Statistical evaluation of the geochemical variability in overbank sediments in Spain.

The overall objective of this study is to estimate, detect and specify the main sources of variance which affect the contents of the different elements in overbank sediments across Spain. These sources of variance were assessed and compared by means of a series of analyses of variance (ANOVAs), by regarding two parameters: their significance and their contribution to the total variance. Overbank sediments, sampled in erosion banks, were studied in several locations, in basins which drain different types of geological backgrounds and land uses (urban, mining, agricultural or pristine) across the Iberian Peninsula. Forty-eight elements (mostly in the < 63 µm fraction) were analysed by ICP-OES, ICP-MS and INAA. After an isometric log ratio (ilr) transformation of the data, three ANOVA analyses were performed considering three perspectives: (1) local scale, (2) regional scale: within-profile perspective and (3) regional scale: inter-profile perspective. On a local scale, it was observed that the variability of rare earth elements (REE) depends mostly on the grain size and that heavy metals are also influenced by depth. In the analysis carried out on a regional scale, from a within-profile perspective, depth and duplicates do not influence significantly the variability of the element contents. Finally, from an inter-profile perspective, the selected sources of variance were land use and provenance, whose significance is the highest. While grain size and the selection of depth are of crucial importance in the final results, on local studies, land use and provenance are the ones that influence the most the composition of sediments in regional studies.

Compositional analysis of topsoil metals and its associations with cancer mortality using spatial misaligned data.

The presence of toxic metals in soil per se, and in soil impacted by mining, industry, agriculture and urbanisation in particular, is a major concern for both human health and ecotoxicology. The dual aim of this study was: to ascertain whether topsoil composition could influence the spatial distribution of mortality due to different types of cancer and to identify possible errors committed by epidemiological studies which analyse soil composition data as a closed number system. We conducted an ecological cancer mortality study, covering 861,440 cancer deaths (27 cancer sites) in 7917 Spanish mainland towns, from 1999 to 2008. Topsoil levels of Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by ICP-MS at 13,317 sampling points. We transformed the topsoil data in two ways, i.e. log transformation and centred logratio transformation. Principal factor analysis was performed to obtain independent latent factors for the transformed variables. To estimate the effect on mortality of topsoil factor loadings, we fitted Besag, York and Mollié models embedded in geostatistical-spatial models. This model included soil sample locations and town centroids (non-aligned data), fitted using the integrated nested Laplace approximation (INLA) as a tool for Bayesian inference and stochastic partial differential equations (SPDE). All results were adjusted for socio-demographic variables. The results indicated that soil composition could have an influence on the spatial distribution and mortality patterns of cancer. The analysis adjusted for socio-demographic variables showed excess male mortality due to digestive system tumours in areas with soils containing higher Cd, Pb, Zn, Mn and Cu concentrations, bladder cancer in areas with soils containing higher Cd concentrations, and brain cancer in areas with soils containing As. In both sexes, cancer of oesophagus was associated with soils containing a higher lead content, while lung cancer was associated with soils containing a higher copper content. Stress should be laid on the importance of taking into account the compositional nature of the data in this type of analysis.

Association between heavy metal and metalloid levels in topsoil and cancer mortality in Spain.

