Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Stress orientation to 5 km depth in the basement below Basel (Switzerland) from borehole failure analysis

A vertical profile of maximum horizontal principal stress, SHmax, orientation to 5 km depth was obtained beneath the Swiss city of Basel from observations of wellbore failure derived from ultrasonic televiewer images obtained in two 1 km distant near-vertical boreholes: a 2755 m exploration well (OT2) imaged from 2550 m to 2753 m across the granitic basement-sediment interface at 2649 m; and a 5 km deep borehole (BS1) imaged entirely within the granite from 2569 m to 4992 m. Stress-related wellbore failure in the form of breakouts or drilling-induced tension fractures (DITFs) occurs throughout the depth range of the logs with breakouts predominant. Within the granite, DITFs are intermittently present, and breakouts more or less continuously present over all but the uppermost 100 m where they are sparse. The mean SHmax orientations from DITFs is 151 ± 13° whereas breakouts yield 143 ± 14°, the combined value weighted for frequency of occurrence being N144°E ± 14°. No marked depth dependence in mean SHmax orientation averaged over several hundred meters depth intervals is evident. This mean SHmax orientation for the granite is consistent with the results of the inversion of populations of focal mechanism solutions of earthquakes occurring between depths of 10–15 km within regions immediately to the north and south of Basel, and with the T-axis of events occurring within the reservoir (Deichmann and Ernst, this volume). DITFs and breakouts identified in OT2 above and below the sediment-basement interface suggest that a change in SHmax orientation to N115°E ± 12° within the Rotliegendes sandstone occurs near its interface with the basement. The origin of the 20–30° change is uncertain, as is its lateral extent. The logs do not extend higher than 80 m above the interface, and so the data do not define whether a further change in stress orientation occurs at the evaporites. Near-surface measurements taken within 50 km of Basel suggest a mean orientation of N–S, albeit with large variability, as do the orientation of hydrofractures at depths up to 850 m within and above the evaporite layers and an active salt diapir, also within 50 km of Basel. Thus, the available evidence supports the notion that the orientation of SHmax above the evaporites is on average more N–S oriented and thus differs from the NW–SE inferred for the basement from the BS1/OS2 wellbore failure data and the earthquake data. Changes in stress orientation with depth can have significant practical consequences for the development of an EGS reservoir, and serve to emphasise the importance of obtaining estimates from within the target rock mass.     

Implications for Future Survival of Delta Smelt from Four Climate Change Scenarios for the Sacramento–San Joaquin Delta, California

Changes in the position of the low salinity zone, a habitat suitability index, turbidity, and water temperature modeled from four 100-year scenarios of climate change were evaluated for possible effects on delta smelt Hypomesus transpacificus, which is endemic to the Sacramento–San Joaquin Delta. The persistence of delta smelt in much of its current habitat into the next century appears uncertain. By mid-century, the position of the low salinity zone in the fall and the habitat suitability index converged on values only observed during the worst droughts of the baseline period (1969–2000). Projected higher water temperatures would render waters historically inhabited by delta smelt near the confluence of the Sacramento and San Joaquin rivers largely uninhabitable. However, the scenarios of climate change are based on assumptions that require caution in the interpretation of the results. Projections like these provide managers with a useful tool for anticipating long-term challenges to managing fish populations and possibly adapting water management to ameliorate those challenges.     

The origin of Ag–Au–S–Se minerals in adularia-sericite epithermal deposits: constraints from the Broken Hills deposit, Hauraki Goldfield, New Zealand

