Zr In Rutile
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2021 ◽  
Vol 11 (18) ◽  
pp. 8756
Changming Wang ◽  
Shicheng Rao ◽  
Kangxing Shi ◽  
Leon Bagas ◽  
Qi Chen ◽  

Rutile is an important ore mineral to meet the increasing demand of critical metal Ti in various sectors. Here we report a rare example of rutile deposits hosted within the Baishugang–Wujianfang amphibolite-facies metamorphic rocks in the East Qinling Orogen, central China. The rutiles are mostly located within or along the margins of biotite and show 94.6 to 99 wt% TiO2. Rutiles occur as chains, thin layers along the foliation, and dense clusters. The grains are coexisted with magnetite. Based on Zr-in-rutile thermometer the estimated crystallisation temperature is at 630 °C at 7.0 kba. Based on Cr/Nb ratio, the source of the rutile is correlated with Ti-bearing silicate minerals such as biotite from aluminous sedimentary protoliths. The rutile deposit formed during lower amphibolite-facies metamorphism, and is distinct from the eclogite- and granulite-related types elsewhere in the orogen. The LA-ICP-MS U–Pb analyses of rutiles from the deposit yield lower intercept 238U/206Pb ages of 386 ± 16 Ma at the Baishugang–Wujianfang district. These ages correspond to a Devonian arc–continent collisional event between the South and North Qinling domains in the East Qinling Orogen.

Minerals ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 968
Xingying Wen ◽  
Fangfang Zhang ◽  
Yinhong Wang ◽  
Min Sun ◽  
Wei Zhang ◽  

The chemical composition of rutile has been used as an indicator in magmatic and metamorphic-related diagenetic systems, but rarely in porphyry-style ore systems. The Tuwu deposit (557 Mt at 0.58% Cu) is a large porphyry-style Cu mineralization in Eastern Tianshan, Xinjiang, with typical disseminated, stockwork mineralized veins hosted in tonalite and diorite porphyry, and to a lesser extent in volcanic rocks of the Qi’eshan Group. We first present determination of rutile minerals coupled with chlorite identified in mineralized porphyries from Tuwu to reveal their geochemical features, thus providing new insights into the ore-forming processes and metal exploration. Petrographic and BSE observations show that the rutile generally occurs as large crystals (30 to 80 µm), in association with hydrothermal quartz, chlorite, pyrite, and chalcopyrite. The rutile grains display V, Fe, and Sn enrichment and flat LREE-MREE patterns, indicating a hydrothermal origin. Titanium in rutile (TiO2) is suggested to be sourced from the breakdown and re-equilibration of primary magmatic biotite and Ti-magnetite, and substituted by Sn4+, high field strength elements (HFSE; e.g., Zr4+ and Hf4+), and minor Mo4+ under hydrothermal conditions. The extremely low Mo values (average 30 ppm) in rutile may be due to rutile formation postdating that of Mo sulfides (MoS2) formation in hydrothermal fluids. Chlorite analyses imply that the ore-forming fluids of the main stage were weakly oxidized (logfO2 = −28.5 to −22.1) and of intermediate temperatures (308 to 372 °C), consistent with previous fluid inclusion studies. In addition, Zr-in-rutile geothermometer yields overestimated temperatures (>430 °C) as excess Zr is incorporated into rutile, which is likely caused by fast crystal growth or post crystallization modification by F-Cl-bearing fluid. Thus, application of this geothermometer to magmatic-hydrothermal ore systems is questionable. Based on the comparison of rutile characteristics of porphyry Cu with other types of ore deposits and barren rocks, we suggest that porphyry Cu-related rutile typically has larger grain size, is enriched in V (average 3408 ppm, compared to <1500 ppm of barren rocks) and to a lesser extent in W and Sn (average 121 and 196 ppm, respectively), and has elevated Cr + V/Nb + Ta ratios. These distinctive signatures can be used as critical indicators of porphyry-style Cu mineralization and may serve as a valuable tool in mineral exploration.

