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Rare earth elements (REEs) have become increasingly important to our modern society due to their strategic significance and numerous high technological applications. Regolith-hosted heavy rare earth element (HREE) deposits in South China are currently the main source of the HREEs, but the ore-forming processes are poorly understood. In these deposits, the REEs are postulated to accumulate in regolith through adsorption on clay minerals. In the Zudong deposit, the world's largest regolith-hosted HREE deposit, clay minerals are dominated by short, stubby, nanometer-scale halloysite tubes (either 10 or 7 Å) and microcrystalline kaolinite in the saprolite and lower pedolith and micrometer-sized vermicular kaolinite in the humic layer and upper pedolith. A critical transformation of the clay minerals in the upper pedolith is coalescence and unrolling of halloysite to form vermicular kaolinite. Microcrystalline kaolinite also transformed to large, well-crystalline vermicular kaolinite. This transformation could result in significant changes in different physicochemical properties of the clay assemblages. Halloysite-abundant clay assemblages in the deep regolith have specific surface area and porosity significantly higher than the kaolinite-dominant clay assemblages in the shallow soils. The crystallinity of clay minerals also increased, exemplified by decrease in Fe contents of the kaolinite group minerals (from ∼1.2 wt% in the lower saprolite to ∼0.35 wt% in the upper pedolith), thereby indicative of less availability of various types of adsorption sites. Hence, halloysite-abundant clay minerals of high adsorption capacity in deep regolith could efficiently retain the REEs released from weathering of the parent granite. Reduction in adsorption capacity during the clay transformation in shallow depth partially leads to REE desorption, and the released REEs would be subsequently transported to and adsorbed at deeper part of the soil profile. Hence, the clay-adsorbed REE concentration in the lower pedolith and saprolite (∼2500 ppm on average) is much higher than the uppermost soils (∼400 ppm on average). Therefore, weathering environments that favor the release of the REEs in the shallow soils but preservation of halloysite in the deep regolith can continuously adsorb REEs in the clay minerals to form economically valuable deposits.

Although REE (lanthanides+Sc+Y) mineralization in alkaline silicate systems is commonly accompanied with Zr mineralization worldwide, our understanding of the relationship between Zr and REE mineralization is still incomplete. The Baerzhe deposit in Northeastern China is a reservoir of REE, Nb, Zr, and Be linked to the formation of an Early Cretaceous, silica-saturated, alkaline intrusive complex. In this study, we use in situ laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analyses of zircon and monazite crystals to constrain the relationship between Zr and REE mineralization at Baerzhe. Three groups of zircon are identified and are differentiated based upon textural observations and compositional characteristics. Type Ia zircons display well-developed oscillatory zoning. Type Ib zircons are darker in cathodoluminescence images and have more irregular zoning and resorption features than type Ia zircons. In addition, type Ib zircons can locally occur as overgrowths on type Ia zircons. Type II zircons contain irregular but translucent cores and rims with oscillatory zoning that are murky brown in color and occur in aggregates. Textural features and compositional data suggest that types Ia and Ib zircon crystallized at the magmatic stage, with type Ia being least-altered and type Ib being strongly altered. Type II zircons, on the other hand, precipitated during the magmatic to magmatic-hydrothermal transition. Whereas the magnitude of the Eu anomaly is moderate in the barren alkaline granite, both magmatic and deuteric zircon exhibit pronounced negative anomalies. Such features are difficult to explain exclusively by feldspar fractionation and could indicate the presence of fluid induced modification of the rocks. Monazite crystals occur mostly through replacement of zircon and sodic amphibole; monazite clusters are also present. Textural and compositional evidence suggests that monazite at Baerzhe is hydrothermal. Types Ia and Ib magmatic zircon yield 207Pb-corrected 206Pb/238U ages of 127.2±1.3 and 125.4±0.7 Ma, respectively. Type II deuteric zircon precipitated at 124.9±0.6 Ma. The chronological data suggest that the magmatic stage of the highly evolved Baerzhe alkaline granite lasted less than two million years. Hydrothermal monazite records a REE mineralization event at 122.8±0.6 Ma, approximately 1 or 2 million years after Zr mineralization. We therefore propose a model in which parental magmas of the Baerzhe pluton underwent extensive magmatic differentiation while residual melts interacted with aqueous hydrothermal fluids. Deuteric zircon precipitated from a hydrosilicate liquid, and subsequent REE mineralization, exemplified by hydrothermal monazite, correlates with hydrothermal metasomatic alteration that postdated the hydrosilicate liquid event. Such interplay between magmatic and hydrothermal processes resulted in the formation of discrete Zr and REE mineralization at Baerzhe.

