Physicochemical characterization of particulate emissions from a compression ignition engine: the influence of biodiesel feedstock.

This study undertook a physicochemical characterization of particle emissions from a single compression ignition engine operated at one test mode with 3 biodiesel fuels made from 3 different feedstocks (i.e., soy, tallow, and canola) at 4 different blend percentages (20%, 40%, 60%, and 80%) to gain insights into their particle-related health effects. Particle physical properties were inferred by measuring particle number size distributions both with and without heating within a thermodenuder (TD) and also by measuring particulate matter (PM) emission factors with an aerodynamic diameter less than 10 µm (PM(10)). The chemical properties of particulates were investigated by measuring particle and vapor phase Polycyclic Aromatic Hydrocarbons (PAHs) and also Reactive Oxygen Species (ROS) concentrations. The particle number size distributions showed strong dependency on feedstock and blend percentage with some fuel types showing increased particle number emissions, while others showed particle number reductions. In addition, the median particle diameter decreased as the blend percentage was increased. Particle and vapor phase PAHs were generally reduced with biodiesel, with the results being relatively independent of the blend percentage. The ROS concentrations increased monotonically with biodiesel blend percentage but did not exhibit strong feedstock variability. Furthermore, the ROS concentrations correlated quite well with the organic volume percentage of particles - a quantity which increased with increasing blend percentage. At higher blend percentages, the particle surface area was significantly reduced, but the particles were internally mixed with a greater organic volume percentage (containing ROS) which has implications for using surface area as a regulatory metric for diesel particulate matter (DPM) emissions.

Physicochemical characterization of particulate emissions from a compression ignition engine employing two injection technologies and three fuels.

Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%-84%) reductions were achieved at half load operation (1% increase-43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels.

Odour sampling 1: Physical chemistry considerations.

The selection of an odour sampling device may influence the composition of the resulting odour sample. Limited comparison of emission rates derived from turbulent and essentially quiescent sampling devices confirms that the emission rates derived from these devices are quite different. There is therefore compelling evidence that current odour sampling practice should have greater regard for fundamental physical and chemical principles, the nature of the odour source and the conditions created by the sampling device. Such consideration may identify the most appropriate situations under which the use of these devices may or may not be correct.

Odour sampling. 2. Comparison of physical and aerodynamic characteristics of sampling devices: a review.

Sampling devices differing greatly in shape, size and operating condition have been used to collect air samples to determine rates of emission of volatile substances, including odour. However, physical chemistry principles, in particular the partitioning of volatile substances between two phases as explained by Henrys Law and the relationship between wind velocity and emission rate, suggests that different devices cannot be expected to provide equivalent emission rate estimates. Thus several problems are associated with the use of static and dynamic emission chambers, but the more turbulent devices such as wind tunnels do not appear to be subject to these problems. In general, the ability to relate emission rate estimates obtained from wind tunnel measurements to those derived from device-independent techniques supports the use of wind tunnels to determine emission rates that can be used as input data for dispersion models.

Long-term assessment of efficacy of permeable pond covers for odour reduction.

Three anaerobic ponds used to store and treat piggery wastes were fully covered with permeable materials manufactured from polypropylene geofabric, polyethylene shade cloth and supported straw. The covers were assessed in terms of efficacy in reducing odour emission rates over a 40-month period. Odour samples were collected from the surface of the covers, the surface of the exposed liquor and from the surface of an uncovered (control) pond at one of the piggeries. Relative to the emission rate of the exposed liquor at each pond, the polypropylene, shade cloth and straw covers reduced average emission rates by 76%, 69% and 66%, respectively. At the piggery with an uncovered control pond, the polypropylene covers reduced average odour emission rates by 50% and 41%, respectively. A plausible hypothesis, consistent with likely mechanisms for the odour reduction and the olfactometric method used to quantifying the efficacy of the covers, is offered.

Airborne particles in indoor environment of homes, schools, offices and aged care facilities: The main routes of exposure.

