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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Energy Efficiency Assistance for Galena Alaska

The City of Galena sits along the north bank of the Yukon River with no road access. Temperatures regularly reach negative 20°F in the winter and sunlight extends for up to 21 hours a day in the summer. Galena’s 400 residents, including members of the Koyukuk Athabascan culture, primarily use fuel oil and locally forested wood for heating and electricity generation. Because these resources are costly to obtain, local households have a high energy burden, spending 7% of their annual income on energy (averaging $4,000 per year). To reduce this burden, the City of Galena joined the U.S. Department of Energy’s (DOE) Remote Alaska Community Energy Efficiency (RACEE) Competition, where they received financial and technical assistance to implement energy savings solutions across their community, including building envelope improvements, solar panels, and LED lighting. Additionally, Galena installed new energy monitoring equipment to continue measuring the impacts of this work beyond the RACEE project.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2019

Electrochemical, Spectroscopic, and Computational Investigations on Redox Reactions of Selenium Species on Galena Surfaces

Despite previous studies investigating selenium (Se) redox reactions in the presence of semiconducting minerals, Se redox reactions mediated by galena (PbS) are poorly understood. In this study, the redox chemistry of Se on galena is investigated over a range of environmentally relevant Eh and pH conditions (+0.3 to −0.6 V vs. standard hydrogen electrode, SHE; pH 4.6) using a combination of electrochemical, spectroscopic, and computational approaches. Cyclic voltammetry (CV) measurements reveal one anodic/cathodic peak pair at a midpoint potential of +30 mV (vs. SHE) that represents reduction and oxidation between HSeO3− and H2Se/HSe−. Two peak pairs with midpoint potentials of −400 and −520 mV represent the redox transformation from Se(0) to HSe− and H2Se species, respectively. The changes in Gibbs free energies of adsorption of Se species on galena surfaces as a function of Se oxidation state were modeled using quantum-mechanical calculations and the resulting electrochemical peak shifts are (−0.17 eV for HSeO3−/H2Se, −0.07 eV for HSeO3−/HSe−, 0.15 eV for Se(0)/HSe−, and −0.15 eV for Se(0)/H2Se). These shifts explain deviation between Nernstian equilibrium redox potentials and observed midpoint potentials. X-ray photoelectron spectroscopy (XPS) analysis reveals the formation of Se(0) potentials below −100 mV and Se(0) and Se(−II) species at potentials below −400 mV.

Cook, Peter (ORCID:0000000193156255)↗
DOE OSTI2026

Lead Isotope Fingerprinting of Nanoscale Mineral Particles via Single Particle Inductively Coupled Plasma Mass Spectrometry

Determining lead (Pb) isotopic ratios is of broad interest across chemical disciplines for source tracing and age determinations, but the technique is inherently limited when multiple sources of Pb are present in a single sample. Single particle methods offer a solution to directly resolve multiple distinct isotopic ratios within individual samples. In this study, single particle inductively coupled plasma-mass spectrometry (spICP-MS) was performed using time-of-flight (TOF) and multicollector (MC)-based platforms to measure the Pb isotopic composition of individual nanoscale particles. Distinct Pb isotope ratios were measured in particles from four powdered galena samples of different origins (average single-particle 206Pb/207Pb ratios ranging from 0.91 to 1.28) using both the TOF and the MC-based platforms. Differentiation of galena particles in a mixture (liberated grains and those hosted in a silicate matrix) was possible due to detecting their unique multielemental fingerprints. The differing behavior of the two galena samples during digestion was investigated; undigested galena particles trapped within silicate minerals were detected using spICP-MS, which has implications for Pb recovery in bulk-scale isotopic analysis. The multinuclide detection capability of the ICP-TOF-MS instrument allowed for the simultaneous detection of secondary constituent elements within the nanoparticles and the identification of multiple populations of isotopically distinct Pb-bearing particles in a copper ore sample, whereas the increased sensitivity of the MC instrument enabled quantification of 204Pb, allowing differentiation using multiple isotopic ratios. A single particle isotope ratio analysis module was developed within an open-source spICP-TOF-MS data processing platform, enabling its adoption across chemical disciplines.

