Karen D. Kelley

Environmental geochemistry of shale-hosted AgPbZn massive sulfide deposits in northwest Alaska: natural background concentrations of metals in water from mineralized areas

Abstract Red Dog, Lik and Drenchwater are shale-hosted stratiform Ag Pb Zn massive sulfide deposits in the northwestern Brooks Range. Natural background concentrations of metals in waters from the undisturbed (unmined) Drenchwater prospect and Lik deposit were compared to pre-mining baseline studies conducted at Red Dog. The primary factors affecting water chemistry are the extent of exposure of the deposits, the grade of mineralization, the presence of carbonate rocks in the section, and the proportion of Fe-sulfide in the ore. Surface water samples from the Drenchwater prospect, which has pyrite-dominant mineralization exposed in outcrop, have pH values as low as 2.8 and high dissolved concentrations of metals including as much as 95 mg l−1 Al, 270 mg l−1 Fe, 8 μl−1 Cd, 10 μl−1 Pb, and 2600 μl−1 Zn, with As up to 26 μgl−1. Surface waters from the Red Dog deposit prior to mining were also acidic and metal-rich, however, dissolved metal concentrations in Red Dog waters were many times greater. The higher metal concentrations in Red Dog waters reflect the high Zn grades and the abundant sphalerite, pyrite, and galena that were present in outcrop prior to mining. In contrast,l despite significant mineralization at the Lik deposit, carbonate rocks in the section buffer the system, resulting in less acidic, mostly near-neutral pH values with low concentrations of most metals except Zn.

Porphyry Cu indicator minerals in till as an exploration tool: example from the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA

ABSTRACT Porphyry Cu indicator minerals are mineral species in clastic sediments that indicate the presence of mineralization and hydrothermal alteration associated with porphyry Cu and associated skarn deposits. Porphyry Cu indicator minerals recovered from shallow till samples near the giant Pebble Cu-Au-Mo porphyry deposit in SW Alaska, USA, include apatite, andradite garnet, Mn-epidote, visible gold, jarosite, pyrite, and cinnabar. Sulphide minerals other than pyrite are absent from till, most likely due to the oxidation of the till. The distribution of till samples with abundant apatite and cinnabar suggest sources other than the Pebble deposit. With three exceptions, all till samples up-ice of the Pebble deposit contain <10 grains/10kg of garnet (0.25–0.5 mm). Samples in the immediate vicinity of the Pebble deposit contain 10–20 grains, whereas samples with the most grains (>40grains/10kg) are in close proximity to smaller porphyry and skarn occurrences in the region. The distribution of Mn-epidote closely mimics the distribution of garnet in the till samples and further supports the interpretation that these minerals most likely reflect skarns associated with the porphyry deposits. All but two till samples, including those up-ice from the deposit, contain some gold grains. However, tills immediately west and down-ice of Pebble contain more abundant gold grains, and the overall number of grains decreases in the down-ice direction. Furthermore, all samples in the immediate vicinity of Pebble contain more than 65 % pristine and modified grains compared to mostly re-shaped grains in distal samples. The pristine gold in till reflects short transport distances and/or liberation of gold during in-situ weathering of transported chalcopyrite grains. Jarosite is also abundant (1–2 500 grains/10kg) in samples adjacent to and up to 7 km down-ice from the deposit. Most jarosite grains are rounded and preliminary Ar/Ar dates suggest the jarosite formed prior to glaciation and it implies that a supergene cap existed over Pebble West. Assuming this interpretation is accurate, it suggests a shallow level of erosion of the Pebble deposit by glacial processes. Overall the results of this study indicate that porphyry Cu indicator minerals in till samples may be useful in the exploration for porphyry deposits in SW Alaska.

Coupled heat and fluid flow modeling of the CarboniferousKuna Basin, Alaska: implications for the genesis of the Red Dog PbZnAgBa ore district

The Red Dog deposit is a giant 175 Mton (16% Zn, 5% Pb), shale-hosted PbZnAgBa ore district situated in the Carboniferous Kuna Basin, Western Brooks Range, Alaska. These SEDEX-type ores are thought to have formed in calcareous turbidites and black mudstone at elevated sub-seafloor temperatures (120–150 °C) within a hydrogeologic framework of submarine convection that was structurally organized by large normal faults. The theory for modeling brine migration and heat transport in the Kuna Basin is discussed with application to evaluating flow patterns and heat transport in faulted rift basins and the effects of buoyancy-driven free convection on reactive flow and ore genesis. Finite element simulations show that hydrothermal fluid was discharged into the Red Dog subbasin during a period of basin-wide crustal heat flow of 150–160 mW/m2. Basinal brines circulated to depths as great as 1–3 km along multiple normal faults flowed laterally through thick clastic aquifers acquiring metals and heat, and then rapidly ascended a single discharge fault zone at rates ∼ 5 m/year to mix with seafloor sulfur and precipitate massive sulfide ores.

