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At least 1,063 records · Page 59

Toward Molecule-Specific Geochemistry of Heavy Ends: Application to the Upstream Oil Industry

Detailed molecular analysis of the composition of petroleum is typically performed on only the light (volatile) fraction, using analyses involving gas chromatography (GC). Heavier (nonvolatile) components such as kerogen, bitumen, and asphaltenes, which are relevant to conventional reservoirs and particularly to unconventional gas shale and tight oil formations, are not amenable to analysis by GC and instead are typically studied by more phenomenological techniques. This report describes a suite of analytical techniques that can provide sufficient average molecular information on the heavy ends (defined as the nonvolatile fraction) to be useful for a variety of industrial applications, expanding the discipline of molecule-specific geochemistry into the non-GC amenable fractions of petroleum materials. Heavy ends are composed of the elements C, H, N, S, and O, and the bonding environments of each can be measured by various solid state spectroscopies: nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies for C, H, and O; X-ray absorption near-edge structure (XANES) spectroscopy for S and N. Additionally, advances in mass spectrometry, including techniques such as laser desorption laser ionization mass spectrometry (L2MS), can be used to measure the molecular weight and dominant molecular architecture of asphaltenes. Moreover, higher-order structures can be measured: samples of kerogen with representative pore geometry can be prepared, and those pore systems are analyzed with techniques such as X-ray diffraction and neutron scattering. Colloidal structures of asphaltenes can be measured with a variety of techniques, which reveal a hierarchical aggregation structure. These analyses provide sufficient structural data to enable structure–property and structure–function relationships to be determined, which can be applied to the characterization of conventional and unconventional resources. In gas shale and tight oil formations, which contain abundant inorganic minerals as well as kerogen, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used for simultaneous analysis of mineralogy, kerogen content, and maturity, typically performed at the wellsite. In conventional reservoirs, spatial variations in the asphaltene concentration measured by downhole fluid analysis logging tools are being interpreted with a recently developed equation of state to address upstream issues such as reservoir connectivity, tar mat formation, and fault block migration. Furthermore, as more heavy end analyses are developed, further scientific knowledge and industrial applications of heavy end geochemistry are anticipated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Genome sequence and functional genomic analysis of the oil-degrading bacterium Oleispira antarctica

Ubiquitous bacteria from the genus Oleispira drive oil degradation in the largest environment on Earth, the cold and deep sea. Here we report the genome sequence of Oleispira antarctica and show that compared with Alcanivorax borkumensis—the paradigm of mesophilic hydrocarbonoclastic bacteria—O. antarctica has a larger genome that has witnessed massive gene-transfer events. We identify an array of alkane monooxygenases, osmoprotectants, siderophores and micronutrient-scavenging pathways. We also show that at low temperatures, the main protein-folding machine Cpn60 functions as a single heptameric barrel that uses larger proteins as substrates compared with the classical double-barrel structure observed at higher temperatures. With 11 protein crystal structures, we further report the largest set of structures from one psychrotolerant organism. The most common structural feature is an increased content of surface-exposed negatively charged residues compared to their mesophilic counterparts. Our findings are relevant in the context of microbial cold-adaptation mechanisms and the development of strategies for oil-spill mitigation in cold environments.

59 BASIC BIOLOGICAL SCIENCES↗

Emissions leakage and economic losses may undermine deforestation-linked oil crop import restrictions

Import restrictions on deforestation-linked commodities are being considered strategies to reduce global deforestation and emissions. However, limited market share of importers imposing such restrictions and the potential for emissions leakage could reduce their effectiveness. Moreover, they could result in negative economic implications for producers and consumers. We quantify future emissions and economic implications of oil palm and soybean import restrictions. Current EU restrictions will likely have minimal impact due to the EU’s otherwise small and diminishing share of global palm and soy demand. If extended beyond the EU, such import restrictions could drive reductions in cumulative LUC emissions by 2050 in key oil crop exporting regions— up to 0.9% in Indonesia, 1.5% in the rest of Southeast Asia, 3.8% in Argentina and 6.7% in Brazil, relative to a scenario with no import restrictions. However, these key exporters could also face losses ranging $\$$4.1-$\$$61 billion in cumulative agricultural production revenue by 2050.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Daily Satellite Observations of Methane from Oil and Gas Production Regions in the United States

