Genesis of REE minerals in the karstic bauxite in western Guangxi,China, and its constraints on the deposit formation conditions

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce^3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce^4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce^3 + was oxidized into Ce^4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.     

Mineralogical and geochemical investigations of the Mombi bauxite deposit,Zagros Mountains,Iran

The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al₂O₃, SiO₂, Fe₂O₃ and TiO₂ are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce³⁺ to Ce⁴⁺), ionic potential, and complexation of Ce⁴⁺ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation.     

Geochemical and mineralogical characteristics of weathered ore in the Dalucao REE deposit,Mianning–Dechang REE Belt,western Sichuan Province,southwestern China

The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.     

Mineralogical and geochemical studies of brecciated ores in the Dalucao REE deposit,Sichuan Province,southwestern China

The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (⁴⁰Ar/³⁹Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO₂ derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ¹⁸O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ¹⁸O_V-SMOW from 8.0‰ to 11.6‰, and δ¹³C _V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite.     

Content and mode of occurrences of rare earth elements in the Zagrad karstic bauxite deposit (Nikšić area,Montenegro)

Three vertical sections through the Zagrad deposit of Jurassic karst bauxite in central Montenegro have provided knowledge of the vertical distribution of major and some selected trace elements, including rare earth elements (REE). Variations in the mineralogy, particularly those hosting REE, have been studied. This has revealed the presence of authigenic mineral phases such as xenotime, mottramite and monazite (best proved using Raman microprobe analysis) as well as residual phases such as zircon, titanite and monazite. The mobility of the elements during bauxitization processes has been studied to show that the REE minerals ensure progressive concentration of these elements during removal of major elements through weathering. The similarity of normalized REE in the bauxite to the typical Post-Archean Australian Shales (PAAS) and Upper Continental Crust (UCC) profile, and the preserved Eu anomaly, are evidence that the bauxite was not derived from carbonates and represents alteration of shale, marly limestone and volcanogenic or proximal igneous sourced detritus that accumulated in the original karst landform. Mass change during bauxitization, using Ti as “index” element and compared to PAAS composition, revealed almost 100% depletion of Si and weak enrichment in Al. Deeper parts of the deposit with authigenic minerals exhibit very strong enrichment in all REE. The bauxite ores have high ΣREE contents (693.5–6953.4 ppm), especially ΣLREE contents (582.8–4882.9 ppm), while ΣHREE contents (106.6–2070.5 ppm) are much lower.     

In-situ LA-ICP-MS trace elemental analyses of magnetite: The Bayan Obo Fe-REE-Nb deposit,North China

The Bayan Obo Fe-REE-Nb deposit in northern China is the world's largest light REE deposit, and also contains considerable amounts of iron and niobium metals. Although there are numerous studies on the REE mineralization, the origin of the Fe mineralization is not well known. Laser ablation (LA) ICP-MS is used to obtain trace elements of Fe oxides in order to better understand the process involved in the formation of magnetite and hematite associated with the formation of the giant REE deposit. There are banded, disseminated and massive Fe ores with variable amounts of magnetite and hematite at Bayan Obo. Magnetite and hematite from the same ores show similar REE patterns and have similar Mg, Ti, V, Mn, Co, Ni, Zn, Ga, Sn, and Ba contents, indicating a similar origin. Magnetite grains from the banded ores have Al + Mn and Ti + V contents similar to those of banded iron formations (BIF), whereas those from the disseminated and massive ores have Al + Mn and Ti + V contents similar to those of skarn deposits and other types of magmatic-hydrothermal deposits. Magnetite grains from the banded ores with a major gangue mineral of barite have the highest REE contents and show slight moderate REE enrichment, whereas those from other types of ores show light REE enrichment, indicating two stages of REE mineralization associated with Fe mineralization. The Bayan Obo deposit had multiple sources for Fe and REEs. It is likely that sedimentary carbonates provided original REEs and were metasomatized by REE-rich hydrothermal fluids to form the giant REE deposit.     

