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227 records · Page 13

M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗

Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions: Two-Dimensional Uranyl Borates: From Conventional to Extreme Synthetic Conditions

A systematic investigation of uranyl borates under different synthetic conditions resulted in five new 2D compounds, namely, (H 3 O)[(UO 2 )(BO 3 )], Li[(UO 2 )(BO 3 )] · (H 2 O), α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ], β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 . (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O) were obtained from hydrothermal reactions at 220 °C using the same mineralizer. Both materials possess the uranophane sheet topology with different symmetry of the unit cells. In the structure of (H 3 O)[(UO 2 )(BO 3 )] and Li[(UO 2 )(BO 3 )] · (H 2 O), UO 7 pentagonal bipyramids share edges and vertexes with four BO 3 planar triangles. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] and β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] are polytypes. α-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was synthesized from a high-temperature solid-state reaction under ambient pressure; whereas β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] was obtained from a high-temperature/high-pressure (HT/HP) reaction. Both structures have an identical anion topology, but β-K 4 [(UO 2 ) 5 (BO 3 ) 2 O 4 ] crystallizes in space group with higher symmetry. In K 2.5 [(UO 2 ) 5 (BO 3 ) 2 O 2.5 (OH) 1.5 ] · (H 2 O) 2.5 , which was obtained from a hydrothermal reaction, UO 7 polyhedra share vertexes and edges with two independent BO 3 triangles, forming the most complex uranyl borate layers among all five compounds. The different synthetic routes, novel topologies, thermal behavior and Raman spectra are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determining the Biogenicity of Microfossils in the Apex Chert, Western Australia, Using Transmission Electron Microscopy

For over a decade, the oldest evidence for life on this planet has been microfossils in the 3.5 Ga Apex Chert in Western Australia. Recently, the biogenicity of these carbon-rich structures has been called into question through reanalysis of the local geology and reinterpretation of the original thin sections. Although initially described as a stratiform, bedded chert of siliceous clasts, the unit is now thought to be a brecciated hydrothermal vein chert. The high temperatures of a hydrothermal environment would probably have detrimental effects to early non-hyperthermophilic life, compared to that of a shallow sea. Conversely, a hydrothermal origin would suggest that if the microfossils were valid, they might have been hyperthermophilic. Apex Chert controversy. The Apex Chert microfossils were originally described as septate filaments composed of kerogen similar in morphology to Proterozoic and modern cyanobacteria. However new thin section analysis shows that these carbonaceous structures are not simple filaments. Many of the original microfossils are branched and have variable thickness when the plane of focus is changed. Hydrothermal alteration of organic remains has also been suggested for the creation of these strange morphologies. Another point of contention lies with the nature of the carbon material in these proposed microfossils. Kerogen is structurally amorphous, but transforms into well-ordered graphite under high pressures and temperatures. Raman spectrometry of the carbonaceous material in the proposed microfossils has been interpreted both as partially graphitized kerogen and amorphous graphite. However, these results are inconclusive, since Raman spectrometry cannot adequately discriminate between kerogen and disordered graphite. There are also opposing views for the origin of the carbon in the Apex Chert. The carbon would be biogenic if the proposed microfossils are indeed the remains of former living organisms. However, an inorganic Fischer- Tropsch-type synthesis is also a possible explanation for the formation of large-aggregate carbonaceous particles and could also account for the depletion of (13)C observed.

DeGregorio, B. T.↗

Bioprocessing, Recovery, and Mass Balance of Vegetative Lipids from Metabolically Engineered “Oilcane” Demonstrates Its Potential as an Alternative Feedstock for Drop-In Fuel Production

Plant oils are increasingly in demand as renewable feedstocks for biodiesel and biochemicals. Currently, oilseeds are the primary source of plant oils. Although the vegetative tissues of plants express lipid metabolism pathways, they do not hyper- accumulate lipids. Elevated synthesis, storage, and accumulation of lipids in vegetative tissues have been achieved by metabolic engineering of sugarcane to produce “oilcane”. This study evaluates the potential of oilcane as a renewable feedstock for the co- production of lipids and fermentable sugars. Oilcane was grown under favorable climatic and field conditions in Florida (FLOC) as well as during an abbreviated growing season, outside its typical growing region, in Illinois (ILOC). The potential lipid yield of 0.35 tons/ha was projected from the hyperaccumulation of fatty acids in the stored vegetative biomass of FLOC, which is approaching the lipid yield of soybean (0.44 tons/ha). Processing of the vegetative tissues of oilcane recovered 0.20 tons/ha, which represents the recovery of 55% of the total lipids from FLOC. Chemical-free hydrothermal bioprocessing of ILOC and FLOC bagasse and leaves at 180 °C for 10 min prevented the degeneration of in situ plant lipids. Here, this allowed the recovery of lipids at the end of the bioprocess with a major fraction of lipids remaining in the biomass residues after pretreatment and saccharification. Improvements through refined biomass processing, crop management, and metabolic engineering are expected to boost lipid yields and make oilcane a prime feedstock for the production of biodiesel.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data for Bioprocessing, Recovery, and Mass Balance of Vegetative Lipids from Metabolically Engineered ‘Oilcane’ Demonstrates Its Potential as an Alternative Feedstock for Drop-In Fuel Production

