Mississippi Valley-type Deposits Research Articles

Not so fast: Million-years of metal precipitation in Mississippi Valley type deposits inferred from in-situ petrochronology of hydrothermal carbonates

Mississippi Valley-type (MVT) deposits contain about 20% of global zinc resources and host critical raw materials crucial to the development of green technologies. Despite their economic and strategic importance, there is a lack of consensus on the duration of mineralizing fluid flow events in MVT systems. This study couples in-situ U-Pb dating with Sr-isotope and trace element analysis of syn- and post-ore gangue carbonates to establish: (1) timing and duration, (2) redox evolution, and (3) flow rates of mineralizing fluids in the world-class San Vicente Zn-(Pb) deposit (Peru). New radiometric ages bracket the crystallization of syn-mineralization dolomite, characterized by high Fe and Mn contents and Sr isotopic values overlapping with that of host carbonates, between 103.2 ± 4.1 Ma and 70.6 ± 5.6 Ma. This age interval reveals a direct genetic relationship between flow of mineralizing fluids and late Cretaceous Andean compressional tectonics. Basinal fluid expulsion coeval with known tectonic events continues in the district until Pliocene times, driving episodic crystallization of post-ore hydrothermal carbonates between 61.6 ± 9.3 and 2.7 ± 0.2 Ma. The low Mn and Fe content and high 87Sr/86Sr values characteristic of these post-ore, bedding-parallel and cross-cutting carbonate veins indicate a colder, oxidized environment. Our findings highlight the contribution of paired carbonate geochemistry and U-Pb geochronology in drawing links between tectonic events, fluid expulsion and the waxing and waning of mineralization potential in foreland basins. The results of this study challenge our understanding of timescales in MVT systems and imply that anomalous metal enrichment in basinal fluids over a short temporal interval is not a necessary precondition to form economic-sized, sediment-hosted Zn-Pb deposits. Rather, it is the coexistence of a focused fluid flow in an interconnected aquifer with suitable metal depositional mechanisms over a prolonged period of time (106–107 yr) that allows precipitation of economic amount of base metals at a specific site in the upper crust.

Deposit type discrimination based on trace elements in sphalerite

Sphalerite can form in different geological environments and is the main ore mineral of most Pb-Zn deposits. Trace elements in sphalerite combined with machine learning (ML) methods have been used for deposit type discrimination. However, the performance of different multivariate and ML methods is not systematically compared. Here more than four thousand laser ablation inductively coupled plasma mass spectrometry data from more than one hundred deposits were compiled and investigated by different multivariate and ML methods. Unsupervised multivariate and ML methods including principal component analysis (PCA) and t-distributed stochastic neighbor embedding (t-SNE), and supervised multivariate and ML methods including partial least squares-discriminant analysis (PLS-DA), logistic regression (LR), support vector machine (SVM), K-nearest neighbors (KNN), random forest (RF), naïve Bayes (NB), and neural network (NN) are used to classify deposit types. The models are constructed for five deposit types, Mississippi Valley-type (MVT), Volcanogenic Massive Sulfide (VMS), sedimentary exhalative (SEDEX), Epithermal, and Skarn deposits, based on twelve elements in sphalerite, Fe, Pb, Mn, Co, Cu, Ga, Ge, Ag, Cd, In, Sn, and Sb.The PCA and PLS-DA methods show similar clustering results, where Epithermal, MVT, SEDEX, and Skarn deposits can be separated from other deposit types. The t-SNE method is only efficient in discriminating MVT, SEDEX, and Epithermal deposits. The KNN, RF, and NN methods show better performance than LR, SVM, and NB in terms of average accuracy and precision. The PCA, t-SNE, and PLS-DA methods have advantages in data visualization, whereas KNN, NN, and RF methods are more suitable for classification tasks. Feature importance analyses of the PLS-DA and RF methods show that the most important discriminant elements in the classification are Ge, Mn, In, Sn, Ga, and Sb. The models based on PCA, PLS-DA, KNN, NN, and RF are used to predict sphalerite samples with uncertain origins. All the models give similar classification results for deposit types, which are consistent with the ore-forming geological setting. The multivariate and ML models, including discrimination diagrams of PCA and PLS-DA, can be used as the first screening for the type of Pb-Zn mineralization in mineral exploration.

The world-class carbonate-hosted Fankou Zn-Pb deposit in China. Part II. Alterations: C-O isotopic halos footprint the nature and transfer pathway of ore-fluids, and quantitative water-rock interaction process