The 7.1 Ma Broken Hills adularia-sericite Au–Ag deposit is currently the only producing rhyolite-hosted epithermal deposit in the Hauraki Goldfield of New Zealand. The opaque minerals include pyrite, electrum, acanthite (Ag₂S), sphalerite, and galena, which are common in other adularia-sericite epithermal deposits in the Hauraki Goldfield and elsewhere worldwide. Broken Hills ores also contain the less common minerals aguilarite (Ag₄SeS), naumannite (Ag₂Se), petrovskaite (AuAgS), uytenbogaardtite (Ag₃AuS₂), fischesserite (Ag₃AuSe₂), an unnamed silver chloride (Ag₂Cl), and unnamed Ag?±?Au minerals. Uytenbogaardtite and petrovskaite occur with high-fineness electrum. Broken Hills is the only deposit in the Hauraki Goldfield where uytenbogaardtite and petrovskaite have been identified, and these phases appear to have formed predominantly from unmixing of a precursor high-temperature phase under hypogene conditions. Supergene minerals include covellite, chalcocite, Au-rich electrum, barite, and a variety of iron oxyhydroxide minerals. Uytenbogaardtite can form under supergene and hypogene conditions, and textural relationships between uytenbogaardtite and associated high-fineness electrum may be similar in both conditions. Distinguishing the likely environment of formation rests principally on identification of other supergene minerals and documenting their relationships with uytenbogaardtite. The presence of aguilarite, naumannite, petrovskaite, and fischesserite at Broken Hills reflects a Se-rich mineral assemblage. In the Hauraki Goldfield and the western Great Basin, USA, Se-rich minerals are more abundant in provinces that are characterized by bimodal rhyolite–andesite volcanism, but in other epithermal provinces worldwide, the controls on the occurrences of Se-bearing minerals remain poorly constrained, in spite of the unusually high grades associated with many Se-rich epithermal deposits.     

The effects of K2O on the compositions of near-solidus melts of garnet peridotite at 3 GPa and the origin of basalts from enriched mantle

Enrichment in K₂O in oceanic island basalts (OIB) is correlated with high SiO₂, low CaO/Al₂O₃, and radiogenic isotopic signatures indicative of enriched mantle sources (EM1 and EM2). These are also chemical characteristics of the petit-spot lavas, which are highly enriched in K₂O (3–4 wt%) compared to other primitive oceanic basalts. We present experimentally derived liquids with varying concentrations of K₂O in equilibrium with a garnet lherzolite residue at 3 GPa to test the hypothesis that the major element characteristics of EM-type basalts are related to their enrichment in K₂O. SiO₂ is known to increase with K₂O at pressures less than 3 GPa, but it was previously unknown if this effect was significant at the high pressures associated with partial melting at the base of the lithosphere. We find that at 3 GPa for each 1 wt% increase in the K₂O content of a garnet lherzolite saturated melt, SiO₂ increases by ~0.5 wt% and CaO decreases by ~0.5 wt%. MgO and $K_{D}^{{{\text{Fe}} - {\text{Mg}}}}$ K D Fe - Mg each decrease slightly with K₂O concentration, as do Na₂O and Cr₂O₃. The effect of K₂O alone is not strong enough to account for the SiO₂ and CaO signatures associated with high-K₂O OIB. The SiO₂, CaO, and K₂O concentrations of experimentally derived partial melts presented here resemble those of petit-spot lavas, but the Al₂O₃ concentrations from the experimental melts are greater. Partitioning of K₂O between peridotite and melt suggests that petit spots, previously considered to sample ambient asthenosphere, require a source more enriched in K₂O than the MORB source.     

The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ¹⁸O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ¹⁸O value of +3.5%., which corresponds to equilibration at 295°–360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al³⁺ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.     

Reconstructing the event stratigraphy from the complex structural – stratigraphic architecture of an Archaean volcanic – intrusive – sedimentary succession: the Boorara Domain,Eastern Goldfields Superterrane,Western Australia

Two main deformational phases are recognised in the Archaean Boorara Domain of the Kalgoorlie Terrane, Eastern Goldfields Superterrane, Yilgarn Craton, Western Australia, primarily involving south-over-north thrust faulting that repeated and thickened the stratigraphy, followed by east-northeast – west-southwest shortening that resulted in macroscale folding of the greenstone lithologies. The domain preserves mid-greenschist facies metamorphic grade, with an increase to lower amphibolite metamorphic grade towards the north of the region. As a result of the deformation and metamorphism, individual stratigraphic horizons are difficult to trace continuously throughout the entire domain. Volcanological and sedimentological textures and structures, primary lithological contacts, petrography and geochemistry have been used to correlate lithofacies between fault-bounded structural blocks. The correlated stratigraphic sequence for the Boorara Domain comprises quartzo-feldspathic turbidite packages, overlain by high-Mg tholeiitic basalt (lower basalt), coherent and clastic dacite facies, intrusive and extrusive komatiite units, an overlying komatiitic basalt unit (upper basalt), and at the stratigraphic top of the sequence, volcaniclastic quartz-rich turbidites. Reconstruction of the stratigraphy and consideration of emplacement dynamics has allowed reconstruction of the emplacement history and setting of the preserved sequence. This involves a felsic, mafic and ultramafic magmatic system emplaced as high-level intrusions, with localised emergent volcanic centres, into a submarine basin in which active sedimentation was occurring.     

