Nonlinear dynamical analysis of ground level ozone concentrations at different temporal scales

The nonlinear dynamical analysis of ground level ozone concentration is carried out by using correlation integral method to examine its scale invariance property. The dynamics of the time series is often studied at one temporal scale. It is assumed that if the time series is determined to be chaotic at one temporal scale, its behavior at another scale can be determined as the scale shifts are allowed due to scale invariance property. The actual dynamics at other scales is however not yet analyzed. The assumption of scale invariance of the time series at different time scales is tested in this study. The analysis is carried out for ground ozone levels observed during 2006 at two sites of different land use characteristics, as traffic and mixed-use in Delhi at four temporal scales as 1 h, 4 h, 8 h and 24 h. The chaotic nature is observed for the ozone concentration with 1 h and 4 h frequency, whereas at 8 h and 24 h time scale, the ozone concentration shows random behavior. As expected, a decrease in the variability is observed in the ozone levels with increase in the scales from 1 h to 24 h. The results indicated the temporal scale shifts are allowed from 1 h to 4 h resolution and vice versa. The ozone time series at 8 h and 24 h scalings however, should be dealt separately. Further analysis for corresponding NO₂ concentration at two sites suggested finite d₂ for 1 h, 4 h and 8 h scalings with higher value at traffic site than that at mixed-use site. The analysis also indicated same degrees of freedom for ozone and NO₂ concentration at traffic site whereas at mixed-use site the number of variables governing the NO₂ pollution are less than the ozone concentration.     

The frequency and causes of elevated concentrations of ozone at ground level at rural sites in north-west England

Ozone concentration data measured in 1977–1979 and 1981–1983 at rural sites in north-west England have been analysed in relation to elevated concentrations. Overall, concentrations exceed 60 ppb on 11.2% of days, 80 ppb on 4.2% of days and reach levels in excess of 100 ppb on 1.5% of days monitored. It is concluded that photochemical pollution is the most frequent cause of elevated concentrations, and that both long-range (continental) and middle-distance (U.K. urban) sources contribute. On a smaller percentage of days, elevated ozone levels arise from enhanced intrusions of stratospheric air associated with vigorous frontal activity. The meteorological situations associated with tropospheric photochemical ozone formation are summer anticyclonic conditions, in common with other observations in the U.K. and other parts of the world.     

Factors influencing the ground level distribution of ozone in Europe

Ozone is a widely distributed pollutant in the atmospheric boundary layer over north west Europe. Three main sources have been identified: the stratosphere, the free troposphere and boundary layer photochemical production. The pattern of ground level ozone concentrations resulting from these three sources cannot be accurately specified. Ozone shows significant variations in space and time but because of the high cost of continuous monitoring equipment, spatial variations on a national and international basis have not been studied in detail. Variations in ozone concentrations at individual monitoring sites have been given a great deal of attention and experience gained from United Kingdom monitoring sites is described in some detail. The averaging time statistical model of Larsen is employed to relate the exposure levels measured over different averaging periods. Diurnal variations have a major influence on exposure levels at sites nominally exposed to the same regional ozone distribution. The physical and chemical mechanisms which give rise to diurnal variations are detailed so that sites can be screened for different diurnal behaviour characteristics.     

Maximum ground level concentrations of washed chimney emissions

A theoretical study is made of the effect of gas washing on the behaviour and dispersion of chimney effluent from tall stacks. For recirculatory washers emitting at or above the adiabatic saturation temperature of the combustion gases it is concluded that conventional methods of calculating the rise and dispersion of buoyancy dominated plumes may be used. However, for washers operating at lower temperatures the emission buoyancy flux is reduced to the extent that other factors which were hitherto absent or negligible now require consideration. The significance of these factors is discussed and methods for calculating the rise and dispersion of weakly buoyant and negatively buoyant emissions are developed. Calculations are made for both 500 MW and 2000 MW power stations which illustrate the effects on ground level concentrations of gas washing at various wash-water temperatures with and without reheat.     