The giant Fankou Zn-Pb deposit (more than 10 Mt Zn + Pb metals, grading at 15 %), situated in northern margin of the Quren Basin, is one of the largest Zn-Pb deposits in China. The stratiform orebodies are jointly bounded by both the strata (in the specific layers of Middle to Upper Devonian Donggangling and Tianziling carbonate sequences) and the fault system (a three-order thrusting fault system). Ore textures of carbonate dissolution, replacement-infilling and cementation are widespread in Fankou, analogous to a MVT (Mississippi Valley-type) deposit. Owing to the poorly developed fluid inclusions, the nature of the Fankou ore fluids remains indeterminate. To address this problem, we herein utilize micro-petrography, carbon-oxygen (C-O) isotopes and quantitative isotopic exchange modelling to trace the ore-fluids and water-rock interaction process. A total of ninety-three (93) carbonate samples, covering the majorities of stratigraphic horizons, planar locations, and various alteration intensities, were systematically collected. Micro-petrography reveals the primitively sedimentary bioclastic limestone suffer from heterogeneous dolomitization and carbonatization followed by massive Zn-Pb precipitation. These carbonate samples display a widely-ranged, δ18O- and δ13C-depleted isotope signature (δ18O = 12.57 to 23.82 ‰, δ13C = −7.79 to −0.46 ‰), relative to normal marine carbonates (δ18O = 25 ‰, δ13C = 0 ‰). Further modelling of isotopic exchange indicates a low-temperature (100 to 250 °C), δ18O-depleted (−3 to 7 ‰) and δ13C-depleted (−10 to −7‰) ore fluid equilibrated with the host rock by a relatively low water-rock ratio (W/R = 1 to 10). In terms of space, we identified a relatively decreasing trend of δ18O and δ13C isotopic compositions of carbonates, from southeast to northwest, and from bottom to up. Based upon the previous structural analysis, we interpret that the δ18O and δ13C isotopic distribution patterns are caused by a northwestwards transfer pathway of ore-fluids along the thrusting fault system, and the metalliferous, δ18O- and δ13C-depleted fluids are sourced from the interior of the Quren Basin. Collectively, we clarify the deep southeastern part of the Fankou Zn-Pb deposit and the interiors of the Quren Basin is the favorable exploration target in future.

Source and genesis of Chapai carbonate-hosted Zn-Pb deposit, South China: Constraints from in-situ S and Pb isotopes of sulfide and sulfate minerals

Chapai deposit is a special medium-sized carbonate-hosted Zn-Pb deposit (4.27Mt of sulfide ore with 8.15 % Zn, 3.44 % Pb, and 53.39 g/t Ag, as well as 0.82Mt of oxidized ore with 2.8 % Zn and 1.2 % Pb and 27.68 g/t Ag) with upper oxidized ore and lower sulfide ore of South China. Due to the shortage of detailed geological and geochemical constraints, the ore genesis of single stage magmatic hydrothermal mineralization or superposition of multi-stage mineralization remains unclear. Therefore, detailed geological and geochemical analyses of in-situ S isotopic compositions of sulfide and sulfate, trace elements of sphalerite, and ore Pb isotopic compositions were performed to decode the source and genesis of the Chapai deposit. Based on the investigation and microscopic observation, mineralization of the Chapai Zn–Pb deposit has obvious early hydrothermal alternation in the early hydrothermal sulfide stage (S1) and the late hydrothermal sulfide stage (S2) as well as the supergene oxidized mineralization stage (S3). The trace elements Cu, Ag, Ga, Sb, As and Ge are incorporated into S1 and S2 stages of sphalerite mainly through the following substitution mechanisms: Zn2+↔ (Fe2+, Cd2+),2Zn2+↔ (Ag+, Cu+) +(As3+, Ga3+, Sb3+), 3Zn2+↔ Ge4++2(Cu++Ag+), 4Zn2+↔(Cu++Ag+) + Sb3++Ge4++□(vacancy). In situ δ34S values of sulfides and sulfates are within a greater range (–3.0 to + 32.2 ‰), and are significantly higher in S2 compared to S1 stage, implying the mixing of two isotopically different end-members of hydrothermal fluids and wall rocks by sulfate reduction. The S isotope of sphalerite and galena crystallized in the early stage close to 0 ‰ may be controlled by magmatic-hydrothermal fluid source, while the increased S isotope in the late stage may be derived from the increased decomposition of organic matter and organic sulfate reduction (TSR). The Pb isotopic data (206Pb/204Pb = 18.355 ∼ 18.819, 207Pb/204Pb = 15.720 ∼ 15.778, and 208Pb/204Pb = 38.912 ∼ 39.222) indicate that the sources of metallogenic materials in the Chapai deposit are primarily upper crust basement rocks. The geothermometer studies of sphalerite in Chapai deposit show that it was generated from a medium–low temperature (142 ∼ 255 °C) condition. The low Zn/Cd ratios and high concentrations of Cd and Ge in sphalerite are in agreement with those of Mississippi Valley-type (MVT) deposits. Hence, the Chapai deposit was formed in a medium–low temperature magmatic- hydrothermal system and can be categorized as a MVT deposit within Nanling region (NR).

