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1.
Geobiology ; 2020 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-32542902

RESUMO

Microtextures of titanite (CaTiSiO5 ) in exceptionally preserved Archean pillow lavas have been proposed as the earliest examples of microbial ichnofossils. An origin from microbial tunneling of seafloor volcanic glass that is subsequently chloritized and the tunnels infilled by titanite has been argued to record the activities of subseafloor microbes. We investigate the evidence in pillow lavas of the 3.35 Ga Euro Basalt from the Pilbara Craton, Western Australia, to evaluate the biogenicity of the microtextures. We employ a combination of light microscopy and chlorite mineral chemical analysis by EPMA (electron probe micro-analysis) to document the environment of formation and analyze their ultrastructure using FIB-TEM (focussed ion beam combined with transmission electron microscopy) to investigate their mode of growth. Petrographic study of the original and re-collected material identified an expanded range of titanite morphotypes along with early anatase growth forming chains and aggregates of coalesced crystallites in a sub-greenschist facies assemblage. High-sensitivity mapping of FIB lamellae cut across the microtextures confirm that they are discontinuous chains of coalesced crystallites that are highly variable in cross section and contain abundant chlorite inclusions, excluding an origin from the mineralization of previously hollow microtunnels. Comparison of chlorite mineral compositions to DSDP/IODP data reveals that the Euro Basalt chlorites are similar to recent seafloor chlorites. We advance an abiotic origin for the Euro Basalt microtextures formed by spontaneous nucleation and growth of titanite and/anatase during seafloor-hydrothermal metamorphism. Our findings reveal that the Euro Basalt microtextures are not comparable to microbial ichnofossils from the recent oceanic crust, and we question the evidence for life in these Archean lavas. The metamorphic reactions that give rise to the growth of the Euro Basalt microtextures could be commonplace in Archean pillow lavas and need to be excluded when seeking traces of life in the subseafloor on the early Earth.

2.
J Phys Chem Lett ; : 4990-4997, 2020 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-32498513

RESUMO

Polar surfaces of ionic crystals are of growing technological importance, with implications for the efficiency of photocatalysts, gas sensors, and electronic devices. The creation of ionic nanocrystals with high percentages of polar surfaces is an option for improving their efficiency in the aforementioned applications but is hard to accomplish because they are less thermodynamically stable and prone to vanish during the growth process. Herein, we develop a strategy that is capable of producing polar surface-dominated II-VI semiconductor nanocrystals, including ZnS and CdS, from copper sulfide hexagonal nanoplates through cation exchange reactions. The obtained wurtzite ZnS hexagonal nanoplates have dominant {002} polar surfaces, occupying up to 97.8% of all surfaces. Density functional theory calculations reveal the polar surfaces can be stabilized by a charge transfer of 0.25 eV/formula from the anion-terminated surface to the cation-terminated surface, which also explains the presence of polar surfaces in the initial Cu1.75S hexagonal nanoplates with cation deficiency prior to cation exchange reactions. Experimental results showed that the HER activity could be boosted by the surface polarization of polar surface-dominated ZnS hexagonal nanoplates. We anticipate this strategy is general and could be used with other systems to prepare nanocrystals with dominant polar surfaces. Furthermore, the availability of colloidal semiconductor nanocrystals with dominant polar surfaces produced through this strategy opens a new avenue for improving their efficiency in catalysis, photocatalysis, gas sensing, and other applications.

