Assessment of metal and metalloid contamination in soils trough compositional data: the old Mortórios uranium mine area, central Portugal.

Soils from the old Mortórios uranium mine area were studied to look for contamination, as they are close to two villages, up to 3 km away, and used for agriculture. They are mainly contaminated in U and As and constitute an ecological threat. This study attempts to outline the degree to which soils have been affected by the old mining activities through the computation of significant hot clusters, Traditional geostatistical approaches commonly use raw data (concentrations) accepting that the analyzed elements represent the soil's entirety. However, in geochemical studies these elements are just a fraction of the total soil composition. Thus, considering compositional data is pivotal. The spatial characterization, considering raw and compositional data together, allowed a broad discussion about not only the concentrations' spatial distribution, but also a better understanding on the possibility of trends of "relative enrichment" and, furthermore an insight in U and As fate. The highest proportions (compositional data) on U (up to 33%), As (up to 35%) and Th (up to 13%) are reached in the south-southeast segment. However, the highest concentrations (raw data) occur in north and northwest of the studied area, pointing out to a "relative enrichment" toward the south-southeast zone. The Mondego Sul area is mainly contaminated in U and As, but also in Co, Cu, Pb and Sb. The Mortórios area is less contaminated than the Mondego Sul area.

Potential toxic elements in stream sediments, soils and waters in an abandoned radium mine (central Portugal).

The Alto da Várzea radium mine (AV) exploited ore and U-bearing minerals, such as autunite and torbernite. The mine was exploited underground from 1911 to 1922, closed in 1946 without restoration, and actually a commercial area is deployed. Stream sediments, soils and water samples were collected between 2008 and 2009. Stream sediments are mainly contaminated in As, Th, U and W, which is related to the AV radium mine. The PTEs, As, Co, Cr, Sr, Th, U, W, Zn, and electrical conductivity reached the highest values in soils collected inside the mine influence. Soils are contaminated with As and U and must not be used for any purpose. Most waters have pH values ranging from 4.3 to 6.8 and are poorly mineralized (EC = 41-186 µS/cm; TDS = 33-172 mg/L). Groundwater contains the highest Cu, Cr and Pb contents. Arsenic occurs predominantly as H2(AsO4)- and H(AsO4)2-. Waters are saturated in goethite, haematite and some of them also in lepidocrocite and ferrihydrite, which adsorbs As (V). Lead is divalent in waters collected during the warm season, being mobile in these waters. Thorium occurs mainly as Th(OH)3(CO3)-, Th(OH)2(CO3) and Th(OH)2(CO3) 22- , which increase water Th contents. Uranium occurs predominantly as UO2CO3, but CaUO2(CO3) 32- and CaUO2(CO3)3 also occur, decreasing its mobility in water. The waters are contaminated in NO2-, Mn, Cu, As, Pb and U and must not be used for human consumption and in agricultural activities. The water contamination is mainly associated with the old radium mine and human activities. A restoration of the mining area with PTE monitoring is necessary to avoid a public hazard.

Human health risks in an old gold mining area with circum-neutral drainage, central Portugal.

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 NO2-, 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 × 10-6) 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.

Potential risk assessment in stream sediments, soils and waters after remediation in an abandoned W>Sn mine (NE Portugal).

The mining complex of Murçós belongs to the Terras de Cavaleiros Geopark, located in Trás-os-Montes region, northeast Portugal. A stockwork of NW-SE-trending W>Sn quartz veins intruded Silurian metamorphic rocks and a Variscan biotite granite. The mineralized veins contain mainly quartz, cassiterite, wolframite, scheelite, arsenopyrite, pyrite, sphalerite, chalcopyrite, galena, rare pyrrhotite, stannite, native bismuth and also later bismuthinite, matildite, joseite, roosveltite, anglesite, scorodite, zavaritskite and covellite. The exploitation produced 335t of a concentrate with 70% of W and 150t of another concentrate with 70% of Sn between 1948 and 1976. The exploitation took place mainly in four open pit mines as well as underground. Three lakes were left in the area. Remediation processes of confination and control of tailings and rejected materials and phytoremediation with macrophytes from three lakes were carried out between 2005 and 2007. Stream sediments, soils and water samples were collected in 2008 and 2009, after the remediation process. Most stream sediments showed deficiency or minimum enrichment for metals. The sequential enrichment factor in stream sediments W>Bi>As>U>Cd>Sn=Ag>Cu>Sb>Pb>Be>Zn is mainly associated with the W>Sn mineralizations. Stream sediments receiving drainage of a mine dump were found to be significantly to extremely enriched with W, while stream sediments and soils were found to be contaminated with As. Two soil samples collected around mine dumps and an open pit lake were also found to be contaminated with U. The waters from the Murçós W>Sn mine area were acidic to neutral. After the remediation, the surface waters were contaminated with F(-), Al, As, Mn and Ni and must not be used for human consumption, while open pit lake waters must also not be used for agriculture because of contamination with F(-), Al, Mn and Ni. In most waters, the As occurred as As (III), which is toxic and is easily mobilized in the drainage system. The remediation promoted a decrease in metals and As concentrations of soils and waters, however the applied processes were not enough to rehabilitate the area.