Availability and bio-accessibility of metals in the clay fraction of urban soils of Sevilla.

The availability of Cd, Cr, Cu, Ni, Mn, Pb and Zn present in the finest size particles of urban soils is studied by comparing the concentrations in the clay fraction with those extracted from the whole soil by either single-extraction or sequential extraction method. Many metals are preferentially present in the finest particles as compared to coarser fractions. This is true for most metals studied, except Mn and, perhaps, Cd. Those metals present in the clay fraction are often in easily bio-accessible forms, especially Cu, Pb and Zn. The results suggest that bio-accessible forms of these three metals are distributed among the three sequential fractions, and even the fraction considered as 'residual' is also bio-accessible to a significant extent. The statistical analysis shows some distinctions among metals that are compared to the 'urban', 'natural', or intermediate behaviour of the various metals as proposed earlier in the literature.

Potentially toxic elements contamination in urban soils: a comparison of three European cities.

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.

Estimating the extractability of potentially toxic metals in urban soils: a comparison of several extracting solutions.

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils.

Variability in concentrations of potentially toxic elements in urban parks from six European cities.

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.

Concentrations of potentially toxic metals in urban soils of seville: relationship with different land uses.

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.

Copper and zinc retention by an organically amended soil.

This paper describes changes in retention of Cu and Zn in laboratory experiments by a sandy soil that had been amended in the field with different composted wastes. The amounts of the metals retained increased as a result of the amendments, especially after two years. Desorption of the sorbed metals was always negligible, regardless of the treatment. The proportion of Cu retained was considerably higher than that of Zn, suggesting a higher affinity of the soil for the former. The greater sorption in the amended soils indicates a build-up of fresh sites for metal retention. The use of 'log(activity) vs. pH' plots showed that the nature of the surfaces retaining metals on the untreated and amended soils is different. At comparable pH values, the amended soils gave higher solution metal concentrations. Some of the possible environmental consequences of the use of these amendments for remediation purposes are discussed.

Heavy metal pollution of soils affected by the Guadiamar toxic flood.

Total heavy metal concentrations were determined in soil samples of seven selected areas along the Guadiamar river valley affected by the toxic flood, after removal of the deposited sludge. Mean total concentrations of nine elements (As, Au, Bi, Cd, Cu, Pb, Sb, Tl and Zn) out of the 23 (As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, In, Mn, Mo, Ni, Pb, Sb, Sc, Sn, Th, Tl, U, V, Y and Zn) analysed were higher in sludge-covered soils than in unaffected soils. Mean values of total As, Au, Pb, Sb, Tl and Zn in sludge-affected soils were higher than the upper limits for normal soils world-wide. Mean concentrations of Bi, Cd and Cu were within these ranges, although some individual values exceeded the upper limits. In all sampling areas, severe heavy metal pollution was observed in the superficial layers (0-20 cm) of most of the affected soils, which decreased downward in the soil profile. Generally, in soils with more than 25% of clay, concentration of heavy metals below the 20-cm depth decreased to values close to those of the background level of the Guadiamar valley soils, while in coarser soils, heavy metal pollution penetrated below this depth, being noticeable down to a depth of at least 50-80 cm.

Release of metals from homogeneous soil columns by wastewater from an agricultural industry.

The effect of discharging olive mill wastewater (OMW) in soils on the release of metals previously retained by them is simulated by leaching homogeneous soil columns with a solution of the residue after passing solutions of Cu or Zn through the columns. The effect of other residues, previously added to the soil as composts in field experiments, on the behaviour observed in the laboratory is also discussed. OMW shows a strong power for releasing the metals retained. Previous addition of a compost made from olive mill sludge and plant refuse to the soil causes a significant reduction of the release of retained metal by liquid OMW. Previous addition of concentrated sugarbeet vinasse causes much less significant effects.