Geology topics
Sarah M. Hayes
Publications and source records attributed to Sarah M. Hayes.
Critical minerals in mine waste
Introduction Critical minerals are commodities with vulnerable supply chains that play a vital role in supporting the United States’ economy, national defense and security, emerging technologies, and energy independence. The prosperity of our Nation depends on generating a resilient supply of domestic critical minerals; mine waste may be an untapped source of these commodities. Mine waste from centuries of legacy mining persist on the landscape and may contain critical minerals and other valuable commodities previously deemed uneconomic to recover. At modern mines, the financial viability of recovering byproduct critical minerals, which are not the primary target, may be marginal and can ultimately destine them to mine waste. Further, mine waste can be a liability for the mining company or, at legacy mines, the taxpayer because of its effect on the landscape. The U.S. Geological Survey (USGS) has several initiatives to evaluate critical mineral resources in various types of waste. This factsheet highlights studies of mine waste carried out by USGS scientists at the Geology, Energy & Minerals Science Center in collaboration with other science centers funded through the USGS Mineral Resources Program. Recovery of critical minerals from mine waste can aid in remediation efforts and increase domestic supply of vital mineral resources.
Editorial: Micro-to nano-analytical challenges towards trace element characterization of ore minerals: New perspectives and applications for sustainable georesources
No abstract available.
A novel non-destructive workflow for examining germanium and co-substituents in ZnS
A suite of complementary techniques was used to examine germanium (Ge), a byproduct critical element, and co-substituent trace elements in ZnS and mine wastes from four mineral districts where germanium is, or has been, produced within the United States. This contribution establishes a comprehensive workflow for characterizing Ge and other trace elements, which captures the full heterogeneity of samples through extensive pre-characterization. This process proceeded from optical microscopy, to scanning electron microscopy and cathodoluminescence (CL) imaging, to electron microprobe analysis, prior to synchrotron-based investigations. Utilizing non-destructive techniques enabled reanalysis, which proved essential for verifying observations and validating unexpected results. In cases where the Fe content was <0.3 wt% in ZnS, cathodoluminescence imaging proved to be an efficient means to qualitatively identify trace element zonation that could then be further explored by other micro-focused techniques. Micro-focused X-ray diffraction was used to map the distribution of the non-cubic ZnS polymorph, whereas micro-focused X-ray fluorescence (μ-XRF) phase mapping distinguished between Ge 4+ hosted in primary ZnS and a weathering product, hemimorphite [Zn 4 Si 2 O 7 (OH) 2 ·H 2 O]. Microprobe data and μ-XRF maps identified spatial relationships among trace elements in ZnS and implied substitutional mechanisms, which were further explored using Ge and copper (Cu) X-ray absorption near-edge spectroscopy (XANES). Both oxidation states of Ge (4+ and 2+) were identified in ZnS along with, almost exclusively, monovalent Cu. However, the relative abundance of Ge oxidation states varied among mineral districts and, sometimes, within samples. Further, bulk XANES measurements typically agreed with micro-focused XANES (μ-XANES) spectra, but unique micro-environments were detected, highlighting the importance of complementary bulk and micro-focused measurements. Some Ge μ-XANES utilized a high energy resolution fluorescence detector, which improved spectral resolution and spectral signal-to-noise ratio. This detector opens new opportunities for exploring byproduct critical elements in complex matrices. Overall, the non-destructive workflow employed here can be extended to other byproduct critical elements to more fully understand fundamental ore enrichment processes, which have practical implications for critical element exploration, resource quantification, and extraction.
Germanium redistribution during weathering of Zn mine wastes: Implications for environmental mobility and recovery of a critical mineral
Germanium (Ge) is a metal used in emerging energy technologies, communications, and defense, and has been deemed critical by the United States due to its essential applications and scarce supply. Germanium is recovered as a byproduct of zinc (Zn) sulfides, and mining and processing of these materials lead to waste that could act both as a source of extractable Ge and a source for exposure to humans and ecosystems. Yet the distribution, speciation, and mineral hosts of Ge in mining-impacted areas are poorly understood. The Tar Creek Superfund Site, a former Zn mining area and Ge producer, is a natural laboratory to understand the environmental behavior and economic implications of Ge in mine wastes. We studied the distribution and behavior of Ge in solid wastes at the Tar Creek Superfund Site using bulk and microanalytical techniques. In wastes at this site we find that Ge has been redistributed from its original host, sphalerite (ZnS), to the fine-grained weathering product hemimorphite (Zn4Si2O7(OH)2·H2O), which impacts germanium's mobility, bioaccessibility, and potential for recovery. We provide chemical and mineralogical evidence of this redistribution, along with an evaluation of the oxidation state and molecular-scale substitution of Ge into sphalerite, hemimorphite, and quartz. Geochemical modeling shows that hemimorphite is more stable than sphalerite in waste piles and provides a stable secondary repository for Ge. However, hemimorphite is fine-grained, and if ingested or inhaled is readily soluble, with the potential to release Ge. Lastly, we discuss other sites internationally where similar behavior may be important. This study shows that weathering can have a significant impact on the distribution, speciation, and mineral hosts of Ge in mine wastes; directly influence mobilization from waste piles and subsequent availability to humans and ecosystems; and dictate metallurgical strategies to target Ge for recovery.
