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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Corrosion interactions between stainless steel and lead vanado-iodoapatite nuclear waste form part II

This paper studied the release of iodine from lead vanado-iodoapatite (I-APT, Pb 9.85 (VO 4 ) 6 I 1.7 ), a potential nuclear waste form for the radioactive waste element of I-129, which can be enhanced when crevice corrosion of stainless steel (SS) occurring nearby. Reference corrosion studies of I-APT were performed in different bulk solutions including DI water, 0.6 M and 6 M NaCl, and 0.1 M HNO 3 without metal crevice corrosion interactions. The localized enrichment of Cl – , one of the major consequences of SS crevice corrosion, was found to be the decisive factor that led to the enhanced release of iodine. A surface alteration layer consisting of a mixture of nanocrystalline I-APT and Cl-rich apatite (Cl-APT) formed on I-APT surface. Meanwhile, large Cl-APT crystals formed at the crevice mouth on the I-APT surface. This study reveals a new near-field corrosion mechanism for ceramic waste forms when they are exposed to aggressive local corrosive conditions created by the electrochemical reactions of nearby metals. The insight gained in this study could be beneficial for a more accurate prediction of waste form degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Accessing crystal–crystal interaction forces with oriented nanocrystal atomic force microscopy probes

Biominerals serve as crucial structures of living systems and play an important role for biochemical processes. Understanding their crystallization mechanisms is therefore central to many areas of biology, biogeoscience and biochemistry. Some biominerals, such as bone and dentin, are hierarchical nanocomposite structures constructed by sequentially added individual oriented nanocrystals. The driving forces that enable this oriented assembly are still poorly understood, with advances in understanding limited in part by the availability of techniques that can precisely measure the delicate interactions between nanocrystals, as a function of their separation distance and mutual orientation. Here we provide a novel and comprehensive protocol for i.) fabricating oriented single nanocrystal atomic force microscopy (AFM) probes using focus ion beam (FIB) milling - probes that are capable of accessing the nanoscale forces between oriented single-crystal faces, and ii.) performing oriented nanocrystal interaction force measurements using dynamic force spectroscopy (DFS) and environmental transmission electron microscopy (ETEM)-AFM techniquqes. These methods have recently led to seminal breakthroughs in force quantification for understanding oriented aggregation at the nanoscale. First, we detail two FIB milling based methods to fabricate AFM nanocrystal probes. One method requires careful pre-coating with a protective layer to avoid FIB damage to the face of interest, which is later chemically removed, and the other entails removal of the FIB damage layer with in situ polishing. We illustrate how to fabricate oriented nanocrystal force probes using commercial bulk crystals or nano/micro-crystals of calcite, zinc oxide, and rutile; the methods are fully transferrable to the apatites comprising bone minerals. The typical protocol for fabricating one AFM crystal probe takes 2-3 h. Finally, we describe how to measure interaction forces between nanocrystals in solution conditions of interest by performing AFM based DFS, or in the controlled environment of ETEM, using the resulting oriented nanocrystal probes. In addition, we illustrate how to quantify the direction-specific interaction forces for a given pair of interacting oriented nanocrystal faces, and how to relate this information generally to understanding crystallization by particle attachment.

Zhang, Xin (ORCID:000000032000858X)↗
DOE OSTI2017

Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth

Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soil depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Galápagos tortoise stable isotope ecology and the 1850s Floreana Island Chelonoidis niger niger extinction

