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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Sex-specific respiratory and systemic endocrine effects of acute acrolein and trichloroethylene inhalation

Acrolein and trichloroethylene (TCE) are priority hazardous air pollutants due to environmental prevalence and adverse health effects; however, neuroendocrine stress-related systemic effects are not characterized. Comparing acrolein, an airway irritant, and TCE with low irritancy, we hypothesized that airway injury would be linked to neuroendocrine-mediated systemic alterations. Male and female Wistar-Kyoto rats were exposed nose-only to air, acrolein or TCE in incremental concentrations over 30 min, followed by 3.5-hr exposure to the highest concentration (acrolein - 0.0, 0.1, 0.316, 1, 3.16 ppm; TCE - 0.0, 3.16, 10, 31.6, 100 ppm). Real-time head-out plethysmography revealed acrolein decreased minute volume and increased inspiratory-time (males>females), while TCE reduced tidal-volume. Acrolein, but not TCE, inhalation increased nasal-lavage-fluid protein, lactate-dehydrogenase activity, and inflammatory cell influx (males>females). Neither acrolein nor TCE increased bronchoalveolar-lavage-fluid injury markers, although macrophages and neutrophils increased in acrolein-exposed males and females. Systemic neuroendocrine stress response assessment indicated acrolein, but not TCE, increased circulating adrenocorticotrophic hormone, and consequently corticosterone, and caused lymphopenia, but only in males. Acrolein also reduced circulating thyroid-stimulating hormone, prolactin, and testosterone in males. Furthermore, acute acrolein inhalation resulted in sex-specific upper respiratory irritation/inflammation and systemic neuroendocrine alterations linked to hypothalamic-pituitary-adrenal axes activation, which is critical in mediating extra-respiratory effects.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Probing molecular vibrations by monochromated electron microscopy

Chemical bonds fundamentally determine molecular properties and are prevalently characterized by various spectroscopic means such as infrared and Raman spectroscopies. However, the spatial resolution of these conventional approaches is insufficient to reveal nanoscale features. Recently, monochromated electron energy-loss spectroscopy (EELS) in the transmission electron microscope achieved a groundbreaking energy resolution of a few millielectronvolts and enabled direct observation of molecular vibrational spectrum with unmatched spatial resolution. Vibrational EELS is widely applicable to both organic and inorganic matter in the solid state or liquid phase. In this study, we introduce recent advancements and key concepts of this method, compare with other spectroscopic techniques, and discuss future developments for potential applications in research fields centered on catalysts, polymers, and live cells.

Vibrational Spectroscopy↗
DOE OSTI2023

The effect of current and lambda on white-etch-crack failures

White etching cracks (WECs) have been associated with premature failure of wind turbine roller bearings. Various drivers for the generation of WECs have been identified such as loading conditions, slip, steel quality, lubrication, hydrogen embrittlement, corrosion fatigue cracking, and stray electrical currents passing through the surface. Here, in this work, a benchtop test rig utilizing a three-ring-on-roller test configuration was used to investigate the effect of electrical current and operation in different lubricating regimes, defined by lambda (λ), on high-quality bearing steel samples tested in a commercially available power transmission EP gear lubricant. It was observed that there is an inverse correlation between the magnitude of electric current applied to the ring/ roller system and time-to-failure. Higher current magnitudes lead to shorter time-to-failure than lower current magnitudes, with macropitting as the main failure mode. Sub-surface investigation revealed the presence of WECs in all cases. For the same current magnitude, tests conducted in boundary and mixed lubrication regimes showed that time-to-failure increased as lambda increased, and the tests resulted in WEC related macropits, whereas tests conducted in near-hydrodynamic regime resulted in surface damage with no macropit. It was also noted that a shift toward near-hydrodynamic lubrication resulted in a distinct surface distress on the roller surface. Furthermore, there seems to be a transition in the mixed regime during which the surface distress occurred. The damage on the surface of the test samples resembled non-spatially, periodic, groove-like corrugations and, in some cases, crater-like depressions. Sub-surface imaging, performed by sequential sectioning, revealed the presence of WECs in all cases, and broad, branching cracks that were more prevalent under the more severe boundary conditions.

