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Alan E. Koenig

Publications and source records attributed to Alan E. Koenig.

11 recordsLinked to original sources

Petrogenesis and rare earth element mineralization of the Elk Creek carbonatite, Nebraska, USA

Although carbonatites are the primary source of the world’s rare earth elements (REEs), the processes responsible for ore-grade REE enrichment in carbonatites are still poorly understood. In this study, we present a petrologic, geochemical, and isotopic evaluation of the Elk Creek carbonatite in southeast Nebraska to constrain the origin of REE mineralization. The Elk Creek carbonatite is a multilithologic carbonatite comprised of an early apatite-dolomite carbonatite, a middle/heavy REE-enriched magnetite-dolomite carbonatite, and a late-stage light REE-enriched, barite-dolomite carbonatite, as well as a suite of breccias. Neodymium, strontium, and carbon isotopic data from the early apatite-dolomite carbonatite, ε Nd (T) = 2.3 to 3.4, 87 Sr/ 86 Sr (i) = 0.702704 to 0.702857, and δ 13 C = −3.3 to −3.4, indicate that the parental magma and REEs were derived from the mantle, and textural and chemical data suggest that hydrothermal processes played an important role in reaching ore-grade enrichment. Higher initial 87 Sr/ 86 Sr values (∼0.7041) of REE-mineralized lithologies are evidence that these fluids were derived, in part, from meteoric water that interacted with the country rock. Modeling of the C-O isotopic data reveals that some of the isotopic variation results from closed-system Rayleigh fractionation of an evolving carbonatitic magma between 300 and 500 °C, but an excursion to heavier δ 18 O is likely the result of interaction with H 2 O-CO 2 -fluids at temperatures from 400 to 100 °C. Hydrothermal dolomite has higher 87 Sr/ 86 Sr values than early-formed magmatic dolomite, consistent with metasomatism by fluids derived, in part, from a more radiogenic source such as the Precambrian-age wall rock. Rare earth element mineralization occurs primarily in fine-grained, cavity filling minerals including monazite, bastnäsite, parisite, and synchysite along with barite, dolomite, quartz, and iron oxides. We interpret the LREE enrichment at Elk Creek to be the product of hydrothermal fluids derived from the evolving carbonatite magma and fluids from the wall rock. The REEs likely became enriched in late-stage fluids from the evolving magma as well as being remobilization by the dissolution of earlier formed minerals. Middle/heavy REE-enrichment in the magnetite-dolomite carbonatite is hosted in hydrothermal dolomite and is attributed to variations in the composition of hydrothermal fluids.

Nebraska

Mercury and trace element distribution in density separates of a South African Highveld (#4) coal: Implications for mercury reduction and preparation of export coal

Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm 3 , and the sink fraction for 2.0 g/cm 3 . Bulk analysis of the separates shows strong (R 2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.

International Journal of Coal Geology

Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit, West Qinling orogen, central China: An in situ SIMS study with implications for the source of sulfur

High spatial resolution textural (scanning electron microscope (SEM)), chemical (electron microprobe (EMP)) and laser ablation-inductively coupled plasma-mass spec- trometry (LA-ICP-MS)), and sulfur isotopic (secondary ion mass spectrometry (SIMS)) analyses of pyrite from the Qiuling sediment-hosted gold deposit (232±4 Ma) in the West Qinling orogen, central China were conducted to distinguish pyrite types and gain insights into the source and evolution of sulfur in hydrothermal fluids. The results reveal an enormous variation (−27.1 to +69.6‰) in sulfur isotopic composition of pyrite deposited during three paragenetic stages. Pre-ore framboidal pyrite, which is characterized by low concentra- tions of As, Au, Cu, Co, and Ni, has negative δ34S values of −27.1 to −7.6‰ that are interpreted in terms of bacterial re- duction of marine sulfate during sedimentation and diagenesis of the Paleozoic carbonate and clastic sequences, the predom- inant lithologies in the deposit area, and the most important hosts of many sediment-hosted gold deposits throughout the West Qinling orogen. The ore-stage hydrothermal pyrite con- tains high concentrations of Au, As, Cu, Sb, Tl, and Bi and hasa relatively narrow range of positive δ34S values ranging from +8.1 to +15.2‰. The sulfur isotope data are comparable to those of ore pyrite from many Triassic orogenic gold deposits and Paleozoic sedimentary exhalative (SEDEX) Pb-Zn de- posits in the West Qinling orogen, both being hosted mainly in the Devonian sequence. This similarity indicates that sulfur, responsible for the auriferous pyrite at Qiuling, was largely derived from the metamorphic devolatization of Paleozoic marine sedimentary rocks. Post-ore-stage pyrite, which is sig- nificantly enriched in Co and Ni but depleted in Au and As, has unusually high δ34S values ranging from +37.4 to +69.6 ‰, that are interpreted to result from thermochemical reduc- tion of evaporite sulfates in underlying Cambrian sedimentary rocks with very high δ34S values. The variations in Au content and sulfur isotopic compositions across a single ore-stage py- rite grain may reflect displacement of indigenous groundwater with low δ34S values by auriferous metamorphic fluids with high δ34S values. The very low-grade metamorphism of the host rocks and the metamorphic derivation of sulfur for the ore pyrite indicate that the Qiuling sediment-hosted gold deposit is an epizonal manifestation of an orogenic gold system in the West Qinling orogen.