A consequence of over 400 years of human exploitation of Galápagos tortoises (Chelonoidis niger ssp.) is the extinction of several subspecies and the decimation of others. As humans captured, killed, and/or removed tortoises for food, oil, museums, and zoos, they also colonized the archipelago resulting in the introduction of invasive plants, animals, and manipulated landscapes for farming, ranching, and infrastructure. Given current conservation and revitalization efforts for tortoises and their habitats, here we investigate nineteenth and twentieth century Galápagos tortoise dietary ecology using museum and archaeological specimens coupled with analysis of carbon (δ 13 C collagen and δ 13 Capatite), nitrogen (δ 15 N), hydrogen (δD) and oxygen (δ 18 O apatite ) stable isotopes and radiocarbon dating. We identify that Galápagos tortoise diets vary between and within islands over time, and that long-term anthropogenic impacts influenced change in tortoise stable isotope ecology by using 57 individual tortoises from 10 different subspecies collected between 1833 and 1967—a 134-year period. On lower elevation islands, which are often hotter and drier, tortoises tend to consume more C 4 vegetation (cacti and grasses). Our research suggests human exploitation of tortoises and anthropogenic impacts on vegetation contributed to the extinction of the Floreana Island tortoise (C. n. niger) in the 1850s.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Iron and iron-bound phosphate accumulate in surface soils of ice-wedge polygons in arctic tundra

Phosphorus (P) is a limiting or co-limiting nutrient to plants and microorganisms in diverse ecosystems that include the arctic tundra. Certain soil minerals can adsorb or co-precipitate with phosphate, and this mineral-bound P provides a potentially large P reservoir in soils. Iron (Fe) oxyhydroxides have a high capacity to adsorb phosphate; however, the ability of Fe oxyhydroxides to adsorb phosphate and limit P bioavailability in organic tundra soils is not known. In this study, we examined the depth distribution of soil Fe and P species in the active layer (<30 cm) of low-centered and high-centered ice-wedge polygons at the Barrow Environmental Observatory on the Alaska North Slope. Soil reservoirs of Fe and P in bulk horizons and in narrower depth increments were characterized using sequential chemical extractions and synchrotron-based X-ray absorption spectroscopy (XAS). Organic horizons across all polygon features ( e.g. , trough, ridge, and center) were enriched in extractable Fe and P relative to mineral horizons. Soil Fe was dominated by organic-bound Fe and short-range ordered Fe oxyhydroxides, while soil P was primarily associated with oxides and organic matter in organic horizons but apatite and/or calcareous minerals in mineral horizons. Iron oxyhydroxides and Fe-bound inorganic P (P i ) were most enriched at the soil surface and decreased gradually with depth, and Fe-bound P i was >4× greater than water-soluble P i . These results demonstrate that Fe-bound P i is a large and ecologically important reservoir of phosphate. We contend that Fe oxyhydroxides and other minerals may regulate P i solubility under fluctuating redox conditions in organic surface soils on the arctic tundra.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Amyloid-like amelogenin nanoribbons template mineralization via a low-energy interface of ion binding sites

Protein scaffolds direct the organization of amorphous precursors that transform into mineralized tissues, but the templating mechanism remains elusive. Motivated by models for the biomineralization of tooth enamel, wherein amyloid-like amelogenin nanoribbons guide the mineralization of apatite filaments, we investigated the impact of nanoribbon structure, sequence, and chemistry on amorphous calcium phosphate (ACP) nucleation. Using full-length human amelogenin and peptide analogs with an amyloid-like domain, films of β-sheet nanoribbons were self-assembled on graphite and characterized by in situ atomic force microscopy and molecular dynamics simulations. All sequences substantially reduce nucleation barriers for ACP by creating low-energy interfaces, while phosphoserines along the length of the nanoribbons dramatically enhance kinetic factors associated with ion binding. Furthermore, the distribution of negatively charged residues along the nanoribbons presents a potential match to the Ca–Ca distances of the multi-ion complexes that constitute ACP. These findings show that amyloid-like amelogenin nanoribbons provide potent scaffolds for ACP mineralization by presenting energetically and stereochemically favorable templates of calcium phosphate ion binding and suggest enhanced surface wetting toward calcium phosphates in general.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Determination of fluorine distribution in shark teeth by laser-induced breakdown spectroscopy

