Open-system behaviour of detrital zircon during weathering: an example from the Palaeoproterozoic Pretoria Group, South Africa

Detrital zircon in six surface samples of sandstone and contact metamorphic quartzite of the Magaliesberg and Rayton formations of the Pretoria Group (depositional age c. 2.20–2.06 Ga) show a major age fraction at 2.35–2.20 Ga, and minor early Palaeoproterozoic – Neoarchaean fractions. Trace-element concentrations vary widely, with Ti, Y and light rare earth elements (LREEs) spanning over three orders of magnitude. REE distribution patterns range from typical zircon patterns (LREE depletion, heavy REE enrichment, well-developed positive Ce and negative Eu anomalies) to patterns that are flat to concave downwards, with indistinct Ce and Eu anomalies. The change in REE pattern correlates with increases in alteration-sensitive parameters such as Ti concentration and (Dy/Sm) + (Dy/Nd), U–Pb discordance and content of common lead, and with a gradual washing-out of oscillatory zoning in cathodoluminescence images. U and Th concentrations also increase, but Th/U behaves erratically. Discordant zircon scatters along lead-loss lines to zero-age lower intercepts, suggesting that the isotopic and chemical variations are the results of disturbance long after deposition. The rocks sampled have been in a surface-near position (at least) since Late Cretaceous time, and exposed to deep weathering under intermittently hot and humid conditions. In this environment, even elements commonly considered as relatively insoluble could be mobilized locally, and taken up by radiation-damaged zircon. Such secondary alteration effects on U–Pb and trace elements can be expected in zircon in any ancient sedimentary rock that has been exposed to tropical–subtropical weathering, which needs to be considered when interpreting detrital zircon data.

Geochemistry of the Paleocene Clastic Rocks From the Southwestern Jianghan Basin, Central China Reveal Their Provenance, Tectonic Setting, and Palaeoenvironment

This paper intends to learn about the provenance, tectonic setting and paleoenvironment of the Paleocene Shashi Formation in the southern Jianghan Basin by the bulk-rock geochemistry. The K2O/Al2O3 and SiO2/Al2O3 ratios indicate that the major proportion of samples are litharenite. The chondrite-normalized REE distribution pattern of the Shashi Formation’s mudstones are characterized by enriched LREE and flat HREE similar to those of UC with negative Eu anomalies. Combined with the geochemical element ratio discriminant diagram, such as Al2O3-TiO2, Zr-TiO2, La/Sc-Co/Th, and Hf-La/Th, so on, these samples were sourced from mixed felsic/basic rock. Moreover, the discriminant diagrams of K2O/Na2O-SiO2/Al2O3, La-Th-Sc, and Th-Co-Zr/10 suggest that the samples were formed under the tectonic settings of active continental margin and continental island arc. The values of CIA, CIW, PIA, ICV, Zr/Sc-Th/Sc, and ternary diagrams of A-(CN)-K and Al2O3-Zr-TiO2 indicate that weathering in the source area was weak and source rocks have not been reformed by depositional recirculation and hydraulic sorting. And the palaeoenvironmental indicators of C-value, Ni/Co, V/Cr, V/(V+Ni) and Sr/Cu, Ga/Rb indicate that the climate was cool and arid during the evaporite deposition period in the southern Jianghan Basin, and the water was in the condition of oxidation.

Zircons of fenites of Ilmeno-Vishnevogorsky Complex (Southern Urals)