Enrichment of Mississippi Valley-type (MVT) deposits in the Tethyan domain linked to organic matter-rich sediments

Enrichment of Mississippi Valley-type (MVT) deposits in the Tethyan domain linked to organic matter-rich sediments

Geology, fluid inclusions and C−O−S−Pb isotopic compositions of the Chahmileh Pb-Zn deposit, Central Iran: Implications for ore genesis

AbstractThe Chahmileh Pb–Zn deposit, located northwest of the Central Iran Zone, is a sediment-hosted Pb–Zn deposit in the ‘Yazd-Anarak Metallogenic Belt’. It is hosted in Middle Triassic carbonate rocks and is mainly controlled by NW-trending faults. The main ore minerals are galena and sphalerite with minor chalcopyrite, pyrite, and quartz, dolomite, along with minor calcite and baryte as gangue minerals. Cerussite, hemimorphite, wulfenite, mimetite, smithsonite, malachite and iron oxy-hydroxides are the main non-sulphide ore minerals. The main styles of mineralization are vein-veinlet, breccia, disseminated and replacement in association with silicification and dolomitization. Microthermometry of fluid inclusions in dolomite and quartz indicates that the ore precipitated from a warm to hot basin-derived saline fluid. Dolomite samples have δ13CVPDB and δ18OVSMOW values of −0.99 to +1.99‰ and +20.74 to +25.48‰, respectively, and are plotted in the marine carbonate rocks field. These isotopic values suggest that CO2 in the hydrothermal fluids mainly originated from marine carbonate rock. The δ34S values range from +6.3 to +8.2‰ for galena, +5.9 to +6.2‰ for sphalerite, +1.4 to +3.4‰ for chalcopyrite and +15.0 to +17.4‰ for bayite are compatible with a predominant thermochemical sulphate reduction process, and with sulphur sourced from Triassic seawater. Galena samples have a homogeneous Pb isotopic composition that is indicative of a continental crustal reservoir as the main source of lead and probably for the other ore metals. Based on geology, mineralogy, texture and fluid characteristics, the Chahmileh deposit is classified as a carbonate-hosted Mississippi Valley-type deposit.

Continental evaporites as brine sources for formation of SEDEX and MVT deposits: Implications from boron isotope compositions of tourmaline

In this study, the boron isotopic composition of Paleoproterozoic seawater is reconstructed using δ11B of tourmaline from the Paleoproterozoic Pb-Zn deposits of Rajpura-Dariba, Zawarmala, and Rampura-Agucha in the Aravalli-Delhi Fold Belt (ADFB) as well as non-mineralized tourmaline bearing metapelites from the Mangalwar Complex (MC) and Gangpur Schist Belt (GSB). This is then used to constrain the source of the mineralizing fluids in Sedimentary Exhalative (SEDEX)- and Mississippi Valley Type (MVT)-deposits. Based on textural relations and chemical variations, tourmaline in the Rajpura-Dariba and Zawarmala deposits can be grouped into two generations: syn-mineralization Tur-I and metamorphic Tur-II. In contrast, a single generation of metamorphic tourmaline is identified in the Rampura-Agucha deposit and in the MC. Tur-I from Rajpura-Dariba has XMg of 0.14–0.56, while Tur-II is more magnesian (XMg = 0.58–0.77). Similarly, Tur-I from Zawarmala has a wide compositional range (XMg = 0.22–0.67), whereas Tur-II is Mg-rich (XMg = 0.39–0.67). Tourmalines from Rampura-Agucha and MC are also magnesian (XMg = 0.66–0.70 and 0.59–0.69, respectively). The δ11B values of syn-ore tourmaline from Rajpura-Dariba and Zawarmala vary between −18.8‰ and −16.1‰, and between −6.6‰ and −4.0‰, respectively. Metamorphic tourmalines from Rajpura-Dariba, Zawarmala, Rampura-Agucha and MC have δ11B values between −19.1‰ and −7.7‰.The δ11B of the pelitic sediments in Rajpura-Dariba, Rampura-Agucha, the MC and the GSB were estimated from the δ11B of metamorphic tourmaline hosted in them using mass balance constraints and P-T pseudosection modelling. Applying the B-isotope fractionation factor between Miocene shale and modern clay (Δ11Bmiocene shale − modern clay = −3.8‰ to −2.2‰) to the modelled δ11B of post-diagenetic protoliths of the metapelites, the δ11B of marine sediments for these basins were constrained between −15.1‰ and −10.2‰. Subsequently, using the B-isotope fractionation factor between modern clay and seawater (Δ11Bmodern clay − modern seawater = −45.2‰ to −40.8‰), the δ11B of Paleoproterozoic seawater is estimated to have been between +27.3‰ and +33.4‰.The isotopically light δ11B of syn-mineralization tourmaline from Rajpura-Dariba and Zawarmala (−18.8‰ to −16.1‰ and −6.6‰ to −4.0‰, respectively), and worldwide SEDEX/MVT-type deposits in general (a median value of −9.6‰; compilation of Trumbull et al., 2020), implies that the B was most likely sourced from continental evaporites and not evaporated seawater and/or connate brine. Dissolution of early rift-related continental evaporites most likely act as a major source of basinal brines for the formation of SEDEX/MVT deposits during the sag-phase of basin development.

Supernormal enrichment of cadmium in sphalerite via coupled dissolution-reprecipitation process

Supernormal enrichment of cadmium in sphalerite is frequently observed in some sedimentary-hosted zinc-lead deposits, although related fluid process remains unconstrained. At the Jinding Mississippi Valley-type deposit, a considerable portion of cadmium has been remobilized from early sphalerite through coupled dissolution-reprecipitation reaction to form high-grade ores. Here we report natural occurrence of various sulfide nanoparticles and related textures in sphalerite that help document this process. A nanoscale study by transmission electron microscopy provides a rare glimpse of phase transition of cadmium from lattice-bond impurity, composition anomaly along planar defects, aggregates of hexagonal cadmium sulfide nanoparticles, to crystalline greenockite inclusions. Such a process may be mediated by oxidative dissolution on early-formed cadmiferous sphalerite during injection of cadmium-rich oxidative acidic fluids. This study provides an alternative mechanism versus exclusively solid-state diffusion for dispersed elements’ redistribution in hydrothermal ore deposits. It also sheds light on artificial synthesis of II-VI semiconductor nanomaterials by similar methods.

