Simulation of boundary layer trajectory dispersion sensitivity to soil moisture conditions: MM5 and Noah-based investigation

In this study, the sensitivity of trajectory paths to anomalous soil moisture was analyzed during three different synoptic episodes in June 2006. The MM5 and Noah land surface models were used to simulate the response of the planetary boundary layer. The HYSPLIT model was used for trajectory analysis. It was found that the response in horizontal lower-level wind field was larger at regions where vertical wind velocity changes were also large. In addition, the sensitivity to soil moisture changes was significant and localized where convective activity was well developed and synoptic effects did not dominate. A non-local effect was felt over the rest of the domain where convection was not present since the model atmosphere reacted as a whole to compensate for induced changes in vertical velocity. This finding was supported by the fact that domain averaged vertical velocities changes were of the order of 0.2 cm s^?1 or less at about 650 hPa and about 200 times smaller than modeled local vertical velocity changes. The largest change in horizontal wind field near the surface was found for weak synoptic events on June 11–12 and June 22–23 while the stronger synoptic event of June 17–18 showed smaller differences. These changes in wind field conditions impacted the transport and dispersion of pollutants. To quantify the sensitivity of air quality estimates to soil moisture uncertainty, we have used three well known measures of trajectory differences: the absolute horizontal transport deviation (AHTD), the relative horizontal transport deviation (RHTD) and the absolute vertical transport deviation (AVTD) for an ensemble of 98 trajectories departing from a region well within the computational domain. For the June 11–12 event it was found that for wet and dry soil moisture experiments, AHTD, RHTD, and AVGTD can reach values in the range 60–100 km, 10–20% and 500–900 m at 24 h run time, respectively. For the June 17–18 and June 22–23 events these values of trajectory differences were reduced more than half. These differences in behavior between time periods are largely attributed to the combined effects of synoptic forcing and the sensitivity of planetary boundary layer to soil moisture changes during well developed convection. The implication for air quality studies is that the soil moisture anomaly and related uncertainty in planetary boundary layer response needs to be incorporated in order to construct an ensemble of the most probable scenarios in which pollutants are released and transported throughout a given target region.     

Lidar measurements of sulfur dioxide and ozone in the boundary layer during the 1983 Fos Berre Campaign

Studies of the dispersion of pollutants (SO₂, O₃) in the planetary boundary layer have been performed during the Fos Berre 1983 International Campaign using ground-based DIAL lidar operating in the u.v. wavelength range. Multidimensional measurements of both SO₂ and O₃ were obtained with a spatial resolution better than 500 m, a temporal resolution of 3 mn and a maximum horizontal range of 3 km. The overall accuracy as assessed by various comparisons with other measurement systems was always better than 20%. Examples of application to studies of SO₂ dispersion in the planetary boundary layer, of plume evolution and of horizontal inhomogeneities in the ozone field are given.     

Sensitivity of nitrogen dioxide concentrations to oxides of nitrogen controls in the United Kingdom

There is a possibility of further controls on emissions to the atmosphere of nitrogen oxides to meet air quality objectives in the UK. Data in the National Air Quality Archive were used to calculate the likely sensitivity of hourly concentrations of nitrogen dioxide in ambient urban air to changes in the total oxides of nitrogen. Since the role of atmospheric chemical reactions is to make the response non-linearly dependent on the emissions control, we seek to establish the magnitude and sign of the effects that this non-linearity might cause. We develop a quantitative approach to analysing the non-linearity in the data. Polynomial curve fits have been developed for the empirical ratio NO₂ : NO_x (the ‘yield’). They describe nitrogen dioxide concentrations using total oxides of nitrogen. The new functions have the important feature of increased yield in winter episodes. Simpler functions tend to omit this feature of the yields at the highest hourly concentrations. Based on this study, the hourly nitrogen dioxide objective in the UK may require emissions control of no more than ≈50% on total oxides of nitrogen at the most polluted sites: other sites require less or even no control.     