Research subject. U-Pb zircon dating, as well as a petrological and geochemical study of pyroxene-amphibole-, pyroxeneamphibole- biotite- and biotite-bearing fenites from the Central Alkaline Band Ilmeno-Vishnevogorsky Complex.Methods. The age of zircons was determined by an ion mass spectrometer (SHRIMP II, Centre of Isotopic Research VSEGEI). The content of REE and trace elements was estimated by secondary ion mass spectrometer methods (CAMECA IMS-4F, Valiev Institute of Physics and Technology RAS).Results. The mineralogical and geochemical (U, Th, REE) features of zircons, as well as fenites, reflect their polygenic-polychronous nature. Most zircon crystals have a metastable matrix and are characterized by averaged REE contents between igneous and hydrothermal types. These crystals are distinguished from magmatic zircons by high LREE contents and low values of Ce anomalies, and from hydrothermal zircons – by differentiated REE distribution spectra. Three ages of zircon were established: 2066–1686 (PR1), 425–404 (S2) and 284–266 (P1) Ma. PR1 zircons reflect the primary features and the degree of changes in the fenite substrate. S2 zircons, limited only to the biotite- bearing fenite, correspond to the age of the miaskite formation process. The P1 zircons clearly reflect the metasomatic process of fenitization initiated by late shear deformations. The temperature of the phenitization processes (based on the Ti content in zircons) was estimated at 630–670°C for S2 and ≤ 600°C for P1 fenites, respectively.Conclusions. Central Alkaline Band fenites were formed by the metasomatic process of PR1 substrate fenitization in the late stage (P1) of shear strains, which are widely expressed in the Ilmeno-Vishnevogorsky Complex.

U-Pb age and trace elements composition of titanite from granites of Belokurikhinsky massif, Gorny Altai

As a result of isotope-geochemical study, the age data (U-Pb method, ID-TIMS) of titanite from the first phase granites of the Belokurikhinsky granite massif, Gorny Altai, were obtained for the first time. The concordant value of the titanite age of 255 ± 2 Ma coincides within the margin of error with the previously published results of dating micas from granites of the second and third phases of the Belokurikha massif by the Ar-Ar method (250 ± 3 Ma). At the same time, the results of dating differ significantly from the previously published age values for the granites of the Belokurikha massif (232 ± 5 Ma, U-Pb method for the monofraction of zircon grains; 245 ± 8 Ma, Rb-Sr method for the whole rocks). Therefore, there is every reason to narrow the time interval of the formation of the Belokurikha granite massif to 255-250 Ma. The study of the trace element composition of titanite by SIMS demonstrated their zonal structure. The central part of the titanite grain differs from the rim by a noticeably higher content of REE, Cr, Y, and Nb. The content of V, Zr and Ba decreases to a lesser extent towards the rim, the content of Sr and U remains constant. At the same time, the REE distribution spectra in the central and rim parts are conformal to each other, having a convex spectrum for LREE and a concave one for HREE. Titanite is characterized by a negative Eu-anomaly, the depth of which decreases to the rim of the grain. A negative Eu-anomaly indicates the co-crystallization of titanite and plagioclase. The REE distribution spectra in titanite from the Belokurikha massif correspond to the characteristics of a typical magmatic titanite from granitoids and differ significantly from the distribution spectra in metamorphic titanite.

Mineralization of the Tuwu Porphyry Cu Deposit in Eastern Tianshan, NW China: Insights From In Situ Trace Elements of Chlorite and Pyrite

