Urban geochemistry: research strategies to assist risk assessment and remediation of brownfield sites in urban areas.

Urban geochemical maps of Wolverhampton and Nottingham, based on multielement analysis of surface soils, have shown distribution patterns of "total" metals concentrations relating to past and present industrial and domestic land use and transport systems. Several methods have been used to estimate the solubility and potential bioavailability of metals, their mineral forms and potential risks to urban population groups. These include sequential chemical extraction, soil pore water extraction and analysis, mineralogical analysis by scanning electron microscopy, source apportionment by lead isotope analysis and the development of models to predict metal uptake by homegrown vegetables to provide an estimate of risk from metal consumption and exposure. The results from these research strategies have been integrated with a geographical information system (GIS) to provide data for future land-use planning.

Dispersion of As and selected heavy metals around a coal-burning power station in central Slovakia.

A power station in central Slovakia emitted arsenic (As) in large quantities for over 30 years as a result of burning As-rich brown coal. Nowadays emissions of As are low. Over the lifetime of the plant's operation over 3000 tonne of As have been emitted into the environment. This paper aims to examine the concentrations of As in the soil around the power station, and also to investigate whether the coal burnt in the plant, and consequently the emissions from it, contained raised levels of six further heavy metals. Soil concentrations were compared to ground level air As concentrations predicted by an air dispersion model. Coal samples were taken from the power station and analysed to determine concentrations of As, Zn, Pb, Cu, Cr, Ni and Cd. Soil samples (n=113) were taken up to 12 km from the plant along a transect designed to follow the valley floor in which the power station is situated. Soil samples were analysed for concentrations of those elements for which coal was tested. Concentrations of As in coal were high (AM 518 mug/g). Those of other heavy metals were, in general, low. Concentrations of soil As were substantially raised in the near vicinity of the plant but decreased within 5 km to concentrations similar to those in the rest of the district. Overall, levels within 10 km of the plant were slightly above those recommended for residential levels in the UK. Soil concentrations of other heavy metals were higher in the vicinity of the plant but none, overall was raised. Comparison of results from a previous air dispersion model of ground level air arsenic concentrations showed a moderate correlation (r=0.6) between modelled and measured values. Over its period of operation the power plant has contributed to raised levels of soil As in the local soils, though not substantially of other elements. Though now airborne As emissions are controlled, concern remains regarding soil arsenic concentrations and fugitive emissions from the plant that could be contributing to exposure of the local population and of the workforce.

The influence of soil characteristics on the extractability of Cd, Pb and Zn in upland and moorland soils.

A study was undertaken to investigate the feasibility of using existing data sets of total soil metal concentrations and soil parameters, such as pH, to predict available metal concentrations on a regional or national basis. The attraction of such an approach is that it would provide valuable data for initiatives requiring information on the availability and mobility of metals in soils without the need for costly soil sampling and analysis. Ninety-seven topsoil and subsoil samples were collected from 6 soil series in a catenary sequence in north Wales to provide data for the development of an empirical model. These were analysed for total, 0.01 M CaCl2-extractable and porewater metal concentrations and for a range of soil properties including pH, solid and dissolved organic matter and cation exchange capacity. Regression analysis showed that, of the soil parameters measured, pH was the most important predictor variable for the estimation of CaCl2-extractable Cd, Pb and Zn. pH accounted for up to 86% of the variance in the proportion of 'total' metals which were extracted by CaCl2, a reagent that is commonly used to estimate plant uptake of elements. However, the relationships recorded between soil parameters and Kd (total metal/porewater metal) were much weaker, indicating that porewater metal concentrations can less readily be predicted from total soil metal concentrations and soil properties.

Contamination of surface soils, river water and sediments by trace metals from copper processing industry in the Churnet River Valley, Staffordshire, UK.

The impacts of a functional and a demolished copper processing works on the aquatic and terrestrial environment in the vicinity of the works was investigated by determining the levels of selected trace metals in river water, river sediments, channel margin sediments and overbank soils. Samples were taken at five sites within an area of the Churnet Valley in Staffordshire, where the River Churnet flows through the two works. Analysis of river water samples by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) has shown that only copper is present above background levels considered to typify uncontaminated rivers. Analysis of river sediments, channel margin sediments and overbank soils by nitric-perchloric acid digestion and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analysis has indicated contamination by arsenic, cadmium and copper in the vicinity of both works. Arsenic and copper are deposited primarily within the aquatic environment, although some contamination of the terrestrial environment by copper is also observed. Cadmium is deposited primarily within the terrestrial environment. The deposition of arsenic and copper in river and channel margin sediments respectively is also related to current and historical contamination.

Mechanisms of copper tolerance by Armeria maritima in Dolfrwyong Bog, north Wales--initial studies.

Preliminary field studies were carried out at Dolfrwynog Bog in July 2000. Replicate samples of water, Armeria maritima plants and the soils adhering to its roots were collected and analysed for copper. Concentrations of up to 6486 mg kg-1 of copper in the soils were recorded. Accumulation of copper by the plant as expressed by concentration factors (CF) show that it is acting mainly as a copper excluder. Of the copper that is taken up, most of it is retained within the roots with very little being transported to the shoots of the plant. Moreover, a further possible mechanism of tolerance is exhibited by the excretion of copper through its decaying leaves. Towards the use of in vitro cultures to study the copper tolerance mechanisms in A. maritima a micropropagation protocol has been developed. The ex vitro plants have been rooted and established in compost.

