Greg Morrison

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.

Levels and risk assessment for humans and ecosystems of platinum-group elements in the airborne particles and road dust of some European cities

Traffic is the main source of platinum-group element (PGE) contamination in populated urban areas. There is increasing concern about the hazardous effects of these new pollutants for people and for other living organisms in these areas. Airborne and road dusts, as well as tree bark and grass samples were collected at locations in the European cities of Göteborg (Sweden), Madrid (Spain), Rome (Italy), Munich (Germany), Sheffield and London (UK). Today, in spite of the large number of parameters that can influence the airborne PGE content, the results obtained so far indicate significantly higher PGE levels at traffic sites compared with the rural or non-polluted zones that have been investigated (background levels). The average Pt content in airborne particles found in downtown Madrid, Göteborg and Rome is in the range 7.3-13.1 pg m(-3). The ring roads of these cities have values in the range 4.1-17.7 pg m(-3). In Munich, a lower Pt content was found in airborne particles (4.1 pg m(-3)). The same tendency has been noted for downtown Rh, with contents in the range 2.2-2.8 pg m(-3), and in the range 0.8-3.0 and 0.3 pg m(-3) for motorway margins in Munich. The combined results obtained using a wide-range airborne classifier (WRAC) collector and a PM-10 or virtual impactor show that Pt is associated with particles for a wide range of diameters. The smaller the particle size, the lower the Pt concentration. However, in particles <PM-10, some of the highest values correspond to the fraction <0.39 microm. Considering an average Pt content in all particles of approximately 15 pg m(-3), which is representative for all countries and environmental conditions, the tracheobronchial fraction represents approximately 10% and the alveolar fraction approximately 8% of the total particles suspended in air. However, from the environmental risk point of view, an exposure to PGEs in traffic-related ambient air is at least three orders of magnitude below the levels for which adverse health effects might theoretically occur (of approx. 100 ng m(-3)). Therefore, today inhalation exposure to PGEs from automotive catalysts does not seem to pose a direct health risk to the general population. Even though the data available today indicate no obvious health effects, there are still a number of aspects related to PGEs and catalysts that justify further research. First, continual monitoring of changes in PGE levels in air and road dust is warranted, to make sure that there is no dramatic increase from todays levels. Secondly, more detailed information on the chemical composition of the PGE-containing substances or complexes leaving the catalyst surface and the size distribution of the PGE-containing particles released during driving will facilitate a more in-depth human risk assessment.

Determination of palladium, platinum and rhodium concentrations in urban road sediments by laser ablation-ICP-MS

The introduction of catalytic converter technology to cars has alleviated gaseous exhaust emissions but in turn has resulted in emissions of the three platinum group metals (PGMs), Pd, Pt and Rh, contained in the automobile catalyst. The environmental effects of PGMs are still largely unknown and their accurate determination is particularly difficult because concentrations are at trace levels. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a direct trace element measurement technique and can be used for the rapid characterization of metals in solid environmental matrices. Here, the capability of LA-ICP-MS for the direct quantitative determination of PGMs in road sediments was assessed. Two Nd:YAG laser systems operating at 266 and 1064 nm, respectively, were coupled to an ICP-MS. Uncontaminated road sediments were spiked with PGMs, both as solution and as solid certified reference material, and used to assess the analytical performance of the technique and to calibrate the instrument. Interferences due to the formation of molecular ions and double charged ions were investigated. The LA-ICP-MS was then used to determine the concentration of PGMs in a recent urban road sediment and the results were compared with high resolution-ICP-MS measurements after microwave sample digestion with Aqua Regia. The LA-ICP-MS allows the quantitative analysis of Pd, Pt, and Rh in road sediments at sub microgram per gram levels with a relative standard deviation of 10% and with estimated detection limits in the lower nanogram per gram range. Good agreement between LA-ICP-MS and HR-ICP-MS analysis could be obtained for Pt and Rh (<3% R.S.D. at ca. 100 ng g−1) whereas the determination of Pd remains subject to interferences.

Highway and Urban Environment

Today, half of the world’s population lives in urban areas and the rapid urbanization we are seeing is expected to continue in the next decades. The growth of urban areas around the world presents many challenges and needs to be supported by the development of adequate and sustainable infrastructures. This work offers comprehensive coverage of critical issues on the highway and urban environment which are key to understanding sustainability in the worlds expanding urban areas. It offers a highly relevant round-up of the proceeding of the Highway and Urban Environment Symposium held in Nicosia, Cyprus, last year. The Proceedings describe recent research on vehicle emissions, air quality, urban runoff quality and treatment, contaminated areas, traffic management and sustainable transport strategies. This book is ideal for all those working in related fields, from research engineers to urban planners and transport officers.

