Trace-element composition and zoning in clinopyroxene- and amphibole-group minerals: Implications for element partitioning and evolution of carbonatites

The present work is a first comprehensive study of the trace-element composition and zoning in clinopyroxene- and amphibole-group minerals from carbonatites, incorporating samples from 14 localities worldwide (Afrikanda, Aley, Alnö, Blue River, Eden Lake, Huayangchuan, Murun, Oka, Ozernaya Varaka, Ozernyi, Paint Lake, Pinghe, Prairie Lake, Turiy Mys). The new electron-microprobe data presented here significantly extend the known compositional range of clinopyroxenes and amphiboles from carbonatites. These data confirm that calcic and sodic clinopyroxenes from carbonatites are not separated by a compositional gap, instead forming an arcuate trend from nearly pure diopside through intermediate aegirine–augite compositions confined to a limited range of CaFeSi₂O₆ contents (15–45 mol%) to aegirine with < 25 mol% of CaMgSi₂O₆ and a negligible proportion of CaFeSi₂O₆. A large set of LA-ICPMS data shows that the clinopyroxenes of different composition are characterized by relatively low levels of Cr, Co and Ni (≤ 40 ppm) and manifold variations in the concentration of trivalent lithophile and some incompatible elements (1–150 ppm Sc, 26–6870 ppm V, 5–550 ppm Sr, 90–2360 ppm Zr, and nil to 150 ppm REE), recorded in some cases within a single crystal. The relative contribution of clinopyroxenes to the whole-rock Rb, Nb, Ta, Th and U budget is negligible. The major-element compositional range of amphiboles spans from alkali- and Al-poor members (tremolite) to Na–Al-rich Mg- or, less commonly, Fe-dominant members (magnesiohastingsite, hastingsite and pargasite), to calcic–sodic, sodic and potassic–sodic compositions intermediate between magnesio-ferrikatophorite, richterite, magnesioriebeckite, ferri-nyböite and (potassic-)magnesio-arfvedsonite. In comparison with the clinopyroxenes, the amphiboles contain similar levels of tetravalent high-field-strength elements (Ti, Zr and Hf) and compatible transition elements (Cr, Co and Ni), but are capable of incorporating much higher concentrations of Sc and incompatible elements (up to 500 ppm Sc, 43 ppm Rb, 1470 ppm Sr, 1230 ppm Ba, 80 ppm Pb, 1070 ppm REE, 140 ppm Y, and 180 ppm Nb). In some carbonatites, amphiboles contribute as much as 25% of the Zr + Hf, 15% of the Sr and 35% of the Rb + Ba whole-rock budget. Both clinopyroxenes and amphiboles may also host a significant share (~ 10%) of the bulk heavy-REE content. Our trace-element data show that the partitioning of REE between clinopyroxene (and, in some samples, amphibole) and the melt is clearly bimodal and requires a revision of the existing models assuming single-site REE partitioning. Clinopyroxenes and amphiboles from carbonatites exhibit a diversity of zoning patterns that cannot be explained exclusively on the basis of crystal chemistry and relative compatibility of different trace-element in these minerals. Paragenetic analysis indicates that in most cases, the observed zoning patterns develop in response to removal of selected trace elements by phases co-precipitating with clinopyroxene and amphibole (especially magnetite, fluorapatite, phlogopite and pyrochlore). With the exception of magnesiohastingsite–richterite sample from Afrikanda, the invariability of trace-element ratios in the majority of zoned clinopyroxene and amphibole crystals implies that fluids are not involved in the development of zoning in these minerals. The implications of the new trace-element data for mineral exploration targeting REE, Nb and other types of carbonatite-hosted rare-metal mineralization are discussed.     

Geochemistry of S,Cu, Ni,Cr and Au-PGE in the garnet amphibolites from the Akom II area in the Archaean Congo Craton,Southern Cameroon

