Association of 210Po(210Pb), 239+240Pu and 241Am with different mineral fractions of a beach sand at Seascale, Cumbria, UK

Automotive catalytic converters, in which Pt, Pd and Rh (platinum-group elements; PGEs) are the active components for eliminating several noxious components from exhaust fumes, have become the main source of environmental urban pollution by PGEs. This work reports on the catalyst morphology through changes in catalyst surface by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and laser-induced breakdown spectrometry (LIBS) from fresh to aged catalytic converters. The distribution of these elements in the fresh catalysts analysed (Pt-Pd-Rh gasoline catalyst) is not uniform and occurs mainly in a longitudinal direction. This heterogeneity seems to be greater for Pt and Pd. PGEs released by the catalysts, fresh and aged 30,000 km, were studied in parallel. Whole raw exhaust fumes from four catalysts of three different types were also examined. Two of these were gasoline catalysts (Pt-Pd Rh and Pd-Rh) and the other two were diesel catalysts (Pt). Samples were collected following the 91,441 EUDC driving cycle for light-duty vehicle testing. The results show that at 0 km the samples collected first have the highest content of particulate PGEs and although the general tendency is for the release to decrease with increasing number of samples taken, exceptions are frequent. At 30,000 km the released PGEs in gasoline and diesel catalysts decreased significantly. For fresh gasoline catalysts the mean of the total amount released was approximately 100, 250 and 50 ng km(-1) for Pt, Pd and Rh, respectively. In diesel catalysts the Pt release varied in the range 400-800 ng km-1. After ageing the catalysts up to 30,000 km, the gasoline catalysts released amounts of Pt between 6 and 8 ng km(-1), Pd between 12 and 16 ng km(-1) and Rh between 3 and 12 ng km(-1). In diesel catalysts the Pt release varied in the range 108-150 ng km(-1). The soluble portion of PGEs in the HNO3 collector solution represented less than 5% of the total amount for fresh catalysts. For 30,000 km the total amount of soluble PGEs released was similar or slightly higher than for 0 km.     

Platinum group elements in the environment and their health risk

Accumulation of platinum group elements (PGEs) in the environment has been increased over the time. Catalytic converters of modern vehicles are considered to be the main sources of PGE pollution, since the correlation is between the Pt:Rh ratios in various environmental compartments and in converter units. The present literature survey shows that the concentration of these metals has increased significantly in the last decades in diverse environmental matrices; like airborne particulate matter, soil, roadside dust and vegetation, river, coastal and oceanic environment. Generally, PGEs are referred to behave in an inert manner and to be immobile. However, there is an evidence of spread and bioaccumulation of these elements in the environment. Platinum content of road dusts can be soluble, consequently, it enters the waters, sediments, soil and finally, the food chain. The effect of chronic occupational exposure to Pt compounds is well-documented, and certain Pt species are known to exhibit allergenic potential. However, the toxicity of biologically available anthropogenic Pt is not clear. Hence, there is a need to study the effect on human health of long-term chronic exposure to low levels of Pt compounds.     

Platinum and rhodium distribution in airborne particulate matter and road dust

In this work the platinum and rhodium content in the atmosphere of Madrid was monitored for 1 year at seven different sites. Samples were taken with medium volume PM-10 collectors (< 10 microm) for 48 h and analysed by ICP-MS. The Pt and Rh content was dependent on the sampling site, ranging from < 0.1 to 57.1 and < 0.2 to 12.2 pg m(-3) with a medium value of 12.8 and 3.3 pg m(-3), respectively. These results show that the Pt and Rh content in airborne samples depends on the traffic density per day and also on medium driving speed. Road dust < 63 microm was analysed at the same time and at the same location. The Pt and Rh content at the six sites analysed was in the 31-2252 and 11-182 ng g(-1) range with an average of 317 and 74 ng g(-1), respectively. The average Pt/Rh ratio obtained was 4.3. similar to that obtained for airborne particles (4.0), and agrees with that of the more commonly used gasoline car catalyst [J.J. Mooney, Encyclopaedia of Chemical Technology (1996) 982]. Platinum distribution as a function of particle size in airborne particulate matter was also studied, by sampling with two high-volume sample collectors, a five-stage WRAC (from 10 to 65.3 microm and total) and a seven-stages PM-10) cascade impactor (from 9 to < 0.39 microm). Platinum is associated with a wide range of particle diameters. Due to the ultratrace level of Pt in airborne samples, its distribution in the atmosphere could not be considered as homogeneous. No trend could be established in Pt distribution in the different fractions, except that in most cases the highest value of Pt was obtained in the < 0.39-microm fraction. The Pt content was usually high in airborne samples when the Pb, Ce, Zr and Hf content was also high, thus confirming that the source of these pollutants is from traffic.     

