Rapid encapsulation of true ferns and arborane/fernane compounds fossilised in siderite concretions supports analytical distinction of plant fossils.

Fossilised true ferns (Pecopteris sp.) preserved in siderite concretions from the Mazon Creek Lagerstätte (Illinois) presented a unique opportunity to characterise the organic signatures of these late Carboniferous plants. Localised analyses of true fern fossils showed several highly abundant phytohopanoids and fernane/arborane derived aromatic products, which were present only negligibly within their siderite matrix, as well as from other types of fossilised plants. These terpenoids had been recognised in some extant ferns, but scarcely in sedimentary organic matter and their exact source remained ambiguous. The present fossil biomarker data confirms an ancient true fern origin. Furthermore, the excellent concretion preservation of a series of related terpenoid products provided a rare insight into their diagenetic formation. The benign properties of carbonate concretions could be exploited further for biomarker evidence of other fossilised organisms, with one important caveat being that biomarker signals attributed to isolated fossils be significantly distinct from background organic matter pervading the concretion matrix. For instance, hydrocarbon profiles of seed ferns (pteridosperms) and articulates (horsetails) also preserved in Mazon Creek concretions were indistinguishable from separate analysis of their concretion matrix, preventing biomarker recognition.

Electrochemically Assisted Construction of a La2NiO4+δ@Pt Core-Shell Structure for Enhancing the Performance and Durability of La2NiO4+δ Cathodes.

Ruddlesden-Popper oxide La2NiO4+δ (LNO) has a high ionic conductivity and good thermal match with the electrolyte of solid oxide fuel cells (SOFCs); however, LNO suffers from performance decay owing to the La surface segregation under the operation conditions of SOFCs. Herein, we report an in situ electrochemical decoration strategy to improve the electrocatalytic activity and durability of LNO cathodes. We show that the electrochemical polarization leads to in situ construction of the LNO@Pt core-shell structure, significantly suppressing the detrimental effect of La surface segregation on the LNO cathode. The initial peak power density of a single cell with the LNO cathode is 0.71 W cm-2 at 750 °C, increasing to 1.39 W cm-2 by the in situ construction of the LNO@Pt core-shell structure after polarization at 0.5 A cm-2 for 20 h. The LNO@Pt core-shell structure is also highly durable without noticeable performance degradation over the duration of the test for 180 h. The findings shed light on the design and fabrication of highly active and durable LNO-based cathodes for SOFCs.

Crystallographic Texture and Substructural Phenomena in 316 Stainless Steel Printed by Selective Laser Melting.

There is a fast-growing interest in the use of selective laser melting (SLM) for metal/alloy additive manufacturing. Our current knowledge of SLM-printed 316 stainless steel (SS316) is limited and sometimes appears sporadic, presumably due to the complex interdependent effects of a large number of process variables of the SLM processing. This is reflected in the discrepant findings in the crystallographic textures and microstructures in this investigation compared to those reported in the literature, which also vary among themselves. The as-printed material is macroscopically asymmetric in terms of both structure and crystallographic texture. The <101> and <111> crystallographic directions align parallel with the SLM scanning direction (SD) and build direction (BD), respectively. Likewise, some characteristic low-angle boundary features have been reported to be crystallographic, while this investigation unequivocally proves them to be non-crystallographic, since they always maintain an identical alignment with the SLM laser scanning direction, irrespective of the matrix material's crystal orientation. There are also 500 ± 200 nm columnar or cellular features, depending on the cross-section, which are generally found all over the sample. These columnar or cellular features are formed with walls made of dense packing of dislocations entangled with Mn-, Si- and O-enriched amorphous inclusions. They remain stable after ASM solution treatments at a temperature of 1050 °C, and therefore, are capable of hindering boundary migration events of recrystallization and grain growth. Thus, the nanoscale structures can be retained at high temperatures. Large 2-4 µm inclusions form during the solution treatment, within which the chemical and phase distribution are heterogeneous.

Biofilm formation on the surface of monazite and xenotime during bioleaching.