Routes for Bioaccumulation and Transformation of Platinum in the Urban Environment

Platinum occurs naturally at very low concentrations. However, a potential problem appears with the presence of Pt in the urban environment due to its increasing use as an autocatalyst. The potential contamination of the environment by Pt has started a debate over the health risks posed by increased exposure to Pt. Toxic effects have been reported for microorganisms, plants and animals. It is also known that Pt has potential human health effects, even at small doses, with allergenic reactions initiated by platinum salts, e.g. hexachloroplatinate, and mutagenic/carcinogenic effects linked to the anti-cancer drug cisplatin (Lindell 1997). This critical review focuses on the pathways and transformations of Pt in the environment. Environmental effects can only be understood through an assessment of the bioavailability of Pt and in this perspective, the environmental routes of Pt are of interest.

Sources and storm loading variations of metal species in a gullypot catchment.

The temporal variations of metal species in the outflow from a single gullypot catchment are discussed for two storms with differing hydrological characteristics, and the major contributing sources within the system are identified from an analysis of six discrete storm events. Under low flow conditions the dissolved metals are complexed by organics present in the gullypot liquor and interstitial sediment waters, and the strongly bound fraction predominates in the gullypot outflow. As the flow increases the Chelex removable fraction becomes important due to acid washing initially of road-surface sediments and subsequently of the mobilized gullypot sediments. The particulate-associated metals exhibit distinct temporal similarities to the storm hydrograph and chemograph for suspended solids with the exchangeable fraction being dominant. Hydrodynamic sorting mechanisms on the road surface produce the earlier contributions for this fraction, with later inputs, particularly for Cd and Pb, from chemical exchange processes within overturned gullypot sediment. This basal sediment also provides important inputs of the carbonate and hydrous oxide fraction for Cu and Zn as the gullypot contents become oxygenated later in the storm. The consequences of these findings are discussed in terms of gullypot maintenance and the water quality of stormwater outfalls.

Colloid-facilitated metal transport in peat filters.

The effect of colloids on metal retention in peat columns was studied, with the focus on colloids from two sources-organic matter leached from peat, and introduced organic and hydrous ferric oxide (HFO) colloids. A significant fraction of metals was found to be associated with peat-produced organic colloids; however the concentrations of organic colloids leached are low (trace concentrations) and temporal and have a limited effect on the efficiency of peat filters. In contrast, the presence of organic and HFO colloids in the input water causes a significant decrease in the performance of peat filters. Organic colloids were identified as the main vector of cadmium, copper, nickel, and zinc, while lead is transported by both organic and HFO colloids. The colloidal distribution of metals obtained in this study has important implications for the mobility of trace metals in porous media. The occurrence of colloids in the input waters and their characteristics must be considered when designing water treatment facilities.

Peat filter performance under changing environmental conditions

Peat is a candidate filter material for in situ treatment of urban runoff, contaminated groundwater and landfill leachates. Until now research has focused on peat sorption in batch experiments and there is a lack of knowledge on peat performance in filter beds. In this project column tests were carried out to evaluate the capacity of peat to remove As, Cd, Cu, Cr, Ni, Pb and Zn in multi-metal solution under a range of environmental conditions that may be encountered in real-life applications (draining, water stagnation, freezing, change in pH and metal concentrations, input of NaCl and elevated DOC). The removal capacity was 91-98% for Cd, Cu, Zn, Ni and Pb and the efficiency was unaffected by the changes of physical factors, but temporarily inhibited for solutions containing NaCl. Leaching of DOC from peat was detected in the initial samples and temporarily decreased metal removal. The peat filters showed high removal rates for Cd, Cu, Zn, Ni and Pb under all experimental conditions and are recommended for treatment of waters containing these elements. In contrast, peat was not found to be efficient for treatment of As and Cr in the multi-metal contaminated water at the pH range (6.7-8.0) studied.

Influence of complexing agents and surfactants on metal speciation analysis in road runoff.

A combination of medium exchange and sample acidification techniques is used to enable the calculation of the individual effects of complexing agents and surfactants on the deposition and stripping steps in anodic stripping voltammetry for copper, lead and cadmium in road and urban runoff. A simple acidification procedure is presented for determination of the toxic fraction.