Effect of methyl tertiary butyl ether concentrations on exhaust emissions from gasoline used in the metropolitan area of Mexico City

In this work, the primary objective was to assess the impact of oxygenated fuel on the exhaust emissions from an important fraction of vehicles in the Metropolitan Area of Mexico City (MAMC). The results aim to provide information on the actual effect of MTBE on a fleet that represents more than 60% of the in-use vehicles in the MAMC. Ten vehicles were tested with a low-octane base gasoline, and 10 more with a regular-grade unleaded base gasoline. Three MTBE concentrations, 5, 10, and 15 vol %, were tested following the U.S. Federal Test Procedure (FTP). CO, total HC, and NOx from the exhaust gases were quantitatively evaluated and also characterized for FTP speciated organic emissions. From this data, the O3-forming potential of the fuels was calculated. Results show that for the fleet using low-octane gasoline, the addition of 10% MTBE substantially reduced CO emissions, but total HC concentration in the exhaust showed a modest decrease. For the regular gasoline, the 10% MTBE blend seemed to be the best choice, but there was not a significant decrease in emissions. The specific reactivity of each fuel, expressed in grams of O3 per gram of nonmethane organic gases, increased with MTBE concentration in both cases. This result is important to consider, especially for a region like Mexico City, which has high atmospheric O3 concentrations.     

Demonstrating attainment in Atlanta using urban airshed model simulations: impact of boundary conditions and alternative forms of the NAAQS

Urban Airshed Model-Version IV (UAM-IV) simulations on 7–8 July, 1988 for the Atlanta, Georgia, nonattainment area are used to investigate how recent changes in the National Ambient Air Quality Standard (NAAQS) and changes in boundary concentrations may affect attempts to comply with the standard through local emissions reductions. According to model results, the recently promulgated 8 h NAAQS at a level of 0.08 ppmv will require larger emission reductions to comply with the standard than those that are necessary to comply with the previous 1 h/0.12 ppmv NAAQS. Regardless of the form of the NAAQS or the magnitude of the concentrations of O₃ and its precursors at the model domain boundary, UAM-IV simulations for Atlanta predict that NO_x (NO+NO₂) emission reductions are more effective than volatile organic compound reductions in mitigating O₃ pollution. Moreover, the simulations indicate that NO_x emission reductions greater than 60–75% would be required to demonstrate attainment under either form of the standard, even if boundary concentrations of O₃ and its precursors were substantially reduced. Further research is necessary to determine if this weak response to emission controls is truly representative of the real atmosphere, or is a result of the meteorological conditions specific to this episode, or is an artifact of the UAM-IV model or its inputs.     

A gas/aerosol air pollutants study over the urban area of Rome using a comprehensive chemical transport model

The aim of this study was to identify areas of potential relevant exposure to pollutants within Rome's urban core. To meet this goal, intensive field campaigns were conducted and simulations were performed, using the flexible air quality regional model (FARM), to study winter and summer pollution episodes. The simulations were performed using a complete emission inventory that included traffic flow model results of the Roman street network to better describe, with respect to the available diffuse national emission inventory, the hourly variation of traffic emissions in the city. The meteorological reconstruction was performed by means of both prognostic and diagnostic models by using experimental data collected during the field campaigns. To evaluate the capability of the FARM model to capture the main features of the selected episodes, a comparison of modelled results against observed air quality data for different pollutants was performed at urban and rural sites. FARM performed well in predicting ozone (O₃) and nitrogen dioxide (NO₂) concentrations, showing a good reproduction of both daily peaks and their diurnal variations. The model also showed a good capability to reproduce the magnitude of volatile alkane, aromatic and carbonyl compound concentrations. PM₁₀ model results revealed the tendency to under-predict the observed values. PM composition model results were compared with observed data, evidencing good results for elemental carbon (EC), nitrate (NO₃⁻) and ammonium (NH₄⁺), underestimation for sulphate (SO₄²⁻) and poor performance for organic matter (OM). The soil components of PM were found to be significantly under-predicted by the model, especially during Saharan dust episodes. Overall, the study results show large areas of high O₃ and PM₁₀ concentrations where levels of pollutants should be carefully monitored and population exposure evaluated.     

