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.     

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.     

Dispersal and accumulation of Pt, Pd and Rh derived from a roundabout in Sheffield (UK): From stream to tidal estuary

The Coisley Hill roundabout, a typical urban source for PGE in stream sediments, has anomalously high values of up to 408 ppb Pt, 444 ppb Pd and 113 ppb Rh in road dust, up to 416 ppb Pt and 278 ppb Pd in gulley sediment and up to 606 ppb Pt and 1050 ppb Pd in verge soil. For samples collected at the same time, the road dust values are much higher than in sediments in the Shire Brook stream, that drains the roundabout, with values of 3-64 ppb Pt, 4-57 ppb Pd and up to 7 ppb Rh. Downstream sediments from rivers Rother and Don have lower values of 2-35 ppb Pt, 2-14 ppb Pd and up to 3 ppb Rh. The Humber estuary values are low with 6-8 ppb Pt, 5-8 ppb Pd and 1-2 ppb Rh. Pt/Pd increases down catchment with Coisley Hill 0.8, Shire Brook 1.0, Trent and Don 1.5 and the Humber estuary 2.0. Pt/Rh and Pd/Rh also increase downstream. Precious metals are generally dispersed away from their vehicle catalytic source and Pd is dispersed more than Pt and Rh but Pt and Pd are re-concentrated in acid mine drainage in the Shire Brook, with concentrations varying with stream flow. Pt and Pd values are slightly elevated at the tidal limit and in mud deposited when the river is in spate. On Coisley Hill, values of 133 ppb Pt and 230 ppb Pd occur in dust from a new road surface (two weeks old when sampled). These are similar to those on much older road surfaces suggesting that Pt and Pd collect and disperse rapidly from roads. Au is low in road dust and higher values in conurbations suggest the presence of more Au sources in urban rather than in rural areas. Au values are not diluted downstream as much as PGE suggesting different processes of dispersion and sedimentation.     

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.     

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.     

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.     

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.     

Platinum-group elements in sewage sludge and incinerator ash in the United Kingdom: Assessment of PGE sources and mobility in cities

Platinum-group element (PGE) concentrations in sewage sludge and incinerator ash compared with average PGE concentrations in road dust show a common pattern, characterized by a negative Rh anomaly. This similarity, found at 9 UK incinerators, suggests that there is a universal characteristic PGE pattern produced by common processes of dispersal of Pt, Pd and Rh derived from automobile catalytic converters.Ninety-one sewage sludge and incinerator ash samples from the sewage treatment facilities in Sheffield, Birmingham and 7 other UK cities were analyzed for PGE. The highest concentrations are 602 ppb Pt and 710 ppb Pd with lower maximum concentrations of 65 ppb Rh, 100 ppb Ru, 33 ppb Ir and 12 ppb Os. Ash from incinerated sewage was found to have higher PGE concentrations compared to the original sludge and the PGE ratios are preserved during incineration.Rh is more mobilized and dispersed than the other PGE as it is transported from roads into the drainage system and into sewage. Pt/Pd ratios of 1.0 in road dust and 0.9 in sewage and incinerator ash suggest that Pd is more mobile than Pt during dispersal. PGE abundances in stored incinerator ash of varying ages appear to have been affected by the variation in use of Pt, Pd and Rh in catalytic converters due to variation in their market prices.Concentrations of Os, Ir and Ru in ashes are greater in Sheffield and London than all the other city sites and may be derived from point industrial sources.     

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.     

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.     

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.     

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.     

A pilot study on the content and the release of Ni and other allergenic metals from cheap earrings available on the Italian market