3.
Geobiology ; 2020 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-32463178

RESUMO

Fibrous-radiating carbonate spherulites spatially associated with poorly crystalline Mg-Si substances have formed within conical microbialites in modern hypersaline lakes on Rottnest Island, Western Australia. Two spherulitic fabrics can be distinguished based on compositional and textural differences. The oldest (lowermost) fabric comprises variably intergrown aragonitic spherulites 100-500 µm wide, containing micritic nuclei with coccoid cell molds in various stages of cell division. Spherulite matrices contain aggregates of individual nanospheres 150-200 nm wide, composed of a poorly crystalline Mg-Si phase, locally containing cell molds with similar dimensions to those within spherulite nuclei. The younger (upper) fabric comprises sub-polyhedral networks of mineralized EPS composed of an Mg-Si substance. The polyhedrons contain aragonite-replaced coccoid cells, voids, and polyhedral spherulites 8-12 µm wide with a morphology determined by fossil EPS, interpreted to have been produced by coccoid cyanobacteria. These spherulites are composed of high-Mg calcite, inferred to have formed in association with heterotrophic bacteria. Stable isotope data, textural relationships, and geochemical modeling are consistent with cyanobacterial oxygenic photosynthesis influencing the precipitation of Mg-Si substances and aragonitic spherulites by locally increasing the pH. The morphology of the polyhedral spherulites suggests the former presence of EPS and that faceted spherulites with similar dimensions in the geological record may represent biosignatures. The Rottnest Island conical microbialites demonstrate an intimate association between microbial features and processes and spherulitic fabrics, potentially providing insights into texturally and compositionally similar features in the geological record.

4.
Geobiology ; 18(4): 415-425, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32359013

RESUMO

The shallow marine and subaerial sedimentary and hydrothermal rocks of the ~3.48 billion-year-old Dresser Formation are host to some of Earth's oldest stromatolites and microbial remains. This study reports on texturally distinctive, spherulitic barite micro-mineralization that occur in association with primary, autochthonous organic matter within exceptionally preserved, strongly sulfidized stromatolite samples obtained from drill cores. Spherulitic barite micro-mineralization within the sulfidized stromatolites generally forms submicron-scale aggregates that show gradations from hollow to densely crystallized, irregular to partially radiating crystalline interiors. Several barite micro-spherulites show thin outer shells. Within stromatolites, barite micro-spherulites are intimately associated with petrographically earliest dolomite and nano-porous pyrite enriched in organic matter, the latter of which is a possible biosignature assemblage that hosts microbial remains. Barite spherulites are also observed within layered barite in proximity to stromatolite layers, where they are overgrown by compositionally distinct (Sr-rich), coarsely crystalline barite that may have been sourced from hydrothermal veins at depth. Micro-spherulitic barite, such as reported here, is not known from hydrothermal systems that exceed the upper temperature limit for life. Rather, barite with near-identical morphology and micro-texture is known from zones of high bio-productivity under low-temperature conditions in the modern oceans, where microbial activity and/or organic matter of degrading biomass controls the formation of spherulitic aggregates. Hence, the presence of micro-spherulitic barite in the organic matter-bearing Dresser Formation sulfidized stromatolites lend further support for a biogenic origin of these unusual, exceptionally well-preserved, and very ancient microbialites.

5.
Adv Mater ; 31(49): e1905540, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31631407

RESUMO

Molecular surfactants are widely used to control low-dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single-layer growth for 2D materials. A scalable stacking-hinderable strategy to not only enable exclusive single-layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single-layer TMDs' photoredox activities is developed. The single-layer growth mechanism is well explained by theoretical calculation. Three types of single-layer TMDs, including MoS2 , WS2 , and ReS2 , are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen-stored liquid carrier-methanol. Such H2 fuel production from single-layer MoS2 nanosheets is COx -free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g-1 h-1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol-storable solar H2 fuel with facile chemical rebonding actualized by 2D single-layer photocatalysts.

6.
Geobiology ; 17(6): 691-707, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31478592

RESUMO

On rocky planets such as Earth and Mars the serpentinization of olivine in ultramafic crust produces hydrogen that can act as a potential energy source for life. Direct evidence of fluid-rock interaction on Mars comes from iddingsite alteration veins found in martian meteorites. In the Yamato 000593 meteorite, putative biosignatures have been reported from altered olivines in the form of microtextures and associated organic material that have been compared to tubular bioalteration textures found in terrestrial sub-seafloor volcanic rocks. Here, we use a suite of correlative, high-sensitivity, in situ chemical, and morphological analyses to characterize and re-evaluate these microalteration textures in Yamato 000593, a clinopyroxenite from the shallow subsurface of Mars. We show that the altered olivine crystals have angular and micro-brecciated margins and are also highly strained due to impact-induced fracturing. The shape of the olivine microalteration textures is in no way comparable to microtunnels of inferred biological origin found in terrestrial volcanic glasses and dunites, and rather we argue that the Yamato 000593 microtextures are abiotic in origin. Vein filling iddingsite extends into the olivine microalteration textures and contains amorphous organic carbon occurring as bands and sub-spherical concentrations <300 nm across. We propose that a martian impact event produced the micro-brecciated olivine crystal margins that reacted with subsurface hydrothermal fluids to form iddingsite containing organic carbon derived from abiotic sources. These new data have implications for how we might seek potential biosignatures in ultramafic rocks and impact craters on both Mars and Earth.