Goodman, Aaron J. [University of Montreal, Quebec,↗
DOE OSTI2021

Mineralogy-dependent sulfide oxidation via polysulfide and thiosulfate pathways during weathering of mixed-sulfide bearing mine waste rock

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O 2 and Fe 3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S 2– , $S_{2}O_{2}^{2–}$, S 8 , $S_{2}O_{3}^{2–}$, and $S_{2}O_{4}^{2–}$) in a weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S 8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S 8 and $S_{2}O_{3}^{2–}$), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

58 GEOSCIENCES↗
DOE OSTI2019

Six Quaternary Chalcogenides of the Pavonite Homologous Series with Ultralow Lattice Thermal Conductivity

Six new quaternary chalcogenides belonging to the pavonite sulfosalt mineral family with the general formula M n+1 (Bi/ Sb) 2 Q n+5 (n = 2-7) were synthesized by direct reactions of the elements at high temperatures. The compounds include InPbBi 3 S 7 (n = 2), In 0.5 Mn 2 Bi 3.5 Se 8 (n = 3), CdPb 2 Bi 4 S 9 (n = 4), Ag 1.5 CdBi 5.5 Se 10 (n = 5), Ag 2 CdBi 6 Se 11 (n = 6), and Ag 2.5 CdSb 6.5 Se 12 (n = 7) and crystallized in the monoclinic space group C2/m. The pavonite structure consists of two alternating slabs, a thinner slab composed of pairs of monocapped trigonal prisms separated by octahedra and a thicker slab with a galena-like structure motif. In the general formula, n corresponds to the number of octahedra along the diagonal direction of the galena-like slab. The complex compositions, mixed occupancies of the cations, and quasi-two-dimensional structures endow compounds of this family with extremely low thermal conductivity. Here, the charge and thermal transport properties of CdPb 2 Bi 4 S 9 and CdAg 2 Bi 6 Se 11 were characterized from 300 to 810 K, and both materials exhibited n-type semiconductor behaviors and ultralow lattice thermal conductivities of less than 0.35 W·m –1 ·K –1 for CdAg 2 Bi 6 Se 11 and 0.73 W·m –1 ·K –1 for CdPb 2 Bi 4 S 9 in the measured temperature range. Density functional theory calculations revealed the origins of this low lattice thermal conductivity to be a combination of the low Debye temperature, small phonon velocities, and large Grüneisen parameters. Thermoelectric properties were measured, and the highest ZT values of 0.53 and 0.95 for undoped CdPb 2 Bi 4 S 9 and CdAg 2 Bi 6 Se 11 , respectively, were attained at 775 K.

36 MATERIALS SCIENCE↗
NASA NTRS1973

Effects of atmospheric moisture on rock resistivity.

This study examines the changes in resistivity of rock samples as induced by atmospheric moisture. Experiments were performed on samples of hematitic sandstone, pyrite, and galena. The sandstone underwent a change in resistivity of four orders of magnitude when it was measured in a vacuum of 500 ntorr and in air of 37% relative humidity. Pyrite and galena showed no variations in resistivity when they were measured under the same conditions. These results, plus others obtained elsewhere, indicate that rocks of the resistive type are affected in their electrical properties by atmospheric moisture, whereas rocks of the conductive type are not. The experimental evidence obtained is difficult to reconcile with a model of aqueous electrolytic conduction on the sample surface. It is instead suggested that adsorbed water molecules alter the surface resistivity in a manner similar to that observed in semiconductors and insulators.

Alvarez, R.↗
DOE OSTI2014

TiO{sub 2} flower-like nanostructures decorated with CdS/PbS nanoparticles

Highlights: • TiO{sub 2} flower-like nanostructures were prepared with the use of Ti foil and 30% H{sub 2}O{sub 2}. • QDs of CdS and PbS were deposited using the SILAR method. • The SILAR method makes it possible to control the size of QDs. • Band gap energy of CdS was found to be 2.35 eV. • Sensitization of TiO{sub 2} with CdS or PbS improves the photoelectrochemical properties. - Abstract: Flower-like nanostructures of TiO{sub 2} were prepared by immersing Ti foil in 30% H{sub 2}O{sub 2} at 80 °C for times varying from 15 to 240 min. Upon annealing at 450 °C in an Ar atmosphere, the received amorphous samples crystallized in an anatase structure with rutile as a minority phase. SEM images revealed that partially formed flowers were present at the surface of the prepared samples as early as after 15 min of immersion. The size of the individual flowers increased from 400–800 nm after 15 min of reaction to 2.5–6.0 μm after 240 min. It was also found that surface is very rough and surface development is considerable. After 45 min of immersion, the nanoflowers were sensitized with CdS and PbS quantum dots (QDs-CdS/QDs-PbS) deposited using the SILAR method from water- and methanol-based precursor solutions at different concentrations (0.001–0.1 M). QDs-CdS crystallized in the hawleyite structure, while QDs-PbS in the galena form. SEM analysis showed the tendency of quantum dots to agglomerate at high concentrations of the precursor in water-based solutions. QDs obtained from methanol-based solutions were uniformly distributed. The produced QDs-PbS were smaller than QDs-CdS. Based on the optical reflectance spectra, the band-gap energies of TiO{sub 2} nanostructures with and without QDs were calculated to be 3.32 eV for flower-like TiO{sub 2} nanostructures and 2.35 eV for QDs-CdS. The photoelectrochemical behaviour of nanoflowers was found to improve significantly after the deposition of QDs-CdS.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Light in the darkening on Naica gypsum crystals