Microbial attachment and biofilm formation is a ubiquitous behaviour of microorganisms and is the most crucial prerequisite of contact bioleaching. Monazite and xenotime are two commercially exploitable minerals containing rare earth elements (REEs). Bioleaching using phosphate solubilizing microorganisms is a green biotechnological approach for the extraction of REEs. In this study, microbial attachment and biofilm formation of Klebsiella aerogenes ATCC 13048 on the surface of these minerals were investigated using confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). In a batch culture system, K. aerogenes was able to attach and form biofilms on the surface of three phosphate minerals. The microscopy records showed three distinctive stages of biofilm development for K. aerogenes commencing with initial attachment to the surface occurring in the first minutes of microbial inoculation. This was followed by colonization of the surface and formation of a mature biofilm as the second distinguishable stage, with progression to dispersion as the final stage. The biofilm had a thin-layer structure. The colonization and biofilm formation were localized toward physical surface imperfections such as cracks, pits, grooves and dents. In comparison to monazite and xenotime crystals, a higher proportion of the surface of the high-grade monazite ore was covered by biofilm which could be due to its higher surface roughness. No selective attachment or colonization toward specific mineralogy or chemical composition of the minerals was detected. Finally, in contrast to abiotic leaching of control samples, microbial activity resulted in extensive microbial erosion on the high-grade monazite ore.

Direct age constraints on the magnetism of Jack Hills zircon.

A potential record of Earth's magnetic field going back 4.2 billion years (Ga) ago is carried by magnetite inclusions in zircon grains from the Jack Hills. This magnetite may be secondary in nature, however, meaning that the magnetic record is much younger than the zircon crystallization age. Here, we use atom probe tomography to show that Pb-bearing nanoclusters in magnetite-bearing Jack Hills zircons formed during two discrete events at 3.4 and <2 Ga. The older population of clusters contains no detectable Fe, whereas roughly half of the younger population of clusters is Fe bearing. This result shows that the Fe required to form secondary magnetite entered the zircon sometime after 3.4 Ga and that remobilization of Pb and Fe during an annealing event occurred more than 1 Ga after deposition of the Jack Hills sediment at 3 Ga. The ability to date Fe mobility linked to secondary magnetite formation provides new possibilities to improve our knowledge of the Archean geodynamo.

Rubble pile asteroids are forever.

Rubble piles asteroids consist of reassembled fragments from shattered monolithic asteroids and are much more abundant than previously thought in the solar system. Although monolithic asteroids that are a kilometer in diameter have been predicted to have a lifespan of few 100 million years, it is currently not known how durable rubble pile asteroids are. Here, we show that rubble pile asteroids can survive ambient solar system bombardment processes for extremely long periods and potentially 10 times longer than their monolith counterparts. We studied three regolith dust particles recovered by the Hayabusa space probe from the rubble pile asteroid 25143 Itokawa using electron backscatter diffraction, time-of-flight secondary ion mass spectrometry, atom probe tomography, and 40Ar/39Ar dating techniques. Our results show that the particles have only been affected by shock pressure of ca. 5 to 15 GPa. Two particles have 40Ar/39Ar ages of 4,219 ± 35 and 4,149 ± 41 My and when combined with thermal and diffusion models; these results constrain the formation age of the rubble pile structure to ≥4.2 billion years ago. Such a long survival time for an asteroid is attributed to the shock-absorbent nature of rubble pile material and suggests that rubble piles are hard to destroy once they are created. Our results suggest that rubble piles are probably more abundant in the asteroid belt than previously thought and provide constrain to help develop mitigation strategies to prevent asteroid collisions with Earth.

Rapid prototyping of grating magneto-optical traps using a focused ion beam.

We have developed a rapid prototyping approach for creating custom grating magneto-optical traps using a dual-beam system combining a focused ion beam and a scanning electron microscope. With this approach we have created both one- and two-dimensional gratings of up to 400 µm × 400 µm in size with structure features down to 100 nm, periods of 620 nm, adjustable aspect ratios (ridge width : depth ∼ 1 : 0.3 to 1 : 1.4) and sidewall angles up to 71°. The depth and period of these gratings make them suitable for holographic trapping and cooling of neutral ytterbium on the 1S0 → 1P1 399 nm transition. Optical testing of the gratings at this wavelength has demonstrated a total first order diffraction of 90% of the reflected light. This work therefore represents a fast, high resolution, programmable and maskless alternative to current photo and electron beam lithography-based procedures and provides a time efficient process for prototyping of small period, high aspect ratio grating magneto-optical traps and other high resolution structures.

The effects of long-term fertilizations on soil hydraulic properties vary with scales.

