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Carlin J. Green

Publications and source records attributed to Carlin J. Green.

6 recordsLinked to original sources

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis↗

Tungsten skarn potential of the Yukon-Tanana Upland, eastern Alaska, USA—A mineral resource assessment

Tungsten (W) is used in a variety of industrial and technological applications and has been identified as a critical mineral for the United States, India, the European Union, and other countries. These countries rely on W imports mostly from China, which leaves them vulnerable to supply disruption. Consequently, the U.S. government has a current initiative to understand domestic resource potential. The eastern Alaska portion of the Yukon-Tanana Upland (YTU), is prospective for W skarn deposits, the major source of global W supply. The regional geology consists of juxtaposed Paleozoic lithotectonic packages that were reaccreted to North America in the Mesozoic . Multiple subsequent episodes of arc-related magmatism intruded the lithotectonic packages, accompanied by W skarn formation mostly associated with 100–90 Ma intrusions; major W skarn deposits in Canada are part of the same metallogenic event (e.g., Mactung, Cantung). In this paper, we present an assessment for undiscovered W skarn resources for parts of the lesser-explored western (Alaskan) portion of the YTU. We used GIS proximity analysis to map the intersection of pluton and carbonate-bearing rocks to define three permissive tracts for W skarn deposits. The permissive tracts were qualitatively assessed by mineral potential mapping using region-wide sediment geochemistry and mineral concentrate datasets. This analysis showed that much of the western YTU has high potential for undiscovered W skarn deposits, whereas the eastern and southern YTU had only isolated areas of medium to high potential. Historical production and the quality of the geochemistry data of the western YTU tract (ca. 9200 km 2 ) permitted a quantitative assessment of undiscovered W resources. Probabilistic estimates by a panel of 20 experts predicted a 70% chance of one to three undiscovered W skarn deposits in the western YTU tract. The rationale for favorability employed by the expert panel included favorable lithology, previous production, clustering of previously mined deposits, W placers in the area, lack of recent exploration, pan concentrates containing W minerals, and W geochemical anomalies. Estimates were combined with a global grade and tonnage model for W skarns in a Monte Carlo simulation and provided a median estimate of undiscovered resources of 94 kt WO 3 . If the undiscovered W skarn deposits are located close to infrastructure (e.g., near Fairbanks, or close to roads and/or power grid), application of an economic filter indicates that the median total economically recoverable WO 3 is 63 kt with a net present value (NPV) of $330 million USD (2008 dollars). Whereas if deposits are far from infrastructure, median recoverable WO 3 is only 30 kt and the NPV is $44 million. Our models for contained WO 3 resources and NPV estimates for the western YTU tract are considerably lower than the known resources in skarns in adjacent areas in Canada. Estimates for the western YTU are also lower than preliminary estimates for undiscovered W skarn deposits in areas of the western conterminous United States. We speculate that lower permeability and continuity of favorable carbonate rock horizons in the relatively higher-grade metamorphic country rocks in the Alaska portion of the YTU may explain some of the differences in prospectivity. More detailed geologic mapping, modern geochemistry, and geophysical surveys are needed to refine the resource potential of the whole YTU. Regardless, quantitative mineral resource assessment provides a useful tool for making first-order regional estimates of undiscovered resources, identifying target areas for new data acquisition, and guiding research on the fundamental controls of district-scale metallogenic endowments.

Alaska↗

Behavior of potentially toxic elements from stoker-boiler fly ash in Interior Alaska: Paired batch leaching and solid-phase characterization