Granite-related wolframite-quartz veins are the world's most important tungsten mineralization and production resource. Recent progress in revealing their hydrothermal processes has been greatly facilitated by the use of infrared microscopy and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of both quartz- and wolframite-hosted fluid inclusions. However, owing to the paucity of detailed petrography, previous fluid inclusion studies on coexisting wolframite and quartz are associated with a certain degree of ambiguity. To better understand the fluid processes forming these two minerals, free-grown crystals of intergrown wolframite and quartz from the giant Yaogangxian W deposit in South China were studied using integrated in situ analytical methods including cathodoluminescence (CL) imaging, infrared microthermometry, Raman microspectroscopy, and fluid inclusion LA-ICP-MS analysis. Detailed crystal-scale petrography with critical help from CL imaging shows repetition of quartz, wolframite, and muscovite in the depositional sequence, which comprises a paragenesis far more complex than previous comparable studies. The reconstruction of fluid history in coexisting wolframite and quartz recognizes at least four successive fluid inclusion generations, two of which were entrapped concurrently with wolframite deposition. Fluctuations of fluid temperature and salinity during precipitation of coexisting wolframite and quartz are reflected by our microthermometry results, according to which wolframite-hosted fluid inclusions do not display higher homogenization temperature or salinity than those in quartz. However, LA-ICP-MS analysis shows that both primary fluid inclusions in wolframite and quartz-hosted fluid inclusions associated intimately with wolframite deposition are characterized by strong enrichment in Sr and depletion in B and As compared to quartz-hosted fluid inclusions that are not associated with wolframite deposition. The chemical similarity between the two fluid inclusion generations associated with wolframite deposition implies episodic tungsten mineralization derived from fluids exhibiting distinct chemical signatures. Multiple chemical criteria including incompatible elements and Br/Cl ratios of fluid inclusions in both minerals suggest a magmatic-sourced fluid with the possible addition of sedimentary and meteoric water. Combined with microthermometry and Raman results, fluid chemical evolution in terms of B, As, S, Sr, W, Mn, Fe, and carbonic volatiles collectively imply fluid phase separation and mixing with sedimentary fluid may have played important roles in wolframite deposition, whereas fluid cooling and addition of Fe and Mn do not appear to be the major driving factor. This study also shows that fluid inclusions in both wolframite and coexisting quartz may contain a substantial amount of carbonic volatiles (CO2 ± CH4) and H3BO3. Ignoring the occurrence of these components can result in significant overestimation of apparent salinity and miscalculation of LA-ICP-MS elemental concentrations. We suggest that these effects should be considered critically to avoid misinterpretation of fluid inclusion data, especially for granite-related tungsten-tin deposits.

A large proportion of ores in magmatic sulfide deposits consist of mixtures of cumulus silicate minerals, sulfide liquid, and silicate melt, with characteristic textural relationships that provide essential clues to their origin. Within silicate-sulfide cumulates, there is a range of sulfide abundance in magmatic-textured silicate-sulfide ores between ores with up to about five modal percent sulfides, called \"disseminated ores,\" and \"net-textured\" (or \"matrix\") ores containing about 30 to 70 modal percent sulfide forming continuous networks enclosing cumulus silicates. Disseminated ores in cumulates have various textural types relating to the presence or absence of trapped interstitial silicate melt and (rarely) vapor bubbles. Spherical or oblate spherical globules with smooth menisci, as in the Black Swan disseminated ores, are associated with silicate-filled cavities interpreted as amygdales or segregation vesicles. More irregular globules lacking internal differentiation and having partially facetted margins are interpreted as entrainment of previously segregated, partially solidified sulfide. There is a textural continuum between various types of disseminated and net-textured ores, intermediate types commonly taking the form of \"patchy net-textured ores\" containing sulfide-rich and sulfide-poor domains at centimeter to decimeter scale. These textures are ascribed primarily to the process of sulfide percolation, itself triggered by the process of competitive wetting whereby the silicate melt preferentially wets silicate crystal surfaces. The process is self-reinforcing as sulfide migration causes sulfide networks to grow by coalescence, with a larger rise height and hence a greater gravitational driving force for percolation and silicate melt displacement. Many of the textural variants catalogued here, including poikilitic or leopard-textured ores, can be explained in these terms. Additional complexity is added by factors such as the presence of oikocrysts and segregation of sulfide liquid during strain-rate dependent thixotropic behavior of partially consolidated cumulates. Integrated textural and geochemical studies are critical to full understanding of ore-forming systems.