Quantifying the chemical composition of fast-growing hard tissues in the environment can shed valuable information in terms of understanding ecosystems both prehistoric and current. Changes in chemical composition can be correlated with environmental conditions and can provide information about the organism's life. Sharks can lose 0.1 to 1.1 teeth/day, depending on species, which offers a unique opportunity to record environmental changes over a short duration of time. Shark teeth contain a biomineral phase that is made up of fluorapatite [Ca 5 (PO 4 ) 3 F], and the F distribution within the tooth can be correlated to tooth hardness. Typically, this is determined by bulk acid digestion, energy-dispersive X-ray spectroscopy (EDS), or wavelength-dispersive spectroscopy. Here we present laser-induced breakdown spectroscopy (LIBS) as an alternative and faster approach for determining F distribution within shark teeth. Using a two-volume laser ablation chamber (TwoVol3) with innovative embedded collection optics for LIBS, shark teeth were investigated from sand tiger (Carcharias Taurus), tiger (Galeocerdo Cuvier), and hammerhead sharks (Sphyrnidae). Fluorine distribution was mapped using the CaF 603 nm band (CaF, Β 2 Σ + → X 2 Σ + ) and quantified using apatite reference materials. In addition, F measurements were cross referenced with EDS analyses to validate the findings. Distributions of F (603 nm), Na (589 nm), and H (656 nm) within the tooth correlate well with the expected biomineral composition and expected tooth hardness. This rapid methodology could transform the current means of determining F distribution, particularly when large sample specimens (350 mm 2 , presented here) and large quantities of specimens are of interest.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Combined computed tomography and position-resolved X-ray diffraction of an intact Roman-era Egyptian portrait mummy

Hawara Portrait Mummy 4, a Roman-era Egyptian portrait mummy, was studied with computed tomography (CT) and with CT-guided synchrotron X-ray diffraction mapping. These are the first X-ray diffraction results obtained non-invasively from objects within a mummy. The CT data showed human remains of a 5-year-old child, consistent with the female (but not the age) depicted on the portrait. Physical trauma was not evident in the skeleton. Diffraction at two different mummy-to-detector separations allowed volumetric mapping of features including wires and inclusions within the wrappings and the skull and femora. Additionally, the largest uncertainty in origin determination was approximately 1.5 mm along the X-ray beam direction, and diffraction- and CT-determined positions matched. Diffraction showed that the wires were a modern dual-phase steel and showed that the 7 × 5 × 3 mm inclusion ventral of the abdomen was calcite. Tracing the 00.2 and 00.4 carbonated apatite (bone's crystalline phase) reflections back to their origins produced cross-sectional maps of the skull and of femora; these maps agreed with transverse CT slices within approximately 1 mm. Coupling CT and position-resolved X-ray diffraction, therefore, offers considerable promise for non-invasive studies of mummies.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Assessment of diagenesis in archaeological human second metacarpal bones using the intensity of the small angle X-ray scattering D -period peak

Bone consists mainly of carbonated apatite (cAp) nanoplatelets embedded in a matrix of collagen fibrils. Earlier, high-energy small angle X-ray scattering (SAXS) studies of archaeological adult human second metacarpal bones (mc2) found collagen D-period peaks with high-intensity I D in specimens in which microcomputed tomography (microCT) showed little diagenesis and I D ~ 0 for specimens where microCT revealed severe diagenesis (Park et al. 2022 Int. J. Osteoarchaeol. 32, 170–181 (doi:10.1002/oa.3053); Stock et al. 2022 Int. J. Osteoarchaeol. 32, 120–131 (doi:10.1002/oa.3049)). Here, the present paper uses SAXS at beamline 1-ID, Advanced Photon Source, Argonne National Laboratory and other techniques to study a set of 10 mc2 from an early Medieval cemetery at Greding, Germany. We hypothesized that non-invasive measurement of I D would provide an accurate and rapid (approx. 6 min/specimen) assessment of diagenesis in archaeological mc2. Results of Raman spectroscopy, laboratory microCT and backscattered electron, reflected light and polarized transmitted light microscopies confirmed the SAXS determinations, but lattice parameter values from X-ray diffraction were uncorrelated with I D value. Age-at-death estimates placed the 10 mc2 in three age categories (young adult, middle adult, old adult): lattice parameters from X-ray diffraction were uncorrelated with age at death. Cross-sectional bone area fraction from microCT dropped noticeably for the older age cohort.