Mineralium Deposita

Rare earth elements in sedimentary phosphate deposits: Solution to the global REE crisis?

The critical role of rare earth elements (REEs), particularly heavy REEs (HREEs), in high-tech industries has created a surge in demand that is quickly outstripping known global supply and has triggered a worldwide scramble to discover new sources. The chemical analysis of 23 sedimentary phosphate deposits (phosphorites) in the United States demonstrates that they are significantly enriched in REEs. Leaching experiments using dilute H 2 SO 4 and HCl, extracted nearly 100% of their total REE content and show that the extraction of REEs from phosphorites is not subject to the many technological and environmental challenges that vex the exploitation of many identified REE deposits. Our data suggest that phosphate rock currently mined in the United States has the potential to produce a significant proportion of the world's REE demand as a byproduct. Importantly, the size and concentration of HREEs in some unmined phosphorites dwarf the world's richest REE deposits. Secular variation in phosphate REE contents identifies geologic time periods favorable for the formation of currently unrecognized high-REE phosphates. The extraordinary endowment, combined with the ease of REE extraction, indicates that such phosphorites might be considered as a primary source of REEs with the potential to resolve the global REE (particularly for HREE) supply shortage.

Gondwana Research

Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

Procedia Earth and Planetary Science

Geochemistry of magnetite from porphyry Cu and skarn deposits in the southwestern United States

A combination of petrographic observations, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and statistical data exploration was used in this study to determine compositional variations in hydrothermal and igneous magnetite from five porphyry Cu&ndash;Mo and skarn deposits in the southwestern United States, and igneous magnetite from the unmineralized, granodioritic Inner Zone Batholith, Japan. The most important overall discriminators for the minor and trace element chemistry of magnetite from the investigated porphyry and skarn deposits are Mg, Al, Ti, V, Mn, Co, Zn, and Ga&mdash;of these the elements with the highest variance for (I) igneous magnetite are Mg, Al, Ti, V, Mn, Zn, for (II) hydrothermal porphyry magnetite are Mg, Ti, V, Mn, Co, Zn, and for (III) hydrothermal skarn magnetite are Mg, Ti, Mn, Zn, and Ga. Nickel could only be detected at levels above the limit of reporting (LOR) in two igneous magnetites. Equally, Cr could only be detected in one igneous occurrence. Copper, As, Mo, Ag, Au, and Pb have been reported in magnetite by other authors but could not be detected at levels greater than their respective LORs in our samples. Comparison with the chemical signature of igneous magnetite from the barren Inner Zone Batholith, Japan, suggests that V, Mn, Co, and Ga concentrations are relatively depleted in magnetite from the porphyry and skarn deposits. Higher formation conditions in combination with distinct differences between melt and hydrothermal fluid compositions are reflected in Al, Ti, V, and Ga concentrations that are, on average, higher in igneous magnetite than in hydrothermal magnetite (including porphyry and skarn magnetite). Low Ti and V concentrations in combination with high Mn concentrations are characteristic features of magnetite from skarn deposits. High Mg concentrations (<1,000 ppm) are characteristic for magnetite from magnesian skarn and likely reflect extensive fluid/rock interaction. In porphyry deposits, hydrothermal magnetite from different vein types can be distinguished by varying Ti, V, Mn, and Zn contents. Titanium and V concentrations are highly variable among hydrothermal and igneous magnetites, but Ti concentrations above 3,560 ppm could only be detected in igneous magnetite, and V concentrations are on average lower in hydrothermal magnetite. The highest Ti concentrations are present in igneous magnetite from gabbro and monzonite. The lowest Ti concentrations were recorded in igneous magnetite from granodiorite and granodiorite breccia and largely overlap with Ti concentrations found in hydrothermal porphyry magnetite. Magnesium and Mn concentrations vary between magnetite from different skarn deposits but are generally greater than in hydrothermal magnetite from the porphyry deposits. High Mg, and low Ti and V concentrations characterize hydrothermal magnetite from magnesian skarn deposits and follow a trend that indicates that magnetite from skarn (calcic and magnesian) commonly has low Ti and V concentrations.

