Evaluation of Pollutant Emissions Related to the Use of MMT in Gasoline

Since 1976, methylcyclopentadienyl manganese tricarbonyl (MMT), an organic derivative of Mn, has been used in Canada as an anti-knock agent in unleaded gasoline. In a preliminary evaluation of the contribution of MMT to urban air pollution, the CO and NO_x emissions of 10 vehicles each having traveled less than 17 000 miles were sampled. Five of these vehicles were filled with MMT-free gasoline and the remaining five with MMT-added gasoline. The emissions were evaluated according to the Federal Test Procedure which simulates urban and highway driving cycles. As for the NO_x and CO analysis, it was carried out by means of infrared spectrometry, while the concentration of Mn in the gasoline was determined through neutron activation. Overall, the amount of CO emitted by the vehicles using MMT-added gasoline was 1.48 g mile^-1 ± 1.77. The amount emitted by the vehicles using clear (MMT-free) gasoline was 0.74 g mile^-1 ± 0.88. As for the NO_x emission level, it was 0.20 g mile^-1 ± 0.15 for the vehicles using MMT-added gasoline vs 0.17 g mile^-1 ± 0.18 for the vehicles using clear gasoline. However, probably due to the small sample size and the very high level of emission of one of the vehicles using MMT-added gasoline, these differences are not statistically significant. Further studies should take into account variables such as the driving history and the representativity of the fleet of vehicles tested.     

Gaseous Emissions During the Coal Mining Activity and Neutralizing Capacity of Ammonium

This paper presents the simultaneous measurement of atmospheric concentration of gaseous NH₃, SO₂ and NO₂, and particulate NH ₄ ⁺ released from the mining activities of coal-mine area, Tirap colliery, Margherita (Assam). Gas samples were collected by impinger method and were analyzed colorimetrically. The vapor-phase concentration of NH₃, SO₂, and NO₂ range between 4.7?C40.03, 1.47?C6.14, and 1.92?C2.40???g/m³. The NH ₄ ⁺ concentration in PM₁₀ and PM_2.5 ranges between 0.02?C0.07 and 0.008?C0.03???g/m³, respectively. Moderately high concentrations of NH₃ and SO₂ on the first day were due to the coal-burning activity near the sampling site, while the low concentration of NO₂ is due to less vehicle density near the sampling point. All the observed concentrations are below than those reported for the urban areas and the prescribed limit fixed by National Ambient Air Quality Standard, India. Study indicates that ammonia is the major neutralizing agent for sulfate and nitrate ions present in the particulate matter during mining activities.     

The Effect of Air Pollution on Yield and Quality of Mung Bean Grown in Peri-Urban Areas of Varanasi

There is growing concern that air pollution may have adverse impacts on crops in developing countries, yet this has been little studied. This paper addresses this issue, for a major leguminous crop of the Indian sub continent, examining the effect of air pollution in and around an Indian city. A field study was conducted using a gradient approach to elucidate the impact of air pollutants on selected production characteristics of Vigna radiata L. cv. Malviya Jyoti (mung bean) plants grown from germination to maturity at locations with differing concentrations of air pollutants around peri-urban and rural areas of Varanasi. The 6 -h daily mean SO₂, NO₂ and O₃ concentrations varied from 8.05 to 32.2 ppb, 11.7 to 80.1 ppb and 9.7 to 58.5 ppb, respectively, between the sites. Microclimatic conditions did not vary significantly between the sites. Changes in plant performance at different sites were evaluated with reference to ambient air quality status. Reductions in biomass accumulation and seed yields were highest at the site experiencing highest concentrations of all three gaseous pollutants. The magnitude of response indicated that at peri-urban sites SO₂, NO₂ and O₃ were all contributing to these effects, whereas at rural sites NO₂ and O₃ combinations appeared to have more influence. The quality of seed was also found to be negatively influenced by the ambient levels of pollutants. It is concluded that the air pollution regime of Varanasi City causes a major threat to mung bean plants, both in terms of yield and crop quality, with serious implications for the nutrition of the urban poor.     