Pretreatment with nitrogen dioxide modifies plant response to ozone

Plant growth inhibition by ozone is significantly affected by previous exposure to nitrogen dioxide. Experiments on the early growth of four crop species showed that daily pretreatment with NO₂ (0.08–0.10 ppm for 3 h) immediately prior to exposure to O₃ (0.08–0.10 ppm for 6 h) increased the inhibition of radish and wheat growth, decreased the inhibition of bush bean growth, but had no effect on the growth of mint. The magnitudes of the interactive effects indicate that in regions where relatively high concentrations of O₃ are produced by photochemical processes, for example, downwind from urban centres, assessments of the impact of O₃ on vegetation based on knowledge of response to O₃ alone may be seriously flawed.     

Modelling of indoor exposure to nitrogen dioxide in the UK

A dynamic multi-compartment computer model has been developed to describe the physical processes determining indoor pollutant concentrations as a function of outdoor concentrations, indoor emission rates and building characteristics. The model has been parameterised for typical UK homes and workplaces and linked to a time-activity model to calculate exposures for a representative homemaker, schoolchild and office worker, with respect to NO₂. The estimates of population exposures, for selected urban and rural sites, are expressed in terms of annual means and frequency of hours in which air quality standards are exceeded. The annual mean exposures are estimated to fall within the range of 5–21 ppb for homes with no source, and 21–27 ppb for homes with gas cooking, varying across sites and population groups. The contribution of outdoor exposure to annual mean NO₂ exposure varied from 5 to 24%, that of indoor penetration of outdoor air from 17 to 86% and that of gas cooking from 0 to 78%. The frequency of exposure to 1 h mean concentrations above 150 ppb was very low, except for people cooking with gas.     

Response of spinach and kidney bean plants to nitrogen dioxide

Different responses of spinach and kidney bean plants to various concentrations of NO(2) in the light and in the dark were shown. Spinach is more resistant than NO(2) than kidney bean. It is not only due to its greater tolerance to NO(2)(-) accumulated in leaves, but also to its stronger ability to metabolize NO(2)(-). The injury of spinach induced by the exposure to high concentration NO(2) in the light was not caused by the accumulation of NO(2)(-), but concerned the large amount of accumulated NH(3). The primary causes of NH(3) accumulation were that the activity of nitrite reductase was not affected by the fumigation on the one hand, and the activities of glutamine synthetase and glutamate synthase were inhibited on the other.     

Concentrations of ammonia and nitrogen dioxide at roadside verges, and their contribution to nitrogen deposition

Bimonthly integrated measurements of NO2 and NH3 have been made over one year at distances up to 10 m away from the edges of roads across Scotland, using a stratified sampling scheme in terms of road traffic density and background N deposition. The rate of decrease in gas concentrations away from the edge of the roads was rapid, with concentrations falling by 90% within the first 10 m for NH3 and the first 15 m for NO2. The longer transport distance for NO2 reflects the production of secondary NO2 from reaction of emitted NO and O3. Concentrations above the background, estimated at the edge of the traffic lane, were linearly proportional to traffic density for NH3 (microg NH3 m(-3) = 1 x 10(-4) x numbers of cars per day), reflecting emissions from three-way catalysts. For NO2, where emissions depend strongly on vehicle type and fuel, traffic density was calculated in terms of 'car equivalents'; NO2 concentrations at the edge of the traffic lane were proportional to the number of car equivalents (microg NO2 m(-3) = 1 x 10(-4) x numbers of car equivalents per day). Although absolute concentrations (microg m(-3)) of NH3 were five times smaller than for NO2, the greater deposition velocity for NH3 to vegetation means that approximately equivalent amounts of dry N deposition to road side vegetation from vehicle emissions comes from NH3 and NO2. Depending on traffic density, the additional N deposition attributable to vehicle exhaust gases is between 1 and 15 kg N ha(-1) y(-1) at the edge of the vehicle lane, falling to 0.2-10 kg N ha(-1) y(-1) at 10 m from the edge of the road.     

