Mississippi Valley-type Pb-Zn Deposits Research Articles

Pb-Zn-Ba deposits in the Nigerian Benue Trough: A synthesis on deposits classification and genetic model

The Benue Trough stretching about 800–1000 km with a width ranging between 100 and 150 km, is a megarift structure whose origin was related to the opening of the south Atlantic during the early Cretaceous. This mega rift structure contains economically significant Pb-Zn-Ba-F deposits that form well-defined metallogenic belt about 600 km long in Nigeria. In the Southern Benue Trough (SBT), the Pb-Zn-Ba-F deposits are localized in four districts namely Abakaliki, Ishiagu, Wanikande and Gabu-Oshina and are hosted by carbonaceous shale; in the Central Benue Trough (CBT) the deposit is hosted in the silicified limestone and arkosic sandstone localized in Arufu, Akwana and Azara districts; while in the Northern Benue Trough (NBT) ores deposits occur in the arenaceous sediments of Yolo, Gombe and Gulani districts. Previously published sulfur (S) isotopic data of sulfides suggest that the ore-forming S was sourced from marine sulfates and the reduction of sulfate mainly by thermochemical sulfate reduction process in the CBT and NBT. Whereas in the SBT, bacterial sulfate reduction process is dominant. The compiled C-O isotopic compositions suggest that limestone and slightly metamorphosed sedimentary rocks supplied ore-forming materials to the hydrothermal systems through water/rock interaction. The available bulk Pb isotopic compositions for the ore minerals, the host sedimentary and crystalline rocks comprising the basement rocks as well as the basaltic rocks from the Trough suggest that the arkosic sandstone which is composed of detrital feldspars that was eroded from the Precambrian basement rocks could be the likely source of ore-forming metals. Our model proposed that the ore-forming fluids were sourced from the hot connate-brine that was expelled through compaction during the development of the deep sedimentary basins. Mesozoic magmatic events distributed throughout the basin likely provided the initial thermal flow and elevated the geothermal gradient. The hot brines could have leached the metals from the syn-rift continental formations. The tensional fractures serve as the conduit through which the metals migrated, leached abundant sulphate and precipitated their contents in the transcurrent fault system as sulfides, barite and associated polymetallic ores. The geological, mineralogical, and geochemical characteristics of the Nigerian Benue Trough Pb-Zn deposits are consistent with Mississippi Valley-type (MVT) Pb-Zn deposits in North Africa and the typical MVT ore deposits worldwide.

Metal sources and fluid pathways of karst-hosted Mississippi Valley-type Zn–Pb deposits in the fold-thrust belt: A case study of the Changdong deposit in the southeastern Himalayan-Tibetan orogen

The metal sources and fluid pathways for Mississippi Valley-type (MVT) Zn–Pb deposits in fold-thrust belts remain open topics of debate. To develop a more comprehensive understanding of these issues, this study presents the sulfide morphology, S and Pb isotopes, and trace element data of the paleokarst-hosted Changdong MVT Zn–Pb deposit in the “Sanjiang” fold-thrust belt. Bulk Pb isotopic ratios for galena were homogenous and indicated potential metal sources. These sources include Triassic to Early Jurassic volcanic rocks at the western margin of the Simao Basin, Cenozoic intrusive rocks at the eastern margin, and Jurassic clastic rocks. The spatial distribution of the in situ Pb isotopic ratios, combined with the spatial relationship between the faults and ore bodies, suggest that the tensile faults acted as vertical pathways for the fluid. The galena grains displayed oscillatory zones of As and Sb elements, indicating that alternating ore-forming fluids with varying chemical compositions entered the local reservoir. The δ34SV-CDT values of sulfides in substage I range from −19.3 to 29.6 ‰, and in substage II, they range from −21.2 to 52.6 ‰. The high fractionation degree (approximately 38.9 ‰) and the presence of microspherulitic morphology suggest that the reduced sulfur originated from a bacterial sulfate reduction. A GGIMFis geothermometer revealed that the precipitation temperatures of substage I sphalerite ranged from 56.68 to 211.58 °C and were higher than substage II. This indicated that the mixing of Zn–Pb-bearing fluid with reduced sulfur was the main controlling factor for sphalerite precipitation, and the temperature decrease represented another important factor. In the fold-thrust system, the complete process of Zn–Pb mineralization was established as follows: the fluid extracted metals from regional rocks and then migrated laterally over long distances. During the regional transition from compression to extension, metal-bearing fluid was injected into the deposit along the normal faults through seismic pumping. The fluid was then mixed with reduced sulfur to precipitate Zn–Pb sulfides. This study provides new insights into the metal sources and fluid pathways of MVT Zn–Pb deposits developed in a fold-thrust belt.