Naica mine is located in a semi-desertic region at the central-south of Chihuahua State. The Cave of Swords was discovered in 1910 and the Cave of Crystals 90 years later at Naica mines. It is expected that during the last century the human presence has changed the microclimatic conditions inside the cave, resulting in the deterioration of the crystals and the deposition of impurities on gypsum surfaces. As a contribution to the clarification of the mentioned issues, the present work refers to the use of synchrotron radiation for the identification of phases on these surfaces. All the experiments were performed at the Stanford Synchrotron Radiation Lightsource. Grazing incidence X-ray diffraction (GIXRD) and radiography-aided X-ray diffraction (RAXRD) experiments were performed at beamline 11-3. X-Ray micro-fluorescence (μ-SXRF) and micro-X-ray absorption (μ-XANES) were measured at beamline 2-3. Representative results obtained may be summarized as follows: a) Gypsum, galena, sphalerite, hematite and cuprite at the surface of the gypsum crystals were determined. b) The samples micro-structure is affected by impurities. c) The elemental distributions and correlations (0.6-0.9) of Cu, K, Fe, Mn, Pb, Zn, Ca and S were identified by μ-SXRF. The correlations among elemental contents confirmed the phase identification, with the exception of manganese and potassium due to the amorphous nature of some impurity compounds in these samples. The compounds hematite (Fe{sub 2}O{sub 3}), β-MnO{sub 2}, Mn{sub 2}O{sub 3}, MnO and/or MnCO{sub 3}, PbS, PbCO{sub 3} and/or PbSO4, ZnO{sub 4}, ZnS and/or smithsonite (ZnCO{sub 3}), CuS + Cu Oxide were identified by XANES. Plausibly, these latter compounds do not form crystalline phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Oxidation state and coordination environment of Pb in U-bearing minerals

This study examines the oxidation and coordination of lead (Pb) in the uranium (U) minerals uraninite (UO 2 ), coffinite (USiO 4 ), and brannerite (UTi 2 O 6 ), and minerals that have U as a minor constituent, zircon (ZrSiO 4 ) and titanite (CaTiSiO 5 ). The characterization of Pb was conducted through a combination of micro-synchrotron X-ray fluorescence mapping (µSXRF) and micro-X-ray absorption spectroscopy (µXAS), collected at the Pb L II and L III edge on characterized grains (electron microscopy and X-ray diffraction) from a range of geological settings and ages. For all minerals considered in this study, Pb L II and L III X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicate that Pb exists as Pb 2+ . In the case of uraninite, DFT structure optimization calculations suggest that the substitution of Pb 2+ for U 4+ is facilitated by the stereochemically active electron lone pair indicative of Pb 2+ , which effectively takes the place of an oxygen vacancy (coupled substitution Pb 2+ + = U 4+ + O 2- ). In detail, however, the EXAFS and XANES data, supported by first principle calculations of the XANES associated with Pb 2+ replacing U 4+ in the crystal lattice of uraninite, indicate that Pb 2+ is present in a less distorted coordination than suggested by DFT, which may reflect a yet to be characterized link between interstitial oxygen defects and Pb 2+ incorporation, rather than a simple oxygen vacancy. For coffinite, the XANES data demonstrate that Pb exists mainly as Pb 2+ in the form of galena, indicating limited stability of the isomorphous substitution in coffinite. In contrast, Pb is homogeneously distributed in the metamict mineral brannerite, which displays a distinct XANES spectrum suggestive of Pb 2+ bonded to oxygens in a highly distorted coordination environment. Pb L II XANES indicate that radiogenic Pb exists predominantly as Pb 2+ within the crystal lattice of zircon and as distinct mineral PbO nano-scale inclusions or domains. Additionally, Pb L II XANES measurements also indicate that Pb 2+ exists within titanite although the coordination environment is unclear. Overall, these data suggest that the previous indications of the presence of Pb 4+ in radioactive minerals need to be reconsidered. The nature of radiogenic Pb 2+ incorporation in U-bearing minerals controls the mobilization of Pb in hydrothermal fluids and the utility of a mineral as a geochronometer. The Pb valence and coordination data presented in this study provide fundamental constraints imperative for our understanding of the controls governing the mobilization of radiogenic Pb during water-rock interaction and metamorphism.

