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At least 19 records

Photochemical reactions of water and carbon monoxide in earth's primitive atmosphere

The gas-phase photolysis of H2O at 1849 A in the presence of CO yields mainly CO2 and H2 and a variety of organic compounds, including C1-C3 hydrocarbons, alcohols, aldehydes, acetone, and acetic acid. The overall quantum yield for conversion of CO to organic compounds varies between 0.23 and 0.03 as a function of the CO abundance. These results indicate that even if primitive earth's atmosphere initially contained no molecular hydrogen and contained carbon only in the form of CO or a mixture of CO and CO2, the prebiotic environment would have become enriched with a variety of organic compounds produced by photochemical processes.

Bar-Nun, A.↗

Thermodynamic Equilibrium in the Origin of Organic Matter

Theoretical and experimental support is presented for the hypothesis that organic compounds occurring in carbonaceous chondrites may have formed under equilibrium or near equilibrium conditions. The equilibrium distributions of organic compounds at temperature between 300 and 1000 K and pressures of 10(exp 16) to 50 atmospheres for the C-H-O system have been computed. At high temperatures and low pressures aromatic compounds may form even in the presence of excess hydrogen. Equilibrium concentrations of numerous compounds possible at 1000 K when N, S, and C1 are added to the system have also been determined. A limited equilibrium method is employed in which those few compounds which form with most difficulty are excluded from the computations. This approach is shown to be useful in the interpretation of certain experimental data. In preliminary experiments it has been found that gases, converted to the plasma state by high energy radio frequency discharge, yield product mixtures which are in qualitative agreement with those predicted.

CHEMICAL EQUILIBRIUM↗

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Millan, M.↗

Study of some superconducting and magnetic materials on high T sub c oxide superconductors

On the basis of existing data it appears that the high-temperature superconductivity above 77 K reported here, occurs only in compound systems consisting of a phase other than the K2NiF4 phase. A narrow superconducting transition was obtained with T sub c0 = 98 K and T sub c1 = 94 K in Y-Ba-Cu-O (YBCO). Preliminary results indicate that YBCO is rather different from the layered LaBCO, LaSCO, and LaCCO. While electron-photon interaction cannot be absent from this compound system, nonconventional enhanced superconducting interactions due to interfaces, Resonating Valence Bond (RVB) states, or even a superconducting state beyond the BCS framework, may be required to account for the high T sub c in YBCO. It is believed that study of the possible subtle correlation between magnetism and superconductivity will definitely provide important insight into the superconducting mechanism in YBCO and other oxides.

Wu, M. K.↗

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗

Origin of organic matter in the early solar system. VII - The organic polymer in carbonaceous chondrites

Degradation techniques, including pyrolysis, depolymerization, and oxidation, were used to study the insoluble polymer from the Murchison C2 chondrite. Oxidation with Cr2O7(2-) or O2/UV led to the identification of 15 aromatic ring systems. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably derive from bridging groups or ring substituents. Depolymerization with CF3COO4 yielded some of the same ring systems, as well as alkanes (C1 through C8) and alkenes (C2 through C8), alkyl (C1 through C5) benzenes and naphthalenes, and methyl- or dimethyl -indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200 C, and are therefore probably indigenous constituents. The properties of the meteoritic polymer were compared with the properties of a synthetic polymer produced by the Fischer-Tropsch reaction. It is suggested that the meteoritic polymer was also produced by surface catalysis.

Hayatsu, R.↗

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗

Organic compounds in meteorites and their origins

The current investigation represents an extensively updated version of a review conducted by Anders et al. (1973). The investigation takes into account the literature through mid-1980. It is pointed out that Type 1 carbonaceous chondrites (C1) contain 6% of their cosmic complement of carbon, mainly in the form of organic matter. Most authors now agree that this material represents primitive prebiotic matter. The principal questions remaining are what abiotic processes formed the organic matter, and to what extent these processes took place in locales other than the solar nebula, such as interstellar clouds or meteorite parent bodes. The problem is approached in three stages. It is attempted to reconstruct the physical conditions during condensation from the clues contained in the inorganic matrix of the meteorite. The condensation behavior of carbon under these conditions is determined on the basis of thermodynamic calculations. Model experiments on the condensation of carbon are performed, and the synthesized compounds are compared with those actually found in meteorites.