Increase of platinum group element concentrations in soils and airborne dust in an urban area in Germany

Since 1993, all new cars sold in the European Union had to be fitted with catalytic converters. Undoubtedly, these measures brought about a great progress concerning traffic emission controls. However, this technology also led to new emissions. A rapid accumulation of the catalytic active noble metals Pt, Pd, and Rh in the environment was observed and concern arose about potential environmental and health risks. This work aimed at a contribution to a monitoring of platinum group element (PGE) emission and accumulation by comparing analytical data, all generated in 1999 and in 2005 in an urban area in Germany. Oriented at the 1999 sampling strategy, soil and airborne dust samples were taken in 2005 at the same sampling sites located mainly close to heavily used roads in the region of Braunschweig. For the enrichment of the analytes, conditioned soil samples as well as loaded glass fiber filters from air sampling were transferred to the nickel sulphide fire assay. For analyses, the ICP-MS technique was applied. High Pt, Pd, and Rh concentrations were detected especially in top soil layers (0-2 cm) directly at the roadsides or on center strips. At one road outside the city, where traffic moved with a constant speed of about 80 km/h, maximum concentrations in soil were found to be 50.4 microg/kg for Pt, 43.3 microg/kg for Pd, and 10.7 microg/kg for Rh. PGE concentrations were the highest close to that road and exponentially declined with growing distance. At a second road, where vehicles run with a constant speed of 50 km/h, the highest concentrations were detected in the center strip soil: 88.9 microg/kg (Pt), 77.8 microg/kg (Pd), and 17.6 microg/kg (Rh). At a third crowded street in the centre of Braunschweig with stop and go traffic, the highest soil concentrations were determined, namely 261 microg/kg for Pt, 124 microg/kg for Pd and 38.9 microg/kg for Rh. The sampling of airborne dust at this roadside revealed for Pt 159 pg/m(3) air or 1730 microg/kg dust, for Pd 37.8 pg/m(3) air or 410 microg/kg dust, and for Rh 10.0 pg/m(3) air or 110 microg/kg dust. A comparison of analytical results of 2005 with those of 1999 revealed a distinct increase of PGE concentrations in soils closely along heavy traffic roads by a factor of 2.1 to 8.9; once even a factor of 15 was determined. The findings also document, that especially Pt and Rh concentrations were elevated in airborne dust.     

Bioaccumulation of platinum group elements and characterization of their species in Lolium multiflorum by size-exclusion chromatography coupled with ICP-MS

The bioaccumulation of Pt, Pd and Rh by grass grown hydroponically with nutrient solutions containing these ions at elevated (38.7 mg l(-1) Pt, 21.7 mg l(-1) Pd and 7.1 mg l(-1) Rh) and medium (3.6 mg l(-1) Pt, 4.4 mg l(-1) Pd and 0.5 mg l(-1) Rh) concentrations was studied by using inductively coupled plasma sector field mass spectrometry (ICP-SFMS). The highest bioaccumulation factors were obtained for Pd and Rh in roots and for Pt in leaves. The obtained results showed that most of the studied metals were accumulated in roots, and only a small fraction was really metabolised and transported to leaves. The multi-element capability of ICP-SFMS has been exploited to study the metabolism of platinum group elements (PGEs) in cultivated plants. The species of studied metals were extracted from roots and leaves and separated into two mass fractions by ultra-filtration. The low molecular mass (<10 kDa) fractions of the root and the leaf extracts were investigated by size-exclusion chromatography (SEC) coupled on-line to ICP-SFMS. The presence of Ca, Cu, S and C in the same fractions as Pt, Pd and Rh may indicate the interaction of PGEs with phytochelatins and carbohydrates.     