Mixing depths and wind speed in an urban airshed: A note on the limits to a relationship

The relationship between mean mixing depth and wind speed in an urban airshed was tested with data from 125 airsonde flights. The experiment sustained the theory that the two variables are inversely related. However, the area of significant correlation was restricted to winds between zero and 4 m s⁻¹. An increase in wind speed beyond 4 m s⁻¹ did not appear to have a consistently decremental effect on mixing depth.     

A comparison of the predictions of a simple gaussian plume dispersion model with measurements of pollutant concentration at ground-level and aloft

The NO_x pollution arising from a nitric acid works has been analysed. Measurements were taken at ground-level using continuous monitors over a 6 month period, and aloft at three heights within the plume using a specially constructed bag sampler. The measured concentrations and σ_z values have been compared with the predictions of a simple Gaussian plume dispersion model using the Turner (1970) values of σ_y and σ_z derived from Pasquill-Gifford stability categories. It was found that ground-level concentrations at 1–2 km distance from the source could be predicted reliably, but that close to the source predicted values of σ_z were greater than those measured experimentally.     

Spray irrigation of landfill leachate: estimating potential exposures to workers and bystanders using a modified air box model and generalised source term

Generalised source term data from UK leachates and a probabilistic exposure model (BPRISC(4)) were used to evaluate key routes of exposure from chemicals of concern during the spraying irrigation of landfill leachate. Risk estimates secured using a modified air box model are reported for a hypothetical worker exposed to selected chemicals within a generalised conceptual exposure model of spray irrigation. Consistent with pesticide spray exposure studies, the key risk driver is dermal exposure to the more toxic components of leachate. Changes in spray droplet diameter (0.02-0.2 cm) and in spray flow rate (50-1000 l/min) have little influence on dermal exposure, although the lesser routes of aerosol ingestion and inhalation are markedly affected. The risk estimates modelled using this conservative worst case exposure scenario are not of sufficient magnitude to warrant major concerns about chemical risks to workers or bystanders from this practice in the general sense. However, the modelling made use of generic concentration data for only a limited number of potential landfill leachate contaminants, such that individual practices may require assessment on the basis of their own merits.     

Low cost measurements of nitrogen and sulphur dry deposition velocities at a semi-alpine site: gradient measurements and a comparison with deposition model estimates

The conditional time averaged gradient method was used to measure air-surface exchange of nitrogen and sulphur compounds at a semi-alpine site in Southern Norway. Dry deposition velocities were then obtained from the bi-weekly concentration gradient measurements. Annual deposition velocities were found to be 1.4, 11.8 and 4.0 mm s(-1) for NH3, HNO3 and SO2, respectively, if all data were included, and to be 10.8, 11.8 and 13.0 mm s(-1), respectively, if only positive values were included. Measured deposition velocities were compared to two sets of values estimated from a big-leaf dry deposition module applying to two different land types (short grass and forbs, and tundra), driven by measured micrometeorological parameters. The deposition module gives reasonable values for this site throughout the year, but does not reproduce the large variability as shown in the measured data. No apparent seasonal variations were found from either measurements or module estimates due to the very low productivity of the studied area.     

The chernobyl accident: Modelling of dispersion over europe of the radioactive plume and comparison with air activity measurements

Following the release of radionuclides from the Chernobyl power plant accident, a long-range transport and deposition model is used to describe the plume dispersion over Europe. The aim of this study is the validation of a fast Lagrangjan model and a better understanding of the relative impact of some mechanisms, such as the initial plume rise. Comparisons between results and ¹³⁷Cs measurement activity are discussed according to spatial and temporal variations. It is shown that many measurements can be explained only if the initial plume rise taken at 925, 850 and 700mb is considered.     

Application of a Lagrangian particle model to assess the impact of harbour,industrial and urban activities on air quality in the Taranto area,Italy

