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At least 19 records

Organic chemical evolution

The course of organic chemical evolution preceding the emergence of life on earth is discussed based on evidence of processes occurring in interstellar space, the solar system and the primitive earth. Following a brief review of the equilibrium condensation model for the origin and evolution of the solar system, consideration is given to the nature and organic chemistry of interstellar clouds, comets, Jupiter, meteorites, Venus and Mars, and the prebiotic earth. Major issues to be resolved in the study of organic chemical evolution on earth are identified regarding condensation and accretion in the solar nebula, early geological evolution, the origin and evolution of the atmosphere, organic production rates, organic-inorganic interactions, environmental fluctuations, phase separation and molecular selectivity.

Chang, S.↗

Measurement of volatile organic chemicals at selected sites in California

Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

Singh, Hanwant B.↗

Genetic toxicity studies of organic chemicals found as contaminants in spacecraft cabin atmospheres

Astronauts can be exposed during spaceflight to organic chemical contaminants in the spacecraft cabin atmosphere. Toxic exposures may cause lesions in the cellular DNA which are subsequently expressed as sister-chromatid exchanges (SCE). Analysis of SCE is a sensitive short term assay techinque to detect and quantitate exposures to DNA damaging (mutagenic) substances. The increase in SCE incidence over baseline (control) levels is generally proportional to the concentration of the mutagen and to the duration of exposure. The BHK-21 baby hamster kidney cell line was the in vitro test system used. Test organics were added to the culture media for 18 hrs, in concentrations ranging from one to 20 ppm. Acetaldehyde and carbon disulfide were chosen for this study since they have occurred as atmospheric contaminants in many of the STS flights, and have been reported to have toxic and mutagenic effects in various test systems. Glutaraldehyde was chosen because few data are available on the mutagenicity of this common fixative, which is carried on STS flights for use in biological experiments. Acetaldehyde was a very strong inducer of SCE at concentrations of 2 ppm and above. Glutaraldehyde and carbon disulfide failed to induce SCE.

Torres, Joseph, Jr.↗

In vitro cytogenetic studies of organic chemicals found as contaminants in spacecraft cabin atmospheres

Astronauts can be exposed during spaceflight to organic chemical contaminants in the spacecraft cabin atmosphere. Toxic exposures may cause lesions in the cellular DNA which are subsequently expressed as sister-chromatid exchanges (SCE). Analysis of SCE is a sensitive short-term assay technique to detect and quantitate exposures to DNA-damaging (mutagenic) substances. The increase in SCE incidence over baseline (control) levels is generally proportional to the concentration of the mutagen and to the duration of exposure. Dichloromethane (methylene chloride) was chosen for this study since it occurred as an atmospheric contaminant in ten of the first 12 STS flights, and has been reported to have toxic and mutagenic effects in various test systems. Glutaraldehyde was chosen because relatively few data are available on the toxicity or mutagenicity of this common biological fixative, which is carried on STS flights for use in biological experiments. The BHK-21 baby hamster kidney cell line was the in vitro test system used in this study. Neither dichloromethane (10 ppm to 500 ppm) nor glutaraldehyde (1 ppm to 10 ppm) increased SCE levels following 20-hour exposure of BHK-21 cells to the test chemicals.

Torres, J.↗

Oxygenated Organic Chemicals in the Pacific Troposphere: Distribution, Sources and Chemistry

Airborne measurements of a large number of oxygenated organic chemicals (Oxorgs) were carried out in the Pacific troposphere (0.1-12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measuremen ts included acetone, methylethyl ketone (MEK), methanol, ethanol, ace taldehyde, propionaldehyde, PANS, and organic nitrates. Complementary measurements of formaldehyde, organic peroxides, and tracers were al so available. Ox-orgs were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Their mixing ratios were typically highest in the lower troposphere and declined toward s the upper troposphere and the lowermost stratosphere. Their total a bundance (Ox-orgs) significantly exceeded that of NMHC (C2-C8 NMHC). A comparison of these data with observations collected some seven yea rs earlier (Feb.-March, 1994), did not reveal any significant changes . Throughout the troposphere mixing ratios of Ox-orgs were strongly c orrelated with each other as well as with tracers of fossil and bioma sshiof'uel combustion. Analysis of the relative enhancement of selected Oxorgs with respect to CH3Cl and CO in twelve sampled plumes, origi nating from fires, is used to assess their primary and secondary sour ces from biomass combustion. The composition of these plumes also ind icates a large shift of reactive nitrogen into the PAN reservoir ther eby limiting ozone formation. The Harvard 3-D photochemical model, th at uses state of the art chemistry and source information, is used to compare simulated and observed mixing ratios of selected species. A 1 -D model is used to explore the chemistry of aldehydes. These results will be presented.