Palladium and platinum concentration in soils from the Napoli metropolitan area,Italy: possible effects of catalytic exhausts

Soils from the Napoli metropolitan area (Italy) were evaluated for Pt and Pd concentrations. One hundred and ninety-five (195) samples were collected from residual soils and non-residual soils from flower-beds in a 120 km(2) area on a 0.5 km grid in the downtown-urbanized area and on 1 km grid in suburban zones. The soils <100 mesh size fraction (150 microm) was analyzed for Pt, Pd and 37 other elements by ICP-ES and ICP-MS after aqua regia digestion. Pt and Pd contents range between <2 and 52 microg/kg and between <10 and 110 microg/kg, respectively. A large number of samples from the metropolitan area were characterized by anomalous values for Pt (>6 microg/kg) and Pd (>17 microg/kg). Non-residual soils from flower-beds are located mainly in the urbanized downtown areas subject to heavy traffic and have higher Pt and Pd contents than residual soils from suburban areas. Geochemical maps show a strong correlation between roads with major traffic flow and high Pt and Pd concentrations. In addition, data from most of the downtown flower-beds fall within the three-way catalytic converters (TWC) field identified by [Ely JC, et al. Environ Sci Technol; 35:3816-3822]. This suggests that emissions of abraded fragments from vehicle exhausts may be the source of the high values and geographic distributions of Pd and especially Pt in urban soils of Napoli. Catalytic converters (Pt/Pd/Rh) have been mandatory for gasoline-powered vehicles in Europe since 1993. Italy permitted the use of non-catalytic motor until January, 2002. This is responsible for the high values for both Pt and Pd in the non-residual soils of the urban areas of Napoli.     

Bioaccumulation of palladium, platinum and rhodium from urban particulates and sediments by the freshwater isopod Asellus aquaticus.

The three-way catalytic converters introduced to oxidize and reduce gaseous automobile emissions represent a source of platinum group elements (PGEs), in particular platinum, palladium and rhodium, to the urban environment. Abrasion of automobile exhausts leads to an increase of the concentration of PGEs in environmental matrices such as vegetation, soil and water bodies. The bioaccumulation of Pd, Pt and Rh by the freshwater isopod Asellus aquaticus was studied in natural ecosystems and under laboratory conditions. Owing to the low concentration level (ng g(-1)) of PGEs in the animals studied. analyses were performed with a quadrupole inductively coupled plasma mass spectrometry (ICP-MS) and hafnium, copper, yttrium, rubidium, strontium and lead were monitored for spectral interference correction. Asellus aquaticus collected in an urban river showed a content (mean +/- s) of 155.4 +/- 73.4, 38.0 +/- 34.6, and 17.9 +/- 12.2 ng g(-1) (dry weight) for Pd, Pt and Rh, respectively. The exposure of Asellus aquaticus to PGE standard solutions for a period of 24h give bioaccumulation factors of Bf: 150, 85, and 7 for Pd, Pt and Rh, respectively. Exposure of Asellus aquaticus to environmental samples for different exposure periods demonstrated that PGE bioaccumulation is time dependent. and shows a higher accumulation for the materials with a higher PGE content. While all three elements have the same uptake rate for exposure to catalyst materials, for exposure to environmental materials they havc a different uptake rate which can be attributed to transformations of the PGE species in the environment.     

The distribution of automobile catalysts-cast platinum, palladium and rhodium in soils adjacent to roads and their uptake by grass

The introduction of automobile catalysts has raised environmental concern, as this pollution control technology is also an emission source for the platinum group elements (PGE). The main aim of this study was to assess the concentrations of Pt, Pd, Rh and Au in soil and grass herbage collected adjacent to 5 roads. Soil and grass samples were collected from 4 fixed distances (0, 1, 2 and 5 m) from the road edge at each site. PGE and Au were determined by ICP-MS in all samples after acid digestion. The maximum soil Pt, Rh and Pd concentrations were measured at the road perimeters. Averaged across the sites, the Pt and Rh concentrations of 15.9+/-7.5 microg Pt kg(-1) and 22.40+/-4.73 microg Rh kg(-1) at 0-m distance decreased to 2.04+/-1.7 microg Pt kg(-1) and 3.51+/-1.96 microg Rh kg(-1), respectively at 5-m away from the roads. Pd concentrations were much higher than Pt or Rh, ranging from 120.8+/-12.0 microg Pd kg(-1) (0-m) to 84.2+/-10.9 microg Pd kg(-1) (5-m), possibly due to differences in its use, emission and/or soil chemistry. Au showed little or no change with distance from the roads. However, the average Au concentration of 18.98+/-0.98 microg Au kg(-1) provides clear evidence of some input possibly due to attrition of automobile electronics. No straightforward influence of traffic flow rates on PGE distribution was found. A combination of dispersal impeding local features and slow moving and stop-and-start traffic conditions or fast moving traffic with flat open spaces may have offset the expected impacts. Rh and Pt soil concentration accounted for 66% and 34% (P<0.01) of the variability observed, respectively in their plant concentrations. Grass Pd and Au concentrations had no relationship with their respective soil concentrations.     