The Tuwu porphyry copper deposit is located on the Dananhu-Haerlik island arc in eastern Tianshan, NW China. Based on geology, petrology, and in situ trace element studies of pyrite and chlorite, we redefined the characteristics of hydrothermal fluids and the following three mineralization stages: premineralization stage (stage Ⅰ), porphyry metallogenic stage (stage Ⅱ), and superimposed transformation stage (stage Ⅲ). Pyrite stage Ⅰ (Py-I) has the highest Co/Ni ratios, and the precipitation crystallization of chlorite (Chl-I2) has the similar rare earth element distribution patterns with those of volcanic rocks Carboniferous Qieshan (CQ), indicating intense volcanic hydrothermal activity. The Co/Ni ratios of Py-II1 and Py-II2 (stage Ⅱ) tend to decrease over time. Moreover, the rare earth element (REE) distribution patterns of Chl-II have similar LREE enrichment, and the Eu anomalies in Chl-II1, Chl-II2, and Chl-II3 range from positive to negative. The initial ore-forming fluid was mainly magmatic hydrothermal fluid, and with the late-stage addition of meteoric water and continuous sulfide precipitation, the trace element composition of the fluid changed, and the whole system became more oxidizing. Py-III (stage Ⅲ) has the lowest Co/Ni ratios, and the REE distribution pattern of Chl-III is characterized by LREE enrichment. Moreover, the Chl-III shows obvious shear deformation characteristics. The results indicate that the host rocks experienced intensely superimposed reformation. By combining and integrating our results with the regional evolution processes in the eastern Tianshan, we propose that the Tuwu porphyry deposit has undergone magmatic hydrothermal and metamorphic hydrothermal processes. Volcanism (stage Ⅰ) provided the space and initial conditions for the emplacement of the metallogenic body. With the emplacement of the plagiogranite porphyry (stage Ⅱ), the main copper mineralization occurred in the porphyry and surrounding rocks. After porphyry mineralization (stage Ⅲ), regional ductile shearing and collisional compression led to a copper reaction, and its accumulation along the faults formed an ore shoot.

Geochemical characteristics and geologic significance of rare earth elements in oil shale of the Yan’an Formation in the Tanshan area, in the Liupanshan Basin, China

In the Tanshan area, which is at the Liupanshui Basin, abundant oil shale resources are associated with coals. We analyzed the cores, geochemistry of rare earth elements (REE) and trace element of oil shale with ICP-MS technology to define the palaeo-sedimentary environment, material source and geological significance of oil shale in this area. The results of the summed compositions of REE, and the total REE contents (SREE), in the Yan'an Formation oil shale are slightly higher than the global average of the composition of the upper continental crustal (UCC) and are lower than that of North American shales. The REE distribution pattern is characterized by right-inclined enrichment of light rare earth elements (LREE) and relative loss of heavy rare earth elements (HREE), which reflects the characteristics of crustal source deposition. There is a moderate degree of differentiation among LREE, while the differences among HREE are not obvious. The dEu values show a weak negative anomaly and the dCe values show no anomaly, which are generally consistent with the distribution of REE in the upper crust. The characteristics of REE and trace elements indicate that the oil shale formed in an oxygen-poor reducing environment and that the paleoclimatic conditions were relatively warm and humid. The degree of differentiation of REE indicates that the sedimentation rate in the study area was low, which reflected the characteristics of relatively deep sedimentary water bodies and distant source areas. The results also proved that the source rock mainly consisted of calcareous mudstone, and a small amount of granite was also mixed in.

Ocean-Floor Sediments as a Resource of Rare Earth Elements: An Overview of Recently Studied Sites

The rare earth elements (REE), comprising 15 elements of the lanthanum series (La-Lu) together with yttrium (Y) and scandium (Sc), have become of particular interest because of their use, for example, in modern communications, renewable energy generation, and the electrification of transport. However, the security of supply of REE is considered to be at risk due to the limited number of sources, with dependence largely on one supplier that produced approximately 63% of all REE in 2019. As a result, there is a growing need to diversify supply. This has resulted in the drive to seek new resources elsewhere, and particularly on the deep-ocean floor. Here, we give a summary of REE distribution in minerals, versatile applications, and an update of their economic value. We present the most typical onshore methods for the determination of REE and examine methods for their offshore exploration in near real time. The motivation for this comes from recent studies over the past decade that showed ΣREE concentrations as high as 22,000 ppm in ocean-floor sediments in the Pacific Ocean. The ocean-floor sediments are evaluated in terms of their potential as resources of REE, while the likely economic cost and environmental impacts of deep-sea mining these are also considered.