The Bougrine Zn-Pb deposit, the largest salt diapir-related Mississippi Valley-type deposit in the Eastern Maghreb salt diapir province, Tunisia

The Bougrine Zn-Pb sulfide deposit (5.5 Mt @ 12 % Zn + 2.5 % Pb) in the Eastern Maghreb salt diapir province of Tunisia is located at the northeastern end of the Lorbeus-Bougrine diapir. The several-km large diapir is composed of Triassic evaporite that intruded about 10 km-thick Jurassic and Cretaceous marine sedimentary rocks during the Cretaceous and Tertiary. Mineralization occurs in breccia zones at the contact with the Triassic diapir and in the peridiapiric Cretaceous strata. Most of the ore is stratabound (F2 orebody) with microsphalerite disseminations in organic-rich laminated black limestone of the Cenomanian-Turonian Bahloul Formation, where sphalerite occurs as infill of Globigerina shells, as massive replacement of Globigerina-rich layers, as banded colloform sphalerite and in voids as euhedral, coarse-grained crystals together with skeletal galena and minor marcasite. Abundant degraded oil seepages in the orebodies and their host rocks testify to the existence of a (former) hydrocarbon reservoir.The various sphalerite generations have highly variable Mn and Fe contents; Cd has an average content of 445 ppm; As and Hg contents are in the 200 ppm range; Tl content is about 40 ppm; Ga content is about 10 ppm; and In content is consistently <1 ppm. Fluid inclusions in celestite, coarse-grained late-stage sphalerite and calcite indicate moderate fluid salinities (16 ± 2 wt% NaCl eq.) and moderate temperatures (85 to 146 °C). The empirical trace-element sphalerite geothermometer gives 184 ± 38 °C for the main-stage microsphalerite and the banded colloform sphalerite which have no measurable fluid inclusions.A wide range of δ13C (-13.6 to 5.6 ‰) and δ18O (-19.8 to 33 ‰) values is observed in ore-stage and post-ore calcite. Ore-stage calcite commonly has negative δ13C values reflecting involvement of carbon from organic matter; its δ18O composition with an average of 22.6 ± 2 ‰ (19.7 to 26.0 ‰) may be explained by a moderate-temperature hydrothermal fluid. There is no systematic δ34S variation between and across the different styles of mineralization. The range of δ34S of 6–19 ‰ with a mean of 13 ‰ is close to the δ34S value of local and regional Triassic marine sulfate (δ34S = 16 ‰). Thermochemical reduction of Triassic sulfate, likely mediated by hydrocarbons, is the most probable source for sulfur in the ores. Lead isotope data on galena are within a narrow field of upper crustal signature (206Pb/204Pb = 18.71–18.77; 207Pb/204Pb = 15.66–15.70; 208Pb/206Pb = 38.81–38.97) indicating a homogeneous ore fluid.The major characteristics of the Bougrine ore deposit are typical of Mississippi Valley type Pb-Zn deposits and indicate large-scale fluid circulation likely related to stacking and uplift in the northern Tunisian Nappes Zone during the Miocene. Both the hydraulic load of meteoric water and over-pressured basinal and basement fluids during compressional movements favored southward fluid migration along basement discontinuities and most permeable strata in the Mesozoic-Cenozoic sedimentary pile. Low-pressure domains around salt diapirs in a rifting environment allowed focused upward fluid flow, and the hydrocarbon reservoir of the Bahloul Formation then provided the geochemical trap for efficient base metal deposition.

Mississippi Valley-type Zn–Pb deposits in orogenic thrust belts: ore formation in response to synorogenic crustal transpression or extension

Mississippi Valley-type Zn–Pb deposits in orogenic thrust belts: ore formation in response to synorogenic crustal transpression or extension

Genetic relationship between the Maoping Pb-Zn deposit and paleo-oil reservoir in the northern Yunnan-Guizhou depression: Evidence from bitumen trace elements and the in-situ sulfur isotope of pyrite associated with bitumen