A further discussion of the factors controlling the distribution of Pt, Pd, Rh and Au in road dust, gullies, road sweeper and gully flusher sediment in the city of Sheffield, UK

Forty paired road dust and gully sediments from the city of Sheffield in NE England show that high platinum, palladium and rhodium concentrations derived from catalytic converters depend on proximity to both roundabouts rather than traffic lights and to topographic lows. Road dust outside schools and control samples, further away on the same road, show that Pt, Pd and Rh concentrations are dependant on passing traffic flow rather than numbers of stopping vehicles. Highest values of Pt + Pd in road dust are 852 ppb and 694 ppb in gullies. Rh has maximum values of 113 ppb in road dust and 49 ppb in gullies. Pt and Pd values of a few ppb to just over 100 ppb occur in road dust where traffic does not stop, on roads away from junctions. Pt, Pd, Rh and Au are all picked up by road sweepers and gully flushers both with maximum values of just over 100 ppb Pt and Pd. High Au values (maximum 610 ppb in a road dust) were located on pavements, in suburbs, outside schools and in road sweepers collecting in residential areas rather than on high traffic flow roads. Stratification of Pt and Pd in gullies was not observed whereas a high Au value was recorded at the bottom of a gully suggesting gravity concentration for Au. Anomalous Pd grades of 1050 ppb in road dust from a school entrance and 2040 ppb in a street sweeper sample were recorded. These high Pd- and Au-bearing samples do not have anomalous Pt or Rh values and may be sourced from jewellery or dental fillings. However, most samples have consistent Pt/Pd ratios of about 1 and Pt/Rh values of 4 to 5 indicating a catalytic converter source. Pt and Pd are concentrated in road dust at levels well above background in all the samples, including on high and low traffic flow roads.     

The estimation of the bioavailabilities of platinum, palladium and rhodium in vehicle exhaust catalysts and road dusts using a physiologically based extraction test

Platinum group element (PGE) levels in the environment have increased following the introduction of vehicle exhaust catalysts (VECs). In order to evaluate the potential pathways of PGEs from VECs into humans, a physiologically based extraction test (PBET) was used to study the uptake of PGEs by the human digestive tract. The PBET assay was implemented in two phases, to first simulate the passage of ingested soil through the acid conditions of the stomach before it enters the near neutral conditions of the small intestine. The results showed that Pt, Pd and Rh did not undergo precipitation reaction when passing from the acid environment of the stomach to the neutral environment of the small intestine. The greatest fractions of bioavailable PGEs (up to 68%) were observed in road dust samples, possibly due to the presence of mobile PGE species formed in the roadside environment. Higher percentages of Pd and Rh were bioavailable than Pt, probably due to the differences in their mobilities and tendencies to form soluble complexes. Pt showed the highest absolute bioavailability however, due to its greater concentration in environmental samples. The solubilization of PGEs in the human digestive tract could involve the formation of PGE-chloride complexes, with perhaps increased health-hazard issues because of the known toxic and allergenic effects of these species.     

