E. Ferreira da Silva

Levels, sources and potential human health risks of organic pollutants in urban soils.

Urban soil quality may be severely affected by PAH and PCB contamination, impairing environmental and human health. A comprehensive study was conducted in two contrasting Portuguese urban areas (Lisbon and Viseu) in order to assess the levels of these contaminants and potential risks to human health, to identify sources and study their behavior in soils. The concentrations of PAHs and PCBs were related to the size of the city. The concentrations found in the larger city (Lisbon) were similar to other urban areas. Differences between profiles of the two urban areas were observed for both groups of contaminants, which could be attributed to differences of sources or climate. Lisbon seems to be affected by nearby sources (traffic, industry and incineration processes) whereas in the smaller city atmospheric transport may be playing an important role. Cluster analysis revealed that PAHs and PCBs were associated with anthropogenic toxic elements (Cu, Pb, Zn and Hg in Lisbon; Pb and Hg in Viseu), therefore reflecting common sources. It was also found that organic carbon was an important factor for PAHs and high chlorinated PCB retention in soils. The incremental probability of developing cancer over lifetime, based on a reasonable maximum exposure to PAHs present in Lisbon residential soils, was 9.0 × 10(-6) and 2.4 × 10(-6) for an occupational exposure, both slightly higher than the target risk of 1 × 10(-6). Similarly, the mutagenic risk of PAHs in Lisbon was 3.3 × 10(-5) for residential soils and 1.8 × 10(-6) in recreational areas.

Evaluation of an approach for the characterization of reactive and available pools of twenty potentially toxic elements in soils: Part I – The role of key soil properties in the variation of contaminants’ reactivity

Harmful effects of potentially toxic elements (PTEs) in soils relate to their geochemically reactive fraction. To assess the degree of the reactivity, specific extractions or models are needed. Here we applied a 0.43 M HNO(3) chemical extraction to assess reactive pools of a broad range of PTEs in 136 contaminated and non-contaminated soils. Furthermore we derived Freundlich-type models based on commonly available soil properties (pH, organic carbon and clay) as well as extended models that used other properties such as amorphous Al and Fe oxides and evaluated their possible use in risk assessment. The approach allowed to predict the reactivity of As, Hg, Co, U, Ba, Se, Sb, Mo, Li, Be (r(2): 0.55-0.90) elements not previously included in such studies, as well as that of Cd, Zn, Cu, Pb, Ni and Cr (r(2): 0.73-0.90). The inclusion of pH, organic carbon and clay improved the performance of all models except for Be and Mo, although the role of clay is not completely clear and requires further investigation. The ability of amorphous metal oxides to affect the reactivity of As, Hg, Cu, Ni, Cr, Sb, Mo and Li was expressed by the models in agreement with known geochemical processes leading to the retention of PTEs by the solid matrix. Hence, such approach can be a useful tool to account for regional differences in soil properties during the identification of risk areas and constitute a significantly more powerful tool than the analysis of total pools of PTEs in soils.

A review of regulatory decisions for environmental protection: Part I — Challenges in the implementation of national soil policies

Since many soil studies have already revealed the possible risks to human health and the environment arising from contaminated soils it is therefore crucial to preserve soil quality under current and future conditions. In the last three decades a number of countries already introduced national policies and practices for the management of contaminated sites, and in 2002, an EU Thematic Strategy for Soil Protection was proposed by the European Commission. In this paper we review and analyse several national contaminated land policy regimes already in place in order to assess common elements and to identify specific needs in the development of national soil policies. We propose a framework that combines the D-P-S-I-R structure of policy evaluation with the Source-Pathway-Receptor approach to health risk assessment to support the development of effective country specific regulatory decisions for managing contaminated land in countries where these are yet to be implemented. The framework proposed allows decision makers to effectively use available information and to identify existing data gaps. As a result it is apparent that while there are technical aspects of site characterisation, risk assessment and remediation processes that could be commonly implemented at an EU level there are certain trans-scientific aspects that require political choices and need to be customized by EU Member States.

The prediction of PAHs bioavailability in soils using chemical methods: state of the art and future challenges.

