Arsenic uptake by natural calcite: An XAS study

As-bearing travertine rocks from Tuscany (Italy), where previous studies suggested the existence of a CO₃²⁻ ⇔ AsO₃³⁻ substitution in the calcite lattice, were investigated with X-ray Absorption Spectroscopy (XAS) at the As K-edge (11,867 eV). In two of the studied samples, XANES indicates that As is in the 5+ oxidation state only, and EXAFS analysis reveals a local environment typical of arsenate species. For these samples, the lack of detectable second shell signals suggests a poorly ordered environment, possibly corresponding to an adsorption onto oxide and/or silicate phases. On the other hand, in the third sample XANES reveals a mixed As oxidation state (III and V). This sample also presents evident next nearest neighbor coordination shells, attributed to As-Ca and As-As contributions. The occurrence of next neighbor shells is evidence that part of As is incorporated in an ordered lattice. Furthermore, the local structure revealed by EXAFS is compatible with As incorporation in the calcite phase, as further supported by DFT simulations. The observation of next neighbors shells only in the As(III)-rich sample suggests the substitution of the arsenite group in place of the carbonate one (CO₃²⁻ ⇔ AsO₃³⁻). The conclusion of this work is that uptake of As by calcite is in general less favored than adsorption onto iron oxhydroxides, but could become environmentally important wherever the latter phenomenon is hindered.     

Impact of ancient metal smelting on arsenic pollution in the Pecora River Valley,Southern Tuscany,Italy

A significant As anomaly has been reported in the literature for stream sediments and unlithified Quaternary deposits of the Pecora River valley in Southern Tuscany, extending from the “Colline Metallifere” pyrite-base metals district to the Tyrrhenian Sea. The As anomaly spreads over several square kilometers around a core that exceeds 500 ppm. Several source contributions (from natural to anthropogenic) have been invoked to explain the observed As distribution in the Pecora Valley, including the metal-working industry which was active in this area, particularly in Etrusco-Roman times and in the Middle Ages. In order to evaluate the contribution of ancient mining and metallurgical activities in the Pecora Valley to elevated As concentrations in the environment, a detailed mineralogical and geochemical survey of metallurgical slags and smelted ore minerals was undertaken from six different sites through the Pecora Valley: Poggio Butelli (Etrusco-Roman iron slags); Sata Creek, Arialla, Marsiliana, Forra and Cascata sites (all Medieval base metals slags). The As content of Etrusco-Roman slags is relatively low (few tens of ppm), whereas Medieval slags show variable, but higher amounts of base metals (±Ag) (ranging from tens to tens of thousands ppm) and As (up to 267 ppm, with average contents of about 40 ppm). Arsenic is mostly partitioned in sulfides disseminated through the glassy groundmass rather than in solid solution with the glassy matrix. Remnants of the ore used for base metal and Ag smelting during the Middle Ages had the highest As contents (up to about 1000 ppm).     

Metamorphogenic barite-pyrite (Pb-Zn-Ag) veins at pollone, apuane alps, tuscany: vein geometry, geothermobarometry, fluid inclusions and geochemistry

Summary The barite-pyrite-(Pb-Zn-Ag) deposit of Pollone is located in the southernmost tip of the Apuane Alps metamorphic core complex, and is hosted by a siliciclastic formation of pre-Norian age. The southern sector of the deposit mainly consists of stratiform, supposedly syngenetic, barite-pyrite orebodies, whereas the northern area is characterized by a barite-pyrite-(Pb-Zn-Ag) vein system. Vein geometry in the northern area is controlled by a shear zone, developed during the greenschist facies metamorphism which affected the Apuane Alps core complex between 27 and 8 Ma, that was responsible for fluid focusing and vein emplacement. At Pollone, arsenopyrite and chlorite geothermometers show broadly comparable results, and suggest local metamorphic peak temperatures between 320 and 350°C. Phengite geobarometry indicates minimum pressures of about 3.5 kbar. Fluid inclusion data and mineral equilibria suggest that the mineralizing fluids were initially hotter than the country rocks (about 450°C at 3.5–4.0 kbar). Rocks in direct contact with the orebodies are depleted in Rb and enriched in Sr in comparison to similar rocks elsewhere in the area. This is attributed to the presence of Rb-poor muscovite and Sr-rich barite. Rb-depleted muscovites suggest mineral-fluid interaction in a rock reservoir characterized by a different (modal) mineralogical composition than the Pollone host rocks. The progressive decrease of Sr in barite with increasing distance from the orebodies may be explained with a temperature decrease along the infiltration paths of mineralizing fluids (i.e., from the vein into the wall rocks). The similar O-isotope composition of quartz from veins and host rocks is explained with the overall homogeneous O-isotope composition of the Alpi Apuane basement rocks. This indicates a limited interaction between mineralizing fluids and the rocks exposed at Pollone. Remobilization of syngenetic orebodies was conceivably of minor importance in the production of metamorphogenec veins. Fluid cooling along a major tectonic lineament is thought to be responsible for barite deposition.