PGEs and other traffic-related elements in roadside soils from São Paulo, Brazil

The distribution of platinum, palladium, and rhodium in soils adjacent to a major road in S?o Paulo, Brazil, is presented. Sampling was made at four sites with varying traffic volumes and driving styles (stop/start vs. constant speed). High-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) with NiS fire assay collection and Te coprecipitation was used as analytical procedure. The platinum group element (PGE) pattern distribution in the analyzed roadside soil was similar to that of other traffic-related elements such as Zn and Cu, characterized by a strong decrease of the PGE content with increasing distance from the traffic lane. The results indicate that the PGE concentrations in roadside soil are directly influenced by traffic conditions and distance, which characterize their catalytic converter origin. Pt, Pd, and Rh contents range between 0.3 and 17 ng g(-1), 1.1 and 58 ng g(-1), and 0.07 and 8.2 ng g(-1) respectively. Lower levels of Pt and lower Pt/Pd ratios in relation to similar studies in other countries were observed due to the different Pt/Pd ratios in Brazilian automobile catalytic converters. This is the first study to assess traffic-derived Pt, Pd, and Rh deposition in Brazil.     

Determination of anthropogenic input of Ru, Rh, Pd, Re, Os, Ir and Pt in soils along Austrian motorways by isotope dilution ICP-MS

A joint study with the Federal Environment Agency of Austria was carried out to determine the distribution of Ru, Rh, Pd, Os, Ir and Pt (PGE) and Re in soils along major motorways. Emphasis was put on Ir as to date little is known about its anthropogenic input as this metal is now also used in automobile catalytic converters. Soil samples were analysed by ICP-MS through online-coupling of a chromatographic column to separate the PGEs from interfering matrix constituents. At all sampled sites not only Rh, Pd and Pt but also Ir and Re significantly exceed natural background values; concentrations reached 13 ng/g, 25 ng/g, 134 ng/g, 1.1 ng/g and 9.8 ng/g, respectively. The analytical procedure proved to be very selective and sensitive and, therefore applicable to routine soil analysis.     

Accumulating characteristics of platinum group elements (PGE) in urban environments, China

The three-way catalytic converters [mainly using platinum, palladium and rhodium of platinum group elements (PGE)] have been widely used to reduce the pollution arising from vehicular traffic. Since the late 1990s, the Chinese government has implemented measures for new vehicles, equipped with the three-way catalytic converters in metropolitan cities. However, the PGE spreading on environments has not been strongly concerned in developing countries. This study investigated the accumulation characteristics of PGE in urban environments in China. A few samples from India were also analyzed and compared with those from China. The collected soil, aerosol and plant samples were determined for PGE by inductively coupled plasma-mass spectrometry (ICP-MS) after nickel sulphide fire assay preconcentration. The results have shown higher PGE contents in the samples from the cities where vehicles were fitted with autocatalysts for longer time periods. The highest values are 160 ng/g for Pt, 107 ng/g for Pd and 34.5 ng/g for Rh in Hong Kong soils, whereas the lowest values are 2.59 ng/g for Pt, 1.31 ng/g for Pd and 0.40 ng/g for Rh in Kolkata soils. In Beijing and Guangzhou aerosol samples, the PGE concentrations are 6.22 to 24.3 pg/m³ for Pt and 1.16 to 8.60 pg/m³ for Rh and 7.68 to 12.2 pg/m³ for Pt and 2.15 to 5.15 pg/m³ for Rh, respectively. The levels of PGE abundances in the urban environments of China have been significantly elevated with increasing number of vehicles equipped with autocatalysts.     

Impact of diesel policy banning on PM levels in urban areas

Increased use of diesel engine in on‐road vehicles presents a serious health concern, particularly in traffic‐congested urban areas. Diesel exhaust contains various gaseous and particulate pollutants, which, at high concentrations, pose adverse health effects. In this respect, various policy measures are being adopted worldwide to curtail emissions from diesel engines. This paper presents an assessment of diesel engine policy banning in the Greater Beirut Area. For this purpose, particulate matter levels in the air were measured after the ban and compared with concentrations reported prior to the ban. Health‐based socio‐economic benefits associated with improvement in air quality were then estimated using the long‐term decrease of particulate matter as an indicator.     