Hayatsu, R.↗

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Socki, Richard A.↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

Intercomparison of the representations of the atmospheric chemistry of pre-industrial methane and ozone in earth system and other global chemistry-transport models

An intercomparison has been set up to study the representation of the atmospheric chemistry of the pre-industrial troposphere in earth system and other global tropospheric chemistry-transport models. The intercomparison employed a constrained box model and utilised tropospheric trace gas composition data for the pre-industrial times at ninety mid-latitude surface locations. Incremental additions of four organic compounds: methane, ethane, acetone and propane, were used to perturb the constrained box model and generate responses in hydroxyl radicals and tropospheric ozone at each location and with each chemical mechanism. Although the responses agreed well across the chemical mechanisms from the selected earth system and other global tropospheric chemistry-transport models, there were differences in the detailed responses between the chemical mechanisms that could be tracked down by sensitivity analysis to differences in the representation of C1–C3 chemistry. Inter-mechanism ranges in NOx compensation points were about 0.17 ± 0.12 when expressed relative to the inter-mechanism average. Monte Carlo uncertainty analysis carried out with a single chemical mechanism put the intra-mechanism range a factor of three higher at 0.50 ± 0.12. Similar differences between inter-mechanism and intra-mechanism ranges were found for hydroxyl radical depletion but were up to a factor of six wider for ozone formation from incremental additions of organic compounds. The cause of the discrepancies between the inter- and intra-mechanism ranges was found to be the large uncertainties that are present in the laboratory determinations of the rate coefficients and product channel branching ratios of some key chemical reactions involving organic peroxy radicals and hydroperoxides. Whilst these large uncertainties are present in the laboratory determinations, there will be irreducible uncertainties in the predictions from the earth system and other chemistry-transport models of methane and tropospheric ozone trends since pre-industrial times and hence their contributions to the radiative forcing of climate change. Further definitive laboratory studies of the reaction rates and product yields of the reactions of the simple organic peroxy radicals and hydroperoxides are required to resolve and reduce current uncertainties in earth system and chemistry-transport model predictions.

atmospheric chemistry↗

Singlet Excited States of Cl and Br Molecules: New Theories Applied to the -XO and -XO2 (X=C1 and Br) Chromophores

Electronic excitation energies are determined using single-reference based theories derived from response equations involving perturbation theory and coupled-cluster theory. These methods are applied to the singlet manifold of excited electronic states of the HClO, HBrO, HOClO, HOBrO, HClO2, and HBrO2 molecules. The reliability of the various perturbation theory approaches is assessed by comparison to the linear-response singles and doubles coupled-cluster (LRCCSD) method. The excitation energies for the Y-XO compounds are compared and contrasted for Y=H and HO, and X=Cl and Br. A similar comparison is performed for the H-XO2 compounds.

Lee, Timothy J.↗

Compositions and textures of relic forsterite in carbonaceous and unequilibrated ordinary chondrites

The compositions and textures of olivines in equilibrated ordinary chondrites, C1, C2, and C3 meteorites are described. The olivines are classified by color into blue, red, or dark olivines. The characteristic features of blue olivines are examined. It is observed that the texture of the olivine: (1) forms cores in single olivine grains; (2) shows subhedral to euhedral boundaries against rim olivines; (3) rarely contains inclusions; (4) has embayments containing olivines similar to that of the rim; and (5) occurs within chondrules. The mode of formation for blue olivines, the relation between blue olivine and high temperature compounds, and modifications in the features of blue olivines are analyzed. It is noted that the olivine is a product of condensation, has been modified by additions of olivine formed from a liquid, and that these olivines represent relic grains that are similar to olivines found in cosmic particles and in cores of some deep sea particles.

Steele, I. M.↗

The Production and Potential Detection of Hexamethylenetetramine-Methanol in Space

Numerous laboratory studies of astrophysical ice analogues have shown that their exposure to ionizing radiation leads to the production of large numbers of new, more complex compounds, many of which are of astrobiological interest. We show here that the irradiation of astrophysical ice analogues containing H2O, CH3OH, CO, and NH3 yields quantities of hexamethylenetetramine-methanol (hereafter HMT-methanol; C7N4H14O) that are easily detectible in the resulting organic residues. This molecule differs from simple HMT, which is known to be abundant in similar ice photolysis residues, by the replacement of a peripheral H atom with a CH2OH group. As with HMT, HMT-methanol is likely to be an amino acid precursor. HMT has tetrahedral (T(d)) symmetry, whereas HMT-methanol has C1 symmetry. We report the computed expected infrared spectra for HMT and HMT-methanol obtained using ab initio quantum chemistry methods and show that there is a good match between the observed and computed spectra for regular HMT. Since HMT-methanol lacks the high symmetry of HMT, it produces rotational transitions that could be observed at longer wavelengths, although establishing the exact positions of these transitions may be challenging. It is likely that HMT-methanol represents an abundant member of a larger family of functionalized HMT molecules that may be present in cold astrophysical environments.

Materese, Christopher K.↗

C-13/C-12 ratio in methane from the flooded Amazon forest

The C1-C4 hydrocarbon concentrations and the C-13/C-12 ratio in CH4 detected in air samples collected in the Amazon region (3.5 deg S latitude and 5.9 deg W longitude) are analyzed. It is observed that the CH4 concentrations of each sample are enhanced over the background concentration for remote locations, and the C-13/C-12 ratio in this biogenic methane is depleted in C-13 relative to atmospheric CH4. It is concluded, from the C2-C4 hydrocarbon data, that minor yields of C2-C4 hyrocarbons are released coincident with CH4; however, the minor yields do not contribute to the regionally enhanced concentrations of hydrocarbons found in Amazonia and the global atmosphere release of C2-C4 compounds.

Tyler, Stanley C.↗