The coexistence of numerous Mississippi Valley-type (MVT) Pb-Zn deposits and oil/gas reservoirs in the world demonstrates that a close genetic link between them. The northern Yunnan–Guizhou depression (NYGD) is a tectonic unit containing Pb–Zn deposits, paleo-oil reservoirs and shale gas. However, previous studies on the relationship between hydrocarbon accumulation and Pb–Zn mineralization have been ignored. The Maoping Pb–Zn deposit is a large-sized MVT deposit in the NYGD where a large amount of solid bitumen (i.e., a paleo-oil reservoir) occurs, and it is an ideal area to study the relationship between hydrocarbon accumulation and lead–zinc mineralization. In this paper, the bitumen and pyrite associated with bitumen from the Xujiazhai (discovered in this study) and Xiaocaoba paleo-oil reservoirs and the Maoping Pb–Zn deposit are researched. Geological observation has revealed that bitumen occurs in dissolution pores, fractures and intercrystalline pores in dolomite of the Upper Devonian and Carboniferous. The bitumen from Xujiazhai, Maoping and Xiaocaoba with high and similar Raman equivalent reflectance (RmcRo%) indicates they are in over-mature level and may be derived from the cracking of early-accumulated crude oils. The bitumen in the Xujiazhai paleo-oil reservoir and Maoping deposit has an abundant Pb and Zn content, indicating petroleum liquids may act as the transporting agents of metallogenic metal elements, carrying them to sites where mineralization may take place. The source rocks may have provided not only the oil for paleo-oil/gas reservoirs, but also a portion of ore metals for the Pb-Zn mineralization. The bacterial sulfate reduction (BSR) and thermochemical sulfate reduction (TSR) processes were recorded by the pyrite in the paleo-oil reservoir, which was consistent with the mechanism of reduced sulfur formation in the Maoping deposit. In addition, the large negative (−27.7‰ to −5.7‰) and positive (.9‰ to 19.2‰) δ34S values of the pyrite associated with the bitumen in the paleo-oil reservoir were similar to those of the sulfide in the Maoping deposit. We believe that the formation and evolution of the paleo-oil reservoirs are closely related to the metallogenic process of the Maoping Pb–Zn deposit, and the sulfides in them have the same sulfur source and formation mechanism as reduced sulfur. BSR phenomena could occur in prior to migration of the hydrocarbons into the reservoir or low mature oil stage in paleo-oil reservoir; a small amount of H2SBSR was combined with metal ions in ancient oil reservoirs and deposits to form early subhedral, xenomorphic granular, fine-grained strawberry aggregate pyrite and/or gelatinous sphalerite. The paleo-gas reservoir formed by the evolution of the paleo-oil reservoir in the main metallogenic period potentially participated in the mineralization; that is, organic gas acted as a reducing agent and transformed SO42− in the upper Devonian Zaige Formation gypsum strata on the periphery of the Maoping lead–zinc mining area into H2STSR through TSR, providing reduced sulfur and creating the environmental conditions for mineralization. During or after the transformation of the paleo-oil reservoir to a paleo-gas reservoir, the decoupling of metals and organic complexes may have provided the ore metals for mineralization. Massive sulfide precipitation may have occurred during or after the paleo-oil reservoir cracked into the paleo-gas reservoir.

Mineralization Process of MVT Zn-Pb Deposit Promoted by the Adsorbed Hydrocarbon: A Case Study from Mayuan Deposit on the North Margin of Sichuan Basin

The Mayuan Zn-Pb deposit on the northern margin of the Sichuan Basin is rich in Zn-Pb deposit resources. Additionally, a large amount of bitumen is observed in outcrops, and these deposits represent a key template for exploring the migration of hydrocarbon fluids and metal elements within an ancient oil reservoir. In this study, a chemical experimental method was used to extract the adsorbed hydrocarbon from the chosen five groups of samples, and mathematical statistical methods were also used. The varied metal concentrations before and after the extraction experiments have been noticed, due to the direct carrying action of the adsorbed hydrocarbon. In addition, a strong correlation was observed between the Mayuan Zn-Pb deposit and their source rocks, as well as the same distribution trend from the rare earth element distribution curve. A moderate correlation was observed between the two groups of black shales and Mayuan Zn-Pb ores, and the rare earth partition curve showed consistent trends. The results show that organic matter exists in two forms, among which hydrocarbon organic matter is extracted due to the carrying effect of extraction experiment, and the remaining non-hydrocarbon organic matter is combined with metal elements to form a metal complex. Hydrocarbons are involved in mineralization, asphaltenes are derived from bitumen, and one of the potential sources of Pb/Zn in the Mississippi Valley type (MVT) Zn-Pb deposit is black shale rich in organic matter.

Genetic Relationship between Mississippi Valley-Type Pb–Zn Mineralization and Hydrocarbon Accumulation in the Wusihe Deposits, Southwestern Margin of the Sichuan Basin, China

The coexistence of numerous Mississippi Valley-type (MVT) Pb–Zn deposits and oil/gas reservoirs in the world suggests a close genetic relationship between mineralization and hydrocarbon accumulation. The Wusihe MVT Pb–Zn deposits are located along the southwestern margin of the Sichuan Basin. Based on the spatiotemporal relation between Pb–Zn deposits and paleo-oil/gas reservoirs, ore material sources, and processes of mineralization and hydrocarbon accumulation, a new genetic relationship between mineralization and hydrocarbon accumulation is suggested for these deposits. The Wusihe Pb–Zn deposits are hosted in the Ediacaran Dengying Formation dolostone, accompanied by a large amount of thermally cracked bitumen in the ore bodies. The Pb–Zn deposits and paleo-oil/gas reservoirs are distributed along the paleokarst interface; they overlap spatially, and the ore body occupies the upper part of the paleo-oil/gas reservoirs. Both the Pb–Zn ore and sphalerite are rich in thermally cracked bitumen, in which µm sized galena and sphalerite may be observed, and the contents of lead and zinc in the bitumen are higher than those required for Pb–Zn mineralization. The paleo-oil/gas reservoirs experienced paleo-oil reservoir formation, paleo-gas reservoir generation, and paleo-gas reservoir destruction. The generation time of the paleo-gas reservoirs is similar to the metallogenic time. The source rocks from the Cambrian Qiongzhusi Formation not only provided oil sources for paleo-oil reservoirs but also provided ore-forming metal elements for mineralization. Liquid oil with abundant ore-forming metals accumulated to form paleo-oil reservoirs with mature organic matter in source rocks. As paleo-oil reservoirs were buried, the oil underwent in situ thermal cracking to form overpressure paleo-gas reservoirs and a large amount of bitumen. Along with the thermal cracking of the oil, the metal elements decoupled from organic matter and H2S formed by thermochemical sulfate reduction (TSR) and minor decomposition of the organic matter dissolved in oilfield brine to form the ore fluid. The large-scale Pb–Zn mineralization is mainly related to the destruction of the overpressured paleo-gas reservoir; the sudden pressure relief caused the ore fluid around the gas–water interface to migrate upward into the paleo-gas reservoirs and induced extensive metal sulfide precipitation in the ore fluid, resulting in special spatiotemporal associated or paragenetic relations of galena, sphalerite, and bitumen.