The fresh and weathered garnet amphibolites, from the Akom II area in the Archaean Congo Craton, were investigated to determine the S, Cu, Ni, Cr, and Au-PGE values. The garnet amphibolites are composed of amphibole, plagioclase, garnet, quartz, and accessory apatite, spinel, sericite, pyrite, chalcopyrite and non-identified opaque minerals. The presence of apatite, sericite, and two generations of opaque minerals suggests that they might be affected by hydrothermal alteration. They are characterized by moderate Al₂O₃, Fe₂O₃, CaO, V, Zn, and Co contents with negative Eu- and Ce-anomalies. The sulfur concentrations are variable (380–1710 ppm). According to the sulfur contents, amphibolites can be grouped into two: amphibolites with low contents, ranging between 380 and 520 ppm (av. = 457 ppm); and amphibolites with elevated contents, varying from 1140 to 1710 ppm (av. = 1370 ppm). Amphibolites contain contrast amounts of Cu (∼ 1800 to 5350 ppm) while nickel contents attain 121 ppm. Chromium contents vary from 43 to 194 ppm. Sulfur correlates positively with Cu and Cr, but negatively with Ni and Ni/Cr ratio. The total Au-PGE contents attain 59 ppb.The presence of amphibole and feldspars confirms the low degree of amphibolite weathering. The secondary minerals are constituted of kaolinite, gibbsite, goethite and hematite. Despite the accumulation of some elements, the major and trace element distribution is quite similar to that of fresh amphibolites. Nevertheless, the weathering processes lead to the depletion of several elements such as S (239–902 ppm), Cu (520–2082 ppm), and Ni (20–114 ppm). Chromium and Au-PGE show an opposite trend marked by a slight enrichment in the weathered amphibolites. Amidst the Au-PGE, Pd (60 ppb) and Pt (23 ppb) have elevated contents in the fresh rocks as well as in the weathered materials. The PPGE contents are much higher than IPGE contents in both types of materials. The Pd/Pt, Pd/Rh, Pd/Ru, Pd/Ir, Pd/Os, and Pd/Au values indicate that Pt, Rh, Ru, Ir, Os and Au are more mobile than Pd. Chondrite-normalized base metal patterns confirm the abundance of Pd and the slight enrichment of Au-PGE in weathered rocks. Palladium, Rh and Ir are positively correlated with S. Conversely Pt and Ru are negatively correlated with S and Au is not correlated with S. Despite the high and variable S and Cu contents, the garnet amphibolites possess low Au-PGE and other base metals contents.     

Strongly peraluminous leucogranite (Ebrahim-Attar granite) as evidence for extensional tectonic regime in the Cretaceous,Sanandaj Sirjan zone,northwest Iran

The Ebrahim-Attar (EBAT) leucogranite body is intruded within the Jurassic metamorphic complex of the Ghorveh area, located in the northern part of the Sanandaj Sirjan zone (SaSZ) of northwest Iran. The granite comprises alkali feldspar, quartz, Na-rich plagioclase and to a lesser extent, muscovite and biotite. Garnet and beryl are also observed as accessory minerals. Additionally, high SiO₂ (71.4–81.0wt %) and Rb (145–440 ppm) content; low MgO (<0.12wt %), Fe₂O₃ (< 0.68 wt.%), Sr (mainly < 20 ppm), Ba (<57 ppm), Zr (10–53 ppm) and rare earth elements (REEs) low content (3.88–94.9 ppm with an average = 21.2 ppm); and flat REE patterns with a negative Eu anomaly characterize these rocks. The chemical composition and mineral paragenesis indicate that the rocks were formed by the partial melting of siliciclastic to pelitic rocks and can be classified as per-aluminous leucogranite or strongly per-aluminous (SP) granite. The Rb-Sr whole rock and mineral isochrons confirm that crystallization of the body occurred at 102.5 ± 6.1 Ma in Albian. The ⁸⁷Sr/⁸⁶Sr(i) and ¹⁴³Nd/¹⁴⁴Nd(i) ratios are 0.7081 ± 0.009 and 0.51220 ± 0.00005, respectively, and ε_Nd(t) values range from −5.8 to −1.6. These values verify that the source of this body is continental crust. The Nd model ages (T_DM2) vary between 1.0 and 1.3 Ga and are more consistent with the juvenile basement of Pan African crust. Based on these results, we suggest that the upwelling of the hot asthenospheric mantle in the SaSZ (likely during the Neo-Tethys rollback activity) occurred after the late Cimmerian orogeny. Consequently, we suggest that this process was responsible for a thinning and heating of the continental crust, from which the SP granite was produced by the partial melting of muscovite rich in pelitic or felsic-metapelitic rocks in the northern SaSZ.     

Petrogenesis of coexisting high-silica aluminous and peralkaline rhyolites from Yunshan (Yongtai), southeastern China

The Late Cretaceous bimodal Yunshan (Yongtai) volcanics in Fujian province contain peralkaline rhyolites, the only presence of such rhyolites in southeastern China. Whole-rock and mineral chemical compositions are analyzed for the coexisting aluminous (metaluminous to weakly peraluminous)-peralkaline high-silica rhyolites from the Yunshan volcanics. They are sparsely porphyritic, and contain K-feldspar, ferromagnesian minerals, quartz, magnetite, and titanomagnetite phenocrysts, as well as accessory minerals such as fayalite, chevkinite, apatite and zircon. The mineral assemblage indicates an oxidizing pre-eruption condition. These rhyolites exhibit diagnostic geochemical features of A-type granites, such as elevated 10⁴ * Ga/Al (mostly greater than 2.6) and FeO^T/(FeO^T + MgO) ratios, enrichment in high field strength elements (HFSE) such as Zr (>400 ppm) and Nb, and strong depletion in Al₂O₃ (<13 wt%), CaO, Ba and Sr. On the basis of their petrographic and geochemical characteristics, it is suggested that the rhyolite magmas are derived from partial melting of H₂O-poor (meta) granitic igneous rocks in the deep crust, and cannot be fractionated from the coeval Yunshan mafic magmas. Geochemical variations of major and trace elements indicate the possible fractionation of K-feldspar, calcium-rich pyroxene, Fe–Ti oxides and minor chevkinite during the magma evolution. In peralkaline rhyolites, we found that the pre-existing Fe–Ti oxide and hedenbergite phenocrysts had been transformed into aegirine + oxide and aegirine + oxide + fluorite assemblages, respectively. These mineral assemblages are the products of the subsolidus reaction of pre-existing phenocrysts and extraneous Na–F-rich fluids. Such Na–F-rich fluids may be derived from the degassing of the subvolcanic rocks. The reactions indicate that the Yunshan peralkaline rhyolites could be generated through the reaction of highly fractionated aluminous silica magmas and Na–F-rich fluids.     