This paper evaluates controls on cassiterite crystallization under hydrothermal conditions based on the textural setting and geochemistry of cassiterite from six different mineralization environments from the world-class Gejiu tin district, southwest China. The cassiterite samples feature diverse internal textures, as revealed by cathodoluminescence (CL) imaging, and contain a range of trivalent (Ga, Sc, Fe, Sb), quadrivalent (W, U, Ti, Zr, Hf), and pentavalent (Nb, Ta, V) trace elements, with Fe, Ti, and W being the most abundant trace elements. Cassiterite Ti/Zr ratios tend to decrease with distance away from the causative granite intrusion, and so has potential to be used as a broad tool for vectoring toward a mineralized intrusive system. Elemental mapping of cassiterite grains reveals that trace-element concentration variations correspond closely to CL zoning patterns. The exceptions are distinct irregular domains that sharply cut across the primary oscillatory zoning, as defined by the concentrations of W, U, Sb, and Fe. These zones are interpreted to have formed after primary cassiterite growth via fluid-driven dissolution-reprecipitation processes. Zones with low W and U (and Sb) and high Fe are interpreted to have formed during interaction with relatively oxidized fluids in which W and U are stripped from cassiterite due to cation exchange with Fe3+. Systematics of W, U, Sb, and Fe partitioning into cassiterite can, therefore, be used as a monitor of the relative oxidation state of the hydrothermal fluid from which cassiterite precipitates. Cassiterite U-Pb geochronology results obtained by LA-ICP-MS return ages between 77 and 83 Ma, which is consistent with previous geochronology from the region. Ages determined on zones of dissolution-reprecipitation are similar to ages for primary cassiterite growth, indicating a short (<3 m.y.) timespan of hydrothermal activity. These results confirm the potential of U-Pb dating of cassiterite for directly constraining the timing of Sn deposition.

The Shimensi deposit (South China) is a newly discovered W-Cu-Mo polymetallic deposit with a reserve of 0.76 million tones WO3, one of the largest tungsten deposits in the world. We report elemental and Sr-Nd isotopic data for scheelites from the giant deposit, to determine the source region and genesis of the deposit. Scheelite is the most important ore mineral in the Shimensi deposit. Trace elements (including REEs) and Nd-Sr isotopic compositions of scheelites were used to constrain the origin of the mineralizing fluids and metals. Our data reveal that the REEs of scheelite are mainly controlled by the substitution mechanism 3Ca2+ = 2REE3++ ∎Ca, where ∎Ca is a Ca-site vacancy. Scheelites from the Shimensi deposit show negative Eu anomalies in some samples, but positive Eu anomalies in others in the chondrite-normalized REE patterns. The variation of Eu anomalies recorded the ore-forming processes. Considering the close spatial and temporal relationship between the mineralization and porphyritic granite, we think the negative Eu anomalies were inherited from the porphyritic granite and the positive ones from destruction of plagioclase of country rock during fluid-rock interaction. The variation of cathodeluminescence (CL) color of a single scheelite from red to blue and to yellow was likely associated with the increase of REE contents. The scheelites hosted in the Mesozoic porphyritic granite with negative Eu anomalies formed in a primitive ore-forming fluid, whereas the scheelites hosted in Neoproterozoic granite with positive Eu anomalies precipitated in an evolved ore-forming fluid. The high Nb, Ta, LREE contents, and LREE-enriched REE patterns of scheelites from the Shimensi deposit reveal a close relationship with magmatic hydrothermal fluids. The scheelites from the Shimensi deposit are characterized by low εNd(t) values (-6.1 ∼ -8.1) and unusually high and varied initial 87Sr/86Sr ratios (0.7230∼0.7657). The εNd(t) values of scheelites are consistent with those of the Mesozoic porphyritic granite, but the Sr isotopic ratios are significantly higher than those of the granites, and importantly, beyond the Sr isotopic range of normal granites. This suggests that the ore-forming fluids and metals cannot be attributed to the Mesozoic porphyritic granites alone, the local Neoproterozoic Shuangqiaoshan Group schists/gneisses with high Rb/Sr ratios and thus radiogenic Sr isotopic compositions should have contributed to the ore-forming fluids and metals, particularly, in a later stage of ore-forming process, by intense fluid-rock interaction. This is different from a commonly accepted model that the ore-forming fluids and metals were exsolved exclusively from the granite plutons.

