Auswahl der wissenschaftlichen Literatur zum Thema „Aromatic reconstructions“

The peat from the Cherny Yar section at the Vychegda river was studied by a complex of palynological and geochemical methods. We determined that among the aliphatic hydrocarbons of bitumen, the maximum concentrations were characteristic for odd n-alkanes with a predominance of C27-C31 homologues, as well as 18-norabietane. Aromatic hydrocarbons are mainly represented by structures formed during the fossilization of diterpenoids and triterpenoids of higher vegetation. Among the aromatic diterpenoids, there are 18-norabieta-8,11,13-triene, 18-norsimonellite and retene, which are markers of conifers, as well as 18-norabietane of the aliphatic fraction. Among the aromatic triterpenoids, numerous transformation products of compounds with the carbon skeleton of lupan, oleanan, and ursane, characteristic of angiosperms, have been identified. For example, dinorolean(ursa)-1,3,5(10),13(18)-tetraene, dinorolean(ursa)-1,3,5(10)-triene, pentanoroleana-1,3,5(10), 6,8,11,13,17(18)-octaene and others. The data on the composition of hydrocarbons confirm the palynological data about the presence of coniferous and hardwood pollen in the composition of peat. The change in the composition of hydrocarbons along the section confirms the change in the species composition of vegetation in the study area, diagnosed by microfossils. The comparison of the composition of peat biomarker hydrocarbons with palynological data revealed their consistency with each other and possibility of conjugated use of these methods in paleogeographic reconstructions.

Thirty-five semivolatile compounds from the phenolic, chlorinated hydrocarbon, and polynuclear aromatic hydrocarbon classes are analyzed with the use of lightpipe-based gas chromatography/infrared spectrometry in order to determine the minimum identifiable quantities (MIQ) as defined in the U.S. Environmental Protection Agency Method 8410. MIQs for all compounds studied are in the range of 1 to 20 nanograms. The present results represent an improvement of about an order of magnitude over those reported earlier in U.S. EPA studies. An important factor in achieving this improvement is the use of selected wavelength chromatogram reconstructions for locating high-noise chromatogram data files. These data suggest that target analysis of complex semivolatile environmental organic samples is achievable by lightpipe GC/FT-IR.

As water availability becomes a growing challenge in various regions throughout the world, desalination and wastewater reclamation through technologies such as reverse osmosis (RO) are becoming more important. Nevertheless, many open questions remain regarding the internal structure of thin-film composite RO membranes. In this work, fully aromatic polyamide films that serve as the active layer of state-of-the-art water filtration membranes were investigated using high-angle annular dark-field scanning transmission electron microscopy tomography. Reconstructions of the 3D morphology reveal intricate aspects of the complex microstructure not visible from 2D projections. We find that internal voids of the active layer of compressed commercial membranes account for less than 0.2% of the total polymer volume, contrary to previously reported values that are two orders of magnitude higher. Measurements of the local variation in polyamide density from electron tomography reveal that the polymer density is highest at the permeable surface for the two membranes tested and establish the significance of surface area on RO membrane transport properties. The same type of analyses could provide explanations for different flux variations with surface area for other types of membranes where the density is distributed differently. Thus, 3D reconstructions and quantitative analyses will be crucial to characterize the complex morphology of polymeric membranes used in next-generation water-purification membranes.

A Gram-negative, motile, rod-shaped bacteria, designated D7T, was isolated by using the dilution-to-extinction method, from a soil sample taken from Rambla Salada (Murcia, Spain). Growth of strain D7T was observed at 15–40 °C (optimum, 37 °C), pH 5–9 (optimum, 7) and 0–7.5% (w/v) NaCl (optimum, 3%). It is facultatively anaerobic. Phylogenetic analysis based on 16S rRNA gene sequence showed it belongs to the genus Marinobacterium. The in silico DDH and ANI against closest Marinobacterium relatives support its placement as a new species within this genus. The major fatty acids of strain D7T were C16:0, summed feature 3 (C16:1 ω7c/C16:1 ω6c) and summed feature 8 (C18:1 ω7c/C18:1 ω6c). The polar lipid profile consists of phosphatidylethanolamine, phosphatidylglycerol and two uncharacterized lipids. Ubiquinone 8 was the unique isoprenoid quinone detected. The DNA G + C content was 59.2 mol%. On the basis of the phylogenetic, phenotypic, chemotaxonomic and genomic characterization, strain D7T (= CECT 9818T = LMG 31312T) represents a novel species of the genus Marinobacterium for which the name Marinobacterium ramblicola sp. nov. is proposed. Genome-based metabolic reconstructions of strain D7T suggested a heterotrophic and chemolitotrophic lifestyle, as well as the capacity to biosynthetize and catabolize compatible solutes, and to degrade hydrocarbon aromatic compounds.