This paper evaluates the relative impact on air quality of harbour emissions, with respect to other emission sources located in the same area. The impact assessment study was conducted in the city of Taranto, Italy. This area was considered as representative of a typical Mediterranean harbour region, where shipping, industries and urban activities co-exist at a short distance, producing an ideal case to study the interaction among these different sources. Chemical and meteorological field campaigns were carried out to provide data to this study. An emission inventory has been developed taking into account industrial sources, traffic, domestic heating, fugitive and harbour emissions. A 3D Lagrangian particle dispersion model (SPRAY) has then been applied to the study area using reconstructed meteorological fields calculated by the diagnostic meteorological model MINERVE. 3D short term hourly concentrations have been computed for both all and specific sources. Industrial activities are found to be the main contributor to SO₂. Industry and traffic emissions are mainly responsible for NO_x simulated concentrations. CO concentrations are found to be mainly related to traffic emissions, while primary PM₁₀ simulated concentrations tend to be linked to industrial and fugitive emissions. Contributions of harbour activities to the seasonal average concentrations of SO₂ and NO_x are predicted to be up to 5 and 30 μg m⁻³, respectively to be compared to a overall peak values of 60 μg m⁻³ for SO₂ and 70 μg m⁻³ for NO_x. At selected urban monitoring stations, SO₂ and NO_x average source contributions are predicted to be both of about 9% from harbour activities, while 87% and 41% respectively of total concentrations are predicted to be of industrial origin.     

Modeling air/sea flux parameters in a coastal area: A comparative study of results from the TOGA COARE model and the NOAA Buoy model

Because estuaries and coastal regions are particularly susceptible to nutrient over-enrichment due to their close proximity to source-rich regions, a goal of the BRACE study was to improve estimates of nitrogen air/sea transfer rates in the Tampa Bay Estuary. Our objective was to critically evaluate two air/sea gas exchange models to determine their efficacy for use in a coastal region, with the ultimate goal of improving nitrogen exchange estimates in Tampa Bay. We used meteorological data and oceanographic parameters collected hourly at an instrumented tower located in Middle Tampa Bay, Florida. The data was used to determine the friction velocity and the turbulent flux of heat and moisture across the air/sea interface and then compared with modeled parameters at the same offshore site. On average both models underpredicted sensible heat flux and there was considerable scatter in the data during stable conditions, indicating that nitrogen gas exchange rates may also be underestimated. Model improvement, however, was observed with friction velocity comparisons. Model inter-comparisons of sensible heat flux and friction velocity suggest excellent agreement between the TOGA COARE and the NOAA Buoy models, but model estimated heat transfer coefficients and latent heat fluxes did not agree as well. Based on our analysis, we conclude that both models are suitable for use in a coastal environment to estimate nitrogen air/sea gas exchange, although the NOAA Buoy model requires fewer meteorological inputs. However, if the purpose is to conduct more sophisticated microscale modeling of air/sea interactions, we recommend the TOGA COARE model.     

Mercury and methyl mercury in higher fungi and their relation with the substrata in a cinnabar mining area

195 specimens of higher fungi and their substrata collected in the Hg mining area of M.Amiata and around Siena (Central Italy), were analyzed for their total Hg content. Whereas wood decomposers and many species of mycorrhizal fungi accumulated the metal at a very low rate, some mycorrhizal species and all the humus decomposers may accumulate up to 100 μg.g^?1d.w. of Hg and in the least contaminated sites, up to 63 times as much Hg as the substratum. Instead in mineralized areas the concentration factor rarely exceeded 1. The methyl mercury content of 35 species (almost all edible), ranged between 0.01 and 3.7 μg.g^?1 d.w..The possible significance of these findings and the toxicologic implications for local co$\text{n}$ sumers are considered.     

Monitoring air quality with lichens: a comparison between mapping in forest sites and in open areas

Four different methods of epiphytic lichen mapping were used for the assessment of air quality in the region under the influence of the Sostanj Thermal Power Plant (Salek Valley, Slovenia). Three methods were based on the presence of different lichen species (VDI, EU and ICP-Forest), the fourth on a frequency and coverage assessment of different growth forms of epiphytic lichens, e.g. crustose, foliose and fruticose (SI). A comparison of the results from the assessment of air quality between forest sites (ICP-Forest, SI) and open areas (VDI, EU and SI), obtained by the different methods of epiphytic lichen mapping, is presented in the contribution. Data showed that lichen species richness is worse in forest sites in comparison with open areas. From the data obtained it can be concluded that epiphytic lichen mapping in open areas is a better method for the assessment of air pollution in a given area than mapping in forest sites. The species-based methods in open areas are more powerful and useful for air quality assessment in polluted research areas than the SI and ICP-Forest methods.     

