A biotite granodiorite and seven Sn-bearing two-mica granites crop out in the Gouveia area, central Portugal. A SHRIMP U-Th-Pb zircon age from the granodiorite, and monazite ages from four of the two-mica granites, show that they are of Early Ordovician (~480 Ma) and Permo-Carboniferous, i.e. Variscan (~305 and 290 Ma) age respectively. The Variscan two-mica granites are late-and post-D3. Major and trace element variation in the granitic rocks and their biotite and muscovite indicate mainly individual fractionation trends. The granitic rocks are mostly depleted in HREE relative to LREE. The biotite granodiorite is probably derived from igneous lower crust, as evidenced by low initial 87 Sr/ 86 Sr (0.7036), high εNd T (+ 2.5) and moderate δ 18 O (8.8‰). The two-mica granites are probably derived by partial melting of heterogeneous mid-crustal metasediments, mainly metapelite and some metagraywacke, as evidenced by their high initial 87 Sr/ 86 Sr (0.7076-0.7174), δ 18 O (10.7-13.4‰) and major element compositions. However, variation diagrams for major and trace elements from two of the muscovite N biotite granites and their micas define fractionation trends. Rb-Sr whole-rock analyses from the two granites are perfectly fitted to a single isochron and the rocks have subparallel REE patterns; the younger granite is derived from the older by fractional crystallization of quartz, plagioclase, biotite and ilmenite (tested by modelling major and trace elements). Most of the Sn-bearing granites are derived from distinct magma batches. They result from partial melting of a heterogeneous midcrustal metasediment. They do not represent a crustal anomaly in tin. Fractional crystallization is responsible for the increase in the Sn contents of the granites and their micas. Muscovite has a higher Sn content than coexisting biotite and is the principal host mineral for Sn in these rocks.

The main purpose of this study is to assess arsenic and antimony availability in soils, as well as Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn availability in soils derived from the schist-metagraywacke complex close to old SbAu mines and in soils developed from Ordovician slates and close to an old As-Au mine in Portugal. The availability was determined using a European certified sequential extraction procedure (BCR). The results demonstrated that metalloids are not readily bioavailable, because they are mainly associated with the residual fraction. Arsenic and antimony proportions in exchangeable fractions are up to 3 and 1%, respectively. However, arsenic is up to 24% in oxy-hydroxide fractions, while antimony is up to 4% in them, demonstrating the highest bioavailability of arsenic compared to that of antimony, as metalloids are weakly bound to the soils in that fraction. Therefore, arsenic tends to be more toxic than antimony in all soils studied. However, the pseudo-total contents show that both metalloids are above the Italian and Dutch guidelines. Therefore, if physico-chemical changes occur arsenic and antimony will show higher potential environmental risk than evidenced by Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn.

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The former mine of Escádia Grande was active at the middle of 1900 and was exploited for Au and Ag. The mineralized quartz veins consist mainly of quartz, arsenopyrite, pyrite, rare chalcopyrite, galena, sphalerite, gold and argentite. The mine dumps and tailings were deposited close to a stream, and there is a river beach downstream used for recreational proposes. Two villages are also located close to the old mining area. Mine wastes contained up to 8090 mg/kg of As and 70.1 mg/kg of Sb. The waters of the stream that cross the mining area have circum-neutral pH values and contained elevated concentrations of As reaching up to 284 µg/L. However, geochemical speciation modeling (Phreeq C) revealed that As was mainly present as As (V). Arsenic concentrations in waters are attenuated throughout the stream, mainly by the iron-(hydro)-oxides adsorption upstream. However, at 2 km downstream of mine wastes in the river beach, the waters still exceeded 10 µg/L of As, the drinking water limit. The waters also have NO, Cu and Cd concentrations higher than drinking water limit. The stream sediments have As concentrations up to 45 times higher (3140 mg/kg) than the limit of the sediment guideline values of NWQMS (2000). The maximum arsenic concentrations in soils are also up to 27 times higher (5940 mg/kg) than the maximum concentrations in streams from FOREGS Geochemical Atlas of Europe. The use of river beach for recreational purposes causes cancer risk (4.48 × 10) higher than USEPA limit, mainly due to the arsenic exposure. Even for recreational purposes, stream sediments and soils in the old mining area have high non-carcinogenic effects (2.76 and 4.78, respectively) for children, also related to the arsenic exposure mainly by the ingestion pathway, and the risk is unacceptable according to the limits of USEPA. Moreover, the cancer risk resulting from exposure of adults to arsenic in soils also has unacceptable non-cancer risk (1.13). Arsenic is the main trace element that causes a human health concern in the Escádia Grande mining area.