A. P. Reis

Geochemistry, mineralogy, solid-phase fractionation and oral bioaccessibility of lead in urban soils of Lisbon

AbstractAn urban survey of Lisbon, the largest city in Portugal, was carried out to investigate its environmental burden, emphasizing metallic elements and their public health impacts. This paper examines the geochemistry of lead (Pb) and its influence on human health data. A total of 51 soil samples were collected from urban recreational areas used by children to play outdoors. The semi-quantitative analysis of Pb was carried out by inductively coupled plasma mass spectrometry after an acid digestion. X-ray diffraction was used to characterize the soil mineralogy. The solid-phase distribution of Pb in the urban soils was investigated on a subset of 7 soils, out of a total of 51 samples, using a non-specific sequential extraction method coupled with chemometric analysis. Oral bioaccessibility measurements were obtained using the Unified BARGE Method developed by the Bioaccessibility Research Group of Europe. The objectives of the study are as follows: (1) investigation of Pb solid-phase distribution; (2) interpretation of Pb oral bioaccessibility measurements; (3) integration of metal geochemistry with human health data; and (4) understanding the influence of geochemistry and mineralogy on oral bioaccessibility. The results show that the bioaccessible fraction of Pb is lower when major metal fractions are associated with less soluble soil phases such as Fe oxyhydroxides, and more increased when the metal is in the highly soluble carbonate phase. However, there is some evidence that the proportion of carbonates in the soil environment is also a key control over the oral bioaccessibility of Pb, irrespective of its solid-phase fractionation.

Lead availability in soils from Portugal’s Centre Region with special reference to bioaccessibility

Previous environmental biomonitoring studies indicated higher environmental lead (Pb) pollution levels at the districts of Aveiro and Leiria (Portugal). In evaluating the risk for human health, which is associated with contaminated soils after oral uptake, total soil concentrations have generally been held against criteria established from toxicological studies based upon the assumption that the uptake of the contaminant is similar in the toxicological studies and from the soils assessed. This assumption is not always valid, as most toxicological studies are carried out with soluble forms of the contaminants, whereas many soil contaminants are or become embedded in the soil matrix and thus exhibit limited availability. This study intends to estimate the soluble fraction of Pb in the soils from central Portugal, and to assess the bioaccessibility of Pb and, hence, infer exposure and risk for human health. Yet, as the physical–chemical properties of the soil exert some control over the solubility of Pb in the surface environment, the relation between such soil properties and the estimated soluble and/or bioaccessible fractions of Pb is also investigated. Other objective, with a more practical nature, was to give some contribution to find a suitable in vitro mimetic of the gastrointestinal tract environment. The results indicate relatively low total metal concentrations in the soils, even if differences between regions were observed. The Aveiro district has the higher total Pb concentration and the metal is in more soluble forms, that is, geoavailable. Soils with higher concentrations of soluble Pb show higher estimates of bioaccessible Pb. Soil pH seems to influence human bioaccessibility of Pb.

Assessment of human exposure to environmental heavy metals in soils and bryophytes of the central region of Portugal

This study intends to identify the spatial patterns of variation for some metals and metalloids, in soils and mosses, in the central region of Portugal. The purposes were: (i) to identify relationships amongst five elements (Cu, Pb, Zn, Cr and As) in three different media (topsoil, bottom soil and bryophytes) and with some site-specific characteristics, using Multiple Correspondence Analysis; (ii) to define spatial patterns of variation for the associations identified by Multiple Correspondence Analysis using Variography and Ordinary Kriging; and (iii) to assess atmospheric deposition as a source of heavy metals to the topsoil by crossing results with the biomonitors. The results indicated relatively low metal concentrations in soils and mosses. Some metal associations and dissociations were identified. The spatial patterns of variation of bottom and topsoil are distinct. There is some evidence that different site-specific characteristics control the spatial distribution of different elements. The areas within the central region of Portugal with a higher vulnerability to metal contamination were identified.

Assessing human exposure to aluminium, chromium and vanadium through outdoor dust ingestion in the Bassin Minier de Provence, France

The Western part of the “Bassin Minier de Provence”, a former coal mining area, is still occupied by old polluting industries such as a coal-fired power plant and an alumina factory. The identified pollution sources that raise more concern in the population are the emission of gases and dusts, as well as the storage of raw and transformed materials. In 2011, a preliminary survey was carried out in the area as the first step to an exposure and health risk-assessment study. This first survey intends to assess human exposure through ingestion and health risk associated with potentially harmful elements (PHEs) in ground-level dusts collected in recreational areas used by children. Dust samples were taken at 19 sites distributed across the study area, depending on the location of public parks, public gardens, playgrounds and schools. Pseudo-total concentrations of 53 elements were determined by ICP-MS. Bioaccessible concentrations were estimated using the unified bioaccessibility method. This study presents the results obtained for Al, V and Cr, which seem to be related with industry and show similar distribution patterns. PHEs presumably related to traffic or other urban pollution sources are not discussed in this study. The highest total concentrations occur in dusts near the alumina plant that have significant amounts of Al mineral phases (gibbsite and alumina). However, in these dusts only small fractions of the elements under study are in bioaccessible forms. The highest bioaccessible fractions occur in dusts collected near the coal-fired power plant. Further investigation is required to assess potential pathways of exposure and health risk in this area.