Abstract. Paleoclimate reconstructions across Iceland provide a template for past changes in climate across the northern North Atlantic, a crucial region due to its position relative to the global northward heat transport system and its vulnerability to climate change. The roles of orbitally driven summer cooling, volcanism, and human impact as triggers of local environmental changes in the Holocene of Iceland remain debated. While there are indications that human impact may have reduced environmental resilience during late Holocene summer cooling, it is still difficult to resolve to what extent human and natural factors affected Iceland's late Holocene landscape instability. Here, we present a continuous Holocene fire record of northeastern Iceland from proxies archived in Stóra Viðarvatn sediment. We use pyrogenic polycyclic aromatic hydrocarbons (pyroPAHs) to trace shifts in fire regimes, paired with continuous biomarker and bulk geochemical records of soil erosion, lake productivity, and human presence. The molecular composition of pyroPAHs and a wind pattern reconstruction indicate a naturally driven fire signal that is mostly regional. Generally low fire frequency during most of the Holocene significantly increased at 3 ka and again after 1.5 ka BP before known human settlement in Iceland. We propose that shifts in vegetation type caused by cooling summers over the past 3 kyr, in addition to changes in atmospheric circulation, such as shifts in North Atlantic Oscillation (NAO) regime, led to increased aridity and biomass flammability. Our results show no evidence of faecal biomarkers associated with human activity during or after human colonisation in the 9th century CE. Instead, faecal biomarkers follow the pattern described by erosional proxies, pointing toward a negligible human presence and/or a diluted signal in the lake's catchment. However, low post-colonisation levels of pyroPAHs, in contrast to an increasing flux of erosional bulk proxies, suggest that farming and animal husbandry may have suppressed fire frequency by reducing the spread and flammability of fire-prone vegetation (e.g. heathlands). Overall, our results describe a fire frequency heavily influenced by long-term changes in climate through the Holocene. They also suggest that human colonisation had contrasting effects on the local environment by lowering its resilience to soil erosion while increasing its resilience to fire.

Abstract Methane is the second most important greenhouse gas on earth. It is produced by methanogenic archaea, which play an important role in the global carbon cycle. Three main methanogenesis pathways are known: in the hydrogenotrophic pathway H2 and carbon dioxide are used for methane production, whereas in the methylotrophic pathway small methylated carbon compounds like methanol and methylated amines are used. In the aceticlastic pathway, acetate is disproportionated to methane and carbon dioxide. However, next to these conventional substrates, further methanogenic substrates and pathways have been discovered. Several phylogenetically distinct methanogenic lineages (Methanosphaera, Methanimicrococcus, Methanomassiliicoccus, Methanonatronarchaeum) have evolved hydrogen-dependent methylotrophic methanogenesis without the ability to perform either hydrogenotrophic or methylotrophic methanogenesis. Genome analysis of the deep branching Methanonatronarchaeum revealed an interesting membrane-bound hydrogenase complex affiliated with the hardly described class 4 g of multisubunit hydrogenases possibly providing reducing equivalents for anabolism. Furthermore, methylated sulfur compounds such as methanethiol, dimethyl sulfide, and methylmercaptopropionate were described to be converted into adapted methylotrophic methanogenesis pathways of Methanosarcinales strains. Moreover, recently it has been shown that the methanogen Methermicoccus shengliensis can use methoxylated aromatic compounds in methanogenesis. Also, tertiary amines like choline (N,N,N-trimethylethanolamine) or betaine (N,N,N-trimethylglycine) have been described as substrates for methane production in Methanococcoides and Methanolobus strains. This review article will provide in-depth information on genome-guided metabolic reconstructions, physiology, and biochemistry of these unusual methanogenesis pathways. Key points • Newly discovered methanogenic substrates and pathways are reviewed for the first time. • The review provides an in-depth analysis of unusual methanogenesis pathways. • The hydrogenase complex of the deep branching Methanonatronarchaeum is analyzed.