Cretaceous to Cenozoic sequential kinematics in the forearc–arc transition: effects of changing oblique plate convergence and the San Andreas system with implications for the La Paz fault (southern Baja California, Mexico)

We studied metasediments and mylonitic arc granitoids from the forearc–arc transition of southern Baja California, Mexico. Thin section analyses and field evidence show that metamorphism of the forearc–arc transition is of the high T/P active margin type. The heat was provided by Cretaceous arc intrusions. Field observations and thin section analyses, including the time/temperature deformation path, demonstrate that the study area was first affected by dextral, ductile shearing followed by ductile, sinistral, possibly transpressive strike-slip parallel to the magmatic arc during the Cretaceous. Both intervals are related to changing oblique plate convergence and, thus, identified as trench-linked strike-slip effects. The geometric relationship between arc-dipping foliation, stretching lineation and shear sense indicates that the arc may have been pressed onto the rocks of the study area during sinistral shearing. The sinistral interval lasted up until regional cooling (Early Cenozoic?). Because the La Paz fault is closely associated with the forearc–arc transition, it must have the same Cretaceous to Early Cenozoic kinematic history. The northern segment of the La Paz fault is a modern, brittle, strike-slip fault interpreted as a dextral synthetic fault of the San Andreas system which opened the Gulf of California (Mar de Cortés/Golfo de California). We found no evidence for Miocene Basin and Range extension.     

Geochemistry of igneous rocks associated with ultramafic–mafic-hosted Cu (Co, Ni, Au) VMS deposits from the Main Uralian Fault (Southern Urals, Russia)

Ultramafic–mafic- and ultramafic-hosted Cu (Co, Ni, Au) volcanogenic massive sulfide (VMS) deposits from ophiolite complexes of the Main Uralian Fault, Southern Urals, are associated with island arc-type igneous rocks. Trace element analyses show that these rocks are geochemically analogous to Early Devonian boninitic and island arc tholeiitic rocks found at the base of the adjacent Magnitogorsk volcanic arc system, while they are distinguished both from earlier, pre-subduction volcanic rocks and from later volcanic products that were erupted in progressively more internal arc settings. The correlation between the sulfide host-rocks and the earliest volcanic units of the Magnitogorsk arc suggests a connection between VMS formation and infant subduction-driven intraoceanic magmatism.     

New interpretation of the Franciscan mélange at San Simeon coast,California: tectonic intrusion into an accretionary prism

Many concepts and interpretations on the formation of the Franciscan mélange have been proposed on the basis of exposures at San Simeon, California. In this paper, we show the distribution of chaotic rocks, their internal structures and textures, and the interrelationship between the chaotic rocks and the surrounding sandstones (turbidites). Mélange components, particularly blueschists, oceanic rocks, including greenstone, pillow lava, bedded chert, limestone, sandstone, and conglomerate, have all been brecciated by retrograde deformation. The Cambria Slab, long interpreted as a trench slope basin, is also strongly deformed by fluidization, brecciation, isoclinal folding, and thrusting, leading us to a new interpretation that turbiditic rocks (including the Cambria Slab) represent trench deposits rather than slope basin sediments. These rocks form an accretionary prism above mélanges that were diapirically emplaced into these rocks first along sinistral-thrust faults, and then along dextral-normal faults. Riedel shear systems are observed in several orders of scale in both stages. Although the exhumation of the blueschist blocks is still controversial, the common extensional fractures and brecciation in most of the blocks in the mélanges and further mixture of various lithologies into one block with mélange muddy matrix indicate that once deeply buried blocks were exhumed from considerable depths to the accretionary prism body, before being diapirically intruded with their host mélange along thrust and normal faults, during which retrograde deformation occurred together with retrograde metamorphism. Recent similar examples of high-pressure rock exhumation have been documented along the Sofugan Tectonic Line in the Izu forearc areas, in the Mineoka belt in the Boso Peninsula, and as part of accretionary prism development in the Nankai and Sagami troughs of Japan. These modern analogues provide actively forming examples of the lithological and deformational features that characterize the Franciscan mélange processes.     