Raman spectroscopy↗
DOE OSTI2019

Precision lattice parameter determination from transmission diffraction of thick specimens with irregular cross sections

Accurate determination of lattice parameters from X-ray diffraction requires that the diffraction angles be measured very precisely, and significant errors result if the sample–detector separation differs from that assumed. Transmission diffraction from bones, which have a complex cross section and must be left intact, is a situation where this separation is difficult to measure and it may differ from position to position across the specimen. Here, this article describes a method for eliminating the effect of variable sample cross section. Diffraction patterns for each position on the specimen are collected before and after 180° rotation about an axis normal to the cross section of interest. This places the centroid of the diffracting mass at the center of rotation and provides the absolute lattice parameters from the average apparent lattice parameters at the two rotation angles. Diffraction patterns were collected across the cross section of three specimens: a 3D-printed elliptical cylinder of Hyperelastic Bone (HB), which is composed primarily of synthetic hydroxyapatite (hAp), a 3D-printed HB model of the second metacarpal bone (Mc2), and a modern human Mc2 containing nanocrystalline carbonated apatite (cAp). Rietveld refinement was used to determine precise unit-cell parameters a apparent and c apparent for each pattern of each scan, and these values determined the actual average < a > and < c > for each sample. In conclusion, the results indicate that the 0°/180° rotation method works well enough to uncover variations approaching 1 × 10 -3 Å in cAp unit-cell parameters in intact bones with irregular cross sections.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Polymorphism of Pb 5 (PO 4 ) 3 OH δ within the LK-99 mixture

During the synthetic exploration targeting the polycrystalline compound LK-99, an unexpected phase, Pb 5 (PO 4 ) 3 OH δ , was identified as a byproduct. We elucidated the composition of this compound through single-crystal X-ray diffraction analysis. Subsequent synthesis of the target compounds was achieved via high-temperature solid-state pellet reactions. The newly identified Pb 5 (PO 4 ) 3 OH δ has an orthorhombic crystal structure with space group Pnma , representing a unique structure differing from the hexagonal apatite phases of Pb 10 (PO 4 ) 6 O and Pb 5 (PO 4 ) 3 OH. Comprehensive temperature- and magnetic-field-dependent magnetization studies unveiled a temperature-independent magnetic characteristic of Pb 5 (PO 4 ) 3 OH δ . Solid-state nuclear magnetic resonance spectroscopy was employed to decipher the origins of the phase stability and confirm the presence of hydrogen atoms in Pb 5 (PO 4 ) 3 OH δ . These investigations revealed the presence of protonated oxygen sites, in addition to the interstitial water molecules within the structure, which may play critical roles in stabilizing the orthorhombic phase.

Xu, Mingyu (ORCID:0000000171386009)↗
DOE OSTI2019

Burial and exhumation of the Hoh Xil Basin, northern Tibetan Plateau: Constraints from detrital (U‐Th)/He ages

