Modeling toxic compounds from nitric oxide emission measurements

Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO_x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.     

Sequencing diurnal air flow patterns for ozone exposure assessment around Houston,Texas

Understanding the human health impacts of ground level ozone requires detailed knowledge of its spatial–temporal distribution beyond that provided by surface monitoring networks. Here, a novel methodology based on unsupervised multivariate statistical techniques has been developed and used to identify the transport and dispersion patterns of tropospheric ozone. The hierarchical clustering method is used to visualize air flow patterns at two time scales relevant for ozone buildup. Sequentially executed statistical methods consider hourly 1-h surface wind field measurements. First, clustering is performed at the hourly time scale to identify 1-h surface flow patterns. Then, sequencing is performed at the daily time scale to identify groups of days sharing similar diurnal cycles for the surface flow. Selection of appropriate numbers of air flow patterns allows inference of regional transport and dispersion patterns for understanding population exposure to ozone. The methods are applied to the Houston, Galveston, and Beaumont-Port Arthur, TX study domain. Representative hourly wind field patterns are determined for the entire 2004 ozone season. Then, sequencing is performed for the 32 days in exceedance of the NAAQS for 8-h ozone. Four diurnal flow patterns capturing different ozone exceedance scenarios are isolated; each scenario is associated with a distinct spatial distribution for atmospheric pollutants.     

An examination of the 6:00 a.m.-9:00 a.m. measurements of ozone precursors in the New York City metropolitan area

In recent years, ambient measurements of hourly ozone precursor concentrations, namely speciated and total nonmethane organic compounds (NMOCs), have become available through the Photochemical Assessment Monitoring Stations (PAMS) program. Prior to this, NMOCs were measured in the central business district using a canister to obtain the 3-hr integrated sample for the 6:00 a.m.-9:00 a.m. period. Such sampling had been carried out annually for nearly a decade at three locations in the New York City metropolitan area. The intent of these measurements, along with measurements of the other ozone precursor, NO(x), was to provide an understanding of ozone formation and the emissions loading and mix in the urban area. The analysis of NMOC and NO(x) measurements shows a downward trend in the case of NMOC. In addition, we compared the canister-based NMOC concentrations with data obtained from the PAMS program for the 6:00 a.m.-9:00 a.m. period. Analysis of the NMOC concentrations reveals poor spatial correlation between the various monitors, reflecting the effect of localized emissions. This suggests that NMOC measurements made at a single location cannot be viewed as representative of the entire region. On the other hand, correlations were found to be higher among the NO(x) monitors, indicating the commonality of emission     

Estimates of AOT ozone indices from time-integrated ozone data and hourly air temperature measurements in southwest Sweden

Surface ozone concentration and surface air temperature was measured hourly at three coastal sites, four low elevation inland sites and two high elevation inland sites in southwestern Sweden. Diurnal ozone concentration range (DOR) and diurnal temperature range (DTR) were strongly correlated, both spatially and temporally, most likely because both depended on atmospheric stability. Accumulated ozone exposure above a threshold concentration of x nmol mol⁻¹ (AOTx) was estimated from time-integrated ozone concentration (as from diffusive sampling) and measures of ozone concentration variability. Two methods both estimated 24-h AOTx with high accuracy (modelling efficiencies >90% for x ≤ 40 nmol mol⁻¹). Daytime (08:00–20:00) AOTx could not be equally well estimated. Estimates were better for lower AOT thresholds. Diffusive ozone concentration sampling, combined with hourly temperature monitoring, could be a valuable complement to ozone concentration monitoring with continuous instruments.     

Influence of synoptic and mesoscale meteorology on ozone pollution potential for San Joaquin Valley of California

The distribution of historical ozone levels for a region is tabulated as a function of its prevailing synoptic and mesoscale influences. Meteorological patterns are determined sequentially from extended records of hourly surface wind measurements sampling relevant low-level flows. A visualization method is presented to readily indicate the likelihoods for exceedances to occur under a variety of meteorological conditions. The study domain is San Joaquin Valley (SJV) of California, which is divided into three subregions (North, Central, and South). Each day from May–October of 1996–2004 is labeled using synoptic (single-day) and mesoscale (intra-day) patterns. Emissions levels are assumed roughly constant for this period following the introduction of reformulated gasoline to California. Synoptic motions largely control the regional SJV ozone pollution potential; the same single-day patterns are identified for all three SJV subregions. Additionally, a unique mesoscale flow feature is identified in each subregion that strongly affects its ozone levels: flows through minor Coast Range gaps for N-SJV, the Fresno Eddy for C-SJV, and flows through Mojave Pass for S-SJV. The strength of each mesoscale feature is characterized using 1-h surface u or v wind components that explain local ozone pollution potentials.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.     

