Occurrence of thorite and radioactive zircon in syenite pegmatite,North of Ashwaraopet,Khammam district,Andhra Pradesh,India

This paper reports the occurrence of thorite and confirms the earlier find of radioactive zircon by Subbarao, Murali and others from syenite pegmatite in the Vinayakapuram-Kunavaram alkaline belt in the Khammam district of Andhra Pradesh, India. Thorite has also been found as residual concentrations in soil overlying the pegmatite.     

Thorite versus huttonite: stability, electronic properties and X-ray emission spectra from first-principle calculations

The structural, electronic properties and stability of thorium orthosilicate ThSiO₄ polymorphs: thorite and huttonite are investigated by means of the full-potential linearized augmented-plane-wave method with the generalized gradient approximation for the exchange-correlation potential (FLAPW-GGA). The forbidden gaps of thorite and huttonite are estimated at about 7.8 and 7.6 eV, respectively. It is found that Th5f states in ThSiO₄ partially overlap with occupied O2p bands. The data obtained showed that thorite is more stable than huttonite; in turn both ThSiO₄ polymorphs are unstable with respect to their constituent binary oxides (thorianite ThO₂ and α-quartz SiO₂) in agreement with the experiments. The theoretical shapes of X-ray emission (XES) (Si,O)Kα,β spectra for thorite, huttonite as well as for SiO₂ and ThO₂ are calculated and discussed. We show that the XES spectroscopy near the (Si,O)K edge may be very useful technique not only for detailed investigation of the bulk-electronic structure of Th silicates but also for the phase analysis of complex mineral samples containing these species.     

藏南程巴岩体副矿物研究:岩浆源区的指示

藏南程巴岩体具有埃达克岩的地球化学性质,但其形成年代、产出位置和成矿组合不同于冈底斯带成矿斑岩。利用背反射图像和电子探针成分分析发现其具有钙碱性花岗岩不常见的副矿物组合:Fe-Ti氧化物+锆石+磷灰石+榍石+独居石+钍石+氟碳铈矿+晶质铀矿+水氟碳钙钍矿,其中独居石富Th,钍石富U,独居石和钍石经富F、CO₂流体交代形成氟碳铈矿和水氟碳钙钍矿。在(⁸⁷Sr/⁸⁶Sr)_i和Th含量图解中,冈底斯带含矿斑岩与程巴岩体落在一条混合线线上,程巴岩体位于已证明受到上地壳物质或其他富集组分混染的甲马含矿斑岩和其他冈底斯含矿斑岩之间,表明程巴岩体在其源区或演化过程中也受到了富集端元的混染,但加入量少于甲马斑岩。     

High and low temperature alteration of uranium and thorium minerals, Um Ara granites, south Eastern Desert, Egypt

The Um Ara area, in the south Eastern Desert of Egypt contains a number of uranium occurrences related to granitic rocks. U-rich thorite, thorite and zircon are the main primary uranium- and thorium-bearing minerals found in mineralized zones of the Um Ara alkali-feldspar granites; uranophane is the most common secondary uranium mineral. U-rich thorite contains blebs of galena, has rims of uranophane and contains inclusions of Zr-rich thorite. Electron probe microanalysis (EPMA) provides an indication of a range of solid solution between thorite and zircon, in which intermediate phases, such as Th-rich zircon and Zr-rich thorite, were formed. These phases have higher sum of all cations per formula (2.05 to 2.06 apfu, for 4 oxygen atoms) than that of ideal thorite and zircon. This is attributed to the presence of substantial amount of interstitial cations such as Ca, U and Al in these phases. Some zircon grains are stoichiometric in composition, other altered grains display lower SiO₂ and ZrO₂ contents. Enrichment of Th and U in altered zircon preferentially involves coupled substitution (Ca²⁺ + (Th,U)⁴⁺ ↔ 2Zr⁴⁺ + 2Si⁴⁺), implying that significant U and Th may enter the Zr and Si position in zircon. Negative correlation of Zr vs. Hf and Al may indicate that Hf and Al have been introduced to the zircon during later fluid alteration rather than during the primary magmatic event. A two-stage metallogenetic model is proposed for the alteration processes and origin of U- and Th-bearing minerals in the Um Ara alkali-feldspar granite: 1) the first stage was dominated by hydrothermal alteration and accompanied by albitization, k-feldspathization, desilicification, chloritization, hematitization, silicification, argillization, fluoritization and corrosion of primary U-bearing minerals. Solid-solution between thorite and zircon occurred during this stage. The second stage occurred at the near-surface profile where circulating meteoric water played an important role in mobilizing the early formed primary U-bearing minerals. Uranium was likely transported as a calcium uranyl carbonate complexes. When these complexes lost their stabilities by precipitation of calcite, they decomposed in the presence of silica to form uranophane.     

