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Hydrocarbons in hydrothermal vent fluids: the role of chromium-bearing catalysts.

Fischer-Tropsch type (FTT) synthesis has long been proposed to account for the existence of hydrocarbons in hydrothermal fluids. We show that iron- and chromium-bearing minerals catalyze the abiotic formation of hydrocarbons. In addition to production of methane (CH4aq), we report abiotic generation of ethane (C2H6aq) and propane (C3H8aq) by mineral-catalyzed hydrothermal reactions at 390 degrees C and 400 bars. Results suggest that the chromium component in ultramafic rocks could be an important factor for FTT synthesis during water-rock interaction in mid-ocean ridge hydrothermal systems. This in turn could help to support microbial communities now recognized in the subsurface at deep-sea vents.

Archaea↗

Microbial oxidation and assimilation of propylene.

Hydrocarbon-utilizing microorganisms in our culture collection oxidized propylene but could not utilize it as the sole source of carbon and energy. When propane-grown cells of Mycobacterium convulutum were placed on propylene, acrylate, the terminally oxidized, three-carbon unsaturated acid, accumulated. A mixed culture and an axenic culture (strain PL-1) that utilized propylene as the sole source of carbon and energy were isolated from soil. Respiration rates, enzyme assays, fatty acid profiles, and 14CO2 incorporation experiments suggest that both the mixed culture and strain PL-1 oxidize propylene via attack at the double bond, resulting in a C2+C1 cleavage of the molecule.

Acetates↗

Characterization of branched and unsaturated fatty acids in Mycobacterium vaccae strain JOB5.

After growth of Mycobacterium vaccae strain JOB5 on acetate or propane, the cellular fatty acids were isolated and identified by a combination of gas-chromatographic, mass-spectral, and chemical means. The fatty acids ranged from C12 to C19 and were a mixture of saturated, monounsaturated, and methyl-branched components. The double bond was in the delta9 position in the C15 to C18 unsaturated acids. The single methyl branch was located on the C10 position of Br-C17, Br-C18, and Br-C19 fatty acids. Branched-chain synthesis occurs at the expense of an unsaturated precursor fatty acid; the double bond serves as the site of methylation. Results suggest that S-adenosylmethionine is the methyl donor involved.

Acetates↗

Role of molecular diffusion in conventional and high frequency ventilation.

The influence of molecular diffusion on gas-mixing during conventional mechanical ventilation (CMV) and high frequency ventilation (HFV) was studied by observing the wash-in of six poorly soluble, inert gases in arterial blood. Anesthetized dogs were ventilated either with CMV or HFV. Following a step change in inspired gas composition, the increase in arterial concentrations of hydrogen, helium, methane, ethane, isobutane, and sulfur hexafluoride was determined by gas chromatography. The relative gas diffusivities encompassed a range of almost one order of magnitude. Propane, present in inspired gas during both the control and wash-in phases, served as an internal reference for calculation of blood tracer concentrations. The wash-in of all six inert gases followed a single exponential time course during both CMV and HFV. The rate of wash-in of each gas decreased with increasing molecular weight (MW). The relationship of rate constants to a measure of relative diffusivity (MW-0.5) was significantly different than zero for both types of ventilation. The slope of this relationship was three times larger for CMV than HFV, indicating that molecular diffusion has a greater role in gas mixing during ventilation with large tidal volumes. Diffusion has a minor role in gas mixing during high frequency ventilation with small tidal volumes. Demonstration of the presence of gas separation secondary to molecular diffusion during HFV is enhanced by measuring wash-in, rather than wash-out, of inert gases because gas separation is likely to be obscured as exhaled gases pass through the well-mixed central airways during gas wash-out.

Animals↗

Volatile organic compounds in the exhaled breath of young patients with cystic fibrosis.

Inflammatory mediators in the exhaled breath are receiving growing medical interest as noninvasive disease markers. Volatile organic compounds have been investigated in this context, but clinical information and methodological standards are limited. The levels of ethane, propane, n-pentane, methanol, ethanol, 2-propanol, acetone, isoprene, benzene, toluene, dimethyl sulphide (DMS) and limonene were measured in repeated breath samples from 20 cystic fibrosis patients and 20 healthy controls (aged 8-29 yrs). Three end-exhaled and one ambient air sample were collected per person and analysed on a customised gas chromatography system. Intra-subject coefficients of variation ranged between 9 and 34%, and hydrocarbon breath levels were influenced by their inspired concentrations. The alveolar gradient for pentane was higher in cystic fibrosis patients than in healthy controls (0.36 versus 0.21 ppb) and inversely proportional to forced expiratory volume in one second; highest values were observed in patients with pulmonary exacerbations (0.73 versus 0.24 ppb). Cystic fibrosis patients also exhibited a lower output of DMS (3.9 versus 7.6 ppb). Group differences were not significant for ethane and the remaining substances. It was concluded that chemical breath analysis for volatile organic compounds is feasible and may hold potential for the noninvasive diagnosis and follow-up of inflammatory processes in cystic fibrosis lung disease.