58 GEOSCIENCES↗
DOE OSTI2014

Metal-sulfide mineral ores, Fenton chemistry and disease. Particle induced inflammatory stress response in lung cells

The inhalation of mineral particulates and other earth materials, such as coal, can initiate or enhance disease in humans. Workers in occupations with high particulate exposure, such as mining, are particularly at risk. The ability of a material to generate an inflammatory stress response (ISR), a measure of particle toxicity, is a useful tool in evaluating said exposure risk. ISR is defined as the upregulation of cellular reactive oxygen species (ROS) normalized to cell viability. This study compares the ISR of A549 human lung epithelial cells after exposure to well-characterized common metal-sulfide ore mineral separates. The evaluation of the deleterious nature of ore minerals is based on a range of particle loadings (serial dilutions of 0.002 m 2 /mL stock) and exposure periods (beginning at 30 min and measured systematically for up to 24 h). There is a wide range in ISR values generated by the ore minerals. The ISR values produced by the sphalerite samples are within the range of inert materials. Arsenopyrite generated a small ISR that was largely driven by cell death. Galena showed a similar, but more pronounced response. Copper-bearing ore minerals generated the greatest ISR, both by upregulating cellular ROS and generating substantial and sustained cell death. Chalcopyrite and bornite, both containing ferrous iron, generated the greatest ISR overall. Particles containing Fenton metals as major constituents produce the highest ISR, while other heavy metals mainly generate cell death. Furthermore, this study highlights the importance of evaluating the chemistry, oxidation states and structure of a material when assessing risk management.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Molecular Dynamics Simulation and Analysis of Interfacial Water at Selected Sulfide Mineral Surfaces under Anaerobic Conditions

In this paper, we report on a molecular dynamics simulation (MDS) study of the behavior of interfacial water at selected sulfide mineral surfaces under anaerobic conditions. The study revealed the interfacial water structure and wetting characteristics of the pyrite (100) surface, galena (100) surface, chalcopyrite (012) surface, sphalerite (110) surface, and molybdenite surfaces (i.e., the face, armchair-edge, and zigzag-edge surfaces), including simulated contact angles, relative number density profiles, water dipole orientations, hydrogen-bonding, and residence times. For force fields of the metal and sulfur atoms in selected sulfide minerals used in the MDS, we used the universal force field (UFF) and another set of force fields optimized by quantum chemical calculations for interactions with interfacial water molecules at selected sulfide mineral surfaces. Simulation results for the structural and dynamic properties of interfacial water molecules indicate the natural hydrophobic character for the selected sulfide mineral surfaces under anaerobic conditions as well as the relatively weak hydrophobicity for the sphalerite (110) surface and two molybdenite edge surfaces. Part of the financial support for this study was provided by the U.S. Department of Energy (DOE) under Basic Science Grant No. DE-FG-03-93ER14315. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE, funded work performed by Liem X. Dang. Battelle operates Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES. The authors are grateful to Professor Tsun-Mei Chang for valuable discussions.

Jin, Jiaqi↗
DOE OSTI2025

Evidence for metal sources, fluid-mixing processes, and S isotope recycling within the feeder zone of an Irish type Zn-Pb deposit

The origin and evolution of fluids in Irish-type Zn-Pb deposits remains debated, particularly regarding the mobility of metals such as Cu and Ni, sources of sulphur, and the role of fluid mixing and replacement. The Lisheen Zn-Pb deposit, Ireland, offers a well-defined natural laboratory to investigate these questions. While most studies have focused on the Waulsortian Limestone Formation, the primary sulphide host, less is known about mineralisation in underlying units, such as the Lisduff Oolite Member (LOM). The LOM displays enrichment in Cu and Ni and displays intense replacement textures compared to other hosts at Lisheen, making it an ideal target for studying metal mobility and sulphur recycling in carbonate-hosted systems. Through characterising and studying LOM-hosted sulphides, valuable insights into mineralisation processes, especially related to Cu-Ni metals, can be defined. This study integrates petrography, EMPA, and in situ sulphur isotope (δ 34 S) analysis to investigate sulphide paragenesis, mineral chemistry, and fluid evolution across LOM ore zones. Results reveal a multistage mineralising system involving extensive replacement of early pyrite (Py0, δ 34 S = −28.4 to −21.9 ‰) by sphalerite and galena, with zoned pyrite (Py1) enriched in As-Cu-Ni-Tl. The δ 34 S values and trace element trends indicate mixing between hydrothermal and bacteriogenic sulphur-rich fluids, with evidence for sulphur recycling during replacement. Pyrite textures and compositions capture this evolving fluid regime, with trace element enrichment linked to paragenetic stage. The steel ore region, adjacent to major fault intersections, records intense hydrothermal fluid interaction, hosting Ni- and As-rich phases such as nickeline, gersdorffite, and arsenopyrite. These findings highlight the importance of structural controls and fluid mixing in metal transport and deposition, positioning the LOM as a key stratigraphic unit for understanding ore-forming processes in Irish-type systems. These results have implications for targeting similar carbonate-hosted systems globally, especially where deeper or structurally complex ore zones remain underexplored.