Exposure of Gas Station Attendants to Methylcyclopentadienyl Manganese Tricarbonyl (MMT) Used in Gasoline

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic derivative of manganese (Mn) used in Canada as an antiknock agent and octane enhancer in gasoline. In a recent study, we measured the atmospheric concentrations of MMT at selected outdoor sites in Montreal. Results ranged from 0.18 to 25 ng m^-3 (expressed as Mn) and do not reflect personal exposure levels. The highest values were obtained at a gas station (mean of 12 ng m^-3). By extension, evaluation of the personal exposure of gas station attendants constitutes a promising area of research. In an earlier study, the sampling method used allowed the possibility that the samples could have included ultra-fine particles, which may have passed through the filters used, and the chemical analysis used (neutron activation) did not discriminate between MMT and other Mn compounds. The present study aims to validate an improved sampling method and to assess personal exposure of gas station attendants to MMT. The MMT recovery of the new sampling method was found to be 91.6%. The exposure of 13 gas station attendants was measured on 1 to 6 occasions each (n = 32). They were working in two busy gas stations located in Montreal and they were asked to wear a portable pump for 2 hr. The air was pumped through two tubes in series filled with the adsorbent Tenax TA?, with glass wool plugs at both ends. The tubes were wrapped in aluminum foil and samples were analyzed for MMT by gas chromatograph-atomic emission detector (GC-AED). Results vary between 0.3 and 11.4 ng m^-3, with a mean of 3.9 ng m^-3. The highest values obtained in the first study may be due to the analytical techniques used previously, where detection of different Mn compounds other than MMT was possible. Since GC-AED is specific to MMT in the samples, the MMT found in air raises doubt as to the time required for the photodegradation of MMT.

     

Reduced Atmospheric Manganese in Montreal Following Removal of Methylcyclopentadienyl Manganese Tricarbonyl (MMT)

Methylcyclopentadienyl manganese tricarbonyl (MMT) was used between 1990 and 2003 as an antiknock agent and as an octane booster in Canadian unleaded gasoline. Its combustion leads to Mn emissions. The objective of this research was to examine the variations in atmospheric Mn in Montreal (Canada) from 2001 to 2007, covering the period prior (2001?C2003) to and following (2005?C2007) MMT use. Three sampling stations were selected because of their proximity to roads with widely differing and well-known traffic patterns. Filters from 2001 to 2007 were obtained from the Montreal Urban Community. The first sample of each month was selected, and Mn analysis was performed by neutron activation analysis. Total suspended particulates (TSP) was calculated by weighing the filters before and after dust collection. Results show a significant decrease of Mn over time at each station, whereas TSP decreased significantly in two stations. Comparing atmospheric Mn during and after the period of use of MMT 2001?C2003 vs 2005?C2007 showed a significant decrease at all stations. For TSP, only one station showed borderline significant decline between these two periods. Overall, between the two periods, Mn and TSP decreased by 39% and 17%, respectively. These data suggest that the combustion of MMT led to an increase of airborne Mn of approximately 22%. These findings should help in decision-making processes concerning the use of MMT in gasoline in other countries.     

An Integrated Assessment Model for Fine Particulate Matter in Europe

Exposure to fine particles in the ambient air is recognized as a significant threat to human health. Two pathways contribute to the particle burden in the atmosphere: Fine particles originate from primary emissions, and secondary organic and inorganic particles are formed from the gas phase from the emissions of 'conventional' pollutants such as SO₂, NO_x, VOC and NH₃. Both types of particulate matter can be transported over long distances in the atmosphere. An integrated assessment model for particulate matter developed at IIASA addresses the relative importance of the different types of particulates, distinguishing primary and secondary particles and two size fractions. The model projects these emissions into the future and seeks cost-effective strategies for reducing health risks to population. The model integrates the control of primary emissions of fine particles with strategies to reduce the precursor emissions for the secondary aerosols. Preliminary results addressing the PM_2.5 fraction of both primary and secondary particulate matter indicate that in Europe the exposure to particulates will be significantly reduced as a side effect of the emission controls for conventional air pollutants (SO₂, NO_x, NH₃).     

