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Santiago de Compostela, Spain

Martinez Cortizas A.,Facultade de Bioloxia | Lopez-Merino L.,Brunel University | Bindler R.,Umea University | Mighall T.,University of Aberdeen | Kylander M.,University of Stockholm
Journal of Paleolimnology

Extensive mining took place in Spain during the Iron Age and Roman times, although a detailed chronology is still lacking due to the inherent difficulties in dating mining structures. In this study we sampled and analyzed a core from La Molina mire in the Asturias region, northern Spain. Because more than 100 Roman mines have thus far been found within 20 km of the mire, our aim was to shed light on local mining history, which we can then compare to the wider narrative of early mining pollution in Spain. We focus on the section from ~500 BC to AD ~600, which has a high temporal resolution of 6-15 year per sample. Geochemical analyses included the determination of major, minor and trace lithogenic elements (Si, Al, Fe, Ti, Ga, Rb, Y, Zr, Th) as markers of mineral content of the peat, and trace metals/metalloids (Mn, Cu, Ni, As, Pb) as well stable Pb isotopes, as potential markers of atmospheric metal pollution. The use of principal components analysis enabled the identification of a dominant geogenic component and a secondary pollution component. The earliest pollution signal of the covered period was recorded by ~300 BC, coinciding with the late local Iron Age. Average 206Pb/207Pb ratios of samples with ages older than this date was 1.204 ± 0.002, while all samples with a younger age had a less radiogenic ratio. Based on the metal pollution component four phases were identified: I, ~500 to 300 BC; II, ~300 to 20 BC; III, ~20 BC-AD 480; IV, AD ~480 to 600. The lowest isotopic ratio and highest proportion of pollution Pb (206Pb/207Pb ratio of 1.157 and 89 % of total accumulated Pb) was reached at peak Pb production during Roman times (AD ~180 to 340), indicating that this was the period of most intense metal contamination in the area over the studied period. It is remarkable that the La Molina record shows a more extended period (two centuries) of active mining in comparison with other areas in Iberia, and a pattern of repeated shifts in Pb pollution of short duration, which is likely related to the local history of exploitation and exhaustion of mines within the area. © 2013 Springer Science+Business Media Dordrecht. Source

Cortizas A.M.,Facultade de Bioloxia | Vazquez C.F.,Facultade de Bioloxia | Kaal J.,Pyrolyscience | Biester H.,TU Braunschweig | And 3 more authors.
Geochimica et Cosmochimica Acta

Recent investigations showed that bromine is incorporated to soil organic matter (SOM), its content increasing with humification. But few research was done on its long-term accumulation and the role played by pedogenetic processes, as those involved in organic matter stabilization. We investigated bromine content and distribution in four deep, acidic, organic-rich, Holocene soils from an oceanic area of Western Europe. Bromine concentrations (93-778μgg-1) in the silt+clay (<50μm) fraction were on average 3-times higher than those (17-250μgg-1) in the fine earth (<2mm), the former containing almost all bromine (90±5%). Inventories were between 148 and 314gm-2, indicating a rather large variability in a small area, and total estimated retention was low (6-16%). The degree of SOM bromination, expressed as the Br/C molar ratio, varied between 0.03 and 1.20mmol Br/mol C. The ratio was highly correlated (n=23, r2 0.88, p<0.01) with the age of the SOM for the last ~12ka. Partial least squares modeling indicates that bromine concentration depends on the amount of organic matter stabilized as aluminium-OM associations, and to a lesser extent on soil acidity (pH) and iron-OM associations. Thus, at scales of thousands of years, bromine accumulation in acidic soils is linked to the pool of metal-clay-stabilized organic matter. © 2015 Elsevier Ltd. Source

Cortizas A.M.,Facultade de Bioloxia | Muniz I.R.,Facultade de Bioloxia | Taboada T.,Facultade de Bioloxia | Giralt S.,CSIC - Institute of Earth Sciences Jaume Almera | And 2 more authors.
Solid Earth

We sampled a short (57 cm) sediment core in Limnopolar Lake (Byers Peninsula, Livingston Island, South Shetland Islands), which spans the last ca. 1600 years. The core was sectioned at high resolution and analyzed for elemental and mineralogical composition, and scanning electron microscope and energy dispersive X-ray spectrometer (SEM-EDS) analysis of glass mineral particles in selected samples. The chemical record was characterized by a contrasted pattern of layers with high Ca, Ti, Zr, and Sr concentrations and layers with higher concentrations of K and Rb. The former were also enriched in plagioclase and, occasionally, in zeolites, while the latter were relatively enriched in 2 : 1 phyllosilicates and quartz. This was interpreted as reflecting the abundance of volcaniclastic material (Ca rich) versus Jurassic-Lower Cretaceous marine sediments (K rich) - the dominant geological material in the lake catchment. SEM-EDS analysis revealed the presence of abundant volcanic shards in the Ca-rich layers, pointing to tephras most probably related to the activity of Deception Island volcano (located 30 km to the SE). The ages of four main peaks of volcanic-rich material (AD ca. 1840-1860 for L1, AD ca. 1570-1650 for L2, AD ca. 1450-1470 for L3, and AD ca. 1300 for L4) matched reasonably well the age of tephra layers (AP1 to AP3) previously identified in lakes of Byers Peninsula. Some of the analyzed metals (Fe, Mn, Cu, and Cr) showed enrichments in the most recent tephra layer (L1), suggesting relative changes in the composition of the tephras as found in previous investigations. No evidence of significant human impact on the cycles of most trace metals (Cu, Zn, Pb) was found, probably due to the remote location of Livingston Island and the modest research infrastructures; local contamination was found by other researchers in soils, waters and marine sediments on areas with large, permanent research stations. Chromium is the only metal showing a steady enrichment in the last 200 years, but this cannot be directly attributed to anthropogenic pollution since recent research supports the interpretation that climatic variability (reduced moisture content and increased wind intensity) may have resulted in enhanced fluxes of mineral dust and trace elements (Cr among them) to Antarctica. At the same time, some features of the chemical record suggest that climate may have also played a role in the cycling of the elements, but further research is needed to identify the underlying mechanisms. © Author(s) 2014. Source

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