Geological and geochemical constraints on the Cheshmeh-Frezi volcanogenic stratiform manganese deposit,southwest Sabzevar basin,Iran

The Cheshmeh-Frezi Mn deposit belongs to the southwest Sabzevar basin to the north of the Central Iranian microcontinent. This basin, which hosts abundant mineral deposits including Mn exhalative and Besshi-type Cu-Zn volcanogenic massive sulfide deposits, followed an evolution closely related to the subduction of the Neo-Tethys oceanic crust beneath the Central Iranian microcontinent. Two major sedimentary sequences are recorded within this basin: (I) the Lower Late Cretaceous volcano-sedimentary sequence (LLCVSS) and (II) the Upper Late Cretaceous sedimentary dominated sequence (ULCSS). The Cheshmeh-Frezi Mn deposit is hosted within red tuff with interbeds of green tuffaceous sandstone of the LLCVSS. Mineralization occurs as stratiform blanket-like and tabular orebodies. Psilomelane, pyrolusite and braunite are the main minerals of the ore, which display a variety of textures. Such as layered, laminated, disseminated, massive, replacement or open space fillings. The footwall and hanging-wall volcanic rocks are predominantly andesite and trachyandesite rocks. Footwall and hangingwall volcanic rocks at Cheshmeh-Frezi are enriched in light rare earth elements (LREEs) compared to chondrite, have steep REE patterns, and generally show Ta and Nb depletions relative to chondrite which are characteristic of back-arc environments. The significant geochemical characteristics of ore such as high Mn content (12.41–33.14 wt%; average 19.41 wt%), low concentration of Fe (0.64–2.27 wt%; average 1.63 wt%), high Ba (49.7–9901 ppm, average 2728.67 ppm), LREE > HREE, and negative Ce and Eu anomalies reveal a primary distal hydrothermal-exhalative source for mineralization. Cheshmeh-Frezi deposit, in comparison with different types of volcanogenic manganese deposits shows broad similarities with the Cuban-type Mn deposits such as tectonic, host and associated rock types, geometry, textures, structures, mineralogy and lithogeochemistry.     

In–situ LA–ICP–MS trace elemental analyzes of magnetite: The Tieshan skarn Fe–Cu deposit,Eastern China

The Tieshan Fe–Cu deposit is located in the Edong district, which represents the westernmost and largest region within the Middle–Lower Yangtze River Metallogenic Belt (YRMB), Eastern China. Skarn Fe–Cu mineralization is spatially associated with the Tieshan pluton, which intruded carbonates of the Lower Triassic Daye Formation. Ore bodies are predominantly located along the contact between the diorite or quartz diorite and marbles/dolomitic marbles. This study investigates the mineral chemistry of magnetite in different skarn ore bodies. The contrasting composition of magnetite obtained are used to suggest different mechanisms of formation for magnetite in the western and eastern part of the Tieshan Fe–Cu deposit. A total of 178 grains of magnetite from four magnetite ore samples are analyzed by LA–ICP–MS, indicating a wide range of trace element contents, such as V (13.61–542.36 ppm), Cr (0.003–383.96 ppm), Co (11.12–187.55 ppm) and Ni (0.19–147.41 ppm), etc. The Ti/V ratio of magnetite from the Xiangbishan (western part of the Tieshan deposit) and Jianshan ore body (eastern part of the Tieshan deposit) ranges from 1.32 to 5.24, and 1.31 to 10.34, respectively, indicating a relatively reduced depositional environment in the Xiangbishan ore body. Incorporation of Ti and Al in magnetite are temperature dependent, which hence propose that the temperature of hydrothermal fluid from the Jianshan ore body (Al = 3747–9648 ppm, with 6381 ppm as an average; Ti = 381.7–952.0 ppm, with 628.2 ppm as an average) was higher than the Xiangbishan ore body (Al = 2011–11122 ppm, with 5997 ppm as an average, Ti = 302.5–734.8, with 530.8 ppm as an average), indicating a down–temperature precipitation trend from the Jianshan ore body to the Xiangbishan ore body. In addition, in the Ca + Al + Mn versus Ti + V diagram, magnetite is plotted in the skarn field, consideration with the ternary diagram of TiO₂–Al₂O₃–MgO, proposing that the magnetite ores are formed by replacement, instead of directly crystallized from iron oxide melts, which provide a better understanding regarding the composition of ore fluids and processes responsible for Fe mineralization in the Tieshan Fe–Cu deposit.     