Trace elements in Zn–Pb–Ag deposits and related stream sediments, Brooks Range Alaska, with implications for Tl as a pathfinder element

ABSTRACT The Zn–Pb–Ag metallogenic province of the western and central Brooks Range, Alaska, contains two distinct but mineralogically similar deposit types: shale-hosted massive sulphide (SHMS) and smaller vein-breccia occurrences. Recent investigations of the Red Dog and Anarraaq SHMS deposits demonstrated that these deposits are characterized by high trace-element concentrations of As, Ge, Sb and Tl. This paper examines geochemistry of additional SHMS deposits (Drenchwater and Su-Lik) to determine which trace elements are ubiquitously elevated in all SHMS deposits. Data from several vein-breccia occurrences are also presented to see if trace-element concentrations can distinguish SHMS deposits from vein-breccia occurrences. Whole-rock geochemical data indicate that Tl is the most consistently and highly concentrated characteristic trace element in SHMS deposits relative to regional unmineralized rock samples. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of pyrite and sphalerite indicate that Tl is concentrated in pyrite in SHMS. Stream sediment data from the Drenchwater and Su-Lik SHMS show that high Tl concentrations are more broadly distributed proximal to known or suspected mineralization than As, Sb, Zn and Pb anomalies. This broader distribution of Tl in whole-rock and particularly stream sediment samples increases the footprint of exposed and shallowly buried SHMS mineralization. High Tl concentrations also distinguish SHMS mineralization from the vein-breccia deposits, as the latter lack high concentrations of Tl but can otherwise have similar trace-element signatures to SHMS deposits.

An exploration hydrogeochemical study at the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA, using high-resolution ICP-MS

A hydrogeochemical study using high resolution ICP-MS was undertaken at the giant Pebble porphyry Cu-Au-Mo deposit and surrounding mineral occurrences. Surface water and groundwater samples from regional background and the deposit area were collected at 168 sites. Rigorous quality control reveals impressive results at low nanogram per litre (ng/l) levels. Sites with pH values below 5.1 are from ponds in the Pebble West area, where sulphide-bearing rubble crop is thinly covered. Relative to other study area waters, anomalous concentrations of Cu, Cd, K, Ni, Re, the REE, Tl, SO42− and F− are present in water samples from Pebble West. Samples from circum-neutral waters at Pebble East and parts of Pebble West, where cover is much thicker, have anomalous concentrations of Ag, As, In, Mn, Mo, Sb, Th, U, V, and W. Low-level anomalous concentrations for most of these elements were also found in waters surrounding nearby porphyry and skarn mineral occurrences. Many of these elements are present in low ng/l concentration ranges and would not have been detected using traditional quadrupole ICP-MS. Hydrogeochemical exploration paired with high resolution ICP-MS is a powerful new tool in the search for concealed deposits.

Metal dispersion and mobility in soils from the Lik Zn–Pb–Ag massive sulphide deposit, NW Alaska: environmental and exploration implications

The Lik deposit in northern Alaska is a largely unexposed shale-hosted Zn–Pb–Ag massive sulphide deposit that is underlain by continuous permafrost. Residual soils overlying the mineralized zone have element enrichments that are two to six times greater than baseline values. The most prominent elements are Ag, Mo, P, Se, Sr, V by total 4-acid digestion and Tl by a weak partial digestion (Enzyme Leach or EL) because they show multi-point anomalies that extend across the entire mineralized zone, concentration ranges are 0.5–2.6 ppm Ag, 4–26 ppm Mo, 0.1–0.3% P, 3–22 ppm Se, 90–230 ppm Sr, 170–406 ppm V, and 1.6–30 ppb Tl. Lead, Sb, and Hg are also anomalous (up to 178 ppm, 30 ppm, and 1.9 ppm, respectively), but all are characterized by single point anomalies directly over the mineralized zone, with only slightly elevated concentrations over the lower mineralized section. Zinc (total) has a consistent baseline response of 200 ppm, but it is not elevated in soils overlying the mineralized zone. However, Zn by EL shows a distinct single-point anomaly over the ore zone that suggests it was highly mobile and partly adsorbed on oxides or other secondary phases during weathering. In situ analyses (by laser ablation ICP-MS) of pyrite and sphalerite from drill core suggest that sphalerite is the primary residence for Ag, Cd, and Hg in addition to Zn, and pyrite contains As, Fe, Sb, and Tl. The level and degree of oxidation, and the proportion of reacting pyrite and carbonate minerals are two factors that affected the mobility and transport of metals. In oxidizing conditions, Zn is highly mobile relative to Hg and Ag, perhaps explaining the decoupling of Zn from the other sphalerite-hosted elements in the soils. Soils are acidic (to 3.9 pH) directly over the deposit due to the presence of acid-producing pyrite, but acid-neutralizing carbonate away from the mineralized zone yield soilsthat are near neutral. The soils therefore formed in a complex system involving oxidation and weathering (mechanical and chemical) of sulphide minerals, dissolution of carbonate minerals, and precipitation of iron and manganese oxide minerals.