Environmental Assessment of the Caveira Abandoned Mine (Southern Portugal): Part 1: Characterization of Metal Contaminated Soil

Mine activity in Portugal had a huge impact on the growth of the regions where it took place, like in the Iberian Pyrite Belt. Nowadays, most of these mines are abandoned, as is the case for the Caveira mine. Soil geochemistry indicates that high contents of Cu, Pb, Zn, As, Cd, and Hg occur in the soils collected near the tailings. Multiple Correspondence Analysis identifies two areas with high concentrations of Pb, As, Hg, Sb, Mo, and Tl. However, the results suggest a different geochemistry for each of the areas. The non-site-specific methods (Hazard Index and GLC guidelines) classify all the areas as contaminated. Metal fractionation in the soil phases is different for the several elements studied. The articulation of the metal fractionation results with the GLC guidelines reduces the area of soil contaminated by Pb, but not by As.

Source and pathway analysis of lead and polycyclic aromatic hydrocarbons in Lisbon urban soils.

One hundred soil samples were collected from urban spaces, in Lisbon, Portugal, in two surveys that were carried out in consecutive years, to assess the potential adverse human health effects following exposure to potentially toxic elements and organic compounds in the urban soils. The study hereby described follows on from the earlier work of the authors and aims at performing a source-pathway-fate analysis of lead (Pb) and polycyclic aromatic hydrocarbons (PAHs) in the urban soils in order to increase current knowledge on factors influencing exposure of the population. Various techniques were combined to achieve the proposed goal. Geogenic and anthropogenic sources were apportioned by means of Pb isotope mixing models. Isotope data was further coupled with geographic information system mapping to assess local mixed sources of Pb and PAHs. Unleaded vehicle exhaust and cement production show the largest relative contribution to the total soil-Pb, but their respective importance depends on factors such as location and urban landscape. The primary sources of PAHs to the urban soils are probably air and land traffic. Multivariate analysis was used to investigate which soil properties could influence mobility and fate of the contaminants. Whilst principal components analysis indicates carbonates and other calcium phases as probable factors controlling the dispersion of Pb in the urban soils, the linear models obtained from stepwise multiple regression analysis show that soil phosphorous (P) and manganese (Mn) are good predictors of the total soil Pb content. No robust model was obtained for the PAHs, impeding identifying environmental factors most likely to influence their dispersion in the urban soils. The solid-phase distribution study provided critical information to untangle the, at a first glance, contradictory results obtained by the multivariate analysis. Carbonates and other calcium phases, having these a probable anthropogenic origin, are soil components containing major fractions of Pb, P, and Mn.

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

Abstract 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.

Geochemical associations and their spatial patterns of variation in soil data from the Marrancos gold–tungsten deposit: a pilot analysis

ABSTRACT This paper discusses the results of a soil geochemical exploration survey in the environs of the Marrancos gold–tungsten deposit, dealing with 144 samples of topsoil, analysed for 53 chemical elements. At this initial stage of the project the main objectives were: (1) to identify associations between chemical elements; (2) to estimate spatial patterns of variation for such associations in the surficial materials. The associations were established using principal component analysis (PCA). Variography was used to obtain the theoretical model of spatial continuity of each variable. These models were used in the interpolation method (kriging) selected to estimate surficial dispersion patterns. The results of PCA and PCA mapping indicate distinct distribution patterns for the metals related to the primary mineralogical or geochemical association, as identified for this deposit. Based on the results, six of the 53 chemical elements studied were selected to estimate spatial patterns of dispersion in the topsoil. This approach allows the recognition of the geochemical signature of the deposit, and the selection of several target areas for follow-up work. Several sites were selected for water sampling (surficial and groundwater), and the soil samples to be used in partial extractions are now defined.

Assessing soil quality using p-field simulation: application to the Marrancos mining area, Portugal

Abstract The purpose of this study was to assess the negative impact on soil caused by several mining episodes that occurred at Marrancos mine, an old gold/silver mine. The main aims were to: (i) assess the quality of the soil and the delineation of areas potentially contaminated by arsenic; (ii) assess the uncertainty attached to the assignment; and (iii) present a method of stochastic simulation (probability field simulation) as an alternative technique to predict pollutant concentrations of heavy metals, or metalloids, at unsampled locations. Indicator kriging was used to model the uncertainty attached to the concentration values at the unsampled sites and p-field simulation produced probability maps that allowed assessment of the probability that the arsenic concentrations did not exceed a regulatory threshold. The probability maps were then used to identify hazardous areas. About 90 realisations were generated for the variable, meaning 90 equiprobable scenarios for the spatial distribution of arsenic. The use of a potential risk-based standard as contamination threshold shows a wide area of soils classified as hazardous for ecosystems that need further investigation to determine the urgency for remediation.

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.