Production of oil and natural gas in North America is at an all-time high due to the development and use of horizontal drilling and hydraulic fracturing. Methane emissions associated with this industrial activity are a concern because of the contribution to climate radiative forcing. We present new measurements from the space-based TROPOspheric Monitoring Instrument (TROPOMI) launched in 2017 that show methane enhancements over production regions in the United States. In the Uintah Basin in Utah, TROPOMI methane columns correlated with in-situ measurements, and the highest columns were observed over the deepest parts of the basin, consistent with the accumulation of emissions underneath inversions. In the Permian Basin in Texas and New Mexico, methane columns showed maxima over regions with the highest natural gas production and were correlated with nitrogen-dioxide columns at a ratio that is consistent with results from in-situ airborne measurements. The improved detail provided by TROPOMI will likely enable the timely monitoring from space of methane emissions associated with oil and natural gas production.

54 ENVIRONMENTAL SCIENCES↗

Quantitative 13 C NMR characterization of fast pyrolysis oils

Quantitative 13 C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

09 BIOMASS FUELS↗

Active motion of multiphase oil droplets: emergent dynamics of squirmers with evolving internal structure

Synthetic soft matter systems, when driven beyond equilibrium by active processes, offer the potential to achieve dynamical states and functions of a complexity found in living matter. Emulsions offer the basis of a simple yet versatile system for identification of the physicochemical principles underlying active soft matter, but how multiple internal phases within emulsion droplets (e.g., Janus morphologies) organize to impact emergent dynamics is not understood. Here, we create multiphase oil droplets with ultralow interfacial tensions but distinct viscosities, and drive them into motion in aqueous micellar solutions. Preferential solubilization of select components of the oil both drives the droplet motion and yields a progression of internal phase morphological states with distinct symmetries. In this work, we find the active droplets to exhibit five dynamical states during morphogenesis. By quantifying microscopic flow fields, we show that it is possible to map the diverse droplet behaviors to squirmer models of spherical microswimmers in Stokes flow, thus showing that multiphase droplets offer the basis of a versatile platform with which to study and engineer the hydrodynamics of microswimmers.

36 MATERIALS SCIENCE↗

The Effects of Polyolefin Structure and Source on Pyrolysis-Derived Plastic Oil Composition

Seven types of plastics were pyrolyzed in a fluidized bed reactor: post-consumer recycled (PCR) high-density polyethylene (HDPE), PCR polypropylene (PP), virgin resins of varying molecular weights of HDPE, virgin resins of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and (PP). Pyrolysis produced non-condensable gases (C1-C3), liquid phase products (C4-C40), and solids (C40+ and chars), with alkane, alkene, alkadiene, aromatic, and multi-cycloaromatics as the predominant compounds. Polymer structure had the greatest impact on product distribution, with minimal influence from molecular weight. Branches in polyethylene (PE) acted as thermal defects initiating degradation. Higher branch density in PE led to increased concentrations of aromatics, branched alkanes, and internal alkenes. PP and PE exhibited distinct degradation mechanisms, with PP requiring less energy for decomposition and yielding more oil. Here, pyrolysis oil from PCR HDPE and PCR PP contained a higher proportion of branched compounds. Additives in PCR plastics may promote isomerization during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of synthesis time on graphene growth from palm oil as green carbon precursor

Graphene is the new material that arises after carbon nanotubes (CNTs) era and has extraordinary optical, electronic and mechanical properties compared to CNTs. The 2D graphene is the sp{sup 2} carbon allotropes compared to other dimensionality. It also can be in three forms that are zero-dimensional, one-dimensional or three-dimensional. The different dimensionality also called fullerenes, nanotubes and graphite. Therefore, the graphene is known as centre potential materials in expanding research area than others ever. The 2 cm × 2 cm silicon wafer was seeded with nickel (Ni) at different thickness by using sputter coater. The palm oil, carbon source, was placed in the precursor furnace and the silicon was placed in the second furnace (deposition furnace). The palm oil will mix with Nitrogen gas was used as carrier gas in the CVD under certain temperature and pressure to undergo pyrolysis proses. The deposition temperature was set at 1000 °C. The deposition time varied from 3 minutes, 5 minutes and 7 minutes. The graphene was growth at ambient pressure in the CVD system. Electron microscopy and Raman Spectrometer revealed the structural properties and surface morphology of the grapheme on the substrate. The D and G band appear approximately at 1350 cm{sup −1} and 1850 cm{sup −1}. It can be concluded that the growth of graphene varies at different deposition time.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Genome features of a novel hydrocarbonoclastic Chryseobacterium oranimense strain and its comparison to bacterial oil-degraders and to other C. oranimense strains