Singh, Hanwant B.↗

OVOC (Oxygenated Volatile Organic Chemicals) in the Global Atmosphere: Atmospheric Budgets, Oceanic Concentrations, and Uncertainties

Airborne measurements of oxygenated volatile organic chemicals (OVOC), OH free radicals, and tracers of pollution were performed over the Pacific during Winter/Spring of 2001. Large concentrations of OVOC are present in the global troposphere and are expected to play an important role in atmospheric chemistry. Their total abundance (SIGMAOVOC) was nearly twice that of non-methane hydrocarbons (SIGMAC2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NHMC. A comparison of these data with western Pacific observations collected some seven years earlier (Feb.-March, 1994) did not reveal significant differences. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in twelve plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. These data are combined with other observations and interpreted with the help of a global 3-D model to assess OVOC global sources and sinks. We further interpret atmospheric observations with the help of an air-sea exchange model io show that oceans can be both net so~rces and sinks. An extremely large oceanic reservoir of OVOC, that exceeds the atmospheric reservoir by more than an order of magnitude, can be inferred to be present. We conclude that OVOC sources are extremely large (150-500 TgC y-1) but remain poorly quantified. In many cases, measured concentrations are uncertain and incompatible with our present knowledge of atmospheric chemistry. Results based on observations from several field studies and critical gaps will be discussed.

Singh, Hanwant B.↗

Optical Detection of Organic Chemical Biosignatures at Hydrothermal Vents

We have developed a non-contact, optical life detection instrument that can detect organic chemical biosignatures in a number of different environments, including dry land, shallow aqueous, deep marine or in ice. Hence, the instrument is appropriate as a biosignature survey tool both for Mars exploration or in situ experiments in an ice-covered ocean such as one might wish to explore on Europa. Here, we report the results we obtained on an expedition aboard the Russian oceanographic vessel Akademik Mstislav Keldysh to hydrothermal vent sites in the Pacific Ocean using our life detection instrument MCDUVE, a multichannel, deep ultraviolet excitation fluorescence detector. MCDUVE detected organic material distribution on rocks near the vent, as well as direct detection of organisms, both microbial and microscopic. We also were able to detect organic material issuing directly from vent chimneys, measure the organic signature of the water column as we ascended, and passively observe the emission of light directly from some vents.

Conrad, P. G.↗

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗

Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications

The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

Collis, Ward J.↗

Comparison of dermal and inhalation routes of entry for organic chemicals

The quantitative comparison of the chemical concentration inside the body as the result of a dermal exposure versus an inhalation exposure is useful for assessing human health risks and deciding on an appropriate protective posture. In order to describe the relationship between dermal and inhalation routes of exposure, a variety of organic chemicals were evaluated. The types of chemicals chosen for the study were halogenated hydrocarbons, aromatic compounds, non-polar hydrocarbons and inhalation anesthetics. Both dermal and inhalation exposures were conducted in rats and the chemicals were in the form of vapors. Prior to the dermal exposure, rat fur was closely clipped and during the exposure rats were provided fresh breathing air through latex masks. Blood samples were taken during 4-hour exposures and analyzed for the chemical of interest. A physiologically based pharmacokinetic model was used to predict permeability constants (cm/hr) consistent with the observed blood concentrations of the chemical. The ratio of dermal exposure to inhalation exposure required to achieve the same internal dose of chemical was calculated for each test chemical. The calculated ratio in humans ranged from 18 for styrene to 1180 for isoflurane. This methodology can be used to estimate the dermal exposure required to reach the internal dose achieved by a specific inhalation exposure. Such extrapolation is important since allowable exposure standards are often set for inhalation exposures, but occupational exposures may be dermal.

Jepson, Gary W.↗

Distribution of volatile organic chemicals in outdoor and indoor air

The EPA volatile organic chemistry (VOC) national ambient data base (Shah, 1988) is discussed. The 320 chemicals included in the VOC data base are listed. The methods used to obtain the data are reviewed and the availability, accessibility, and operation of the data base are examined. Tables of the daily outdoor concentrations for 66 chemicals and the daily indoor concentrations for 35 chemicals are presented.

Shah, Jitendra J.↗

Biological and Organic Chemical Decomposition of Silicates

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geo- chemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth surface.

Silverman, M. P.↗

Measurements of Oxygenated Organic Chemicals In the Pacific Troposphere During TRACE-P: Higher Aldehydes (less than C(sub 1)), Their Sources, and Potential Role In Atmospheric Oxidation

Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.

Singh, Hanwant B.↗