Platinum-group element (PGE) deposits in the Bushveld Complex and other layered intrusions form when large, incompletely solidified magma chambers undergo central subsidence in response to crustal loading, resulting in slumping of semi-consolidated cumulate slurries to the centres of the intrusions and hydrodynamic unmixing of the slurries to form dense layers enriched in sulfides, oxides, olivine and pyroxene and less dense layers enriched in plagioclase. The most economic PGE, Cr and V reefs form in large, multiple-replenished intrusions because these cool relatively slowly and their central portions subside prior to termination of magmatism and complete cumulate solidification. The depth of emplacement has to be relatively shallow as, otherwise, ductile crust would not be able to flex and collapse. In smaller intrusions, cooling rates are faster, subsidence is less pronounced and, where it occurs, the cumulate may be largely solidified, resulting in insignificant mush mobility and mineral sorting. Layering is thus less pronounced and less regular and continuous and the grades of the reefs are lower, but the reefs can be relatively thicker. An additional factor controlling the PGE, Cr and V prospectivity of intrusions is their location within cratons. Intra-cratonic environments offer more stable emplacement conditions that are more amenable to the formation of large, layered igneous bodies. Furthermore, intrusions sited within cratons are more readily preserved because cratons are underlain by thick, buoyant keels of harzburgite that prevent plate tectonic recycling and destruction of crust.

The newly discovered Nayongzhi Zn-Pb deposit (>20 Mt ores at 1.11-15.65 wt% Zn and 0.59-0.97 wt% Pb) in NW Guizhou province, South China, is hosted by late Ediacaran and early Cambrian carbonate rocks. The ore body is structurally controlled by a kilometer-scale reverse fault-anticline system and occurs as stratiform, lentiform, or steeply dipping vein structures. Its geological feature is comparable to that of the Mississippi Valley-type (MVT) Zn-Pb deposits. δ34S values (+11.8 to +33.0 ppm) of sulfide minerals determined by NanoSIMS have a larger range than those determined by conventional bulk analysis (δ34S = +18.12 to +24.79 ppm). This suggests that S isotopes determined by in situ analysis can reflect the nature of fractionation involved in mineralization. Furthermore, cores of sulfide crystals have higher δ34S values (+26.1 to +33.0 ppm) than their rims (+11.8 to +24.5 ppm). This implies a mixture of multiple S reservoirs or a Rayleigh fractionation of S isotopes occurred during ore formation process. Additionally, both S isotopic compositions determined by in situ and bulk analyses reflect the enrichment of 34S in hydrothermal fluid (δ34Sfluid > +11.8 ppm), a typical characteristic of marine sulfate-derived S. Such S isotopic signatures also show that thermochemical sulfate reduction (TSR) is the dominant mechanism for the incorporation of S2- from SO42-. Pb isotopic ratios of galena obtained by femtosecond LA-MC-ICPMS plot in the field that overlaps with the Pb evolution curve of upper crust contributed to the orogeny and the field of modern lower crust, and can be compared to the Proterozoic metamorphic rocks. The means that the majority of Pb metal is sourced from the basement rocks. Although δ13C values (-4.1 to +0.5 ppm) of calcite separates and corresponding fluids are similar to both fresh limestone (-1.7 to +1.3 ppm) and typical marine carbonate rocks, the δ18O values (+12.4 to +14.1 ppm) are significantly lower than both limestone (+24.1 to +25.5 ppm) and marine carbonate rocks. Such C-O isotopic characteristics suggest that the source of C is ore-hosting carbonate rocks, whereas O has a mixed source of metamorphic fluids and carbonate rocks resulting from water/rock (W/R) interaction. This study demonstrates that (1) fluid mixing caused rapid sulfide precipitation, resulting in significant fractionation of S isotopes; and (2) both the W/R interaction and CO2 degassing controlled local carbonate cyclic process of dissolution → re-crystallization, which provided metastable physical and chemical conditions for giant sulfide mineralization. These two processes are crucial in forming MVT deposits.