Wastewater treatment plants and landfills emit volatile methyl siloxanes (VMSs) to the atmosphere: investigations using a new passive air sampler

Volatile methyl siloxanes (VMSs) are a class of chemicals with an increasing range of applications and widespread distribution in the environment. Passive air samplers (PAS) comprising sorbent-impregnated polyurethane-foam (SIP) disks were first calibrated and then deployed around two wastewater treatment plants (WWTPs) and at two landfill sites to investigate inputs of VMSs to air. SIP-derived air concentrations for ΣVMSs (ng/m³) at background sites on the perimeter of the WWTP were 479 ± 82.3 and comparable to results for the upwind samples at the landfills (333 ± 194). Order of magnitude higher concentrations of ΣVMSs (ng/m³) were found for on-site samples at the WWTPs (3980 ± 2620) and landfills (4670 ± 3360). Yearly emissions (kg/yr) to air were estimated and ranged from 60-2100 and 80-250, respectively, for the cyclic VMSs. These findings demonstrate and quantify for the first time, waste sector emissions of VMSs to the atmosphere.     

Emission and Fate Assessment of Methyl Tertiary Butyl Ether in the Boston Area Airshed Using a Simple Multimedia Box Model: Comparison with Urban Air Measurements

Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m³ MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m³ and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

Analysis of photochemical pollution in summer and winter using a photochemical box model in the center of Tokyo, Japan.

In order to give an effective and rapid analysis of the photochemical pollution and information for emission control strategies, a photochemical box model (PBM) was applied to one moderate summer episode, 11 July 1996, and one typical winter episode, 3 December 1996, in the center of Tokyo, Japan. The box model gave a good prediction of the photochemical pollution with minimal investment. As expected, the peak ozone in summer is higher than in winter. The NOx concentrations in winter are higher than those in summer. In summer, NO and NO2 have one peak in the morning. In winter, NO and NO2 show two peaks during the day. Three model runs including no reactions, a zero ozone boundary condition and dark reactions were conducted to understand the photochemical processes. The effects of emission reduction on the formation of the photochemical pollution in the center of Tokyo have been studied. The results show that the reduction of NMHC emission can decrease the ozone, however, the reduction of NOx emission can increase the ozone. It can be concluded that if the NOx emission are reduced, the reduction of NMHC should be more emphasized in order to decrease the ozone concentration in the center of Tokyo, Japan, especially the reduction of the NMHC from stationary source emission.     

UV-C-activated persulfate oxidation of a commercially important fungicide: case study with iprodione in pure water and simulated tertiary treated urban wastewater

Recently, the European Food Safety Authority (EFSA) has banned the use of iprodione (IPR), a common hydantoin fungicide and nematicide that was frequently used for the protective treatment of crops and vegetables. In the present study, the treatment of 2 mg/L (6.06 μM) aqueous IPR solution through ultraviolet-C (UV-C)-activated persulfate (PS) advanced oxidation process (UV-C/PS) was investigated. Baseline experiments conducted in distilled water (DW) indicated that complete IPR removal was achieved in 20 min with UV-C/PS treatment at an initial PS concentration of 0.03 mM at pH?=?6.2. IPR degradation was accompanied with rapid dechlorination (followed as Cl^? release) and PS consumption. UV-C/PS treatment was also effective in IPR mineralization; 78% dissolved organic carbon (DOC) was removed after 120-min UV-C/PS treatment (PS?=?0.30 mM) compared with UV-C at 0.5 W/L photolysis where no DOC removal occurred. LC analysis confirmed the formation of dichloroaniline, hydroquinone, and acetic and formic acids as the major aromatic and aliphatic degradation products of IPR during UV-C/PS treatment whereas only dichloroaniline was observed for UV-C photolysis under the same reaction conditions. IPR was also subjected to UV-C/PS treatment in simulated tertiary treated urban wastewater (SWW) to examine its oxidation performance and ecotoxicological behavior in a more complex aquatic environment. In SWW, IPR and DOC removal rates were inhibited and PS consumption rates decreased. The originally low acute toxicity (9% relative inhibition towards the photobacterium Vibrio fischeri) decreased to practically non-detectable levels (4%) during UV-C/PS treatment of IPR in SWW.