It has been shown that the exposure to airborne particulate matter is one of the most significant environmental risks people face. Since indoor environment is where people spend the majority of time, in order to protect against this risk, the origin of the particles needs to be understood: do they come from indoor, outdoor sources or both? Further, this question needs to be answered separately for each of the PM mass/number size fractions, as they originate from different sources. Numerous studies have been conducted for specific indoor environments or under specific setting. Here our aim was to go beyond the specifics of individual studies, and to explore, based on pooled data from the literature, whether there are generalizable trends in routes of exposure at homes, schools and day cares, offices and aged care facilities. To do this, we quantified the overall 24h and occupancy weighted means of PM10, PM2.5 and PN - particle number concentration. Based on this, we developed a summary of the indoor versus outdoor origin of indoor particles and compared the means to the WHO guidelines (for PM10 and PM2.5) and to the typical levels reported for urban environments (PN). We showed that the main origins of particle metrics differ from one type of indoor environment to another. For homes, outdoor air is the main origin of PM10 and PM2.5 but PN originate from indoor sources; for schools and day cares, outdoor air is the source of PN while PM10 and PM2.5 have indoor sources; and for offices, outdoor air is the source of all three particle size fractions. While each individual building is different, leading to differences in exposure and ideally necessitating its own assessment (which is very rarely done), our findings point to the existence of generalizable trends for the main types of indoor environments where people spend time, and therefore to the type of prevention measures which need to be considered in general for these environments.

Tropospheric volatile organic compounds in China.

Photochemical smog, characterized by high concentrations of ozone (O3) and fine particles (PM2.5) in the atmosphere, has become one of the top environmental concerns in China. Volatile organic compounds (VOCs), one of the key precursors of O3 and secondary organic aerosol (SOA) (an important component of PM2.5), have a critical influence on atmospheric chemistry and subsequently affect regional and global climate. Thus, VOCs have been extensively studied in many cities and regions in China, especially in the North China Plain, the Yangtze River Delta and the Pearl River Delta regions where photochemical smog pollution has become increasingly worse over recent decades. This paper reviews the main studies conducted in China on the characteristics and sources of VOCs, their relationship with O3 and SOA, and their removal technology. This paper also provides an integrated literature review on the formulation and implementation of effective control strategies of VOCs and photochemical smog, as well as suggestions for future directions of VOCs study in China.

Factors influencing the outdoor concentration of carbonaceous aerosols at urban schools in Brisbane, Australia: Implications for children's exposure.

This comprehensive study aimed to determine the sources and driving factors of organic carbon (OC) and elemental carbon (EC) concentrations in ambient PM2.5 in urban schools. Sampling was conducted outdoors at 25 schools in the Brisbane Metropolitan Area, Australia. Concentrations of primary and secondary OC were quantified using the EC tracer method, with secondary OC accounting for an average of 60%. Principal component analysis distinguished the contributing sources above the background and identified groups of schools with differing levels of primary and secondary carbonaceous aerosols. Overall, the results showed that vehicle emissions, local weather conditions and secondary organic aerosols (SOA) were the key factors influencing concentrations of carbonaceous component of PM2.5 at these schools. These results provide insights into children's exposure to vehicle emissions and SOA at such urban schools.

Particle and carbon dioxide emissions from passenger vehicles operating on unleaded petrol and LPG fuel.

A comprehensive study of the particle and carbon dioxide emissions from a fleet of six dedicated liquefied petroleum gas (LPG) powered and five unleaded petrol (ULP) powered new Ford Falcon Forte passenger vehicles was carried out on a chassis dynamometer at four different vehicle speeds--0 (idle), 40, 60, 80 and 100 km h(-1). Emission factors and their relative values between the two fuel types together with a statistical significance for any difference were estimated for each parameter. In general, LPG was found to be a 'cleaner' fuel, although in most cases, the differences were not statistically significant owing to the large variations between emissions from different vehicles. The particle number emission factors ranged from 10(11) to 10(13) km(-1) and was over 70% less with LPG compared to ULP. Corresponding differences in particle mass emission factor between the two fuels were small and ranged from the order of 10 microg km(-1) at 40 to about 1000 microg km(-1) at 100 km h(-1). The count median particle diameter (CMD) ranged from 20 to 35 nm and was larger with LPG than with ULP in all modes except the idle mode. Carbon dioxide emission factors ranged from about 300 to 400 g km(-1) at 40 km h(-1), falling with increasing speed to about 200 g km(-1) at 100 km h(-1). At all speeds, the values were 10% to 18% greater with ULP than with LPG.

Separation and determination of selenium(IV) and molybdenum(VI) in mixtures by selective precipitation with potassium thiocarbonate.