Provenance of lateritic bauxite deposits in the Wuchuan–Zheng’an–Daozhen area,Northern Guizhou Province,China: LA-ICP-MS and SIMS U–Pb dating of detrital zircons

The provenance of the large and super-large scale bauxite deposits developed in the Wuchuan–Zheng’an–Daozhen (WZD) alumina metallogenic province in the Yangtze Block of South China is poorly understood. LA-ICP-MS and SIMS U–Pb dating of detrital zircons from bauxite ores and the underlying Hanjiadian Group in the WZD area provide new constrains on the provenance of the WZD bauxite and provide new insight on the bauxite ore-forming process. The ages of the detrital zircons in the bauxites and the zircons in the Hanjiadian Group are similar suggesting that the bauxites are genetically related to the Hanjiadian sediments. The detrital zircon populations of the four samples studied show four primary age peaks: 2600–2400 Ma, 1900–1700 Ma, 1300–700 Ma and 700–400 Ma. The age distribution of detrital zircons indicates that they are probably derived from various sources including Neoproterozoic, Mesoproterozoic, Paleoproterozoic, Archean and some minor Paleozoic sources. The most abundant age population contains a continuous range of ages from 1300 to 700 Ma, ages consistent with subduction-related magmatic activities (1000–740 Ma) along the western margin of the Yangtze Block and the worldwide Grenville orogenic events (1300–1000 Ma). Thus, it is suggested that the main provenances of the WZD bauxite and the Hanjiadian Group are the Neoproterozoic igneous rocks in the western Yangtze Block and the Grenville-age igneous rocks in the southern Cathaysia Block. In addition, this work verifies that the global Grenville orogenic events and subduction-related magmatic activities associated with the Yangtze Block had a significant influence on the formation of the WZD bauxite deposits.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Geological characteristics and metallogenesis of iron deposits in western Tianshan,China

The western Tianshan metallogenic belt is one of the most significant polymetallic iron metallogenic belts in China. Important advances have been achieved recently in iron exploration in the Awulale Mountain in western Tianshan, China. These newly-discovered iron deposits are mainly hosted in the basic-medium andesitic lavas and volcaniclastics, often comprising a number of high-grade ores. Magnetite is predominated in ore mineral assemblages, and pyrite, chalcopyrite, pyrrhotite or sphalerite increase in certain deposits. Wallrock alterations are intensively developed, exemplified as sodic–calcic and potassic alterations which display in different patterns as country rocks and ore-controlled structures vary. Skarn assemblages are commonly developed in ore districts like Beizhan, Dunde and Chagangnuoer, and pyroxene + albite + K-feldspar − epidote + actinolite alterations are dominated around ore bodies in Zhibo deposit, whereas the Shikebutai deposit develops alteration assemblages comprising of jasper, barite, sericite, and chlorite. Thus, iron deposits can be divided into three types including volcanic-sedimentary type, volcanic magmatic-hydrothermal type and iron skarn type. Our preliminary interpretation about the tectonic background of this iron mineralization in this area is in the late stage of a collisional–accretional orogenic belt around Carboniferous, with some extrusional–extensional tectonic transition locally. Iron mineralization is likely to have a close genetic relationship with volcanic–subvolcanic activity, syn- or slightly post- the volcanism which took place besides continental arc. Volcanic eruption contributes to majority of mineralizing iron, with minor extracted from hydrothermal replacement from wall rocks.     