     

Emission measurements of heavy metals with the European standard reference methods EN 14385 and EN 13211—observations from interlaboratory comparison (ILC) measurements performed at waste-to-energy plant in Finland

ABSTRACT

This study presents the heavy metal results obtained during Finnish interlaboratory comparison (ILC) measurements made during 2019. The aim of this measurement campaign was to verify the skills of accredited emission measurement teams and also to evaluate the challenges that stack testing teams face in the future when emission levels decrease. ILCs have been organized in Finland since the 1970s. ILCs provide an important platform for stack testing teams so that they can verify their measurement skills and also for the dissemination of knowledge. The knowledge about the measurement standards and their requirements has improved among stack testing teams during past years in Finland. As emission levels get lower, they still need to pay more attention to some quality assurance procedures, e.g. to method and field blanks. Based on the observations of this ILC for heavy metals it can be noted that the challenges that stack testing teams face are related to the fact that no guidance is given in the standard reference methods EN 13211 and EN 14385 for example on the calculation of measurement uncertainties and how results below limit of quantification should be taken into account. These reference methods were suitable for their purpose at the time they were validated. However, emission levels are now more stringent and it is challenging to measure them with acceptable uncertainty criteria. As a consequence, there is a clear need for harmonized approaches in Europe for consistent implementation of standards and regulations. Key issues where guidance should be provided include realistic measurement uncertainties at low concentration levels, reporting low concentrations and guidance on how measurement uncertainties should be taken into account when the results are used for compliance assessment. The overall aim is to ensure that even with low emission levels, the emission measurement results would be transparent and robust throughout the EU.

Implications: Interlaboratory comparison measurements between stack testing teams are the most important tool to verify the quality of the measurements. Participation in an appropriate ILC is often mandatory to successfully achieve accreditation under ISO/IEC 17025. Such campaigns also provide an efficient platform for dissemination of knowledge. In addition, ILCs can be used to clarify the challenges that teams nowadays face when measuring low emission levels, thus creating important information for the revision work of standards.     

Comparison of the performances of land use regression modelling and dispersion modelling in estimating small-scale variations in long-term air pollution concentrations in a Dutch urban area

The performance of a Land Use Regression (LUR) model and a dispersion model (URBIS – URBis Information System) was compared in a Dutch urban area. For the Rijnmond area, i.e. Rotterdam and surroundings, nitrogen dioxide (NO₂) concentrations for 2001 were estimated for nearly 70 000 centroids of a regular grid of 100 × 100 m.A LUR model based upon measurements carried out on 44 sites from the Dutch national monitoring network and upon Geographic Information System (GIS) predictor variables including traffic intensity, industry, population and residential land use was developed. Interpolation of regional background concentration measurements was used to obtain the regional background. The URBIS system was used to estimate NO₂ concentrations using dispersion modelling. URBIS includes the CAR model (Calculation of Air pollution from Road traffic) to calculate concentrations of air pollutants near urban roads and Gaussian plume models to calculate air pollution levels near motorways and industrial sources. Background concentrations were accounted for using 1 × 1 km maps derived from monitoring and model calculations.Moderate agreement was found between the URBIS and LUR in calculating NO₂ concentrations (R = 0.55). The predictions agreed well for the central part of the concentration distribution but differed substantially for the highest and lowest concentrations. The URBIS dispersion model performed better than the LUR model (R = 0.77 versus R = 0.47 respectively) in the comparison between measured and calculated concentrations on 18 validation sites. Differences can be understood because of the use of different regional background concentrations, inclusion of rather coarse land use category industry as a predictor variable in the LUR model and different treatment of conversion of NO to NO₂.Moderate agreement was found between a dispersion model and a land use regression model in calculating annual average NO₂ concentrations in an area with multiple sources. The dispersion model explained concentrations at validation sites better.     

Semivolatile PAH and n-alkane gas/particle partitioning using the dual model: up-to-date coefficients and comparison with experimental data

The gas/particle partitioning coefficient K _p , of a semivolatile compound is a key parameter for its atmospheric fate. The most complete method of predicting K _p for polycyclic aromatic hydrocarbons (PAHs) is offered by the dual model, as it describes both the adsorption on soot and absorption into organic matter processes. However, experimental and model data exist almost exclusively for PAHs. In order to bridge this gap, experimental data on the phase partitioning of both PAHs and n-alkanes were collected at an urban and a remote site. Moreover, all the necessary parameters (e.g., octanol–air and soot–air partitioning coefficients) for the dual model have been collected and updated or (if missing) estimated for the first time. The results point out that both absorption and adsorption seem to contribute to the partitioning of PAHs and n-alkanes. However, it seems that the dual model always underestimates the particle sorption not only for PAHs but also for n-alkanes.