Abstract The uplift and associated exhumation of the Tibetan Plateau has been widely considered a key control of Cenozoic global cooling. The south‐central parts of this plateau experienced rapid exhumation during the Cretaceous–Palaeocene periods. When and how the northern part was exhumed, however, remains controversial. The Hoh Xil Basin (HXB) is the largest late Cretaceous–Cenozoic sedimentary basin in the northern part, and it preserves the archives of the exhumation history. We present detrital apatite and zircon (U‐Th)/He data from late Cretaceous–Cenozoic sedimentary rocks of the western and eastern HXB. These data, combined with regional geological constraints and interpreted with inverse and forward model of sediment deposition and burial reheating, suggest that the occurrence of ca. 4–2.7 km and ca. 4–2.3 km of vertical exhumation initiated at ca. 30–25 Ma and 40–35 Ma in the eastern and western HXB respectively. The initial differential exhumation of the eastern HXB and the western HXB might be controlled by the oblique subduction of the Qaidam block beneath the HXB. The initial exhumation timing in the northern Tibetan Plateau is younger than that in the south‐central parts. This reveals an episodic exhumation of the Tibetan Plateau compared to models of synchronous Miocene exhumation of the entire plateau and the early Eocene exhumation of the northern Tibetan Plateau shortly after the India–Asia collision. One possible mechanism to account for outward growth is crustal shortening. A simple model of uplift and exhumation would predict a maximum of 0.8 km of surface uplift after upper crustal shortening during 30–27 Ma, which is insufficient to explain the high elevations currently observed. One way to increase elevation without changing exhumation rates and to decouple uplift from upper crustal shortening is through the combined effects of continental subduction, mantle lithosphere removal and magmatic inflation.

Dai, Jin‐Gen↗
DOE OSTI2023

Metasomatic alteration of coarse‐grained igneous calcium‐aluminum‐rich inclusions from CK3 carbonaceous chondrites

Abstract We report on the primary and secondary mineralogies of three coarse‐grained igneous calcium‐aluminum‐rich inclusions (CAIs) (Compact Type A [CTA], Type B [B], and forsterite‐bearing type B [FoB]) from the Northwest Africa (NWA) 5343 (CK3.7) and NWA 4964 (CK3.8) carbonaceous chondrites, compare them with the mineralogy of igneous CAIs from the Allende (CV3.6) chondrite, and discuss the nature of the alteration processes that affected the CK and CV CAIs. The primary mineralogy and mineral chemistry of the CK3 CAIs studied are similar to those from Allende; however, primary melilite and anorthite are nearly completely absent. Although the secondary minerals identified in CK CAIs (Al‐diopside, andradite, Cl‐apatite, clintonite, forsterite, ferroan olivine, Fe,Ni‐sulfides, grossular, ilmenite, magnetite, plagioclase, spinel, titanite, and wadalite) occur also in the Allende CAIs, there are several important differences: (i) In addition to melilite and anorthite, which are nearly completely replaced by secondary minerals, the alteration of CK CAIs also affected high‐Ti pyroxenes (fassaite and grossmanite) characterized by high Ti 3+ /Ti 4+ ratio and spinel. These pyroxenes are corroded and crosscut by veins of Fe‐ and Ti‐bearing grossular, Fe‐bearing Al,Ti‐diopside, titanite, and ilmenite. Spinel is corroded by Fe‐bearing Al‐diopside and grossular. (ii) The secondary mineral assemblages of grossular + monticellite and grossular + wollastonite, commonly observed in the Allende CAIs, are absent; the Fe‐bearing grossular + Fe‐bearing Al‐diopside ± Fe,Mg‐spinel, Fe‐bearing grossular + Fe,Mg‐olivine ± Fe,Mg‐spinel, and Ca,Na‐plagioclase + Fe‐bearing Al‐diopside + Fe‐bearing grossular assemblages are present instead. These mineral assemblages are often crosscut by veins of Fe‐bearing Al‐diopside, Fe,Mg‐olivine, Fe,Mg‐spinel, and Ca,Na‐plagioclase. The coarse‐grained secondary grossular and Al‐diopside often show multilayered chemical zoning with distinct compositional boundaries between the layers; the abundances of Fe and Ti typically increase toward the grain edges. (iv) Sodium‐rich secondary minerals, nepheline and sodalite, commonly observed in the peripheral portions of the Allende CAIs, are absent; Ca,Na‐plagioclase is present instead. We conclude that coarse‐grained igneous CAIs from CK3.7–3.8 s and Allende experienced an open‐system multistage metasomatic alteration in the presence of an aqueous solution–infiltration metasomatism. This process resulted in localized mobilization of all major rock‐forming elements: Si, Ca, Al, Ti, Mg, Fe, Mn, Na, K, and Cl. The metasomatic alteration of CK CAIs is more advanced and occurred under higher temperature and higher oxygen fugacity than that of the Allende CAIs.