Re-examination of the Aïn Allegua-Aguiba celestite-Pb-Zn salt diapir-related Mississippi Valley-type deposits (Nappes zone, Northwestern Tunisia): New conceptual model

The celestite-rich and Pb-Zn-poor Aïn Allegua deposits are located at the northeastern extremity of the Dougas diapir in the Nappes zone of northern Tunisia. The Sr-Ba-Zn-Pb mineral system studied in this paper is enclosed in a Triassic breccia, labeled cap rock, located between the Triassic diapir and the surrounding Cretaceous to Lutetian marine sediments. It consists of evaporite dissolution float breccia where Triassic dolostone clasts are floating in a Triassic matrix of anhydrite and argillites. Five mineralizing stages are recognized, which are from early to late: celestite (stage 1); hydrothermal dolomite (stage 2); crosscutting galena-barite or sphalerite-galena-barite-calcite (stage 3); (4) fracture and karst filled by barite, celestite, and galena (stage 4); and late supergene mineralization (strontianite, smithsonite, and cerussite) (stage 5). The present study shows that the celestite and Pb-Zn mineralization formed from the circulation in the cap rock of at least three fluids: (1) fluid A (100–150 °C; 10 to 25 wt% NaCl eq.) deposited the celestite; (2) fluid B (125 to 185 °C; 29 to 34 wt% NaCl eq.) deposited the hydrothermal dolomite, and (3) fluid C (temperatures around 90 °C; 14 to 22 wt% NaCl eq.) deposited the calcite that accompanied sphalerite and galena precipitation. The δ34S values for sphalerite and galena fall within a narrow range from + 10.4‰ to + 18.9‰ (avr. 13‰) indicating a homogeneous source of sulfur. The δ34S values of celestite and barite are also relatively homogeneous from + 14.7 to + 23‰ (ave. + 16.5‰) and match those of Tunisian Triassic gypsum and Triassic marine sulfates (δ34S = +15‰). The temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate. The lead isotopes in galena show that Pb, and probably Zn and Ba were extracted from the upper crustal rocks. Part of the strontium is derived from the Triassic anhydrite and the other part is probably transported to the cap rock in formation waters. The tectonic setting, the carbonated nature of the host rocks, the epigenetic style of the mineralization, and the mineral associations, together with fluid inclusions data and sulfur and lead isotopes show that the Aïn Allegua deposit belongs to the diapir-related Mississippi Valley-type (MVT) deposits of the Eastern Maghreb salt diapirs province, that formed, as the most of the MVT deposits and districts in the world, from basinal brines with no mixing with metamorphic and/or magmatic fluid or involvement of a heat source from a concealed sill or magmatic intrusion.

Neoproterozoic Zn-Pb mineralization in the world-class Sichuan-Yunnan-Guizhou Zn-Pb triangle, southwest China: Insights from apatite geochemistry and in situ sericite Rb-Sr geochronology of the Daxiao deposit

The Sichuan-Yunnan-Guizhou (SYG) zinc-lead triangle, located in southwestern China, is an important producer of zinc, lead, silver, and critical raw metals such as germanium. In this region, most Zn-Pb deposits hosted in the later Ediacaran to Permian carbonate rocks are believed to be Mississippi Valley-type (MVT) deposits, while the origin of the Zn-Pb deposits found in the Mesoproterozoic basement remains controversial. To address this gap, our study conducted in situ LA-ICP-MS/MS muscovite Rb-Sr dating and apatite major, trace and Sr isotope analysis on the Daxiao deposit hosted in the Mesoproterozoic basement. The in situ Rb-Sr dating of sericite yielded a Neoproterozoic age of 766 ± 31.3 Ma, challenging the previously proposed Indosinian orogen-related MVT model. Instead, it links the formation of this deposit to an extensional setting that coincided with the breakup of the Rodinia. We identified a specific type of apatite, recognized as ore-stage apatite based on texture and analyzed composition, within the deposit. The ore-stage apatite exhibits high 87Sr/86Sr ratios (ranging from 0.78384 to 0.81082), similar to those of the Archean basement rocks.Based on our study and previous data, we proposed a new genetic model for the Daxiao Zn-Pb deposit, and possibly other basement-hosted Zn-Pb deposits in the SYG triangle. During the Neoproterozoic (∼766 Ma), the study area experienced an extensional setting characterized by crustal thinning and magmatic activity resulting from the breakup of the Rodinia. Basinal brines infiltrated the deep Archean basement along faults and were heated to high temperatures by magma and/or high geothermal gradients. These hot brines continuously extracted Pb, Zn from the Archean basement and migrated upward into the Mesoproterozoic host rock, where they precipitated lead–zinc ores in favorable structural positions. The Daxiao Zn-Pb deposit, along with the coexisting sediment-hosted stratabound copper (SSC) deposits, basement-hosted gold and uranium deposits, and late sulfide mineralization in the iron oxide-copper–gold (IOCG) deposits, suggests a Neoproterozoic regional mineralization event associated with the breakup of Rodinia. Our study also highlights the potential of using in situ sericite Rb-Sr dating to precisely determine the age of other hydrothermal ore deposits, such as Carlin-type Au deposits, which have long been a subject of uncertainty.