Arizona, New Mexico

Deep-sea coral record of human impact on watershed quality in the Mississippi River Basin

One of the greatest drivers of historical nutrient and sediment transport into the Gulf of Mexico is the unprecedented scale and intensity of land use change in the Mississippi River Basin. These landscape changes are linked to enhanced fluxes of carbon and nitrogen pollution from the Mississippi River, and persistent eutrophication and hypoxia in the northern Gulf of Mexico. Increased terrestrial runoff is one hypothesis for recent enrichment in bulk nitrogen isotope (δ 15 N) values, a tracer for nutrient source, observed in a Gulf of Mexico deep-sea coral record. However, unambiguously linking anthropogenic land use change to whole scale shifts in downstream Gulf of Mexico biogeochemical cycles is difficult. Here we present a novel approach, coupling a new tracer of agro-industrialization to a multiproxy record of nutrient loading in long-lived deep-sea corals collected in the Gulf of Mexico. We found that coral bulk δ 15 N values are enriched over the last 150–200 years relative to the last millennia, and compound-specific amino acid δ 15 N data indicate a strong increase in baseline δ 15 N of nitrate as the primary cause. Coral rhenium (Re) values are also strongly elevated during this period, suggesting that 34% of Re is of anthropogenic origin, consistent with Re enrichment in major world rivers. However, there are no pre-anthropogenic measurements of Re to confirm this observation. For the first time, an unprecedented record of natural and anthropogenic Re variability is documented through coral Re records. Taken together, these novel proxies link upstream changes in water quality to impacts on the deep-sea coral ecosystem.

Mississippi River Basin

Peralkaline- and calc-alkaline-hosted volcanogenic massive sulfide deposits of the Bonnifield District, East-Central Alaska