Spatio-temporal cancer mortality studies in Spain have revealed patterns for some tumours which display a distribution that is similar across the sexes and persists over time. Such characteristics would be common to tumours that shared risk factors, including the geochemical composition of the soil. The aim of this study was to assess the possible association between heavy metal and metalloid levels in topsoil (upper soil horizon) and cancer mortality in mainland Spain. Ecological cancer mortality study at a municipal level, covering 861,440 cancer deaths (27 different tumour locations) in 7917 Spanish mainland towns, from 1999 to 2008. The elements included in this analysis were Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Topsoil levels (partial extraction) were determined by ICP-MS at 13,317 sampling points. For the analysis, the data on the topsoil composition have been transformed by the centred logratio (clr-transformation). Principal factor analysis was performed to obtain independent latent factors for the transformed variables. To estimate the effect of heavy metal levels in topsoil composition on mortality, we fitted Besag, York and Mollié models, which included each town's factor scores as the explanatory variable. Integrated Nested Laplace Approximation (INLA) was used as a tool for Bayesian inference. All results were adjusted for sociodemographic variables. The results showed an association between trace contents of heavy metals and metalloids in topsoil and mortality due to tumours of the digestive system in mainland Spain. This association was observed in both sexes, something that would support the hypothesis that the incorporation of heavy metals into the trophic chain might be playing a role in the aetiology of some types of cancer. Topsoil composition and the presence of potentially toxic elements in trace concentrations might be an additional component in the aetiology of some types of cancer, and go some way to determine the ensuing geographic differences in mortality in Spain. The results support the interest of inclusion of heavy metal levels in topsoil as a hypothesis in analytical epidemiological studies using biological markers of exposure to heavy metals and metalloids.

Application of lead isotopic methods to the study of the anthropogenic lead provenance in Spanish overbank floodplain deposits.

Changes in the principal sources of Pb in overbank sediment profiles have been documented for two Spanish areas by using Pb isotopes and Pb concentrations. These locations (Madrid and Tinto-Odiel basin) represent two of the most contaminated regions in Spain. The Community of Madrid is characterized by heavy industrial and urban activity, focused mainly in Madrid City. The Tinto-Odiel basin drains the Iberian Pyrite Belt, which hosts many polymetallic massive sulphides and is heavily affected by mining activities in their headwaters. It has been proven that the influence of anthropogenic activity is reflected in these overbank deposits by variations in Pb concentrations that, in general, correlate with shifts in the (206)Pb/(207)Pb ratio. Rivas profile (downstream of Madrid) was found to be the most anthropogenically influenced site. The sediments within this profile which were recently deposited (170 ± 40 years BP) have the least radiogenic signatures. (206)Pb/(207)Pb ratios ranged between 1.1763 and 1.1876 indicating significant contributions of anthropogenic Pb. In contrast, profiles upstream of Madrid possess an average (206)Pb/(207)Pb ratio of 1.2272. It is difficult to clearly identify the most prominent source as the sediments appear to be characterized by an input from several sources. The floodplain profiles in the Tinto-Odiel basin exhibit uniform (206)Pb/(207)Pb ratios ranging from 1.1627 (Odiel river) to 1.1665 (Tinto river). These ratios are similar to the ones possessed by sulphide ores in the area and differ from the ratios of other nonmineralized formations in the basin, indicating that mining activities are the primary, if not sole, source of Pb to the sediments.

A geochemical study of overbank sediments in an urban area (Madrid, Spain).

Overbank and stream sediments have been studied in the Community of Madrid. Four vertical profiles have been sampled corresponding to Guadarrama, Jarama, and finally Manzanares River, where two profiles have been studied upstream (El Pardo profile) and downstream (Rivas profile) Madrid city. Sieved samples (<63 µm) were subjected to total (ICP-MS/ICP-OES and INAA) and partial analysis (ICP-MS). AMS radiocarbon dating techniques revealed a young age (170 ± 40 years BP) at 2.40-2.65 m depth for Rivas profile. It has not been possible to detect pristine or pre-industrial overbank sediments, since in the rest of the studied profiles, anthropogenic wastes were found even in the lower levels. Three main sources of sediment have been detected in the area. Granitic and arkosic geology, located in the northern part of Madrid (U, Th, W, K, Na, or rare earth elements); clays located in the southeast of Madrid (Ni, Cr, or V), and finally an anthropogenic source has been identified (Au, Ag, Pb, Zn, or Sb) in Rivas profile. The influence of the anthropogenic activity has been established based on the contents distribution of contaminant elements in the profile. This can be associated to the growth of industrial activities and population in the city of Madrid during the last decades. The comparison of the profiles by a k-means cluster analysis showed some similarities for these samples that could have analogous sources (anthropogenic and geological).