Eight stratigraphic sections from well-exposed outcrops of the Early to Middle Miocene Tanjong Formation in the Kalabakan area, southeast Sabah, were investigated using an integrated approach, in which a comprehensive sedimentological facies analysis was linked with bulk geochemistry and palynological analyses. The integration of facies analysis, elemental CHNS, Fourier-transform infrared spectroscopy (FTIR), and palynological data provided a refined evaluation of the origin of organic matter (OM) and the reconstruction of the paleodepositional model. Seven facies associations were classified in the studied Tanjong Formation from 12 lithofacies components, interpreted as environments ranging from fluvial-deltaic to shallow marine: FA1—Floodplain, FA2—Fluvial channel, FA3—Coastal peat mires, FA4—Tidal flat, FA5—Delta front, FA6—Mouth bar, and FA7—Upper shoreface. Evaluation of the C/N ratio ranged between 4 and 48, and the total sulfur content ranged from 0.5 to 3. Elemental CHNS analysis suggests that the organic matter extracted from the coal and mudstone originated from terrestrial plants and fresh marine plankton. Accordingly, the three most prevalent FTIR spectra from the coal and mudstone samples were the OH- functional group stretching, the absorption spectrum of aromatic C=C stretching, and aromatic in-plane/out-of-plane C-H bending. Terrestrially derived organic matter within the examined samples was further validated by the predominance of aromatic compounds, and the palynological analysis indicated a back-mangrove freshwater pollen assemblage and a lower coastal plain setting proximal to the marine environment. The integrated findings from this research are vital in reconstructing a paleodepositional environment model that will improve the predictability of the petroleum system mechanisms and the future hydrocarbon potential for conventional petroleum exploration.

Before being put to use, wooden railway sleepers are impregnated with creosote to increase their longevity and protect them from any adverse environmental impact. Creosote consists of a number of chemical substances, and some of those substances, namely, the polycyclic aromatic hydrocarbons, phenolic compounds and heterocyclic aromatic compounds, are potent carcinogens. Apart from polycyclic aromatic hydrocarbons and phenolic compounds, during their use, sleepers are mostly contaminated with heavy metals and petroleum products. Upon railway reconstruction, wooden railway sleepers become the waste, which must be handled by the current legislation of the European Union. After determining the concentration of contaminants with laboratory research, it is possible to identify their hazard level and classify them as hazardous or non-hazardous waste. After conducting laboratory research on the waste of wooden railway sleeper analysed, they are classified as hazardous waste.

Molecular group composition analysis of mineral oils is helpful to predict the performance of a future lubricant and to assess the compatibility of plasticizer oil with rubbers. The method of pulsed low-frequency NMR relaxation was used to determine the molecular group composition of 11 mineral oil samples, and the ratio of aromatic and non-aromatic hydrocarbons in them was calculated. NMR measurements were performed on a Chromatec-Proton 20M NMR analyzer with a 1H resonance frequency of 20 MHz. The method used consists in recording free induction decay signals, reconstructing the total signal amplitude, estimating the relative signal amplitude per unit mass of the sample, and calculating the proportion of aromatic hydrocarbons in the sample. The results were compared with those obtained by the standard chromatographic method. A high degree of correlation (R2 = 0.99) was observed between the results.