Mineralization of MVT Pb-Zn Deposits in the Process of Hydrocarbon Accumulation and Destruction in the Strong Structural Deformation Area of Eastern Sichuan, South China

The Mississippi Valley-type (MVT) Pb-Zn deposits and hydrocarbon reservoirs coexist around the margin of the eastern Sichuan basin. This study examined the fluid inclusions, Sr isotope and systematic Rb-Sr, Sm-Nd geochronology for the distinct ore and gangue minerals of four orebodies from two MVT Pb-Zn deposits in the margin of the eastern Sichuan basin, combined with the existing research foundation of oil and gas accumulation and evolution, which was designed to understand the internal relationship between oil and gas accumulation and the involvement of organic matter in metal mineralization. High-density methane, moderate temperature, and salinity inclusions were discovered in the studied MVT Pb-Zn deposits, combined with relatively higher 87Sr/86Sr ratios (0.71088~0.714749), indicating that the ore-forming fluids were derived largely from the hydrocarbon associated basinal brines. Rb-Sr isochron of paragenetic sphalerites and pyrites and Sm-Nd isochron of paragenetic fluorites and calcite from the studied MVT Pb-Zn deposits define isochron ages of 144.5 Ma~138.5 Ma, and 147.6 Ma, respectively, indicating that the Late Jurassic to Early Cretaceous Yanshanian orogeny was an important metallogenic event in the margin of the eastern Sichuan basin. The close temporal and spatial relationship between the MVT mineralization and hydrocarbon accumulation and destruction in the strong structural deformation area of the margin of the eastern Sichuan basin allows us to propose a possible model in which the Yanshanian compressional tectonics drove a large-scale flow of metal- and sulfate- bearing basinal fluids passed under or through methane-bearing carbonate reservoirs, resulting in the MVT mineralization and hydrocarbon accumulation and destruction.

Sulphur and metal sources of polymetallic vein-type, sedimentary exhalative-type and Mississippi Valley-type Zn–Pb deposits along the southeast margin of the Yangtze Block

Three types of zinc-lead deposits, including polymetallic vein-type, sedimentary-exhalative (SEDEX), and Mississippi valley-type (MVT) Zn–Pb deposits, have been discovered along the southeast margin of the Yangtze Block. A systematically comparative study on the sulphur and metal sources for these deposits, is absent, which significantly limits the understanding of the metallogenic model and geological exploration. Thus, in order to reveal the S and Pb sources of Pb–Zn deposits, an investigation of trace elements of sphalerite and of S–Pb isotopic compositions of sulphides in these three types of Zn–Pb deposits was conducted in this study. We found that, in the vein-type, SEDEX, and MVT Zn–Pb deposits, (1) the sulphur was derived respectively from granitic magmatism related to the Guangxi Orogeny, early Cambrian stratified seawater and connate water; (2) the lead isotope variation indicates that the ore-forming metals were mainly derived from the granitic hydrothermal fluids for vein-type deposits, from basement rocks for SEDEX deposits, and mainly from early Cambrian sedimentary rocks for MVT mineralization. The Nanhua rifting lead to the syngenetic Zn-Pb mineralization, while the Guangxi Orogeny resulted in magmatic-hydrothermal vein mineralization at depth and in MVT mineralization at the shallow crustal levels.

A shift from BSR to TSR caused the formation of the Chipu Pb-Zn deposit, South China

The widely varying sulfur isotopes in some Mississippi Valley-type (MVT) Pb-Zn deposits are often attributed to bacterial sulfate reduction (BSR), whether thermo-chemical sulfate reduction (TSR) also contributes is debatable. The Chipu Pb-Zn deposit in South China (0.7 Mt Pb + Zn reserves @ 10.4 wt%) is hosted by late Ediacaran organic-rich evaporitic dolostone and contains three assemblage types of hydrothermal minerals: pyrite (stage I), sphalerite-pyrite-galena (stage II; main ore stage), and galena-pyrite (stage III). High spatial resolution in situ S isotopic data of pyrite and sphalerite have a wide range of δ34S values from −31.1‰ to +33.8‰, which differ from previously reported data (δ34S = −5.6‰ to +21.9‰). Also, an important feature is that stage I pyrite has extremely low δ34S values (-31.1‰ to −17.3‰), while stage II (δ34S=+12.5‰-+16.2‰) and III (δ34S=+19.8‰-+33.8‰) sulfide minerals have heavy sulfur isotopes. Such isotope signatures indicate different stages of sulfides may have different reduction mechanisms. Together with in situ Pb isotopes, we propose that both BSR and TSR of local marine sulfate were involved during the formation of the Chipu deposit. Furthermore, the arrival of the hot, basement-derived fluids caused a change from BSR to TSR that occurred in sulfate-open to nearly sulfate-closed systems.

