The Formation, Structure, and Ageing of As-Rich Hydrous Ferric Oxide at the Abandoned Sb Deposit Pezinok (Slovakia)

Journal Article · Mon Jan 01 04:00:00 EST 2007 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2007.06.053· OSTI ID:929960

Majzlan, J; Lalinska, B; Chovan, M; Jurkovic, L; Milovska, S; Gottlicher, J

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold {approx}380,000 m{sup 3} of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 {+-} 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS{sub 2}; arsenopyrite, FeAsS; berthierite, FeSb{sub 2}S{sub 4}) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ {mu}-XANES experiments indicate that As in the weathering rims is fully oxidized (As{sup 5+}). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As{sub 2}O{sub 5} and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As{sup 5+}. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 {angstrom}, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

• Research Organization: Brookhaven National Laboratory (BNL) National Synchrotron Light Source
• Sponsoring Organization: Doe - Office Of Science
• DOE Contract Number: AC02-98CH10886
• OSTI ID: 929960
• Report Number(s): BNL--80563-2008-JA
• Journal Information: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 71; ISSN GCACAK; ISSN 0016-7037
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
ADSORPTION
ARSENATES
ARSENIC
ATOMS
CARBONATES
CHEMICAL BONDS
DECOMPOSITION
DEPOSITS
IONS
IRON
IRON OXIDES
MINING
PH VALUE
POLLUTION
POLYMERIZATION
PYRITE
SEMIMETALS
SLOVAKIA
SOILS
SPECTRA
SULFIDES
TAILINGS
VALENCE
WATER
X-RAY DIFFRACTION
national synchrotron light source