Preliminary background ozone concentrations in the mountain and coastal areas of Bulgaria

Urban and non-urban rural ozone (O3) concentrations are high in Bulgaria and often exceed the European AOT40 ecosystem as well as the AOT60 human health standards. This paper presents preliminary estimates to establish background, non-urban O3 concentrations for the southern region of Bulgaria. Ozone concentrations from three distinctly different sites are presented: a mountain site influenced by mountain-valley wind flow; a coastal site influenced by sea-breeze wind flow; and a 1700-m mountain peak site without 'local' wind flow characteristics. The latter offers the best estimate of 46-50 ppb for a background O3 level. The highest non-urban hourly value, 118 ppb, was measured at the mountain-valley site.     

Terrain-induced downwash effects on ground level SO2 concentrations

A field study was conducted at the Tennessee Valley Authority's (TVA) Widows Creek Steam Plant from March to 1 May 1979 to investigate the effects of terrain-induced downwash. The Widows Creek Plant is located in a valley formed by Sand Mountain to the southeast and the Cumberland Plateau to the northwest. With southeasterly winds, a downward component of velocity is induced by the terrain as the air moves from Sand Mountain across the valley. Because of the proximity of the plant to Sand Mountain, the plumes are caught in this terrain-induced downwash, which then causes a significant increase in the ground level SO₂ concentrations.An SO₂-monitoring network was established in the downwash region and the measured SO₂ concentrations were correlated with the meteorological parameters and plant operating conditions.The maximum SO₂ concentrations were measured within 1.3 km of the source at locations approximately perpendicular to the Sand Mountain ridge line. The ground level concentration per unit emission rate increased with increasing wind speed and the ratio of wind speed to stack exit velocity.Neither the magnitude nor the trends predicted by the CRSTER model compared well with measured data unless the plume was assumed to be suppressed by the terrain-induced downwash. The CRSTER model predicted a maximum concentration for class A stability and negligible values for class D to G. Ground level concentrations were not measured during the few periods of class A stability that occurred. The highest concentrations were measured for stability class C and D conditions.     

Influence of ship emissions on ozone concentrations around coastal areas during summer season

The influence of ship emissions on ozone (O₃) concentrations in a coastal area (CA) including Busan port, Korea was examined based on a numerical modeling approach during a high O₃ episode. The analysis was performed by two sets of simulation scenarios: (1) with ship emissions (e.g., TOTAL case) and (2) without ship emissions (e.g., BASE case). A process analysis (PA) (the integrated processes rate (IPR) and integrated reaction rate (IRR) analyses) was used to evaluate the relative contributions of individual physical and chemical processes in O₃ production in and around the CA (e.g., sites of Dong Sam (DS) and Dae Yeon (DY)). The model study suggested the possibility that pollutant gases emitted from the ships traversing Busan port can exert a direct impact on the O₃ concentration levels in the CA. Largest impacts of ship emissions on the O₃ concentrations were predicted at the coast (up to 15 ppb) and at inland locations (about 5 ppb) due to both the photochemical production of pollutant gases emitted from the ships and meteorological conditions. From the PA, the photochemical production of O₃ (P(O₃)) due to ship emissions in the CA was found to increase by a mean of 1.5 ppb h^?1 (especially by ≥10 ppb h^?1 at the DS site) during the day.     

Comparison of ozone temporal scales for large urban, small urban, and rural areas in Georgia

Ground-level ozone (O3) time series are characterized by the sum of several distinct temporal scales: long-term, seasonal, synoptic, diurnal (daily), and intraday variation. In this study, the authors use a Kolmorogov-Zurbenko filter to separate the 1981-2001 O3 time-series from many sites in and around Georgia into these various components. The authors compare the temporal components to examine differences between small and large metropolitan areas and between urban and rural areas. They then focus on the synoptic component to define a predominant transport region or airshed for each site.     

Trends in meteorologically adjusted ozone concentrations in six Kentucky metro areas, 1998-2002

Meteorologically adjusted ozone (O3) concentrations during five recent O3 seasons (1998-2002) were computed for six Kentucky metro areas using a nonlinear regression model originally developed for forecasting ground-level O3 concentrations. The meteorological adjustment procedure was based on modifying actual measured O3 concentrations according to model-predicted responses to climate departures with respect to a reference year. For all six Kentucky metro areas, meteorologically adjusted O3 concentrations declined over the five-year period. The linear best-fit rate of decline in mean adjusted O3 concentrations ranged from 0.9 to 2.6 ppb/yr for these metro areas; the average rate of decline was 1.6 ppb/yr. The rates of decline in meteorologically adjusted extreme value (e.g., 95th percentile) concentrations were approximately the same, but there is greater statistical uncertainty concerning the extreme value trends.     

