Availability of polycyclic aromatic hydrocarbons to earthworms in urban soils and its implications for risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) are a global problem, and in urban soils they can be found at potentially hazard levels. Nevertheless, the real risks that these contaminants pose to the environment are not well known, since the bioavailability of PAHs in urban soils has been poorly studied. Therefore, the bioavailability of PAHs in some selected urban soils from Lisbon (Portugal) was evaluated. Moreover, the applicability of a first screening phase based on total contents of PAHs was assessed. Results show that bioavailability of PAHs is reduced (low levels in earthworms, low accumulation percentages, and low biota-to-soil accumulation factors values), especially in more contaminated soils. The aging of these compounds explains this low availability, and confirms the generally accepted assumption that accumulation of PAHs in urban areas is mostly related with a long-term deposition of contaminated particles. The comparison of measured PAHs concentrations in earthworm tissues with the ones predicted based on theoretical models, reinforce that risks based on total levels are overestimated, but it can be a good initial approach for urban soils. This study also highlights the need of more reliable ecotoxicological data.

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.

Biomonitoring of several toxic metal(loid)s in different biological matrices from environmentally and occupationally exposed populations from Panasqueira mine area, Portugal.

In the Panasqueira mine area of central Portugal, some environmental media show higher metal(loid) concentrations when compared with the local geochemical background and the values proposed in the literature for these environmental media. In order to evaluate the effect of the external contamination on selected indexes of internal dose, As, Cd, Cu, Cr, Fe, Hg, Mg, Mn, Mo, Ni, Pb, S, Se, Si, and Zn were quantified by inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry in blood, urine, hair and nail samples from individuals environmentally (N = 41) and occupationally exposed (N = 41). A matched control group (N = 40) was also studied, and data from the three groups were compared. Results obtained agreed with those reported by environmental studies performed in this area, pointing to populations living nearby and working in the mine being exposed to metal(loid)s originated from mining activities. Arsenic was the element with the highest increase in exposed populations. The concentration of other elements such as Cr, Mg, Mn, Mo, Ni, Pb, S, Se, and Zn was also increased, although at a lesser extent, specifically in the individuals environmentally exposed and in females. These findings confirm the need for competent authorities to act as soon as possible in this area and implement strategies aimed to protect exposed populations and the entire ecosystem.

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.

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.

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.

A review of regulatory decisions for environmental protection: part II - the case-study of contaminated land management in Portugal.

This paper provides a case-study analysis of the challenges in the implementation of national soil policies, which was developed by the authors in Part I of the review of regulatory decisions for environmental protection [Rodrigues SM, Pereira ME, Ferreira da Silva E, Hursthouse A, Duarte AC. A review of regulatory decisions for environmental management: Part I-challenges in the implementation of national soil policies. Environ Int 2009. doi:10.1016/j.envint.2008.08.007]. The Portuguese case was selected as a case-study since specific regulatory decisions for contaminated land management are still in the early stages of development. Given the gap between the situation at the EU level and the state of Portuguese soil policy development, it is of merit to consider national contaminated land policy regimes already in place within the EU and to see if these provide a suitable basis to define the main challenges and research needs for the implementation of a Portuguese contaminated land management strategy. A framework combining the D-P-S-I-R (drivers-pressures-sources-impacts-responses) structure of policy evaluation with the Source-Pathway-Receptor approach to health risk assessment is proposed to derive an effective regulatory framework for managing contaminated land in Portugal, using available information and only to develop new data and research where knowledge gaps exist. Funding site clean-up and assigning liability were identified as relevant factors currently hampering site remediation. Most relevant research needs for the development of contaminated land management practices in Portugal are those associated to the definition of a risk assessment framework and setting guidelines for the evaluation of risks posed to both humans and ecosystems. Other relevant and innovative features are the integration of soil function analysis into site investigations and the definition of a framework that combines risk assessment with soil function analysis. The analysis of the Portuguese case also provides insight into the discussions needed for the effective development of regulatory decisions for contaminated land management in countries with no history of implementing specific soil policies.

Spatial patterns of dispersion and pollution sources for arsenic at Lousal mine, Portugal.

This study uses geostatistical modelling to identify hot spots of metal contamination produced by hazardous mining tailings from an inoperative Portuguese mine. Lousal is one of the many massive sulphide deposits of the Iberian Pyrite Belt. The mine is now closed, but the heavy metal enriched tailings remain at the site. Applying geostatistics to the diagnosis of this potentially contaminated area we aim to assess the quality of the soil, namely through a risk probability mapping for arsenic, for a better knowledge about the vulnerability of the soil to arsenic contamination. To achieve this aim, the initial variable was transformed into two indicator variables using the risk-based standards (intervention values) for soils, as proposed by Swartjes (1999), as the limit value. To account for the spatial structure, sample variograms were computed for the main directions of the sampling grid and a spherical model was fitted to the variables (arsenic raw data and indicator variables). The parameters of the model were used in the estimation process. To assess the vulnerability of the soil towards the mining works, a soil quality probability mapping for arsenic was carried out showing contamination probabilities in the area. The use of indicator kriging, as an alternative to other more complex kriging methods, in the soil data of the Lousal mine, produced unbiased soil quality maps.

Application of geostatistical methods to arsenic data from soil samples of the Cova dos Mouros mine (Vila Verde-Portugal).

A total of 286 soil samples were collected in the Cova dos Mouros area. All samples were dry sieved into the <200 mesh size fraction and analysed for Fe, Cu, Zn, Pb, Co, Ni, Bi and Mn by atomic absorption spectrometry (AAS) and for As, Se, Sb and Te by atomic absorption spectrometry-hydrid generation (AAS-HG). Only the results of arsenic are discussed in this paper although the survey was extended to all analysed chemical elements. The purpose of this study was to make a risk probability mapping for arsenic that would allow better knowledge about the vulnerability of the soil to arsenic contamination. To achieve this purpose, the initial variable was transformed into an indicator variable using as thresholds the risk-based standards (intervention values) for soils, as proposed by [Swartjes 1999. Risk based assessment of soil and groundwater quality in the Netherlands: Standards and remediation. J. Geochem. Explor.73 1-10]. To account for spatial structure, sample variograms were computed for the main directions of the sampling grid and a spherical model was fitted to each sample variogram (arsenic variable and indicator variables). The parameters of the spherical model fitted to the arsenic variable were used to predict arsenic concentrations at unsampled locations. A risk probability mapping was also done to assess the vulnerability of the soil towards the mining works. The parameters of the spherical model fitted to each indicator variable were used to estimate probabilities of exceeding the corresponding threshold. The use of indicator kriging as an alternative to ordinary kriging for the soil data of Cova dos Mouros produced unbiased probability maps that allowed assessment of the quality of the soil.