Magmatic–hydrothermal rare-element mineralization in the Songshugang granite (northeastern Jiangxi,China): Insights from an electron-microprobe study of Nb–Ta–Zr minerals

The Songshugang granite, hidden in the Sinian metasedimentary stratum, is a highly evolved rare-element granite in northeastern Jiangxi province, South China. The samples were systematically taken from the CK-102 drill hole at the depth of 171–423 m. Four types of rocks were divided from the bottom upwards: topaz albite granite as the main body, greisen nodules, topaz K-feldspar granite and pegmatite layer. Electron-microprobe study reveals that the rare-element minerals of the Songshugang granite are very different from those of other rare-element granites. Mn^# [Mn/(Fe + Mn)] and Ta^# [Ta/(Nb + Ta)] of columbite-group minerals and Hf^# [Hf/(Zr + Hf)] of zircon are nearly constant within each type of rocks. However, back-scattered electron imaging revealed that Nb–Ta oxides and zircon of the Songshugang granite, especially those of topaz albite granite, topaz K-feldspar granite and greisen, are commonly characterized by a specific two-stage texture on the crystal scale. The early-stage Nb–Ta oxide is simply subhedral-shaped columbite-(Fe) (CGM-I) with low Mn^# (0.16–0.37) and Ta^# (0.05–0.29). Columbite-(Fe) is penetrated by the later-stage tantalite veinlets (CGM-II) or surrounded by complex Nb–Ta–Sn–W mineral assemblages, including tantalite-(Fe), wodginite (sl), cassiterite, and ferberite. Tantalite has wide range of Mn^# values (0.15–0.88) from Fe-dominance to Mn-dominance. Wodginite with Ta>Nb has large variable concentrations of W, Sn and Ti. Cassiterite and ferberite are all enriched in Nb and Ta (Nb₂O₅ + Ta₂O₅ up to 20.12 wt.% and 31.42 wt.%, respectively), with high Ta^# (>0.5). Similar to Nb–Ta oxides and Nb–Ta–Sn–W mineral assemblages, the early-stage zircon is commonly included by the later-stage zircon with sharply boundary. They have contrasting Hf contents, and HfO₂ of the later-stage zircon is up to 28.13 wt.%. Petrographic features indicate that the early-stage of columbite and zircon were formed in magmatic environment. However, the later-stage of rare-element minerals were influenced by fluxes-enriched fluids. Tantalite, together with wodginite, cassiterite, and ferberite implies a Ta-dominant media. An interstitial fluid-rich melt enriched in Ta and flux at the magmatic–hydrothermal transitional stage is currently a favored model for explaining the later-stage of rare-element mineralization.     

Re–Os isotopic constraints on the source of platinum-group minerals (PGMs) from the Vestřev pyrope-rich garnet placer deposit,Bohemian Massif

Mineralogical studies of the heavy fraction from a Holocene pyrope-rich garnet placer deposit at Vestřev (Krkonoše Piedmont Basin, Bohemian Massif) have identified the presence of very rare grains of platinum group minerals (PGM). Pt–Fe alloy grains are accompanied by Os–Ir–Ru minerals (native osmium, iridium, and ruthenium) with inclusions of Pt–Fe alloy and hongshiite (PtCu). This mineral assemblage is typical for several mantle settings including ophiolites. The chemistry of the Os–Ir–Ru minerals shows an enrichment of the PGM in Ru, which is typical of ophiolites. The grain morphology of PGM and pyrope-rich garnet (mostly rounded with numerous euhedral/subhedral grains) does not exclude a common source. In-situ laser-ablation MC-ICP-MS was used to measure the Re–Os isotopic compositions of single Os-rich grains, which show heterogeneous subchondritic Os isotopic compositions (¹⁸⁷Os/¹⁸⁸Os = 0.12082–0.12505 ± 0.00003). This precludes their low-temperature origin and indicates derivation of platinum-group elements (PGEs) essentially from mantle-derived rocks without a significant contribution of crustal Os. The mantle model age (T_MA) and Re-depletion model age (T_RD) model ages range from ~ 0.4 to ~ 1.0 Ga and most likely reflect a long history of melt depletion that affected the mantle sources of PGM.     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Peat Accretion Histories During the Past 6,000 Years in Marshes of the Sacramento–San Joaquin Delta,CA, USA

The purpose of this study was to determine how vertical accretion rates in marshes vary through the millennia. Peat cores were collected in remnant and drained marshes in the Sacramento–San Joaquin Delta of California. Cubic smooth spline regression models were used to construct age–depth models and accretion histories for three remnant marshes. Estimated vertical accretion rates at these sites range from 0.03 to 0.49 cm year⁻¹. The mean contribution of organic matter to soil volume at the remnant marsh sites is generally stable (4.73% to 6.94%), whereas the mean contribution of inorganic matter to soil volume has greater temporal variability (1.40% to 7.92%). The hydrogeomorphic position of each marsh largely determines the inorganic content of peat. Currently, the remnant marshes are keeping pace with sea level rise, but this balance may shift for at least one of the sites under future sea level rise scenarios.     