Nakhlak carbonate-hosted Pb(Ag) deposit,Isfahan province,Iran: a geological,mineralogical, geochemical,fluid inclusion,and sulfur isotope study

The Upper Cretaceous Nakhlak epigenetic vein-type Pb(Ag) deposit is located 55 km northeast of the town of Anarak in Isfahan Province, Iran. The deposit contains 7 Mt of galena-barite ore with an average grade of 8.33% Pb, 0.38% Zn, and 72 ppm Ag. The ore mineralization occurs as stratabound, epigenetic, steeply dipping, east-west–trending veins in faulted- or fracture-controlled Upper Cretaceous Sadar carbonates. Galena and barite are the primary minerals. Minor sphalerite, tennantite-tetrahedrite, pyrite, and chalcopyrite occur as inclusions in galena. Cerussite with minor amounts of anglesite and plattnerite formed in the oxidized supergene zone. The ore and ore-related minerals were deposited in the hydrothermally dolomitized carbonate host rock containing saddle-shaped dolomite. Geochemically, the dolomitized carbonate host rocks are enriched in MgO, Fe₂O₃, MnO, Pb, Zn, and Ba, but depleted in CaO. The galena concentrate contains high values of Ag (932 ppm), Sb (342 ppm), Cu (422 ppm), As (91 ppm), and Zn (296 ppm); the presence of these trace elements indicates a low-temperature type of galena mineralization. This interpretation is corroborated by fluid inclusions containing 12.98 wt.% NaCl equivalent salinity; the inclusions homogenize at the low temperature of about 152.1 °C. The similarity between δ³⁴S_(V-CDT) values in Nakhlak barite and Permian–Triassic δ³⁴S marine sulfate values indicates that the Nakhlak sulfur was probably provided from evaporates of Permian–Triassic age. The δ³⁴S_(V-CDT) values of galena and barite samples occupy the ranges of − 1.04‰ to + 8.62‰ and + 10.95‰ to + 13.71‰, respectively, and are similar to Mississippi Valley–type (MVT) deposits. The low-temperature basinal fluids, evaporate-originated sulfur, and fault- or fracture-controlled galena-rich veins in the Nakhlak deposit resemble the type of geological features documented in Pb-rich MVT deposits.     

Geology and molybdenite Re–Os age of the Dahutang granite-related veinlets-disseminated tungsten ore field in the Jiangxin Province,China

This is a brief research report about the recently-discovered and currently being explored Dahutang tungsten deposit (or ore field) in northwestern Jiangxi, south-central China. The deposit is located south of the Middle–Lower Yangtze River valley Cu–Au–Mo–Fe porphyry–skarn belt (YRB). The mineralization is genetically associated with Cretaceous porphyritic biotite granite and fine-grained biotite granite and is mainly hosted within a Neoproterozoic biotite granodiorite batholith. The Dahutang ore field comprises veinlets-disseminated (~ 95% of the total reserve), breccia (~ 4%) and wolframite–scheelite quartz vein (~ 1%) ore styles. The mineralization and alteration are close to the pegmatite shell between the Cretaceous porphyritic biotite granite and Neoproterozoic biotite granodiorite and the three styles of ore bodies mentioned above are related to zoned hydrothermal alteration that includes greisenization, K-feldspar alteration, silicification, carbonatization, chloritization and fluoritization arranged in time (early to late) and space (bottom to top).Five samples of molybdenite from the three types of ores have been collected for Re/Os dating. The results show Re/Os model ages ranging from 138.4 Ma to 143.8 Ma, with an isochron age of 139.18 ± 0.97 Ma (MSWD = 2.9). The quite low Re content in molybdenite falls between 0.5 ppm and 7.8 ppm that is indicative of the upper crustal source. This is quite different from molybdenites in the YRB Cu–Au–Mo–Fe porphyry–skarn deposits that contain between 53 ppm and 1169 ppm Re, indicating a mantle source.The Dahutang tungsten system is sub-parallel with the YRB porphyry–skarn Cu–Au–Mo–Fe system. Both are situated in the north margin of the Yangtze Craton and have a close spatial–temporal relationship. This possibly indicates a comparable tectonic setting but different metal sources. Both systems are related to subduction of the Paleo-Pacific plate beneath the Eurasian continent in Early Cretaceous. The Cu–Au–Mo–Fe porphyry–skarn ores are believed genetically related to granitoids derived from the subducting slab, whereas the porphyry W deposits are associated with S-type granitoids produced by remelting of the upper crust by heat from upwelling asthenoshere.     