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Die metamorphogenen Baryt-Pyrit (Pb-Zn-Ag) Gänge von Pollone, Apuanische Alpen, Toskana: Geometrie der Gänge, Geothermobarometrie, Flüssigkeitseinschlüsse und Geochemie

Zusammenfassung Die Baryt-Pyrit (Pb-Zn-Ag) Lagerstätte von Pollone liegt im südlichsten Ende des metamorphen Kern-Komplexes der Apuanischen Alpen, und sitzt in einer siliziklastischen Formation prä-Norischen Alters auf. Der südliche Sektor der Lagerstätte besteht hauptsächlich aus stratiformen, wahrscheinlich syngenetischen Baryt-Pyrit-Erzkörpern, während der nördliche Teil des Gebietes durch ein Baryt-Pyrit (Pb-Zn-Ag) Gangsystem charakterisiert wird. Die Geometrie der Gänge im Nordteil wird durch eine Scherzone kontrolliert, die während einer grünschieferfaziellen Metamorphose entstanden ist, die den Kernkomplex der Apuanischen Alpen zwischen 27 und 8 Ma betroffen hat. Diese Scherzone war auch für die Zufuhr der Fluide und die Platznahme der Gänge verantwortlich. In Pollone zeigen Arsenopyrit- und Chlorit-Geothermometrie weithin vergleichbare Ergebnisse und weisen auf lokale Maximaltemperaturen der Metamorphose zwischen 320 und 350°C hin. Phengit-Geobarometrie läßt Minimal-Drucke von ungefähr 3,5 kbar erkennen. Fluidflüssigkeitseinschluß-Daten und Mineral-Gleichgewichte zeigen, daß die erzbringenden Fluide ursprünglich heißer als die Wirtsgesteine waren (ca. 450 °C für P von 3,5 bis 4 kbar). Gesteine, die im direkten Kontakt mit den Erzkörpern sind, zeigen eine Anreicherung an Rb und eine Anreicherung an Sr, im Vergleich mit ähnlichen Gesteinen, die im Gebiet anzutreffen sind. Dies wird auf das Vorkommen von Rb-armen Muscovit und Sr-reichen Baryt zurückgeführt. An Rbabgereicherte Muscovite legen Mineral-Fluid-Reaktionen nahe, die in einem Gesteinsreservoir abliefen, das durch eine andere mineralogische Zusammensetzung als die Wirtsgesteine von Pollone charakterisiert war. Der zunehmende Verlust von Sr im Baryt mit zunehmender Entfernung von den Erzkörpern, kann durch einen Temperaturabfall entlang der Infitrations-Pfade der erzführenden Lösungen erklärt werden (d.h. von Gang in die Nebengeseine). Die ähnliche Sauerstoff-Isotopen-Zusammensetzung für Quarz aus den Gängen und den Nebengesteinen läßt sich auf die allgemein homogene Sauerstoffisotopen-Signatur des Basements der Apuanischen Alpen zurückführen. Dies weist auf beschränkte Wechselwirkung zwischen erzführenden Lösungen und den in Pollone anstehenden Gesteinen hin. Die Remobilisation von syngenetischen Erzkörpern in Pollone war nur von geringer Bedeutung für die Entstehung der metamorphogenen Gänge. Abkühlung der Fluide an einem wichtigen tektonischen Lineament gilt als Ursache für den Absatz von Baryt.