For the first time, we report the whole genome sequence of a hydrocarbonoclastic Chryseobacterium oranimense strain isolated from Trinidad and Tobago (COTT) and its genes involved in the biotransformation of hydrocarbons and xenobiotics through functional annotation. The assembly consisted of 11 contigs with 2,794 predicted protein-coding genes which included a diverse group of gene families involved in aliphatic and polycyclic hydrocarbon degradation. Comparative genomic analyses with 18 crude-oil degrading bacteria in addition to two C. oranimense strains not associated with oil were carried out. The data revealed important differences in terms of annotated genes involved in the hydrocarbon degradation process that may explain the molecular mechanisms of hydrocarbon and xenobiotic biotransformation. Notably, many gene families were expanded to explain COTT’s competitive ability to manage habitat-specific stressors. Gene-based evidence of the metabolic potential of COTT supports the application of indigenous microbes for the remediation of polluted terrestrial environments and provides a genomic resource for improving our understanding of how to optimize these characteristics for more effective bioremediation.

59 BASIC BIOLOGICAL SCIENCES↗

Elastic full-waveform inversion and parameterization analysis applied to walk-away vertical seismic profile data for unconventional (heavy oil) reservoir characterization

We report seismic full-waveform inversion (FWI) methods hold strong potential to recover multiple subsurface elastic properties for hydrocarbon reservoir characterization. Simultaneously updating multiple physical parameters introduces the problem of interparameter tradeoff, arising from the covariance between different physical parameters, which increases nonlinearity and uncertainty of multiparameter FWI. The coupling effects of different physical parameters are significantly influenced by model parameterization and acquisition arrangement. An appropriate choice of model parameterization is critical to successful field data applications of multiparameter FWI. The objective of this paper is to examine the performance of various model parameterizations in isotropic-elastic FWI with walk-away vertical seismic profile (W-VSP) dataset for unconventional heavy oil reservoir characterization. Six model parameterizations are considered: velocity-density (α, β and ρ'), modulus-density (κ, μ and ρ), Lamé-density (λ, μ' and ρ'''), impedance-density (IP, IS and ρ''), velocity-impedance-I (α', β' and I' P ), and velocity-impedance-II (α'', β'' and I'S). We begin analyzing the interparameter tradeoff by making use of scattering radiation patterns, which is a common strategy for qualitative parameter resolution analysis. In this paper, we discuss the advantages and limitations of the scattering radiation patterns and recommend that interparameter tradeoffs be evaluated using interparameter contamination kernels, which provide quantitative, second-order measurements of the interparameter contaminations and can be constructed efficiently with an adjoint-state approach. Synthetic W-VSP isotropic-elastic FWI experiments in the time domain verify our conclusions about interparameter tradeoffs for various model parameterizations. Density profiles are most strongly influenced by the interparameter contaminations; depending on model parameterization, the inverted density profile can be over-estimated, under-estimated or spatially distorted. Among the six cases, only the velocity-density parameterization provides stable and informative density features not included in the starting model. Field data applications of multicomponent W-VSP isotropic-elastic FWI in the time domain were also carried out. Finally, the heavy oil reservoir target zone, characterized by low α-to-β ratios and low Poisson’s ratios, can be identified clearly with the inverted isotropic-elastic parameters.

58 GEOSCIENCES↗

Packaging “vegetable oils”: Insights into plant lipid droplet proteins

Abstract Plant neutral lipids, also known as “vegetable oils”, are synthesized within the endoplasmic reticulum (ER) membrane and packaged into subcellular compartments called lipid droplets (LDs) for stable storage in the cytoplasm. The biogenesis, modulation, and degradation of cytoplasmic LDs in plant cells are orchestrated by a variety of proteins localized to the ER, LDs, and peroxisomes. Recent studies of these LD-related proteins have greatly advanced our understanding of LDs not only as steady oil depots in seeds but also as dynamic cell organelles involved in numerous physiological processes in different tissues and developmental stages of plants. In the past 2 decades, technology advances in proteomics, transcriptomics, genome sequencing, cellular imaging and protein structural modeling have markedly expanded the inventory of LD-related proteins, provided unprecedented structural and functional insights into the protein machinery modulating LDs in plant cells, and shed new light on the functions of LDs in nonseed plant tissues as well as in unicellular algae. Here, we review critical advances in revealing new LD proteins in various plant tissues, point out structural and mechanistic insights into key proteins in LD biogenesis and dynamic modulation, and discuss future perspectives on bridging our knowledge gaps in plant LD biology.