LA-ICP-MS Trace Element Geochemistry of Sphalerite and Metallogenic Constraints: A Case Study from Nanmushu Zn–Pb Deposit in the Mayuan District, Shaanxi Province, China

The Nanmushu Zn–Pb deposit is a large-scale and representative deposit in the Mayuan ore field on the northern margin of the Yangtze Block. This study investigates the trace element geochemistry of sphalerite from this deposit using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The results show that the main trace elements in sphalerite include various trace elements, such as Mn, Fe, Cu, Ga, Ge, Ag, Cd, Pb, Co, Hg, Tl, In, Sn, and Sb. Among them, Ag, Ge, Cd, and Cu are valuable components that may be recovered during mineral processing or smelting techniques. The histograms, LA-ICP-MS time-resolved depth profiles, and linear scan profiles indicated that most trace elements occur in sphalerite as isomorphs, while partial Pb, Fe, and Ag occur as tiny mineral inclusions. The correlation diagrams of trace elements revealed that Fe2+, Mn2+, Pb2+, and Tl3+ can substitute Zn2+ in sphalerite through isomorphism. In sphalerite, Cd2+ and Hg2+ together or Mn2+, Pb2+, and Tl3+ together can replace Zn2+, i.e., ((3Mn, 3Pb, 2Tl)6+, 3(Cd, Hg)2+) ↔ 3Zn2+. Moreover, there is a mechanism of Ge4+ with Cu+ or Ga3+ with Cu+ replacing Zn2+ in the Nanmushu deposit, i.e., Ge4+ + 2Cu+ ↔ 3Zn2+ or 2Ga3+ + 2Cu+ ↔ 4Zn2+. Furthermore, the trace element compositions indicate that the Nanmushu Zn mineralization occurred under low-temperature conditions (<200 °C) and should be classified as a Mississippi Valley-type (MVT) deposit. This study provides new insights into the occurrence and substitution mechanisms of trace elements in sphalerite and the metallogenic constraints of the Nanmushu deposit.

Impact of deformation and metamorphism on sphalerite chemistry – Element mapping of sphalerite in carbonate-hosted Zn-Pb sulfide deposits of the Kootenay Arc, southern British Columbia, Canada and northeastern Washington, USA

Sphalerites from the Kootenay Arc in British Columbia and Washington State were selected to represent three types of carbonate-hosted massive sulfide deposits, including Mississippi Valley-type (MVT), Irish-type, and fracture-controlled replacement type (FCR). These deposits were variably deformed and metamorphosed during the Cordilleran orogen. Laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) analyses of the trace element distributions within the sphalerites are combined with petrography and sulfur isotope analyses to evaluate the influence of primary trace element signatures, along with the variable influence of post-ore metamorphism and deformation on sulfide remobilization and trace element redistribution.Mississippi Valley-type (Josephine orebodies) and Irish-type (Yellowhead orebodies) at Pend Oreille mine are only weakly deformed and recrystallized, so their sulfide minerals commonly retain primary ore textures. The sphalerite from the Irish-type deposit has positive narrow range of δ34S values (17.9–20.5‰, mean 19.2‰), and it is enriched in Ge, Tl and Pb, but depleted in Cd, Mn, and Cu relative to MVT and FCR deposits. Germanium is concentrated in dark-brown acicular-colloform bands where micro-inclusions of a germanium oxide mineral (argutite (GeO2)) and galena have been detected. Other MVT deposits of the Kootenay Arc (Reeves MacDonald, Jersey-Emerald, HB, Jackpot-Lerwick, Duncan) are more deformed and metamorphosed than the Irish-type deposit of the Pend Oreille mine and primary ore textures are only locally preserved. There is a progressive increase in deformation and degree of recrystallization from Reeves MacDonald, located away from intrusions, to deposits within the contact metamorphic aureoles of intrusions (HB, Jersey-Emerald, Jackpot-Lerwick). Sphalerite from the least metamorphosed Reeves MacDonald deposit has high Cd, Ga, Pb, and Tl contents, high Cd/Ge and Ga/In values, and the lowest δ34S values (7.4 to 11.1‰, mean 8.8‰). In contrast, sphalerites from contact metamorphosed HB, Jersey-Emerald and Jackpot-Lerwick deposits have higher δ34S values (13.3 to 28.5‰, mean 19.2‰), are enriched in Mn and Fe, with higher Zn/Cd and Mn/Fe values relative to Reeves MacDonald deposit. These enrichments and fractionations correspond to the breakdown of pyrite and pyrrhotite and the thermal annealing of sphalerite caused by contact metamorphism. Sulfide minerals from the FCR deposit (Abbott-Wagner) are undeformed (except for microfractures) and only weakly recrystallized. Sphalerite from the FCR Abbott-Wagner deposit is enriched in Cu, Ga, In, and Sn as primary source signatures relative to sphalerite from MVT and Irish-type deposits. This reflects the more complex mineral assemblage of galena, sphalerite, pyrite, chalcopyrite, and tetrahedrite in this deposit. The presence of chalcopyrite and tetrahedrite is consistent with a higher-temperature origin of the FCR deposit relative to the lower-temperature MVT and Irish-type deposits.This study demonstrates that the high spatial resolution of in-situ LA-ICP-MS analyses of trace element within sphalerites, in combination with petrography and other analytical techniques (e.g., electron microprobe, secondary ion mass spectrometry, field emission scanning electron microscopy) characterizes the behavior and distribution of trace elements in sphalerite for three deposit types and variable conditions of regional and contact metamorphism. Understanding the effects of metamorphism and deformation on trace elements can be very useful in exploration for deposits rich in critical metals.