ABSTRACT In this study, the carotenoid biosynthetic pathways of Brevibacterium linens DSMZ 20426 were reconstructed, redesigned, and extended with additional carotenoid-modifying enzymes of other sources in a heterologous host Escherichia coli. The modular lycopene pathway synthesized an unexpected carotenoid structure, 3,4-didehydrolycopene, as well as lycopene. Extension of the novel 3,4-didehydrolycopene pathway with the mutant Pantoea lycopene cyclase CrtY2 and the Rhodobacter spheroidene monooxygenase CrtA generated monocyclic torulene and acyclic oxocarotenoids, respectively. The reconstructed β-carotene pathway synthesized an unexpected 7,8-dihydro-β-carotene in addition to β-carotene. Extension of the β-carotene pathway with the B. linens β-ring desaturase CrtU and Pantoea β-carotene hydroxylase CrtZ generated asymmetric carotenoid agelaxanthin A, which had one aromatic ring at the one end of carotene backbone and one hydroxyl group at the other end, as well as aromatic carotenoid isorenieratene and dihydroxy carotenoid zeaxanthin. These results demonstrate that reconstruction of the biosynthetic pathways and extension with promiscuous enzymes in a heterologous host holds promise as a rational strategy for generating structurally diverse compounds that are hardly accessible in nature.

The Apicomplexa are a phylum of single celled parasitic organisms that cause a wide range of diseases from human malaria and encephalitis in AlDs patients to coccidiosis in chickens and East Coast fever in cattle. There has been a huge effort in recent years to sequence the genomes of many of these pathogens. This thesis begins by taking a comparative genomics approach to predict novel metabolic pathways from the newly sequenced genomes of Toxoplasma gondii and Eimeha tenella.

L’arôme fruité des vins rouges est décrit par une large gamme de descripteurs, allant des fruits frais aux fruits mûrs et confiturés, en passant par les fruits confits jusqu'aux notes de pruneaux. La qualité fruitée d’un vin rouge est décrite par des notes de fruits rouges et noirs frais et confiturés. Bien que de nombreux attributs sensoriels soient mentionnés dans la littérature, les connaissances concernant l'arôme fruité qualitatif des vins rouges par rapport à leur composition chimique nécessitent encore d'être approfondies. Cependant, au moins une composante de cette expression fruitée est le reflet d’interactions perceptives impliquant en majorité des esters, mais également d’autres familles de molécules aromatiques. Au cours de ces dernières années, des changements dans l’expression fruitée des vins rouges de Bordeaux, caractérisés par l’apparition des notes de fruits cuits et secs, ont été rapportés et corrélés au changement climatique. Ainsi, les techniciens du secteur vitivinicole et les scientifiques, soulignent la nécessité de prendre des précautions pour préserver l’arôme fruité frais des vins rouges de Bordeaux. Pour cela, une des stratégies d’adaptation consiste à introduire dans le vignoble bordelais des cépages tardifs sélectionnés pour leur cycle végétatif potentiellement adapté aux futures conditions climatiques. Cette thèse propose une meilleure compréhension de l’arôme fruité des vins rouges issus de cépages de Bordeaux, mais également de cépages cultivés autour du bassin méditerranéen, zone simulant les futures conditions climatiques de Bordeaux. Grâce à des approches sensorielles, il a été montré que des vins rouges de Bordeaux présentaient des similitudes avec des vins rouges issus de cépages implantés dans le pourtour méditerranéen au niveau de leur caractère fruité. Une caractérisation approfondie de la contribution des composés volatils d’intérêt dans la perception des notes fruitées a été réalisée. Des interactions perceptives entre des composés de la famille des monoterpènes et des C13-norisoprénoïdes en mélange avec des esters, ont révélé l’importance de ces composés dans la perception des notes fruitées. Enfin, l’addition de ces composés volatils dans un vin rouge montre une diminution des notes de fruits cuits et une augmentation des notes de fruits noirs frais. Ces travaux de recherche ouvrent de nouvelles perspectives en œnologie telles que la maîtrise des teneurs de ces composés d’intérêt par diverses pratiques, mais également la potentielle introduction des « nouveaux » cépages dans l’assemblage des vins de Bordeaux
The fruity aroma of red wines is described by a wide range of descriptors, ranging from fresh fruits to ripe and jammy fruits, to candied fruits and prunes notes. The fruity quality of a red wine is characterized by notes of fresh and jammy red- and black-berry fruits. Although many sensory attributes are mentioned in the literature, knowledge regarding the qualitative fruity aroma of red wines in relation to their chemical composition still requires further investigation. However, at least one component of this fruity expression reflects perceptual interactions primarily involving esters, as well as other families of aromatic molecules. In recent years, changes in the fruity expression of Bordeaux red wines, characterized by the emergence of notes of cooked and dried fruits, have been reported and correlated with climate change. Thus, technicians in the wine industry and scientists emphasize the need to take precautions to preserve the fresh fruity aroma of Bordeaux red wines. One adaptation strategy involves introducing late-ripening grape varieties selected for their potentially suitable vegetative cycle under future climatic conditions into Bordeaux vineyard. This thesis proposes a better understanding of the fruity aroma of red wines derived from Bordeaux grape varieties, as well as those cultivated around the Mediterranean basin, simulating the future climatic conditions in Bordeaux. Through sensory approaches, it has been demonstrated that Bordeaux red wines exhibit similarities with red wines derived from grape varieties grown around the Mediterranean in terms of their fruity character. A detailed characterization of the contribution of volatile compounds of interest in the perception of fruity notes has been conducted. Perceptual interactions between compounds from the monoterpene and C13 norisoprenoid families, mixed with esters, have revealed the importance of these compounds in the perception of fruity notes. Finally, the addition of these volatile compounds to a red wine shows a decrease in cooked fruit notes and an increase in fresh black-berry fruits notes. This research opens up new perspectives in oenology, such as controlling the levels of these compounds of interest through various practices, as well as the potential introduction of "new" grape varieties into Bordeaux wine blends