The capability of alloys used in cheap jewellery to release metal ions on contact with the skin causing allergic contact dermatitis (ACD) is generally acknowledged. To reduce the diffusion of the Ni-induced ACD the Council Directive 94/27/EC [Council Directive 94/27/EC of 30 June 1994. Official Journal L 188, 22/07/1994, 1.] limited the total Ni content in alloys and its release rate in artificial sweat. In this work, three different aspects were explored: i) the frequency of skin sensitization to Ni-containing earrings in patients before and after the introduction of the Directive's limit; ii) metal composition of alloys by X-ray analysis; iii) metal leaching in artificial sweat followed by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS) quantification. Well-known allergenic metals, as Ni, Cr and Co, and possible emergent allergens, as Al, Ag, Au, Cd, Cu, Fe, Ir, Mn, Pb, Pd, Pt, Rh, Sn, V and Zn, were studied. Results showed that the frequency of allergy due to earrings did not decrease after the introduction of the Ni limit: in 1994 and in 2005 patients positive to Ni patch tests were 54.3% and 53.5%, respectively. The earring components analyzed were Fe-based or alloys of Cu/Zn or Fe/Cr/Ni, plated with a thin film of precious metal (Ag, Au) which, in several cases, was combined with a Ni layer beneath. Five out of 10 items were not in compliance with the Ni Directive 94/27/EC having a total Ni content >0.05%. In three cases the release of Ni concentrations was higher than the safe sensitizing limit given by the above mentioned Regulation (i.e., <0.5 microg/cm(2)/week). The release of Cu and Zn was very variable among the different pieces (Cu: 0.134-30.9 microg/cm(2)/week; Zn: 0.141-160 microg/cm(2)/week); two objects released high amounts of Fe (358 and 586 microg/cm(2)/week) and one released considerable Mn (21 microg/cm(2)/week). Lead was released from 70% of the objects, while Ag, Al, Cd, Co, Cr and Sn from ca. 30% of the items and concentrations of these elements were well below 0.5 microg/cm(2)/week. Vanadium was released by only one item whereas Au, Ir, Pd, Pt and Rh were never leached.     

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.     

Monitoring Pt and Rh in urban aerosols from Buenos Aires, Argentina

Vehicular traffic is the main source of platinum group elements (PGEs) in highly populated urban areas like Buenos Aires where a traffic density of 1,500,000 vehicles day(-1) (corresponding to 7,500 vehicles km(-2)) is estimated. Since there is no information on the levels of PGEs in Buenos Aires, a pilot study was undertaken to ascertain the amount of two major PGEs, namely Pt and Rh, in the atmosphere of this city. To this end, 49 samples of PM-10 particulate matter were collected during 7 days in seven representative sampling sites located downtown Buenos Aires and spread over an area of about 30 km(2). The collection of particulate matter was performed on ash-free glass-fiber filters using high volume samplers with PM-10 sampling heads. Filters loaded with the particulate matter were subjected to microwave (MW)-assisted acid digestion using a combination of HNO(3), HF and HClO(4). The resulting solutions were evaporated and then diluted with 0.1 mol l(-1) HCl. Analyses were performed by sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) and special attention was paid to the control of mass interferences. Statistical analysis was performed on the experimental data obtained for the element concentrations taking also into account local meteorological data for the monitored period. The highest concentrations of Pt and Rh were detected at two sites (Hospital Alemán and Casa Rapallini) located in streets with traffic consisting mostly of passenger cars. The Pt content (in pg m(-3)) in airborne particulate matter was found to vary from 2.3 to 47.7, with a mean value of 12.9+/-7, and that of Rh from 0.3 to 16.8, with a mean value of 3.9+/-2.8. These concentrations are by far below the levels for which adverse health effects might be expected to occur, i.e., around 100 ng m(-3). On the other hand, monitoring of PGEs should be carried out in a systematic fashion to detect possible dramatic increases from today's levels.     

Airborne particulate matter, platinum group elements and human health: A review of recent evidence

Environmental concentrations of the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) have been on the rise, due largely to the use of automobile catalytic converters which employ these metals as exhaust catalysts. It has generally been assumed that the health risks associated with environmental exposures to PGE are minimal. More recent studies on PGE toxicity, environmental bioavailability and concentrations in biologically relevant media indicate however that environmental exposures to these metals may indeed pose a health risk, especially at a chronic, subclinical level. The purpose of this paper is to review the most recent evidence and provide an up-to-date assessment of the risks related to environmental exposures of PGE, particularly in airborne particulate matter (PM).This review concludes that these metals may pose a greater health risk than once thought for several reasons. First, emitted PGE may be easily mobilised and solubilised by various compounds commonly present in the environment, thereby enhancing their bioavailability. Second, PGE may be transformed into more toxic species upon uptake by organisms. The presence of chloride in lung fluids, for instance, may lead to the formation of halogenated PGE complexes that have a greater potential to induce cellular damage. Third, a significant proportion of PGE found in airborne PM is present in the fine fraction that been found to be associated with increases in morbidity and mortality. PGE are also a concern to the extent that they contribute to the suite of metals found in fine PM suspected of eliciting a variety of health effects, especially in vulnerable populations. All these factors highlight the need to monitor environmental levels of PGE and continue research on their bioavailability, behaviour, speciation and associated toxicity to enable us to better assess their potential to elicit health effects in humans.     