Carbonate- and silicate-rich globules in the kimberlitic rocks of northwestern Tarim large igneous province,NW China: Evidence for carbonated mantle source

We report carbonate- and silicate-rich globules and andradite from the Wajilitage kimberlitic rocks in the northwestern Tarim large igneous province, NW China. The carbonate-rich globules vary in size from 1 to 3 mm, and most have ellipsoidal or round shape, and are composed of nearly pure calcite. The silicate-rich globules are elliptical to round in shape and are typically larger than the carbonate-rich globules ranging from 2 to several centimeters in diameter. They are characterized by clear reaction rims and contain several silicate minerals such as garnet, diopside and phlogopite. The silicate-rich globules, reported here for the first time, are suggested to be related to the origin of andradite within the kimberlitic rocks. Our results show that calcite in the carbonate-rich globules has a high X_Ca (>0.97) and is characterized by extremely high concentrations of the total rare earth elements (up to 1500 ppm), enrichment in Sr (8521–10,645 ppm) and LREE, and remarkable depletion in Nd, Ta, Zr, Hf and Ti. The calcite in the silicate-rich globules is geochemically similar to those in the carbonate-rich globules except the lower trace element contents. Garnet is dominantly andradite (And_{59.56–92.32}Grs_5.67–36.03Pyr_0.36–4.61Spe_0–0.33) and is enriched in light rare earth elements (LREEs) and relatively depleted in Rb, Ba, Th, Pb, Sr, Zr and Hf. Phlogopite in the silicate-rich globules has a high Mg^# ranging from 0.93 to 0.97. The composition of the diopside is Wo_{45.82–51.39}En_{39.81–49.09}Fs_0.88–0.95 with a high Mg^# ranging from 0.88 to 0.95. Diopside in the silicate-rich globules has low total rare earth element (REE) contents (14–31 ppm) and shows middle REE- (Eu to Gd), slight light REE- and heavy REE-enrichment with elevated Zr, Hf and Sr contents and a negative Nb anomaly in the normalized diagram. The matrix of the kimberlitic rocks are silica undersaturated (27.92–29.31 wt.% SiO₂) with low Al₂O₃ (4.51–5.15 wt.%) and high CaO (17.29–17.77 wt.%) contents. The samples are characterized by incompatible element enrichment with high (La/Yb)_N values (41–58) and remarkable negative anomalies in HFSEs (e.g. Ta, Zr, Hf). Our new data suggest that the carbonate-rich globule most likely crystallized at high-temperature and does not represent immiscible liquids, whereas the silicate-rich globules are related to carbonate-rich deuteric hydrothermal fluids during the later-stage of melt evolution. The fluids reacted with the surrounding silicate melts resulting in the formation of skarn minerals such as phlogopite, diopside and andradite. The presence of the carbonate-bearing globules indicates that the Wajilitage kimberlitic rocks are carbonate-rich and most likely derived from an enriched mantle with abundant carbonate. We correlate the carbonated mantle to metasomatism by the migration of deep-seated fluids (carbonate-rich) in response to the impingement of the early Permian mantle plume.     

Genesis of Luobuzhen Pb–Zn veins: Implications for porphyry Cu systems and exploration targeting at Luobuzhen-Dongshibu in western Gangdese belt,southern Tibet