The evaluation of the available fraction of hydrophobic organic contaminants (HOCs) is extremely important for assessing their risk to the environment and human health. This available fraction, which can be solubilized and/or easily extracted, is believed to be the most accessible for bioaccumulation, biosorption and/or transformation by organisms. Based on this, two main types of chemical methods have been developed, closely related to the concepts of bioaccessibility and freely available concentrations: non-exhaustive extractions and biomimetic methods. Since bioavailability is species and compound specific, this work focused only in one of the most widespread group of HOCs in soils: polycyclic aromatic hydrocarbons (PAHs). This study aims at producing a state of the art knowledge base on bioavailability and chemical availability of PAHs in soils, clarifying which chemical methods can provide a better prediction of an organism exposure, and which are the most promising ones. Therefore, a review of the processes involved on PAHs availability to microorganisms, earthworms and plants was performed and the outputs given by the different chemical methods were evaluated. The suitability of chemical methods to predict bioavailability of the 16 US EPA PAHs in dissimilar naturally contaminated soils was not yet demonstrated, being especially difficult for high molecular weight compounds. Even though the potential to predict microbial mineralization using non-exhaustive extractions is promising, it will be very difficult to achieve for earthworms and plants, due to the complexity of accumulation mechanisms which are not taken into account by chemical methods. Yet, the existing models could be improved by determining compound, species and site specific parameters. Moreover, chemical availability can be very useful to understand the bioavailability processes and the behavior of PAHs in soils. The inclusion of chemical methods on risk assessment has been suggested and it is promising, despite some methods overpredict risks.

Assessment of Water Quality in the Caima and Mau River Basins (Portugal) using Geochemical and Biological Indices

In order to study the anthropogenic impact of trace metals in the Caima and Mau River basins (north-central Portugal), 415 stream sediment samples were randomly collected in the main streams of these rivers and the minus 80-mesh fraction was analysed by Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES). The presence of abandoned mines was identified as the main source of Cu, Pb, Cd and Ni in the area. A strong pair-wise correlation between Pb, Zn, Cd and Ni was found. In this study, the geochemical indices (Contamination Index (CI) and Multiple Pollution Index (MPI)), and the diatom indices (Specific Pollution Index (SPI) and Biological Diatom Index (BDI)) are used to define the Caima and Mau River basins environmental quality. The estimation of the CI and MPI indices shows that the sediments near Coval da Mó area are enriched with Pb, Cd, Zn Ni and Co suggesting an anthropogenic origin of metal contamination in this zone. In order to evaluate the biological effects caused by the trace metals, 17 sites were selected from the two River basins. Surface water and epilithic diatom communities were sampled during the summer of 2001. In general, the water and diatom data showed medium to good water quality. However, samples collected near the mining areas (Coval da Mó) revealed low abundance and diversity of diatom taxa indicating a stressed environment. Some diatoms showed morphologically abnormal valves that may be related to the high level of metal pollution in this area.

Water-soluble fraction of mercury, arsenic and other potentially toxic elements in highly contaminated sediments and soils.

The water-soluble contents of mercury, arsenic and other potentially toxic elements in highly contaminated sediment and soil samples from Portugal were determined. Mercury and arsenic concentrations were detectable and reproducible among replicate experiments. Despite the acidic pH, the low organic carbon content and the exceptionally high levels of contamination of certain samples (total mercury contents varied between 0.15 and 3180 mg kg(-1) while total arsenic concentrations ranged from 11 to 6365 mg kg(-1)), the water-soluble percentages of both mercury (<1.2%) and arsenic (<4.6%) were generally low. The variability of the water-soluble fractions of these two elements among these samples and at the occurring pH conditions seems not to be associated with the release of other potentially toxic elements. The highest water-soluble concentrations of the remaining potentially toxic elements were generally observed in the 15-25 cm depth layer of sediments from areas colonised with plants (Halimione portulacoides) and in mining soil samples. Zinc, cobalt, copper and cadmium showed the highest water-soluble percentages of elements in relation to total metal contents. Given the high contamination levels, the availability of potentially toxic elements in these areas as well as possible risks to the environment and humans should be further investigated. The presence of plants (H. portulacoides) appears to cause significant changes in the sediment matrix that increase the mobility of several potentially toxic elements, particularly in the 15-25 cm depth layer. The effects of vegetation on the fractionation of potentially toxic elements on these sediments should be further studied.

Application of selective extraction techniques in metal-bearing phases identification: a South European case study

The study described herein concerns the application of selective extraction techniques on metal-bearing phases identified in gossan samples. Specifically, the study is directed towards the detection of Zn- and Pb-bearing phases in Balsa-Portel area (southern Portugal). In order to identify the metal-bearing phases, samples were submitted to sequential extraction procedures using the following reagents: NH4 acetate; hydroxylamine hydrochloride; oxalate in darkness; H2O2; oxalate under UV irradiation; and finally, mixed acids (HCl–HNO3–HF). In the Balsa-Portel area, the Zn- and Pb-bearing phases generally occurring in the gossan samples are lepidocrocite, Mn-oxides, cerussite and smithsonite, dissolved by oxalate under UV irradiation (lepidocrocite), hydroxylamine hydrochloride (Mn-oxides) and ammonium acetate (cerussite and smithsonite).

