REE in skarn systems: A LA-ICP-MS study of garnets from the Crown Jewel gold deposit

Metamorphic and magmatic garnets are known to fractionate REE, with generally HREE-enriched patterns, and high Lu/Hf and Sm/Nd ratios, making them very useful as geochemical tracers and in geochronological studies. However, these garnets are typically Al-rich (pyrope, almandine, spessartine, and grossular) and little is known about garnets with a more andraditic (Fe³⁺) composition, as frequently found in skarn systems. This paper presents LA-ICP-MS data for garnets from the Crown Jewel Au-skarn deposit (USA), discusses the factors controlling incorporation of REE into garnets, and strengthens the potential of garnet REE geochemistry as a tool to help understand the evolution of metasomatic fluids.Garnets from the Crown Jewel deposit range from Adr₃₀Grs₇₀ to almost pure andradite (Adr_>99). Fe-rich garnets (Adr_>90) are isotropic, whereas Al-rich garnets deviate from cubic symmetry and are anisotropic, often showing sectorial dodecahedral twinning. All garnets are extremely LILE-depleted, Ta, Hf, and Th and reveal a positive correlation of ΣREE³⁺ with Al content. The Al-rich garnets are relatively enriched in Y, Zr, and Sc and show “typical” HREE-enriched and LREE-depleted patterns with small Eu anomalies. Fe-rich garnets (Adr_>90) have much lower ΣREE and exhibit LREE-enriched and HREE-depleted patterns, with a strong positive Eu anomaly. Incorporation of REE into garnet is in part controlled by its crystal chemistry, with REE³⁺ following a coupled, YAG-type substitution mechanism , whereas Eu²⁺ substitutes for X²⁺ cations. Thermodynamic data (e.g., H_mixing) in grossular-andradite mixtures suggest preferential incorporation of HREE in grossular and LREE in more andraditic compositions.Variations in textural and optical features and in garnet geochemistry are largely controlled by external factors, such as fluid composition, W/R ratios, mineral growth kinetics, and metasomatism dynamics, suggesting an overall system that shifts dynamically between internally and externally buffered fluid chemistry driven by fracturing. Al-rich garnets formed by diffusive metasomatism, at low W/R ratios, from host-rock buffered metasomatic fluids. Fe-rich garnets grow rapidly by advective metasomatism, at higher W/R ratios, from magmatic-derived fluids, consistent with an increase in porosity by fracturing.     

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations

Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m³ filled with limestone sand and wood shavings, and one tank of 1 m³ with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m³/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO₃ equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)₃ and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.     

Structural characterisation of the high-pressure phase CaAl4Si2O11

Single crystals of CaAl₄Si₂O₁₁ were synthesised at 1,500?°C and 14 GPa in a multi-anvil press, and the structure of the phase determined by single-crystal X-ray diffraction at room conditions. The structure-type is that of the “hexagonal barium ferrites”. The space group of the average structure is P6 ₃ /mmc and the cell parameters are a?=?5.4223(4) Å, c?=?12.7041(6) Å, V?=?323.28(5) ų, with Z?=?2, and its density is 3.905?g?cm^?3, which is reasonable for a high-pressure alumino-silicate phase. The 22 oxygen and two calcium atoms within the unit-cell form an approximate hexagonal-close-packed array. Ten of the twelve octahedral interstices within this array that have only oxygen atoms for apices are filled with Si and/or Al. M1 octahedra share edges to form a spinel-like sheet of octahedra. The average bond length ?=?1.833 Å suggests mixed occupancy by Si and Al. The M1 octahedral sheets are linked by shared corners to pairs of face-sharing M2 octahedra containing Al, with ?= 1.918 Å. The remaining two cations of the unit-cell contents statistically occupy four tetrahedrally-coordinated interstices, which occur as face-sharing pairs. The average bond length for these sites (1.742 Å) suggests that they are occupied by Al, although Si occupancy cannot be excluded by the data. It is proposed that only one interstice of each pair is locally occupied, with the possibility of some short-range ordering of such occupancies. Complete long-range order leading to the acentric space group P6 ₃ mc is excluded by the data, as is the possibility of the average structure being comprised of merohedral (0?0?0?1) twins of P6 ₃ mc symmetry.     

Late pleistocene/early holocene environments and climates,fauna, and human occupation in the argentine altiplano

The Barro Negro site (23°S lat., 65°37′W long.) in the Altiplano (Puna) of northwestern Argentina contains a well stratified sequence of remains of Hippidion, the American extinct horse, camelids, and archaeological materials, which is the focus of this study. In addition to establishing a reliable chronology, paleoenvironmental information was obtained based on analyses of pollen and stable isotopes (oxygen and carbon) from bone and marl. The data indicate that Hippidion was present at the site between 12,000 and 10,000 yr B. P., at a time when Altoandean grasslands had expanded to lower elevations. By 10,000 yr B.P., when modern semi-arid sub-puna scrub had replaced the Altoandean grasslands, only camelids (Lama or Vicugna) were present, simultaneous with the first evidence of local human occupation. This suggests that a climatic shift from cool and moist (winter rain regime) to warm and dry (summer rain regime) conditions took place simultaneously with the disappearance of the American horse and the appearance of camelids and man.     

Hydrothermal alteration of plagioclase in granitic rocks from Proterozoic basement of SE Sweden

Petrographic examinations and electron microprobe analyses of Proterozoic granitic rocks, SE Sweden aimed to characterize and unravel the mechanisms and conditions of plagioclase alterations. These alterations include saussuritization, albitization and replacement of plagioclase by K‐feldspar. The hydrothermal alterations, which are inferred to have occurred at ca. 250–400°C, resulted in concomitant formation of Al‐rich titanite, epidote, calcite, pumpellyite, prehnite and iron oxides. Replacement of plagioclase by K‐feldspar occurs in red‐stained zones, which have developed close to thin fractures owing to the precipitation of tiny Fe‐oxide pigment particles within the altered plagioclase, whereas saussuritized plagioclase has less systematic spatial relationships to these fractures. Albitization of plagioclase occurred in rocks that are poor in biotite compared to rocks that suffered extensive saussuritization. The chemical and textural characterization of various types of plagioclase alterations allows elucidation of the granitic hydrothermal systems. Features of feldspar alteration in the granitic rocks are similar to those encountered in feldspathic sandstones and should hence be considered in studies on diagenetic changes of siliciclastic successions during basin evolution. Copyright © 2009 John Wiley & Sons, Ltd.