Assuntos
Meio Ambiente Extraterreno/química , Compostos de Ferro/química , Compostos de Magnésio/química , Marte , Meteoroides , Silicatos/química , Exobiologia
7.
J Phys Chem Lett ; 10(12): 3465-3471, 2019 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-31184156

RESUMO

Herein we employed a first-principles method based on density functional theory to investigate the surface energy and growth kinetics of wurtzite nanoplatelets to elucidate why nanoplatelets exhibit a uniform thickness of eight monolayers. We synthesized a series of wurtzite nanoplatelets (ZnSe, ZnS, ZnTe, and CdSe) with an atomically uniform thickness of eight monolayers. As a representative example, the growth mechanism of 1.39 nm thick (eight monolayers) wurtzite ZnSe nanoplatelets was studied to substantiate the proposed growth kinetics. The results show that the growth of the seventh and eighth layers along the [112̅0] direction of 0.99 nm (six monolayers) ZnSe magic-size nanoclusters is accessible, whereas the growth of the ninth layer is unlikely to occur because the formation energy is large. This work not only gives insights into the synthesis of atomically uniform thick wurtzite semiconductor nanoplatelets but also opens up new avenues to their applications in light-emitting diodes, catalysis, detectors, and lasers.

8.
Sci Rep ; 9(1): 9068, 2019 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-31227773

RESUMO

Exceptional microfossil preservation, whereby sub-cellular details of an organism are conserved, remains extremely rare in the Precambrian rock record. We here report the first occurrence of exceptional cellular preservation by the rare earth element (REE) phosphates monazite and xenotime. This occurs in ~1 billion-year-old lake sediments where REEs were likely concentrated by local erosion and drainage into a closed lacustrine basin. Monazite and xenotime preferentially occur inside planktonic cells where they preserve spheroidal masses of plasmolyzed cell contents, and occasionally also membranous fragments. They have not been observed associated with cell walls or sheaths, which are instead preserved by clay minerals or francolite. REE phosphates are interpreted to be the earliest minerals precipitated in these cells after death, with their loci controlled by the micro-scale availability of inorganic phosphate (Pi) and REEs, probably sourced from polyphosphate granules within the cells. The strong affinity of REEs for phosphate and the insolubility of these minerals once formed means that REE phosphates have the potential for rapid preservation of cellular morphology after death and durability in the rock record. Hence, authigenic REE phosphates provide a promising new target in the search for the preservation of intra-cellular components of fossilised microorganisms.

9.
Adv Sci (Weinh) ; 6(10): 1802066, 2019 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-31131190

RESUMO

Iron single atom catalysts (Fe SACs) are the best-known nonprecious metal (NPM) catalysts for the oxygen reduction reaction (ORR) of polymer electrolyte membrane fuel cells (PEMFCs), but their practical application has been constrained by the low Fe SACs loading (<2 wt%). Here, a one-pot pyrolysis method is reported for the synthesis of iron single atoms on graphene (FeSA-G) with a high Fe SAC loading of ≈7.7 ± 1.3 wt%. The as-synthesized FeSA-G shows an onset potential of 0.950 V and a half-wave potential of 0.804 V in acid electrolyte for the ORR, similar to that of Pt/C catalysts but with a much higher stability and higher phosphate anion tolerance. High temperature SiO2 nanoparticle-doped phosphoric acid/polybenzimidazole (PA/PBI/SiO2) composite membrane cells utilizing a FeSA-G cathode with Fe SAC loading of 0.3 mg cm-2 delivers a peak power density of 325 mW cm-2 at 230 °C, better than 313 mW cm-2 obtained on the cell with a Pt/C cathode at a Pt loading of 1 mg cm-2. The cell with FeSA-G cathode exhibits superior stability at 230 °C, as compared to that with Pt/C cathode. Our results provide a new approach to developing practical NPM catalysts to replace Pt-based catalysts for fuel cells.