In situ Re–Os isotopic analysis of platinum-group minerals from the Mayarí-Cristal ophiolitic massif (Mayarí-Baracoa Ophiolitic Belt,eastern Cuba): implications for the origin of Os-isotope heterogeneities in podiform chromitites

Chromitite pods in the Mayarí-Cristal ophiolitic massif (eastern Cuba) were formed in the Late Cretaceous when island arc tholeiites and MORB-like back-arc basin basalts reacted with residual mantle peridotites and generated chromite-rich bodies enclosed in dunite envelopes. Platinum-group minerals (PGM) in the podiform chromitites exhibit important Os-isotope heterogeneities at the kilometric, hand sample and thin section scales. ¹⁸⁷Os/¹⁸⁸Os calculated at the time of chromitite crystallization (~90 Ma) ranges between 0.1185 and 0.1295 (γOs = −7.1 to +1.6, relative to enstatite chondrite), and all but one PGM have subchondritic ¹⁸⁷Os/¹⁸⁸Os. Grains in a single hand sample have initial ¹⁸⁷Os/¹⁸⁸Os that spans from 0.1185 to 0.1274, and in one thin section it varies between 0.1185 and 0.1232 in two PGM included in chromite which are only several millimeters apart. As the Os budget of a single micrometric grain derives from a mantle region that was at least several m³ in size, the variable Os isotopic composition of PGM in the Mayarí-Cristal chromitites probably reflects the heterogeneity of their mantle sources on the 10–100 m scale. Our results show that this heterogeneity was not erased by pooling and mingling of individual melt batches during chromitite crystallization but was transferred to the ore deposits on mineral scale. The distribution of the Os model ages calculated for PGM shows four main peaks, at ~100, 500, 750 and 1,000 Ma. These variable Os model ages reflect the presence of different depleted domains in the oceanic (Pacific-related) upper mantle of the Greater Antilles paleo-subduction zone. The concordance between the age of crystallization of the Mayarí-Cristal chromitites and the most recent peak of the Os model age distribution in PGM supports that Os in several grains was derived from fertile domains of the upper mantle, whose bulk Os isotopic composition is best approximated by that of enstatite chondrites; on the other hand, most PGM are crystallized by melts that tapped highly refractory mantle sources.     

P-T-X conditions,origin, and evolution of Cu-bearing fluids of the shear zone-hosted Huogeqi Cu–(Pb–Zn–Fe) deposit,northern China

Huogeqi is a shear zone-hosted epigenetic deposit within the greenschist-amphibolite facies of the Mesoproterozoic Langshan Group in the Langshan district on the northern margin of the North China Craton (NCC). Copper mineralization in the Huogeqi deposit was formed in two stages: a main-stage controlled by the shear zone and characterized by brittle-ductile ore-forming structures and a lower greenschist facies mineral assemblage, and a late stage characterized by open space-filling textures and low-temperature minerals. Based on microthermometric and Raman microprobe analysis, the main-stage Cu-bearing fluid was mesothermal, low-salinity and H₂O–CH₄-dominant, and was generated by an interaction between a deep-crustal metamorphic fluid and graphite-bearing host rocks. This interaction resulted in a more CH₄-rich fluid, which was more amenable to be immiscible. We showed that immiscibility of the H₂O–CH₄ fluid occurred due to temperature decrease, prior to the main-stage Cu mineralization; Cu was finally precipitated from the resultant H₂O-rich aqueous fluid. Main-stage Cu mineralization temperature was obtained using various methods: 310–370 °C by intersection of isochors of coexistent CH₄ and aqueous inclusions; 364 ± 41 °C on average by pressure correction of the homogenization temperatures of aqueous inclusions; and 362 ± 26 °C using the chlorite geothermometer. Pressure during Cu-deposition fluctuated between lithostatic and hydrostatic at depths of ca. 10–12 km, but it seemingly had no effect on the mineralization process. The late-stage Cu-bearing fluid was a low temperature, low salinity, H₂O of meteoric origin.