The concentrations of air pollutants such as nitrogen oxides and ozone characterised by very fast chemical reactions can significantly vary within urban street-canyon due to the short distances between sources and receptor. With the primary objective to analyse this issue, NO, NO₂, NO_x, O₃, BTX, and wind flow field were continuously measured for 1 week at two heights (a street-level yard and a 25-m-high rooftop) in an urban canyon in Suzhou (China). The yard ozone concentrations were found to be up to six times lower than on the roof. Different frequency distributions (FD), dynamical and chemical processes of the pollutant variations from yard to roof are discussed to explain the findings. The predominant factors for the dissimilar pollutant vertical diffusion at the two measurement locations were associated to dissimilar fluid-dynamic and heterogeneous removal effects that likely induced dissimilar ozone chemical processes relative to NO_x and BTX precursors.     

Long term changes in nitrogen oxides and volatile organic compounds in Toronto and the challenges facing local ozone control

Ground level ozone represents a significant air quality concern in Toronto, Canada, where the national 65 ppb 8-h standard is repeatedly exceeded during the summer. Here we present an analysis of nitrogen dioxide (NO₂), ozone (O₃), and volatile organic compound (VOC) data from federal and provincial governmental monitoring sites from 2000 to 2007. We show that summertime VOC reactivity and ambient concentrations of NO₂ have decreased over this period of time by up to 40% across Toronto and the surrounding region. This has not resulted in significant summertime ozone reductions, and in some urban areas, it appears to be increasing. We discuss the competing effects of decreased ozone titration leading to an increase in O₃, and decreased local ozone production, both caused by significant decreases in NO_x concentrations. In addition, by using local meteorological data, we show that annual variability in summer ozone correlates strongly with maximum daily temperatures, and we explore the effect of atmospheric transport from the southwest which has a significant influence on early morning levels before local production begins. A mathematical model of instantaneous ozone production is presented which suggests that, given the observed decreases in NO_x and VOC reactivity, we would not expect a significant change in local ozone production under photochemically relevant conditions. These results are discussed in the context of Toronto's recent commitment to cutting local smog-causing pollutants by 20% by 2012.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.     

Aldehyde and monocyclic aromatic hydrocarbon mixing ratios at an urban site in Las Vegas, Nevada

Oxidation of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air, of significance due to, for example, the potential for O3 formation, is believed to be initiated by OH attack on the ring (addition) or on the alkyl side chain (H abstraction). A series of ring-breaking reactions follows, with major products predicted to be alpha-dicarbonyls, simple aldehydes, and organic acids. To test this prediction, ambient air mixing ratios of aldehydes (formaldehyde, acetaldehyde, benzaldehyde, glyoxal, and pyruvaldehyde), along with some supporting BTEX data, were measured at an urban site in Las Vegas, NV. Samples were collected on sorbents and determined by chromatographic methods; mixing ratios were compared to ambient levels of CO, O3, and NOx. A meteorological analysis (temperature, wind speed, and wind direction) was also included. Statistically significant relationships were noted among the BTEX hydrocarbons (HCs) and among the photochemically derived species (e.g., O3, NO2, and some of the aldehydes), although there was seasonal variation. The observations are consistent with a common primary source (i.e., vehicular exhaust or fuel evaporation) for the BTEX compounds and a common secondary source (e.g., OH attack) for glyoxal and pyruvaldehyde.     

Economic impacts of regional ozone standards on agricultural crops

Implementing ozone (O3) standards on regional air sheds on the basis of crop losses requires more precise analysis than statewide or even national assessments. An economic model that measures crop losses by air basins in California is described. The ability of the model to respond to subtle regional changes in O3 standards is tested. Substantial differences in economic benefits between different standards and regions result from the model simulations. Regional standards are shown to capture a large proportion of the benefits at a lower cost.     

Nitrogen oxides and ozone in Portugal: trends and ozone estimation in an urban and a rural site

Environmental Science and Pollution Research - This study provides an analysis of the spatial distribution and trends of NO, NO2 and O3 concentrations in Portugal between 1995 and 2010....     

固定源氮氧化物排放及控制技术应用

固定源是氮氧化物排放的一个主要来源。通过对主要固定源氮氧化物生成机理及现有的排放控制技术进行论述，分析我国固定源氮氧化物排放的实际情况，提出我国固定源氮氧化物排放控制还处于起步阶段，氮氧化物排放标准相对宽松，氮氧化物排放控制技术有待进一步普及，并提出固定源氮氧化物排放治理的一些建议。     

The influence of sampling protocol on nonmethane hydrocarbon mixing ratios

The effect of sampling protocol on ambient air hydrocarbon mixing ratios was examined on eight sampling days in Los Angeles during 2007 and 2008. Four protocols, which were based on previously published multi-city urban hydrocarbon studies in the United States, were compared and differences were quantified. Whole air canister samples were collected and analyzed for nonmethane hydrocarbons (NMHCs). Differing sampling protocols resulted in large differences in mixing ratios, up to an order of magnitude, for certain NMHCs on the same sampling day. However, the magnitude of the variability between NMHC levels obtained by the four protocols was not consistent throughout the eight sampling days. It was found that sampling time, followed by sampling location, had the greatest influence on the magnitude of the mixing ratio. Ratios between hydrocarbons, often used in urban studies to gain information on emission sources, also varied depending on the protocol used. Comparison of absolute NMHC mixing ratios collected in urban environments using differing sampling protocols should be made with care.     