The Characterization of Ozone,Sulfur Dioxide,and Nitrogen Dioxide for Selected Monitoring Sites in the Federal Republic of Germany

Ambient ozone, sulfur dioxide, and nitrogen dioxide data collected at 11 rural gaseous air pollution monitoring stations located throughout the Federal Republic of Germany (FRG) were characterized to provide a basis for investigating the effect these air pollutants may have on forest decline. For any given year, with the exception of the Waldhof site, the ozone monitoring sites did not experience more than 50 occurrences of hourly mean concentrations equal to or above 0.10 ppm. In most cases, the number of occurrences equal to or above 0.10 ppm at the FRG ozone monitoring sites was below the number experienced at a rural forested site located at Whiteface Mountain, New York. Several of the FRG monitoring sites experienced a large number of occurrences of hourly mean ozone concentrations between 0.08 and 0.10 ppm. Hof, Selb, Arzberg, and Waldhof experienced several occurrences of elevated levels of sulfur dioxide concentrations. The nitrogen dioxide 24-h mean concentrations were low for all sites. Because the 24-h mean data may mask the occurrence of a few high concentration events, it is not known if any of the sites that monitored nitrogen dioxide experienced short-term elevated concentrations. To gain further insight into the possible effect of pollutant mixtures on vegetation, future efforts should involve characterizing the timing of multi-pollutant exposures.     

Measurements of fine and ultrafine particles formation in photocopy centers in Taiwan

This study investigates the levels of particulate matter smaller than 2.5 μm (PM_2.5) and some selected volatile organic compounds (VOCs) at 12 photocopy centers in Taiwan from November 2004 to June 2005. The results of BTEXS (benzene, toluene, ethylbenzene, xylenes and styrene) measurements indicated that toluene had the highest concentration in all photocopy centers, while the concentration of the other four compounds varied among the 12 photocopy centers. The average background-corrected eight-hour PM_2.5 in the 12 photocopy centers ranged from 10 to 83 μg m⁻³ with an average of 40 μg m⁻³. The 24-h indoor PM_2.5 at the photocopy centers was estimated and at two photocopy centers exceeded 100 μg m⁻³, the 24-h indoor PM_2.5 guideline recommended by the Taiwan EPA. The ozone level and particle size distribution at another photocopy center were monitored and indicated that the ozone level increased when the photocopying started and the average ozone level at some photocopy centers during business hour may exceed the value (50 ppb) recommended by the Taiwan EPA. The particle size distribution monitored during photocopying indicated that the emitted particles were much smaller than the original toner powders. Additionally, the number concentration of particles that were smaller than 0.5 μm was found to increase during the first hour of photocopying and it increased as the particle size decreased. The ultrafine particle (UFP, <100 nm) dominated the number concentration and the peak concentration appeared at sizes of under 50 nm. A high number concentration of UFP was found with a peak value of 1E+8 particles cm⁻³ during photocopying. The decline of UFP concentration was observed after the first hour and the decline is likely attributable to the surface deposition of charged particles, which are charged primarily by the diffusion charging of corona devices in the photocopier. This study concludes that ozone and UFP concentrations in photocopy centers should be concerned in view of indoor air quality and human health. The corona devices in photocopiers and photocopier-emitted VOCs have the potential to initiate indoor air chemistry during photocopying and result in the formation of UFP.     

Development of a Speciated,Hourly, and Gridded Air Pollutants Emission Modeling System—A Case Study on the Precursors of Photochemical Smog in the Seoul Metropolitan Area,Korea

ABSTRACT

A speciated, hourly, and gridded air pollutants emission modeling system (SHEMS) was developed and applied in predicting hourly nitrogen dioxide (NO₂) and ozone (O₃) levels in the Seoul Metropolitan Area (SMA). The primary goal of the SHEMS was to produce a systemized emission inventory for air pollutants including ozone precursors for modeling air quality in urban areas.