Research advance in geochronology of the Mississippi Valley-type Pb-Zn deposits: Debate on the metallogenic age of the Jinding deposit

金属矿床精确定年仍是国内外科学研究的难题，妨碍了对成矿规律的认识和资源勘探目标的优选评价。针对密西西比河谷型（MVT）铅锌矿床，前期有人分别利用Re-Os法、U-Pb法、⁴⁰Ar-³⁹Ar法、Rb-Sr法、Sm-Nd法、古地磁测年法和裂变径迹法等不同手段对其成矿时代进行了探索性尝试。其中，Re-Os同位素测年技术虽然仍是疑难金属矿床直接定年的有效手段，但现有Re-Os同位素定年技术还达不到锆石U-Pb法的精度水平。本文以三江特提斯兰坪盆地金顶铅锌镉铊矿床为研究对象，在精细解剖矿床的基础上，开展单阶段硫化物精确识别和高纯提取，建立不同阶段硫化物矿物学标志。前期研究侧重于金顶矿床脉石矿物和黄铁矿等非直接成矿矿物的定年，且年龄变化范围较大（114~23Ma），难以对该矿床的形成时代给出精确的制约；为此，本文对该矿床的成矿矿物开展了高精度定年。5件闪锌矿矿物的Re-Os等时线年龄为129&#177;10Ma （MSWD=126，<i>n</i>=5），对应成矿时代早于古新统云龙组和白垩系景星组赋矿围岩，尚不能代表真实的铅锌成矿时代。闪锌矿测年结果可能受富含Re和Os的有机质的影响。随着同位素地质年代学持续的发展与革新，加之高纯提取方法不断进步，精确定年为MVT铅锌矿床研究提供了更多的技术支撑。

Critical metals in sediment-hosted Pb-Zn deposits in China

<p indent=0mm>Sediment-hosted Pb-Zn deposits are mainly comprised of Mississippi Valley-type (MVT) deposits situated in carbonate-dominated sedimentary rocks and clastic-dominated (CD) deposits located in siliciclastic-dominated sequences. They are significant sources of critical metals such as cadmium, gallium, and germanium, as well as indium, cobalt, and thallium. In China, sediment-hosted Pb-Zn deposits are found in 5 metallogenic belts/districts, namely the Sanjiang belt, the Yangtze Block district, the Tarim Craton district, the Changba belt, and the Langshan belt. They provide 54% of China’s Pb-Zn resources, but their resource endowment and the metallogenic characteristics of these associated critical metals remain unclear. After briefly reviewing the main critical metals in sediment-hosted Pb-Zn deposits and sediment-hosted Pb-Zn deposits in China, this review summarizes the distribution and enrichment mechanisms of critical metals in sediment-hosted Pb-Zn deposits in China and recommends future research. These critical metals are unevenly enriched in sediment-hosted Pb-Zn deposits in China. Compared to the crustal elemental abundances, Cd, Ge, and In are the most enriched, Tl and Co have lower enrichment degrees, and Ga has the lowest enrichment degree. Cd, Ga, Ge, and Tl are rich in MVT deposits, while In and Co are rich in CD deposits. In all five sediment-hosted Pb-Zn belts/districts, Cd is relatively abundant. However, other critical metals are enriched to a different degree in each belt/district. In terms of distribution, Cd is well enriched in all five sediment-hosted Pb-Zn belts/districts, particularly in the Sanjiang belt of the Qinghai-Tibet Plateau, and the Yangtze Block district; Ge is most abundant in the Yangtze Block district, followed by the Changba belt in the Qinling orogenic belt, and Sanjiang belt; In and Co are enriched in the Sanjiang belt, followed by the Yangtze Block district and the Changba belt; Tl is enriched in the Sanjiang belt, the Yangtze Block district, and the Changba belt; and, Ga is most enriched in the Changba belt and Yangtze Block, followed by the Sanjiang belt. Based on these characteristics, two enrichment mechanisms are occurring in sediment-hosted Pb-Zn deposits. First, sediment-hosted Pb-Zn deposits are selective for the enrichment of critical metals, and second, the degrees of enrichment of critical metals in these deposits are different. The first enrichment mechanism results from the similarity in physicochemical properties between the critical metal elements and dominant elements (such as Zn and Fe) in the ore and gangue sulfides (such as sphalerite and pyrite). The second mechanism is associated with substitution forms of critical metal elements and host minerals, as well as physicochemical conditions and tectonic conditions of the deposits and tectonomagmatic processes throughout geological history. Research into critical metals in sediment-hosted Pb-Zn deposits in China abounds in the Yangtze platform Pb-Zn metallogenic belt and MVT Pb-Zn deposits; however, this research is still in the pipeline. A database of critical metal resources hosted by sediment-hosted Pb-Zn deposits in China is urgently needed, as is comprehensive research into the metallogenic mechanism of different critical metals, and the determination of the regional metallogenic regularity of these critical metals.