The nitration of pyrene adsorbed on silica particles by nitrogen dioxide

Conversion of NO2, HNO2 gas, their mixture and a mixed gas of HNO2 and HNO3 on silica particles was investigated under simulated atmospheric conditions. Both HNO2 and HNO3 were detected as the products from conversion of NO2 on silica particles. However, unlike HNO3, which increased with conversion time, HNO2 underwent an increase-decrease time course due to the increased HNO3 further transformed HNO2 into NO+ on silica particles. Considering the catalytic effect of HNO3 and HNO2 on the nitration of pyrene adsorbed on silica particles by NO2, another electrophilic nitration path, analogous to the one that we previously reported, with NONO2+ and NON2O4+ as electrophiles was suggested. The two paths together gave an appropriate explanation for the catalytic effect of HNO2, HNO3 and their mixed gas on the nitration of the adsorbed pyrene by NO2.     

The vertical distribution of NO3 in the atmospheric boundary layer

Recent urban measurements suggest that NO₃ concentrations vary significantly with altitude in the lowest few hundred metres of the atmosphere. Calculations using a one-dimensional boundary layer model show that NO₃ concentrations are small near the ground and increase with altitude to a maximum near the top of the nocturnal boundary layer (NBL). These results show that the NBL is not well mixed, and that where there are surface sources and sinks two-box models of the NBL are inadequate, and surface measurements are not representative and may lead to an underestimate of the oxidising capacity of the atmosphere.     

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.     

Effects of nitrogen dioxide on leaf chlorophyll and nitrogen content of soybean

One-month-old soybean (Glycine max [L.] Merrill), cultivar 'Williams', plants were exposed to nitrogen dioxide (0.1, 0.2, 0.3 and 0.5 ppm) and carbon filtered air (control), 7 h per day, for 5 days, under a controlled environment. Leaf chlorophyll content (Ch a, Ch b, and total Ch content) and foliar nitrogen content (%N) were determined before and after the exposure. The influence of NO(2) treatments up to 0.3 ppm on leaf chlorophyll content was negligible although a stimulatory effect was evident in Ch a and total Ch content with 0.2 ppm NO(2). Marked decline in Ch content was observed with 0.5 ppm treatment; the reductions in Ch a and total Ch were 45% and 47%, respectively. Foliar-N contents of plants treated with 0.2 and 0.3 ppm NO(2) were higher than the control; plants exposed to 0.5 ppm NO(2) showed a 41% reduction in foliar-N compared to pre-exposure values.     

Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology

Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.     

The reaction of nitrogen dioxide with lung surface components: The reaction with cholesterol

The reaction of nitrogen dioxide (NO₂) with cholesterol was investigated. NO₂ reacted with the hydroxyl group in cholesterol to produce cholesteryl nitrite. In this reaction, other minor products were observed. Cholesteryl nitrate, however, was not detected as was reported by other workers. Water accelerates and oxygen retards this reaction.     

Rural concentrations of nitrogen dioxide pollution throughout Wales

Monitoring of nitrogen dioxide was carried out at over 50 rural sites in Wales throughout 1986. All sites were chosen so as to be remote from any local sources of NO(2) and the values obtained were deemed to be minimum values for the different regions. Measurements were made using a diffusion tube technique which aimed to give mean concentrations of NO(2) for 2-week exposure periods. The results obtained have been used to generate pollution maps to show mean monthly levels of NO(2) for rural environments throughout Wales. It is apparent that levels of NO(2) are generally higher during the winter months. In addition, annual mean concentrations of the pollutant are greatest in the north-eastern and south-eastern parts of Wales with the lowest levels being found along the western coast. The work marks the completion of the first national survey of nitrogen dioxide pollution in Wales. The data are discussed in terms of the potential threat rural concentrations of NO(2) pose to crops and natural vegetation.     