Chemical Composition of Air, Soil and Vegetation in Forests of the Silesian Beskid Moutains, Poland

For the first time concentrations of trace nitrogenous (N) air pollutants, gaseous nitric acid (HNO₃), nitrous acid (HNO₂), ammonia (NH₃), and fine particulate nitrate (NO₃) and ammonium (NH₄), were measured in the montane forests of southern Poland. Determinations were performed in two forest locations of the Silesian Beskid Mountains in the western range of the Carpathian Mountains, and in an industrial/urban location in Karowice, Poland. The measurements performed in summer 1997 with honeycomb denuder/filter pack systems showed elevated concentrations of the studied pollutants. These findings agree with the low carbon/nitrogen (C/N) ratios and the results of ¹⁵N analyses of soil and moss samples. High concentrations of N air pollutants help to explain previously determined high levels of NO₃ and NH4 deposition to Norway spruce (Picea abies Karst.) canopies in these mountains. Ambient concentrations of sulfur dioxide (SO2) and ozone (O3) were elevated and potentially phytotoxic. Deficiencies of phosphorus (P) and magnesium (Mg) in Norway spruce foliage were found while concentrations of other nutrients were normal.     

A Computational Approach Based on GIS Technology for the Development of an Anthropogenic Emission Inventory of Gaseous Pollutants in Greece

This paper describes a computational system developed for the compilation of an anthropogenic emission inventory of gaseous pollutants for Greece. The inventory was developed using a geographical information system integrated with SQL programming language to provide high temporal gridded emission fields for CO, NO₂, NO, SO₂, NH₃ and 23 non-methane volatile organic compounds (NMVOCs) species for the reference year 2003. Activity and statistical data from national sources were used for the quantification of emissions from the road transport, the other mobile sources and machinery sectors and from range activities using top-down or bottom-up methodologies. Annual emission data from existing national and European emission databases were also used. The emission data were spatially and temporally disaggregated using source-specific spatiotemporal indicators. On national scale, the road transport sector produces about 60% of the annual CO and NMVOC total emissions, with gasoline vehicles being the main CO and NMVOC emissions source. The road transport is responsible for approximately half of the higher alkanes and for more than half of the ethene and toluene emissions. The maritime sector accounts for about 40% of the annual total NO_x emissions, most of which are emitted by the international shipping subsector, whilst SO₂ is emitted mainly by the energy sector. The evaluation of the emissions inventory suggests that it provides a good representation of the amounts of gaseous pollutants emitted on national scale and a good characterisation of the relative composition of CO and NO_x emission in the large urban centres.     

Effects of air pollution on the searching behaviour of an insect parasitoid

To assess the impact of air pollutants on the population dynamics of herbivores, the effects of pollutants on their natural enemies including predators, parasites, and pathogens must be evaluated in addition to direct effects and indirect effects mediated via the host plant. Insect parasitoids are an important group of such natural enemies providing many examples of partial or complete biological control of pest species. This study examined the effects of air pollutants (ozone (O₃), sulphur dioxide (SO₂), and nitrogen dioxide (NO₂)) on the searching behaviour of insect parasitoids. A series of experiments comprising short-term, closed chamber fumigations of O₃, SO₂, and NO₂ (100 nl l^?1) of the braconid parasitoid (Asobara tabida) and aggregated distributions of its host larvae (Drosophila subobscura) was set up. Analysis of chamber results showed that the proportion of hosts parasitised and the searching efficiency of the parasitoids were both significantly reduced with O₃ fumigation, but not with NO₂ or SO₂ fumigations. O₃ fumigation reduced percentage parasitism by approximately 10%. Parasitoids were able to avoid patches with no hosts, both in filtered air controls and when exposed to pollutants. However in the O₃ and NO₂ treatments they appeared less able to discriminate between different host densities, suggesting that pollutants may interfere with the olfactory responses of the parasitoids. These results indicate the potential for air pollutants, particularly O₃, to negatively influence the searching behaviour of parasitoids, and hence reduce the efficiency of natural enemy control of many pest species.     