Genesis of the carbonate-hosted zinc–lead deposits in the southwestern Yangtze Craton, SW China: Insights from the Maoping deposit

The southwestern Yangtze Craton represents one of the world's largest zinc–lead provinces and contains over 26 million tons of zinc–lead resources. It comprises more than four hundred carbonate-hosted zinc–lead deposits with various sizes; however, genesis of the deposits has long been debated and still remains controversial, due to a lack of comprehensive understanding on the geology and metallogeny. Located in the north of the area, the giant Maoping zinc–lead deposit (Zn + Pb: 3 Mt @ 10–30 wt%) provides an ideal objective to illustrate this issue. In this paper, we conduct detailed field geological investigation at Maoping and present new in situ LA–ICP–MS data of sulfur and lead isotopes and trace elements from 25 sulfide samples. The δ34S values of the sulfides vary from −22.8 ‰ to +22.5 ‰, and the ratios of 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb of the sulfides vary in ranges of 18.247–18.767, 15.712–15.768, and 38.548–39.435, respectively. Combined with previous studies, we interpret that reduced sulfur is likely sourced from marine sulfates in the carbonate of the Upper Devonian Zaige Formation, and ore metals are mainly derived from the Neoproterozoic basement and the Zaige Formation carbonate. Titanium, Cr, Mn, Co, Ni, Cu, Zn, Ge, As, Se, Ag, Cd, Sb, and Pb are enriched in pyrite within the Maoping deposit, and low abundances of Co and Ni (0.01 × 10−6–21.09 × 10−6) and low Co/Ni ratios (0.04–4.95) in pyrite constrain its low-temperature hydrothermal origin. New geological and geochemical data demonstrate that geology, mineralization, and geochemistry of the Maoping deposit coincide with those of the Mississippi-Valley type (MVT) deposits worldwide. Together with previous studies, we suggest that genesis of the carbonate-hosted zinc–lead deposits in the southwestern Yangtze Craton resemble the MVT deposits.

The world-class carbonate-hosted Fankou Zn-Pb deposit in China. Part I. Structural analysis: Evolutionary three-order thrusting structures control on the localization of Zn-Pb orebodies

The Fankou giant deposit (with exceeding 10 Mt Zn + Pb metals, grading at 15 wt%) is a carbonate-hosted, stratabound Zn-Pb deposit in the northern Quren Basin, South China. Lenticular, stratiform and wedge-shaped orebodies are strictly hosted in specific layers of Upper Devonian to Lower Carboniferous carbonate sequences along a series of NE and NNE trending faults. Previous ore geological and geochemical studies proposed that the Fankou can be analogous to a Mississippi Valley-type (MVT) deposit, but how the evolution of complex fault system controls ore-forming fluids migration, metals accumulation and orebodies localization remains unclear. To address this question, we conducted a deposit-scale structural analysis based on the geological mapping, underground works, and diamond drills logging. We identified three-order structures gradually growing in the Fankou deposit, including: 1) The first-order fault represented by F203 is a NW-striking thrust fault penetrating basement and acts as a major conduit for ultimate hydrothermal fluids migrations from depth; 2) The second-order faults include a spectrum of NNW-striking faults F2, F3, F4, F4, F5, F6, F7, F8 and F9. They are intersected with F203 in depth, and soon before and synchronous activities with Zn-Pb mineralization; 3) The third-order faults contain a series of NNE-striking F100, F101 and F102 with limited scale, which is subordinate to second-order faults and control the terminal localization of Zn-Pb orebodies. Collectively, we conclude that the evolutionary three groups of deposit-scale faults, derived from the regional NE-striking Wuchuan-Sihui Fault, jointly control the ore-forming fluids migrations from deep to shallow and from SE to NW in space. It is noteworthy that the second- to third-order faults act as the direct metal precipitation space when the upwards metalliferous fluids replaced with the favorable lithological layers. Therefore, we highlight that the southeast part of the mining area, where the metalliferous fluids came from, is a promising exploration target area in future.