Soil structure is an indicator of soil quality and its alterations following cropping system conversion or fertilization change evolve slowly. How such alterations vary with scale remains elusive. We investigated this based on the Rothamsted long-term wheat experiment (since 1843) in the UK. Triplicate cores 7 cm high and 10 cm in diameter were taken from plots that have been under different fertilizations or returned to natural woodland for more than one century for imaging using X-ray computed tomography with the voxel size being 40 µm. We then broke each core and sampled three aggregates from it to scan with the voxel size being 1.5 µm. For each core and aggregate sample, we calculated its pore size distribution, permeability and tortuosity. The results showed that the fertilization change >170 years ago reshaped the soil structure differently between the core scale and the aggregate scale. Macro-porosity of the pores (>40 µm) in the cores unfertilized or fertilized with inorganic fertilizers was low and the pores were poorly connected in the top 10 cm of soil, compared to those given farmyard manure or in the woodland. In all treatments, the pores in the core images were hydraulically anisotropic with their permeability in the horizontal direction being higher than that in the vertical direction, whereas the aggregates were comparatively isotropic. The fertilization affected image porosity and permeability at core scale more significantly than at aggregate scale, and the aggregates fertilized with farmyard manure and in the woodland were more permeable than the aggregates in other treatments. It was also found that compared to no-fertilization or fertilization with complete fertilizers, fertilizing without phosphorus over the past 20 years increased the porosity and permeability of the aggregates but not of the cores. Fertilization with inorganic fertilizers increased the tortuosity of the macropores in the cores but not of the intra-aggregate pores, compared to no-fertilization. Porosity-permeability relationship for aggregates unfertilized or fertilized with inorganic fertilisers followed a power law with R 2 > 0.8. In contrast, the permeability of the aggregates in farmyard manure and in the woodland trended differently as their porosity increased. The results also revealed that the transport ability of the aggregates and cores responded differently to carbon in that with soil carbon increasing, the permeability of the aggregates increased asymptotically while the permeability of the cores, especially its horizontal component, increased exponentially.

Novel Applications of FIB-SEM-Based ToF-SIMS in Atom Probe Tomography Workflows.

Atom probe tomography (APT) is used to quantify atomic-scale elemental and isotopic compositional variations within a very small volume of material (typically <0.01 µm3). The small analytical volume ideally contains specific compositional or microstructural targets that can be placed within the context of the previously characterized surface in order to facilitate a correct interpretation of APT data. In this regard, careful targeting and preparation are paramount to ensure that the desired target, which is often smaller than 100 nm, is optimally located within the APT specimen. Needle-shaped specimens required for atom probe analysis are commonly prepared using a focused ion beam scanning electron microscope (FIB-SEM). Here, we utilize FIB-SEM-based time-of-flight secondary ion mass spectrometry (ToF-SIMS) to illustrate a novel approach to targeting <100 nm compositional and isotopic variations that can be used for targeting regions of interest for subsequent lift-out and APT analysis. We present a new method for high-spatial resolution targeting of small features that involves using FIB-SEM-based electron deposition of platinum "buttons" prior to standard lift-out and sharpening procedures for atom probe specimen manufacture. In combination, FIB-ToF-SIMS analysis and application of the "button" method ensure that even the smallest APT targets can be successfully captured in extracted needles.

Direct Observation of Nanoparticulate Goethite Recrystallization by Atom Probe Analysis of Isotopic Tracers.

Goethite (α-FeOOH) is dispersed throughout the earth's surface, and its propensity to recrystallize in aqueous solutions determines whether this mineral is a source or sink for critical trace elements in the environment. Under reducing conditions, goethite commonly coexists with aqueous Fe(II) (Fe(II)aq), which accelerates recrystallization by coupled electron transfer and atom exchange. Quantifying the amount of the mineral phase that exchanges its structural Fe(III) atoms with Fe(II)aq is complicated by recrystallization models with untested assumptions of whether, and to what extent, the recrystallized portion of the mineral continues to interact with the solution. Here, we reacted nanoparticulate goethite with 57Fe-enriched Fe(II)aq and used atom probe tomography (APT) to resolve the three-dimensional distribution of Fe isotopes in goethite at the sub nm scale. We found that the 57Fe tracer isotope is enriched in the bulk structure (tens of nanometers deep), with some samples having 57Fe penetration throughout at a level that is similar to the isotopic composition of Fe(II)aq. This suggests that some particles undergo near-complete recrystallization. In other cases, however, the distribution of 57Fe is more heterogeneous and generally concentrates near the particle periphery. Nanoparticle encapsulation and subsequent APT can hence capture hidden recrystallization mechanisms which are critical to predicting mineral reactivity in aqueous solutions.

Analysis of Natural Rutile (TiO2) by Laser-assisted Atom Probe Tomography.