Porphyry systems are known to form in magmatic arc environment and commonly include porphyry Cu, epithermal Pb–Zn–Au–Ag, skarn polymetallic mineralization, etc. The systems are rarely reported in collisional zones, such as the Gangdese belt in southern Tibet where many postcollisional porphyry copper deposits occurred. In addition, other types of mineral systems are rarely present except porphyry copper mineralization in the Gangdese belt. In this study, we present Pb–Zn-bearing quartz veins at Luobuzhen in the western Gangdese belt. The Luobuzhen Pb–Zn veins cross-cut dacite of the Linzizong Group with zircon U–Pb age of 50.1 ± 0.2 Ma and monzogranite with zircon U–Pb age of 17.1 ± 0.1 Ma. Ore minerals include sphalerite, galena, chalcopyrite, and pyrite; gangue minerals are quartz with minor chlorite and sericite. Primary fluid inclusions of quartz are liquid-rich, aqueous, and two-phase inclusions. The homogenization temperatures of these primary inclusions are moderate to high (267–400 °C), and salinities range from 8.9 to 18.4 wt.% NaCl equiv. Quartz has δ¹⁸O_SMOW values of 6.2–9.3‰, while sulfides have δ³⁴S_V-CDT values of −5.1‰ to 0.1‰, ²⁰⁶Pb/²⁰⁴Pb of 18.722–18.849, ²⁰⁷Pb/²⁰⁴Pb of 15.640–15.785, and ²⁰⁸Pb/²⁰⁴Pb of 39.068–39.560. These data suggest that magmatic fluids with contribution from meteoric water, magmatic sulfur, and lead derived from upper crust and metasomatized mantle by Indian continental materials would be critical for the Luobuzhen base metal mineralization.The Dongshibu area, located at ∼2 km east of the Luobuzhen, is characterized by high concentrations of Cu (up to 1450 ppm) and Mo (up to 130 ppm) of stream sediments, which is quite different from high concentrations in Pb, Zn, Ag, and Au shown in the Luobuzhen area. In addition, porphyry copper mineralization-related alteration and veins/veinlets occur in the Miocene monzogranite at Dongshibu. The monzogranite is characterized by high Sr/Y ratios, which are also shown on ore-forming intrusions in the Gangdese postcollisional porphyry copper deposits, and shows similar zircon Hf isotopes to the ore-related high Sr/Y intrusions from the Zhunuo porphyry copper deposit which is located ∼20 km northeast of the Luobuzhen-Dongshibu. A comprehensive analysis allows us to infer that the base metal veins at Luobuzhen are components of a porphyry Cu system with porphyry Cu mineralization likely present at Dongshibu and epithermal Au–Ag veins possibly occurring at Luobuzhen, which are indicative of the existence of porphyry copper systems in collisional zones. The potential porphyry Cu mineralization and epithermal Au–Ag veins should be targeted in future exploration at Luobuzhen-Dongshibu.     

REE fractionation,mineral speciation,and supergene enrichment of the Bear Lodge carbonatites,Wyoming, USA

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ¹⁸O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO₄³⁻/CO₃²⁻ and F⁻/CO₃²⁻ ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.     

Petrology of Karoo volcanic rocks in the southern Lebombo monocline,Mozambique

The Karoo volcanic sequence in the southern Lebombo monocline in Mozambique contains different silicic units in the form of pyroclastic rocks, and two different basalt types. The silicic units in the lower part of the Lebombo sequence are formed by a lower unit of dacites and rhyolites (67–80 wt.% SiO₂) with high Ba (990–2500 ppm), Zr (800–1100 ppm) and Y (130–240 ppm), which are part of the Jozini–Mbuluzi Formation, followed by a second unit, interlayered with the Movene basalts, of high-SiO₂ rhyolites (76–78 wt.%; the Sica Beds Formation), with low Sr (19–54 ppm), Zr (340–480 ppm) and Ba (330–850 ppm) plus rare quartz-trachytes (64–66 wt.% SiO₂), with high Nb and Rb contents (240–250 and 370–381 ppm, respectively), and relatively low Zr (450–460 ppm). The mafic rocks found at the top of the sequence are basalts and ferrobasalts belonging to the Movene Formation. The basalts have roughly flat mantle-normalized incompatible element patterns, with abundances of the most incompatible elements not higher than 25 times primitive mantle. The ferrobasalt has TiO₂ ∼ 4.7 wt.%, Fe₂O_3t = 16 wt.%, and high Y (100 ppm), Zr (420 ppm) and Ba (1000 ppm). The Movene basalts have initial (at 180 Ma) ⁸⁷Sr/⁸⁶Sr = 0.7052–0.7054 and ¹⁴³Nd/¹⁴⁴Nd = 0.51232, and the Movene ferrobasalt has even lower ⁸⁷Sr/⁸⁶Sr (0.70377) and higher ¹⁴³Nd/¹⁴⁴Nd (0.51259). The silicic rocks show a modest range of initial Sr-(⁸⁷Sr/⁸⁶Sr = 0.70470–0.70648) and Nd-(¹⁴³Nd/¹⁴⁴Nd = 0.51223–0.51243) isotope ratios. The less evolved dacites could have been formed after crystal fractionation of oxide-rich gabbroic cumulates from mafic parental magmas, whereas the most silica-rich rhyolites could have been formed after fractional crystallization of feldspars, pyroxenes, oxides, zircon and apatite from a parental dacite magma. The composition of the Movene basalts imply different feeding systems from those of the underlying Sabie River basalts.     

Gold-hosting high Ba-Sr granitoids in the Xincheng gold deposit,Jiaodong Peninsula,East China: Petrogenesis and tectonic setting