2-Propanol↗

Aerosol generation by metered-dose inhalers containing dimethyl ether/propane inverse microemulsions.

Water soluble compounds were incorporated into metered-dose inhalers (MDIs) by using water-in-propellant lecithin microemulsions, in which dimethyl ether (DME) and propane acted as both continuous phase and propellant. Lecithin, water, and water soluble compounds were added to glass MDI containers, valves were crimped on, and propellants were added using a pressure burette. Aerosols were produced using commercially available actuators, and inertial impaction was used to determine the mass median aerodynamic diameter (MMAD), geometric standard deviation (GSD), and fine particle fraction (FPF) of the resulting aerosols. The DME/propane/lecithin microemulsion MDIs generated aerosols with particle size distributions suitable for pulmonary delivery (eg, MMAD 3.1 microm, FPF 59% for DME with lecithin content 3%, water content 2.5% [wt/wt]). Increasing water concentration (up to 8% wt/wt) was correlated with a reduction in FPF. Freezing and rewarming had no adverse effect on MMAD, GSD, or FPF. Storage of microemulsion samples for up to 3 weeks did not adversely affect the MMAD, GSD, or FPF. This approach may enable the pulmonary delivery of water soluble therapeutic agents via MDIs.

Administration, Inhalation↗

Toxicity of combustion products from burning polymers: development and evaluation of methods.

Laboratory and room-scale experiments were conducted with natural and synthetic polymers: cotton, paper, wood, wool, acetate, acrylic, nylon, and urethane. Smoke and off-gases from single materials were generated in a dual-compartment 110-liter exposure chamber. Multicomponent, composite fuel loads were burned within a 100 m(3) facility subdivided into rooms. In chamber experiments, mortality depended on the amount of material burned, i.e., fuel consumption (FC). Conventional dose (FC)/mortality curves were obtained, and the amount of fuel required to produce 50% mortality (FC(50)) was calculated. With simple flame ignition, cotton was the only material that produced smoke concentrations lethal to rats; FC(50) values for cotton ranged from 2 g to 9 g, depending on the configuration of the cotton sample burned. When supplemental conductive heat was added to flame ignition, the following FC(50) values were obtained; nylon, 7 g; acrylic, 8 g; newsprint, 9 g; cotton, 10 g; and wood, 11 g. Mortality resulting from any given material depended upon the specific conditions employed for its thermal decomposition. Toxicity of off-gasses from pyrolysis of phosphorus-containing trimethylol propane-polyurethane foams was markedly decreased by addition of a flame ignition source. Further studies are needed to determine the possible relevance of single-material laboratory scale smoke toxicity experiments. Room-scale burns were conducted to assess the relative contributions of single materials to toxicity of smoke produced by a multicomponent self-perpetuating fire. Preliminary results suggest that this approach permits a realistic evaluation of the contribution of single materials to the toxicity of smoke from residential fires.

Animals↗

Combined coherent anti-Stokes Raman spectroscopy and linear Raman spectroscopy for simultaneous temperature and multiple species measurements.

The simultaneous application of pure rotational coherent anti-Stokes Raman spectroscopy (CARS) and vibrational linear Raman spectroscopy (LRS) for the measurement of temperature and species concentrations in combustion systems is demonstrated. In addition to the standard rotational CARS experimental setup, only one detection system (spectrometer and intensified CCD camera) for the collection of the LRS signals was applied. The emission of the broadband dye laser used for CARS was shifted to the deep red to avoid interferences with the LRS signals located in the visible region. First experimental results from a vaporizing propane spray using an engine injection system are shown.

Computer Simulation↗

Mercapturic acid formation in the developing rat.