Plant oils are increasingly in demand as renewable feedstocks for biodiesel and biochemicals. Currently, oilseeds are the primary source of plant oils. Although the vegetative tissues of plants express lipid metabolism pathways, they do not hyper-accumulate lipids. Elevated synthesis, storage, and accumulation of lipids in vegetative tissues have been achieved by metabolic engineering of sugarcane to produce “oilcane.” This study evaluates the potential of oilcane as a renewable feedstock for the co-production of lipids and fermentable sugars. Oilcane was grown under favorable climatic and field conditions in Florida (FLOC) as well as during an abbreviated growing season, outside its typical growing region, in Illinois (ILOC). The potential lipid yield of 0.35 tons/ha was projected from the hyperaccumulation of fatty acids in the stored vegetative biomass of FLOC, which is approaching the lipid yield of soybean (0.44 tons/ha). Processing of the vegetative tissues of oilcane recovered 0.20 tons/ha, which represents the recovery of 55% of the total lipids from FLOC. Chemical-free hydrothermal bioprocessing of ILOC and FLOC bagasse and leaves at 180 °C for 10 min prevented the degeneration of in situ plant lipids. This allowed the recovery of lipids at the end of the bioprocess with a major fraction of lipids remaining in the biomass residues after pretreatment and saccharification. Improvements through refined biomass processing, crop management, and metabolic engineering are expected to boost lipid yields and make oilcane a prime feedstock for the production of biodiesel.

Conversion↗

Electrocatalytic benchmarking of ruthenium-based bimetallic anodes for the electrocatalytic oxidation of biomass-derived wastewater

In this paper, we report on the synthesis, characterization, and use of ruthenium oxide (RuO 2 ) doped with a secondary metal (M2) to enhance electrochemical activity and stability for the electrocatalytic oxidation (ECO) of biomass-derived wastewaters. We used different electrochemical methods such as cyclic voltammetry (CV), electrochemical surface area (ECSA), and Tafel analysis as well as physical characterization such as grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy to understand how the introduction of M2 affects electrochemical performance. Our results show that including an M2 improves the ECO performance regardless of the composition of the electrolyte. Specifically, we saw increase in ECSA, which could be due to enhanced charge transfer for the pH ranges evaluated. Furthermore, the introduction of organic compounds in wastewater generated during the hydrothermal liquefaction of food waste affected the ECO performance differently, depending on M2, the electrolyte composition, and anodic half-cell potential, highlighting the need to properly control the reaction conditions when testing and characterizing the electrocatalysts under different reaction regimes. We developed an in situ electrocatalytic benchmarking protocol, Boruah – Lopez-Ruiz – Strange (BLoRS), to quickly assess if the presence of M2 improves the ECO performance; thus, saving time and resources in ex situ characterization, testing, and product analysis. This foundational work provides the basis for characterization and benchmarking of electrodes of the ECO of organic compounds.

Electrocatalysis↗

RIO Tinto Faulted Volcanosedimentary Deposits as Analog Habitats for Extant Subsurface Biospheres on Mars: A Synthesis of the MARTE Drilling Project Geobiology Results

Geochemistry and mineralogy on Mars surface characterized by the MER Opportunity Rover suggest that early Mars hosted acidic environments in the Meridiani Planum region [1, 2]. Such extreme paleoenvironments have been suggested to be a regional expression of the global Mars geological cycle that induced acidic conditions by sulfur complexation and iron buffering of aqueous solutions [3]. Under these assumptions, underground reservoirs of acidic brines and, thereby, putative acidic cryptobiospheres, may be expected. The MARTE project [4, 5] has performed a drilling campaign to search for acidic and anaerobic biospheres in R o Tinto basement [6] that may be analogs of these hypothetical communities occurring in cryptic habitats of Mars. This Rio Tinto geological region is characterized by the occurrence of huge metallic deposits of iron sulfides [7]. Late intensive diagenesis of rocks driven by a compressive regimen [8] largely reduced the porosity of rocks and induced a cortical thickening through thrusting and inverse faulting and folding. Such structures play an essential role in transporting and storing water underground as any other aquifers do in the Earth. Once the underground water reservoirs of the Ro Tinto basement contact the hydrothermal pyrite deposits, acidic brines are produced by the release of sulfates and iron through the oxidation of sulfides [9].