     

Sericitic alteration at the La Crocetta deposit (Elba Island,Italy): interplay between magmatism,tectonics and hydrothermal activity

The La Crocetta mine near Porto Azzurro (Elba Island, Tuscany, Italy) is an important producer of raw material for the ceramic industry. Exploitation focuses on a pervasively sericitized porphyritic aplite of the Tuscan Magmatic Province, locally known as "eurite", which underwent significant potassium enrichment during sericitic alteration. Eurites are located along the hanging wall of the Elba Centrale Fault, a low-angle extensional lineament of regional significance. A later carbonatization stage, apparently associated with high-angle extensional tectonics, locally overprinted the sericitized facies. It is expressed by carbonate ± pyrite ± quartz veins, with adverse effects on ore quality. Sericitization was accompanied by addition of potassium, and loss of Na (± Ca, Fe). Rubidium was not enriched along with potassium during sericitization, contrary to what would be expected for interaction with late-magmatic fluids. New ⁴⁰Ar–³⁹Ar data from eurites provide an isochron age of about 6.7 Ma for the sericitization, whereas the age of the unaltered protolith is ca. 8.8 Ma. Field evidence indicates the Elba Centrale Fault to be the main channel for the hydrothermal fluids. On the other hand, the involvement of heat and/or fluids contributed by the Porto Azzurro pluton, which crops out in the La Crocetta area, is ruled out by field, geochemical and geochronological data (⁴⁰Ar–³⁹Ar age of Porto Azzurro =5.9 Ma, i.e. significantly younger than the sericitization event). Fluid inclusion studies suggest that sericitization was associated with a low-temperature (<250 °C) hydrothermal system. Fluids were locally boiling, of variable salinity (4–17 wt% NaCl equiv.), and contained some CO₂ (XCO₂≤0.027). Their ultimate source is not unequivocally constrained; meteoric and/or magmatic contributions may be possible. Low-salinity (≤2.6 wt% NaCl equiv.), low-temperature (<250 °C) fluids are associated with the late carbonate veining. They are considered to be of dominantly meteoric nature because of their low salinity. In summary, sericitization at La Crocetta is regarded as the product of a detachment fault-related, low temperature hydrothermal system, resulting from the structurally controlled focusing of meteoric and possibly magmatic fluids. Hence, potential targets for exploration for similar resources are represented by aplitic bodies located in the hanging wall of Elba Centrale Fault. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00126-002-0279-2.     

Source of metals in metamorphic ore-forming processes in the Apuane Alps (NW Tuscany,Italy): Constraints by Pb-isotope data

Summary A total of 19 samples of sulfides, barite and country rocks from three important deposits of the Apuane Alps district (Bottino, Pollone and Monte Arsiccio) were analyzed for Pb-isotopic compositions. Ore lead shows a fairly homogeneous isotopic signature (206/204: 18.2-18.4; 207/204 15.7; 208/204: 38.5-38.6), defining a high , high W province suggestive of an evolution in a crustal environment since at least the Middle Proterozoic. Pb-Pb model age of the ores is in the order of 350 Ma, in gross agreement with the Lower-Middle Paleozoic age assigned to most country rocks. The present-day Pb-isotope ratios of presumed exhalative tourmalinites associated with the Bottino deposit and of other country rocks from mineralized areas are also similar. Moreover, most of these rocks show relatively high total Pb contents (> 70 ppm). HCl-soluble lead in these samples also has a roughly similar isotopic signature. In contrast, rock samples collected at greater distances from mineralized bodies have lower Pb concentrations (< 10 ppm) and more radiogenic 206/204 and 208/204 ratios (18.6 to 18.9 and 38.9 to 39.3 respectively). HCl-soluble lead in these samples has distinctly lower 208/204, and to a lesser extent 206/204 ratios (38.6 to 38.9 and 18.5 to 18.9 respectively). In agreement with previously established genetic models, these results may be interpreted in terms of a major episode of lead extraction in the Paleozoic, possibly in association with exhalative tourmalinites, followed by remobilization and reconcentration in vein mineralization during the Apenninic orogeny. The isotopic signature of country rocks in mineralized areas may be ascribed to a Pb-isotope halo effect induced by metamorphism. When compared with Pb-isotope data from deposits of the southern Tuscany mining district, the ore lead in Apuane Alps exhibits similar isotopic patterns, but with lower 208/204 and 206/204 ratios. This fact suggests for the two districts source(s) with similar evolutions of their U/Pb and Th/Pb ratios, but distinctly different times of Pb extraction.

