Finding of a Cs-rich pharmacosiderite-like mineral: preliminary data Petrini Elisa 1 , Bellatreccia Fabio 1 and Cavallo Andrea 2 1 University of ROMA3, Dept. Earth Sciences, L.go S.Leonardo Murialdo 1, 00146 Roma, Italy 2 Istituto Nazionale di Geofisica e Vulcanologia, Via di Vigna Murata 605, 00143 Roma, Italy In north western Argentina (Jujuy Province), in some volcanic areas, soils and waters are affected by high natural background levels of arsenic (As). Elevated As content can create serious health hazard to the populations settled in the surrounding areas. In this area As is mainly present in the pyroclastic rocks of the volcano Tuzgle (5486 m) whose activity is mainly characterized by emission of andesitic and rhyodacitic products. High concentration levels of As associated with solphur containing Fe and Pb that characterized many deposits along the Andine Cordillera belt TUZGLE volcano During the study of rhyolitic rock, collected near hydrothermal spring, it was observed a Cs-rich arsenate phase. The mineral occurs as a thin crusts into the rock cavities formed by very small tetrahedral shape crystals (> 2 m) covering the walls of cavities rock Preliminary SEM/EDS and EMPA analysis on thin section, suggested the mineral to be very close to pharmacosiderite KFe 4 (AsO 4 ) 3 (OH) 4 · 6-7(H 2 O), but with anomalously high Cs contents The structure of pharmacosiderite [1] consists of FeO 6 octahedra and AsO 4 tetrahedra connected to each other to form a three-dimensional network of channels. The pore has 8-membered ring openings, with alternating As tetrahedra and Fe octahedra. Each channel, approximately 3 Å in diameter, is occupied by charge neutralizing K + extra-framework cations and H 2 O molecules [2]. Buerger et al. [1] investigated a synthetic Cs- pharmacosiderite obtained treating natural pharmacosiderite with an aqueous solution of CsOH at room temperature. So, it was observed the K Cs cationic exchange because of their ionic radius are very similar and the large canals can host the Cs cation The images obtained by means of FEG-FIB Dual Beam (LIME) shows the morphology of Cs- mineral that is clearly constituited by tetrahedra. (photo: D. De Felicis) References: [1] Buerger M.J., Dollase W.A., Garaycochea-Wittke I. Z. Kristallogr. 125, 92 (1967) [2] Yakubovich O.V., Massa W., Dimitrova O.V. Crystallography Reports 53, 409 (2008 [3] Behrens E.A., Sylvester P., Clearfield A. Environ. Sci. Technol. 32, 101 (1998) Acknowledgements: A. Mottana and M.F. Brigatti Where is the Cesium? However, until now the occurrence of a natural Cs-pharmacosiderite was not yet observed. If confirmed, K Cs (> 50%) cationic exchange, this will imply the definition of a new mineral belonging to the pharmacosiderite group. Moreover, the occurrence of a new Cs-bearing natural phase Could be relevant to development for new 137 Cs isotope selective absorbers from solutions of radioactive wastes and storage units for radioactive metals disposal [3]. C O N C L U S I O N S The formula unit, calculated on the basis of 3 As+P apfu, is (Cs 0.47 K 0.42 ) =0.89 ∑ Fe 3+ 4.25 (As 0.96 P 0.04 O 4 ) 3 (OH) 4 · 6.43H 2 O Rapresentative EMPA analysis expressed in wt% (sum 100%) As 2 O 5 36.20 P 2 O 5 0.88 F 2 O 3 37.00 K 2 O 2.17 Cs 2 O 7.18 H 2 O [calc] 16.57

Finding of a Cs-rich pharmacosiderite-like mineral: preliminary data

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Preliminary SEM/EDS and EMPA analysis on thin section, suggested the mineral to be very close to pharmacosiderite KFe 4 (AsO 4 ) 3 (OH) 4 · 6-7(H 2 O), but with anomalously high Cs contents. - PowerPoint PPT Presentation

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Finding of a Cs-rich pharmacosiderite-like mineral: preliminary data

Petrini Elisa1, Bellatreccia Fabio1 and Cavallo Andrea2

1University of ROMA3, Dept. Earth Sciences, L.go S.Leonardo Murialdo 1, 00146 Roma, Italy2Istituto Nazionale di Geofisica e Vulcanologia, Via di Vigna Murata 605, 00143 Roma, Italy

In north western Argentina (Jujuy Province), in some volcanic areas, soils and waters are affected by high natural background levels of arsenic (As). Elevated As content can create serious health hazard to the populations settled in the surrounding areas. In this area As is mainly present in the pyroclastic rocks of the volcano Tuzgle (5486 m) whose activity is mainly characterized by emission of andesitic and rhyodacitic products.High concentration levels of As associated with solphur containing Fe and Pb that characterized many deposits along the Andine Cordillera belt

TUZGLE volcano

During the study of rhyolitic rock, collected near hydrothermal spring, it was observed a Cs-rich arsenate phase. The mineral occurs as a thin crusts into the rock cavities formed by very small tetrahedral shape crystals (> 2 m) covering the walls of cavities rock

Preliminary SEM/EDS and EMPA analysis on thin section, suggested the mineral to be very close to pharmacosiderite KFe4(AsO4)3(OH)4 · 6-7(H2O), but with anomalously high Cs contents

The structure of pharmacosiderite [1] consists of FeO6 octahedra and AsO4 tetrahedra connected to each other to form a three-dimensional network of channels. The pore has 8-membered ring openings, with alternating As tetrahedra and Fe octahedra. Each channel, approximately 3 Å in diameter, is occupied by charge neutralizing K+ extra-framework cations and H2O molecules [2].

Buerger et al. [1] investigated a synthetic Cs-pharmacosiderite obtained treating natural pharmacosiderite with an aqueous solution

of CsOH at room temperature. So, it was observed the K Cs cationic exchange because of their ionic radius are very similar and

the large canals can host the Cs cation

The images obtained by means of FEG-FIB

Dual Beam (LIME) shows the morphology of Cs-mineral that is

clearly constituited by tetrahedra.

(photo: D. De Felicis)

References:[1] Buerger M.J., Dollase W.A., Garaycochea-Wittke I. Z. Kristallogr. 125, 92 (1967)[2] Yakubovich O.V., Massa W., Dimitrova O.V. Crystallography Reports 53, 409 (2008[3] Behrens E.A., Sylvester P., Clearfield A. Environ. Sci. Technol. 32, 101 (1998) Acknowledgements: A. Mottana and M.F. Brigatti

Where is the Cesium?

However, until now the occurrence of a natural Cs-pharmacosiderite was not yet observed. If confirmed, K Cs (> 50%) cationic exchange, this will imply the definition of a new mineral belonging to the pharmacosiderite group. Moreover, the occurrence of a new Cs-bearing natural phase Could be relevant to development for new 137Cs isotope selective absorbers from solutions of radioactive wastes and storage units for radioactive metals disposal [3].

CON

CLUSIO

The formula unit, calculated on the basis of 3 As+P apfu, is

(Cs0.47K0.42)∑=0.89 Fe3+4.25 (As0.96P0.04O4)3 (OH)4 · 6.43H2O

Rapresentative EMPA analysis

expressed in wt% (sum 100%)

As2O5 36.20

P2O5 0.88

F2O3 37.00

K2O 2.17

Cs2O 7.18

H2O[calc] 16.57