The solid-solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales.

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.

Platinum concentrations in urban road dust and soil, and in blood and urine in the United Kingdom.

Increasing Pt concentrations from vehicle catalysts have been reported from a number of countries. Analysis of Pt and Pd in soils and road dusts taken from areas of high and low traffic flows in SE England show concentrations of Pt in the range < 0.30-40.1 ng g-1 and Pd in the range < 2.1-57.9 ng g-1. Higher concentrations of Pt are associated with high traffic densities. Samples taken from streets of lower traffic flows were found to contain the lower concentrations of the ranges. Pilot studies of Pt concentrations in blood and urine using ICP-MS have been carried out. Platinum concentrations in whole blood were: precious metal workers, 780-2170, mean 1263 pmol l-1 (0.152-0.423, mean 0.246 microgram l-1); motorway maintenance workers, 645-810, mean 744 pmol l-1 (0.126-0.158, mean 0.145 microgram l-1); Imperial College staff, 590-713, mean 660 pmol l-1 (0.115-0.139, mean 0.129 microgram l-1). Platinum concentrations in urine in pmol Pt per mmol creatinine were: precious metal workers, 122-682, mean 273 [0.21-1.18, mean 0.47 microgram Pt (g creatinine)-1]; motorway maintenance workers, 13-78, mean 33.7 [0.022-0.135, mean 0.058 microgram Pt (g creatinine)-1]; Imperial College staff, 28-130, mean 65.6 [0.048-0.224, mean 0.113 microgram Pt (g creatinine)-1]. Detection limits were 0.03 microgram l-1 for both blood and urine. The possible health effects of increasing Pt in the environment are discussed. Platinum provides an excellent example of the significance of speciation in metal toxicity. Platinum allergy is confined to a small group of charged compounds that contain reactive ligand systems, the most effective of which are chloride ligand systems. Metallic Pt is considered to be biologically inert and non allergenic and since the emitted Pt is probably in the metallic or oxide form, the sensitising potential is probably very low. Platinum from road dusts, however, can be solubilised, and enter waters, sediments, soils and the food chain. There is at present no evidence for any adverse health effects from Pt in the general environment, particularly allergic reactions.

Urinary arsenic species in Devon and Cornwall residents, UK. A pilot study.

First void urine samples were collected from 24 residents in an area of past intense mining and smelting activity of arsenical ores. Seven samples were also taken from a control village. The arsenic species in the urine were separated and quantified with an HPLC-ICP-MS system equipped with a hydraulic high-pressure nebulizer. The detection limit for arsenic in urine using this system is 0.05 microgram dm-3. Creatinine was also determined for all samples to remove the influence of urine density and all results were expressed in microgram As g-1 creatinine. The results showed elevated levels of both organic and inorganic arsenic compounds in the 'exposed' population's urine when compared with those of the control group. The total As concentrations (less arsenobetaine) in the 'exposed' population were in the range 2.7-58.9 micrograms g-1 creatinine (mean 13.4, median 9.2 micrograms g-1) compared with the control group data range 2.5-5.3 micrograms g-1 (mean 4.2, median 4.7 micrograms g-1).

Trace element concentrations in the fruit peels and trunks of Musa paradisiaca.

Chemical analyses for the elementary compositions of the ashes of the fruit peels and trunks of the tropical plantain Musa paradisiaca have been undertaken. The elements, categorized as trace elements, generally are found to have higher mean concentrations in the fruit peels than in the trunks (except in the case of Zn). Their peel-trunk uptake ratios have been calculated and range between 1 and 4, showing normal levels of accumulations in the fruit peels over the trunks.

Platinum metal concentrations in urban road dust and soil in the United Kingdom.

Concentrations of Pt, Pd, Rh and Au in soils and road dusts taken from areas of high and low traffic flows in the London Borough of Richmond and from a section of the Kingston bypass (A3) at New Malden, Surrey, have been measured. High concentrations of platinum are associated with high traffic densities. Samples taken from streets of lower traffic flows were found to contain the lower concentrations of the ranges. These values correlated well with the levels of lead which were also high at roundabouts. If the preliminary results obtained in this study apply more generally throughout the UK, then the potential for exposure to enhanced levels of Pt would appear to be higher for road users and for those living in urban environments or along major highways.

A preliminary investigation of pollution in the River Yamuna, Delhi, India: Metal concentrations in river bank soils and plants.

A preliminary study of inorganic elements in the river bank soil and plants from the River Yamuna in Delhi has been carried out. Soil at Okhla, near the Water Works plant has a high zinc content (1,215 µg g(-1) and this is reflected in the high concentration of zinc (2,029 µg g(-1)) in Eichhornia plants growing in the river at this point. Although in general the aluminium content of the soils is low in comparison with the world mean, soil near the effluent from the ash settling basins of the Indraprathsa Power Station contains elevated aluminium.Eichhornia plants growing near this effluent are stunted and unhealthy, and is suggested that, taking into account the high pH, possible causes are toxicity from aluminium or boron.