Effects of 10% biofuel substitution on ground level ozone formation in Bangkok,Thailand

The Thai Government's search for alternatives to imported petroleum led to the consideration of mandating 10% biofuel blends (biodiesel and gasohol) by 2012. Concerns over the effects of biofuel combustion on ground level ozone formation in relation to their conventional counterparts need addressing. Ozone formation in Bangkok is explored using a trajectory box model. The model is compared against O₃, NO, and NO₂ time concentration data from air monitoring stations operated by the Thai Pollution Control Department. Four high ozone days in 2006 were selected for modeling. Both the traditional trajectory approach and a citywide average approach were used. The model performs well with both approaches but slightly better with the citywide average. Highly uncertain and missing data are derived within realistic bounds using a genetic algorithm optimization. It was found that 10% biofuel substitution will lead to as much as a 16 ppb peak O₃ increase on these four days compared to a 48 ppb increase due to the predicted vehicle fleet size increase between 2006 and 2012. The approach also suggests that when detailed meteorological data is not available to run three dimensional airshed models, and if the air is stagnant or predominately remains over an urban area during the day, that a simple low cost trajectory analysis of O₃ formation may be applicable.     

Spatial and seasonal variations of atmospheric BTEX,sulfur dioxide,nitrogen dioxide,and ozone concentrations in Istanbul,and health risk assessment of BTEX

Volatile organic compounds (VOCs) such as benzene, toluene, ethylbenzene, and xylene (BTEX) along with inorganic gases such as sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and ozone (O₃) levels were found in the atmosphere of the Kemerburgaz region where environmental issues became a major concern due to nearby incineration plant and waste disposal facility in Istanbul. Ten sampling locations were selected considering possible sources in the study area. The sampling areas were classified as suburban, industrial, rural, and background regions. Sampling campaigns were carried out for four-week periods from March 2011 to August 2012 in all locations. Elevated concentrations of BTEX around roads and the industrial locations indicated that vehicle exhaust and industrial activities were the main sources of these pollutants in the region. Concentrations of NO₂ were also high around roads. A much more uniform distribution was observed for SO₂ during sampling periods. However higher levels were observed at suburban locations due to the use of coal for local heating especially during winter. Ozone concentrations were low at the industrial locations and roadsides, but high in suburban and rural locations downwind from the sources. The results of these organic and inorganic gases meet the national limit values. Furthermore, a lifetime risk assessment methodology was used to evaluate the potential adverse health effects of BTEX. The mean cancer risk level for benzene was estimated to be 7.71E-07 that is lower than assigned acceptable risk level of 1.0E-04. Toluene, ethylbenzene, and xylenes were lower than the specified level of 1.0 with respect to mean non-carcinogenic risks. The findings reveal that determined BTEX emissions do not pose a health threat to residents in the studied region.     

On ground truth in cross-border ozone transport

Cross-border transport of ozone is one of the most contentious issues of air pollution management in the U.S. Yet, both the modeling and observational studies are lacking. Models are normally validated by comparing predicted and observed ozone concentrations. However, proper validation of cross-border transport model requires a comparison of predictions against observation-based benchmarks of cross-border ozone transport. Such benchmarks are unavailable, as published observation-based studies always deal only with a combination of local production and cross-border transport, not a cross-border transport itself. We show how to extract necessary benchmarks from observations of rural monitoring sites near state borders. On example of the western border of New York, we find that in about two-thirds of the most polluted days all the ozone came in a steady cross-border inflow after previously passing over one or more large urban areas to the west. In all the enumerated days with direct cross-border inflow, daily maximum 8-hr concentrations of ozone just upwind of the border were over 60 ppb, with an average value of 68 ppb, just short of the 70 ppb ozone regulatory threshold, information also useful to state air pollution authorities.