Anthropogenic platinum group element (Pt, Pd and Rh) concentrations in road dusts and roadside soils from Perth, Western Australia

The emission of platinum group elements (PGE) from automobile catalytic converters has led to rapid increases in Pt, Pd and Rh concentrations in roadside media. This article represents the first detailed study to assess PGE levels in road dusts and roadside soils in Australia. Road dust and roadside soil samples were analysed by ICP-MS following microwave digestion and cation exchange. All samples show elevation of PGE above average upper crust values, with maximum values of 420 ng g(-1) Pt, 440 ng g(-1) Pd and 91 ng g(-1) Rh. PGE ratios in road dusts and soils are consistent with known catalytic converter compositions and while Pt and Rh abundances are comparable with European studies, Pd levels are substantially higher in Australian samples. PGE in these samples are not correlated with Pb, though positive correlations with Ce, Cu and Y are evident. No straightforward relationship between traffic volume and PGE abundance is evident and factors such as driving style, topography, road drainage and potentially climate exert considerable influences.     

Temporal variations and spatial distribution of ambient PM2.2 and PM10 concentrations in Dhaka, Bangladesh

Concentrations and characteristics of airborne particulate matter (PM(10), PM(2.2) and BC) on air quality have been studied at two air quality-monitoring stations in Dhaka, the capital of Bangladesh. One site is at the Farm Gate area, a hot spot with very high pollutant concentrations because of its proximity to major roadways. The other site is at a semi-residential area located at the Atomic Energy Centre, Dhaka Campus, (AECD) with relatively less traffic. The samples were collected using a 'Gent' stacked filter unit in two fractions of 0-2.2 mum and 2.2-10 mum sizes. Samples of fine (PM(2.2)) and coarse (PM(2.2-10)) airborne particulate matter fractions collected from 2000 to 2003 were studied. It has been observed that fine particulate matter has a decreasing trend, from prior year measurements, because of Government policy interventions like phase-wise plans to take two-stroke three-wheelers off the roads in Dhaka and finally banned from January 1, 2003. Other policy interventions were banning of old buses and trucks to ply on Dhaka city promotion of the using compressed natural gas (CNG), introducing air pollution control devices in vehicles, etc. It was found that both local (mostly from vehicular emissions) and possibly some regional emission sources are responsible for high PM(2.2) and BC concentrations in Dhaka. PM(2.2), PM(2.2-10) and black carbon concentration levels depend on the season, wind direction and wind speed. Transport related emissions are the major source of BC and long-range transportation from fossil fuel related sources and biomass burning could be another substantial source of BC.     

Autocatalyst-derived platinum, palladium and rhodium (PGE) in infiltration basin and wetland sediments receiving urban runoff

The emission of platinum group elements (PGE) from automobile catalytic converters has led to rapid increases in Pt, Pd and Rh concentrations in roadside media. Significant quantities of the PGE may enter and accumulate in fluvial systems via road runoff. This paper examines the occurrence and spatial distribution of autocatalyst-derived PGE in surface sediments of infiltration basin and wetland sediments receiving road-runoff in Perth, Western Australia. Samples were analysed by ICP-MS following microwave digestion and cation exchange. PGE concentrations ranged between 1.5-17.2 Rh, 5.4-61.2 Pd and 9.0-103.8 ng g(-1) Pt. The highest levels of PGE were generally found at basin topographic low points and these concentrations were found to be strongly related to the area of road surface drained and the traffic volume. PGE ratios in infiltration basin and wetland sediments were within the typical range of catalytic converter compositions. However, comparisons of PGE ratios between parent road dusts and infiltration basin sediments revealed a systematic shift in Pt/Pd ratios, suggesting that PGE fractionation can occur during transport through the drainage system and that a small portion of Pd in road dust may be solubilised under natural conditions.     

Environmental risk of particulate and soluble platinum group elements released from gasoline and diesel engine catalytic converters

A comparison of platinum-group element (PGE) emission between gasoline and diesel engine catalytic converters is reported within this work. Whole raw exhaust fumes from four catalysts of three different types were examined during their useful lifetime, from fresh to 80,000 km. Two were gasoline engine catalysts (Pt-Pd-Rh and Pd-Rh), while the other two were diesel engine catalysts (Pt). Samples were collected following the 91441 EUDC driving cycle for light-duty vehicle testing, and the sample collection device used allowed differentiation between the particulate and soluble fractions, the latter being the most relevant from an environmental point of view. Analyses were performed by inductively coupled plasma-mass spectrometry (ICP-MS) (quadrupole and high resolution), and special attention was paid to the control of spectral interference, especially in the case of Pd and Rh. The results obtained show that, for fresh catalysts, the release of particulate PGE through car exhaust fumes does not follow any particular trend, with a wide range (one-two orders of magnitude) for the content of noble metals emitted. The samples collected from 30,000-80,000 km present a more homogeneous PGE release for all catalysts studied. A decrease of approximately one order of magnitude is observed with respect to the release from fresh catalysts, except in the case of the diesel engine catalyst, for which PGE emission continued to be higher than in the case of gasoline engines. The fraction of soluble PGE was found to represent less than 10% of the total amount released from fresh catalysts. For aged catalysts, the figures are significantly higher, especially for Pd and Rh. Particulate PGE can be considered as virtually biologically inert, while soluble PGE forms can represent an environmental risk due to their bioavailability, which leads them to accumulate in the environment.     