Minerals ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 661
Federica Zaccarini ◽  
Giorgio Garuti ◽  
George L. Luvizotto ◽  
Yuri de Melo Portella ◽  
Athokpam K. Singh

Trace element distribution and Zr-in-rutile temperature have been investigated in accessory rutile from stratiform (UG2, Merensky Reef, Jacurici), podiform (Loma Peguera), and metamorphic chromitites in cratonic shields (Cedrolina, Nuasahi). Rutile from chromitite has typical finger-print of Cr-V-Nb-W-Zr, whose relative abundance distinguishes magmatic from metamorphic chromitite. In magmatic deposits, rutile precipitates as an intercumulus phase, or forms by exsolution from chromite, between 870 °C and 540 °C. The Cr-V in rutile reflects the composition of chromite, both Nb and Zr are moderately enriched, and W is depleted, except for in Jacurici, where moderate W excess was a result of crustal contamination of the mafic magma. In metamorphic deposits, rutile forms by removal of Ti-Cr-V from chromite during metamorphism between 650 °C and 400 °C, consistent with greenschist-amphibolite facies, and displays variable Cr-Nb, low V-Zr, and anomalous enrichment in W caused by reaction with felsic fluids emanating from granitoid intrusions. All deposits, except Cedrolina, contain Rutile+PGM composite grains (<10 µm) locked in chromite, possibly representing relics of orthomagmatic assemblages. The high Cr-V content and the distinctive W-Nb-Zr signature that typifies accessory rutile in chromitite provide a new pathfinder to trace the provenance of detrital rutile in placer deposits.

E. Adlakha ◽  
K. Hattori

Basement rocks below the Athabasca Basin, Saskatchewan, have been intensely altered through paleoweathering and multiple hydrothermal events, including the formation of world-class unconformity-type uranium deposits. Here, we demonstrate the utility of Ti-oxide thermochronology for identifying thermotectonic events in these altered rocks leading to uranium mineralization along basement structures. Rutile grains along the P2 fault, a major fault in the eastern Athabasca Basin, exhibit 207Pb/206Pb ages of ca. 1850−1700 Ma, with a weighted mean of 1757 ± 6 Ma (mean square of weighted deviation [MSWD] = 1.4, n = 116). The older ages (&gt;1770 Ma) record regional metamorphism reaching a temperature of 875 °C during the Trans-Hudson orogeny. Pb diffusion modeling indicates that metamorphic rutile should exhibit cooling ages of 1760−1750 Ma. Rutile grains showing young ages, &lt;1750 Ma, reflect isotopic resetting during regional asthenospheric upwelling between 1770 and 1730 Ma related to the emplacement of the Kivalliq igneous suite to the north. This thermotectonic event (temperature &gt; 550 °C) promoted hydrothermal activity to produce silicified rocks, i.e., “quartzite,” along the P2 fault, which later focused mineralizing fluids for unconformity-type uranium deposits. The young rutile ages also indicate that the basement rocks remained hot until 1700 Ma, providing the maximum age for the deposition of the Athabasca sediments. Anatase yields a concordia age of 1569 ± 31 Ma (MSWD = 0.30, n = 5), which is within uncertainty of the oldest ages for uraninite of the McArthur River deposit. This age corresponds to the incursion of basinal fluids in the basement along the P2 fault during uranium mineralization.

Minerals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 553
Jakub Kotowski ◽  
Krzysztof Nejbert ◽  
Danuta Olszewska-Nejbert