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Die Herkunft von Metallen bei metamorphen erzlagerstättenbildenden Prozessen in den Apuanischen Alpen (NW Toskana, Italien): Eigebnisse von Pb-Isotopendaten

Zusammenfassung In den Apuanischen Alpen (NW Toskana) treten prämetamorphe, schichtförmige Fe-Ba Erzlagerstätten in grünschieferfaziell metamorphen Serien sedimentären und vulkanosedimentären Ursprungs auf (e.g. Pollone und Monte Arsiccio), die von syn- bis spätkinematisch gebildeten, diskordanten Vererzungen begleitet werden. Ein Gangsystem mit Quarz, Karbonat und Pb-Zn-Ag (Bottino) wird von einem stratiformen Turmalinithorizont mit erhöhten Metallgehalten begleitet.Um die Frage eines metamorphogenen Ursprungs der gangförmigen Vererzungen im Gefolge der Appenninischen Metamorphose (Oligozän-Miozän) und die vermutete Herkunft der Metalle aus den schichtförmigen Lagerstätten und Metallanreicherungen zu überprüfen, wurden Pb-Isotopenuntersuchungen an Sulfiden, Bariten, Turmaliniten und Nebengesteinen durchgeführt. Das Erzblei aus stratiformen wie auch gangförmigen Lagerstätten zeigt nur geringe Variationen der Pb-isotopenverhältnisse und ist innerhalb eines Vorkommens homogen (206/204: 18.2-18.4; 207/204: 15.68; 208/204: 38.538.6). Seine relativ hohen - and W-Werte weisen auf eine Bleientwicklung in kontinentalem Krustenmilieu, spätestens seit dem mittleren Proterozoikum hin. Die 207/206 Modellalter von ca. 350 Ma stimmen größenordnungmäßig mit dem vermuteten paläozoischen Alter des Nebengesteins überein, sind aber für die gangförmigen tertiären Vorkommen zu hoch. Baryt-, Turmalinit- und Gesamtgesteinsproben aus der Nähe der Lagerstätten zeigen alle ähnliche Pb-Isotopenverhältnisse wie die Sulfide. Die Gesteine weisen hohe Pb-Gehalte von > 70 ppm auf. In größerer Entfernung zu den Lagerstätten sind die Pb-Gehalte mit < 10 ppm deutlich niedriger und die Pb-Isotopenverhältnisse sind radiogener (206/204: 18.8-18.9; 208/204: 38.9-39.3). Ihr HCl-1ösliches Blei ist hingegen weniger radiogen.Die Resultate stützen die neueren Ansichten, daß es im Paläozoikum zur Bildung von exbalativen Turmaliniten verbunden mit einer Metallanreicherung und von stratiformen Fe-Ba-Lagerstätten kam. Während der appenninischen Metamorphose wurden die Metalle remobilisiert, und es kam zur Bildung von gangförmigen Vorkommen und Lagerstätten. Die hohen Pb-Gehalte der Nebengesteine und die Isotopensignatur des HC1-löslichen Bleis deuten auf eine metamorphogene Halo-Bildung. Die Bleiisotopen von jungtertiären Erzen aus der südlichen Toskana sind im Vergleich mit dem apuanischen Erzblei radiogener. Sie weisen aber dieselben hohen - und W-Werte auf. Das heißt, das Blei stammt aus Gesteinen, die eine qualitativ wie auch quantitativ ähnliche Entwicklung bezüglich der U/Pb und Th/Pb Verhältnisse durchlaufen haben wie jene, die das Blei der apuanischen Lagerstätten geliefert haben.

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This paper was presented at the IGCP 291 Project Symposium Metamorphic Fluids and Mineral Deposits, ETH Zürich, March 21–23, 1991.