Effects of gaseous air pollutants on secondary chemistry of Scots pine and norway spruce seedlings

Plant secondary compounds have an important role in defense responses against herbivores and pathogens. This study summarises published and some unpublished data from a series of fumigation experiments where Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) seedlings were exposed to different concentrations of gaseous air pollutants, ozone (O₃), sulphur dioxide (SO₂) or nitrogen dioxide (NO₂), in growth chambers. Concentrations of monoterpenes, resin acids and total phenolics were studied. Overall, needle monoterpenes were not affected by pollutants. Only very high level of O₃ (600 ppb) decreased concentration of some individual monoterpenes in pine needles. O₃ did not have effect on concentrations of resin acids in pine needles. In contrast, the concentration of some individual resin acids increased in O₃-exposed pine shoots and in O₃-exposed needles of one spruce clone. The highest dose of SO₂ decreased concentrations of resin acids in pine needles, but low exposure levels did not have effects. However, SO₂ had no effects on the resin acids concentrations of spruce needles, except some minor individual compounds were affected in clonal spruces. Increased concentrations of resin acids was found in pine shoots exposed to NO₂. Total phenolics of needles were not affected by pollutants. These observations suggest that among secondary compounds there is variation in sensitivity to air pollutants and genetically different trees have different responses to air pollutants.     

Evidence of Long-Range Transport of Pollutants from the Size-Fractionated Ionic Composition of Aerosols in the Jeju Island of Korea

The ionic composition of total suspended particulate (TSP) and fine (PM_2.5) fractions was investigated from an 1,100 site in the middle of Mt. Halla in Jeju Island, Korea from March to November 2006. The sum concentrations of cation and anion species in TSP fraction were 205 ± 170 and 183 ± 164 neq m^?3, respectively, while those for PM_2.5 as 118 ± 129 and 88.5 ± 89.3 neq m^?3, respectively. In TSP, the concentration of the major ions changed in the order of SO₄ ^2? > NH₄ ⁺ > Ca²⁺ > Na⁺ > NO₃ ^? > Mg²⁺ > K⁺ > Cl^?, while its PM_2.5 counterpart as NH₄ ⁺ > SO₄ ^2? > Ca²⁺ > NO₃ ^? > Na⁺ > Mg²⁺ > K⁺ > Cl^?. Inspection of the temporal variabilities of ionic components indicated that most ions peaked in spring or fall months. The back trajectory analysis showed that the atmospheric composition of the major ionic species was affected fairly sensitively by long-range transport from China under the favorable meteorological conditions. In contrast, the lowest ionic concentration levels were seen most abundantly, when air masses passed from South Sea. Hence, the analysis of ionic concentration data suggests that their distributions are controlled by the combined effects of various source processes including the most prominent Chinese origin and the meteorological condition favorable for such transport.     

SO2 Transformation in controlled atmosphere leading to the production of aerosol particles

The photochemical transformation of SO₂ and the generation of aerosol particles are investigated in a variety of atmospheres, with and without initial aerosols, in clean and polluted air, and with various pollutants. The pollutants in addition to the SO₂ include O₃, NO, NO₂ and water vapor in a variety of combinations. The most striking finding is, that only with the combination of SO₂, NO₂, and H₂O is the aerosol particle production large.     