A simple method for the separation and determination of selenium(IV) and molybdenum(VI) in mixtures, based on selective precipitation with potassium thiocarbonate, has been developed. The procedure allows quantitative determination of 10-100 mg of selenium or 10-70 mg of molybdenum at pH 0.5-1.0. No interference by a wide range of other metal ions is observed.

Emissions from a vehicle fitted to operate on either petrol or compressed natural gas.

The purpose of this work was to evaluate the physical and chemical properties of emission products from a six-cylinder sedan car under a variety of operating conditions, before and after it has been converted to compressed natural gas (CNG) fuel. The specific focus of the measurements was on emission levels and characteristics of ultra fine particles and the emission levels together with the emissions of gaseous pollutants for a range of operating conditions before and up to 3 months after the vehicle was converted are presented and discussed in the paper. The investigations showed that converting a petrol operating vehicle to CNG has the potential of reducing some of the emissions and thus risks, while it does not appear to have an impact on others. In particular there was no statistically significant change in the emission of particles for the vehicle operating on petrol, before the conversion, compared to the emissions for the vehicle operating on CNG, after the conversion. There was a significant lowering of emissions of total polycyclic aromatic hydrocarbons and formaldehyde when the vehicle was operated on CNG, and a reduction of global warming potential was also observed when the vehicle was run on CNG, but the later gain is only at high vehicle speeds/loads, and would thus have to be considered in view of traffic and transport models for the region (in these models vehicle speed is an important parameter).

Which emission sources are responsible for the volatile organic compounds in the atmosphere of Pearl River Delta?

A field measurement study of volatile organic compounds (VOCs) was simultaneously carried out in October-December 2007 at an inland Pearl River Delta (PRD) site and a Hong Kong urban site. A receptor model i.e. positive matrix factorization (PMF) was applied to the data for the apportionment of pollution sources in the region. Five and six sources were identified in Hong Kong and the inland PRD region, respectively. The major sources identified in the region were vehicular emissions, solvent use and biomass burning, whereas extra sources found in inland PRD included liquefied petroleum gas and gasoline evaporation. In Hong Kong, the vehicular emissions made the most significant contribution to ambient VOCs (48 ± 4%), followed by solvent use (43 ± 2%) and biomass burning (9 ± 2%). In inland PRD, the largest contributor to ambient VOCs was solvent use (46 ± 1%), and vehicular emissions contributed 26 ± 1% to ambient VOCs. The percentage contribution of vehicular emission in Hong Kong in 2007 is close to that obtained in 2001-2003, whereas in inland PRD the contribution of solvent use to ambient VOCs in 2007 was at the upper range of the results obtained in previous studies and twice the 2006 PRD emission inventory. The findings advance our knowledge of ozone precursors in the PRD region.

Safety, tolerability and efficacy of sublingual allergoid immunotherapy with three different shortened up-dosing administration schedules.

Sublingual immunotherapy with monomeric allergoid, given according to the standard schedule, was reported to be effective and safe in many clinical trials. However, a long period of time may elapse before achievement of a clinical benefit. This study was thus performed using two different shortened (4-day) induction (= up-dosing) schedules, which allowed a rapid achievement of the maintenance dosage. Overall, 86 patients suffering from rhinitis and oculorhinitis have been recruited, none of whom had received immunotherapy before. The study design was prospective, randomized, with three parallel groups receiving, according to a randomization list, one of the three induction (two up-dosing one no-up-dosing) phase schedules under study. A fourth group of patients served as controls, and did not receive any sublingual immunotherapy but only rescue medications if and when necessary. All patients were evaluated to assess their baseline conditions, and thereafter at 3 and 6 months. The evaluation parameters were: Visual Analogue Scale, symptom-medication scores, nasal provocation test. All three induction schedules under study were well accepted by the patients, with very few adverse reactions. The clinical efficacy, evaluated with Visual Analogue Scale (p < 0.001), symptom-medication scores (p < 0.02) and nasal provocation tests (p < 0.01), was found to be significant in all three sublingual immunotherapy-treated groups of 64 (n86) patients, but was not significant in controls 22 (n86). According to the Authors, with this simplified schedule process, sublingual immunotherapy is a therapeutic option that is becoming increasingly well-accepted not only by allergy specialists but also by patients.

Comparison of odour emission rates measured from various sources using two sampling devices.