Since the introduction of laser-assisted atom probe, analysis of nonconductive materials by atom probe tomography (APT) has become more routine. To obtain high-quality data, a number of acquisition variables needs to be optimized for the material of interest, and for the specific question being addressed. Here, the rutile (TiO2) reference material 'Windmill Hill Quartzite,' used for secondary ion mass spectrometry U-Pb dating and laser-ablation inductively coupled plasma mass spectrometry, was analyzed by laser-assisted APT to constrain optimal running conditions. Changes in acquisition parameters such as laser energy and detection rate are evaluated in terms of their effect on background noise, ionization state, hit-multiplicity, and thermal tails. Higher laser energy results in the formation of more complex molecular ions and affects the ionization charge state. At lower energies, background noise and hit-multiplicity increase, but thermal tails shorten. There are also correlations between the acquisition voltage and several of these metrics, which remain to be fully understood. The results observed when varying the acquisition parameters will be discussed in detail in the context of utilizing APT analysis of rutile within geology.

Palaeobiology of red and white blood cell-like structures, collagen and cholesterol in an ichthyosaur bone.

Carbonate concretions are known to contain well-preserved fossils and soft tissues. Recently, biomolecules (e.g. cholesterol) and molecular fossils (biomarkers) were also discovered in a 380 million-year-old concretion, revealing their importance in exceptional preservation of biosignatures. Here, we used a range of microanalytical techniques, biomarkers and compound specific isotope analyses to report the presence of red and white blood cell-like structures as well as platelet-like structures, collagen and cholesterol in an ichthyosaur bone encapsulated in a carbonate concretion from the Early Jurassic (~182.7 Ma). The red blood cell-like structures are four to five times smaller than those identified in modern organisms. Transmission electron microscopy (TEM) analysis revealed that the red blood cell-like structures are organic in composition. We propose that the small size of the blood cell-like structures results from an evolutionary adaptation to the prolonged low oxygen atmospheric levels prevailing during the 70 Ma when ichthyosaurs thrived. The δ13C of the ichthyosaur bone cholesterol indicates that it largely derives from a higher level in the food chain and is consistent with a fish and cephalopod diet. The combined findings above demonstrate that carbonate concretions create isolated environments that promote exceptional preservation of fragile tissues and biomolecules.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y2 O3 -ZrO2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO3-δ (LC) and Sm0.95 CoO3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm-2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm0.95 Co0.95 Pd0.05 O3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm-2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes.

Polarization-Induced Interface and Sr Segregation of in Situ Assembled La0.6Sr0.4Co0.2Fe0.8O3-δ Electrodes on Y2O3-ZrO2 Electrolyte of Solid Oxide Fuel Cells.

Application of cobaltite-based electrodes such as La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) on Y2O3-ZrO2 (YSZ) electrolyte in solid oxide fuel cells (SOFCs) generally requires the use of a doped ceria barrier layer to prevent the interaction between LSCF and YSZ during sintering at high temperatures. In this paper, we report for the first time an in situ assembly approach to directly incorporate LSCF cathode to YSZ electrolyte without the use of a doped ceria barrier layer and without presintering at high temperatures. A Ni-YSZ anode-supported YSZ electrolyte cell with an in situ assembled LSCF electrode exhibits a peak power density of 1.72 W cm-2 at 750 °C. However, the cell performance degrades significantly at 500 mAcm-2 and 750 °C. The results indicate that cathodic polarization not only induces the formation of the interface but also accelerates the Sr segregation. The segregated Sr migrates to the LSCF electrode/YSZ electrolyte surface and forms an SrO layer. Using a Sr-free LaCoO3-δ composite cathode overcomes the Sr segregation problem, showing an excellent peak power density of 1.2 Wcm-2 and good stability at 750 °C for over 100 h. The present study shows that cobaltite-based perovskites can be directly used on YSZ-based electrolyte via the in situ assembly providing an effective means to advance the application of highly active mixed ionic/electronic conducting cathodes to YSZ electrolyte-based SOFCs.

Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops.

Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 µm often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The (207)Pb/(206)Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages.

Visualization of Diffusion within Nanoarrays.

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems.

Fly ash based geopolymer thin coatings on metal substrates and its thermal evaluation.

Class F fly ash based Na-geopolymer formulations have been applied as fire resistant coatings on steel. The main variables for the coating formulations were Si: Al molar and water: cement weight ratios. We have determined that the adhesive strength of the coatings strongly depend on geopolymer composition. The ease with which geopolymer can be applied onto metal surfaces and the resultant thickness depend on the water content of the formulation. Adhesive strengths of greater than 3.5 MPa have been achieved on mild steel surfaces for compositions with Si:Al of 3.5. Microstructure evolution and thermal properties of the optimised coating formulations show that they have very promising fire resistant characteristics.