Conversion of nitrogen oxides on commercial photocatalytic dispersion paints

In the present study, photocatalytic reactions of nitrogen oxides (NO_x = NO + NO₂) were studied on commercial TiO₂ doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO₂ was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO₂ surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO₃/NO₃^?) was observed with near to unity yield. In addition, traces of H₂O₂ were observed in the gas phase only in the presence of O₂. Formation of the greenhouse gas nitrous oxide (N₂O) could be excluded. The uptake kinetics of NO, NO₂ and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO₂) > 10^?5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO₃/NO₃^? is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.     

Technology innovations and experience curves for nitrogen oxides control technologies

This paper reviews the regulatory history for nitrogen oxides (NOx) pollutant emissions from stationary sources, primarily in coal-fired power plants. Nitrogen dioxide (NO2) is one of the six criteria pollutants regulated by the 1970 Clean Air Act where National Ambient Air Quality Standards were established to protect public health and welfare. We use patent data to show that in the cases of Japan, Germany, and the United States, innovations in NOx control technologies did not occur until stringent government regulations were in place, thus "forcing" innovation. We also demonstrate that reductions in the capital and operation and maintenance (O&M) costs of new generations of high-efficiency NOx control technologies, selective catalytic reduction (SCR), are consistently associated with the increasing adoption of the control technology: the so-called learning-by-doing phenomena. The results show that as cumulative world coal-fired SCR capacity doubles, capital costs decline to approximately 86% and O&M costs to 58% of their original values. The observed changes in SCR technology reflect the impact of technological advance as well as other factors, such as market competition and economies of scale.     

Diversity and sensitivity of epiphytes to oxides of nitrogen in London

This study investigated the distribution and diversity of epiphytes in London in relation to NO(x) using fine-scale atmospheric dispersion modelling. The survey recorded over 3000 epiphytes from 334 trees (Fraxinus excelsior) representing 74 lichen, 14 moss, 7 fungal and 3 algal species. There was a significant inverse relationship between diversity and NO(x). Diversity declined where NO(x) exceeded 70 microg m(-3) and NO2 exceeded 40 microg m(-3), suggesting a phytotoxic effect. However, there was a significant positive relationship between NO(x) and lichen abundance due to the ubiquitous distribution of pollution tolerant species, mainly associated with eutrophication. A scale of lichen sensitivity to NO(x) has been derived.     

Modeling analyses of the effects of changes in nitrogen oxides emissions from the electric power sector on ozone levels in the eastern United States

In this paper, we examine the changes in ambient ozone concentrations simulated by the Community Multiscale Air Quality (CMAQ) model for summer 2002 under three different nitrogen oxides (NOx) emission scenarios. Two emission scenarios represent best estimates of 2002 and 2004 emissions; they allow assessment of the impact of the NOx emissions reductions imposed on the utility sector by the NOx State Implementation Plan (SIP) Call. The third scenario represents a hypothetical rendering of what NOx emissions would have been in 2002 if no emission controls had been imposed on the utility sector. Examination of the modeled median and 95th percentile daily maximum 8-hr average ozone concentrations reveals that median ozone levels estimated for the 2004 emission scenario were less than those modeled for 2002 in the region most affected by the NOx SIP Call. Comparison of the "no-control" with the "2002" scenario revealed that ozone concentrations would have been much higher in much of the eastern United States if the utility sector had not implemented NOx emission controls; exceptions occurred in the immediate vicinity of major point sources where increased NO titration tends to lower ozone levels.     

Future research directions and data requirements for developing ambient ozone guidelines or standards for agroecosystems

The ambient air quality in Central Europe appears to have the potential to adversely affect the productivity of the agroecosystems in that geographic area. Therefore, there is a need to develop, validate, and apply air pollutant exposure-plant response models to explain the relationships between the stochastic chemical climate and ecosystem responses. Such models will have to include numerical terms for the effective air pollutant exposure regime to account for the fluxes of matter, energy and information within the ecosystem and its components. The structure and function of the ecosystem which are influenced by the air pollutant flux can be described by a combination of empirical and mechanistic models. A discussion of such an approach is presented in this paper.     

Atmospheric dynamics and ozone cycles related to nitrogen deposition in the western Mediterranean

Recent results from EU-sponsored projects have shed new light on the workings of the atmosphere in the Mediterranean Basin, where a large airmass becomes trapped and nearly stagnant over the sea during the summer. This work reviews the developments which have led to our present understanding of air pollution dynamics and associated meteorological processes in this region. In summer, the sea breezes combine with upslope winds to create recirculations along the coasts and within the western Mediterranean basin, with residence times in the order of days. Under strong insolation these recirculations become "large natural photo-chemical reactors" where most of the NOx emissions and other precursors are transformed into oxidants, acidic compounds, aerosols and ozone, which can exceed European Union directives for several months of the year. The objective of this paper is to evaluate available experimental evidence and complementary modelling results to help in the interpretation of observed ozone cycles and to anticipate possible scenarios for anthropogenic nitrogen deposition in the region.