The Evolution of the Delaware Basin - Preliminary Results

Sediment-hosted Zn-Pb and Cu deposits in China include Mississippi Valley-type (MVT) deposits, clastic-dominated (CD) deposits (also historically called sedimentary-exhalative [SEDEX] deposits by some workers), sandstone-hosted (SSH) Zn-Pb deposits, a few large magmatic-related carbonate-replacement deposits (CRD), and volcanic-hosted massive sulfide (VHMS) deposits that have been mistakenly classified as nonmagmatic-related MVT or CD deposits. There are also areas of China that contain important sediment-hosted copper (SHC) deposits. China is exceptionally endowed with MVT deposits with three of the five largest MVT deposits in the world (Huoshaoyun, Jinding, and Changba-Lijiagou). In contrast, China has one CD deposit (Dongshengmiao) in the top 30 CD deposits in the world. The few SHC deposits are small relative to world-class examples. The largest SHC deposits are located in the Yangtze and the North China cratons and hosted in Proterozoic rocks with indications of massive halokinetic features like those observed in the African copper belt. The MVT ores are most abundant in the Yangtze block, Qinling orogen, and the central and eastern Himalayan-Tibetean orogen. There are many other carbonate-hosted deposits in the North China craton and the Cathaysia block that have been widely classified as MVT or sedimentary-exhalative deposits. These are better classified as CRD or skarn deposits based on their proximity to intrusions, alteration assemblages, trace and minor element signatures, and, in some deposits, the presence of skarns minerals. Numerous sediment-hosted Zn-Pb deposits in China have been traditionally classified as SEDEX or syngenetic deposits based on laminated ore textures and stratiform ores that we interpret to reflect deformation and selective replacement processes rather than synsedimentary ore processes. Only two of these sediment-hosted deposits can be unequivocally classified as CD deposits: Dongshengmiao and Tanyaokou in the Langshan area of the North China craton. They are hosted in a siliciclastic-dominated sequence of a Proterozoic passive margin. The location and genesis of many MVT and SHC deposits in China are directly controlled by evaporites and evaporite facies. Evaporite and evaporite facies had an extremely important role in determining the location of the MVT deposits. The second largest sediment-hosted Zn-Pb deposit in China and fifth largest in Asia, Jinding in the Himalayan-Tibetan orogenic belt, is hosted in a hydrocarbon-reduced sulfur reservoir that formed because of salt diapirism. Other large sediment-hosted Zn-Pb MVT deposits in China that are interpreted to be controlled by structures produced by evaporite diapirism are Daliangzi and Tianbaoshan in the western Yangtze block. The largest Zn-Pb deposit in China is the newly discovered oxidized Huoshaoyun Zn-Pb MVT deposit, also in the Himalayan-Tibetan orogenic belt that is hosted in an evaporite-bearing sequence. The third largest Zn-Pb resource in China is at the Changba-Lijiagou deposit and, together with numerous smaller deposits, define a belt of metaevaporites in a carbonate platform sequence of the northern Yangtze platform. Other evaporite-related MVT ores include the Huize deposits that are hosted in a former Carboniferous evaporite-bearing hydrocarbon reservoir and the extensive Sinian dolostone-hosted Zn-Pb deposits that reflect evaporite dissolution breccias in the Yangtze block. The Tarim craton in northwestern China contains the only significant SSH deposit at Uragen. The ore zone lies in the footwall of an evaporative unit that may have served as a hydrocarbon and reduced sulfur trap. Furthermore, the most significant SHC deposits are hosted in Proterozoic rocks in the North China craton and the Yangtze block that contain extensive halokinetic breccias and structures.

From the first issue in 1905 onward, Economic Geology has been the main publication for those who study mineral deposits; indeed, it is now difficult to imagine economic geology without Economic Geology. It is interesting to ask, therefore, Who were the farsighted people who founded the journal, and Why did they think a specialized publication devoted to mineral deposits was needed?Let us first address the question, Who were the founders? They were the 12 men who collectivelydecided a new publication was needed, who then planned the financial structure to support the venture, and who served as the original editorial group. All were employed by, or associated with, the U.S. Geological Survey. Josiah Edward Spurr suggested the need for a journal sometime in November or December 1904. After informal discussions, nine of the founders met in the office of Waldemar Lindgren in the headquarters of the U.S. Geological Survey in Washington, D.C., on May 16, 1905, and founded the Economic Geology Publishing Company. The sole purpose of the company was the publication of a journal '...devoted primarily to the broad application of geologicprinciples to mineral deposits of economic value, and to the scientific description of such deposits, and particularly to the chemical, physical, and structural problems bearing on their genesis.' Initial financing for the new company was raised by the sale of 80 shares at a cost of $25 per share.Eight of the men at the founding meeting formed the first board of directors; Spurr was president, Frederick L. Ransome, secretary, and George O. Smith, treasurer. Other members were Arthur H. Brooks, Marius R. Campbell, Walter H. Weed, Waldemar Lindgren, and a young academic from Lehigh University in Pennsylvania, John D. Irving. Theninth man at the meeting was H. Foster Bain. Irving was appointed editor. Lindgren, Ransome, and Campbell from the U.S. Geological Survey, together with three academics, James F. Kemp of Columbia University, Heinrich Ries ofCornell University, and Charles K. Leith of the University of Wisconsin, were appointed associate editors. The initial board members, the editor, and associate editors are the people we now recognize as the founders of Economic Geology. Two others, Frank D. Adams, of McGill University in Canada, and John. W. Gregory, of Glasgow University in Scotland, were subsequently added as associate editors, and a third person, W. S. Bayley of the University of Illinois, was appointed as business editor, but

Lead isotope trends and metal sources in the Mississippi Valley-type districts from the mid-continent United States

Interfacial properties of CO2 and liquid sulfur in high-sulfur gas fields: Molecular simulations on carbonate mineral surfaces

Geochemical characteristics of trace occurrences of Mississippi Valley-type mineralization in the U.S. mid-continent: Implications for deposit growth

Two Mississippi Valley-type (MVT) ore deposits, Kicking Horse and Monarch, have been studied with the aim of comparing the ores at the two localities and to characterize the origin of the mineralizing fluids and the ore formation process(es). Both deposits are hosted by the Middle Cambrian Cathedral Formation carbonate host rocks, Kicking Horse on the north and Monarch on the south flank of the Kicking Horse valley near Field (SE British Columbia). The ore bodies are situated at the transition of (western) basinal to (eastern) shallow-water strata of the paleo-Pacific passive margin succession in the Cordilleran Foreland Province of the Western Canada Sedimentary Basin. Both deposits are related spatially to normal faults. In both localities, the ore minerals are dominated by pyrite, sphalerite, and galena. Dolomite, minor quartz, and calcite are also present in close association with the ores. The salinity (21–30 wt% NaCl eq.) and homogenization temperatures (63–182°C) measured in fluid inclusions in carbonate, quartz, and sphalerite lie within the typical range of MVT fluid conditions. The good stoichiometry (50–53 mol% CaCO3), low δ18O values (−21 to −14‰ Vienna Peedee belemnite) and relatively high homogenization temperatures (>95°C) of the dolomite suggest the dolomites were formed under burial diagenesis. The ore-forming fluids probably interacted with siliciclastic units, based on elevated Li contents and 87Sr/86Sr ratios, which are highest in the dolomite type after the main ore stage. We propose that the ores formed from the mixing of a downward-infiltrating, sulfur-bearing halite-dissolution fluid with an upward-migrating, metal-rich evaporated seawater fluid, which had already undergone minor mixing with a dilute fluid.

In other parts of the world, previous workers have shown that sparry dolomite in carbonate rocks may be produced by the generation and movement of hot basinal brines in response to arid paleoclimates and tectonism, and that some of these brines served as the transport medium for metals fixed in Mississippi Valley-type (MVT) and sedimentary exhalative (Sedex) deposits of Zn, Pb, Ag, Au, or barite. Numerous occurrences of hydrothermal zebra dolomite (HZD), comprised of alternating layers of dark replacement and light void-filling sparry or saddle dolomite, are present in Paleozoic platform and slope carbonate rocks on the eastern side of the Great Basin physiographic province. Locally, it is associated with mineral deposits of barite, Ag-Pb-Zn, and Au. In this paper the spatial distribution of HZD occurrences, their stratigraphic position, morphological characteristics, textures and zoning, and chemical and stable isotopic compositions were determined to improve understanding of their age, origin, and relation to dolostone, ore deposits, and the tectonic evolution of the Great Basin. In northern and central Nevada, HZD is coeval and cogenetic with Late Devonian and Early Mississippian Sedex Au, Zn, and barite deposits and may be related to Late Ordovician Sedex barite deposits. In southern Nevada and southwest California, it is cogenetic with small MVT Ag-Pb-Zn deposits in rocks as young as Early Mississippian. Over Paleozoic time, the Great Basin was at equatorial paleolatitudes with episodes of arid paleoclimates. Several occurrences of HZD are crosscut by Mesozoic or Cenozoic intrusions, and some host younger pluton-related polymetallic replacement and Carlin-type gold deposits. The distribution of HZD in space (carbonate platform, margin, and slope) and stratigraphy (Late Neoproterozoic Ediacaran–Mississippian) roughly parallels that of dolostone and both are prevalent in Devonian strata. Stratabound HZD is best developed in Ediacaran and Cambrian units, whereas discordant HZD is proximal to high-angle structures at the carbonate platform margin, such as strike-slip and growth faults and dilational jogs. Fabric-selective replacement and dissolution features (e.g., collapse breccias, voids with geopetal textures) are common, with remaining void space lined with light-colored dolomite crystals that exhibit zoning under cathodoluminescence. Zoned crystals usually contain tiny ( ∼70 °C. The oxygen isotopic compositions of HZD are consistent with formation temperatures of 50–150 °C requiring brine circulation to depths of 2–5 km, or more. The few HZD occurrences with the highest concentrations of metals (especially Fe, Mn, and Zn) and the largest isotopic shifts are closely associated with Sedex or MVT deposits known to have formed from hotter brines (e.g., Th > 150–250 °C). These relationships permit that HZD formed at about the same time as dolostone, from brines produced by the evaporation of seawater during arid paleoclimates at equatorial paleolatitudes. Both dolostone and HZD may have formed as basinal brines, which migrated seaward from evaporative pans on the platform, with dolostone forming at low temperatures along shallow migration pathways through permeable limestones, and HZD forming at high temperatures along deeper migration pathways through basal aquifers and dilatant high-angle faults. The small MVT deposits were chemical traps where hot brines encountered rocks or fluids containing reduced sulfur. The abundant Sedex deposits mark sites where hot brine discharged at the seafloor in adjacent basins. Thus the distribution of HZD may map deep migration pathways and upflow zones between eastern shallow marine facies, where evaporative brine could have been generated, and western Sedex deposits, where heated brines discharged along faults into platform margin, slope, and basin facies. The small size and scarcity of Pb-Zn deposits and the abundance of barite deposits in the Great Basin suggests the brines were generally reduced, possibly due to reactions with carbonaceous rocks along deep migration pathways. While this scenario may have occurred at several times, the age and abundance of Sedex deposits suggest that such a hydrology was best developed in the Late Ordovician, Late Devonian, and Early Mississippian, possibly in response to episodes of extension and forebulge faults associated with the Antler orogeny. The improved understanding of HZD may aid future exploration for ore deposits in the Great Basin.

Evidence for Late-Paleozoic brine migration in Cambrian carbonate rocks of the central and southern Appalachians: Implications for Mississippi Valley-type sulfide mineralization

Although several deposit types have either been shown or suggested to be associated with paleokarst features in carbonate rocks, lead—zinc sulfide deposits of the “Mississippi Valley-type“ (MVT) have received the most research and exploration. MVT deposits are not simply sulfide-filled open caves; rather, they are emplaced in carbonate breccias and consist of sulfides and carbonates, as either matrix or cement, filling spaces between angular carbonate fragments. Evidence of replacement is characteristically minimal, except in high-grade portions of deposits.

Experimental study on fluid migration mechanism related to Pb–Zn super-enrichment: Implications for mineralisation mechanisms of the Pb–Zn deposits in the Sichuan–Yunnan–Guizhou, SW China

The Bongara area, northern Peru, contains Zn-Pb mineralization with characteristics typical of Mississippi Valley-type (MVT) systems. The northwest–southeast-trending late Triassic–Jurassic carbonate host rocks of the Pucara Group were locally replaced by early (D1) and late (D2) dolomite. Fluid inclusion microthermometric data from dolomite and sphalerite are typical of MVT ore fluids (78° to 187°C; ~15–23 wt.% CaCl 2 equivalent), and do not show apparent covariation between temperature and salinity. Homogenization temperature data from D1 and D2 dolomite show a decrease from northern (mean Th = 138°C) to central (mean Th = 126°C) to southern areas (mean Th = 102°C), suggesting fluid flow from north to south. Assuming a geothermal gradient of ~30°C/km and an average surface temperature of ~20°C, the lower temperature limits might approximate the ambient host-rock temperatures, whereas the upper temperature limits may represent minimum temperatures of a deeper aquifer, probably at a maximum depth of ~6000 m. The lower temperature limits are also similar to the estimated temperatures if dolomitization and mineralization took place in the Late Cretaceous at ~2000–3000 m depth, probably during the formation of the Peruvian fold and thrust belt near the present day Peru–Ecuador border. Fluid inclusion data show that the fluids in each studied location had relatively uniform temperatures and salinities during dolomitization and mineralization. A significant salinity drop and a slight temperature decrease are observed during late calcite precipitation, suggesting mixing of brines with dilute, cooler fluids.

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from −0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = −0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from −0.80 to −0.01 per mil (mostly between −0.80 and −0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.

One of the main foundations for increasing trust in geological carbon dioxide (CO2) sequestration is a geomechanical application. A complex geological process for long-term CO2 storage in deep aquifer carbonate formation would irreversibly change the assumed stable state of the sedimentary basin that evolved over millions of years. The proposed project is expected to sequester 13 MMSCFD of CO2 and H2S into Devonian and Silurian formations deeper than 16,000 feet below Lea County in New Mexico's Delaware Basin, a sub-basin of the Permian. The intensive integration of geomechanical parameters and 3D flow simulation can provide insights into storage mechanisms, migration patterns and effects on caprock integrity over 30-year injection and 100 years of shut-in. This research illustrates the comprehensive development of a 3D structural framework on interpreted surfaces and spatial variability of porosity and permeability. The dynamic flow is subsequently furnished with the boundary parameters of relative permeability, geochemical fluid components, temperature, pressure, and injection rate to simulate gas accumulation and diffusion trends. Furthermore, the findings of geomechanical rock properties and strengths are incorporated into the dynamic model to evaluate further the impact of CO2 flow on Woodford caprock stability across injection and shut-in times. Through 3D dynamic simulation, it is estimated that gas storage could reach 7.04 million metric tons with a maximum daily injection rate over the course of 30 years. The gas plume would migrate around 834 acres in the planned sequestration zone, or a radius of 0.64 miles from the injection well. The coupled geomechanical model and CO2 flow assist in exploring the caprock failure on Mohr-Coulomb circle analysis, shear, and tensile safety factors in both spatial and time dimensions of dynamic flow simulation. Despite the thermal effects, stress changes, and geochemical interactions that occur over the injection period, the caprock retains its elastic modulus and is assessed to be far from failures. The study involves solving equations of motion and stress-strain relationships to determine how the caprock will respond to changes in pressure and fluid flow. The exceptional durability of Woodford Shale seal rock will promote the success of the CO2 storage in aquifer Siluro-Devonian carbonate rocks underneath New Mexico and pave the solid way for further long-term CO2 injection wells across the Delaware Basin in the coming decades.

The origin of the mineralization at the world-class Las Cuevas (the largest single fluorite deposit in the world) has been historically disputed, essentially between skarn-related and Mississippi Valley Type (MVT) models. A systematic study of fluid inclusions in these deposits revealed that they were formed by low temperature (49 to 177 °C) and low salinity (0 to 1.9 wt % NaCl equiv) fluids. The obtained δ13C (between −2.39 and 0.20‰ VPDB) and δ18O (between −14.03 and −7.37‰ VPDB) data from local host limestones agreed with regionally representative values in the literature. The obtained δ13C (between −15.60 and −12.99‰ VPDB) and δ18O (between −5.56 and −1.84‰ VPDB) data from hydrothermal calcite associated with fluorite mineralization indicated that the isotopic composition of hydrothermal fluids initially reflected buffering by the host rocks, and then recorded the interaction between meteoric water and basinal brines. It is likely that such processes occurred with concurrent maturation of organic matter, and that the obtained compositions may also have recorded a thermal effect on the local limestones. Halogen geochemical studies in inclusion fluids showed a distribution that suggests that solutes in mineralizing fluids were due to scavenging of Na+ and Cl− through water–rock interaction or halite dissolution, and that secondary sources would have been the evaporation or infiltration of seawater. The basinal brines with which the formation of these deposits was associated were massively diluted by deeply evolved meteoric water, thus making a significant fluorine input by basinal brines unlikely. Fluorine would have been provided by local groundwater through its interaction with Oligocene topaz rhyolites and other F-rich volcanic and hypabyssal rocks. Such a possibility is supported by present-day groundwater, which presents a regional endemic case of fluorosis. The precipitation of fluorite is possible at low temperatures (at which the solubility of this mineral is very low) by means of chemical reactions and physical interactions among very diluted F-poor basinal brines, F-rich groundwater, and host carbonate rocks. The latter systematically experienced hydrothermal karstification, which would have provided Ca2+ for reaction with F− and resulted in the precipitation of fluorite. This scenario stands for a depositional model that recalls those proposed for MVT and associated industrial mineral deposits, but is distinct from common models with regard to the primal source for fluorine and the extremely low salinities of inclusion fluids.

Controls on Mississippi Valley-Type Zn-Pb mineralization in Behabad district, Central Iran: Constraints from spatial and numerical analyses