Geology,fluid inclusion and stable isotope study of the Yueyang Ag-Au-Cu deposit,Zijinshan orefield,Fujian Province,China

The large Yueyang Ag-Au-Cu deposit is commonly regarded as a low-sulfidation epithermal deposit in the Zijinshan orefield, Fujian Province, southeastern China. The Ag-Ag-Cu orebodies hosted in the Zijinshan granitic batholith are mainly stratoid and lens in shape, and controlled by a series of NW-trending listric faults with shallow dip angles. Four mineralization stages are recognized on the basis of mineral assemblage, ore fabrics, and crosscutting relationships of the ore veins, namely: pre-ore (pyrite + sericite + quartz ± chlorite), main Cu (chalcopyrite + pyrite + sericite + quartz ± bornite), main Ag-Au (Ag and Au minerals + pyrite + quartz + adularia ± calcite ± apatite ± chalcopyrite ± galena ± sphalerite) and post-ore (quartz ± chalcedony ± calcite) stages. Fluid inclusions (FIs) in the deposit include aqueous liquid-rich (WL-), aqueous vapor-rich (WV-), and minor carbonic (C-) and daughter mineral-bearing (S-) type ones. WL-subtype is the main inclusion type in the Yueyang deposit, accounting for more than 90% in proportion in each stage. Minor WV-subtype inclusions occur in both the main Cu and Ag stages, while the C-type and S-type ones are only observed in the main Cu stage. Fluid inclusion and H-O isotope study indicated that the ore-forming fluid of the main Cu stage is primarily magmatic vapor, which further underwent fluid boiling and mixing with meteoric water, while the ore-forming fluid of the main Ag stage is meteoric water-dominated, and the precipitation of silver and gold was mainly resulted from fluid boiling and the precipitation of other sulfides. On the basis of the aforementioned geological, fluid inclusion and stable isotope studies, we proposed a two-stage model for the Yueyang deposit, including a magmatic vapor-related porphyry type Cu mineralization and meteoric water-related low-sulfidation epithermal Ag-Au-Cu mineralization, although the porphyry Cu mineralization is very limited in scale. The mineralization and exhumation depths of the Yueyang deposit are estimated to be 448‒527 m and 18‒97 m, respectively. By comparison with the exhumation depths of other deposits in the Zijinshan orefield, it is suggested that more epithermal deposits could be found in the southwest of the orefield due to less uplift and exhumation therein.     

Genesis of Si-rich carbonatites in Huanglongpu Mo deposit,Lesser Qinling orogen,China and significance for Mo mineralization

The Huanglongpu carbonatite-related Mo ore field is located in the Lesser Qinling Orogenic belt in the southern margin of the North China block. The ore field is composed of six deposits, Yuantou, Wengongling, Dashigou, Shijiawan, Taoyuan and Erdaohe, all of which are genetically related to carbonatite dykes except for the Shijiawan deposit which is associated with a granitic porphyry. The Yuantou carbonatite dykes intruded into Archean gneiss and other carbonatites emplaced into Mesoproterozoic volcanic and sediment rocks. The carbonatites are mainly composed of calcite and variable amounts of quartz and K-feldspar and minor molybdenite. Re–Os dating of molybdenite from the Yuantou carbonatite yields a weighted average age of 225.0 ± 7.6 Ma, consistent with the molybdenite age (221 Ma) from the Dashigou deposit. The rocks are characterized by high heavy REE (HREE) contents and consistent flat REE distribution patterns with La/Yb_cn ~ 1. Quartz in the carbonatites from Yuantou and Dashigou deposits shows consistent O isotopes (8.1–10.2‰) similar to the associated calcite (7.2–9.5‰). The quartz and associated K-feldspar contain lower Zr, Hf and higher HREE abundances and negligible Eu anomaly relative to those from the granite porphyry in Shijiawan. Both minerals are primary products in the carbonatitic liquid, and not captured from the wall-rocks or crustal-derived silicate magmas, or a hydrothermal origin. Thus, the Huanglongpu carbonatitic liquids were enriched in Si and Mo, which may be produced by intensely fractional crystallization of non-silicate minerals.     