17 WIND ENERGY↗
DOE OSTI2021

Infant gut strain persistence is associated with maternal origin, phylogeny, and traits including surface adhesion and iron acquisition

Gut microbiome succession affects infant development. However, it remains unclear what factors promote persistence of initial bacterial colonizers in the developing gut. Here, we perform strain-resolved analyses to compare gut colonization of preterm and full-term infants throughout the first year of life and evaluate associations between strain persistence and strain origin as well as genetic potential. Analysis of fecal metagenomes collected from 13 full-term and 9 preterm infants reveals that infants' initially distinct microbiomes converge by age 1 year. Approximately 11% of early colonizers, primarily Bacteroides and Bifidobacterium, persist during the first year of life, and those are more prevalent in full-term, compared with preterm infants. Examination of 17 mother-infant pairs reveals maternal gut strains are significantly more likely to persist in the infant gut than other strains. Enrichment in genes for surface adhesion, iron acquisition, and carbohydrate degradation may explain persistence of some strains through the first year of life.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Emerging roles of circular RNAs in thyroid cancer

As the most common endocrine-related malignant tumor, the prevalence of thyroid cancer (TC) has soared strikingly over the past thirty years then verged to stabilization or even descension temporally. Distributed in a cell-specific manner, circular RNAs (circRNAs) is a novel class of non-coding RNAs characterized by its covalently closed loop without 5′-terminal cap and 3′-terminal poly A tail, which guarantee its distinctive evolutionary conservation and exonucleases resistance. Emerging evidence indicates that circRNA participates in the pathogenesis and carcinogenesis of several cancers including thyroid cancer. In this review, we concentrated on the connection between circRNAs and thyroid cancer so as to obtain a more profound understanding. We aim to discuss this relationship between TC and circRNAs by summarizing the effect of various circRNAs on tumor biological behaviors and clinical application, and systematically outlook the conceivable application of circRNAs in TC diagnosis and therapy.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

YAP/STAT3 promotes the immune escape of larynx carcinoma by activating VEGFR1-TGFβ signaling to facilitate PD-L1 expression in M2-like TAMs

Larynx carcinoma (LC) is the most prevalent head and neck cancer among adults. LC xenograft mouse model was generated to verify the effect of VEGF on macrophage polarization and tumor growth in vivo. EdU assay was performed to measure the cell proliferation. Transwell assay was applied to assess cell migration. The expression of YAP and STAT3 was also significantly increased in LC tumor tissues. Moreover, both YAP and STAT3 overexpression in LC cells promoted the proliferation, migration, as well as the secretion of PD-L1 in M2-like TAMs. Mechanistically, the interaction between YAP and STAT3 facilitated the transcription of VEGF. Moreover, with a co-culture system, VEGF secretion in LC cells enhanced PD-L1 expression in M2-like TAMs via activating VEGFR1-TGFβ signaling pathway. Furthermore, VEGF secreted from LC cells also promoted the tumor growth of LC in vivo. We revealed that dysregulated YAP/STAT3 activity in LC cells could enhance the secretion of VEGF, which then functioned on M2-like TAMs via activating VEGFR1-TGFββ pathway to promote the expression of PD-L1 and immunosuppressive function of M2-like TAMs. Therefore, VEGF and PD-L1 might have a pivotal crosstalk between M2-like TAMs and LC cells, which provided a novel therapeutic target in regulating the metastasis of LC in future.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

ZEB1 induces non-small cell lung cancer development by targeting microRNA-320a to increase the expression of RAD51AP1