The SHEMS is principally composed of three parts: (1) a pre-processor to process emission factors, activity levels, and spatial and temporal information using a geographical information system; (2) an emission model for each source type; and (3) a post-processor to produce report and input data for air quality models through database modeling. The source categories in SHEMS are point, area, mobile, natural, and other sources such as fugitive emissions. The emission database produced by SHEMS contains 22 inventoried compounds: sulfur dioxide, NO₂, carbon monoxide, and 19 speciated volatile organic compounds. To validate SHEMS, the emission data were tested with the Urban Airshed Model to predict NO₂ and O₃ concentrations in the SMA during selected episode days in 1994. The results turned out to be reliable in describing temporal variation and spatial distribution of those pollutants.     

Toxic effects of imidazolium-based ionic liquids on Caenorhabditis elegans: The role of reactive oxygen species

By using Caenorhabditis elegans (C. elegans) as a model animal, the present work is aimed to evaluate the acute toxicity of imidazolium-based bromide Ionic Liquids (ILs), and to elucidate the underlying mechanisms involved. Firstly, 24-h median lethal concentration (LC₅₀) for eight ILs with different alkyl chain lengths and one or two methyl groups in the imidazolium ring were determined to be in a range of 0.09–6.64 mg mL⁻¹. Four ILs were selected to investigate the toxic mechanisms. Mortality, levels of reactive oxygen species (ROS), lipofuscin accumulation and expression of superoxide dismutase 3 in C. elegans were determined after exposed to ILs at sub-lethal concentrations for 12 h. A significant increase in the levels of these biomarkers was observed in accordance with the results of 12-h lethality assay. The addition of 0.5% dimethyl sulfoxide, which acts as a radical scavenger, remarkably rescued the lethality of C. elegans and significantly decreased the ROS level in C. elegans. Our results suggest that ROS play an important role in IL-induced toxicity in C. elegans.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

Spatial variations of ground level ozone concentrations in areas of different scales

The spatial variation of ground level ozone concentrations was investigated for areas of three different scales: (1) an air quality management district (a region about 100×70 km²) in northern Taiwan, (2) the neighborhood (about 2 km in radius) of an air quality monitoring station, and (3) an open field (about 400×600 m²) surrounded by 3- and 4-story buildings in an elementary school. Analysis of data on hourly ozone concentration, obtained at 13 m above the ground at 21 monitoring stations in the air quality management district, showed that the stations downwind of the urban center in the district had significantly higher ozone concentrations. Measurements for 8-h average ozone concentrations at 1.5 m above the ground by passive samplers showed that, in a flat area about 2 km in radius, the ratios of the ozone concentration at open areas to that at the monitoring station (0.86–0.93) were significantly higher than those obtained at areas with higher traffic flow and density of buildings (0.60–0.68). For the open field in an elementary school, the 8-h average ozone concentrations at 1.5 m above the ground at sites less than 10 m from the nearest building were considerably lower than those at sites farther away from buildings. The results indicated that, in areas of small scales, the spatial distributions of ozone concentration were highly non-uniform and there were appreciable day-to-day variability in spatial distribution. Such variability should be taken into account in determining the extent to which an individual is exposed to ozone.     

Spatial mapping of VOC and NOx-limitation of ozone formation in central California

Ambient aerometric data were used to predict whether ozone formation at specific times and locations in central California was limited by the availability of volatile organic compounds (VOC) or oxides of nitrogen (NO_x). The predictions were compared with differences between mean weekday and weekend peak ozone values. The comparison with weekend and weekday ozone levels provided a means for empirically investigating the effects of VOC and NO_x reductions on ozone formation, because the relative proportions and levels of ozone precursor species were significantly different on weekends than on weekdays. Weekend NO_x levels averaged 27 percent lower than weekday levels at the time of the peak ozone hour. Daytime weekend levels of VOC species were also consistently lower than weekday values throughout the region, though the differences between weekends and weekdays were not always statistically significant (p<0.05). Site-to-site differences between weekend and weekday mean peak hourly ozone were related to whether ozone formation was VOC- or NO_x-limited.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

The use of ambient data to corroborate analyses of ozone control strategies

Data from environmental-chamber studies and photochemical box-model simulations were used to evaluate and revise a method for developing a qualitative understanding of the sensitivity of ozone formation at a particular time and place to changes in concentrations of volatile organic compounds (VOC) and oxides of nitrogen (NO_x). The revised method requires measurements of ozone, NO, and either NO_x or NO_y. The sensitivities of the method to biases in measurements were evaluated. The method potentially can be used for qualitative assessment of VOC versus NO_x limitation, comparison with the predictions of grid-based photochemical air-quality models, and evaluation of trends over time in the relative effectiveness of VOC versus NO_x controls.     

