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Biomedical subjects

B R Simoneit

Publications and source records attributed to B R Simoneit.

At least 19 recordsLinked to original sources
PubMed2001

Bile acids and sterols in urban sewage treatment plants.

The composition of bile acids, sterols and sterones in water and sludge from an urban sewage treatment plant has been examined for assessment of the possible use of these compounds as pollution biomarkers. Samples were solvent-extracted, hydrolysed, and fractionated by column chromatography to separate acids, hydrocarbons, sterones and sterols. These fractions, except hydrocarbons, were methylated (acids only) and silylated for instrumental analysis. Gas chromatographic-mass spectrometric analysis was performed in the electron-impact mode, using a non-polar capillary column. Lithocholic acids (3alpha- and 3beta-epimers), coprostanone, coprostanol, cholesterol, cholestenone, and cholestanone were found in sludge and all waters. However, the waters after secondary plant treatment contained mainly lithocholic acids epimers and coprostanone, pointing to these compounds as potential markers for urban treatment plant effluents in natural waters courses.

Bile Acids and Salts↗
PubMed2001

Chemical characterization of fine particle emissions from fireplace combustion of woods grown in the northeastern United States.

A series of source tests was conducted to determine the chemical composition of fine particle emissions from the fireplace combustion of six species of woods grown in the northeastern United States: red maple, northern red oak, paper birch, eastern white pine, eastern hemlock, and balsam fir. Results include fine particle emission rates for total mass, organic and elemental carbon, ionic species, elemental species including potassium, and over 250 specific organic compounds. The data are intended for use in source-apportionment studies that utilize particulate organic compounds as source-specific tracers. The cellulose pyrolysis product levoglucosan was quantified in each of the wood smokes studied and is thus a good candidate as a molecular tracer for wood combustion in general. Differences in emission rates of specific substituted phenols and resin acids can be used to distinguish between the smoke produced when burning hardwoods versus softwoods. Certain organic compounds, such as betulin from paper birch combustion and juvabione and dehydrojuvabione from balsam fir combustion, are unique to those species and can potentially be utilized to trace particulate emissions back to a specific geographical region where those individual tree species are used for firewood.

Air Pollutants↗
PubMed2001

Highly polar organic compounds present in wood smoke and in the ambient atmosphere.

Fine particulate matter emitted during wood combustion is known to contribute a significant fraction of the total fine aerosol concentration in the atmosphere of both urban and rural areas. In the present study, additional organic compounds that may act as wood smoke tracers in the atmosphere are sought. Polar organic compounds in wood smoke fine particulate matter are converted to their trimethylsilyl derivatives and analyzed by gas chromatography/mass spectrometry. Silylation enables the detection of n-alkanols, plant sterols, and a number of compounds derived from wood lignin that have not previously been reported in wood smoke samples, as well as levoglucosan and related sugar anhydrides formed during the combustion of cellulose. The concentrations of these compounds measured in source emissions are compared to the concentrations in atmospheric fine particle samples collected at a rural background site and at two urban sites in California's San Joaquin Valley. On the basis of this analysis, the sugar anhydrides galactosan and mannosan can be listed along with levoglucosan as being among the most abundant organic compounds detected in all samples.

Aerosols↗
PubMed2001

Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood.

Organic compound emission rates for volatile organic compounds (VOC), gas-phase semivolatile organic compounds, and particle-phase organic compounds are measured from residential fireplace combustion of wood. Firewood from a conifer tree (pine) and from two deciduous trees (oak and eucalyptus) is burned to determine organic compound emissions profiles for each wood type including the distribution of the alkanes, alkenes, aromatics, polycyclic aromatic hydrocarbons (PAH), phenol and substituted phenols, guaiacol and substituted guaiacol, syringol and substituted syringols, carbonyls, alkanoic acids, resin acids, and levoglucosan. Levoglucosan is the major constituent in the fine particulate emissions from all three wood types, contributing 18-30% of the fine particulate organic compound emissions. Guaiacol (2-methoxyphenol), and guaiacols with additional substituents at position 4 on the molecule, and resin acids are emitted in significant quantities from pine wood combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional substituents at position 4 on the molecule are emitted in large amounts from oak and eucalyptus firewood combustion, but these compounds are not detected in the emissions from pine wood combustion. Syringol and most of the substituted syringols are found to be semivolatile compounds that are present in both the gas and particle phases, but two substituted syringols that have not been previously quantified in wood smoke emissions, propionylsyringol and butyrylsyringol, are found exclusively in the particle phase and can be used to help trace hardwood smoke particles in the atmosphere. Benzene, ethene, and acetylene are often used as tracers for motor vehicle exhaust in the urban atmosphere. The contribution of wood smoke to the ambient concentrations of benzene, ethene, and acetylene could lead to an overestimate of the contribution of motor vehicle tailpipe exhaust to atmospheric VOC concentrations.

Air Pollutants↗
PubMed2001

Detecting organic tracers from biomass burning in the atmosphere.