10.
ACS Appl Mater Interfaces ; 11(21): 19048-19055, 2019 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-31062967

RESUMO

It is highly attractive but challenging to develop transition-metal electrocatalysts for direct hydrazine fuel cells (DHzFCs). In this work, a nickel crystalline core@nickel phosphide amorphous shell heterostructured electrocatalyst supported by active carbon (Ni@NiP/C) is developed. Ni@NiP/C with a P/Ni molar ratio of 3:100, Ni@NiP3.0/C, exhibits outstanding catalytic activity for the hydrazine oxidation reaction (HzOR) in alkaline solution, achieving a much better catalytic activity (2675.1 A gNi-1@0.25 V vs RHE) and high stability, as compared to Ni nanoparticles supported on carbon (Ni/C) and Pt/C catalysts. The results indicate that formation of the NiP amorphous shell effectively inhibits the passivation of the Ni core active sites and enhances the adsorption of hydrazine on Ni by improving the adsorption energy, leading to high electrochemical activity and stability of the Ni@NiP3.0/C catalysts for HzOR. The density functional theory calculation confirms the structural and electrocatalytic effect of the core-shell heterostructure on the stability and activity of Ni active sites for HzOR. The unique crystalline core/amorphous shell-structured Ni@NiP/C demonstrates promising potential as an effective electrocatalyst for DHzFCs.

11.
Nanoscale ; 11(21): 10190-10197, 2019 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-31112179

RESUMO

Herein we report a nanorod couple heterostructure made of dual semiconductors, in which two parallelly aligned ZnSe nanorods are connected by the growth of ZnS on both end and side facets, producing hetero-ZnS (short arms)-ZnSe (long arms)/ZnS shell nanorod couples. As evidenced by electronic structure studies, both experimental and theoretical, such core/shell nanorod couple heterostructures can act as a platform to precisely tailor the quantum confinement of charge carriers between the constituting components within a single nano-object, generating blue fluorescence after the overgrowth of an alloyed ZnCdS layer on the heterostructures. We foresee the mechanistic insights gained and electronic structures revealed in this work would shed light on the rational design of more complex heterostructures with novel functionalities.

12.
Nanomaterials (Basel) ; 9(3)2019 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-30934596

RESUMO

Impurity doping is one of the common approaches to enhance the photoactivity of semiconductor nanomaterials by increasing photon-capture efficiency in the visible light range. However, many studies on the doping effects have produced inconclusive and conflicting results. There are some misleading assumptions and errors that are frequently made in the data interpretation, which can lead to inconsistent results about the doping effects on photocatalysis. One of them is the determination of the location of dopants. Even using advanced analytical techniques, it is still challenging to distinguish between bulk modification and surface modification. The paper provides a case study of transition-metal-doped ZnO nanoparticles, whereby demonstrating common pitfalls in the interpretation of the results of widely-used analytical methods in detail, and discussing the importance of using a combination of many characterization techniques to correctly determine the location of added impurities, for elucidating the influence of metal doping on the photocatalytic activities of semiconductor nanoparticles.

13.
Chemphyschem ; 20(5): 745-751, 2019 03 04.
Artigo em Inglês | MEDLINE | ID: mdl-30614177

RESUMO

Metal-organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL-53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al-MIL-53 were synthesised via (a) electrodeposition and (b) gas-phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al-MIL-53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.

