Extremely U-depleted (<1 ppm) zircons from H8 banded ores in the East Orebody of the Bayan Obo REE–Nb–Fe deposit are presented, with mineral compositions, textures, 232Th–208Pb SHRIMP ages and petrological context. Cores of East Orebody zircon contain up to 7 wt% HfO2 and are zoned, depicting bipyramidal crystal forms. A distinct generation of patchy, epitaxial rim zircon, similarly depleted in U, is intergrown with rare earth ore minerals (bastnäsite, parisite, monazite). Overprinting aegirine textures indicate paragenetically late, reactive Na-rich fluids. Chondrite-normalized REE patterns without Eu anomalies match closely with those from the Mud Tank and Kovdor carbonatitic zircons. Increased HREE in rims ((Lu/Gd)N 43–112) relative to cores ((Lu/Gd)N 6–7.5) and the localized presence of xenotime are attributable to reactive, mineralizing fluid compositions enriched in Y, REE and P. Cathodoluminescence further reveals HREE fractionation in rims, evidenced by a narrow-band Er3+ emission at 405 nm. The extreme depletion of U in core and rim zircon is characteristic for this mineral deposit and is indicative of a persistent common source. U depletion is also a characteristic for zircons from carbonatitic or kimberlitic systems. 232Th–208Pb (SHRIMP II) geochronological data reveal the age of zircon cores as 1,325 ± 60 Ma and a rim-alteration event as 455.6 ± 28.27 Ma. The combined findings are consistent with a protolithic igneous origin for zircon cores, from a period of intrusive, alkaline–carbonatitic magmatism. Fluid processes responsible for the REE–Nb mineralizations affected zircon rim growth and degradation during the widely reported Caledonian events, providing a new example in a localized context of HREE enrichment processes.
Abstract Some important and interesting data on the O, C and Sr isotopic compositions of rocks associated with the Bayan Obo Fe-Nb- REE deposit have been reported by Le Bas et al. (1997). However, a number of points relating to the interpretation of these data, and also to the terminology adopted, are worthy of further discussion. The essence of this discussion is that some of the geochemical and isotopic signatures found at Bayan Obo are not exclusively consistent with an igneous origin. A replacement hypothesis involving deep-sourced fluids could also explain the pattern of data, if minor carbonatitic intrusions into a sedimentary sequence are considered.
Some important and interesting data on the O, C and Sr isotopic compositions of rocks associated with the Bayan Obo Fe-Nb-REE deposit have been reported by Le Bas et al. (1997). However, a number of points relating to the interpretation of these data, and also to the terminology adopted, are worthy of further discussion. The essence of this discussion is that some of the geochemical and isotopic signatures found at Bayan Obo are not exclusively consistent with an igneous origin. A replacement hypothesis involving deep-sourced fluids could also explain the pattern of data, if minor carbonatitic intrusions into a sedimentary sequence are considered.
Abstract A new protocol for the quantitative determination of zeolite-group mineral compositions by electron probe microanalysis (wavelength-dispersive spectrometry) under ambient conditions, is presented. The method overcomes the most serious challenges for this mineral group, including new confidence in the fundamentally important Si-Al ratio. Development tests were undertaken on a set of natural zeolite candidate reference samples, representing the compositional extremes of Na, K, Cs, Mg, Ca, Sr and Ba zeolites, to demonstrate and assess the extent of beam interaction effects on each oxide component for each mineral. These tests highlight the variability and impact of component mobility due to beam interaction, and show that it can be minimized with recommended operating conditions of 15 kV, 2 nA, a defocused, 20 μm spot size, and element prioritizing with the spectrometer configuration. The protocol represents a pragmatic solution that works, but provides scope for additional optimization where required. Vital to the determination of high-quality results is the attention to careful preparations and the employment of strict criteria for data reduction and quality control, including the monitoring and removal of non-zeolitic contaminants from the data (mainly Fe and clay phases). Essential quality criteria include the zeolite-specific parameters of R value (Si/(Si + Al + Fe 3+ ), the ' E %' charge-balance calculation, and the weight percent of non-hydrous total oxides. When these criteria are applied in conjunction with the recommended analytical operating conditions, excellent inter-batch reproducibility is demonstrated. Application of the method to zeolites with complex solid-solution compositions is effective, enabling more precise geochemical discrimination for occurrence-composition studies. Phase validation for the reference set was conducted satisfactorily with the use of X-ray diffraction and laser-ablation inductively-coupled plasma mass spectroscopy.
Abstract The uptake of inorganic Hg 2+ and organometallic CH 3 Hg + from aqueous solutions by 11 different natural zeolites has been investigated using a batch distribution coefficient (K d ) method and supported by a preliminary voltammetric study. The effect of mercury concentration on the K d response is shown over an environmentally appropriate concentration range of 0.1–5 ppm inorganic and organometallic Hg using a batch factor of 100 ml g -1 and 20 h equilibration. Analcime and a Na-chabazite displayed the greatest methylmercury uptakes (K d values at 1.5 ppm of 4023 and 3456, respectively), with mordenite as the smallest at 578. All uptake responses were greater for methylmercury than for the inorganic mercuric nitrate solutions, suggesting a distinctive sensitivity of zeolites to reaction with different types of solute species. It is likely that this sensitivity is attributable to the precise nature of the resultant Hg-zeolite bonds. Additionally, both the Si-Al ratio and the Na content of the initial natural zeolite samples are shown to influence the K d responses, with positive correlations between K d and Na content for all zeolites excluding mordenite.
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