A combined fluid inclusion and S–Pb isotope study of the Neoproterozoic Pingshui volcanogenic massive sulfide Cu–Zn deposit,Southeast China

The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ³⁴S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.     

The possible synglaciogenic Ediacaran hematitic banded iron salt formation (BISF) at Hormuz Island,southern Iran: Implications for a new style of exhalative hydrothermal iron-salt system

The Ediacaran BISF at Hormuz Island is a newly identified glaciogenic iron-salt deposit in the Tethyan margin of Gondwana. The BISF was formed by synchronous riftogenic A-type submarine felsic volcanism and evaporate deposition. The mineralization occurs in a proximal felsic tuff cone and jaspilitic distal zones and contains 1 million tonne of hematite-rich ore with an average grade of 58% Fe. The ore structure shows cyclicity of macrobandings, mesobandings and microbandings of anhydrite, halite, hematite and chert, which marks a new record in BIFs geohistory. The alteration minerals in the proximal and distal zones are actinolite, ripidolite, epidote, sericite, tourmaline, clinochlore, anhydrite and clay minerals. The occurrence of metamorphosed polygenetic bullet-shape dropstones in BISF attests that there was probably a continuous process of ice melting, episodic submarine volcanism and exhalative hydrothermal banded iron salt formation during the Late Ediacaran time. The non-metamorphosed Neoproterozoic stratigraphy, the presence of genus Collenia, U-Pb dating (558 ± 7 Ma) and the marked negative δ¹³C excursion in cap carbonates are representative of Late Ediacaran glaciation, which has been identified worldwide. The REE+Y display light REE enrichment, unusually strong Tb-Tm anomaly, a weak positive Y anomaly, but no distinguished Eu and Ce anomalies, reflecting the glaciogenic nature of the BISF. The contents of Zr, Hf, Nb, Ta, Th, La, Ce and Y in BISF, dropstones, halite and cap carbonates are similar to those of the Neoproterozoic glaciogenic BIFs. Also, the Ni/Fe, P/Fe ratios and Fe/Ti – Al/Al + Fe + Mn + Ca + Na + K diagram suggest an exhalative hydrothermal Ediacaran-type BISF. The absence of brecciated magnetite in the ore association and the low contents of copper (9–493 ppm) and gold (<5–8 ppb) are not in favor of the IOCG – Kiruna-type iron oxide ores. The co-paragenesis of hematite with several alteration minerals, in particular actinolite, tourmaline and anhydrite, indicates that the exhalative hydrothermal fluids were generated by the interaction of seawater with the felsic rocks and sediments at about 200–500 °C. The interaction of seawater with felsic magma and sediments led to the formation of Mg-rich alteration minerals, leaching Si, Fe, Mn and other elements and forming the potential ore fluids. It is highlighted that the A-type alkaline submarine felsic volcanism could be considered as an exploration target for BISF.     

Mineral chemistry and genesis of the Permian Cihai and Cinan magnetite deposits,Beishan, NW China

