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Materials Data on HgS by Materials Project

HgS is Cinnabar structured and crystallizes in the trigonal P3_121 space group. The structure is one-dimensional and consists of one HgS ribbon oriented in the (0, 0, 1) direction. Hg2+ is bonded in a distorted linear geometry to two equivalent S2- atoms. Both Hg–S bond lengths are 2.39 Å. S2- is bonded in a distorted water-like geometry to two equivalent Hg2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on HgS by Materials Project

HgS is Cinnabar structured and crystallizes in the trigonal P3_221 space group. The structure is one-dimensional and consists of one HgS ribbon oriented in the (0, 0, 1) direction. Hg2+ is bonded in a distorted linear geometry to two equivalent S2- atoms. Both Hg–S bond lengths are 2.39 Å. S2- is bonded in a distorted water-like geometry to two equivalent Hg2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on HgS by Materials Project

HgS is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Hg2+ is bonded to six equivalent S2- atoms to form a mixture of edge and corner-sharing HgS6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Hg–S bond lengths are 2.79 Å. S2- is bonded to six equivalent Hg2+ atoms to form a mixture of edge and corner-sharing SHg6 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗

Materials Data on HgS by Materials Project

HgS is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. Hg2+ is bonded to four equivalent S2- atoms to form corner-sharing HgS4 tetrahedra. All Hg–S bond lengths are 2.60 Å. S2- is bonded to four equivalent Hg2+ atoms to form corner-sharing SHg4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on HgS by Materials Project

HgS is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. Hg2+ is bonded to four equivalent S2- atoms to form corner-sharing HgS4 tetrahedra. There are three shorter (2.60 Å) and one longer (2.61 Å) Hg–S bond lengths. S2- is bonded to four equivalent Hg2+ atoms to form corner-sharing SHg4 tetrahedra.

36 MATERIALS SCIENCE↗

Sonochemical oxidation and stabilization of liquid elemental mercury in water and soil

Over 3000 mercury (Hg)-contaminated sites worldwide contain liquid metallic Hg [Hg(0) 1 ] representing a continuous source of elemental Hg(0) in the environment through volatilization and solubilization in water. Currently, there are few effective treatment technologies available to remove or sequester Hg(0) 1 in situ. We investigated sonochemical treatments coupled with complexing agents, polysulfide and sulfide, in oxidizing Hg(0) 1 and stabilizing Hg in water, soil and quartz sand. Results indicate that sonication is highly effective in breaking up and oxidizing liquid Hg(0) 1 beads via acoustic cavitation, particularly in the presence of polysulfide. Without complexing agents, sonication caused only minor oxidation of Hg(0) 1 but increased headspace gaseous Hg(0) g and dissolved Hg(0) aq in water. However, the presence of polysulfide essentially stopped Hg(0) volatilization and solubilization. As a charged polymer, polysulfide was more effective than sulfide in oxidizing Hg(0) 1 and subsequently stabilizing the precipitated metacinnabar (β-HgS) nanocrystals. Sonochemical treatments with sulfide yielded incomplete oxidation of Hg(0) 1 , likely resulting from the formation of HgS coatings on the dispersed µm-size Hg(0) 1 bead surfaces. Sonication with polysulfide also resulted in rapid oxidation of Hg(0) 1 and precipitation of HgS in quartz sand and in the Hg(0) 1 -contaminated soil. This research indicates that sonochemical treatment with polysulfide could be an effective means in rapidly converting Hg(0) 1 to insoluble HgS precipitates in water and sediments, thereby preventing its further emission and release to the environment. We suggest that future studies are performed to confirm its technical feasibility and treatment efficacy for remediation applications.

36 MATERIALS SCIENCE↗

Mercury sequestration in alkaline salt low-level radioactive waste

Liquid low-level radioactive waste at the Savannah River Site contains several species of mercury, including inorganic, elemental and methylmercury. This waste is solidified and stabilized in a cementitious waste form referred to as saltstone. Soluble mercury is stabilized as β-cinnabar, HgS as the result of reaction between the mercury and sulfur present in blast furnace slag, one of the cementitious regents. In this investigation, Mersorb®, a commercial granular activated carbon impregnated with sulfur, was evaluated as a pretreatment to remove mercury from the solution prior to cementation. Mersorb® was found to remove more than 96 mass percent of the methylmercury in simulated tank waste solution when the mass ratio of Mersorb® to mercury was above 2.5. Slag sequestered relatively more inorganic mercury than organic mercury in simulated tank waste after 24 hours of contact. This is likely due to the mercury-carbon bond being more covalent than the mercury-oxygen bond and therefore more difficult to break and slower to form HgS.