Global tellurium supply potential from electrolytic copper refining
The transition towards renewable energy requires increasing quantities of nonfuel mineral commodities, including tellurium used in certain photovoltaics. While demand for tellurium may increase markedly, the potential to increase tellurium supply is not well-understood. In this analysis, we estimate the quantity of tellurium contained in anode slimes generated by electrolytic copper refining by country between 1986 and 2018, including uncertainties. For 2018, the results indicate that 1930 (1500-2700, 95% confidence interval) metric tons of tellurium were contained in anode slimes globally. This is nearly quadruple the reported tellurium production for that year. China has the greatest potential to increase tellurium supplies. However, most of the tellurium potentially recoverable by Chinese refineries appears to come from copper mined elsewhere. Further research into the business decisions associated with tellurium recovery may help translate the physical availability of tellurium into economic availability. The methodology presented here can be applied to other byproduct elements.
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.
The role of hydrates, competing chemical constituents, and surface composition on CLNO2 formation
Atomic chlorine (Cl • ) affects air quality and atmospheric oxidizing capacity. Nitryl chloride (ClNO 2 ) – a common Cl • source–forms when chloride-containing aerosols react with dinitrogen pentoxide (N 2 O 5 ). A recent study showed that saline lakebed (playa) dust is an inland source of particulate chloride (Cl – ) that generates high ClNO 2 . However, the underlying physiochemical factors responsible for observed yields are poorly understood. To elucidate these controlling factors, we utilized single particle and bulk techniques to determine the chemical composition and mineralogy of playa sediment and dust samples from the southwest United States. Single particle analysis shows trace highly hygroscopic magnesium and calcium Cl-containing minerals are present and likely facilitate ClNO 2 formation at low humidity. Single particle and mineralogical analysis detected playa sediment organic matter that hinders N 2 O 5 uptake as well as 10 Å-clay minerals (e.g., Illite) that compete with water and chloride for N 2 O 5 . Finally, we show that the composition of the aerosol surface, rather than the bulk, is critical in ClNO 2 formation. These findings underscore the importance of mixing state, competing reactions, and surface chemistry on N 2 O 5 uptake and ClNO 2 yield for playa dusts and, likely, other aerosol systems. Therefore, consideration of particle surface composition is necessary to improve ClNO 2 and air quality modeling.
The effects of phosphatization on the mineral associations and speciation of Pb in ferromanganese crusts
The older layers of thick ferromanganese (FeMn) crusts from the central Pacific Ocean have undergone diagenetic phosphatization, during which carbonate fluorapatite (CFA) filled fractures and pore space and replaced carbonates. The effects of phosphatization on individual trace metal concentrations, speciation, and phase associations in FeMn crusts remain poorly understood yet may be important to metal enrichment mechanisms, paleoceanography, and extractive metallurgy. This study examines the concentrations, speciation, and mineral phase associations of Pb in phosphatized and nonphosphatized layers within three Pacific Ocean crusts using standard chemical and mineralogical techniques, in addition to bulk X-ray absorption spectroscopy (XAS) and microfocused X-ray fluorescence (μ-XRF) mapping. Our findings challenge the conclusions of previous works, which reported that most Pb in phosphatized crusts was associated with the CFA-dominated residual phase after sequential leaching experiments. These results were interpreted as an indication of Pb transfer from the oxide phases to diagenetic CFA during phosphatization. However, our results reveal an inverse correlation of Pb with Ca and P in the μ-XRF mapping of in situ FeMn crust sections and bulk chemistry. Furthermore, XAS measurements reveal that Pb speciation in bulk phosphatized FeMn crust layers is very similar to nonphosphatized layers, indicating only minor, if any, change in speciation during diagenetic phosphatization. Small differences in the EXAFS spectra for one highly phosphatized layer indicate that minor amounts of Pb may have been altered during phosphatization, but the new Pb-bearing phase was not unequivocally identified. Taken together, our results demonstrate that Pb speciation is not significantly affected by phosphatization.
