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The revised (four-step) BCR sequential extraction procedure has been applied to fractionate the chromium, copper, iron, manganese, nickel, lead and zinc contents in urban soil samples from public-access areas in five European cities. A preliminary inter-laboratory comparison was conducted and showed that data obtained by different laboratories participating in the study were sufficiently harmonious for comparisons to be made between cities and land types (e.g. parks, roadside, riverbanks, etc.). Analyte recoveries by sequential extraction, with respect to direct aqua regia digestion, were generally acceptable (100 ± 15%). Iron, nickel and, at most sites, chromium were found mainly in association with the residual phase of the soil matrix. Copper was present in the reducible, oxidisable and residual fractions, whilst zinc was found in all four sequential extracts. Manganese was strongly associated with reducible material as, in some cities, was lead. This is of concern because high lead concentrations were present in some soils (>500 mg kg−1) and the potential exists for remobilisation under reducing conditions. As would be expected, extractable metal contents were generally highest in older, more heavily industrialised cities. Copper, lead and zinc showed marked (and often correlated) variations in concentrations between sites within the same city whereas manganese and, especially, iron, did not. No overall relationships were, however, found between analyte concentrations and land use, nor between analyte partitioning and land use

Studies on several cities around the world confirm that urban soils are subject to heavy anthropogenic disturbance. However, these surveys are difficult to compare due to a lack of common sampling and analytical protocols. In this study the soils of Ljubljana (Slovenia), Sevilla (Spain), and Torino (Italy) were extensively sampled and analyzed using common procedures. Results highlighted similarities across the cities, despite their differences in geography, size, climate, etc. Potentially toxic elements (PTE) showed a wide range in concentration reflecting a diffuse contamination. Among the "urban" elements Pb exceeded the legislation threshold in 45% of Ljubljana, 43% of Torino, and 11% of Sevilla samples while Zn was above the limits in 20, 43, and 2% of the soils of Ljubljana, Torino, and Sevilla, respectively. The distribution of PTE showed no depth-dependant changes, while general soil properties seemed more responsive to anthropogenic influences. Multivariate statistics revealed similar associations between PTE in the three cities, with Cu, Pb, and Zn in a group, and Ni and Cr in another, suggesting an anthropogenic origin for the former group and natural one for the latter. Chromium and Ni were unaffected by land use, except for roadside soils, while Cu, Pb, and Zn distribution appeared to be more dependent on the distance from emission sources. Regardless of the location, climate, and size, the "urban" factor--integrating type and intensity of contaminant emission and anthropogenic disturbance--seems to prevail in determining trends of PTE contamination.

Use of a harmonised sampling regime has allowed comparison of concentrations of copper, chromium, nickel, lead and zinc in six urban parks located in different European cities differing markedly in their climate and industrial history. Wide concentrations ranges were found for copper, lead and zinc at most sites, but for chromium and nickel a wide range was only seen in the Italian park, where levels were also considerably greater than in other soils. As might be expected, the soils from older cities with a legacy of heavy manufacturing industry (Glasgow, Torino) were richest in potentially toxic elements (PTEs); soils from Ljubljana, Sevilla and Uppsala had intermediate metal contents, and soils from the most recently established park, in the least industrialised city (Aveiro), displayed lowest concentrations. When principal component analysis was applied to the data, associations were revealed between pH and organic carbon content; and between all five PTEs. When pH and organic carbon content were excluded from the PCA, a distinction became clear between copper, lead and zinc (the ''urban'' metals) on the one hand, and chromium and nickel on the other. Similar results were obtained for the surface (0-10 cm depth) and sub-surface (10-20 cm depth) samples. Comparisons with target or limit concentrations were limited by the existence of different legislation in different countries and the fact that few guidelines deal specifically with public-access urban soils intended for recreational use.