1. Young female rats dosed with 1-bromo[1-14C]propane excrete the same metabolites as adult females but in different relative proportions. Propylcysteine was detected as one of the metabolites in rats of all ages studied but represented a higher proportion of the total metabolites excreted in rats aged 5 and 11 days. 2. Hepatic GSH-S-alkytransferase activity was low in females at birth increasing up to the age of about thirty days. No activity was detected in the livers of the males at birth and up to 6 days of age; thereafter the level of activity increased up to 35-40 days. 3. Propylcysteine was excreted as prophylmercapturic acid and propylmercapturic acid sulphoxide by female rats of all ages. The amount of sulphoxide excreted relative to mercapturic acid excreted was higher in rats up to the age of 16 days than in older animals.

Acetylcysteine↗

1,2-Dichloropropane: metabolism and fate in the rat.

1. The metabolism of 1,2-dichloropropane in the rat has been investigated. The major urinary metabolite has been isolated and identified as N-acetyl-S-(2-hydroxypropyl)cysteine. Two minor metabolites of 1,2-dichloropropane have been identified as beta-chlorolactate and N-acetyl-S-(2,3-dihydroxypropyl)cysteine. 2. The fate of 1-chloro-2-hydroxypropane, a proposed intermediate metabolite of 1,2-dichloropropane, has been investigated. Apart from its known urinary metabolite, N-acetyl-S-(2-hydroxypropyl)cysteine, two oxidative metabolites were detected. These were identified as beta-chlorolactaldehyde and beta-chlorolactate. 3. A pathway is proposed for the metabolism and fate of 1,2-dichloropropane in the rat. This accounts for previous observations made for the fate of radioactivity from administration of 1,2-dichloro[1-14C]propane. 4. The microbial and mammalian metabolism of several halogen-containing foreign compounds is discussed.

Acetylcysteine↗

Acid and base-catalyzed hydrolysis of bisphenol A-related compounds.

In order to ascertain whether an estrogenic bisphenol A is produced from bisphenol A-related monomers by chemical-induced hydrolysis and to clarify their hydrolytic mechanisms, bisphenol A dimethacrylate (Bis-DMA) and bisphenol A bis(glycidyl methacrylate) (Bis-GMA) were reacted with phosphoric acid, hydrochloric acid, and sodium hydroxide in methanol or methanol/water mixed media at 37 degrees C. Amounts of monomethacrylate intermediates as well as bisphenol A (BPA) were determined by the use of high-performance liquid chromatography (HPLC), and time-conversion curves of hydrolytic products were prepared. BPA and bisphenol A monomethacrylate were produced by acid-catalyzed hydrolysis of Bis-DMA. Bis-GMA was partly converted into monomethacrylate by phosphoric acid and into monomethacrylate and 2,2-bis[4-(2,3-dihydroxypropoxy) phenyl]propane (BHP) by hydrochloric acid. Hydrolytic reactions by sodium hydroxide were completed almost within 1 day, resulting in the production of BPA from Bis-DMA, and BHP from Bis-GMA. No BPA was formed from Bis-GMA by chemical-induced hydrolysis. The hydrolytic behaviors of these monomers were discussed.

Benzhydryl Compounds↗

Acute and repetitive human exposure to isobutane.

Eight adult volunteers of both sexes were exposed to isobutane in a controlled-environment chamber for the purpose of monitoring their physiological responses to a series of gas concentrations ranging from 250 to 1,000 ppm. First, the response to exposure periods of 1 min, 2 min, 1 h, 2 h, and 8 h were studied. There being no untoward responses to these acute exposures, the eight volunteers were exposed repetitively to isobutane at concentrations of 500 ppm, 1, 2 or 8 h per day, five days per week for two weeks. Then exposures to two mixtures of isobutane and propane for 1, 2 or 8 h per day for two days were studied. During the investigation all subjects were kept under comprehensive medical surveillance. No untoward subjective responses or abnormal physiological responses occurred during or following these exposures. Special emphasis was placed on evaluating the cardiac and pulmonary response to these exposures through the use of continuous ECG telemetry and serial computerized spirometric measurements. The following serial laboratory studies were unaltered by the exposures: complete blood count, urinalysis, serum alkaline phosphatase, SGOT, LDH, serum bilirubin, blood sugar, serum calcium, serum phosphorus, BUN, spontaneous electroencephalogram, visual evoked response, a battery of cognitive tests, and an ACTH stimulation test.

Adrenal Cortex↗

Carcinogenic activity of di- and trifunctional alpha-chloro ethers and of 1,4-dichlorobutene-2 in ICR/HA swiss mice.