LA-ICP-MS analyses of trace elements in zoned sphalerite: A study from the Maoping carbonate-hosted Pb-Zn(-Ge) deposit, southwest China

In southwest China, many Pb-Zn deposits are described as low temperature carbonate-hosted deposits or Mississippi Valley-type (MVT) deposits. But trace element distribution and concentration in sphalerite between deposits may significantly vary and could possibly imply alternative deposit-types. An investigation was carried out on sphalerite (Sp-II) in the main ore stage of the Maoping carbonate-hosted Pb-Zn(-Ge) deposit (Southwest China), based on laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Here, Sp-II is divided into the dark red, yellow–brown, and light-yellow zones. Principal component analysis revealed element clusters distributed within distinct zoning types in Sp-II: the dark red zones are enriched in Mn, Fe, and Cd; the yellow–brown zones are enriched in Cu, Ge, Ag, and Sb; the light-yellow zones are enriched in Ga. Trace elements in Sp-II record temperature and sulfur fugacity (fS2) evolution of ore-forming fluid system, which tends to decrease from the dark red to yellow–brown to light-yellow zones. The formation of Sp-II may be an external process resulting from the varieties of temperature and fS2 in the ore-forming fluid, which may be driven by rock buffer. Here, Manganese, Fe, and Cd are preferentially incorporated in the relatively higher temperatures and fS2, whereas Ga is preferentially incorporated in the relatively lower those. Regardless of the zoning type, strong binary correlations between Ge and Cu as well as the high similarity of their concentration distribution in mapping images suggest coupled substitutions as Ge4+ + 2Cu+ ↔ 3Zn2+ and/or Ge2+ + 2Cu+ ↔ 2Zn2+ + vacancy. A trace element comparison of various Pb-Zn deposits in the world, including our new data from Maoping shows a distinctive signature for the Maoping deposit. Homogenization temperatures (217–430 ℃, mean 298 ℃) of the newly discovered ore body (No. VI) support that Maoping is a medium–high temperature carbonate-hosted deposit.

Trace Elements of Gangue Minerals from the Banbianjie Ge-Zn Deposit in Guizhou Province, SW China

There are many dispersed element-rich Pb-Zn deposits hosted by Paleozoic carbonate rocks in the Middle-Upper Yangtze Block, China. The origin and nature of the ore-forming fluids that formed them are still much debated (syngenetic vs. epigenetic). The Banbianjie Ge-Zn deposit is located in the southeastern margin of the Yangtze Block, SW China. It is a newly discovered medium-sized Zn (Zn metal reserves > 0.39 Mt, @1.78%–9.5% Zn) and large-scale Ge deposit (Ge metal resources > 900 t, @100 × 10−6–110 × 10−6 Ge) in the Western Hunan–Eastern Guizhou Pb-Zn metallogenic belt, SW China. Gangue minerals in the Banbianjie deposit are very developed, including calcite, dolomite and barite, which are closely associated with sulfides. Hence, the trace elements of gangue minerals could be used to trace the nature, source and evolution of ore-forming fluids, and the ore genesis of this deposit can be discussed. These gangue minerals are nearly horizontally distributed in the plot of La/Ho-Y/Ho, suggesting that they are the products of the same hydrothermal fluids. The total rare earth element (∑REE) contents from calcite and dolomite to barite show an increasing trend, indicating that the REEs in the ore-forming fluids were mainly enriched in barite. Hence, the ∑REE of barite can approximately represent the ΣREE of the hydrothermal fluids, which are quite similar to those of the underlying strata, indicating that the ore-forming fluids were likely originated from and/or flowed through them. The Eu anomalies from dolomite (Eu/Eu* = 0.33–0.66) to calcite (Eu/Eu* = 0.29–1.13) and then to barite (Eu/Eu* = 1.64–7.71) show an increasing trend, suggesting that the ore-forming fluids experienced a shift in the ore-forming environment from reduced to oxidized. Hence, the source of the Banbianjie Ge-Zn deposit is the underlying strata, and the ore-forming physical–chemical condition has experienced a transition from reduction to oxidation during the Ge-Zn mineralization. The ore genesis of the Banbianjie Ge-Zn deposit is most likely a Mississippi Valley-type (MVT) deposit.

Textural and chemical evolution during dedolomitization: A case study of the Benassal Formation, Maestrat Basin, Spain

The process of dedolomitization (dolomite calcitization) has been the subject of several studies, but the mechanisms that control it are still not fully understood. Dedolomitization, i.e. the replacement of dolomite by calcite, is an important diagenetic process that affects dolostones, in certain cases decreasing the local porosity and altering the rock mechanical properties, reservoir quality and fluid flow pathways. In this contribution we report the petrographic and geochemical evidence of the progressive dedolomitization and its impact on the Lower Cretaceous dolostones of the Benicàssim area (Maestrat Basin, Spain) that host Mississippi Valley Type (MVT) ore deposits. Textural observations and geochemical data suggest that replacement was induced by the interface coupled dissolution-precipitation mechanism. Moreover, quantitative chemical content measurements with mass balance calculations show that dedolomitization caused a ∼5% gain of mass during the reaction, associated with 5 vol% of solid volume increase. The lack of microfracture development suggests that the compensation of such volume increase is achieved by microporosity being filled during calcite precipitation. Considering the meteoric origin of the dedolomitizing fluids, the mass balance calculation allows estimating the element mass transfer during the reaction. The fact that the fluid was enriched in Zn supports that the fluid was acidic, and likely percolated through the local MVT deposits. Calculation of the required volume of the reactive fluid (102–104 m3/m3 dolostone) also shows that thermodynamic calculations overestimate the volume of fluid. This study shows the importance of quantifying mass transfer in diagenetic conditions to better understand metasomatic processes and constrain the fluid pathway in the basin history. As a societal impact, this diagenetic process releases ∼11% of the carbon mass but seems to preserve all rare earth elements.