The Xincheng deposit is the only large gold deposit with a proven reserve of >200 t gold hosted by the Early Cretaceous granitoids in northwest Jiaodong Peninsula, East China. The granitoids hosting this ore deposit comprise an inner medium- to fine-grained quartz monzonite and an outer medium- to coarse-grained monzogranite with distinctive K-feldspar megacrysts. LA–ICP–MS zircon dating yields U–Pb ages of 128 ± 1 to 132 ± 1 Ma and 127 ± 2 to 129 ± 1 Ma, for the quartz monzonite and the monzogranite, respectively. The Early Cretaceous ages obtained in our study are comparable with the 126–130 Ma age range reported for the Guojialing granitic suite. The monzogranites, typical high Ba–Sr granites, possess high SiO₂ (70.89–73.35%), K₂O (3.85–4.32%), total alkalis (K₂O + Na₂O = 8.08–8.68%), Sr (634–888 ppm), Ba (1395–2111 ppm) and LREE (59.43–145.88), with low HREE and HFSE contents and insignificant Eu anomalies. The rocks display markedly high Sr/Y (114–297) and (La/Yb)_N (20–79) ratios. They have low MgO (0.23–0.62%), Cr (0.4–8.33 ppm) and Ni (0.47–2.92 ppm) contents. The typical high Ba–Sr signatures of the outer acidic monzogranites are also shared by the inner intermediate-acidic quartz monzonites, with a relatively higher abundance of these elements. The plagioclases in the quartz monzonites and monzogranites are oligoclase–andesine with An contents of 11.7–44.5%, and oligoclase with An contents of 12.9–29.3%, respectively, which both show the reverse zoning texture. The quartz monzonites have zircon ε_Hf(t) values of −21.3 to −13.9 (average −18.7), which are less negative and show larger variations than those of the monzogranites (ε_Hf(t) = −24.7 to −18.1, average −19.5). Detailed elemental, mineralogical and isotopic data suggest that the high Ba–Sr quartz monzonites and monzogranites were most likely generated by partial melting of the basement rocks of the Jiaobei terrane accompanied by crustal assimilation, with minor addition of the intermediate magma derived from the partial melting of juvenile mafic lower crust formed by the earlier underplating of mantle magma, and the quartz monzonites may represent the path of intermediate magma inputting into felsic magma. In combination with previous investigations, we suggest subduction of the paleo-Pacific slab beneath the North China Craton (NCC) and associated asthenosphere upwelling were most likely the mechanism associated with the generation of the high Ba–Sr granites.     

The optimal windows for seismically-enhanced gold precipitation in the epithermal environment

Epithermal gold (Au) deposits result from the combination of a sustained flux of metal-rich fluids and an efficient precipitation mechanism. Earthquakes may trigger gold precipitation by rapid loss of fluid pressure but their efficiency and time-integrated contribution to gold endowment are poorly constrained. In order to quantify the feedbacks between earthquake-driven fracturing and gold precipitation in the shallow crust, we studied the gold-rich fluids in the active Tolhuaca geothermal system, located in the highly seismic Southern Andes of Chile. We combined temperature measurements in the deep wells with fluid inclusion data, geochemical analyses of borehole fluids and numerical simulations of coupled heat and fluid flow to reconstruct the physical and chemical evolution of the hydrothermal reservoir. The effect of seismic perturbations on fluid parameters was constrained using a thermo-mechanical piston model that simulates the suction pump mechanism occurring in dilational jogs. Furthermore, we evaluated the impact of fluid parameters on gold precipitation by calculating the solubility of gold in pressure (P)–enthalpy (H) space. The reconstructed fluid conditions at Tolhuaca indicate that single-phase convective fluids feeding the hydrothermal reservoir reach the two-phase boundary with a high gold budget (~ 1–5 ppb) at saturated liquid pressures between 20 and 100 bar (210 °C < T_sat < 310 °C). We show that if hydrothermal fluids reach this optimal threshold for gold precipitation at a temperature near 250 °C, small adiabatic pressure drops (~ 10 bar) triggered by transient fault-rupture can produce precipitation of 95% of the dissolved gold. Our results at the active Tolhuaca geothermal system indicate that subtle, externally-forced perturbations – equivalent to low magnitude earthquakes (Mw < 2) of a hydrothermal reservoir under optimal conditions – may significantly enhance gold precipitation rates in the shallow crust and lead to overall increases in metal endowment over time.     

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.     

Carboniferous magmatism and mineralization in the area of the Fuxing Cu deposit,Eastern Tianshan,China: Evidence from zircon U–Pb ages,petrogeochemistry, and Sr–Nd–Hf–O isotopic compositions