14.
Nat Nanotechnol ; 13(12): 1148-1153, 2018 12.
Artigo em Inglês | MEDLINE | ID: mdl-30297819

RESUMO

Gold nanorods are one of the most widely explored inorganic materials in nanomedicine for diagnostics, therapeutics and sensing1. It has been shown that gold nanorods are not cytotoxic and localize within cytoplasmic vesicles following endocytosis, with no nuclear localization2,3, but other studies have reported alterations in gene expression profiles in cells following exposure to gold nanorods, via unknown mechanisms4. In this work we describe a pathway that can contribute to this phenomenon. By mapping the intracellular chemical speciation process of gold nanorods, we show that the commonly used Au-thiol conjugation, which is important for maintaining the noble (inert) properties of gold nanostructures, is altered following endocytosis, resulting in the formation of Au(I)-thiolates that localize in the nucleus5. Furthermore, we show that nuclear localization of the gold species perturbs the dynamic microenvironment within the nucleus and triggers alteration of gene expression in human cells. We demonstrate this using quantitative visualization of ubiquitous DNA G-quadruplex structures, which are sensitive to ionic imbalances, as an indicator of the formation of structural alterations in genomic DNA.


Assuntos
Núcleo Celular/genética , DNA/química , Quadruplex G , Ouro/metabolismo , Nanotubos , Compostos de Sulfidrila/metabolismo , Núcleo Celular/metabolismo , DNA/genética , Endocitose , Regulação da Expressão Gênica , Ouro/análise , Células HEK293 , Humanos , Células MCF-7 , Nanotubos/análise , Nanotubos/ultraestrutura , Compostos de Sulfidrila/análise
15.
J Colloid Interface Sci ; 530: 556-566, 2018 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-30005232

RESUMO

Unreliable energy supply and environmental pollution are two major concerns of the human society in this century. Herein, we report a rational approach on preparation of hierarchically-structured cobalt-carbon composites with tunable properties for a number of applications. A facile hydrothermal treatment of cobalt nitrate and sucrose results in the formation of a metallic cobalt-amorphous carbon composite with cobalt nanospheres anchored homogenously on an amorphous carbon substrate. Tuning the calcination conditions in air will generate either a metallic cobalt-cobalt oxide core-shell structure with magnetism or a fully oxidized Co3O4 composite. The different materials are demonstrated as anodes for lithium-ion batteries (LIBs) and catalysts for advanced oxidation-based wastewater remediation. A fully oxidized composite (FC@CS, fully oxidized Co loaded on carbon spheres) as a LIB anode exhibits superior electrochemical performance, possessing a high reversible capacity, high initial columbic efficiency, outstanding cycling performance and excellent rate capability. The anode performance is superior to most reported Co3O4-based electrodes. Meanwhile, the partially oxidized composite (PC@CS, partially oxidized Co loaded on carbon spheres) functions as an efficient and stable catalyst for removal of phenol via peroxymonosulfate (PMS) activation, which is demonstrated via electron paramagnetic resonance (EPR) and quenching experiments for generation of radicals. More importantly, the recycled PC@CS can be further applied as a LIBs anode after full oxidation regeneration, performing comparably to FC@CS. This FC@CS → PC@CS → FC@CS transformation provides an innovative approach for efficient material synthesis, recycling and application.

16.
Adv Mater ; 30(39): e1803351, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-30059172

RESUMO

Quasi-1D cadmium chalcogenide quantum rods (QRs) are benchmark semiconductor materials that are combined with noble metals to constitute QR heterostructures for efficient photocatalysis. However, the high toxicity of cadmium and cost of noble metals are the main obstacles to their widespread use. Herein, a facile colloidal synthetic approach is reported that leads to the spontaneous formation of cadmium-free alloyed ZnSx Se1-x QRs from polydisperse ZnSe nanowires by alkylthiol etching. The obtained non-noble-metal ZnSx Se1-x QRs can not only be directly adopted as efficient photocatalysts for water oxidation, showing a striking oxygen evolution capability of 3000 µmol g-1 h-1 , but also be utilized to prepare QR-sensitized TiO2 photoanodes which present enhanced photo-electrochemical (PEC) activity. Density functional theory (DFT) simulations reveal that alloyed ZnSx Se1-x QRs have highly active Zn sites on the (100) surface and reduced energy barrier for oxygen evolution, which in turn, are beneficial to their outstanding photocatalytic and PEC activities.