Well-Constrained Mineralization Ages by Integrated 40Ar/39Ar and U-Pb Dating Techniques for the Xitian W-Sn Polymetallic Deposit, South China

Abstract Mineralization ages of many mineral deposit types (such as orogenic Au, stratabound Cu, and Mississippi Valley-type Pb-Zn deposits) are still difficult to date by the traditional isotopic chronometry because of the lack of suitable minerals. We have made efforts to establish a widely suitable dating technique to determine ore formation ages using a high-precision 40Ar/39Ar method on ubiquitously present fluid inclusions in quartz, sphalerite, and other nonpotassium minerals from hydrothermal deposits. The Xitian W-Sn polymetallic deposit in central South China contains several minerals suitable for isotopic dating for interchronometer comparison. 40Ar/39Ar laser step heating of 16 micas from ore veins, greisen, and metallogenic granites yields flat age spectra and thus well-defined ore formation ages ranging from 152.4 ± 1.5 (2σ) to 148.1 ± 1.4 Ma with an average of 150.2 ± 0.6 Ma. 40Ar/39Ar progressive crushing of nine quartz samples produces well-defined isochron lines for their primary fluid inclusions corresponding to isochron ages of 153.7–149.9 Ma with an average of 151.6 ± 0.6 Ma. Cassiterites from three hand specimens have weighted mean 206Pb/238U ages of 151.5 ± 1.7 (2σ), 149.7 ± 2.1, and 151.7 ± 2.1 Ma. All these new geochronological dates and previous molybdenite Re-Os ages yield well-constrained mineralization ages of 153–148 Ma for the Xitian W-Sn polymetallic deposit, which also confirms conclusively that the quartz 40Ar/39Ar progressive crushing technique is a feasible, valid dating technique. Furthermore, significant age information on the secondary fluid inclusions is potentially obtained simultaneously by this technique. We expect that this novel dating technique will be widely applied to determine the geologic fluids trapped in minerals during hydrothermal mineralization, hydrocarbon accumulation, metamorphism, tectonic activities, and other geologic processes.

Genetic link between Mississippi Valley-Type (MVT) Zn-Pb mineralization and hydrocarbon accumulation in the Nanmushu, northern margin of Sichuan Basin, SW China

The coexistence of Zn-Pb deposits and oil/gas reservoirs demonstrates that a close genetic link between them. The Nanmushu is a large Mississippi Valley-Type (MVT) Zn-Pb deposit discovered on the northern margin of the Yangtze block in recent years. The deposit is hosted in the Ediacaran Dengying Formation dolostone, accompanied by large amount of bitumen in the orebodies. The MVT Zn-Pb deposit overlaps with the paleo-oil/gas reservoir horizontally, and sandwiched in the paleo-oil/gas reservoirs at depth. The Cambrian Guojiaba Formation may have provided not only the oil for paleo-oil/gas reservoirs, but also ore metals for the Zn-Pb mineralization. With increasing burial depth, the Guojiaba Formation may have become more mature to form metal-rich fluids, and the metals migrated and accumulated with hydrocarbons to form a paleo-oil reservoir. Large-scale Zn-Pb mineralization may have occurred in the destruction process of paleo-gas reservoir. With the deep burial of paleo-oil reservoir, the paleo-oil reservoir may have transformed into a paleo-gas reservoir. Decoupling of metals and hydrocarbons during the paleo-gas reservoir formation may have provided the ore metals. Thermal sulfate reduction (TSR) during the paleo-oil/gas reservoirs formation may have provided the hydrogen sulfide for mineralization. Decompression and cooling during the paleo-gas reservoir destruction may have formed extensive metal sulfide precipitation and mineralization.

Unraveling the early petroleum migration of the Potiguar Basin, Brazil: Constraints from fluid inclusions of the Ubarana and Lorena oilfields