The newly discovered Fuxing porphyry Cu deposit is located in the Dananhu–Tousuquan arc, adjacent to the Tuwu–Yandong Cu deposits of Eastern Tianshan, in the southern Central Asian Orogenic Belt. The Fuxing deposit is hosted by volcanic rocks (basalt and dacite) in the Early Carboniferous Qi'eshan Group and Carboniferous felsic intrusions (plagiogranite porphyry, monzogranite, and quartz diorite). New SIMS zircon U–Pb dating indicates that the plagiogranite porphyry and monzogranite emplaced at 332.1 ± 2.2 Ma and 328.4 ± 3.4 Ma, respectively. The basalts are characterized by low SiO₂ contents (47.47–54.90 wt.%), a lack of Eu anomalies, strong depletion of Na, Ta, and Ti elements but positive Sr, U, and Pb anomalies, high Y (20.8–28.2 ppm) and HREE concentrations (Yb = 2.23–3.06 ppm), and relatively low (La/Yb)_N (2.20–3.92) values; the dacite samples have high SiO₂ contents (66.13–76.93 wt.%), clearly negative Eu anomalies, high Mg^# values (36–51), and high Y (41.8–54.9 ppm) and Yb (5.76–8.98 ppm) concentrations. The basalts and dacites exhibit similar signatures as normal arc rocks, and were considered to be derived from partial melting of mantle-wedge peridotite that was previously metasomatized by slab melts. In contrast, the plagiogranite porphyry, monzogranite, and quartz diorite show the same geochemical affinity with modern adakites, which are characterized by high SiO₂ contents (67.55–79.00 wt.%), minor negative to positive Eu anomalies, strong depletion of heavy rare earth elements (Yb = 0.17–1.19 ppm) and Y (1.86–10.1 ppm), positive K, Rb, Sr, and Ba but negative Nb, Ta, Th, and Ti anomalies, and high (La/Yb)_N ratios and Mg^# values. Moreover, these adakitic felsic intrusions display relatively high positive zircon ε_Hf(t) values (+ 11.4 to + 18.3), low ⁸⁷Sr/⁸⁶Sr (0.706080–0.711239), high ¹⁴³Nd/¹⁴⁴Nd (0.512692–0.512922) ratios, and consistent zircon δ¹⁸O values (4.41‰–5.48‰), suggesting that their parental magma were most likely derived from partial melting of the subducted oceanic crust followed by mantle peridotite interaction. Based on the whole-rock geochemical and Sr–Nd–Hf–O isotopic data, as well as detailed petrographic analyses, we further suggest that the Fuxing igneous rocks and associated porphyry Cu mineralization were generated by the northward subduction of the paleo-Tianshan oceanic plate beneath the Dananhu–Tousuquan island arc during the Early Carboniferous.     

Mineral chemistry and geochemical behavior of hydrothermal alterations associated with mafic intrusive-related Au deposits at the Atud area,Central Eastern Desert,Egypt

Vein-type gold deposits in the Atud area are related to the metagabbro–diorite complex that occurred in Gabal Atud in the Central Eastern Desert of Egypt. This gold mineralization is located within quartz veins and intense hydrothermal alteration haloes along the NW–SE brittle–ductile shear zone, as well as along the contacts between them. By using the mass balance calculations, this work is to determine the mass/volume gains and losses of the chemical components during the hydrothermal alteration processes in the studied deposits. In addition, we report new data on the mineral chemistry of the alteration minerals to define the condition of the gold deposition and the mineralizing fluid based on the convenient geothermometers. Two generations of quartz veins include the mineralized grayish-to-white old vein (trending NW–SE), and the younger, non-mineralized milky white vein (trending NE–SW). The ore minerals associated with gold are essentially arsenopyrite and pyrite, with chalcopyrite, sphalerite, enargite, and goethite forming during three phases of mineralization; first, second (main ore), and third (supergene) phases. Three main hydrothermal alteration zones of mineral assemblages were identified (zones 1–3), placed around mineralized and non-mineralized quartz veins in the underground levels. The concentrations of Au, Ag, and Cu are different from zone to zone having 25–790 ppb, 0.7–69.6 ppm, and 6–93.8 ppm; 48.6–176.1 ppb, 0.9–12.3 ppm, and 39.6–118.2 ppm; and 53.9–155.4 ppb, 0.7–3.4 ppm, and 0.2–79 ppm for zones 1, 2, and 3, respectively.The mass balance calculations and isocon diagrams (calculated using the GEOISO-Windows program) revealed the gold to be highly associated with the main mineralized zone as well as sericitization/kaolinitization and muscovitization in zone 1 more than in zones 2 and 3. The sericite had a higher muscovite component in all analyzed flakes (average X_Ms = 0.89), with 0.10%–0.55% phengite content in wall rocks and 0.13%–0.29% phengite content in mineralized quartz veins. Wall rocks had higher calcite (CaCO₃) contents and lower MgCO₃ and FeCO₃ contents than the quartz veins. The chlorite flakes in the altered wall rocks were composed of pycnochlorite and ripidolite, with estimated formation temperatures of 289–295 °C and 301–312 °C, respectively. Albite has higher albite content (95.08%–99.20%) which occurs with chlorite in zone 3.     

Indium mineralisation in SW England: Host parageneses and mineralogical relations