A Cost-Effective Methodology for Spatial Concentration Distributions of Urban Air Pollutants

A methodology to determine economically the spatial concentration distribution of the air pollutants of carbon monoxide (CO), sulphur dioxide (SO₂), nitrogen monoxide (NO), nitrogen dioxide (NO₂), oxides of nitrogen (NO_x) and traffic rates (TR) is described. It involves the immediate transfer of samples from field to analysers for measurement and a subsequent statistical treatment. The proposed methodology has been applied in Patras using 5 and 50-l Teflon air sample bags, sampling at least 12 to 36-l actual volumes within a 20-min time interval. Totally, 221 pairs of 5-l and 112 single 50-l samples were randomly picked in morning rush hours of working days from 64 locations of a 40.0-km² area during a winter period, when peaks of primary air pollutants usually occur due to high traffic rates and systematic inversions. Measurements were used to statistically calculate spatial average levels approximating 1-h mean concentrations with acceptable mean probable errors less than 25 % for indicative random sampling. The 1-h levels were strongly correlated to the corresponding traffic rates. Iso-concentration diagrams indicated possible zones susceptible to high pollution levels and helped to check the location appropriateness of the existing monitoring stations for (a) fixed urban-background measurements at the Vas. Georgiou A’ Sq., which was ideal, and (b) fixed traffic-oriented measurements, which should be relocated to the Ipsilon Alonion Sq. In addition, data helped to determine other points where indicative measurements should be performed. Data could be very useful for the Patras air quality assessment in conjunction with model predictions and/or objective estimation methods.     

Effects of gaseous pollutants on forests in Eastern North America

The purpose of this paper is to summarize the current state of knowledge concerning direct forest damage caused by atmospheric gaseous pollutants. The major gaseous pollutants affecting forest growth are O₃, SO₂, and HF. Ozone is the most prevalent phytotoxic air pollutant on a regional scale in eastern North America. It has been demonstrated to cause foliar injury and growth effects on trees in both laboratory and field studies. Both SO₂ and HF have been found to cause damage to forests primarily in the vicinity of strong point sources. Case histories of forest damage are reported in the paper which describe foliar and radial growth effects, with associated volume losses. Threshold levels of the gaseous pollutants causing effects on forest growth are provided.     

Evaluation of extreme pollution episodes over Lithuania in 1980–1994

The investigation of SO₂, NO₂, benzo(a)pyrene (BP) and soot (C_el) has been carried out daily in the atmospheric air in the background station Preila (East shore of the Baltic Sea) since 1980. Over this period, daily concentrations of pollutants varied in the wide intervals in warm and cold period as well. From 15 years data typical episodes of highest and lowest concentrations of pollutants are chosen and analysed with respect to the air masses trajectories and meteorological conditions. The highest concentrations of SO₂, NO₂, BP, Cd were fixed, when the air masses passing Lithuania have been formed over Great Britain and Central Europe.     

Dating of a Sediment Core by 210Pbex Method and Pb Pollution Chronology in the Palermo Gulf (Italy)

In a few cases, atmospheric particulate matter characterization was taken into account together with aerobiological monitoring but never in an archive. The aim of this study was to estimate the air quality, by means of both chemical–physical and microbiological studies, at the Ca’ Granda Historical Archive (Milan, Italy) that houses an important collection of documents from the 12th century. Temperature and relative humidity were measured in the rooms. Particulate matter (PM2.5) concentrations were quantified and the chemical composition, in terms of ionic components, elements, and carbonaceous fraction (total, organic, and elemental carbon) determined. The gaseous pollutants NO₂, SO₂, and O₃ and indoor acidity were also measured. Aerobiological monitoring (aerobic heterotrophic bacteria and fungi) was performed as volumes stored in the Archive were composed of organic materials, a potential energy and carbon source. In this paper, we present our findings and propose some guidelines for a better preservation of the documents.     

Effects of gaseous air pollutants on aphid performance on Scots pine and Norway spruce seedlings