Cihai and Cinan are Permian magnetite deposits related to mafic-ultramafic intrusions in the Beishan region, Xinjiang, NW China. The Cihai mafic intrusion is dominantly composed of dolerite, gabbro and fine-grained massive magnetite ore, while gabbro, pyrrhotite + pyrite-bearing clinopyroxenite and magnetite ore comprise the major units in Cinan. Clinopyroxene occurs in both deposits as 0.1–2 mm in diameter subhedral to anhedral grains in dolerite, gabbro and clinopyroxenite. High FeO contents (11.7–28.9 wt%), low SiO₂ (43.6–54.3 wt%) and Al₂O₃ contents (0.15–6.08 wt%), and low total REE and trace element contents of clinopyroxene in the Cinan clinopyroxenite imply crystallization early, at high pressure. This clinopyroxene is FeO-rich and Si and Ti-poor, consistent with the clinopyroxene component of large-scale Cu-Ni sulfide deposits in the Eastern Tianshan and Panxi ares, as well as Tarim mafic intrusion and basalt, implying the Cinan mafic intrusion and sulfide is related to tectonic activity in the Tarim LIP. The similar mineral chemistry of clinopyroxene, apatite and magnetite in the Cihai and Cinan gabbros (e.g., depleted LREE, negative Zr, Hf, Nb and Ta anomalies in clinopyroxene, lack of Eu anomaly in apatite and similarity of oxygen fugacity as indicated by V in magnetite), indicate similar parental magmatic characteristics. Mineral compositions suggest a crystallization sequence of clinopyroxenite/with a small amount of sulfide – gabbro – magnetite ore in the Cinan deposit, and magnetite ore – gabbro – dolerite in Cihai. The basaltic magma was emplaced at depth, with magnetite segregation (and formation of the Cinan magnetite ores) occurring in relatively low fO₂ conditions, after clinopyroxenite and gabbro fractional crystallization. The evolved Fe-rich basaltic magma rapidly rose to intermediate or shallow depths, forming an immiscible Fe-Ti oxide magma as fO₂ increased and leaving a Fe-poor residual magma in the chamber. The residual magmas was emplaced at different levels in the crust, forming the Cihai gabbro and dolerite, respectively. Finally, the immiscible Fe-Ti oxide magma was emplaced into the earlier formed dolerite because of late magma pulse uplift, resulting in a distinct boundary between the magnetite ores and dolerite.     

Models of the REE distribution in the black shale Bazhenov Formation of the West Siberian marine basin,Russia

Rare-earth elements abundance in black shales of the Upper Jurassic (Tithonian Stage)–Lower Cretaceous (Berriassian Stage) Bazhenov Formation is discussed. This formation is the principal oil source rocks of West Siberia. The deposits within the formation can be subdivided into two main marine groups: (a) moderately hemipelagic deposits (clayey-siliceous, including phosphatic and carbonate rocks) and low-density distal clayey turbidites (argillites), both are considered as normal and (b) silty argillites and clayey-silt rocks, which are channel deposits and considered as anomalous. The hemipelagic rocks of normal sections, which are enriched in the rare-earth elements (REE), accumulated under both slow rates of sedimentation (clayey-siliceous rocks) and faster rates of sedimentation (argillites). The channel deposits of anomalous sections, which are impoverished in the REE, accumulated exclusively under fast rates of sedimentation.Within the hemipelagic group the rate of sedimentation of the argillites was faster than of the clayey-siliceous rocks, but the REE concentration in the former rocks (140.4 ppm) is higher than in the latter group (97.4 ppm). The argillites are more than twice enriched in clayey material than clayey-siliceous rocks. It is likely that the clay fraction was the main carrier of REE in these rocks. In the channel group of rocks, the REE abundance in clayey-silt rocks (21.2 ppm) is lower than in the silty argillite (84.6 ppm), in which the clay content is elevated.With respect to redox potential the Bazhenov Formation rocks can be subdivided further into three groups, based on the degree of pyritization index (DOP): (1) the highly reducing clayey-siliceous rocks of normal sections, with high DOP; (2) the substantially reducing argillites and carbonate rocks of normal sections, with intermediate DOP; (3) the moderately reducing rocks of anomalous sections with low DOP. The rocks with the high DOP (group 1) are characterized by ΣLREE/Σ(M+H)REE ratios between 7.37 and 7.5, whereas the rocks with the lower DOP (group 2 and 3) are characterized by ΣLREE/Σ(M+H)REE ratios between 12.8 and 13.5. Negative Ce anomalies are either small or absent in all deposits, which is typical for reducing conditions.Thus, the Bazhenov Formation exemplifies the complex depositional conditions that influence the REE concentration in black shale. However, it is this very complexity that has contributed to the development of six separate depositional models (REE contents in ppm are given in brackets). (1) Phosphatic clayey-siliceous rocks of normal sections (367.95); (2) argillites of normal sections (130.73); (3) clayey-siliceous rocks of normal sections (85.97); (4) carbonate rocks, largely dolomites of normal sections (23.23); (5) silty argillites of anomalous sections (78.7) and (6) clayey-silt rocks of anomalous sections (19.66).     