This is a brief review key to the literature on the determination of organic tracers from biomass burning which are detectable even after long-range global transport in total extracts of atmospheric particles. The major tracers are thermal degradation products from the biopolymer cellulose, namely the didehydromonosaccharide derivatives levoglucosan, galactosan and mannosan and the resin acid derivative dehydroabietic acid, with minor beta-sitosterol. Dehydroabietic acid is emitted primarily from burning of conifer fuel and these tracers are found in most aerosol samples from the North American continent. Particulate matter from the atmosphere over oceanic areas contains organic tracers from both natural and biomass burning emissions. The major biomarker compounds characterized are natural products from continental vegetation consisting primarily of epicuticular wax components and trace components from biomass burning emissions. The presence of these tracers in atmospheric particulate matter over the ocean confirms the long-range transport of smoke from biomass burning off the continents.

Abietanes↗
PubMed2001

Exploratory studies of PM10 receptor and source profiling by GC/MS and principal component analysis of temporally and spatially resolved ambient samples.

For a recent exploratory study of particulate matter (PM) compositions, origins, and impacts in the El Paso/Juarez (Paso del Norte) airshed, the authors relied on solvent extraction (SX)-gas chromatography/mass spectrometry (GC/MS) procedures to characterize 24-hr quartz fiber (QF) filter samples obtained from nine spatially distributed high-volume (Hi-Vol) PM10 samplers as well as on thermal desorption (TD)-GC/MS methods to characterize 45 time-resolved (2-hr) filter samples obtained with modified 1-m3/hr PM10 samplers. Principal component analysis and related chemometric techniques were used for data reduction and data fusion as well as for multiway data correlation. A high degree of correspondence (R2 = 0.821) was found between the rapid TD-GC/MS method (which can be carried out on 2-hr filter slices containing only microgram amounts of sample) and conventional SX-GC/MS procedures. The four main source patterns of organic PM components observed in GC/MS profiles of both temporally and spatially resolved receptor samples obtained in the El Paso/Juarez border airshed during the study period are interpreted to represent (1) vehicular emissions plus resuspended urban dust; (2) biomass combustion; (3) native vegetation detritus and resuspended agricultural dust; and (4) waste burning. Moreover, principal component analysis of combined, variance-weighted, temporally resolved TD-GC/MS data and spatially resolved SX-GC/MS data was used to determine approximate source locations for specific PM components identified in time-resolved receptor sample profiles. The same approach can be used to determine approximate circadian concentration profiles of specific PM components identified in spatially resolved receptor sample profiles.

Agriculture↗
PubMed1999

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate.

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Ferrosoferric Oxide↗
PubMed1999

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions.

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Formates↗
PubMed1998

Biomarkers as tracers for life on early earth and Mars.

Biomarkers in geological samples are products derived from biochemical (natural product) precursors by reductive and oxidative processes (e.g., cholestanes from cholesterol). Generally, lipids, pigments and biomembranes are preserved best over longer geological times and labile compounds such as amino acids, sugars, etc. are useful biomarkers for recent times. Thus, the detailed characterization of biomarker compositions permits the assessment of the major contributing species of extinct and/or extant life. In the case of the early Earth, work has progressed to elucidate molecular structure and carbon isotropic signals preserved in ancient sedimentary rocks. In addition, the combination of bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems permits the modeling of the nature, behavior and preservation potential of primitive microbial communities. This approach uses combined molecular and isotopic analyses to characterize lipids produced by cultured bacteria (representative of ancient strains) and to test a variety of culture conditions which affect their biosynthesis. On considering Mars, the biomarkers from lipids and biopolymers would be expected to be preserved best if life flourished there during its early history (3.5-4 x 10(9) yr ago). Both oxidized and reduced products would be expected. This is based on the inferred occurrence of hydrothermal activity during that time with the concomitant preservation of biochemically-derived organic matter. Both known biomarkers (i.e., as elucidated for early terrestrial samples and for primitive terrestrial microbiota) and novel, potentially unknown compounds should be characterized.

Bacteria↗
PubMed1996

Lipid biomarkers for bacterial ecosystems: studies of cultured organisms, hydrothermal environments and ancient sediments.

This paper forms part of our long-term goal of using molecular structure and carbon isotopic signals preserved as hydrocarbons in ancient sediments to improve understanding of the early evolution of Earth's surface environment. We are particularly concerned with biomarkers which are informative about aerobiosis. Here, we combine bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems to construct models for the nature, behaviour and preservation potential of primitive microbial communities. We use a combined molecular and isotopic approach to characterize lipids produced by cultured bacteria and test a variety of culture conditions which affect their biosynthesis. This information is then compared with lipid mixtures isolated from contemporary hot springs and evaluated for the kinds of chemical change that would accompany burial and incorporation into the sedimentary record. In this study we have shown that growth temperature does not appear to alter isotopic fractionation within the lipid classes produced by a methanotropic bacterium. We also found that cultured cyanobacteria biosynthesize diagnostic methylalkanes and dimethylalkanes with the latter only made when growing under low pCO2. In an examination of a microbial mat sample from Octopus Spring, Yellowstone National Park (USA), we could readily identify chemical structures with 13C contents which were diagnostic for the phototrophic organisms such as cyanobacteria and Chloroflexus. We could not, however, find molecular evidence for operation of a methane cycle in the particular mat samples we studied.