The SW England ore region contains significant amounts of indium (In) in Early Permian granite-related skarn and lode parageneses and, to a lesser extent, Triassic epithermal “crosscourse” veins. Ore parageneses that predate granite emplacement (Devonian and Lower Carboniferous sedimentary exhalative and vein parageneses) are largely devoid of In. Cadmium (Cd) and gallium (Ga) occur widely in all sulphide-bearing parageneses across the region with sphalerite concentrations locally reaching 1.74 wt% Cd and 1750 ppm Ga.Indium displays a strong affinity to sulphide-bearing magmatic-hydrothermal parageneses. It occurs in silicate-sulphide skarns, polymetallic sulphide lodes and sulphide-bearing portions of greisen-bordered sheeted vein systems and quartz-tourmaline lodes across the region. Magnetite-silicate skarns and quartz-tourmaline lodes that are devoid of sulphide, in contrast, were comparatively unfavourable for In precipitation. The highest In concentrations are found in mineral lodes associated with the Carnmenellis and St Agnes granites, which are the districts that had the highest historical production of Sn. Total In concentrations in these areas locally exceed 430 ppm, while concentrations elsewhere are systematically below 200 ppm.The principal In hosts are chalcopyrite, sphalerite and stannite group minerals with local concentrations within cassiterite and tennantite. Surprisingly, chalcopyrite accounts for the majority of the In budget throughout the region, although concentrations are highest in sphalerite and stannite group minerals. Sphalerite locally contains up to 1.42 wt% In, chalcopyrite has up to 2200 ppm and stannite group minerals up to 6800 ppm. No In was detected in löllingite, arsenopyrite, rutile, haematite, magnetite, tourmaline, biotite, chlorite, galena, bornite, chalcocite or pyrrhotite. Scattered concentrations in pyrite relate to impurities rather than incorporation by solid solution. Roquesite and possibly dzhalindite or native In formed locally where In-bearing chalcopyrite or sphalerite has been replaced by bornite and quartz. The In partitioning between sphalerite and chalcopyrite varies broadly between 1:1 and 10:1.Sporadic In was included in Triassic crosscourse veins as a result of interactions between migrating CaCl₂-rich basinal brines and earlier formed granite-related parageneses. The interactions involved at least two distinct components: 1) Incorporation of clasts of magmatic-hydrothermal veins in crosscourse veins during faulting, and 2) Dissolution and re-precipitation of magmatic-hydrothermal vein minerals in crosscourse fluids. Local concentrations reach 140 ppm In.The magmatic-hydrothermal parageneses in SW England are comparable to the South China Tin Belt, Mount Pleasant, as well as Erzgebirge/Krušné Hory. Magmatic-hydrothermal fluids associated with peraluminous granites have developed a variety of skarn, greisen, lode and veins parageneses by interactions with their host rocks and contained fluids. Crosscourse epithermal mineralisation occurred as In was transported by CaCl₂-rich basinal brines in a similar manner as In-bearing veins in the West Shropshire ore field.     

Sulfidic and non-sulfidic indium mineralization of the epithermal Au–Cu–Zn–Pb–Ag deposit San Roque (Provincia Rio Negro,SE Argentina) — with special reference to the “indium window” in zinc sulfide

At San Roque in Patagonia's Rio Negro Province, Argentina, an In–Au–Cu–Zn–Pb–Ag mineralization (< 0.24 wt.% In, < 7 ppm Au, < 0.45 wt.% Cu, < 14.1 wt.% Zn, < 0.55 wt.% Pb, < 60 ppm Ag) is bound to lava, and volcaniclastics of Triassic through Jurassic age. The polymetallic sulfidic and non-sulfidic indium mineralization is attributed to the low-sulfidation (LS) to intermediate sulfidation (IS) epithermal type of mineralization. Its vein-type and stockwork mineralization developed at 39.2 bars under hydrostatic conditions, corresponding to a depth of 400 m below the water level of the paleoaquifer. In the redox-controlled hypogene mineralization, the temperature increased from 130 °C up to as much as 250 °C at depth, while the pH regime changed from slightly acidic near surface to more alkaline conditions around pH 8 at a depth of approximately 150 m. The monophase mineral associations composed of sphalerite, Ag–Bi-enriched and inclusion-free galena (< 1.7 wt.% Ag, < 3.7 wt.% Bi), chalcopyrite, pyrite, gold, silver, digenite, various In–Cu- and Pb–Zn–Ag “intermediate products”, wittichenite, roquesite, sakuraiite, dzhalindite, brochantite, antlerite, cerussite, and “manganomelane” in a quartz and muscovite-rich gangue have been subdivided into three different stages: (1) Stockwork mineralization of LS to IS epithermal type (hypogene), (2) quartz vein mineralization (hypogene), and (3) salar mineralization (supergene–hypogene).Salt–mud flats controlled the youngest mineralization with Mn, Li, Ca, Mg, V, Sr, Cu, Ag and In bound to oxides, hydroxides, sulfates and subordinate carbonates. The quartz vein mineralization is made up of oxides, hydroxides prevailing over sulfides and containing W, Fe, Au, As, Pb, In, and Cu. It formed at the passage from the vadose into the phreatic zones under oxidizing to slightly reducing conditions. The level marks the boiling level of the hydrothermal solutions involved in the mineralizing process. The hypogene stockwork mineralization is exclusively made up of sulfides containing Zn, Pb, Cu, In, Ag and Bi in the phreatic zones. It developed under reducing conditions. Indium is present at all levels within the volcanic rocks and has been derived from sphalerite rich in Cd (< 1.6 wt.% Cd), In (< 7.3 wt.% In) and Cu (< 7.2 wt.% Cu) while the Fe contents are moderate in sphalerite (< 6.8 wt.% Fe). Indium reached economic grade only through the segregation of a Cu–In–S phase in the “indium window” which is defined by a Cd content of sphalerite in the range 0.2–0.6 wt.% Cd. This concentration of In is controlled by the crystal morphology and the lattice parameters of the minerals involved. It is described as a two-stage process with interdiffusion processes in an Fe-enriched system (stage I) and zoned replacement in an Fe-poor system enriched in indium (stage II). Cu-bearing sphalerite decomposed into sphalerite poor in trace elements and into Cu–In-bearing sphalerite. Further indium concentration took place, when roquesite and sakuraiite decomposed along with an increase in oxygen pressure under hypogene and supergene conditions into dzhalindite. The physical–chemical conditions of the mineralogy and chemical changes in the system In–Cu–Zn–Cd observed in nature have been approximated based upon the results obtained during laboratory studies in material sciences that were focused on solar energy.     