17.
Geobiology ; 16(5): 540-555, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-29885252

RESUMO

Lacustrine carbonate chimneys are striking, metre-scale constructions. If these were bioinfluenced constructions, they could be priority targets in the search for early and extraterrestrial microbial life. However, there are questions over whether such chimneys are built on a geobiological framework or are solely abiotic geomorphological features produced by mixing of lake and spring waters. Here, we use correlative microscopy to show that microbes were living around Pleistocene Mono Lake carbonate chimneys during their growth. A plausible interpretation, in line with some recent works by others on other lacustrine carbonates, is that benthic cyanobacteria and their associated extracellular organic material (EOM) formed tubular biofilms around rising sublacustrine spring vent waters, binding calcium ions and trapping and binding detrital silicate sediment. Decay of these biofilms would locally have increased calcium and carbonate ion activity, inducing calcite precipitation on and around the biofilms. Early manganese carbonate mineralisation was directly associated with cell walls, potentially related to microbial activity though the precise mechanism remains to be elucidated. Much of the calcite crystal growth was likely abiotic, and no strong evidence for either authigenic silicate growth or a clay mineral precursor framework was observed. Nevertheless, it seems likely that the biofilms provided initial sites for calcite nucleation and encouraged the primary organised crystal growth. We suggest that the nano-, micro- and macroscale fabrics of these Pleistocene Mono Lake chimneys were affected by the presence of centimetre-thick tubular and vertically stacked calcifying microbial mats. Such carbonate chimneys represent a promising macroscale target in the exploration for ancient or extraterrestrial life.


Assuntos
Carbonatos/química , Sedimentos Geológicos/microbiologia , Lagos/microbiologia , Manganês/química , Monitoramento Ambiental , Microscopia Eletroquímica de Varredura , Microscopia Eletrônica de Transmissão , Difração de Raios X
18.
Adv Mater ; 30(13): e1706287, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29423964

RESUMO

Single-atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1-2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen-doped carbon nanotubes (MSA-N-CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA-N-CNTs, using a new multistep pyrolysis process. Among these materials, NiSA-N-CNTs show an excellent selectivity and activity for the electrochemical reduction of CO2 to CO, achieving a turnover frequency (TOF) of 11.7 s-1 at -0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.

19.
Astrobiology ; 18(5): 539-555, 2018 05.
Artigo em Inglês | MEDLINE | ID: mdl-29461869

RESUMO

The ∼3.48 billion-year-old Dresser Formation, Pilbara Craton, Western Australia, is a key geological unit for the study of Earth's earliest life and the habitats it occupied. Here, we describe a new suite of spheroidal to lenticular microstructures that morphologically resemble some previously reported Archean microfossils. Correlative microscopy shows that these objects have a size distribution, wall ultrastructure, and chemistry that are incompatible with a microfossil origin and instead are interpreted as pyritized and silicified fragments of vesicular volcanic glass. Organic kerogenous material is associated with much of the altered volcanic glass; variable quantities of organic carbon line or fill the insides of some individual vesicles, while relatively large, tufted organic-rich laminae envelop multiple vesicles. The microstructures reported herein constitute a new type of abiogenic artifact (pseudo-fossil) that must be considered when evaluating potential signs of early life on Earth or elsewhere. In the sample studied here, where hundreds of these microstructures are present, the combined evidence permits a relatively straightforward interpretation as vesicular volcanic glass. However, reworked, isolated, and silicified microstructures of this type may prove particularly problematic in early or extraterrestrial life studies since they adsorb carbon onto their surfaces and are readily pyritized, mimicking a common preservation mechanism for bona fide microfossils. In those cases, nanoscale analysis of wall ultrastructure would be required to firmly exclude a biological origin. Key Words: Microfossils-Pseudo-fossils-Volcanic vesicles-Archean life-Pilbara Craton-Dresser Formation. Astrobiology 18, 539-555.


Assuntos
Planeta Terra , Sedimentos Geológicos , Evolução Biológica , Exobiologia , Fósseis , Origem da Vida , Erupções Vulcânicas , Austrália Ocidental
20.
Phys Chem Chem Phys ; 19(22): 14262-14268, 2017 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-28537320

RESUMO

The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO42- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO42-. Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

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