Alkanes↗
PubMed1996

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California.

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Chromatography, Gas↗
PubMed1995

Evidence for organic synthesis in high temperature aqueous media--facts and prognosis.

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to >400 degrees C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS kappa- in the hydrothermal fluids. Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200-350 degrees C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 degrees C.

Amino Acids↗
PubMed1995

Confined-pyrolysis as an experimental method for hydrothermal organic synthesis.

A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic compounds and competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

Alkanes↗
PubMed1993

Aqueous high-temperature and high-pressure organic geochemistry of hydrothermal vent systems.

Hydrothermal systems associated with oceanic spreading centers are now recognized as relatively common phenomena, and the organic chemical alterations occurring there are rapid and efficient. In the marine hydrothermal systems at water depths > 1.5 km, the conditions driving chemical reactions are high temperatures (up to >400 degrees C), confining pressures (>150 bar), and other parameters such as pH, Eh, and mineralogy in an aqueous open flow medium. Continental hydrothermal systems may also be of interest, as, for example, in failed or dormant rifts and regions around piercement volcanoes. Organic matter alteration by reductive reactions to petroleum hydrocarbons occurs in hydrothermal systems over a wide temperature window (approximately 60 to >400 degrees C), under elevated pressure, and in a brief geological time (years to hundreds of years). The products are rapidly moved as bulk phase or in fluids from the regions at higher temperatures to areas at lower temperatures, where the high molecular weight material separates from the bulk. These conditions are conducive to organic chemistry which yields concurrent products by primarily reduction (due to mineral buffering), oxidation (high thermal stress), and synthesis reactions. This chemistry is just beginning to be elucidated by the geochemical community, but there are various industrial applications which provide useful preliminary insight. Therefore, the behavior of organic matter (inclusive of methane to high molecular weight compounds > C40) in warm to supercritical water needs to be characterized to understand the implications of this novel phenomenon in geological and geochemical processes, and the chemistry occurring over the full temperature spectrum of hydrothermal systems is of relevance to origins of life research.

Carbon Radioisotopes↗
PubMed1993

Organochlorines, including chlordane compounds and their metabolites, in peregrine-falcon, prairie-falcon, and clapper-rail eggs from the USA.

Four compounds present in technical chlordane (trans- and cis-nonachlor, and tentatively MC-2 and MC-5) and three metabolites of chlordane (heptachlor epoxide, oxychlordane, and U-4) were identified by GC/MS in peregrine-falcon (Falco peregrinus anatum) eggs. Levels of Heptachlor epoxide, oxychlordane, trans- and cis-chlordane, trans- and cis-nonachlor, MC-2, and MC-5 were quantified by GC/ECD in peregrine-falcon eggs from the US east coast, Colorado, and California; and in prairie-falcon (Falco mexicanus) and light-footed-clapper-rail (Rallus longirostris levipes) eggs from California. The eggs were collected between 1986 and 1989. Oxychlordane, heptachlor epoxide, trans- and cis-nonachlor, MC-2, and MC-5 were detected in every egg analyzed. Heptachlor, trans-, and cis-chlordane were either not detected, or present at low levels in the eggs. The highest Sigmachlordane levels were found in the East Coast peregrine-falcon eggs at a geometric mean (geom. mean) concentrations of 1800 microg/kg (ppb); the lowest levels of Sigmachlordane were found in the prairie-falcon eggs at a concentration of 120 microg/kg (geom. mean). Of the technical chlordane compounds measured, MC-2 bioaccumulated to the greatest degree. SigmaDDT levels in the falcons ranged from 11 000 microg/kg (geom. mean) in the Colorado samples to 8800 microg/kg (geom. mean) in the East Coast and California peregrines. SigmaDDT levels in the rail eggs were 3000 microg/kg (geom. mean). The highest SigmaPCB levels were found in the East Coast peregrine-falcon eggs at a concentration of 14 000 microg/kg (geom. mean); the lowest levels of SigmaPCB were found in the prairie-falcon eggs at a concentration of 350 microg/kg (geom. mean).

Journal Article↗
PubMed1992

Aqueous organic geochemistry at high temperature/high pressure.

It is the purpose of this chapter to provide a description of the fate and chemical alterations of organic matter under hydrothermal conditions, with a brief overview of the geographic localities where these processes have been studied to date. Two major but overlapping aspects will be considered: (a) Alteration and degradation processes and reactions, both reductive and oxidative, and (b) synthesis processes and reactions that are primarily reductive.

Atmospheric Pressure↗