Reconnaissance exploration geochemistry in the central Brooks Range, northern Alaska: Implications for exploration of sediment-hosted zinc-lead-silver deposits

Abstract A reconnaissance geochemical survey was conducted in the southern Killik River quadrangle, central Brooks Range, northern Alaska. The Brooks Range lies within the zone of continuous permafrost which may partially inhibit chemical weathering and oxidation. The minus 30-mesh and nonmagnetic heavy-mineral concentrate fractions of sediment samples were chosen as the sample media for the survey so that mechanical rather than chemical dispersion patterns would be enhanced. A total of 263 sites were sampled within the southern half of the Killik River quadrangle at an average sample density of approximately one sample per 12 km 2 . All samples were submitted for multi-element analyses. In the western and central Brooks Range, several known sediment-hosted Zn-Pb-Ag(-Ba) deposits occur within a belt of Paleozoic rocks of the Endicott Mountains allochthon. Exploration for this type of deposit in the Brook Range is difficult, due to the inherently high background values for Ba, Zn and Pb in shale and the common occurrence of metamorphic quartz-calcite veins, many of which contain traces of sulfide minerals. Stream sediments derived from these sources produce numerous geochemical anomalies which are not necessarily associated with significant mineralization. R-mode factor analysis provides a means of distinguishing between element associations related to lithology and those related to possible mineralization. Factor analysis applied to the multi-element data from the southern Killik River quadrangle resulted in the discovery of two additional Zn-Pb-Ag mineral occurrences of considerable areal extent which are 80–100 km east of any previously known deposit. These have been informally named the Kady and Vidlee. Several lithogeochemical element associations, or factors, and three factors which represent sulfide mineralization were identified: Ag-Pb-Zn (galena and sphalerite) and Fe-Ni-Co-Cu (pyrite ± chalcopyrite) in the concentrate samples and Cd-Zn-Pb-As-Mn in the sediment samples. The distribution of high scores for each individual mineralization factor outlined several relatively large (200–250 km 2 ) geochemically favorable areas. When the distribution of high scores for all three factors were superimposed, samples characterized by high scores for one or both of the concentrate mineralization factors and the mineralization factor in sediments define basin areas of approximately 48 and 64 km 2 surrounding Kady and Vidlee, respectively.

Mineral information at micron to kilometer scales: Laboratory, field, and remote sensing imaging spectrometer data from the orange hill porphyry copper deposit, Alaska, USA

Using imaging spectrometers at multiple scales, the USGS, in collaboration with the University of Alaska, is examining the application of hyperspectral data for identifying large-tonnage, base metal-rich deposits in Alaska. Recent studies have shown this technology can be applied to regional mineral mapping [1] and can be valuable for more local mineral exploration [2]. Passive optical remote sensing of high latitude regions faces many challenges, which include a short acquisition season and poor illumination due to low solar elevation [3]. Additional complications are encountered in the identification of surface minerals useful for mineral resource characterization because minerals of interest commonly are exposed on steep terrain, further challenging reflectance retrieval and detection of mineral signatures. Laboratory-based imaging spectrometer measurements of hand samples and field-based imaging spectrometer scans of outcrop are being analyzed to support and improve interpretations of remote sensing data collected by airborne imaging spectrometers and satellite multispectral sensors.

Investigation of the potential for concealed base-metal mineralization at the Drenchwater Creek Zn-Pb-Ag occurrence, northern Alaska, using geology, reconnaissance geochemistry, and airborne electromagnetic geophysics

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Geochemistry of Sediments and Sedimentary Rocks: Evolutionary Considerations to Mineral Deposit- Forming Environmentsby David Lentz (ed.), Geological Association of Canada, GeoText 4, 2004, 184 pp. US

How can geochemistry be applied to our understanding of the formation and evolution of sedimentary rocks and sedimentary basins? Collectively, the ten papers included in this book address this question and suggest that geochemistry is important for (a) understanding changes that take place in the diagenetic environment, (b) interpreting provenance and developing crustal evolutionary models, (c) dating sedimentary rocks, and (d) understanding the genetic relationships between sedimentary ore deposits and their associated sedimentary sequences. The introduction by David Lentz is a good historical perspective and review of the use of geochemistry in sedimentary rock research that provides perspective for the more data-specific papers that follow. However, a clearer picture of the primary goals of the book and how the papers were chosen would have been useful to help a reader understand the common theme that threads the papers together. The paper by S. McLennan et al. shows the significance that geochemistry can …