A coupled study of fluid inclusions and one-dimensional basin modeling allowed the reconstruction of the early hydrocarbon filling history of the main petroleum systems of the Potiguar Basin, Brazil. Confocal laser scanning microscopy, microthermometry and fluorescence spectra measurements were used to model PVTx properties of petroleum inclusions in samples from the onshore Lorena and the offshore Ubarana oilfields. The fluid inclusion data and basin modeling suggest that the initial filling of the Lorena reservoir (Pendência Formation) occurred during the rift stage in two scenarios at 62.7–80.6 °C (11–16.8 MPa): (i) the late rift phase in the Barremian–Early Aptian (ca. 129–124 Ma) or during the beginning of the uplifting phase in the Aptian (ca. 118–117 Ma). In the Ubarana Oilfield, hydrothermal fluids migrated alongside petroleum during the reservoir initial filling. Fluid inclusion homogenization temperatures for both the Açu (mode interval of homogenization temperatures, Th(LV→L)mode interval = 124–128 °C) and Ponta do Mel (Th(LV→L)mode interval = 115–130 °C) formations are higher than the present-day reservoir temperature (110 °C). Isochoric modeling of saddle dolomite-hosted fluid inclusions from the Ponta do Mel Formation indicates trapping temperatures between 128.9 and 133.1 °C and pressures between 10.6 and 12.9 MPa. Temperatures and salinities (16 and 20 mass % equivalent in NaCl + CaCl2) of aqueous inclusions hosted in saddle dolomite are similar to those of the fluid inclusions trapped in hydrothermal minerals in Mississippi Valley-Type Pb–Zn deposits. No specific timing can be suggested for the hydrothermal event in Ubarana Oilfield. However, this atypical (hydrothermal) petroleum system could be linked to two possible scenarios: (i) the onset of petroleum migration of the Alagamar Formation during the Cenozoic Macau (ca. 48–8.8 Ma) magmatic event; or (ii) an earlier activity of the petroleum system, prior to the peak oil generation (50–10 Ma).

Contribution of ERT on the Study of Ag-Pb-Zn, Fluorite, and Barite Deposits in Northeast Mexico

The results on the effectiveness of five 2D electrical resistivity tomography (ERT) survey profiles for Ag-Pb-Zn, fluorite, and barite exploration Mississippi Valley Type (MVT) and on the magmatic deposits of northeast Mexico, are presented. The profiles were made in areas with mining activities or mineralization outcrops. Schlumberger, dipole-dipole, and Wenner array configurations were used on the measurements. The results showed that electric resistivity can be used to distinguish between mineralized zones. In magmatic-type Pb-Zn and MVT Pb-Zn deposits, resistivity values are shown as low. In magmatic-type fluorite and MVT fluorite deposits, as well as the MVT barite deposit, low-resistivity values are related to Fe sulfides and clays. With these results it is possible to connect observed surface mineralization with underground mineralization. New mineralized zones are also found and their geometries, extensions, and dipping are reported. Therefore, lower resistivity values can be linked to mineral bodies with higher Ag-Pb-Zn contents, as well as bodies enriched in Fe sulfides, Fe oxides, and clays in the fluorite and barite mineralizations. In most ERT models, fractures and faults are identified, indicating a structural control on mineralization. From the geoelectric patterns we can infer the magmatic and MVT origin of these mineral deposits.

Geology and genesis of the Shalipayco evaporite-related Mississippi Valley-type Zn–Pb deposit, Central Peru: 3D geological modeling and C–O–S–Sr isotope constraints

The Shalipayco Zn–Pb deposit, in central Peru, is composed of several stratabound orebodies, the largest of which are the Resurgidora and Intermedios, contained in carbonate rocks of the Upper Triassic Chambara Formation, Pucara group. Petrography suggests that a single ore-forming episode formed sphalerite and galena within vugs, open spaces, and fractures. Three-dimensional (3D) geological modeling has allowed division of the Chambara Formation into four members (Chambara I, II, III, and IV) that better define lithological controls on sulfide formation. Diagenetic replacement of evaporite minerals with the organic matter (OM) presence likely generated secondary porosity and H2S accumulation by bacterial sulfate reduction (BSR), providing ground preparation for the later Zn–Pb mineralizing event. The least-altered host rocks have C–O isotope compositions of 1.8 ± 0.1‰ (VPDB) and 29.9 ± 2.1‰ (VSMOW), respectively, within the Triassic marine carbonate ranges. Early dolomite contains lighter C–O composition (1.1 ± 0.9 and 23.8 ± 2.9‰, respectively) consistent with OM decomposition during burial diagenesis. Post-mineralization calcite has still lighter C–O composition (− 5.1 and 13.3‰, respectively), suggesting meteoric water that had migrated through organic-rich strata. The strontium isotopes of Mitu group basalts (0.709654–0.719669) indicate it as a possible, but not the unique source of strontium and probably of other metals. Highly negative sulfide sulfur isotope values (− 23.3 to − 6.2‰ (VCDT)) indicate a major component of the ore sulfur derived ultimately from BSR. However, multiple lines of evidence suggest that preexisting H2S underwent thermochemical redox cycling prior to ore formation. The influx of hot metalliferous brines to dolomitized zones containing trapped H2S is the preferred model for ore deposition at Shalipayco.

