Fluid inclusions in apatite from Jacupiranga calcite carbonatites: Evidence for a fluid-stratified carbonatite magma chamber

Carbonatites of the Jacupiranga alkaline–carbonatite complex in São Paulo State, Brazil, were used to investigate mineral–fluid interaction in a carbonatite magma chamber because apatite showed a marked discontinuity between primary fluid inclusion-rich cores and fluid inclusion-poor rims. Sylvite and burbankite, apatite, pyrite, chalcopyrite and ilmenite are the common phases occurring as trapped solids within primary fluid inclusions and reflect the general assemblage of the carbonatite. The apatite cores had higher Sr and REE concentrations than apatite rims, due to the presence of fluid inclusions into which these elements partitioned. A positive cerium anomaly was observed in both the core and rim of apatite crystals because oxidised Ce⁴⁺ partitioned into the magma. The combined evidence from apatite chemistry, fluid inclusion distribution and fluid composition was used to test the hypotheses that the limit of fluid inclusion occurrence within apatite crystals arises from: (1) generation of a separate fluid phase; (2) utilization of all available fluid during the first stage of crystallization; (3) removal of crystals from fluid-rich magma to fluid-poor magma; (4) an increase in the growth rate of apatite; or (5) escape of the fluids from the rim of the apatite after crystallization. The findings are consistent with fractionation and crystal settling of a carbonatite assemblage in a fluid-stratified magma chamber. Secondary fluid inclusions were trapped during a hydrothermal event that precipitated an assemblage of anhedral crystals: strontianite, carbocernaite, barytocalcite, barite and norsethite, pyrophanite, magnesian siderite and baddeleyite, ancylite-(Ce), monazite-(Ce) and allanite. The Sr- and REE-rich nature of the secondary assemblage, and lack of a positive cerium anomaly indicate that hydrothermal fluids have a similar source to the primary magma and are related to a later carbonatite intrusion.     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.     

Constraints on the clustering, biasing and redshift distribution of radio sources

We discuss how different theoretical predictions for the variance σ ² of the counts-in-cells distribution of radio sources can be matched to measurements from the FIRST survey at different flux limits. The predictions are given by the integration of models for the angular correlation function w ( θ ) for three different functional forms of the redshift distribution N ( z ), different spatial correlation functions that match the observed present-day shape and by different evolutions of the bias b ( z ) with redshift. We also consider the two cases of open and flat universes. Although the predicted w ( θ ) show substantial differences because of differences in the values of N ( z ), these differences are not significant compared to the uncertainties in the current observations. It turns out that, independent of the geometry of the universe and the flux limit, the best fit is provided by models with constant biasing at all times, although the difference between models with epoch-independent bias and models with bias that evolves linearly with redshift is not very large. All models with strong evolution of bias with epoch are ruled out, as they grossly overestimate the amplitude of the variance over the whole range of angular scales sampled by the counts-in-cells analysis. As a further step we directly calculated w _obs( θ ) at 3 mJy from the catalogue and matched it with our models for the angular correlation function, in the hypothesis that the clustering signal comes from two different populations, namely AGN-powered sources and starbursting galaxies. The results are consistent with a scenario for hierarchical clustering where the fainter starbursting galaxies trace the mass at all epochs, while the brighter AGNs are strongly biased, with b ( z ) evolving linearly with redshift, as suggested by some theories of galaxy formation and evolution.