Cementitious Material↗

The use and abuse of cinnabar in Late Neolithic and Copper Age Iberia

Abstract In this study, total mercury (THg) was analyzed in archaeological human bone from 23 sites dating to between the Middle Neolithic and the Antiquity. A total of 370 individuals from individual or collective burials was sampled, mostly using cortical bone from the humerus. These individuals were recovered from over 50 different funerary structures ranging from tholoi, pits, caves, and hypogea. Although cinnabar (HgS) is a likely cause of mercury poisoning and toxicity for people exposed to this mineral from mining or use as a paint or pigment, not all sites investigated here had cinnabar associated with the burials or other excavated areas. We found unusual levels of THg in many of the sampled individuals that we assume were caused by exposure to cinnabar in life, and not by diagenetic processes or other exposures to mercury such as through diet, which would only cause negligible accumulation of THg in bone. Our data, based on the largest sampling ever undertaken on contamination of human bone through archaeological evidence, provide a baseline for additional research on cinnabar and its use in Prehistory. Moderate to high levels of THg in human bone are mainly associated with societies dating from the second half of the 4th to late 3rd millennia B.C. (Late Neolithic to Middle Chalcolithic) in southern Iberia. By the Late Chalcolithic and Early Bronze Age, the use of cinnabar decreased significantly and became minimal or absent. The use and abuse of cinnabar appears to have been pervasive throughout the above‐mentioned period and particularly between c. 2900–2300 B.C. This occurred in connection with the high symbolic and probably sacred value of the substance, which was sought after, traded, and extensively used in a variety of rituals and social practices.

Emslie, Steven D.↗

Isotope Exchange between Mercuric [Hg(II)] Chloride and Hg(II) Bound to Minerals and Thiolate Ligands: Implications for Enriched Isotope Tracer Studies

Enriched mercury (Hg) stable isotopes have been widely used as tracers in field and laboratory investigations of Hg(II) biogeochemical transformations such as methylation and demethylation. Few studies, however, have considered concurrent isotope exchange reactions between newly spiked and pre-existing Hg(II) in environmental matrices, which may alter redistribution and thus transformation of the spiked and pre-existing Hg(II). Using enriched 198 Hg [as mercuric Hg(II) or HgCl n species], this study investigated isotope exchange between 198 Hg and pre-existing Hg(II) bound to metacinnabar (β-HgS), sediments, low-molecular-weight (LMW) thiols, and dissolved organic matter (DOM). The impact of isotope exchange on methylmercury production in the presence of organic ligands was also evaluated with an iron-reducing bacterium Geobacter sulfurreducens PCA in a phosphate buffered solution (pH 7.4). Here, we found that spiked 198 Hg readily exchanged with mineral-bound ambient Hg(II) despite concurrent Hg(II) adsorption and immobilization on the solids. Rapid exchange (<3 min) was also observed between spiked 198 Hg and 200 Hg pre-equilibrated with LMW thiols and DOM in solution. While the exchange did not cause net changes in Hg(II) chemical speciation, it resulted in redistribution of Hg(II) isotopes bound to the ligands and thus an apparently similar methylation rate and magnitude of the spiked 198 Hg and pre-existing 200 Hg by PCA cells when 198 Hg and 200 Hg were added at 1:1 ratio. These observations underscore the importance of isotope exchange when an enriched Hg isotope is applied in environmental matrices, as the exchange could potentially lead to biased rate calculations of Hg(II) transformation and bioaccumulation and thus risk assessments of new Hg(II) input to the natural ecosystems.

58 GEOSCIENCES↗

Mercury Reduction, Uptake, and Species Transformation by Freshwater Alga Chlorella vulgaris under Sunlit and Dark Conditions

As a major entry point of mercury (Hg) to aquatic food webs, algae play an important role in taking up and transforming Hg species in aquatic ecosystems. However, little is known how and to what extent Hg reduction, uptake, and species transformations are mediated by algal cells and their exudates, algal organic matter (AOM), under either sunlit or dark conditions. In this study, using Chlorella vulgaris (CV) as one of the most prevalent freshwater model algal species, we show that solar irradiation could enhance the reduction of mercuric Hg(II) to elemental Hg(0) by both CV cells and AOM. AOM reduced more Hg(II) than algal cells themselves due to cell surface adsorption and uptake of Hg(II) inside the cells under solar irradiation. Synchrotron radiation X-ray absorption near-edge spectroscopy (SR-XANES) analyses indicate that sunlight facilitated the transformation of Hg to less bioavailable species, such as β-HgS and Hg-phytochelatins, compared to Hg(Cysteine) 2 -like species formed in algal cells in the dark. These findings highlight important functional roles and potential mechanisms of algae in Hg reduction and immobilization under varying lighting conditions and how these processes may modulate Hg cycling and bioavailability in the aquatic environment.