Lung cancer is the most prevalent cancer worldwide, with its mortality rate reported to be in millions annually; one of the two subtypes is non-small cell lung cancer (NSCLC). In this study, we investigated the interactions and expressions of zinc finger E-box binding homeobox 1 (ZEB1), microRNA-320a (miR-320a) and RAD51-associated protein 1 (RAD51AP1) in NSCLC tissues to determine the roles of ZEB1 in regulation of miR-320a and RAD51AP1 in the development and metastasis of NSCLC. First, the expression levels of miR-320a and ZEB1 were quantified in NSCLC tissues and cells. Transfection assay was conducted to identify the effects of miR-320a on the progression of NSCLC cells. The interaction of miR-320a with ZEB1 and RAD51AP1 was predicted and verified using dual-luciferase reporter gene assay and chromatin immunoprecipitation assay. Finally, subcutaneous xenograft tumors of 6-week mice and metastatic model tumors of 8-week mice were established to further explore the in vivo effect of miR-320a/ZEB1/RAD51AP1 on NSCLC. The findings revealed a lower expression of miR-320a in NSCLC tissues and cells, while this result was reversed regarding ZEB1 expression. ZEB1 suppressed miR-320a expression and upregulation of miR-320a resulted in the reduction of proliferation, invasion and metastasis rate of NSCLC cells, and promoted NSCLC cell apoptosis. ZEB1 promoted the expression of RAD51AP1 via inhibition of miR-320a, promoting tumor growth in vivo. ZEB1 transcriptionally inhibited the expression of miR-320a and upregulated the expression of RAD51AP1, thereby promoting metastasis in NSCLC.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Lipid accumulation-induced hepatocyte senescence regulates the activation of hepatic stellate cells through the Nrf2-antioxidant response element pathway

Highlights: • Oxidative stress caused by lipid deposition causes hepatocyte senescence. • Free fatty acid-induced senescent hepatocytes promote hepatic stellate cell activation and development of hepatic fibrosis. • Senescent hepatocytes regulate hepatic fibrosis through the Nrf2-antioxidant response element pathway. Non-alcoholic fatty liver disease (NAFLD) has become the most prevalent chronic liver disease globally. Elderly individuals are at a higher risk of developing NAFLD with severe clinical outcomes. Although NAFLD is closely related to liver aging, the role of hepatocyte senescence in the progression of NAFLD, especially in the development of fibrosis, is still unclear. The early stage of NAFLD is mainly characterized by lipid accumulation in hepatocytes, which could lead to severe oxidative stress, causing cellular senescence. In the present study, hepatocytes cultured in the presence of free fatty acids to induce lipid deposition were used as a hepatocyte senescence model in vitro. Senescent hepatocytes significantly increased the activation of co-cultured primary hepatic stellate cells (HSCs) and the expression of pro-fibrosis molecules. Moreover, the antioxidant regulator nuclear factor erythroid 2-related factor 2 (Nrf2) that was upregulated in senescent hepatocytes was found to be related to the activation of co-cultured HSCs. The Nrf2 agonist sulforaphane, which upregulated the transcriptional activity of the Nrf2-antioxidant response element (ARE) pathway, remarkably inhibited hepatocyte senescence and its activation effect on HSCs. However, the liver tissue obtained from non-alcoholic steatohepatitis (NASH) mice with Nrf2 knockdown showed decreased antioxidation and significant liver senescence and fibrosis. In conclusion, this study confirmed that lipid accumulation induces hepatocyte senescence, which leads to HSC activation and development of hepatic fibrosis. Increasing the activity of the Nrf2-ARE antioxidant pathway in senescent hepatocytes elicited the opposite effect, suggesting that targeting Nrf2 may prevent or delay the progression of aging-related liver fibrosis in NASH.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Structure of the thermal boundary layer in turbulent channel flows at transcritical conditions

Enhanced fluctuations, steep gradients, and intensified heat transfer are characteristics of wall-bounded turbulence at transcritical conditions. Although such conditions are prevalent in numerous technical applications, the structure of the thermal boundary layer under realistic density gradients and heating conditions remains poorly understood. Specifically, statistical descriptions of the temperature field in such flows are provided inconsistently using existing models. To address this issue, direct numerical simulations are performed by considering fully developed transcritical turbulent channel flow at pressure and temperature conditions that cause density changes of a factor of up to $O(20)$ between the hot and cold walls. As a consequence of the proximity of the Widom line to the hot wall, significant asymmetries are observed when comparing regions near the cold wall and near the hot wall. Previous transformations that attempt to collapse the near-wall mean temperature profiles among different cases to a single curve are examined. By addressing model deficiencies of these transformations, a formulation for an improved mean temperature transformation is proposed, with appropriate considerations for real fluid effects that involve strong variations in thermodynamic quantities. Our proposed transformation is shown to perform well in collapsing the slope of the logarithmic region to a single universal value with reduced uncertainty. Coupled with a predictive framework to estimate the non-universal shift parameter of the logarithmic region using a priori information, our transformation provides an analytic profile to model the near-wall mean temperature. These results thus provide a framework to guide the development of models for wall-bounded transcritical turbulence.