Aphids are frequently found on conifers, but mass outbreaks are seldom reported. On trees stressed by air pollutants the natural resistance can be broken and insect attack combined with pollution stress may promote plant damages. To evaluate effects of air pollution on conifer aphids Scots pine and Norway spruce seedlings have been exposed to gaseous pollutants (O₃, SO₂ and NO₂) in growth chambers. The studied aphid species were Cinara pilicornis Hartig on Norway spruce, C. pinea (Mordv.) and Schizolachnus pineti Fabr. on Scots pine in SO₂ fumigations and S. pineti in O₃ and NO₂ fumigations. C. pilicornis nymphs had peaked dose response to SO₂ concentration. Both the first and third instar larvae of C. pilicornis showed highest mean relative growth rate (MRGR) at 100 ppb SO₂ concentration. MRGR of C. pinea peaked at 50 and 150 ppb SO₂ The response of S. pineti was more inconsistent During fumigation the peak MRGR of S. pineti was at 100 ppb and after exposure at 50 ppb SO₂. MRGR of S. pineti nymphs was not significantly affected during fumigation or after the end of fumigation experiment by 100 ppb O₃ or 100 ppb NO₂ or the mixtures. The results suggest that SO₂ affects more distinctively on aphid performance on conifers than O₃ or NO₂. Especially stem-feeding aphids on spruce can exploit physiological disturbance of host plant under pollution stress.     

Sulphur and nitrogen nutrition and misting effects on the response of bluegrass to ozone,sulphur dioxide,nitrogen dioxide or their mixture

Kentucky bluegrass (Poa pratensis L.) plants, cultivars Cheri, Merion and Touchdown were grown at complete nutrition or with low S or low N. Plants were exposed to 10 ppm (v/v) O₃ for 6 h d^?i, 15 pphm SO₂ continuously, 15 pphm NO₂ continuously, or their mixture at these concentrations for 10 days. The severity of injury was much increased by misting with deionized water for 5 min twice daily, especially with SO₂ and NO₂ single gas exposures. The misting did not have consistent effects on total S, total N, leaf area or fresh weight. Exposure to O₃ decreased leaf area without affecting S or N content, while SO₂ usually increased total S and, in some cases, increased total N. Exposure to NO₂ increased total N without affecting total S, and the mixture increased both total S and total N. Low S or low N usually enhanced the effect of SO₂ or NO₂, respectively. Leaf area and fresh weight were not as responsive to the treatments as total S and total N. Rainfall outdoors may be a major meteorological factor affecting plant injury response to gaseous pollutants.     

Simultaneous Determination of Gas and Particle Dry Deposition onto Conditioned Surrogate Surfaces

Aerodynamically designed surrogate surfaces were used to determine the relative importance of gaseous (SO₂, HNO₃, NH₃) and particulate species (SO₄ ^2?, NO₃ ^?, NH₄ ⁺, Ca²⁺) in the dry deposition flux. For 11 sampling periods, we measured the deposition fluxes, ambient gaseous concentrations, size distributions of atmospheric aerosols and some meteorological parameters in Uji. The dry deposition of the gas to a nearly perfect sink was calculated by subtracting the greased surface flux from the total deposition flux to both the greased and reagent impregnated (or water) surface. It was found that the gas phase deposition contributed significantly more (60–93%) than the particulate phase to overall deposition of sulfur and nitrogen compounds. The dry deposition velocities of the species were also calculated using the deposition fluxes and the measured ambient concentrations. Comparisons were made between the measured and modeled particulate deposition flux.     

Chemical Characterization of Acid Fog and Rain in Northern Japan Using Back Trajectory and Oblique Rotational Factor Analysis

Fog/cloud and rain water were collected at the mountainside of Hachimantai range in northern Japan and rain water was also collected at Akita City in order to investigate the air pollutant scavenging mechanism. The concentrations of various ions in these samples were analyzed, and the fog drop size and the wind direction were measured at each fog event. The fog at Hachimantai range had a very high total ion concentration, and was considerably acidified by non sea salt (nss-) SO₄ ^2? and NO₃ ^?, compared with the rain at Akita and all sites in Hachimantai range. Using the oblique rotational factor analysis, three factors were extracted as the air pollutants; A: (NH₄)₂SO₄+H₂SO₄, B: sea salts+HNO₃+H₂SO₄, C: NH₄NO₃+OH^?. These salts are well-known as the cloud condensation nuclei (CCN). Combining the factor analysis with the 72h back trajectory at 850hPa level, the contribution of Factor A was closely connected to the long-range transportation of anthropogenic or natural aerosol in air masses of continental origin.