Major inputs and mobility of potentially toxic elements contamination in urban areas

Soil quality in urban areas is affected by anthropogenic activities, posing a risk to human health and ecosystems. Since the pseudo-total concentrations of potentially toxic elements may not reflect their potential risks, the study of element mobility is very important on a risk assessment basis. This study aims at characterising the distribution and major sources of 34 elements in two Portuguese urban areas (Lisbon and Viseu), with different geological characteristics, industrial and urban development processes. Furthermore, the potential availability of As, Co, Cr, Cu, Ni, Pb and Zn was assessed, by measuring the fraction easily mobilised. Lisbon is enriched in elements of geogenic and anthropogenic origin, whereas in the smaller city, the high levels observed are mainly related to a geogenic origin. Background values can be more relevant than the dimension of the city, even when anthropogenic components may be present, and this parameter should be considered when comparing results from different cities. Regarding the potential available fraction, a high variability of results was observed for elements and for sampling sites with an influence of the soil’s general characteristics. Elements showing very high concentrations due to geological reasons presented, in general, a low mobility and it was not dependent on the degree of contamination. For elements with major anthropogenic origin, only Zn was dependent on the pseudo-total content. Yet, the highest available fractions of some elements, both with major geogenic and anthropogenic origin, were observed in specific contaminated samples. Therefore, a site-specific evaluation in urban soils is important due to the high spatial variability and heterogeneity.

Evaluation of an approach for the characterization of reactive and available pools of 20 potentially toxic elements in soils: Part II – Solid-solution partition relationships and ion activity in soil solutions

To assess environmental risks related to contaminants in soil it is essential to predict the available pool of inorganic contaminants at regional scales, accounting for differences between soils from variable geologic and climatic origins. An approach composed of a well-accepted soil extraction procedure (0.01 M CaCl(2)) and empirical Freundlich-type models in combination with mechanistically based models which to date have been used only in temperate regions was applied to 136 soils from a South European area and evaluated for its possible general use in risk assessment. Empirical models based on reactive element pools and soil properties (pH, organic carbon, clay, total Al, Fe and Mn) provided good estimations of available concentrations for a broad range of contaminants including As, Ba, Cd, Co, Cu, Hg, Mo, Ni, Pb, Sb, Se and Zn (r(2): 0.46-0.89). The variation of the pools of total Al in soils expressed the sorptive capacity of aluminosilicates and Al oxides at the surfaces and edges of clay minerals better than the actual variability of clay contents. The approach has led to recommendations for further research with particular emphasis on the impact of clay on the solubility of As and Sb, on the mechanisms controlling Cr and U availability and on differences in binding properties of soil organic matter from different climatic regions. This study showed that such approach may be included with a good degree of certainty for first step risk assessment procedures to identify potential risk areas for leaching and uptake of inorganic contaminants in different environmental settings.

Risk assessment of urban soils contamination: The particular case of polycyclic aromatic hydrocarbons.

The assessment of soil quality and characterization of potential risks to the environment and human health can be a very difficult task due to the heterogeneity and complexity of the matrix, the poor understanding about the fate of contaminants in the soil matrix, scarcity of toxicological/ecotoxicological data and variability of guidelines. In urban soils these difficulties are enhanced by the patchy nature of urban areas and the presence of complex mixtures of organic and inorganic contaminants resulting from diffuse pollution caused by urban activities (e.g. traffic, industrial activity, and burning of carbon sources for heating). Yet, several tools are available which may help to assess the risks of soil contamination in a simpler, cost effective and reliable way. Within these tools, a tiered risk assessment (RA) approach, first based on a chemical screening in combination with geostatistical tools, may be very useful in urban areas. However, there is still much to improve and a long way to go in order to obtain a reliable RA, especially in the case of hydrophobic organic compounds such as polycyclic aromatic hydrocarbons (PAHs). This paper aims at proposing a RA framework to assess the environmental and human health risks of PAHs present in urban soils, based on existing models. In addition, a review on ecotoxicological, toxicological, and exposure assessment data was made, as well as of the existing soil quality guidelines for PAHs that can be used in the RA process.