Responses of greening bean seedling leaves to nitrogen dioxide and nutrient nitrate supply

Phaseolus vulgaris cv. Kinghorn Wax seedlings grown in darkness at 25 degrees C for 7 days with half strength Hoagland's nutrient solution containing no nitrogen, were transferred to lit continuous stirred tank reactors (CSTRs) in atmospheres containing 0 or 0.3 ppm NO(2) and irrigated with a nutrient solution containing 0 or 5 mm nitrate as sole nitrogen source and allowed to grow for a period of up to 5 days in a 14 h photoperiod. Exposure to NO(2) increased total Kjeldahl nitrogen in the leaves. Further, the exposure to NO(2) increased chlorophyll content from day 3 onwards and inhibited the leaf dry weight substantially on days 4 and 5. The primary leaves of the seedlings exposed to 0.3 ppm NO(2) and supplied with nitrate accumulated some nitrite after 5 days of exposure. Some of the seedlings were returned from CSTRs to growth chambers and allowed to grow for a further period of 5 days in a 14 h photoperiod without NO(2). The growth which developed after the NO(2) exposure growth period, as measured by fresh and dry weights of the leaves, was significantly less in NO(2)-exposed plants than in nitrate-grown plants. The experiments demonstrate that the leaves of greening seedlings are able to assimilate NO(2) and that a reduction in leaf dry weight by prolonged NO(2) exposure in the presence of nutrient nitrate can be associated with nitrite accumulation, and that NO(2) has a carry-over effect beyond the duration of NO(2) exposure. It is apparent that NO(2) induces some durable biochemical or cytological aberration in the presence of nutrient nitrate, which adversely affects subsequent leaf growth.     

Measurements of personal exposure to nitrogen dioxide in four Mexican cities in 1996

Nitrogen dioxide is a ubiquitous pollutant in urban areas. Indoor NO2 concentrations are influenced by penetration of outdoor concentrations and by indoor sources. The objectives of this study were to evaluate personal exposure to NO2, taking into account human time-activity patterns in four Mexican cities. Passive filter badges were used for indoor, outdoor, and personal NO2 measurements over 48 hr and indoor workplace measurements over 16 hr. Volunteers completed a questionnaire on exposure factors and a time-activity diary during the sample period. An unpaired t test, an analysis of variance (ANOVA), and a linear regression were performed to compare differences among cities and mean personal NO2 concentrations involving housing characteristics, as well as to determine which variables predicted the personal NO2 concentration. Sampling periods were in April, May, and June 1996 in Mexico City, Guadalajara, Cuernavaca, and Monterrey. All 122 volunteers in the study were working adults, with a mean age of 34 (SD +/- 7.38); 64% were female, and the majority worked in public offices and universities. The highest NO2 concentrations were found in Mexico City (36 ppb for outdoor, 57 ppb for indoor, and 39 ppb for personal concentration) and the lowest in Monterrey (19 ppb for outdoor, 24 ppb for indoor, and 24 ppb for personal concentration). Significant differences in NO2 concentrations were found among the cities in different microenvironments. During the sampling period, volunteers spent 85% of their time indoors. The highest personal NO2 concentration was found when volunteers kept their windows closed (p = 0.03). In the regression model adjusted by city and gender, the best predictors of personal NO2 concentration were outdoor levels and time spent outdoors (R2 = 0.68). These findings suggest that outdoor NO2 concentrations were an important influence on the personal exposure to NO2, due to the specific characteristics and personal behavior of the people in these Mexican cities.     

The role of nitrogen oxides in nonurban ozone formation in the planetary boundary layer over n America,w europe and adjacent areas of ocean

The status of knowledge on photochemical ozone formation and the effects of nitrogen oxides and peroxyacyl nitrates on such formation have been evaluated. The literature is reviewed on

• 1.(a) nonurban ozone and nitrogen oxide concentration distributions,(b) ozone lifetimes,(c) nitrogen oxide lifetimes, and(d) ozone formation in plumes as related to nitrogen oxide.