Fingerprinting a multistage metamorphic fluid–rock history: Evidence from grain scale Sr,O and C isotopic and trace element variations in high-grade marbles from East Antarctica

Granulite grade marble layers interlayered with metapelitic granulites from Lützow Holm Bay, East Antarctica, provide insight into fluid–rock interactions during burial to and exhumation from lower crustal levels. Sub-millimeter scale strontium, oxygen and carbon isotope variations along with LA-ICPMS trace element geochemistry and mineral chemistry of texturally characterized carbonates and associated minerals helped to reconstruct the multistage metamorphic fluid history.Fluid–rock interaction dating back to prograde metamorphism are still preserved in consistently low oxygen and high strontium isotope compositions (δ¹⁸O = 12‰; ⁸⁷Sr/⁸⁶Sr_(550Ma) = 0.7248) within a massif dolomitic marble layer that escaped significant later metasomatism. In most marbles, total re-crystallization and isotopic resetting occurred in the presence of “externally derived” hyper-saline fluids that circulated along the carbonate layers during the early stages of prograde metamorphism. This leads to a trend of increased radiogenic Sr in marbles towards the value of associated metapelitic rocks that have ⁸⁷Sr/⁸⁶Sr_(550Ma) of 0.764.LA-ICPMS studies on trace elements in carbonate and associated silicate minerals at different textural settings, distinguished using cathodoluminescence microscopy, revealed multiple metasomatic events during retrograde metamorphism. Trace element contents of Ba, Sr, Pb and U gave compelling evidence for metasomatic alteration that postdate the exsolution of carbonate at ~ 600 ºC, which can be correlated with the fluids released from the crystallization of anatectic melts and pegmatites. Subsequently, meteoric fluid infiltration occurred at a shallower level of the crust and caused extreme oxygen isotopic heterogeneity (δ¹⁸O = 14.7 ~ ? 4.9‰) and imprinted high concentration of fluid mobile elements. Taken together our results emphasize the importance of integrating textural and chemical heterogeneities to reveal the multiple episodes of fluid–rock interaction processes in a dynamic continental crust, which has major implications on migration of fluids and material and help in formulating models on the geodynamic evolution of crust.     

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.     

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.     

Hydrothermal and metamorphic fluid-rock interaction associated with hypogene “hard” iron ore mineralisation in the Quadrilátero Ferrífero,Brazil: Implications from in-situ laser ablation ICP-MS iron oxide chemistry

In-situ laser ablation ICP-MS analyses on iron oxides in itabirite and iron ore from the Quadrilátero Ferrífero (Brazil) reveal a wide range in trace element abundances (e.g., average concentrations in hematite: Al = 40–2200 ppm, Mg = 1–930 ppm, Mn = 5–540 ppm, Ti = 3–500 ppm, V = 2–390 ppm, Cr = 1–98 ppm, As = 0.5–60 ppm). The chemistry of early hematite stages is mostly inherited from host rock and precursor magnetite, e.g., Mn concentrations correlate with bulk Mn content in itabirite. With progressive iron ore formation and modification, external fluids play a more prominent role. This is reflected by REE-Y switching from seawater-like Y/Ho ratios (> 44) in early-, to more chondrite-like Y/Ho ratios (< 34), in late-hematite stages, likely due to fluid–rock reactions with country rocks (e.g., phyllites) or exchange with magmatic hydrothermal fluids.The following ore formation stages and key processes, supported by mineral scale mass balance calculations, are constrained: (1) martitisation, cogenetic with gangue leaching, is driven by large volumes of oxidising, Si-undersaturated fluids resulting in an absolute depletion of Mg, Mn, Al, Ti, Ni and Zn, and enrichment of Pb, As, LREE and Y; (2) the formation of granoblastic hematite and locally microplaty hematite represents a largely isochemical recrystallisation of magnetite and/or martite accompanied by a depletion of Mg and Y and an elevated Ti mobility at the mineral scale; and (3) precipitation of schistose and vein-hosted specular hematite along shear and fracture zones is driven by an external Fe–Si-rich hydrothermal fluid likely under high fluid/rock ratios.     

Trace metal distribution and mobility in drill cuttings and produced waters from Marcellus Shale gas extraction: Uranium,arsenic, barium

Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg⁻¹, respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L⁻¹) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals.Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates.