Richard I. Grauch

Cyclic variations of sulfur isotopes in Cambrian stratabound Ni-Mo- ( PGE-Au) ores of southern China

Abstract Cyclic variations of δ 34 S values over a range of at least 48‰ in pyrite nodules from stratabound Ni-Mo-PGE(Au) ores of southern China are attributed to biogenic reduction of seawater sulfate in an anoxic, phosphogenic, and metallogenic basin. Cyclic introduction and mixing of normal seawater into typically stagnant basin waters led to extreme variations in δ 34 S values of aqueous sulfide species present at different times. Intermittent venting of metal-laden hydrothermal fluids into such a bacteriogenic sulfide-rich environment resulted in precipitation of metal sulfides as pseudomorphous replacements of organic debris and as sulfide sediments that record large δ 34 S CDT variations from −26 to +22‰. Apatite and silica dominated the replacement of the organic debris when metals were not being introduced into the basin. The combination of abundant organic debris, localized topographic basins for accumulation of the debris, bacterial production of sulfide species, and introduction of metal-bearing hydrothermal fluids provided the environment necessary to form these unusually rich Ni-Mo ores.

Gold and platinum in shales with evidence against extraterrestrial sources of metals

Abstract Few black shales contain concentrations of precious metals higher than average continental crust (i.e. ∼5 ppb Au). Yet Au and Pt alloys have been reported from the Kupferschiefer in Poland. Moreover, thin sulfide beds in certain Chinese and Canadian shales contain several hundred ppb Au, Pd and Pt and average ∼4% Mo and ∼2.5% Ni in an association that is difficult to explain. Volcanic and non-volcanic exhalations, hydrothermal epigenesis involving either igneous or sedex fluids, biogenic processes and low-temperature secondary enrichment are among the possible factors involved in deriving Ni, PGE and Au for black shales and sulfide beds in black shales. Extraterrestrial sources have been invoked in some cases (e.g., the Cambrian of China). However, available data on abundances of PGE indicate relatively low values for Ir (

Origin of an unusual monazite-xenotime gneiss, Hudson Highlands, New York: SHRIMP U-Pb geochronology and trace element geochemistry

A pod of monazite-xenotime gneiss (MXG) occurs within Mesoproterozoic paragneiss, Hudson Highlands, New York. This outcrop also contains granite of the Crystal Lake pluton, which migmatized the paragneiss. Previously, monazite, xenotime, and zircon from MXG, plus detrital zircon from the paragneiss, and igneous zircon from the granite, were dated using multi-grain thermal ionization mass spectrometry (TIMS). New SEM imagery of dated samples reveals that all minerals contain cores and rims. Thus TIMS analyses comprise mixtures of age components and are geologically meaningless. New spot analyses by sensitive high resolution ion microprobe (SHRIMP) of small homogeneous areas on individual grains allows deconvolution of ages within complexly zoned grains. Xenotime cores from MXG formed during two episodes (1034 ± 10 and 1014 ± 3 Ma), whereas three episodes of rim formation are recorded (999 ± 7, 961 ± 11, and 874 ± 11 Ma). Monazite cores from MXG mostly formed at 1004 ± 4 Ma; rims formed at 994 ± 4, 913 ± 7, and 890 ± 7 Ma. Zircon from MXG is composed of oscillatory-zoned detrital cores (2000-1170 Ma), plus metamorphic rims (1008 ± 7, 985 ± 5, and ∼950 Ma). In addition, MXG contains an unusual zircon population composed of irregularly-zoned elongate cores dated at 1036 ± 5 Ma, considered to be the time of formation of MXG. The time of granite emplacement is dated by oscillatory-zoned igneous cores at 1058 ± 4 Ma, which provides a minimum age constraint for the time of deposition of the paragneiss. Selected trace elements, including all REE plus U and Th, provide geochemical evidence for the origin of MXG. MREE-enriched xenotime from MXG are dissimilar from typical HREE-enriched patterns of igneous xenotime. The presence of large negative Eu anomalies and high U and Th in monazite and xenotime are uncharacteristic of typical ore-forming hydrothermal processes. We conclude that MXG is the result of unusual metasomatic processes during high grade metamorphism that was initiated at about 1035 Ma. This rock was then subjected to repeated episodes of dissolution/reprecipitation for about 150 m.y. during regional cooling of the Hudson Highlands.