Impact of irrigating rice paddies with groundwater containing arsenic in Bangladesh

Soil and soil-water As profiles were obtained from 4 rice paddies in Bangladesh during the wet growing season (May-November), when surface water with little arsenic is used for irrigation, or during the dry season (January-May), when groundwater elevated in arsenic is used instead. In the upper 5 cm of paddy soil, accumulation of 13+/-12 mg/kg acid-leachable As (n=11) was observed in soil from 3 sites irrigated with groundwater containing 80-180 microg/L As, whereas only 3+/-2 mg/kg acid-leachable As (n=8) was measured at a control site. Dissolved As concentrations averaged 370+/-340 microg/L (n=7) in the upper 5 cm of the soil at the 3 sites irrigated with groundwater containing 80-180 microg/L As, contrasting with soil water As concentrations of only 18+/-7 microg/L (n=4) over the same depth interval at the control site. Despite the accumulation of As in soil and in soil water attributable to irrigation with groundwater containing elevated As levels, there is no evidence of a proportional transfer to rice grains collected from the same sites. Digestion and analysis of individual grains of boro winter rice from the 2 sites irrigated with groundwater containing 150 and 180 microg/L As yielded concentrations of 0.28+/-0.13 mg/kg (n=12) and 0.44+/-0.25 mg/kg (n=12), respectively. The As content of winter rice from the control site was not significantly different though less variable (0.30+/-0.07; n=12). The observations suggest that exposure of the Bangladesh population to As contained in rice is less of an immediate concern than the continued use of groundwater containing elevated As levels for drinking or cooking, or other potential consequences of As accumulation in soil and soil-water.     

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.     

The use of vegetation to remediate soil freshly contaminated by recalcitrant contaminants

The use of vegetation to remediate soil contaminated by recalcitrant hydrocarbons was tested under field conditions. Specifically, an evaluation was made of the effectiveness of deep rooting grasses, Johnsongrass and Canadian wild rye in the dissipation of TNT and PBB's in the soils freshly contaminated to an initial concentration of 10.17+/-1.35 for TNT and 9.87+/-1.23 mg/kg for PBB. The experiment used 72 (1.5m long and 0.1m diameter) column lysimeters with four treatments: Johnsongrass; wild rye grass; a rotation of Johnsongrass and wild rye grass; and unplanted fallow conditions. In the laboratory, immunoassay test procedures determined the TNT and PBB concentrations in the soil, leachate, herbage and root samples. The root characteristics such as total root length, rooting density, and root surface area were quantified to a depth of 1.5m. Changes in microbial biomass were assessed for both rhizosphere soil and the bulk soil during the 2-year study. The largest and most rapid loss in soil chemical concentration was for TNT, which decreased to less than 250 microg/kg, the detection limit, by 93 days after germination. The PBB was at or near the detection limit of 500 microg/kg by 185 days after germination. There was no perceptible difference in contaminant concentration in the soil between the vegetation treatments and/or with depth.     

Platinum levels in natural and urban soils from Rome and Latium (Italy): significance for pollution by automobile catalytic converter

Platinum concentrations in topsoil samples collected in 1992 (48) and in 2001 (16) from the urban area of Rome have been determined by ICP-MS. Concentrations in 47 soil samples collected in 1992 from natural sites of Latium (an area around Rome) have been determined for a first assessment of natural background levels. The Pt concentrations in Rome urban soils collected in 1992 range from 0.8 to 6.3 ng/g (mean = 3.8 +/- 1.0) overlapping the concentration range of natural soils from Latium (mean = 3.1 +/- 2.1 ng/g). No significant correlation has generally been found between Pt contents in the 'natural' soils and related bedrock or major pedogenetic parameters. These results suggest that there is no evidence of Pt pollution in Rome urban soils at that time, because the massive use of the automobile catalytic converter has only just started. Higher (up to six times more) Pt concentrations, than those measured in the 1992 samples, have been measured, in some cases, in Rome urban soils collected in 2001, suggesting a possible start of Pt accumulation because of the large-scale use in the last decade of automobile catalytic converters. At the same time, a clear decrease of lead levels in Rome urban soils with respect to the levels measured in 1992 has been observed, paralleling the decreasing number of lead gasoline-fuelled cars. Here we present one of the first systematic studies for defining background levels of Pt in Italian natural soils, thus allowing for monitoring, in the future, should any possible Pt pollution caused by the use of automobile catalytic converter, especially in urban soils, occur.