Summary Soils of the urban area of Sevilla have been scarcely studied, especially concerning their concentrations of potentially toxic metals. A previous paper has shown that moderate pollution exists in soils from some public green areas of the city, and a common pattern was found in the distribution of the concentrations of some particular metals. The present paper is aimed at (i) determining possible seasonal changes in the measured concentrations; (ii) checking possible effects of the observed pollution on plant metal contents, and (iii) finding possible relations between metals by statistical techniques. Samples of 35 soils from the urban area of Sevilla were studied. Comparison with previous data shows that samples from a depth of 0–20 cm are representative of the measured soil properties for the city. We show that in most cases differences in the EDTA‐ and aqua regia‐extractable metal contents between autumn 2000 and summer 2001 are not significant. Only Zn shows significant decreases (P < 0.05), probably because it is more mobile than the other metals studied. Electrical conductivity and pH also show significant changes related to leaching of soluble salts. We found a strong association between ‘urban’ metals (as defined in the literature) and organic matter, as shown by factor analysis, whereas ‘non‐urban’ metals could be related to clay and carbonate contents, perhaps coming from the soil parent materials. The behaviour of the urban metals means that organic matter contributes to their accumulation, either by retention of the incoming metals from the atmosphere, dust or various human activities, or from addition of organic amendments that might provide significant amounts of such metals. Although concentrations of Cu, Pb and Zn at several sites exceeded the limits established elsewhere as acceptable in residential areas, the values in the grass were less than those considered as normal in the literature. This implies that fairly large concentrations in the soil do not necessarily make metals more available.

SUMMARY The reaction of Cu, Zn and Cd with soils with carbonate contents ranging from 0 to 75 mg g−1 was studied before and after removal of soil carbonates with acetate buffer at pH 5. Treatment with acetate buffer caused a strong decrease in metal retention by those soils containing carbonates, although if no carbonate was originally present, the treatment caused little effect or even an increase in the amounts sorbed. Before the treatment, adsorption of increasing amounts of Cu and Zn was accompanied by a continuous increase in Ca + Mg released, and those soils containing carbonate released Ca + Mg in excess of their exchangeable amounts, due to dissolution of carbonates and/or penetration of the heavy metal into the carbonate structure. It is suggested that Cu was preferentially retained by the treated soils through precipitation of Cu oxide, and by adsorption on the soil carbonates in the case of the original samples. Zn was removed from the solution by the original carbonate soils through formation of ZnCO3. Treated soils were likely to retain Zn by cation exchange and/or adsorption. Adsorption was probably the main process involved in retention of Cd. In all cases pH was the master variable in controlling the extent and probably the nature of the reaction.

Fifty-two samples of surface soils were taken in the urban area of Seville, to assess the possible influence of different land uses on their metal contents and their relationship with several soil properties. The samples corresponded to five categories or land uses: agricultural, parks, ornamental gardens, riverbanks, and roadsides. Sequential extraction of metal according to the procedure proposed by the former Community Bureau of Reference (BCR) was carried out, and pseudo-total (aqua regia soluble) metal contents were determined. Lower organic C, total N and available P and K contents were found in riverbank samples, probably due to the lack of manuring of those sites, left in a natural status. In contrast, significantly higher electrical conductivity was found in those sites, due to the tidal influence of the nearby Atlantic Ocean. Other land uses did not show significant differences in the general properties. Concentrations of Cu, Pb and Zn, both aqua-regia soluble and sequentially extracted, were clearly higher in soils from ornamental gardens, whereas the concentrations in the riverbank samples were slightly lower than the other categories. In contrast, other metals (Cd, Cr, Fe, Mn, Ni) were uniformly distributed throughout all land uses. A strong statistical association is found among the concentrations of Cu, Pb, Zn and organic C, suggesting that the larger contents of these metals in ornamental gardens are partly due to organic amendments added to those sites more frequently than to other kinds of sites. Considering the conclusions of previous studies, heavy traffic can also contribute to those ;urban' metals in urban soils. Periodic monitoring of the concentrations of urban metals in busy city centres and of the quality of amendments added to soils of recreational areas are recommended.

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