Geochemistry of the apulian allochthonous karst bauxite,Southern Italy: Distribution of critical elements and constraints on Late Cretaceous Peri-Tethyan palaeogeography

A comprehensive study of pebbles from the 'Salento-type' allochthnous bauxite deposit (Otranto, southern Italy), originally derived from a pristine Campanian bauxite, has been performed for evaluating: 1) the chemical fractionation and inter-elemental relationships, especially for critical elements, 2) the climatic conditions that promoted bauxite formation, and 3) the provenance of the protolith(s) using zircon age data and conservative elemental proxies. The study confirms the capability of bauxite to concentrate many elements defined as critical by the European Union report on critical raw materials. Sc, Co, Ga, and especially Cr, are enriched when compared with the UCC composition and assuming Nb is immobile. Other critical elements such as the REEs, with the exception of La, are moderately depleted. R-mode factor analysis suggests that most of the variance in our chemical dataset is explained by a factor with significant weightings for TiO₂, Al₂O₃, Fe₂O₃, Sc, V, Nb, REEs, Pb and Th. This arises from climate effects affecting the distribution of the more abundant oxides and some trace elements, including the critical metals Nb and REEs. The texture of the pebbles is typical for Apulian karst bauxites and consists of sub-spheroidal ooids composed of boehmite and dispersed in a fine-grained matrix. The growth of the ooids, which formed under dry climate, was described in terms of fractal geometry. The average fractal dimension value of the ooids in the pebbles is close to that of the diffusion-limited aggregation models suggesting the ooid growth can be modelled using a molecular diffusion pattern, based on Fick's first law. The calculated time required for growth of the boehmite concretions is ~ 45 ÷ 310 ka. This finding is consistent with an intra-Campanian emersion event (74–76 Ma) that occurred during a dry and warm climatic stage. Since most of the karst bauxites worldwide have an ooidic texture, evaluation of the composition of concretions and the time required for their growth represents a powerful tool in reconstructing the palaeoenvironment. The zircon grains collected from the pebbles of the Salento-type karst bauxite define several concordant age populations. The youngest cluster, Early Cretaceous in age (99 ÷ 127.5 Ma), suggests that windborne particles from Cretaceous volcanics, possibly originating in the Carpatho-Balkan orogenic belts, provided material for further bauxitisation. The largest cluster (623 ÷ 689 Ma) is of Neoproterozoic age, predominately from the Late Ediacaran and Cryogenian p.p.. The 900–540 Ma Pan-African orogenic cycle was followed by continental-scale uplift and erosion, leading to the deposition of thick Cambrian–Ordovician siliciclastic sequences that represent the most widespread detrital sequence ever deposited on continental crust and that now cover large parts of North Africa. These Cambrian–Ordovician sandstones contain a large population of Neoproterozoic zircons of Cryogenian age. Neoproterozoic zircons also occur in the youngest (Silurian–Mesozoic) sandstones of the Saharan Metacraton. These sandstones also contain 1.0 Ga detrital zircons, suggesting as the oldest zircons found in the Salento-type bauxite pebbles (866 Ma and 941 Ma in age) are younger representatives of the zircon cluster present in this sandstone unit.These zircon age determinations suggest that the source material for the Salento-type bauxite pebbles was a combination of magmatic material from a distant source and clastic material derived from a continental margin (North Africa). This result concurs with the Eu/Eu* vs. Sm/Nd binary diagram, on which bauxite pebbles fall close to a mixing curve with andesite and cratonic sandstone end-members. As our results indicate that material was sourced from the North African continental margin, we suggest that a continental bridge separated oceanic domains in the Late Cretaceous of the Peri-Tethyan domain.