The grossular-andradite solid solutions in garnet from skarn deposits in relation to hydrothermal processes and physicochemical conditions of ore formation remain controversial. Here we investigate garnet occurring in association with calcic and magnesian skarn rocks in the Cuihongshan polymetallic skarn deposit of NE China. The calcic skarn rocks contain three types of garnets. (1) Prograde type I Al-rich anisotropic garnets display polysynthetic twinning and a compositional range of Grs18-80Adr10-75. This type of garnet shows markedly low rare earth element (REE) contents (3.27-78.26 ppm) and is strongly depleted in light rare earth elements (LREE, 0.57-44.65 ppm) relative to heavy rare earth elements (HREE, 2.31-59.19 ppm). They also display a significantly negative Eu anomaly (Eu/Eu* of 0.03-0.90). (2) Fe-rich retrograde type II garnets are anisotropic with oscillatory zoning and own wide compositional variations (Grs1-47Adr30-95) with flat REE (13.73-377.08 ppm) patterns. (3) Fe-rich retrograde type III isotropic garnets display oscillatory zoning and morphological transition from planar dodecahedral {110} crystal faces to {211} crystal faces in the margin. Types III garnets exhibit relatively narrow compositional variations of Grs0.1-12Adr85-97 with LREE-enrichment (0.80-51.87 ppm), flat HREE patterns (0.15-2.46 ppm) and strong positive Eu anomalies (Eu/Eu* of 0.93-27.07 with almost all >1). The magnesian skarn rocks contain euhedral isotropic type IV Mn-rich garnet veins with a composition of Grs10-23Sps48-62Alm14-29. All calcic garnets contain considerable Sn and W contents. Type II garnet containing intermediate compositions of andradite and grossular shows the highest Sn contents (64.36-2778.92 ppm), albeit the lowest W range (1.11-468.44 ppm). Birefringence of garnet is probably caused by strain from lattice mismatch at a twinning boundary or ion substitution near intermediate compositions of grossular-andradite. The fine-scale, sharp, and straight garnet zones are probably caused by self-organization, but the compositional variations of zones from core to rim are probably caused by external factors. The zoning is likely driven by external factors such as composition of the hydrothermal fluid. REE concentrations are probably influenced by the relative proportion and temperature of the system. Moreover, the LREE-HREE fractionation of garnet can be attributed to relative compositions of grossular-andradite system. The W and Sn concentrations in garnet can be used as indicators for the exploration of W-Sn skarn deposits.

Major, minor, and trace element abundances in titanite crystals from four granitic plutons in southern Yidun arc, SW China, have been determined using electron microprobe and laser ablation-inductively coupled plasma-mass spectrometry. The selected plutons are the Cretaceous Xiuwacu (CXWC) pluton, with quartz vein-type Mo mineralization (economic-Mo), the Tongchanggou (TCG) pluton, with porphyry-type Mo mineralization (economic-Mo), the Triassic Pulang (PL) pluton, with porphyry-type Cu mineralization (subeconomic-Mo), and the Triassic Xiuwacu (TXWC) pluton, without any Mo mineralization (Mo-barren). Our study reveals that the chemical compositions of titanite crystals from these plutons such as REE, Sr, Ga, δEu, δCe, Fe2O3/Al2O3, halogens, and Mo can be used to track magma compositions, oxidation states, metal fertility, and crystallization history. The data from this study also show that titanite crystals from these plutons with different potential of Mo mineralization have similar Mo contents and exhibit an irregular variation between Mo and Sr abundances (indicating non-Mo enrichment in the residual melt during the progressive crystallization) for some Mo-mineralized plutons. Our new observations support the recent hypothesis that high initial Mo contents in magma and the enrichment of Mo in residual melts formed by fractional crystallization are not the only requirements to form a granite-related Mo ore deposit. Efficient extraction of the residual melts, possibly facilitated by high concentrations of magmatic F is also critical to the ore formation. Evidence for high-F concentration in felsic magma, which facilitates melt and fluid separation and economic Mo mineralization during magma evolution, may be traced by the presence of F-rich titanite crystals in the two Mo-mineralized granite plutons (CXWC and TCG). These new findings from this study confirm that titanite is indeed a good petrogenetic and metallogenic indicator. However, in light of the limited contribution of metal fertility to Mo mineralization, we suggest that titanite Mo concentrations should be used along with other crucial proxies, such as titanite F contents and Fe2O3/Al2O3 ratios to better evaluate the Mo-mineralized potential of granites.