Chemical weathering intensity and rare earth elements release from a chlorite schist profile in a humid tropical area, Bengbis, Southern Cameroon

RésuméUn profil d’altération développé sur chloritoschistes de la zone de Bengbis (Sud Cameroun) a été choisi pour quantifier l’intensité de l’altération et comprendre le comportement des terres rares. Les valeurs de l’indice d’altération mafique combinées aux diagrammes ternaires du système Al – Fe – Mg – Ca – Na – K montrent que l’hydrolyse des feldspaths est proportionnelle à celle des minéraux mafiques (pertes en Mg), bien que l’hydrolyse des plagioclases (Ca, Na) soit plus intense que celle des minéraux ferromagnésiens. Les matériaux d’altération étudiés sont localisés dans le domaine de la kaolinitisation, à l’exception des matériaux nodulaires qui sont légèrement latritiss. La modification du comportement du Mg dans le milieu d’altération s’exprime par les faibles valeurs du rapport Ca/Mg. Le potassium et Be sont lessivés dans le sol en association avec Mg. L’ordre de mobilité des éléments dans l’environnement d’altération étudié est : Ca ≈ Na > Fe2+ ≈ Sr > Mg ≈ Co > Mn > Li > Ba > Rb > P > Cd > Ni > Si > Be > K > Sn. Les enrichissements en K, Cs et Be dans les saprolites sont liés à la présence d’illite. L’accumulation en Cs dans le sol est due à la présence de kaolinite. Le système le plus stable dans le milieu d’altération étudié est : Hf – Nb – W – U. Les saprolites, les matériaux nodulaires et les matériaux argileux meubles superficiels sont appauvris en terres rares par rapport à la roche mère. Les terres rares présentent trois types de comportement le long du profil d’altération, comme l’indiquent les valeurs du rapport (La/Yb)N ((La/Yb)N < 1, (La/Yb)N ~ 1 et (La/Yb)N > 1). Les terres rares légères et les terres rares moyennes s’accumulent dans les matériaux d’altération pour des valeurs de pH comprises entre 5,5 et 5,6 et pour celles de Eh variant entre +60 et +70mV. L’ordre de mobilité de ces éléments dans ces matériaux est le suivant : terres rares moyennes > terres rares lourdes terres rares légères. Ce fait est contre-intuitif, car les terres lourdes sont plus mobiles dans les environnemenst supergènes que les terres rares légères. L’adsorption ou la co-précipitation de ces terres rares sur les oxydes de fer peut principalement contrôler la concentration de ces éléments dans le profil d’altération. Les faibles anomalies en Ce dans les matériaux d’altération de la zone de Bengbis, dues au changement de Ce3+ en Ce4+, sont probablement dues à la présence de faibles quantités de rhabdophane. Les matériaux d’altération étudiés présentent un fractionnement en Gd (Gd/Gd* ~0.70 – 0.84) dues à une intense lixiviation. Ce fait a rarement été signalé dans un environnement d’altération latéritique. Il semble qu’une partie de la distribution et de la remobilisation du gadolinium soit contrôlée par des minéraux mafiques dans les matériaux d’altération étudiés. La distribution et la mobilisation des terres rares sont donc contrôlées par (1) l’adsorption ou la coprécipitation dans les minéraux mafiques et Fe, (2) et légèrement par les minéraux contenant des terres rares tels que le rhabdophane, rencontrés dans les matériaux d’altération étudiés. Abstract An in situ weathering profile overlying chlorite schists in southern Cameroon was chosen to quantify chemical weathering intensity and to study the behaviour of rare earth elements (REE). Mafic index alteration values combined with the ternary diagrams of the Al – Fe – Mg – Ca – Na – K system show that the hydrolysis of feldspars is proportional to that of mafic minerals (losses in Mg), although the hydrolysis of the plagioclases (Ca, Na) is more intense than that of ferromagnesian minerals. The studied materials are localised in the domain of kaolinitisation, except for nodular materials which are slightly lateritised. The change in the behaviour of Mg in the weathering environment is expressed by the low values in Ca/Mg ratio. Potassium and Be are leached in the soil in association with Mg. The order of mobility of the elements in the weathering environment is: Ca ≈ Na > Fe2+ ≈ Sr > Mg ≈ Co > Mn > Li > Ba > Rb > P > Cd > Ni > Si > Be > K > Sn. The enrichments in K, Cs and Be in saprolites are linked to the presence of illite. Cesium accumulation in the soil is due to the presence of kaolinite. The most stable system is: Hf – Nb – W – U. Saprolites, nodular and loose clayey materials are depleted in REE relative to the parent rock. REE exhibit three types of behaviour along the Bengbis profile like indicated by (La/Yb)N ratio values ((La/Yb)N < 1, (La/Yb)N ~ 1 and (La/Yb)N > 1). Light REE and Middle REE accumulate in the weathering materials for pH values ranging between 5.5 and 5.6 and for those of Eh varying between +60 and +70mV. The order of mobility of REE in these horizons is: Middle REE > Heavy REE ≈ Light REE. This fact is counter-intuitive, because Heavy REE are more mobile in supergene environment than Light REE. Adsorption or co-precipitation of LREE onto Fe oxides mainly may control the concentration of these elements in the profile. Weak Ce anomalies in the weathering materials of Bengbis area, due to the change in Ce3+ to Ce4+, are probably due to the presence of low amounts in rhabdophane. The studied weathering materials show a fractionation in Gd (Gd/Gd* ~0.70 – 0.84) due to intense chemical leaching. This fact has been rarely reported in lateritic weathering environment. It appears that, a part of Gd distribution and remobilization is controlled by mafic minerals in the studied weathered materials. REE distribution and mobilization are thus controlled by (1) adsorption or co-precipitation in mafic and Fe minerals, (2) and slightly by REE-bearing minerals such as rhabdophane found in the studied weathering profile.