A tool for Zn-Pb MVT exploration by combining C and O isotopes and REE geochemistry of dolomite

An exploration guide for Mississippi Valley-type (MVT) deposits is proposed and illustrated in the Riópar area (SE Spain), where extensive dolostone geobodies hosting Zn-(Fe-Pb) MVT mineralization occur. These base metal deposits are found within stratabound and patchy dolostones replacing Upper Jurassic to Lower Cretaceous limestones. However widespread stratabound dolostones, with no Zn-(Fe-Pb) mineralization associated, are also found in the same area replacing Lower Jurassic to Upper Cretaceous carbonates. A detailed sampling of both, Zn-(Fe-Pb) mineralized dolostones (fertile), as well as unmineralized ones (barren), has been performed in an area of ∼106 km2 to characterize their rare earth element (REE) and isotopic (C, O, Sr) compositions. Barren Lower and Middle Jurassic and Upper Cretaceous dolostones show C, O and Sr isotopic characteristics (δ13C = +2.1 to +3.8‰ VPDB, δ18O = +27.6 to +29.8 ‰ VSMOW, 87Sr/86Sr = 0.70736 to 0.70764) like the Jurassic-Cretaceous undolomitized limestones and marine carbonates, and consistent with dolostones produced by low temperature seawater. On the contrary, barren and fertile Upper Jurassic to Lower Cretaceous stratabound and patchy dolomitized limestones are depleted in δ13C and δ18O and relatively enriched in 87Sr/86Sr compared to the host limestones. This δ13C and δ18O composition can be explained by an interaction of warm fluids with regional carbonates (2–3% of fluid/rock interaction at 190–230 °C). The hydrothermal character for the dolomitizing fluid is supported by REE geochemical data (e.g., (Pr/Pr*)PAASN and (Ce/Ce*)PAASN anomalies). Thus, C and O isotopes, as well as (Ce/Ce*)PAASN and (Pr/Pr*)PAASN ratios, can be used to discriminate between low temperature dolostones, formed from cold seawater that do not contain Zn-(Fe-Pb) mineralization (barren), from hydrothermal dolomites (HTDs), which may host Zn-(Fe-Pb) mineralization. Furthermore, most barren HTDs show more restricted and higher δ13C (+0.4 to +0.9 ‰ VPDB) and δ18O values (+26.4 to +27.1 ‰ VSMOW), as well as lower ∑REE contents (5.41 to 7.38 mg kg−1), compared to Zn-(Fe-Pb) mineralized HTDs (δ13C: −2.3 to +0.6 ‰ VPDB; δ18O: +25.1 to +27.1 ‰ VSMOW; ∑REE 14.10 to 54.79 mg kg−1). Therefore, the obtained REE contents, and partially the δ13C values, can be used to discriminate between HTDs associated with Zn-(Fe-Pb) mineralization (fertile dolostones) and barren HTDs, revealing their potential as a new geochemical tool for MVT exploration in dolomitized terrains.

Geology and geochemistry of Zn-Pb(-Ge-Ag) deposits in the Sichuan-Yunnan-Guizhou Triangle area, China: A review and a new type

Mississippi Valley Type (MVT)1 deposits represent the majority of carbonate-hosted Zn–Pb deposits globally. They typically form in an extensional tectonic setting along passive margins. However, studies on carbonate-hosted Zn–Pb deposits in the Sichuan–Yunnan–Guizhou Triangle area (SYGT) reveal differences in terms of the essential features of typical MVT deposits. We discuss the main features of these deposits, controlled by folds and faults, high-grade Zn–Pb ores and symbiotic or associated elements (i.e., abundant Ag and dispersed amounts of Ge, Ga, and Cd) of significant economic value. Based on a comparison of Pb-Zn deposits in SYGT and classical MVT deposits formed in an extensional tectonic setting, as well as a subsequent discussion on deposit classification, we propose that the Huize-style Zn–Pb deposits are a new deposit style, whose basic features can guide future ore exploration. We define the Huize-style deposits based on four factors: i) Hierarchical ore-controlling system of strike-slip fault-fold structures, ii) litho-facies associated with typical alternation and mineralisation, iii) ore-forming geochemical features revealed by typical mineral assemblages, mineralisation alteration zoning, fluid-inclusion, isotope geochemistry and metallogenic acid–alkali geochemical barriers, and iv) different prospecting methods to those typically used for MVT deposits. The Huize-style and typical MVT deposits constitute the carbonate-hosted non-magmatic epigenetic hydrothermal-type (CNHT) Zn–Pb deposits.

Germanium- and gallium-rich sphalerite in Mississippi Valley–type deposits: the San Vicente district and the Shalipayco deposit, Peru

Germanium- and gallium-rich sphalerite in Mississippi Valley–type deposits: the San Vicente district and the Shalipayco deposit, Peru