Lability of potentially toxic elements in soils affected by smelting activities.

Determination of total concentration of potentially toxic elements (PTEs) in soil is not a reliable tool for evaluating potential exposure risk for humans. PTE lability (EDTA, SBET and solution extraction) and chemical speciation (BCR sequential extraction) were investigated for Pb, Cd, Cu, and Zn, as well as how these could be affected by flooding in soils polluted by smelting activities. The flooding experiment was performed in pots from which soil solution was extracted at different time intervals using Rhizon Moisture Samplers. After experiments, the soil was again subjected to the previous extractions (EDTA, SBET, and BCR) in order to reveal the changes which occurred during anoxia. From the results we can conclude that PTE lability is very high and flooding caused the increase in their mobility up to 100% (for bioaccessible Pb). The experiment demonstrated that temporary reducing conditions can increase the risk of contaminants passing to other environmental compartments and the food chain.

An appraisal of soil diffuse contamination in an industrial district in northern Italy.

Soil diffuse contamination is one the major soil threats, especially in regions with a high population density and strong industrialization. In this work agricultural, natural, and periurban soils of an Italian Province (858 km(2)) were sampled and analyzed. Overall, 140 samples were taken at two depths and analyzed for 10 trace elements, 13 rare earth elements and for organic contaminants (PCBs, PCDDs and PAHs). The aim of this work was to obtain an appraisal of soil diffuse contamination in a large Italian Province by applying and validating available tools to quantify background values and evaluate the intensity of contamination. Data were processed, background values estimated, and enrichment and contamination factors calculated. For some contaminants the results allowed a discrimination between natural or anthropic-derived contaminants. Some contaminants revealed clear trends of enrichment in function of the land use (in particular for periurban soils). REEs were found to mostly derive from parent material. The results obtained in this study show the importance of merging the quantification of contaminants with the elaboration of indices of contamination. These require an accurate quantification of background values to be able to discriminate the anthropic contribution. Enrichment factor resulted to be more accurate than contamination factor but it cannot be applied to organic contaminants and requires a careful selection of the reference element to be adopted. This study revealed that some contaminants - Sb, Sn, Pb, and organic contaminants - can be used as tracers of diffuse contamination, and should be therefore always included in similar studies.

Copper lability in soils subjected to intermittent submergence.

Reducing conditions in soils can have significant influences on the availability of nutrient and toxic metals, through their remobilization, their release through reductive dissolution of oxide phases, and from the formation of precipitates. In the literature, contrasting results are reported on the effects of temporary waterlogging conditions on the availability of metals. In the present study, changes in the "labile" or "potentially available" pool of copper (Cu) in soils as a consequence of up to three intermittent soil submergence cycles was investigated using isotopic dilution. The soils (an Oxisol and an Inceprisol) selected were amended in the field with both biosolids-Cu and salt-Cu. Intermittent soil submergence was found to have a significant effect on the lability of Cu in soils, with E(total) values generally increasing in all the treatments with the different submergence cycles, the highest lability of Cu observed in the Cu-salt treatment. The presence of nonexchangeable colloidal forms of Cu, influenced by treatments and submergence cycles, was also reported.

The variability of polychlorinated biphenyls levels in urban soils from five European cities.

The concentration of PCBs in topsoils from five European cities was assessed and the highest levels were found in Glasgow (Scotland), followed by Torino (Italy), Aveiro (Portugal), Ljubljana (Slovenia) and Uppsala (Sweden). All cities showed the presence of local sources in addition to diffuse contamination from global atmospheric transport. The association of general soil parameters with PCBs in Glasgow and with heavier congeners in Torino and Ljubljana indicates that retention of these compounds is occurring. The profiles obtained resemble Aroclor 1254 and 1260, which are important local sources. Nevertheless, differences in PCB profiles were observed among cities, due to the combined effects of the age of the contamination (which determines the time available for volatilisation and degradation), different sources of PCBs and differences in climate (which influence volatilisation and deposition).

Metals in particle-size fractions of the soils of five European cities.

Soils from Aveiro, Glasgow, Ljubljana, Sevilla and Torino have been investigated in view of their potential for translocation of potentially toxic elements (PTE) to the atmosphere. Soils were partitioned into five size fractions and Cr, Cu, Ni, Pb and Zn were measured in the fractions and the whole soil. All PTE concentrated in the <10 microm fraction. Cr and Ni concentrated also in the coarse fraction, indicating a lithogenic contribution. An accumulation factor (AF) was calculated for the <2 and <10 microm fraction. The AF values indicate that the accumulation in the finer fractions is higher where the overall contamination is lower. AF for Cr and Ni are particularly low in Glasgow and Torino. An inverse relationship was found between the AF of some metals and the percentage of <10 microm particles that could be of use in risk assessment or remediation practices.

Availability and bioaccessibility of metals in fine particles of some urban soils.

Metals in urban soils might be transferred to humans via ingestion, dermal contact, or breathing, especially to children due to the "hand to mouth" activity during outdoor activities in playground and recreational areas. This involuntary soil ingestion depends on soil adherence to skin; it is known that the adhesion process tends to exclude particles greater than 50 microm, so the fraction below this diameter would be the most dangerous for health. The aim of this work was to study the "availability", estimated by the EDTA extraction, and "oral bioaccessibility", estimated by the Simple Bioaccessibility Extraction Test (SBET), of several metals in urban soils of two European cities (Sevilla and Torino), as related to the soil particle size distribution. Torino and Sevilla showed different levels of metal contents, availability, and bioaccessibility. In Torino, the finer particles showed metal enrichment of Cu, Zn, and, to a lesser extent, Pb, whereas in Sevilla, all of the studied metals showed this enrichment compared to the whole soils. The whole soil cannot be used as a good general indicator of the bioaccessibility of metals in the finest fractions of the soil. Metal availability was higher in the clay fraction (<2 microm) than in other fractions or whole soils in both cities, and principal component analysis shows that availability is especially due to this fraction. In contrast, Cu and Pb bioaccessibility in the clay fraction seems to be slightly lower than, or comparable to, all of the other fractions and the whole soil. Bioaccessibility of Cr and Ni is clearly greater in the coarser fractions of Sevilla than those of Torino, despite the considerably greater total contents of both metals in the latter city. Adsorbed metal forms are assumed to be preferentially responsible for metals released by EDTA. A different origin is attributed to bioaccessible metal forms. Anthropic influence seems more important in determining metal availability and bioaccessibility in urban soils of both cities than the different geological or industrial characteristics.

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.

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.

The influence of a large city on some soil properties and metals content.

Urban soils differ from the rural ones by the fact that they are more strongly influenced by anthropogenic activities. This influence is often reflected by a high degree of contamination. To investigate the influence a large city can have on its soils and on the surrounding ones, samples within the city of Torino, Italy were compared with a set of surrounding soils developed from the same alluvial parent material. City-country trends were investigated by spatially managing the samples. Results show that the city plays a key role in concentrating some pollutants, such as Pb, Zn, and Cu within its borders. Lead is the element most enriched in the city, presenting a pollution index of 7.5 calculated comparing the two sets of samples. Ni and Cr appear to have a strong natural contribution. The spatial distributions for Pb, Cu and Zn present an abrupt division between urban and rural samples. Unexpectedly, the transport of pollutants from the city to the surrounding areas seems to be limited as no city-country trends with distance are identified. The pH and the sand fraction result also influenced by the city, showing high values. The investigation of possible city-country distance trends has shown to be effective in evaluating the impact a city can have on its soils and on the transport and deposition of contaminants on the surrounding ones.