Formation Mechanism of the Velyka Vyska Syenite Massif (Korsun-Novomyrhorod Pluton, Ukrainian Shield) Derived from Melt Inclusions in Zircon

The formation of leucosyenites in the Velyka Vyska syenite massif was provoked by the liquation layering of magmatic melt. This assumption is based on the presence of two primary melt inclusions of different chemical composition in zircon crystals from Velyka Vyska leucosyenites. They correspond to two types of silicate melts. Type I is a leucosyenite type that contains high SiO2 concentrations (these inclusions dominate quantitatively); type II is a melanosyenite type that contains elevated Fe and smaller SiO2 concentrations. The liquation layering of magmatic melt was slow because the liquates are similar in density; leucosyenite melt, which is more abundant than melt of melanosyenite composition, displays greater dynamic viscosity; the initial sizes of embryos of melanosyenite composition are microscopic. Sulphide melt, similar in composition to pyrrhotite, was also involved in the formation of the massif. Zircon was crystallized at temperatures over 1300°С, as indicated by the homogenization temperatures of primary melt inclusions. The REE distribution spectra of the main parts (or zones,) of zircon crystals from the Velyka Vyska massif are identical to those of zircon from the Azov and Yastrubets syenite massifs with which high-grade Zr and REE (Azov and Yastrubets) ore deposits are associated. They are characteristic of magmatically generated zircon. Some of the grains analyzed contain rims that are contrasting against the matrix of a crystal, look dark-grey in the BSE image and display flattened REE distribution spectra. Such spectra are also typical of baddeleyite, which formed by the partial replacement of zircon crystals. The formation of a dark-grey rim in zircon and baddeleyite is attributed to the strong effect of high-pressure СО2-fluid on the rock. The formation patterns of the Velyka Vyska and Azov massifs exhibit some common features: (а) silicate melt liquation; (b) high ZrO2 concentrations in glasses from hardened primary melt inclusions; (c) the supply of high-pressure СО2-fluid flows into Velyka Vyska and Azov hard rocks. Similar conditions of formation suggest the occurrence of high-grade Zr and REE ores in the Velyka Vyska syenite massif.