Cai, Yingqi (ORCID:0000000203575809)↗

Towards rational control of seed oil composition: dissecting cellular organization and flux control of lipid metabolism

Plant lipids represent a fascinating field of scientific study, in part due to a stark dichotomy in the limited fatty acid (FA) composition of cellular membrane lipids vs the huge diversity of FAs that can accumulate in triacylglycerols (TAGs), the main component of seed storage oils. With few exceptions, the strict chemical, structural, and biophysical roles imposed on membrane lipids since the dawn of life have constrained their FA composition to predominantly lengths of 16–18 carbons and containing 0–3 methylene-interrupted carbon-carbon double bonds in cis-configuration. However, over 450 “unusual” FA structures can be found in seed oils of different plants, and we are just beginning to understand the metabolic mechanisms required to produce and maintain this dichotomy. Here we review the current state of plant lipid research, specifically addressing the knowledge gaps in membrane and storage lipid synthesis from 3 angles: pathway fluxes including newly discovered TAG remodeling, key acyltransferase substrate selectivities, and the possible roles of “metabolons.”

59 BASIC BIOLOGICAL SCIENCES↗

Complete replacement of Arabidopsis oil-producing enzymes with heterologous diacylglycerol acyltransferases

Acyl-CoA:diacylglycerol acyltransferase 1 (DGAT1) and phospholipid:diacylglycerol acyltransferase 1 (PDAT1) share responsibility for triacylglycerol (TAG) biosynthesis, and their selectivities control TAG fatty acid (FA) compositions. For rational metabolic engineering of seed oils, replacing endogenous TAG biosynthesis with exogenous enzymes containing different substrate FA selectivities is desirable; however, the dgat1-1/pdat1-2 double mutant is pollen lethal. Here, we evaluated the ability of 3 DGAT1s, from phylogenetically diverse plants with distinct TAG assembly processes, to completely replace endogenous TAG biosynthesis in Arabidopsis ( Arabidopsis thaliana ). We transformed dgat1-1 mutant plants with expression constructs for DGAT1 s from Camelina sativa , Physaria fendleri , and castor ( Ricinus communis ). Transgene expression was properly “contextualized” by using a previously determined minimum necessary expression unit containing the promoter/5′ UTR and first intron of native AtDGAT1 ; both of these DNA elements are essential for pollen expression. Next, we crossed homozygous lines with a DGAT1/DGAT1/PDAT1/pdat1-2 parent. C. sativa and P. fendleri DGAT1s restored the FA compositions and transcriptional differences of dgat1-1 to near wild-type and rescued the dgat1-1/pdat1-2 pollen lethality. R. communis DGAT1 was active in dgat1-1 seeds but produced unique oil profiles and alterations in the expression of lipid metabolic genes; it also failed to rescue dgat1-1/pdat1-2 lethality. This study confirms that the promoter and first intron of AtDGAT1 can modulate the expression of foreign DGAT1 genes to fit the correct spatiotemporal profile necessary for completely replacing endogenous TAG biosynthesis. Furthermore, it demonstrates an additional layer of unexpected enzyme incompatibility between oilseed lineages, which may complicate bioengineering approaches that seek to replace essential genes with orthologs.

McGuire, Sean T. [Washington State Univ., Pullman,↗

Metabolic flux, metabolite, and transcript analysis uncover reprogramming of metabolism toward higher seed oil

Overexpression of WRINKLED1 (WRI1), a master regulator of glycolysis and fatty acid biosynthesis, together with DIACYLGLYCEROL ACYLTRANSFERASE1 (DGAT1), which catalyzes the final step of triacylglycerol assembly, is a promising strategy for enhancing seed oil content. However, how these regulators coordinate system-wide metabolic reprogramming at the levels of gene expression, metabolite pools, and fluxes remains poorly understood. To address this, we performed 13 C-metabolic flux analysis, metabolomics, and transcriptomics on in vitro cultured pennycress (Thlaspi arvense L.) embryos overexpressing the native WRI1 and DGAT1 homologs. Here, in cultured embryos, WRI1/DGAT1 overexpression increased triacylglycerol accumulation by 28% while reducing protein content by 34%, relative to the wild type. Embryos showed ∼20-fold and 50-fold upregulation of WRI1 and DGAT1 along with induction of WRI1 target genes in glycolysis and fatty acid biosynthesis. Genes associated with photosynthesis and Calvin cycle functions were also upregulated, whereas genes encoding ribosomal proteins and seed storage proteins were strongly repressed, consistent with the observed lipid–protein tradeoff. Flux analysis revealed that enhanced triacylglycerol biosynthesis is supported by increased flux through the Rubisco shunt and cytosolic pyruvate kinase, while the oxidative pentose phosphate pathway and malic enzyme contributed little to NADPH or pyruvate supply. Metabolomic profiling revealed extensive perturbations in glycolytic intermediates, tricarboxylic acid cycle metabolites, and amino acids. In plant grown seeds, WRI1/DGAT1 lines also showed a modest but significant increase in total lipid content. Collectively, these findings reveal how WRI1 and DGAT1 reprogram central metabolism to enhance oil accumulation, with relevance to mature seeds.