42 ENGINEERING↗
DOE OSTI2023

Mixing across stable density interfaces in forced stratified turbulence

Understanding how turbulence enhances irreversible scalar mixing in density-stratified fluids is a central problem in geophysical fluid dynamics. While isotropic overturning regions are commonly the focus of mixing analyses, we here investigate whether significant mixing may arise in anisotropic statically stable regions of the flow. Focusing on a single forced direct numerical simulation of stratified turbulence, we analyse spatial correlations between the vertical density gradient $\partial \rho /\partial z$ and the dissipation rates of kinetic energy $\epsilon$ and scalar variance $\chi$ , the latter quantifying scalar mixing. The domain is characterized by relatively well-mixed density layers separated by sharp stable interfaces that are correlated with high vertical shear. While static instability is most prevalent within the mixed layers, much of the scalar mixing is localized to the intervening interfaces, a phenomenon not apparent if considering local static instability or $\epsilon$ alone. While the majority of the domain is characterized by the canonical flux coefficient $\varGamma \equiv \chi /\epsilon =0.2$ , often assumed in ocean mixing parametrizations, extreme values of $\chi$ within the statically stable interfaces, associated with elevated $\varGamma$ , strongly skew the bulk statistics. Our findings suggest that current parametrizations of turbulent mixing may be biased by undersampling, such that the most common, but not necessarily the most significant, mixing events are overweighted. Having focused here on a single simulation of stratified turbulence, it is hoped that our results motivate a broader investigation into the role played by stable density interfaces in mixing, across a wider range of parameters and forcing schemes representative of ocean turbulence.

Couchman, Miles M. P. (ORCID:0000000246676829)↗
DOE OSTI2021

Congenital toxoplasmosis in humans: an update of worldwide rate of congenital infections

Abstract The morbidity due to congenital toxoplasmosis in humans is very high. Most of these infected children are likely to develop symptoms of clinical toxoplasmosis. Sequelae in fetus resulting from Toxoplasma gondii infections in women who become infected with this parasite during pregnancy can be devastating and enormous efforts are directed in some countries to prevent these consequences. Here, an update on congenital toxoplasmosis in humans, especially the rate of congenital infections in humans worldwide, is provided. Although several countries have surveillance programmes, most information on the rate of congenital transmission is from France and Brazil. Because of compulsory national screening programme in France to detect and treat women with recently acquired T. gondii infection with anti-toxoplasma therapy, the rate of congenital transmission and the severity of disease in children are declining. Infections by this parasite are widely prevalent in Brazil. The severity of clinical toxoplasmosis in Brazilian children is very high and may be associated with the genetic characteristics of T. gondii isolates prevailing in animals and humans in Brazil. Virtually little or no information is available on this topic from China, India and other countries in Asia.

Parasitology↗
DOE OSTI2025

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport↗
DOE OSTI2025

Removal of Homogeneous Broadening from 1 H-Detected Multidimensional Solid-State NMR Spectra

1 H-detected magic-angle spinning (MAS) NMR experiments have revolutionized the NMR studies of biological and inorganic solids by providing unparalleled sensitivity and resolution. Despite these gains, homogeneous broadening, originating from the incomplete removal of homonuclear dipolar interactions under fast MAS, remains highly prevalent and limits the achievable resolution. In direct analogy to super-resolution microscopy methods, we show that resolution beyond that currently achievable by fast MAS alone can be obtained by experiment-driven deconvolution. Following the acquisition of a single 2D NMR spectrum to measure the frequency-dependent homogeneous lineshapes, any number of 1 H-detected spectra can be enhanced in resolution, yielding comparable spectra as obtained with twice the MAS frequency. In conclusion, the versatility of this approach is demonstrated in the enhancement of single- and double-quantum homonuclear correlation spectra, in addition to heteronuclear correlation spectra acquired on a surface organometallic complex and the protein GB1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nitride or Oxynitride? Elucidating the Composition–Activity Relationships in Molybdenum Nitride Electrocatalysts for the Oxygen Reduction Reaction