Geochemistry & Geophysics↗
DOE OSTI2022

Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Data for "Depth of nutrient uptake by deep-rooted plants is regulated by water availability"

The data set consists of strontium (Sr) isotope ratios (87Sr/86Sr), water isotopes, soil cation concentrations, soil water potential sensor data, and results of 87Sr/86Sr mixing model. The plant canopy size files include the dataset of canopy dimension of sagebrush, lupine, and sunflower. The soil and plant ICPMS (Inductively Coupled Plasma Mass Spectrometry) data file includes both of 87Sr/86Sr, and cation concentration dataset from soil exchangeable pool, apatite pool, silicate extract, atmospheric rain deposition, and plant leaf and stem tissues. The plant dendrochronology file includes the dendrochronogical ring width of several sagebrush, and dendrochemical sample data includes the 87Sr/86Sr for each separated growth ring. The modeling result gives the proportion of nutrient sources of each plants (based on their 87Sr/86Sr in leaf tissues and growth rings) from atmospheric deposition and mineral weathering. Soil water potential data includes continuous collection of soil water potential dataset at 2 depths (30 cm and 60 cm, from Nov 24 - Jun 25) of the sampling site. All the samples were collected from 2 sampling campaign June and July 2023, and rain water is a separate sampling from Aug - Sept 2023, at north-facing hillslope near pumphouse site. The data showed that the depth of cation nutrient acquisition is thus tightly coupled with, and likely determined by, water availability in soil, saprolite and bedrock. The enhanced uptake of cations and water from regions of mineral weathering could confer plant and ecosystem resilience during low water years and may impact the rate of bedrock weathering and watershed chemistry during drought. This dataset includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type; a location metadata file (locations.csv); and a samples metadata file (samples.csv). All files are provided as comma-separated values (CSV) files (.csv). This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Hydroxylpyromorphite, a mineral important to lead remediation: Modern description and characterization

Abstract Hydroxylpyromorphite, Pb5(PO4)3(OH), has been documented in the literature as a synthetic and naturally occurring phase for some time but has not previously been formally described as a mineral. It is fully described here for the first time using crystals collected underground in the Copps mine, Gogebic County, Michigan. Hydroxylpyromorphite occurs as aggregates of randomly oriented hexagonal prisms, primarily between about 20–35 μm in length and 6–10 μm in diameter. The mineral is colorless and translucent with vitreous luster and white streak. The Mohs hardness is ~3½–4; the tenacity is brittle, the fracture is irregular, and indistinct cleavage was observed on {001}. Electron microprobe analyses provided the empirical formula Pb4.97(PO4)3(OH0.69F0.33Cl0.06)Σ1.08. The calculated density using the measured composition is 7.32 g/cm3. Powder X-ray diffraction data for the type material is compared to data previously reported for hydroxylpyromorphite from the talc mine at Rabenwald, Austria, and from Whytes Cleuch, Wanlockhead, Scotland. Hydroxylpyromorphite is hexagonal, P63/m, at 100 K, a = 9.7872(14), c = 7.3070(10) Å, V = 606.16(19) Å3, and Z = 2. The structure [R1 = 0.0181 for 494 F>4σ(F) reflections] reveals that hydroxylpyromorphite adopts a column anion arrangement distinct from other members of the apatite supergroup due to the presence of fluorine and steric constraints imposed by stereoactive lone-pair electrons of Pb2+ cations. The F– anion sites are displaced slightly from hydroxyl oxygen anions, which allows for stronger hydrogen-bonding interactions that may in turn stabilize the observed column-anion arrangement and overall structure. Our modern characterization of hydroxylpyromorphite provides deeper understanding to a mineral useful for remediation of lead-contaminated water.

Geochemistry & Geophysics↗