Implications: The purpose of the cross-border ozone pollution models is to predict cross-border transport of ozone, so the ability of the model to accurately represent observed ozone concentrations is necessary but not sufficient for model validation. The accuracy of predicted ozone concentrations is not necessarily the same as the accuracy of the predictions of ozone transport. Proper model validation requires comparisons against observation-based benchmarks of cross-border transport. Such observations, so far absent, can be obtained from rural monitoring sites near state borders, as illustrated by the example of western New York.     

Potential contribution of sulfate production in cumulus cloud droplets to ground level particle sulfur concentrations

The relationships have been examined between the presence or absence of cumulus clouds and 3rd quarter fine particle sulfur concentrations in St Louis. An association between the presence of cumulus clouds with SO₂ conversions in droplets and incrementally higher fine particle sulfur concentrations can be demonstrated. However, diurnal patterns of fine particle sulfur concentrations in the presence of cumulus clouds are not consistent with local contributions from sulfate formation in cumulus clouds. Morning fog often occurs on the same days on which cumulus clouds form later. Reactions of SO₂ in fog droplets appear to make a contribution, but do not account for the major part of the increments in fine particle sulfur concentrations associated with cumulus clouds. The variations in fine particle sulfur concentrations observed can be explained if a substantial part of the sulfate formed in cumulus is transported upwards from the planetary boundary layer into the lower free troposphere. Subsequent multiday regional scale horizontal transport with concurrent gradual vertical transport of sulfate down to the surface would be consistent with the observed results.     

Diurnal and seasonal variations of carbonyls and their effect on ozone concentrations in the atmosphere of Monterrey,Mexico

Few studies have been made regarding carbonyl concentrations in Monterrey, México. The Monterrey Metropolitan Area (MMA) has the third largest population in the country and has increasing pollution issues. The concentrations of 10 aldehydes and two ketones were measured in the MMA, in the spring and fall of 2011 and 2012. Formaldehyde (16–42 ppbv) was the most abundant carbonyl, followed by acetaldehyde (5–15 ppbv) and acetone (7–15 ppbv). The concentrations showed marked diurnal trends with maximum values between 10:00 a.m. and 2:00 p.m., when photochemical activity is intense. Thus, secondary production of carbonyls is statistically significant in the city. Biogenic production of several carbonyls, such as 2-butanone, was supported by their mid correlation with solar radiation and low correlation with propionaldehyde, which is mainly emitted by anthropogenic sources. The seasonal variability of the concentrations was observed in the first three samplings, with the highest levels reached in the fall. The rainy conditions during the fourth sampling did not allow comparison. Carbonyl–NOx–O₃ analysis was made. Results indicated a carbonyl-sensitive atmosphere, especially during the midday samplings of 10:00 a. m. to 2:00 p.m. and 2:00 p.m. and 6:00 p.m. because of the intense solar radiation during these periods.

Implications:?Monitoring of carbonyls in Monterrey, Mexico, was performed to quantify the pollutant concentration in the city’s atmosphere. Although primary emission is significantly important, the secondary production of the pollutants, along with ozone production being carbonyl sensitive, indicates that air pollution controls must address the direct sources and the precursors of the pollutants to achieve air quality.     

Sources and sinks of ozone in rural areas

Based on data collected at rural sites in South Dakota, Louisiana and Virginia during the summers of 1978–1980, the factors controlling the diurnal behavior of O₃ near the surface were determined. At all three sites, the diurnal O₃ profile consisted of a period of O₃ increase from sunrise until mid-afternoon, and a period of O₃ decrease from late afternoon until sunrise. The daily O₃ increase was comprised of two approximately equal portions: one due to downmixing of O₃ from aloft (0600–1000 h), and the other due to photochemistry and possibly some further downmixing (1000–1400 h). Even assuming that all of the O₃ increase during the 1000–1400 h period was due to local photochemistry, only very small amounts of O₃ were formed i.e. about 6 ppb of O₃ per ppb of nitrogen oxides (NO_x). Both bag irradiation and photochemical modeling studies suggested similar, but slightly higher O₃ formation. Comparing the ambient data with the bag irradiation and modeling results, it was concluded that rural photochemistry was not controlled exclusively by NO_x, but depended on hydrocarbons as well.The O₃ decrease (1800 to 0600 h) generally occurred while nocturnal inversions isolated the lower 50 m of the atmosphere from the air aloft. Since the O₃ loss-rate could be parameterized equally well by either zero- or first-order rate laws, we could not distinguish between the two mechanisms. However, concentrations of gaseous species such as terpenes and NO_x that might lead to pseudo zero-order O₃ loss were generally of minor significance. Consequently, it is concluded that O₃ loss was controlled by surface deposition with deposition velocities ranging from 0.06 to 0.34cms⁻¹ at the three sites.     

