Franco Ajmone-Marsan

Soil pollution by PAHs in urban soils: a comparison of three European cities

The purpose of this study was to determine the degree of contamination with polycyclic aromatic hydrocarbons (PAHs) in samples of urban soil from three European cities: Glasgow (UK), Torino (Italy) and Ljubljana (Slovenia). Fifteen PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) were measured in urban soil samples, using harmonised sampling, sample extraction and analyte quantification methods. Although the mean concentration of each PAH in urban soils of each city showed a wide range of values, high levels of contamination were only evident in Glasgow, where the sum of concentrations of 15 PAHs was in the range 1487-51,822 microg kg(-1), cf. ranges in the other two cities were about ten-fold lower (89.5-4488 microg kg(-1)). The three predominant PAHs were phenanthrene, fluoranthene and pyrene, with the sum of these compounds about 40% of the total PAH content. These data, together with some special molecular indices based on ratios of selected PAHs, suggest pyrogenic origins, especially motor vehicle exhausts, to be the major sources of PAHs in urban soils of the three cities. The largest concentrations for PAHs were often found in sites close to the historic quarters of the cities. Overall, the different climatic conditions, the organic carbon contents of soil, and the source apportionment were the dominant factors affecting accumulation of PAHs in soil.

Organic and inorganic diffuse contamination in urban soils: the case of Torino (Italy).

Soils in urban parks are useful tracers of diffuse contamination and could represent a potential health risk for citizens. Soils in the parks of Torino, Italy, were sampled and analysed for a broad range of organic and inorganic contaminants. Concentrations of potentially toxic elements, PAHs, PCBs and polychlorinated dibenzo-p-dioxins and dibenzofurans were often above national legislation limits, and higher than surrounding rural areas or than other cities. Mean concentrations were 233 mg kg(-1) for Cr, 164 mg kg(-1) for Ni, 124 mg kg(-1) for Pb and 170 mg kg(-1) for Zn. Other inorganic contaminants such as Cd, As, and Hg showed high concentrations in some soils. Organic contaminants were also found to be enriched in the sampled parks (e.g. maximum concentrations of PCDDs/DFs and PCBs were 12.6 ng kg(-1) and 0.310 mg kg(-1), respectively). Data from this study reveal an important enrichment of parks for some contaminants, reflecting the intensity of phenomena of diffuse contamination. Historical parks presented the highest degree of contamination, suggesting that the age of soils rather than their proximity to sources of emissions is a key factor in determining soil contamination. Data obtained in this study could be of help in the investigation and remediation practices of urban contaminated sites within large cities.

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.

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.

Are agricultural soils under a continental temperate climate susceptible to episodic reducing conditions and increased leaching of phosphorus

Soil science research has probably underestimated the significance that short-term, episodic cycles of reduction and oxidation has had on phosphorus (P) reactivity. Here, the effects of eleven pulsed reduction-oxidation (including wet-dry) cycles on soil P dynamics are compared for 12 soils having contrasting properties and all overfertilised with respect to P. The laboratory based incubation conditions attempted to simulate transient waterlogging of the soil profile and involved repeated sampling and analysis of both the solution and solid phase P forms. An initial increase in P concentration in solution that occurred up to and including the fourth full cycle was followed by a sharp decline in concentration for all but one soil. Accompanying changes in the main extractable forms of P, which appeared to be cumulative, could be summarised as a general decline in the organic P fraction and an overall increase in amorphous associated inorganic forms of P. The fact that up to 60% of the total soil P was demonstrated to change its sensitivity for a particular extractant suggests that these operationally defined P forms are susceptible to transformation as a consequence of changing environmental conditions. There was also a suggestion that certain of the changes in P forms were irreversible. While the laboratory conditions imposed do represent extreme conditions the soils only experienced cyclic changes in their moisture regime. If timing and frequency of intense precipitation events are likely to increase, as predicted in many climate change scenarios, then these results suggest that the effects of episodic redox pulses may have implications for P cycling in agricultural soils.

Bioaccessibility and size distribution of metals in road dust and roadside soils along a peri-urban transect

Road dust (RD), together with surface soils, is recognized as one of the main sinks of pollutants in urban environments. Over the last years, many studies have focused on total and bioaccessible concentrations while few have assessed the bioaccessibility of size-fractionated elements in RD. Therefore, the distribution and bioaccessibility of Fe, Mn, Cd, Cr, Cu, Ni, Pb, Sb and Zn in size fractions of RD and roadside soils (<2.5μm, 2.5-10μm and 10-200μm) have been studied using aqua regia extraction and the Simple Bioaccessibility Extraction Test. Concentrations of metals in soils are higher than legislative limits for Cu, Cr, Ni, Pb and Zn. Fine fractions appear enriched in Fe, Mn, Cu, Pb, Sb and Zn, and 2.5-10μm particles are the most enriched. In RD, Cu, Pb, Sb and Zn derive primarily from non-exhaust sources, while Zn is found in greater concentrations in the <2.5μm fraction, where it most likely has an industrial origin. Elemental distribution across soils is dependent on land use, with Zn, Ni, Cu and Pb being present in higher concentrations at traffic sites. In addition, Fe, Ni and Cr feature greater bioaccessibility in the two finer fractions, while anthropic metals (Cu, Pb, Sb and Zn) do not. In RD, only Zn has significantly higher bioaccessibility at traffic sites compared to background, and the finest particles are always the most bioaccessible; >90% of Pb, Zn and Cu is bioaccessible in the <2.5μm fraction, while for Mn, Ni, Sb, Fe and Cr, values vary from 76% to 5%. In the 2.5-10μm fraction, the values were 89% for Pb, 67% for Zn and 60% for Cu. These results make the evaluation of the bioaccessibility of size-fractionated particles appear to be a necessity for correct estimation of risk in urban areas.