Volcanogenic massive sulfide (VMS) Zn-Pb-Cu-Ag-Au deposits of the Bonnifield mining district formed during Late Devonian-Early Mississippian magmatism along the western edge of Laurentia. The largest deposits, Dry Creek and WTF, have a combined resource of 5.7 million tonnes at 10% Zn, 4% Pb, 0.3% Cu, 300 grams per tonne (g/t) Ag, and 1.6 g/t Au. These polymetallic deposits are hosted in high field strength element (HFSE)- and rare-earth element (REE)-rich peralkaline (pantelleritic) metarhyolite, and interlayered pyritic argillite and mudstone of the Mystic Creek Member of the Totatlanika Schist Formation. Mystic Creek metarhyolite and alkali basalt (Chute Creek Member) constitute a bimodal pair that formed in an extensional environment. A synvolcanic peralkaline quartz porphyry containing veins of fluorite, sphalerite, pyrite, and quartz intrudes the central footwall at Dry Creek. The Anderson Mountain deposit, located ~32 km to the southwest, occurs within calc-alkaline felsic to intermediate-composition metavolcanic rocks and associated graphitic argillite of the Wood River assemblage. Felsic metavolcanic rocks there have only slightly elevated HFSEs and REEs. The association of abundant graphitic and siliceous argillite with the felsic volcanic rocks together with low Cu contents in the Bonnifield deposits suggests classification as a siliciclastic-felsic type of VMS deposit. Bonnifield massive sulfides and host rocks were metamorphosed and deformed under greenschist-facies conditions in the Mesozoic. Primary depositional textures, generally uncommon, consist of framboids, framboidal aggregates, and spongy masses of pyrite. Sphalerite, the predominant base metal sulfide, encloses early pyrite framboids. Galena and chalcopyrite accompanied early pyrite formation but primarily formed late in the paragenetic sequence. Silver-rich tetrahedrite is a minor late phase at the Dry Creek deposit. Gold and Ag are present in low to moderate amounts in pyrite from all of the deposits; electrum inclusions occur in Dry Creek sphalerite. Contents and ratios of trace elements in graphitic argillite that serve as proxies for the redox state of the bottom waters in the basin indicate that Dry Creek mineralization took place in suboxic to periodically anoxic bottom waters. Trace element data show higher contents of Tl-Mn-As in pyrite from the Anderson Mountain deposit compared to the Dry Creek or WTF deposits and thus suggest that Anderson Mountain may have formed at lower temperatures or under slightly more oxidizing conditions. No exact modern analogue for the tectonic setting of the Bonnifield VMS deposits is known, although the back-arc regions of the Okinawa Trough and Woodlark Basin satisfy the requirement for a submarine, extensional setting adjacent to a continental margin. Limited occurrences of peralkaline volcanic rocks occur in these two potential analogues, but the peralkalinity of those rocks is much less than that of the Mystic Creek Member metarhyolites in the Bonnifield district. The highly elevated trace element (e.g., Zr, Nb) contents of Mystic Creek metarhyolites suggest that a better analogue may be a submarine rifted continental margin. The calc-alkaline composition of the host rocks to the Anderson Mountain deposit suggests that mineralization there formed in a continental margin arc, outboard of the extended continental margin setting of the peralkaline-hosted Dry Creek and WTF deposits.

Alaska

Direct U-Pb dating of Cretaceous and Paleocene dinosaur bones, San Juan Basin, New Mexico: COMMENT

Based on U-Pb dating of two dinosaur bones from the San Juan Basin of New Mexico (United States), Fassett et al. (2011) claim to provide the first successful direct dating of fossil bones and to establish the presence of Paleocene dinosaurs. Fassett et al. ignore previously published work that directly questions their stratigraphic interpretations (Lucas et al., 2009), and fail to provide sufficient descriptions of instrumental, geochronological, and statistical treatments of the data to allow evaluation of the potentially complex diagenetic and recrystallization history of bone. These shortcomings lead us to question the validity of the U-Pb dates published by Fassett et al. and their conclusions regarding the existence of Paleocene dinosaurs.

New Mexico

Whole-rock and sulfide-mineral geochemical data for samples from volcanogenic massive sulfide deposits of the Bonnifield district, east-central Alaska

This Open-File Report presents geochemical data for outcrop and drill-core samples from volcanogenic massive sulfide deposits and associated metaigneous and metasedimentary rocks in the Wood River area of the Bonnifield mining district, northern Alaska Range, east-central Alaska. The data consist of major- and trace-element whole-rock geochemical analyses, and major- and trace-element analyses of sulfide minerals determined by electron microprobe and laser ablation&mdash;inductively coupled plasma&mdash;mass spectrometry (LA-ICP-MS) techniques. The PDF consists of text, appendix explaining the analytical methods used for the analyses presented in the data tables, a sample location map, and seven data tables. The seven tables are also available as spreadsheets in several file formats. Descriptions and discussions of the Bonnifield deposits are given in Dusel-Bacon and others (2004, 2005, 2006, 2007, 2010).

Alaska

The source of Witwatersrand gold: Evidence from uraninite chemistry

An in-situ LA-ICP-MS study of different generations of uraninite from the Mesoarchaean Witwatersrand gold palaeoplacer deposits revealed unusually high Au concentrations in rounded, detrital uraninite grains but no detectable Au in secondary, hydrothermally mobilised uraninite. A Au-enriched uraninite-bearing magmatic host is suggested as a significant source for detrital gold in the Witwatersrand sediments.

Conference Paper