Two commonly used sampling devices (a wind tunnel and the US EPA dynamic emission chamber), were used to collect paired samples of odorous air from a number of agricultural odour sources. The odour samples were assessed using triangular, forced-choice dynamic olfactometry. The odour concentration data was combined with the flushing rate data to calculate odour emission rates for both devices on all sources. Odour concentrations were consistently higher in samples collected with a flux chamber (ratio ranging from 10:7 to 5:1, relative to wind tunnel samples), whereas odour emission rates were consistently larger when derived from wind tunnels (ratio ranging from 60:1 to 240:1, relative to flux chamber values). A complex relationship existed between emission rate estimates derived from each device, apparently influenced by the nature of the emitting surface. These results have great significance for users of odour dispersion models, for which an odour emission rate is a key input parameter.

Influence of diesel fuel sulfur on nanoparticle emissions from city buses.

Particle emissions from twelve buses, operating alternately on low sulfur (LS; 500 ppm) and ultralow sulfur (ULS; 50 ppm) diesel fuel, were monitored. The buses were 1-19 years old and had no after-treatment devices fitted. Measurements were carried out at four steady-state operational modes on a chassis dynamometer using a mini dilution tunnel (PM mass measurement) and a Dekati ejector diluter as a secondary diluter (SMPS particle number). The mean particle number emission rate (s(-1)) of the buses, in the size range 8-400 nm, using ULS diesel was 31% to 59% lower than the rate using LS diesel in all four modes. The fractional reduction was highest in the newest buses and decreased with mileage upto about 500,000 km, after which no further decrease was apparent. However, the mean total suspended particle (TSP) mass emission rate did not show a systematic difference between the two fuel types. When the fuel was changed from LS to ULS diesel, the reduction in particle number was mainly in the nanoparticle size range. Over all operational modes, 58% of the particles were smaller than 50 nm with LS fuel as opposed to just 45% with ULS fuel, suggesting that sulfur in diesel fuel was playing a major role in the formation of nanoparticles. The greatest influence of the fuel sulfur content was observed at the highest engine load, where 74% of the particles were smaller than 50 nm with LS diesel compared to 43% with ULS diesel.

Particle number emissions and source signatures of an industrial facility.

The work presented was conducted within the scope of a larger study investigating impacts of the Stuart Oil Shale project, a facility operating to the north of the industrial city of Gladstone, Australia. The aims of the investigations were threefold: (a) the identification of the plant signatures in terms of particle size distributions in the submicrometer range (13-830 nm) through stack measurements, (b) exploring the applicability of these signatures in tracing the source contributions at locations of interest, at a distance from the plant, and (c) assessing the contribution of the plant to the total particle number concentration at locations of interest. The stack measurements conducted for three different conditions of plant operation showed that the particle size distributions were bimodal with average modal count median diameters (CMDs) of 24 (SD 4) and 52 (SD 9) nm. The average of all the particle size distributions recorded within the plant sector at a site located 4.5 km from the plant, over the sampling period when the plant was operating, also showed a bimodal distribution. The modal CMDs in this case were 27 and 50 nm, similar to those at the stack. This bimodal size distribution is distinct from the size distribution of the most common ambient anthropogenic emission source, which is vehicle emissions, and can be considered as a signature of this source. The average contribution of the plant (for plant sector winds) was estimated to be (10.0 +/- 3.8) x 10(2) particles cm(-3) and constituted approximately a 50% increase overthe local particle ambient concentration for plant sector winds. This increase in particle number concentration compared to the local background concentration, while high compared to the clean environment concentration, is not significant when compared to concentrations generally encountered in the urban environment of Brisbane.

Synthesis and Antifungal Activity of Some Organotin(IV) Carboxylates.

Six diorganotin(IV) carboxylates prepared by reacting diorganotin(IV) dichlorides with the respective silver carboxylate have been tested for antifungal activity against Aspergillus. niger, Aspergilluus flavus and Pencillium. citrinum in Sabourand dextrose broth. The compounds generally exhibit greater fungitoxicity than the diorganotin(IV) dichlorides and the carboxylic acids from which they were synthesized. In keeping with the generally accepted notion that the organotin moiety plays an important role in deciding the antifungal activity of an organotin compound, the diphenyltin(IV) compounds were more active than their di-n-butyltin(IV) analogues. However, the order of increasing fungitoxicity of the compounds parallels that of the uncomplexed carboxylic acids. The implications of the results are discussed.