Copper dynamics under alternating redox conditions is influenced by soil properties and contamination source.

Understanding the effect of soil redox conditions on contaminant dynamics is of significant importance for evaluating their lability, mobility and potential transfer to other environmental compartments. Under changing redox conditions, soil properties and constituents such as Fe and Mn (hydr)oxides and organic matter (OM) may influence the behavior of associated metallic elements (MEs). In this work, the redox-driven release and redistribution of Cu between different soil pools was studied in three soils having different contamination sources. This was achieved by subjecting soil columns to a series of alternating reducing and oxidizing cycles under non-limiting C conditions, and assessing their influence on soil pore water, leachate and solid phase composition. Results showed that, in all soils, alternating redox conditions led to an increase in the distribution of Cu in the more labile fractions, consequently enhancing its susceptibility to loss. This was generally linked to the redox-driven cycling of Fe, Mn and dissolved organic matter (DOM). In fact, results suggested that the reductive dissolution of Fe and Mn (hydr)oxides and subsequent reprecipitation as poorly-ordered phases under oxic conditions contributed to the release and mobilization of Cu and/or Cu-containing organometallic complexes. However, the behavior of Cu, as well as the mechanisms controlling Cu release and loss with redox cycling, was influenced by both soil properties (e.g. pH, contents of easily reducible Fe and Mn (hydr)oxides) and source of Cu contamination.

Quality and comparability of measurement of potentially toxic elements in urban soils by a group of european laboratories

A study has been conducted to assess the quality and comparability of measurement of aqua-regia-soluble cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc in urban soils within a small cohort of European research laboratories specializing in soil science or environmental analytical chemistry. An initial survey indicated that highly variable levels of analytical quality control (e.g. use of certified reference materials) were routinely implemented in participant laboratories. When a set of soil samples—differing in metal contents and in characteristics such as pH and organic-matter content—were exchanged and analysed, approximately 20% of results differed from target values by more than 25%. A principal-component analysis was applied to data for chromium, copper, nickel, lead, and zinc, and proved successful in assessing overall laboratory performance. The study indicates that greater prominence needs to be given to quality assurance and control if comparable data are to be generated in international, collaborative research projects.

Extractive waste management: A risk analysis approach

Abandoned mine sites continue to present serious environmental hazards because the heavy metals associated with extractive waste are continuously released into the environment, where they threaten human life and the environment. Remediating and securing extractive waste are complex, lengthy and costly processes. Thus, in most European countries, a site is considered for intervention when it poses a risk to human health and the surrounding environment. As a consequence, risk analysis presents a viable decisional approach towards the management of extractive waste. To evaluate the effects posed by extractive waste to human health and groundwater, a risk analysis approach was used for an abandoned nickel extraction site in Campello Monti in North Italy. This site is located in the Southern Italian Alps. The area consists of large and voluminous mafic rocks intruded by mantle peridotite. The mining activities in this area have generated extractive waste. A risk analysis of the site was performed using Risk Based Corrective Action (RBCA) guidelines, considering the properties of extractive waste and water for the properties of environmental matrices. The results showed the presence of carcinogenic risk due to arsenic and risks to groundwater due to nickel. The results of the risk analysis form a basic understanding of the current situation at the site, which is affected by extractive waste.

Linking oral bioaccessibility and solid phase distribution of potentially toxic elements in extractive waste and soil from an abandoned mine site: Case study in Campello Monti, NW Italy

Oral bioaccessibility and solid phase distribution of potentially toxic elements (PTE) from extractive waste streams were investigated to assess the potential human health risk posed by abandoned mines. The solid phase distribution along with micro-X-ray fluorescence (micro-XRF) and scanning electron microscopy (SEM) analysis were also performed. The results showed that the total concentrations of PTE were higher in <250 μm size fractions of waste rock and soil samples in comparison to the <2 mm size fractions. Mean value of total concentrations of chromium(Cr), copper (Cu), and nickel (Ni) in waste rocks (size fractions <250 μm) were found to be 1299, 1570, and 4010 mg/kg respectively due to the parent material. However, only 11% of Ni in this sample was orally bioaccessible. Detailed analysis of the oral bioaccessible fraction (BAF, reported as the ratio of highest bioaccessible concentration compared with the total concentration from the 250 μm fraction) across all samples showed that Cr, Cu, and Ni varied from 1 to 6%, 14 to 47%, and 5 to 21%, respectively. The variation can be attributed to the difference in pH, organic matter content and mineralogical composition of the samples. Non-specific sequential extraction showed that the non-mobile forms of PTE were associated with the clay and Fe oxide components of the environmental matrices. The present study demonstrates how oral bioaccessibility, solid phase distribution and mineralogical analysis can provide insights into the distribution, fate and behaviour of PTE in waste streams from abandoned mine sites and inform human health risk posed by such sites .