59 BASIC BIOLOGICAL SCIENCES↗

Quality of goat′s milk cheese as affected by coating with edible chitosan‐essential oil films

The effectiveness of applying chitosan coatings containing rosemary and oregano essential oils to cheeses was analysed. Cheeses were coated by immersing the samples two or three times successively in the different formulations. The ripening indexes, water loss, fungal growth and sensory properties of the coated and noncoated cheeses throughout ripening were evaluated. The coatings both prevented weight loss and improved the microbial safety. The lipolytic and proteolytic activities were reduced in coated cheese, which is in line with the antimicrobial effect of active coatings. Sensory evaluation revealed that the cheeses double‐coated with chitosan–oregano oil were the best evaluated in terms of aroma and flavour.

Cano Embuena, Amalia Isabel↗

Identification and analysis of stem‐specific promoters from sugarcane and energy cane for oil accumulation in their stems

Abstract Considerable recent progress has been achieved in bioengineering oil accumulation in the vegetative tissues of plants, opening an opportunity for large scale production of biodiesel, jet fuel, lubricants, and high‐value lipid bioproducts. For the highly productive C4 crops, such as sugarcane, energy cane, Miscanthus, and fiber sorghums, the bulk of the biomass is the stem. However, little success has been made in accumulating oil in the stem. Since engineering a trait with a constitutive promoter often results in pleiotropic effects that counter trait improvement, identification of stem parenchyma‐specific promoters is a prerequisite for efficient use of the ample photoassimilates stored in mature stem parenchyma cells. In this study, we first identified two TST genes encoding homologues of tonoplast sugar transporters that were strongly and almost exclusively expressed in the stems of canes via a combination of RNA‐seq atlas analysis, in silico analysis of a sugarcane genome, phylogenetic analysis, and quantitative PCR analysis. They were further confirmed in the pith parenchyma cells of the mature stem by RNA in situ hybridization. When fused with the β‐Glucuronidase (GUS) reporter gene, the promoters of two alleles, TST2b‐1A and TST2b‐1C , from one TST gene demonstrated that they could drive the GUS expression exclusively in the stem in Arabidopsis.

09 BIOMASS FUELS↗

Interactive effects of dietary fishmeal level and plant essential oils supplementation on European sea bass, Dicentrarchus labrax : Growth performance, nutrient utilization, and immunological response

Abstract The inclusion of phytogenics in fish feed is a promising strategy to compensate for the negative performance effects of replacing fishmeal (FM) with vegetable sources. The present work assessed the interactive effects of different dietary FM levels (22.5 and 10% of formulation) and the supplementation of a commercial blend of anise, citrus, and oregano essential oils (Digestarom PEP M.G.E 150) on European sea bass, Dicentrarchus labrax growth performance, nutrient utilization, gut morphology, antioxidant status, and immunological response over a 60‐day growth trial. Results showed decreased growth and protein efficiency ratio and increased feed conversion ratio with a low dietary FM level. In contrast, supplementation of the phytogenic product demonstrated improved performance and nutrient utilization together with increased protein and energy retention. Supplementation with the plant essential oils fully compensated for the negative intestinal changes observed in sea bass fed a low‐FM diet but showed little improvement in fish immunological response, except for the 30% increase in lysozyme activity observed in fish fed the low FM‐supplemented diet compared to those fed the standard high‐FM diet. Overall, this study supports the use of this phytogenic product in low‐FM diets as a possible tool to decrease feed costs associated with FM without compromising fish performance, nutrient utilization, and health.

Gonçalves, Rui A.↗