Ammonia emissions from different pig production scales and their temporal variations in the North China Plain

ABSTRACT

Pig production systems in China are shifting from small to industrial scale. Significant variation in housing ammonia (NH₃) emissions can exist due to differences in diet, housing design, and management practices. However, there is a knowledge gap regarding the impacts of farm-scale in China, which may be critical in identifying hotspots and mitigation targets. Here, continuous in-situ NH₃ concentration measurements were made at pig farms of different scales for sows and fattening pigs over periods of 3–6 days during two different seasons (summer vs. winter). For the sow farms, NH₃ emission rates were greater at the small farm (summer: 0.52 g pig^?1 hr^?1; winter: 0.21 g pig^?1 hr^?1) than at the large farm (summer: 0.34 g pig^?1 hr^?1; winter: 0.12 g pig^?1 hr^?1). For the fattening pig farms, NH₃ emission rates were greater at the large farm (summer: 0.22 g pig^?1 hr^?1; winter: 0.16 g pig^?1 hr^?1) than at the small farm (summer: 0.19 g pig^?1 hr^?1; winter: 0.07 g pig^?1 hr^?1). Regardless of farm scale, the NH₃ emission rates measured in summer were greater than those in winter; the NH₃ emission rates were greater in the daytime than at the nighttime; a positive relationship (R² = 0.06–0.68) was established between temperature and NH₃ emission rate, whereas a negative relationship (R² = 0.10–0.47) was found between relative humidity and NH₃ emission rate. The effect of farm-scale on indoor NH₃ concentration could mostly be explained by the differences in ventilation rates between farms. The diurnal variation in NH₃ concentration could be partly explained by ventilation rate (R² = 0.48–0.78) in the small traditional farms and by emission rate (R² = 0.26–0.85) in the large industrial farms, except for the large fattening pig farm in summer. Overall, mitigation of NH₃ emissions from sow farms should be a top priority in the North China Plain.

Implications: The present study firstly examined the farm-scale effect of ammonia emissions in the North China Plain. Of all farms, the sow farm was identified as the greatest source of ammonia emission. Regardless of farm scale, ammonia emission rates were observed to be higher in summer. Ammonia concentrations were mostly higher in the large industrial farms partly due to lower ventilation rates than in the small traditional farms.     

Assessing the risk caused by ground level ozone to European forest trees: a case study in pine, beech and oak across different climate regions

Two different indices have been proposed for estimation of the risk caused to forest trees across Europe by ground-level ozone, (i) the concentration based AOT40 index (Accumulated Over a Threshold of 40 ppb) and (ii) the recently developed flux based AFstY index (Accumulated stomatal Flux above a flux threshold Y). This paper compares the AOT40 and AFstY indices for three forest trees species at different locations in Europe. The AFstY index is estimated using the DO(3)SE (Deposition of Ozone and Stomatal Exchange) model parameterized for Scots pine (Pinus sylvestris), beech (Fagus sylvatica) and holm oak (Quercus ilex). The results show a large difference in the perceived O(3) risk when using AOT40 and AFstY indices both between species and regions. The AOT40 index shows a strong north-south gradient across Europe, whereas there is little difference between regions in the modelled values of AFstY. There are significant differences in modelled AFstY between species, which are predominantly determined by differences in the timing and length of the growing season, the periods during which soil moisture deficit limits stomatal conductance, and adaptation to soil moisture stress. This emphasizes the importance of defining species-specific flux response variables to obtain a more accurate quantification of O(3) risk.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.