Fernandez-Remolar, D. C.↗

The Global Biogeochemical Cycle of Rhenium

Here, this paper is the first comprehensive synthesis of what is currently known about the different natural and anthropogenic fluxes of rhenium (Re) on Earth's surface. We highlight the significant role of anthropogenic mobilization of Re, which is an important consideration in utilizing Re in the context of a biogeochemical tracer or proxy. The largest natural flux of Re derives from chemical weathering and riverine transport to the ocean (dissolved = 62 × 10 6 g yr -1 and particulate = 5 × 10 6 g yr -1 ). This review reports a new global average [Re] of 16 ± 2 pmol L -1 , or 10 ± 1 pmol L -1 for the inferred pre-anthropogenic concentration without human impact, for rivers draining to the ocean. Human activity via mining (including secondary mobilization), coal combustion, and petroleum combustion mobilize approximately 560 × 10 6 g yr -1 Re, which is more than any natural flux of Re. There are several poorly constrained fluxes of Re that merit further research, including: submarine groundwater discharge, precipitation (terrestrial and oceanic), magma degassing, and hydrothermal activity. The mechanisms and the main host phases responsible for releasing (sources) or sequestrating (sinks) these fluxes remain poorly understood. This study also highlights the use of dissolved [Re] concentrations as a tracer of oxidation of petrogenic organic carbon, and stable Re isotopes as proxies for changes in global redox conditions.

58 GEOSCIENCES↗

The relative importance of prebiotic synthesis on the Earth and input from comets and meteorites

The prebiotic synthesis of hydrogen cyanide and formaldehyde was studied by the action of electric discharges on various model primitive atmospheres containing CH4, CO, and CO2. Photochemical production rates would also have been important and were calculated for HCN and H2CO. A reasonable rate of synthesis of amino acids from these sources is about 10 n moles/(sq cm yr) or 0.10 moles/sq cm in 10(exp 7) yrs. This would give a concentration of 3 x 10(exp -4) M in an ocean of the present size (300 liters/sq cm). The amino acids cannot accumulate over a longer period because the entire ocean passes through the 350 C submarine vents in 10(exp 7) yrs, which decomposes all the organic compounds. A number of workers have calculated the influx of comets and meteorites on the primitive earth, both as a destructive process for organic compounds and for any life that was present, as well as a source of organic compounds. Some of the amino acids from the meteorite proposed to have hit the earth 65 x 10(exp 6) yrs ago were detected at the Cretaceous/Tertiary boundary sediments. The problem with proposing a large scale input of organic compounds from meteorites and comets is that they must survive passage through the atmosphere and impact. There are some processes that would allow survival such as showers of centimeter to meter sized meteorites and various aerodynamic braking processes for larger objects. Even if a significant amount of the organic material survived impact, the destructive processes in the hydrothermal vents would remove these compounds on the average in 10(exp 7) yrs or less. If it is assumed that the input rate was sufficient to overcome these destructive processes, then too much carbon and water, especially from comets, would have been added to the surface of the earth. It was concluded that while some organic material was added to the earth from comets and meteorites, the amount available from these sources at a given time was only a few percent of that from earth based syntheses.

Miller, S. L.↗

Investigation of the photoluminescent properties, scintillation behaviour and toxicological profile of various magnesium tungstate nanoscale motifs

We have synthesized several morphologies and crystal structures of MgWO 4 using a one-pot hydrothermal method, producing not only monoclinic stars and large nanoparticles but also triclinic wool balls and sub-10 nm nanoparticles. Herein we describe the importance of reaction parameters in demonstrating morphology control of as-prepared MgWO 4 . Moreover, we correlate structure and composition with the resulting photoluminescence and radioluminescence properties. Specifically, triclinic-phase samples yielded a photoluminescence emission of 421 nm, whereas monoclinic-phase materials gave rise to an emission maximum of 515 nm. The corresponding radioluminescence data were characterized by a broad emission peak, located at 500 nm for all samples. Annealing the wool balls and sub-10 nm particles to transform the crystal structure from a triclinic to a monoclinic phase yielded a radioluminescence (RL) emission signal that was two orders of magnitude greater than that of their unannealed counterparts. Finally, to confirm the practical utility of these materials for biomedical applications, a series of sub-10 nm particles, including as-prepared and annealed samples, were functionalized with biocompatible PEG molecules, and subsequently were found to be readily taken up by various cell lines as well as primary cultured hippocampal neurons with low levels of toxicity, thereby highlighting for the first time the potential of this particular class of metal oxides as viable and readily generated platforms for a range of biomedical applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