54 ENVIRONMENTAL SCIENCES↗

Dynamics of pectic homogalacturonan in cellular morphogenesis and adhesion, wall integrity sensing and plant development

Homogalacturonan (HG) is the most abundant pectin subtype in plant cell walls. Although it is a linear homopolymer, its modification states allow for complex molecular encoding. HG metabolism affects its structure, chemical properties, mobility and binding capacity, allowing it to interact dynamically with other polymers during wall assembly and remodelling and to facilitate anisotropic cell growth, cell adhesion and separation, and organ morphogenesis. HGs have also recently been found to function as signalling molecules that transmit information about wall integrity to the cell. Here we highlight recent advances in our understanding of the dual functions of HG as a dynamic structural component of the cell wall and an initiator of intrinsic and environmental signalling. Here, we also predict how HG might interconnect the cell wall, plasma membrane and intracellular components with transcriptional networks to regulate plant growth and development.

59 BASIC BIOLOGICAL SCIENCES↗

WHOLESCALE: Seismic Survey Data from San Emidio Nevada 2021

This dataset includes raw and processed seismic data from the 2021 seismic survey at the San Emidio geothermal field in Nevada. In April and May 2021, 37 tri-axial short period seismographs were deployed in a 1.8km diameter cluster centered on 40.367278 N, 119.409019 W. The first data record started at 2021-04-06T07:09:10Z UTC and the last record ended at 2021-05-11T02:58:52Z UTC. The 37 stations included 29 SmartSolo IGU-16HR 3C all-in-one 5 Hz seismographs and 8 DataCube seismographs with 4.5 Hz HGS HG-6(B coil) tri-axial geophones. The raw format (level 0) data includes 353 GB of 500 sps SmartSolo data in native DLD format, 113 GB of 400 sps DataCube data in native DataCube format, and 3.4 GB of GPS data collected during the RTK GPS survey. The SAC data (level 1) files include 564 GB of hourly SAC files. The experiment was designed to monitor seismic activity before, during, and after the planned three-day plant maintenance shutdown April 19-21, 2021. The pumping stopped at 2021/04/19 12:51:45 UTC and resumed about 2021/04/21 21:00:00 UTC. The dataset is hosted in an AWS data lake, with an associated GDR data set providing the metadata. Links to both of these resources are included below. Additionally, this collection features data and metadata from a 2016 seismic survey at the same site for comparative analysis.

15 GEOTHERMAL ENERGY↗

WHOLESCALE: Seismic Survey Metadata from San Emidio Nevada 2021

This is a collection of metadata from the 2021 seismic survey at the San Emidio geothermal field in Nevada. In April and May 2021, 37 tri-axial short period seismographs were deployed in a 1.8km diameter cluster centered on 40.367278 deg N, 119.409019 deg W. The first data record started at 2021-04-06T07:09:10Z UTC and the last record ended 2021-05-11T02:58:52Z UTC. The 37 stations included 29 SmartSolo IGU-16HR 3C all-in-one 5 Hz seismographs and 8 DataCube seismographs with 4.5 Hz HGS HG-6(B coil) tri-axial geophones. The raw format (level 0) data includes 353 GB of 500 sps SmartSolo data in native DLD format, 113 GB of 400 sps DataCube data in native DataCube format, and 3.4 GB of GPS data collected during the RTK GPS survey. The SAC data (level 1) files include 564 GB of hourly SAC files. The experiment was designed to monitor seismic activity before, during, and after the planned three-day plant maintenance shutdown April 19-21, 2021. The pumping stopped at 2021/04/19 12:51:45 UTC and resumed about 2021/04/21 21:00:00 UTC. The raw and processed data are in an associated GDR submission, linked below. The metadata here includes files containing experiment details, station locations, seismic data logger specifications, instrumentation specifications, and descriptions of data. Also included are data and metadata from a 2016 seismic survey at the same site.

15 GEOTHERMAL ENERGY↗

Investigation of mechanochemical interactions of hydrogen with earth materials in a subsurface gas storage

The goal of this project is to investigate the molecular interactions of H 2 with earth materials (EMs) that may potentially affect economics and safety of H 2 geological storage (HGS). We investigated (1) the H 2 intercalation into interlayers of phyllosilicates, (2) the competitive adsorption of H 2 /CH 4 onto porous materials, and (3) solubility of H 2 in interfacial and confined hydrocarbons. Our results indicate that (i) H 2 intercalation into hydrated interlayers is thermodynamically unfavorable and H 2 solubility in hydrated clay interlayers is in the same order of magnitude as that in bulk water, (ii) CH 4 outcompetes H 2 in adsorption onto kerogen, due to stronger CH 4 -kerogen interactions than H 2 -kerogen interactions, (iii) H 2 tends to dissolve more in oil than in water, and the introduction of CO 2 as a cushion gas reduces H 2 partitioning near the kaolinite surfaces. The outcomes provide foundational knowledge for preparing the USA for future storage site selection and storage system design, supporting DOE missions in clean and secured energy.

08 HYDROGEN↗