L’impact anthropique sur les cours d’eau a significativement augmenté suite à la révolution industrielle engagée par les pays occidentaux. Ainsi, les modifications de la géomorphologie des cours d’eau pour le stockage de l’eau et la navigation, la conversion des surfaces à des fins agricoles, industrielles et d’urbanisation illustrent cette pression environnementale, qui se traduit, en autre, par une augmentation de rejets de divers contaminants dans les compartiments environnementaux et notamment les rivières. Une part de ces rejets peut donc se retrouver dans les matières en suspension, considérées alors comme des puits de stockage, qui transitent dans les rivières. Les aménagements des rivières et notamment la construction de barrages favorisent alors la sédimentation de ces particules contaminées au cours du temps. Ces sédiments d’origines anthropiques, également appelés legacy sediments, sont donc les témoins des activités anthropiques et permettent de reconstruire les trajectoires temporelles des contaminations au sein des bassins versants. L’Eure, affluent majeur de l’estuaire de Seine, a connu d’importantes pressions anthropiques depuis le vingtième siècle. La reconstruction temporelle des pressions anthropiques a nécessité l’association de différentes approches méthodologiques : (i) une analyse diachronique des modifications morphologiques de la rivière a été menée, conjointement à (ii) une analyse de la dynamique sédimentaire et de la nature des dépôts sédimentaires par couplage de méthodes géophysiques, sédimentologiques et géochimiques, et à (iii) la mise en place d’un réseau de suivi du comportement hydro-sédimentaire avec un échantillonnage en continu des matières en suspensions. De profondes modifications géomorphologiques se sont produites en aval du bassin versant, avec pour principales conséquences un exutoire déplacé d’une dizaine de kilomètres en direction d’un barrage et la formation d’annexes hydrauliques favorisant l’accumulation de sédiments dès les années 1940. Ceux-ci ont permis de montrer que le bassin versant de l’Eure avait connu d’importantes contaminations dont les conséquences sont encore enregistrées malgré l’arrêt des activités ou usages. Les tendances temporelles des éléments traces métalliques et métalloïdes ont montré de fortes contaminations en As dans les années 1940 et des contaminations d’origines industrielles en Cr, Co, Ni, Cu, Zn, Ag et Cd durant les années 1960–1970, ainsi que des contaminations en Sb et Pb en 1990–2000. Ces dernières sont toujours enregistrées malgré l’arrêt des activités responsables des rejets, comme l’ont attesté les résultats issus des matières en suspension actuellement collectées dans le cours d’eau. A l’instar d’une majorité des métaux traces, les contaminants organiques, tels les HAPs, ont montré d’importantes contaminations durant les années 1940–1960, dont les signatures indiquent une origine majoritairement pyrogénique. Les PCBs ont montré des contaminations importantes lors de la période 1950–1970, en lien avec la production et les usages nationaux de mélanges composés en majorité de congénères faiblement chlorés. Enfin, l’intérêt porté à une troisième famille de contaminants organiques persistants, les pesticides organochlorés, a montré l’utilisation de lindane et du DDT notamment lors de la période 1940–1970, et a mis en avant d’une part une utilisation post-interdiction du lindane et d’autre part la présence d’un métabolite du DDT plusieurs décennies après l’arrêt d’utilisation de ce dernier, en lien avec l’augmentation de l’érosion des sols cultivés