58 - GEOSCIENCES↗
DOE OSTI2021

Remote Alaska Communities Energy Efficiency Competition: Energy Efficiency for the Gem of the Yukon (Final Report)

Over the past decade, the City of Ruby has been proactive in working to reduce cost and energy use in the community. Ruby (Tl’aa’ologhe) is a remote city in Alaska located on the south bank of the Yukon River near the Kilbuck-Kuskokwim Mountains, about 50 air miles east of Galena and 230 air miles west of Fairbanks. As of 2019, the community has a population of over 150 people and most of Ruby’s residents are Koyukon Athabascan. Ruby has a long history of promoting local efficiency and clean energy in an effort to become more sustainable. Between 2007-2010, the community hosted Alaska’s first demonstration of an in-river hydrokinetic test project, sponsored by the Yukon River Inter-Tribal Watershed Council. In 2011, a 5kW solar photo-voltaic (PV) array was installed by the Interior Regional Housing Authority. In 2012, the community had a new power plant constructed by the Alaska Energy Authority that supplies waste heat to the washeteria, clinic and public safety garage, saving the community more than 4,000 gallons of heating fuel per year. The clinic, constructed by the Tanana Chiefs Conference, is one of the most energy efficient buildings in the interior and utilizes new building efficiency standards that were passed by the tribes. It has a 5kW solar PV array that provides energy into the local electric grid and offsets approximately 20% of the annual energy use. Building on this legacy, the City of Ruby entered into Department of Energy’s (DOE’s) Remote Alaska Communities Energy Efficiency Competition (RACEE) in 2016, pledging to reduce per-capita energy use 15% by 2020. During the second phase of the competition, 13 communities including Ruby were provided funding for tailored technical assistance to measure energy use and create energy efficiency plans.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2023

Single Crystal Growth of Synthetic Sulfide- and Phosphide-Based Minerals for Physical Measurements

In this work, we review recent advances in the use of high-temperature solution growth that allow for the growth of single crystalline samples of synthetic minerals. We outline how low-melting binary or ternary solutions are attractive solvents for solution growth and provide examples of the growth of bismuthinite (Bi 2 S 3 ), galena (PbS) and parkerite (Ni 3 Bi 2 S 2 ). We then focus on the Rh-S, Pd-S and Ni-P phase spaces to discuss how the low-melting regions near transition metal-main group eutectic compositions make excellent solvents for crystal growth of several binary and ternary minerals containing both high melting and volatile elements as well as for the discovery of new materials. We end by discussing the growth of synthetic canfieldite (Ag 8 SnS 6 ) and argyrodite (Ag 8 GeS 6 ) from Ag 2 S–Sn-S-based solutions.

58 GEOSCIENCES↗
NASA NTRS1981

Infrared spectra of some sulfides and their analogs of binary composition in the long-wave region

The far infrared spectra (500-60/cm) of some simple sulfides and their analogs were studied. In all, 22 minerals with different structure types were investigated, out of which 14 are sulfides (galena, alabandite, pyrrhotite, sphalerite, wurtzite, cinnabar, realgar, orpiment, getchelite antimonite, molybdenite, pyrite, marcasite and heazlewoodite) 6 arsenides (niccolite, domeykite, arsenopyrite, lollingite, rammelsbergite and skutterudite), one telluride (tetradymite) and native arsenic. The main bands of infrared absorption spectra of the minerals are compared with the relative strength of the interatomic bonds and their interpretation is given.

Povarennykh, A. S.↗
NASA NTRS1984

Investigation of the influence of the zeta-potential on the filtration rate in the presence of collectors

The value of the zeta-potential does not have an explicit effect, which is expressed by a simple math correlation, on filtration rate when a solution of the tested collector is filtered through a cake prepared under standard conditions from the examined particulate material. The zeta-potential measurements and filtration tests were carried out on silica and galena with solutions contg. a cationic container ANP and Et xanthane, resp. at PH = 6.5, varying concentration of the agent (0-2500 g/ton), and under a vacuum of 100 to 600 mm Hg.

Provirnina, E. V.↗