Composition and origin of intermediate solid solutions in the system thorite–xenotime–zircon–coffinite

A comprehensive survey of the accessory-mineral assemblages in Variscan granites of the German Erzgebirge and Pan-African granites from Jordan revealed the occurrence of intermediate solid solutions of the tetragonal thorite–xenotime–zircon–coffinite mineral group with partially novel compositions. These solid solutions preferentially formed in evolved and metasomatically altered, P-poor leucogranites of either I- or A-type affinity. Thorite from the Erzgebirge contained up to 18.8 wt.% Y₂O₃, 16.1 wt.% ZrO₂, and 23.3 wt.% UO₂. Xenotime and zircon have incorporated Th in abundances up to 36.3 wt.% and 41.8 wt.% ThO₂, respectively. Extended compositional gradation with only minor gaps is confined to hydrated members of this mineral group, and is observed to exist between thorite and xenotime, thorite and coffinite, and Y–HREE-bearing thorite and zircon. Complex, hydrous solid solutions containing elevated abundances of three or more of the endmembers are subordinate. Previously reported intermediate solid solutions between anhydrous zircon and xenotime, and anhydrous zircon and thorite, are not observed and are in conflict with experimental work demonstrating very limited miscibility between anhydrous species of endmember composition. The majority of hydrous intermediate solid solutions in the Th–Y–Zr–U system are likely thermodynamically unstable. Instead, they are probably metastable responses to unusual physico-chemical conditions involving various parameters and conditions, the relative importance of which is incompletely known. Leaching and dissolution of preexisting accessory phases during interaction with F-bearing hydrous fluids enriched in Th, Y(HREE), Zr, and/or U, and common deposition of the various elements at disequilibrium (supersaturation) seems to play a key role, but other processes may be of similar importance. Experimental work involving hydrous conditions and complex systems composed of more than two endmembers are needed to shed light into the stability relations of the chemically uncommon compositions treated in this study.     

Low-temperature alteration of uranium–thorium bearing minerals and its significance in neoformation of radioactive minerals in stream sediments of Wadi El-Reddah,North Eastern Desert,Egypt

The stream sediments of Wadi El Reddah(North Eastern Desert,Egypt)are geochemically and mineralogically investigated.Their content of radioactive and other heavy minerals is mainly represented by thorite,uranothorite,zircon,monazite,xenotime,columbite,fergusonite,and unknown rare earth elements(REEs)bearing minerals as well as cassiterite.Special emphasis on REE content of thorite,uranothorite,zircon and xenotime has been done to correlate them with the increase of uranium contents in these sediments.The key evidence for the presence lowtemperature alteration processes includes the presence of some zircon crystals as remnants after complete dissolution of the overgrowth zircon in severe acidic environment,the sulphur content,biogenic minerals,occurrence of unusual minerals as cassiterite pore filling in zircon,variation in the REEs content from the surrounding granites to the stream sediments and the abundance of monazite in the surrounding granites.Most minerals are partially and/or completely altered,which indicated by the pseudomorphism of zircon by xenotime,thorite,and uranothorite.