The geochemistry of detrital rutile grains, which are extremely resistant to weathering, was used in a provenance study of the transgressive Albian quartz sands in the southern part of extra-Carpathian Poland. Rutile grains were sampled from eight outcrops and four boreholes located on the Miechów, Szydłowiec, and Puławy Segments. The crystallization temperatures of the rutile grains, calculated using a Zr-in-rutile geothermometer, allowed for the division of the study area into three parts: western, central, and eastern. The western group of samples, located in the Miechów Segment, is characterized by a polymodal distribution of rutile crystallization temperatures (700–800 °C; 550–600 °C, and c. 900 °C) with a significant predominance of high-temperature forms, and with a clear prevalence of metapelitic over metamafic rutile. The eastern group of samples, corresponding to the Lublin Area, is monomodal and their crystallization temperatures peak at 550–600 °C. The contents of metapelitic to metamafic rutile in the study area are comparable. The central group of rutile samples with bimodal distribution (550–600 °C and 850–950 °C) most likely represents a mixing zone, with a visible influence from the western and, to a lesser extent, the eastern group. The most probable source area for the western and the central groups seems to be granulite and high-temperature eclogite facies rocks from the Bohemian Massif. The most probable source area for the eastern group of rutiles seems to be amphibolites and low temperature eclogite facies rocks, probably derived from the southern part of the Baltic Shield.

2021 ◽  
Vol 176 (5) ◽  
Nicola Campomenosi ◽  
Marco Scambelluri ◽  
Ross J. Angel ◽  
Joerg Hermann ◽  
Mattia L. Mazzucchelli ◽  

AbstractThe ultrahigh-pressure (UHP) whiteschists of the Brossasco-Isasca unit (Dora-Maira Massif, Western Alps) provide a natural laboratory in which to compare results from classical pressure (P)–temperature (T) determinations through thermodynamic modelling with the emerging field of elastic thermobarometry. Phase equilibria and chemical composition of three garnet megablasts coupled with Zr-in-rutile thermometry of inclusions constrain garnet growth within a narrow P–T range at 3–3.5 GPa and 675–720 °C. On the other hand, the zircon-in-garnet host-inclusion system combined with Zr-in-rutile thermometry would suggest inclusion entrapment conditions below 1.5 GPa and 650 °C that are inconsistent with the thermodynamic modelling and the occurrence of coesite as inclusion in the garnet rims. The observed distribution of inclusion pressures cannot be explained by either zircon metamictization, or by the presence of fluids in the inclusions. Comparison of the measured inclusion strains with numerical simulations shows that post-entrapment plastic relaxation of garnet from metamorphic peak conditions down to 0.5 GPa and 600–650 °C, on the retrograde path, best explains the measured inclusion pressures and their disagreement with the results of phase equilibria modelling. This study suggests that the zircon-garnet couple is more reliable at relatively low temperatures (< 600 °C), where entrapment conditions are well preserved but chemical equilibration might be sluggish. On the other hand, thermodynamic modelling appears to be better suited for higher temperatures where rock-scale equilibrium can be achieved more easily but the local plasticity of the host-inclusion system might prevent the preservation of the signal of peak metamorphic conditions in the stress state of inclusions. Currently, we cannot define a precise threshold temperature for resetting of inclusion pressures. However, the application of both chemical and elastic thermobarometry allows a more detailed interpretation of metamorphic P–T paths.

2021 ◽  
Kathrin Fassmer ◽  
Peter Tropper ◽  
Hannah Pomella ◽  
Thomas Angerer ◽  
Gerald Degenhart ◽  