The use of conditional probability functions and potential source contribution functions to identify source regions and advection pathways of hydrocarbon emissions in Houston,Texas

In this study, we demonstrate the utility of conditional probability functions (CPFs), potential source contribution functions (PSCFs), and hierarchical clustering analysis (HAC) to identify the source region and transport pathways of hydrocarbons measured at five photochemical assessment monitoring stations (PAMS) near the Houston Ship Channel from June to October 2003. In contrast to scatter plots, which only show the pair-wise correlation of species, commonality in CPF figures shows both correlation and information on the source region of the species in question. In this study, we use over 50 hourly volatile organic compound (VOC) concentrations and surface wind observations to show that VOCs with similar CPF patterns likely have common transport pathways. This was established with the multivariate technique, which uses the hierarchical clustering analysis to define clusters of VOCs having similar CPF patterns. This method revealed that alkenes, and in particular those with geometric isomers such as cis-/trans-2-butene and cis-/trans-2-pentene, have similar CPF patterns and hence, a common area of origin. The alkane isomers often show CPF patterns among themselves, and similarly, aromatic compounds often show similar patterns. We also show how calculated trajectory information can be used in the PSCF analysis to produce a graphic picture that identifies specific geographic areas associated with a given VOC (or other pollutant). The use of these techniques in the chemically and meteorologically complex environment of Houston, Texas, suggests its further utility in other areas with relatively simpler conditions.     

Stochastic model to forecast ground-level ozone concentration at urban and rural areas

Stochastic models that estimate the ground-level ozone concentrations in air at an urban and rural sampling points in South-eastern Spain have been developed. Studies of temporal series of data, spectral analyses of temporal series and ARIMA models have been used. The ARIMA model (1,0,0) x (1,0,1)24 satisfactorily predicts hourly ozone concentrations in the urban area. The ARIMA (2,1,1) x (0,1,1)24 has been developed for the rural area. In both sampling points, predictions of hourly ozone concentrations agree reasonably well with measured values. However, the prediction of hourly ozone concentrations in the rural point appears to be better than that of the urban point. The performance of ARIMA models suggests that this kind of modelling can be suitable for ozone concentrations forecasting.     

Validation of the stomatal flux approach for the assessment of ozone visible injury in young forest trees. Results from the TOP (transboundary ozone pollution) experiment at Curno, Italy

This paper summarises some of the main results of a two-year experiment carried out in an Open-Top Chambers facility in Northern Italy. Seedlings of Populus nigra, Fagus sylvatica, Quercus robur and Fraxinus excelsior have been subjected to different ozone treatments (charcoal-filtered and non-filtered air) and soil moisture regimes (irrigated and non-irrigated plots). Stomatal conductance models were applied and parameterised under South Alpine environmental conditions and stomatal ozone fluxes have been calculated.The flux-based approach provided a better performance than AOT40 in predicting the onset of foliar visible injuries. Critical flux levels, related to visible leaf injury, are proposed for P. nigra and F. sylvatica (ranging between 30 and 33 mmol O₃ m⁻²). Soil water stress delayed visible injury appearance and development by limiting ozone uptake. Data from charcoal-filtered treatments suggest the existence of an hourly flux threshold, below which may occur a complete ozone detoxification.     

Background ozone levels of air entering the west coast of the US and assessment of longer-term changes

An analysis of surface ozone measurements at a west coast site in northern California (Trinidad Head) demonstrates that this location is well situated to sample air entering the west coast of the US from the Pacific Ocean. During the seasonal maximum in the spring, this location regularly observes hourly average ozone mixing ratios 50 ppbv in air that is uninfluenced by the North American continent. Mean daytime values in the spring exceed 40 ppbv. A location in southern California (Channel Islands National Park) demonstrates many of the characteristics during the spring as Trinidad Head in terms of air flow patterns and ozone amounts suggesting that background levels of ozone entering southern California from the Pacific Ocean are similar to those in northern California. Two inland locations (Yreka and Lassen Volcanic National Park) in northern California with surface ozone data records of 20 years or more are more difficult to interpret because of possible influences of local or regional changes. They show differing results for the long-term trend during the spring. The 10-year ozone vertical profile measurements obtained with weekly ozonesondes at Trinidad Head show no significant longer-term change in tropospheric ozone.