Surficial geochemistry and bioaccessibility of tellurium in semi-arid mine tailings
Tellurium (Te) is a critical element due to its use in solar technology. However, some forms are highly toxic. Few studies have examined Te behavior in the surficial environment, thus little is known about its potential human and environmental health impacts. This study characterizes two physicochemically distinct Te-enriched mine tailings piles (big and flat tailings) deposited by historic gold (Au) mining in the semi-arid Delamar mining district, Nevada. The big tailings are characterized by smaller particle size and higher concentrations of potentially toxic elements (up to 290 mg Te kg-1), which are enriched at the tailings surface. In contrast, the flat tailings have larger particle size and properties that are relatively invariant with depth. Based on the sulfate to sulfide ratio, the tailings were determined to be sulfate dominated suggesting a high degree of weathering, although the flat tailings did contain significant amounts of sulfides (~40%). Tellurium x-ray absorption spectroscopy of the big tailings indicates that tellurate, the less toxic Te species, is the principal form of Te. Electron microscopy indicates that most of the Te present at the site is associated with iron (oxy)hydroxides, sometimes with other potentially toxic elements, especially lead and antimony. Physiologically-based extraction tests indicate that substantially more Te is solubilized in synthetic stomach fluids than in lung fluids, with gastric bioaccessibility ranging from 13-31% of total Te. This points to low to medium bioaccessibility, which is common for iron (oxy)hydroxide associated elements. Together, these results represent a preliminary assessment of Te surficial behavior in a semi-arid environment and indicate that Te in these tailings represent a moderate health concern.
Evaluating the utility of principal component analysis on EDS x-ray maps to determine bulk mineralogy
Due to advances in EDS technology, electron microscopy techniques have become an important tool to determine the relative abundance of mineral phases. However, few studies have directly compared EDS X‐ray mineralogy with traditional techniques for assessing bulk mineralogy and elemental composition. We show that analysing a limited area (~ 0.5–3.2 mm 2 ) of fine‐grained metal extraction samples using EDS X‐ray principal component analysis phase mapping yields results that agree within 10% with more traditional techniques for mineral phases present at greater than 5% m / m . Electron beam sensitive minerals, such as the carbonates, have poor correlations between EDS and X‐ray Diffraction (XRD) and/or WD‐XRF. Likewise, poor correlations between methods can be expected for particles that are smaller than the interaction volume of the electron beam (~ 1.5 µm); this strongly affected the phyllosilicates. One strength of EDS phase mapping is that it can identify phases present below the detection limit of powder XRD (< 1%). Our results demonstrate that EDS phase mapping is sufficient to estimate bulk sample mineralogy. If polished thin sections have been prepared, this approach may save time and/or money relative to the more traditional approaches of preparing separate subsamples for XRD and/or WD‐XRF.
Critical minerals: A review of elemental trends in comprehensive criticality studies
Mineral criticality is a subjective concept that has evolved throughout history. An abundance of literature on this topic has been published over the last decade, encompassing a variety of criteria and methodologies. To our knowledge, this work is the first large-scale effort to organize and analyze recent comprehensive criticality studies in order to determine if a consensus exists within the global community as to which elements are critical. Here, we set aside methodological differences and analyze the results of 32 comprehensive nonfuel mineral criticality studies that evaluate at least 10 elements. Of the 56 elements or elemental groups evaluated, the three most commonly identified as critical in these studies are the rare-earth elements (REE), the platinum-group metals (PGM), and indium. Most of the studies also identify tungsten, germanium, cobalt, niobium , tantalum, gallium, and antimonyas critical. These results are consistent with the 11 most recent studies, published post-2014, which also identify bismuth as critical. Furthermore, the same elements identified in the complete dataset, except antimony, were designated as critical when normalized by geographic region. Magnesium was also deemed critical. Elements may be identified consistently as critical for several reasons; similarities in methodologies, which embody evolving perceptions of risk, or changing national and institutional priorities. This work compiles a large number of recent criticality studies in an effort to define a consensus of currently critical materials, essentially defining the modern criticality paradigm, which is valuable when interpreting an individual perspective in more global context.