&lt;p&gt;In collisional orogens continental crust is subducted to (ultra-)high-pressure (HP/UHP) conditions as constrained by petrologic, tectonic and geophysical observations. Despite a wealth of studies on the subduction and exhumation of UHP rocks, the duration of prograde metamorphism during subduction is still not well constrained.&lt;/p&gt;&lt;p&gt;We plan to apply Lu-Hf and Sm-Nd geochronology on metamorphic rock samples to date the duration of garnet growth, which represents a major part of prograde metamorphism from the greenschist-facies onward. Micaschist samples from the Schneeberg and Radenthein Units in the Eoalpine high-pressure belt (Eastern Alps) will be used for dating as they contain cm- to dm-sized garnet blasts, which experienced only one subduction-exhumation cycle. With dating different parts of big garnet grains, we test whether (1) it is possible to resolve the duration of garnet growth within single crystals, and (2) Lu-Hf and Sm-Nd systems date the same events in the PT-path or yield complementary information. Additionally, we will perform U-Pb geochronology on titanite in order to obtain the age of the first stages of exhumation; in addition, dating of rutile inclusions as well as matrix rutiles will be used to test Eoalpine prograde age. We will also apply U-Th-Pb monazite dating (EPMA and LA-ICPMS) to some of the samples. Collectively, these data will allow us to compare the duration of subduction and the timing of initial exhumation in a single sample. We then will constrain the PT-path of the dated samples by pseudosection modeling combined with Zr-in-rutile, quartz-in-garnet, and carbonaceous material geothermo(baro)metry. We already have preliminary results for Zr-in-rutile thermometry of rutile inclusions in garnets and matrix rutiles for samples from both locations. We measured Zr content with an EPMA and used the calibrations of Tomkins et al. (2007) and Kohn (2020). The calibration of Kohn (2020) gives overall slightly lower temperatures, but all obtained temperatures lay in a range of c. 500-600 &amp;#176;C in accordance with previously published data. In addition, EPMA, &amp;#181;-XRF, LA-ICPMS, and &amp;#181;CT will be used to control if garnets preserved major and trace elemental growth zoning and to provide spatial 3D information on inclusion patterns. &amp;#181;CT analyses were already successfully used to obtain the chemical centre of the garnet grains in order to be able to cut them directly through there center. This is important for all in-situ chemical analyses. With dating different parts of single garnet crystals separately with Lu-Hf and Sm-Nd geochronology, we will add tight time constraints to the PT-path and constrain the duration of garnet growth.&lt;/p&gt;&lt;p&gt;With this contribution we formulate the working hypothesis that prograde subduction together with exhumation is a fast process. The basis for testing the idea of fast prograde metamorphism is that many geochronological studies propose a prograde duration of &lt; 10 Ma and studies using geospeedometry sometimes propose an even shorter duration, which is the impetus for this investigation.&lt;/p&gt;&lt;p&gt;References:&lt;/p&gt;&lt;p&gt;Kohn, M.J. (2020). A refined zirconium-in-rutile thermometer. American Mineralogist(105), 963-971.&lt;/p&gt;&lt;p&gt;Tomkins, H.S., Powell, R. &amp; Ellis, D.J. (2007). The pressure dependence of the zirconium-in-rutile thermometer. Journal of Metamorphic Geology(25), 703-713.&lt;/p&gt;

2021 ◽  
Rick Verberne ◽  
Hugo van Schrojenstein Lantman ◽  
Steven Reddy ◽  
Matteo Alvaro ◽  
David Wallis ◽  

&lt;p&gt;The trace-element composition of rutile is commonly used to constrain &lt;em&gt;P-T-t&lt;/em&gt; conditions for a wide range of metamorphic systems. Recent studies have highlighted the importance of micro- and nanostructures in the redistribution of trace elements in rutile via high-diffusivity pathways and dislocation-impurity associations. In this contribution, we investigate the effect of crystal-plastic deformation of rutile on its composition by combining microstructural and petrological analyses with atom probe tomography. The studied sample is from an omphacite vein of the ultrahigh-pressure metamorphic Lago di Cignana unit, Western Alps, Italy. Zr-in-rutile thermometry and inclusions of quartz in rutile and of coesite in omphacite constrain rutile deformation to around the prograde HP-UHP boundary at 500&amp;#8211;550 &amp;#176;C. Crystal-plastic deformation of a large rutile grain resulted in low-angle boundaries that generate a total misorientation of ~25&amp;#176;. Dislocations constituting the low-angle boundary are enriched in common (Fe, Zr) and uncommon trace elements (Ca). The Ca is interpreted to be derived from the grain exterior, suggesting diffusion of trace elements along the dislocation cores. The potential for dislocation microstructures to act as fast diffusion pathways must be evaluated when applying traditional geochemical analyses as compositional disturbances caused by the presence of dislocation might lead to erroneous interpretations.&lt;/p&gt;

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