Structural control and timing of evaporite-related Mississippi Valley-type Zn–Pb deposits in Pucará Group, northern central Peru

The South America MVT belt comprises the deposits of San Vicente, Shalipayco, Florida Canyon, and some minor Zn–Pb occurrences hosting in the carbonates and evaporites of the Pucará Group, in an extension of more than a thousand kilometers from the center to the north of Peru. Structural constraints of the MVT Peruvian deposits are conditioned by deep sub-vertical secondary extension structures with general N, NNE or NNW direction related to strike-slip movements superimposed on previous Andean NW thrust structures. Recent studies on Shalipayco and Florida Canyon deposits point to similar processes of rock formation, diagenesis and mineralization acting in province scale. New isotopic data of Pb–Pb and Rb–Sr in sulfides summed with a compilation of the available data for the evaporite-related MVT deposits and studies on the structural and tectonic evolution of the Peruvian Andes allowed establishing correlations of local process of the deposits to the regional Andean tectonic events. The Florida Canyon saline dome structure was attributed to Juruá Orogeny (157–152 Ma). The stage of dolomitization forming the porous dolostone and evaporite breccia during burial diagenesis is attributed to the period between Juruá and Mochica stages. The oil migration to these reservoir rocks occurred probably during Mochica event (100–95 Ma). The Rb–Sr dating of sphalerite from the Florida Canyon deposit together with temporal field relations indicated that the Zn–Pb sulfide ore formed in or just after Peruvian Orogeny (86-83 Ma).

Sediment-hosted Pb–Zn deposits in the Tethyan domain from China to Iran: Characteristics, tectonic setting, and ore controls

The Tethyan domain from China to Iran hosts many important sediment-hosted Pb–Zn deposits but most have been poorly documented. This study summarizes the salient features of these deposits and discusses the type of ore, tectonic setting, and important ore controls, on the basis of new geological observations and previous publications. The Tethyan domain is characterized by the young and extensive Himalayan–Tibetan and Zagros orogens that formed through collisions between the India/Arabia and Eurasia continents since the Late Cretaceous or early Cenozoic. Abundant Mississippi Valley-type (MVT) and subordinate clastic-dominated (CD, also known as SEDEX) Pb–Zn deposits occur in this domain, including in central and eastern Himalayan–Tibetan orogen in China, the Indian passive margin in southern Pakistan, and various tectonic units of Iran. Economically important deposits contain 0.1–21 Mt Pb + Zn and have total metal resources of ∼75 Mt with ∼48% being oxidized ores. All major deposits known in this domain are MVTs (i.e., the Jinding, Huoshaoyun, Mehdiabad, and Angouran deposits).Mississippi Valley-type Pb–Zn deposits occur in continental-collision-related fold-and-thrust belts and forelands, where deposits are mostly located on the margin of the Eurasian continent, with some in the Indian and Arabian continental margins. Clastic-dominated Pb–Zn deposits occur in central Iran and southern Pakistan, hosted by deep-water siliciclastic sequences of the early Cambrian rifted continental margin of Gondwana and the Jurassic passive continental margin of India, respectively. The youngest mineralized rocks and ages constrain that some important MVT deposits (e.g., the Jinding, Chaqupacha, and Angouran deposits) were formed after a main phase of regional compression, during a regional, large-scale strike-slip or crustal-extension stage in a continental collision setting. In sense of lithologic structure, important ore controls for MVT deposits include evaporite diapir structure, carbonate/evaporite dissolution–collapse structure, pre-existing barite, and porous dolostone. Much of the primary sulfide ore in this domain has been oxidized by supergene processes. This is particularly pronounced in the newly discovered Huoshaoyun deposit, where almost all sulfides have been oxidized to smithsonite and cerussite. An understanding of tectonic setting, ore controls, and supergene processes is essential in exploring for MVT deposits in this domain.

Zinc solubility, speciation and deposition: A role for liquid hydrocarbons as ore fluids for Mississippi Valley Type Zn-Pb deposits

Although the ore fluid for Mississippi Valley Type (MVT) deposits is universally considered to be a basinal brine, the common occurrence of liquid hydrocarbons as inclusions in one of the ore minerals (sphalerite) raises the question of whether liquid hydrocarbons could play a role in metal transport. Here we explore the potential of liquid hydrocarbons to act as an ore fluid by determining the steady-state concentration of zinc in crude oil and evaluating the factors that promote its dissolution. To this end, zinc wires were reacted with a series of oils (labelled oils A, B and C) at 150, 200 and 250 °C, and the steady-state concentration of Zn was determined. Zinc concentrations were observed to increase with temperature and with the Total Acid Number (TAN) of the oils, the latter of which is strongly correlated to the carboxylic acid content of crude oil. Crude oil B, the highest TAN oil, dissolved 1700 ± 0.8 ppm at 250 °C, which is comparable to the highest Zn concentration inferred to have been dissolved in brines interpreted to represent MVT ore fluids. X-ray Photoelectron Spectroscopic (XPS) analyses performed on the residual oil coating the zinc wires after the reaction supported the conclusion that Zn has a strong chemical affinity for carboxylic acids in crude oil. Finally, an experiment designed to precipitate sphalerite crystals from a Zn-rich synthetic oil at room temperature showed that sphalerite precipitation from liquid hydrocarbons proceeds efficiently in a carbonate-buffered, H2S -rich environment.