Lead and zinc concentrations in household dust and toenails of the residents (Estarreja, Portugal): a source-pathway-fate model.

This paper describes a methodology developed to assess and apportion probable indoor and outdoor sources of potentially toxic elements while identifying chemical signatures in the household dust collected from private homes in an industrial city (Estarreja, central Portugal). Oral bioaccessibility estimates and the chemical composition of toenail clippings were used to assess indoor dust ingestion as a potential exposure pathway and further investigate exposure-biomarker relationships. Indoor and paired outdoor dust samples were collected from each household. A total of 30 individuals, who provided toenail clippings and a self-reported questionnaire, were recruited for the study. Total concentrations of 34 elements, including lead and zinc, were determined in washed toenail samples and household dust via Inductively Coupled Plasma-Mass Spectrometry. The oral bioaccessibility was estimated using the Unified BARGE Method. The enrichment factor shows that lead was enriched (10 < EF < 100) while zinc (EF > 100) was anomalously enriched in the household dust, thus indicating potential exposure in the home environment. The results from principal component analysis coupled to cluster analysis and linear discriminant analysis suggested that mixed contamination derived from multiple sources with a predominance of biomass burning. Stepwise multiple linear regression analysis was performed to model toenail data using the indoor dust elemental composition. Whereas the model obtained for lead was not reliable, indoor dust zinc and antimony contents arose as good predictors of toenail zinc. The exposure-biomarker relationships seem to be influenced by the oral bioaccessibility of the elements.

Investigating relationships between biomarkers of exposure and environmental copper and manganese levels in house dusts from a Portuguese industrial city.

This study reports on data obtained from a pilot survey focusing on house dust and toenail metal(loids) concentrations in residents living in the industrial city of Estarreja. The study design hereby described aims at investigating relationships between human toenails and both copper and manganese levels in settled house dusts. A total of 21 households and 30 individuals were recruited for the pilot study: 19 households corresponding to 27 residents living near the industrial complex, forming the exposed group, plus 2 households and 3 residents from residential areas with no anticipated environmental contaminants that were used for comparison. Factorial analysis was used for source identification purposes. Investigation on the potential influence of environmental factors over copper and manganese levels in the toenails was carried out via questionnaire data and multiple correspondence analysis. The results show that copper concentrations are more elevated in the indoor dusts, while manganese concentrations are more elevated in the outdoor dust samples. The geometrical relationships in the datasets suggest that the backyard soil is a probable source of manganese to the indoor dust. Copper and manganese contents in the toenail clippings are more elevated in children than in adults, but the difference between the two age groups is not statistically significant (p > 0.05). Investigation of environmental factors influencing the exposure-biomarker association indicates a probable relationship between manganese contents in indoor dust and manganese levels in toenail clippings, a result that is partially supported by the bioaccessibility estimates. However, for copper, no relationship was found between indoor dusts and the biomarkers of exposure.

Assessment of the influence of traffic-related particles in urban dust using sequential selective extraction and oral bioaccessibility tests.

Urban dust is a heterogeneous mix, where traffic-related particles can combine with soil mineral compounds, forming a unique and site-specific material. These traffic-related particles are usually enriched in potentially harmful elements, enhancing the health risk for population by inhalation or ingestion. Urban dust samples from Estarreja city and traffic-related particles (brake dust and white traffic paint) were studied to understand the relative contribution of the traffic particles in the geochemical behaviour of urban dust and to evaluate the long-term impacts of the metals on an urban environment, as well as the risk to the populations. It was possible to distinguish two groups of urban dust samples according to Cu behaviour: (1) one group with low amounts of fine particles (<38 µm), low contents of organic material, high percentage of Cu in soluble phases, and low Cu bioaccessible fraction (Bf) values. This group showed similar chemical behaviour with the brake dust samples of low- to mid-range car brands (with more than 10 years old), composed by coarser wear particles; and (2) another group with greater amounts of fine particles (<38 µm), with low percentage of Cu associated with soluble phases, and with greater Cu Bf values. This group behaved similar to those found for brake dust of mid- to high-range car brands (with less than 10 years old). The results obtained showed that there is no direct correlation between the geoavailability of metals estimated by sequential selective chemical extraction (SSCE) and the in vitro oral bioaccessibility (UBM) test. Thus, oral bioaccessibility of urban dust is site specific. Geoavailability was greatly dependent on particle size, where the bioaccessibility tended to increase with a reduction in particle diameter. As anthropogenic particles showed high metal concentration and a smaller size than mineral particles, urban dusts are of major concern to the populations' health, since fine particles are easily re-suspended, easily ingested, and show high metal bioaccessibility. In addition, Estarreja is a coastal city often influenced by winds, which favours the re-suspension of small-sized contaminated particles. Even if the risk to the population does not represent an acute case, it should not be overlooked, and this study can serve as baseline study for cities under high traffic influence.

The mobility and human oral bioaccessibility of Zn and Pb in urban dusts of Estarreja (N Portugal).

Twenty-one samples of urban dust were collected from Estarreja city (Portugal). The main objective of this work was to assess the potential availability of Pb and Zn present dust samples from Estarreja city via the oral ingestion exposure route using a combination of geochemical tests: (a) using sequential extraction to identify the fractionation of the Pb and Zn within the geochemical components that make up the dust and (b) in vitro bioaccessibility (BA) measurements to identify which components are the source(s) of the bioaccessible fraction (Bf). These samples were analysed for their quasi-total contents of Pb and Zn by inductively coupled plasma mass spectrometry, for their element solid-phase distribution using selective sequential extraction method and for the Bfs of these elements using a physiologically based extraction test. The study showed that the concentrations of Zn were higher than Pb, but both are site-specific. The sequential extraction test shows that the exchangeable and acid-soluble phases are important bearing phases for Pb and Zn. The BA test showed that a high proportion of the total concentration is available for absorption into the human body (ranges from 22.5 to 84.1% for Pb and 28.7 to 86.3% for Zn).

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.

Speciation of Cd and Pb in dust emitted from sinter plant.

Many studies have provided evidence of the impact of heavy metals in atmospheric emission. Sinter plants represent the first step in steel production, and are important emitters of Cd and Pb. The toxicity of these two metals depends above all on their speciation. Particles collected before and after the filtration system were analysed to determine the Cd- and Pb-bearing phases, using analytical tools such as XRF, EXAFS or ICP-AES and chemical leaching (sequential extractions adapted to steel dusts). Results show that Pb is associated with carbonate and Cd with chloride. These two types of speciation lead to high solubility under common environmental conditions, which may produce impacts on the environment and health.

Determination of zinc speciation in basic oxygen furnace flying dust by chemical extractions and X-ray spectroscopy.

There is a growing concern regarding the environmental and public health risks associated with airborne particulate matter (PM). The basic oxygen furnace is one of the most important atmospheric dust sources of the steel manufacturing process. It emits dust enriched in heavy metal such as Zn, which is assumed to contribute to the toxic potential of atmospheric PM. Dust collected before and after the filtration system was analyzed to determine Zn speciation. To this end, a variety of analytical tools were used and a sequential extraction protocol has been specifically developed for iron and steel dust. The Zn speciation results obtained by EXAFS and sequential extraction were in excellent agreement. Before filtration, the speciation of Zn in BOF was 43% ZnFe(2)O(4), 23% ZnCO(3) and 16% ZnO. The same species were detected after filtration with different proportions. BOF dust after filtration contains more soluble Zn phases which may play a role in the toxic effects of the emissions.