Four bifunctional and one trifunctional alpha-chloro ethers were tested for carcinogenicity. These compounds were bis-1,2-(chloromethoxy)ethane (Compound I), bis-1,4-(chloromethoxy)butane (Compound II), bis-1,6-(chloromethoxy) hexane (Compound III), bis-1,4-(chloromethoxy)-p-xylene (Compound IV), and tris-1,2,3-(chloromethoxy)propane (Compound V). trans-1,4-Dichlorobutene-2 (Compound VI) was tested along with the five alpha-chloro ethers. All six compounds were tested in female ICR/Ha Swiss mice for 502 to 569 days, depending on survival, by skin application or s.c. and i.p. injection. There were 30 or 50 mice/group. The i.p. and s.c. injections were given once weekly at 0.1 or 0.3 mg of compound dissolved in 0.05 ml tricaprylin for Compounds I to V and 0.05 mg/0.05 ml tricaprylin for Compound VI for the duration of the tests. The skin applications, three times weekly, were at doses of 0.3 or 1.0 mg/0.1 ml cyclohexane for the alpha-chloro ethers and 1.0 mg/0.1 ml acetone for Compound VI. Vehicle and no treatment controls were carried out together with the test compounds. Significance values (p) were calculated for all the compounds tested. Three compounds, I, IV and V, gave notable tumor incidences by all three routes of administration. Compounds II, III, and VI were either inactive by one or more routes of administration or gave low tumor yields.

Administration, Topical↗

Informational uncertainties of risk assessment about accidents of chemicals.

An analysis system of informational uncertainties for accidental risk assessment of chemicals is introduced. Statistical test methods and fuzzy sets method can do the quantitative analysis of the input parameters. The uncertainties of the model can be used by quantitative compared method for the leakage accidents of chemicals. The estimation of the leaking time is important for discussing accidental source term. The uncertain analyses of the release accident for pipeline gas (CO) liquid chlorine and liquid propane gas (LPG) have been discussed.

Accidents↗

[Determination of partition coefficient of dissolved gases in transformer oil using phase ratio variation method and static headspace gas chromatography].

The partition coefficients of dissolved gases in transformer oil were determined using a phase ratio variation method and static headspace gas chromatography (GC). A pressure balancing and gas volume-metering device was connected to the vent of a sample loop on a six-port injection valve of the GC. The gas phase sample from the headspace vial of 25 mL was transferred to an 80 microL sample-loop through a fused silica capillary of 0.53 mm i.d., and then separated and determined quantitatively by GC. A 2 m x 1 mm i.d. GDX502 micro-packed column was used for the separation. Five different gas-liquid volume ratios in the headspace vials were measured at different equilibrium concentrations. The partition coefficients of hydrocarbon gases including methane, acetylene, ethylene, ethane and propane dissolved in transformer oil were determined by using linear regression analysis at 20 degrees C and 50 degrees C separately. The errors between the real values and regression values from experimental data were less than 4.14% except methane. Fundamental data for on-line measurement of dissolved gases in transformer oil are provided by GC.

Acetylene↗

[Morbidity with temporary disability of gas-cylinder bus drivers].

Running of gas-cylinder buses (GCB) fueled with liquefied propane-butane mixture added with ethyl mercaptan odorant leads to undesirable medical and social consequences. Statistically proved was considerably higher morbidity rate among GCS drivers in comparison with petrol-fueled buses' drivers. A questionnaire technique was used to show that most GCB drivers (from 61.8% to 98.2% in different bus depots) had been suffering from the irritating smell of the gaseous fuel and consequent headaches, dizziness, slow reactivity and general weakness, specifically by the end of the working shift. The result of the study proved the necessity to stop further running of GCB until technical improvement of the equipment and normal working conditions for GCB drivers have been attained.

Absenteeism↗

Frostbite of the mouth: a case report.

A case report is presented of a young male who sustained a second-degree frostbite injury to the oral cavity, to include lower lip, hard palate, tongue, and buccal mucosa. This unusual injury occurred as a result of substance abuse: an attempt to inhale an aerosolized propane propellant as a means to achieve euphoria.

Adult↗

Substituent effects on the binding constants of arsenical-dithiol adducts.

Proton nuclear magnetic resonance spectroscopy (1H NMR) was used to determine the relative binding constants for several arsenical-dithiol adducts. The compounds investigated were 2,3-dimercaptopropanol (British anti-lewisite; BAL), 1,2-ethane dithiol (ET), and 1,2-propane dithiol (PDT). It was found that PDT has a significantly higher affinity than ET or BAL for phenyldichloroarsine (PDA) in methanol.

Arsenicals↗