Despite significant investigation of fly ash spills and mineralogical controls on the release of potentially toxic elements (PTEs) from fly ash, interactions with the surficial environment remain relatively poorly understood. We conducted 90-day batch leaching studies with paired analysis of supernatant and solid-phase mineralogy to assess the elemental release and transformation of fly ash upon reaction with aquatic media (18 MΩ cm −1 water and simulated rainwater). The fly ash in this study, collected from the University of Alaska Fairbanks stoker-boiler power plant, is high in unburned carbon (~20% LOI) and highly enriched in several PTEs relative to the upper continental crust. Supernatant concentrations of oxyanion-forming elements (e.g., As, Se, Mo, Sb) remained relatively low and constant, suggesting equilibrium with the solid phase, possibly ettringite [Ca 6 Al 2 (SO 4 ) 3 (OH) 12 •26H 2 O], which is known to incorporate and sorb oxyanion-forming PTEs and was identified by X-ray diffraction. Synthetic precipitation leaching procedure (SPLP) results failed to capture important temporal trends. Lead and Ba supernatant concentrations consistently exceeded drinking water standards, as well as others upon exposure to simulated physiological solutions. Seven-day experiments with dissolved organic matter-isolate solutions indicated that for certain elements, liberation was influenced by carbon concentration and/or the identity of the isolate. Overall, this paired approach can serve as a model for future studies, bridging existing gaps between batch leaching and single-element mineralogical, sorption, or speciation studies.

Alaska↗

Grade and tonnage model for tungsten skarn deposits—2020 update

This report presents an updated grade and tonnage model for tungsten skarn deposits. As a critical component of the U.S. Geological Survey’s three-part form of quantitative mineral resource assessment, robust grade and tonnage models are essential to transforming mineral resource assessments into effective tools for decision makers. Using the best data available at the time of publication, this represents the first attempt in nearly 30 years to capture current mineral inventory and cumulative production data for worldwide tungsten skarn deposits. The accuracy of modern assessments of undiscovered tungsten skarn resources is highly influenced by the use of current data on the distribution of the grades and tonnages of well-explored tungsten skarn deposits. Primary factors affecting the changes to these distributions in the model presented here compared with those of previous models are the inclusion of important deposits, especially those in China that had been omitted in previous models; expanded mineral inventories resulting from increased exploration; and changes to international reporting standards. These factors have resulted in dramatic increases in average ore tonnage and slight decreases in the average grade of tungsten skarn deposits compared with previous models. Large increases in contained metal are observed among many of the individual deposits incorporated within this model that were also included in previous tungsten skarn grade and tonnage models. This report also provides recommendations for input parameters related to grade and tonnage models to use with software tools designed to facilitate the three-part form of quantitative mineral resource assessments.

Scientific Investigations Report↗

Geochemical characterization of iron and steel slag and its potential to remove phosphate and neutralize acid

Iron and steel slags from legacy and modern operations in the Chicago-Gary area of Illinois and Indiana, USA, are predominantly composed of Ca (10 - 44 wt. % CaO), Fe, (0.3 - 28 wt. % FeO), and Si (10 - 44 wt. % SiO2), with generally lesser amounts of Al (< 1 15 wt. % Al2O3), Mg (2 11 wt. % MgO), and Mn (0.3 9 wt. % MnO). Mineralogy is dominated by CaMgAl silicates, FeCa oxides, Ca-carbonates, and high temperature SiO2 phases. Chromium and Mn concentrations in most samples may be environmentally significant based on comparison with generic soil contaminant guidelines. However, simulated weathering tests suggest these elements are present in generally insoluble phases making use in water treatment applications possible; generation of high pH and alkaline solutions may be an issue. As for water treatment applications, batch and flow-through experiments document effective removal of phosphate from synthetic solutions for nearly all slag samples. Air-cooled fine fractions (< 10 mm) of modern slag were most effective; other types, including modern granulated, modern air-cooled coarse fractions (> 10 mm), and legacy slag removed phosphate, but to a lesser degree. An additional water treatment application is the use of slag to neutralize acidic waters. Most slag samples are extremely alkaline and have high net neutralization potentials (NNP) (400 830 kg CaCO3/t), with the highest approximately equivalent to 80% the neutralization potential of calcite. Overall, phosphate removal capacity and NNP correlate positively with total Ca content and the dissolution of Ca minerals facilitates secondary Ca phosphate formation and consumes acid during hydrolysis. Utilizing locally available slag to treat waste or agricultural waters in this region may be a higher value alternative than use in construction, potentially offsetting restoration costs to degraded legacy areas and decreasing steel manufacturers current waste footprint.

Minerals↗