Lower cambrian metallogenesis of south China: Interplay between diverse basinal hydrothermal fluids and marine chemistry

The lowermost Cambrian metalliferous black shales of southern China represent a unique metallogenic province. The shales host a wide range of world-class synsedimentary metal deposit types. The diverse metal assemblages in these deposits are best explained by venting of multiple hydrothermal fluids including reduced H2S-rich brines, petroleum, and oxidized brines into the basin. Coinciden formation of shales that are extraordinarity rich in organic carbon and metals suggest a rapid increase in bioproductivity and anoxic/dysoxic conditions during ore formation. We propose that basinal fluids were the source of bioliming nutrients that caused eutrophication and basin-wide anoxia. The dramatic geologic and geochemical changes in this basin demonstrate the possible impacts of hydrothermal systems on the generation and sequestration of organic matter, formation of black metalliferous shales, and chemical changes of seawater.

Chapter 8 Petrogenesis and mineralogic residence of selected elements in the meade peak phosphatic shale member of the permian phosphoria formation, Southeast Idaho

Abstract The Meade Peak Phosphatic Shale Member of the Permian Phosphoria Formation hosts the ore mined by the phosphate industry of southeast Idaho. It also hosts environmentally sensitive elements (ESE) such as Se, As, Hg, Ni, Cd, Zn, and Cr. Primary chemistry, elemental distribution patterns, and mineralogy within the Meade Peak were modified by element migration and possibly the introduction of elements. Fluids moved within the Meade Peak throughout its history, although the passage of fluids was highly variable in space and time, resulting in small domains of different rock chemistry and different mineralogy. Timing of major events affecting the Meade Peak and mineral habit are used to differentiate among detrital, diagenetic, epigenetic, and supergene mineral assemblages. Cross-cutting relationships among minerals are too rare to provide much paragenetic infor- mation. Carbonate fluorapatite (CFA) occurs in several forms, but dominantly as pelloids, some of which may have formed in situ during diagenesis. The other volumetrically signifi- cant form of CFA is interstitial cement that formed during diagenesis. Beginning during diagenesis and continuing intermittently, multiple generations of carbonate (dolomite and calcite) formed overgrowths and texturally complex carbonate cements. Movement and precipitation of silica followed a similar pattern. The ammonium feldspar buddingtonite, which generally rims orthoclase, also formed during diagenesis. Bacteria apparently played a significant role during diagenesis as well as during supergene processes, resulting in extreme fractionation of S isotopes and the possible bacterially mediated formation of minerals such as glauconite and sphalerite. Catagenesis, apparently culminating in oil generation, was the last significant diagenetic change. Thrusting accompanied by fluid (oil and brine) migration began during catagenesis in the Late Jurassic or Cretaceous and continued into the early Eocene. Fluorite ± carbonate ± barite± bitumen veins formed as a result of brittle deformation and accompanying fluid movement. This fracturing event may have been associated with a period of extension and normal faulting (Neogene to Holocene). Passage of the Yellowstone hot spot to the north of the area during the Neogene is marked by silicic domes and basaltic flows. The enrichment of Hg in fracture coatings might be the result of deposition from warm fluids associated with the emplacement of the silicic domes or a generally elevated, regional thermal gradient associated with the volcanism. Many of the fracture systems are still open and continue to provide fluid pathways that are the primary depositional sites for a wide variety of supergene minerals (such as Se, efflorescent salts) and element associations (such as Hg, Cd-S, Fe-Cr-O) in which many of the ESE are concentrated. Native Se is the most commonly identified host of Se in the studied samples. The largest concentration of Se occurs in open-fracture systems that cross-cut waste rock and ore units. The age(s) of native Se formation is not known; how- ever, the latest period of Se mobility is the present. Direct measurement of efflorescent “salts” forming on new mine faces indicate that several ESE, including both Se and Zn, are concentrated on the faces soon after they are exposed. Zinc is present as hydrous sulfates, but the residence of Se in these “salts” is unknown.