Molybdenum nitride (Mo–N) catalysts have shown promising activity and stability for the oxygen reduction reaction (ORR) in acid. However, the effect of oxygen (O) incorporation (from synthesis, catalysis, or exposure to air) on their activity remains elusive. Here, we use reactive sputtering to synthesize three compositions of thin-film catalysts and use extensive materials characterization to investigate the depth-dependent structure and incorporated O. We show that the as-deposited Mo–N films are highly oxidized both at the surface (>30% O) and in the bulk (3–21% O) and that the ORR performance is strongly correlated with the bulk structure and composition. Activity for 4e– ORR is highest for compositions with the highest N/O and N/Mo ratio. Furthermore, H 2 O 2 production for the films with moderate O content is comparable to or higher than the most H 2 O 2 -selective nonprecious metal catalysts in acidic electrolyte, on a moles per mass or surface area of catalyst basis. Density functional theory provides insight into the energetics of O incorporation and vacancy formation, and we hypothesize that activity trends with O/N ratios can be traced to the varying crystallite phases and their interactions with ORR adsorbates. This work demonstrates the prevalence and significance of O in metal nitride electrocatalysts and motivates further investigation into the role of O in other nonprecious metal materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗
DOE OSTI2023

Big Data Analysis and Technical Review of Regeneration for Carbon Capture Processes

Carbon capture remains an integral technology to mitigate pollution from one of the most prevalent greenhouse gases. CO 2 desorption/absorbent regeneration for both solid- and liquid-based systems is widely recognized as an energy-intensive and costly process operation. Consequently, tremendous work was devoted towards developing new absorbents and regeneration processes to promote their economic feasibility for extensive implementation. In this review, we broadly and deeply review more than 10,000 papers and extract the hidden trends of carbon capture and absorbents regeneration in the past few decades, using a novel data-mining analysis technique. We comprehensively analyzed an array of recent absorbent regeneration methods utilized in post-combustion, pre-combustion, carbon capture from industrial point sources, and direct air carbon capture, with an emphasis on sorbent and solvent-based techniques. In conclusion, advanced regeneration methods in these techniques were illustrated and discussed, followed by recommendations for further research efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions

Cobalt sulfide precipitates, key phases in the natural biogeochemical cycling of cobalt and in relevant remediation and resource recovery processes, remain poorly defined under low-temperature aqueous conditions. Here, we systematically studied the Co-(Fe) sulfides precipitated and aged in environmentally relevant solutions, defined by different combinations of pH, initial cobalt-to-iron ratios ([Co] aq /[Fe] aq ), with/without S 0 , and the presence/absence of sulfate-reducing bacteria. The initial abiogenic precipitates without Fe aq were composed exclusively of amorphous Co-sulfide hydrates (CoS· x H 2 O), whose estimated log K* was three orders of magnitude higher than that previously reported for crystalline Co-sulfides. The addition of S 0 , in combination with acidic pH and elevated temperature (60°C), resulted in the recrystallization of the amorphous precipitates into nanocrystalline jaipurite (hexagonal CoS) within one month (which otherwise remained stable for up to two months). In the presence of Fe(II) aq , the abiogenic precipitates were composed of more crystalline Co-sulfide hydrates and/or Co-rich mackinawite, the exact phase being dependent on the specific [Co] aq /[Fe(II)] aq . The biogenic precipitates displayed higher crystallinity for Co sulfides (up to the formation of nanocrystalline cobalt pentlandite, Co 9 S 8 ) and lower crystallinity for Co-rich mackinawite, suggestive of mineral-specific bacterial interaction. The revealed precipitation and transformation pathways of Co-(Fe-)sulfides in this study allows for predicting the prevalent Co-bearing phases in various natural and engineered environments.

58 GEOSCIENCES↗