The modeling approaches applied to ozone formation

• 1.(a) with urban plumes,
• 2.(b) power plant plumes,
• 3.(c) high pressure systems, and
• 4.(d) during longerrange transport of ozone are discussed. In addition, models concerned with the contributions to ozone formation associated with reactions of natural hydrocarbons and nitrogen oxide near ground level and photochemical ozone formation associated with reactions of carbon monoxide and of more persistent organic species with nitrogen oxides in the free troposphere are considered.

It is concluded that urban plumes are major contributors to elevated ozone concentrations measured at nonurban locations, particularly during the passage of high pressure systems. Ozone can survive at significant concentration levels for more than one day of transport. However, the evidence for multiday ozone transport is to a large extent associated with transport over water.Ozone formation during the first day of transport does not appear to be limited by the availability of nitrogen oxides. However, it is likely that multiday formation and transport of ozone within the boundary layer is limited in duration because of the relatively short lifetimes of nitrogen oxides and peroxyacyl nitrates. Photochemical formation of ozone in the free troposphere may be an important contributor to longer-time average ozone concentrations in rural areas. These free tropospheric processes depend in part on anthropogenic sources of precursors and are especially sensitive to the vertical distribution of nitrogen oxides in the atmosphere.     

Atmospheric conversion of sulfur dioxide to particulate sulfate and nitrogen dioxide to particulate nitrate and gaseous nitric acid in an urban area

Sulfur dioxide, nitrogen dioxide, particulate sulfate and nitrate, gaseous nitric acid, ozone and meteorological parameters (temperature and relative humidity) were measured during the winter season (1999-2000) and summer season (2000) in an urban area (Dokki, Giza, Egypt). The average particulate nitrate concentrations were 6.20 and 9.80 microg m(-3), while the average gaseous nitric acid concentrations were 1.14 and 6.70 microg m(-3) in the winter and summer seasons, respectively. The average sulfate concentrations were 15.32 microg m(-3) during the winter and 25.10 microg m(-3) during the summer season. The highest average concentration ratio of gaseous nitric acid to total nitrate was found during the summer season. Particulate sulfate and nitrate and gaseous nitric acid concentrations were relatively higher in the daytime than those in the nighttime. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) defined in the text were calculated from the field measurement data. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) in the summer were about 2.22 and 2.97 times higher than those in the winter season, respectively. Moreover, sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) were higher in the daytime than those in the nighttime during the both seasons. The sulfur conversion ratio (Fs) increases with increasing ozone concentration and relative humidity. This indicates that the droplet phase reactions and gas phase reactions are important for the oxidation of SO2 to sulfate. Moreover, the nitrogen conversion ratio (Fn) increases with increasing ozone concentration, and the gas phase reactions are important and predominant for the oxidation of NO2 to nitrate.     

The effects of prior exposure to sulphur dioxide and nitrogen dioxide on the water relations of timothy grass (Phleum pratense) under drought conditions

Studies of the growth and water relations of the grass Phleum pratense L. (Timothy) were made after simultaneous exposure to SO(2) and NO(2) at concentrations ranging from 80 + 57.4 microg m(-3) to 240 + 172.2 microg m(-3) (SO(2) + NO(2)). Decreased partitioning to the roots was evident during exposure to the pollutants, but when the plants were returned to clean air restrictions in root growth did not persist. Shoot to root partitioning was, however, complicated by the additional factor of changes in the nutritional status of the soil after additional columns of fresh soil were attached to the original tubes. The rate of use of soil water was nevertheless substantially increased by the pollution treatment and after a period of 23 days in which water was withheld, a clear pollution x water stress interaction was seen. The ability of polluted leaves to conserve water under severe water stress was tested by excising the leaves and measuring their water loss over time. The results from this second experiment showed that conservation of water by the leaves was appreciably affected after exposure to 80 + 57.4 microg m(-3) or 133.3 + 95.6 microg m(-3) SO(2) + NO(2). It seems likely that damage to the cells in the epidermal layer, leading to malfunctioning of stomata, is mainly responsible for the reduced ability to conserve water under conditions of extreme stress.