The anthropogenic impact on rivers has significantly increased following the industrial revolutioninitiated by Western countries. Thus, changes in the geomorphology of rivers for water storage andnavigation, the conversion of land for agricultural, industrial and urbanization purposes illustrate thisenvironmental pressure, which results, among other things, in an increase in discharges of variouscontaminants into environmental compartments, particularly rivers. Therefore, part of these dischargescan end up in suspended particulate matter, which is then considered as storage wells, which transit inrivers. River development, particularly the construction of dams, encourages the sedimentation of these contaminated particles over time. These sediments of anthropogenic origin, also called legacy sediments, are therefore witnesses to human activities and make it possible to reconstruct the temporal trajectories of contamination within watersheds. The Eure River, a major tributary of the Seine estuary, has experienced significant anthropogenic pressures since the twentieth century. The temporal reconstruction of anthropogenic pressures has required the combination of different methodological approaches: (i) a diachronic analysis of the morphological modifications of the river was carried out, in conjunction with (ii) an analysis of the sedimentary dynamics and the nature of the sediment deposits by coupling geophysical, sedimentological and geochemical methods, and (iii) the setting up of a network for monitoring the hydro-sedimentary behaviour with continuous sampling of suspended particulate matter. Significant geomorphological changes have occurred in the lower reaches of the watershed, with the main consequences being an outlet moved some ten kilometres in the direction of a dam and the formation of hydraulic annexes favouring the accumulation of sediments as early as the 1940s. These made it possible to show that the Eure River watershed had experienced significant contamination, the consequences of which are still being recorded despite the cessation of activities or uses. The temporal trends of trace metal and metalloid elements showed strong contaminations in As in the 1940s and contaminations of industrial origin in Cr, Co, Ni, Cu, Zn, Ag and Cd in the 1960s and 1970s, as well as contaminations in Sb and Pb in 1990–2000. The latter are still recorded despite the cessation of the activities responsible for the discharges, as evidenced by the results from the suspended particulate matter currently collected in the river. Like most trace metals, organic contaminants such as PAHs showed significant contamination during the 1940–1960s, with signatures indicating a predominantly pyrogenic origin. PCBs showed significant contamination during the period 1950–1970, in connection with the production and national uses of mixtures composed mainly of low chlorinated congeners. Finally, interest in a third family of persistent organic contaminants, organochlorine pesticides, showed the use of lindane and DDT, particularly during the 1940–1970 period, and highlighted the post-ban use of lindane and the presence of a metabolite of DDT several decades after the cessation of its use, in connection with the increase in erosion of cultivated soils

The dynamical properties of liquids may be probed in the time domain in two ways: either in the neat liquid by nonlinear scattering experiments, or else indirectly by studying the solvation dynamics of molecular probes [1,2]. In the latter case, optical excitation of a suitable dye molecule leads to a change in molecular dipole moment. As the surrounding solvent adjusts to a new equlibrium, solvent-solute interaction stabilizes the excited molecule, and this results in a red-shift of the fluorescence spectrum. Typical compounds for this purpose are coumarin or styryl dyes. However their use for ultrafast solvation dynamics is limited by a relatively large spectral width of fluorescence, or by the possibility of geometrical isomerisation. Furthermore, measurement requires fluorescence upconversion and spectral reconstruction which may be quite tedious.