Actual car fleet emissions estimated from urban air quality measurements and street pollution models.

A method to determine emissions from the actual car fleet under realistic driving conditions has been developed. The method is based on air quality measurements, traffic counts and inverse application of street air quality models. Many pollutants are of importance for assessing the adverse impact of the air pollution, e.g. NO2, CO, lead, VOCs and particulate matter. Aromatic VOCs are of special great concern due to their adverse health effects. Measurements of benzene, toluene and xylenes were carried out in central Copenhagen since 1994. Significant correlation was observed between VOCs and CO concentrations, indicating that the petrol engine vehicles are the major sources of VOC air pollution in central Copenhagen. Hourly mean concentrations of benezene were observed to reach values of up to 20 ppb, what is critically high according to the WHOs recommendations. Based on inverse model calculation of dispersion of pollutants in street canyons, an average emission factor of benzene for the fleet of petrol fuelled vehicles was estimated to be 0.38 g/km in 1994 and 0.11 in 1997. This decrease was caused by the reduction of benzene content in Danish petrol since summer 1995 and increasing percentage of cars equipped with three-way catalysts. The emission factors for benzene for diesel-fuelled vehicles were low.     

Elemental carbon and respirable particulate matter in the indoor air of apartments and nursery schools and ambient air in Berlin (Germany)

This study was performed to examine exposure to typical carcinogenic traffic air pollutants in the city center of an urban area. In all, 123 apartments and 74 nursery schools were analyzed with and without tobacco smoke interference and the households in two measuring periods. Simultaneously, the air outside 61 apartment windows as well as the average daily traffic volume were measured. Elemental carbon (EC), the marker for particulate diesel exhaust and respirable particulate matter (RPM) were determined. The thermographic EC analysis was conducted with and without prior solvent extraction of the soluble carbon fraction. Comparison of these two thermographic EC measurements clearly showed that method-related differences in the results, especially for indoor measurements, when high background loads of organic material were present (e.g. tobacco smoke), existed. Solvent extraction prior to EC determination was therefore appropriate. For the first winter measuring period, the EC concentration levels without solvent extraction in the indoor air were about 50% higher than those measured in the spring/summer period. In the second measuring period (i.e. spring/summer), the median EC concentrations after solvent extraction were 1.9 microg/m3 for smokers' apartments and 2.1 microg/m3 for non-smokers' apartments, with RPM concentrations of 57 and 27 microg/m3, respectively. Nursery schools showed high concentrations with median values of 53 microg/m3 for RPM and 2.9 microg/m3 for EC after solvent extraction. A significant correlation between the fine dust and EC concentrations (after solvent extraction) in the indoor and ambient air was determined. Outdoor EC values were also correlated with the average daily traffic volume. The EC ratios between indoor and ambient concentration showed a median of 0.8 (range: 0.3-4.2) in non-smoker households and 0.9 (range: 0.4-1.5) in smoker apartments. Furthermore, the EC/RPM ratio in indoor and ambient air was 0.01-0.15 (median 0.06) and 0.04-0.37 (median 0.09), respectively. PRACTICAL IMPLICATIONS: In the absence of indoor sources a significant correlation with regard to respirable particulate matter (RPM) and elemental carbon concentrations between the indoor and ambient air of apartments was observed. The high degree of certainty resulting from this correlation underscores the importance of ambient air concentrations for indoor air quality. In nursery schools we found higher concentrations of RPM. An explanation of these results could be the high number of occupants in the room, their activity and the cleaning intensity.