Plasma decay in the afterglow of a high-voltage nanosecond discharge in air

The decay of air plasma produced by a high-voltage nanosecond discharge at room temperature and gas pressures in the range of 1–10 Torr was studied experimentally and theoretically. The time dependence of the electron density was measured with a microwave interferometer. The initial electron density was about 10¹² cm⁻³. The discharge homogeneity was monitored using optical methods. The dynamics of the charged particle densities in the discharge afterglow was simulated by numerically solving the balance equations for electron and ions and the equation for the electron temperature. It was shown that, under these experimental conditions, plasma electrons are mainly lost due to dissociative and three-body recombination with ions. Agreement between the measured and calculated electron densities was achieved only when the rate constant of the three-body electron-ion recombination was increased by one order of magnitude and the temperature dependence of this rate constant was modified. This indicates that the mechanism for three-body recombination of molecular ions differs from that of the well-studied mechanism of atomic ion recombination.     

Nonsputtering impulse magnetron discharge

Experiments with quasi-steady high-current discharges in crossed E × B fields in various gases (Ar, N₂, H₂, and SF₆) and gas mixtures (Ar/SF₆ and Ar/O₂) at pressures from 10⁻³ to 5 Torr in discharge systems with different configurations of electric and magnetic fields revealed a specific type of stable low-voltage discharge that does not transform into an arc. This type of discharge came to be known as a high-current diffuse discharge and, later, a nonsputtering impulse magnetron discharge. This paper presents results from experimental studies of the plasma parameters (the electron temperature, the plasma density, and the temperature of ions and atoms of the plasma-forming gas) of a high-current low-pressure diffuse discharge in crossed E × B fields.     

Variations in daytime net carbon and water exchange in a montane shrubland ecosystem in southeast Spain

Carbon and water fluxes in a semiarid shrubland ecosystem located in the southeast of Spain (province of Almería) were measured continuously over one year using the eddy covariance technique. We examined the influence of environmental variables on daytime (photosynthetically active photons, F _P >10 μmol m⁻² s⁻¹) ecosystem gas exchange and tested the ability of an empirical eco-physiological model based on F _P to estimate carbon fluxes over the whole year. The daytime ecosystem fluxes showed strong seasonality. During two solstitial periods, summer with warm temperatures (>15 °C) and sufficient soil moisture (>10 % vol.) and winter with mild temperatures (>5 °C) and high soil moisture contents (>15 % vol.), the photosynthetic rate was higher than the daytime respiration rate and mean daytime CO₂ fluxes were ca. −1.75 and −0.60 μmol m⁻² s⁻¹, respectively. Daytime evapotranspiration fluxes averaged ca. 2.20 and 0.24 mmol m⁻² s⁻¹, respectively. By contrast, in summer and early autumn with warm daytime temperatures (>10 °C) and dry soil (<10 % vol.), and also in mid-winter with near-freezing daytime temperatures the shrubland behaved as a net carbon source (mean daytime CO₂ release of ca. 0.60 and 0.20 μmol m⁻² s⁻¹, respectively). Furthermore, the comparison of water and carbon fluxes over a week in June 2004 and June 2005 suggests that the timing—rather than amount—of spring rainfall may be crucial in determining growing season water and carbon exchange. Due to strongly limiting environmental variables other than F _P, the model applied here failed to describe daytime carbon exchange only as a function of F _P and could not be used over most of the year to fill gaps in the data.     

Nonquasineutral current equilibria as elementary structures of plasma dynamics

A study is made of the fundamental features of current filaments with a nonzero electron vorticity Ω _e ≡ B − (c/e) ▿ × p _ee ≠ 0 and the corresponding Lagrangian invariant I _e . Such current structures can exist on spatial scales of up to ω _pi ⁻¹. It is shown that the dissipative stage of the plasma evolution and the violation of Thomson’s theorem on vorticity conservation in an electron fluid are of fundamental importance for the onset of electron current structures. A key role of the screening of electric and magnetic fields at distances on the order of the magnetic Debye radius r _B = B/(4πen _e )—the main property of such current structures in a Hall medium with σB/(en _e c) ≫ 1—is stressed. Since the minimum size of a vortex structure is the London length c/ω _pe , the structures under consideration correspond to the condition r _B > c/ω _pe or B ² > 4πn _e m _e c ², which leads to strong charge separation in the filament and relativistic electron drift. It is demonstrated that the specific energy content in current structures is high at a filament current of 10–15 kA: from 100 J/cm³ at a plasma density of 10¹⁴ cm⁻³ (the parameters of a lightning leader) to 10⁷ J/cm³ for a fully ionized atmospheric-pressure air. Estimates are presented showing that the Earth’s ionosphere, circumsolar space, and interstellar space are all Hall media in which current vortex structures can occur. A localized cylindrical equilibrium with a magnetic field reversal is constructed—an equilibrium that correlates with the magnetic structures observed in intergalactic space. It is shown that a magnetized plasma can be studied by using evolutionary equations for the electron and ion Lagrangian invariants I _e and I _i . An investigation is carried out of the evolution of a current-carrying plasma in a cylinder with a strong external magnetic field and with a longitudinal electron current turned on in the initial stage—an object that can serve as the simplest electrodynamic model of a tokamak. In this case, it is assumed that the plasma conductivity is low in the initial stage and then increases substantially with time. Based on the conservation of the integral momentum of the charged particles and electromagnetic field in a plasma cylinder within a perfectly conducting wall impenetrable by particles, arguments are presented in support of the generation of a radial electric field in a plasma cylinder and the production of drift ion fluxes along the cylinder axis. A hypothesis is proposed that the ionized intergalactic gas expands under the action of electromagnetic forces.     

Biodegradation of phenol by immobilized Aspergillus awamori NRRL 3112 on modified polyacrylonitrile membrane

Covalent immobilization of Aspergillus awamori NRRL 3112 was conducted onto modified polyacrylonitrile membrane with glutaraldehyde as a coupling agent. The polymer carrier was preliminarily modified in an aqueous solution of NaOH and 1,2-diaminoethane. The content of amino groups was determined to be 0.58 mgeq g⁻¹. Two ways of immobilization were used—in the presence of 0.2 g l⁻¹ phenol and without phenol. The capability of two immobilized system to degrade phenol (concentration—0.5 g l⁻¹) as a sole carbon and energy source was investigated in batch experiments. Seven cycles of phenol biodegradation were conducted. Better results were obtained with the immobilized system prepared in the presence of phenol, regarding degradation time and phenol biodegradation rate. Scanning electron micrographs of the polyacrylonitrile membrane/immobilized Aspergillus awamori NRRL at the beginning of repeated batch cultivation and after the 7th cycle were compared. After the 7th cycle of cultivation the observations showed large groups of cells. The results from the batch experiments with immobilized system were compared to the results produced by the free strain. Phenol biodegradation experiments were carried out also in a bioreactor with spirally wound membrane with bound Aspergillus awamori NRRL 3112 in a regime of recirculation. 10 cycles of 0.5 g l⁻¹ phenol biodegradation were run consecutively to determine the degradation time and rate for each cycle. The design of the bioreactor appeared to be quite effective, providing large membrane surface to bind the strain.     

DNA amounts in the nuclei ofParamecium aurelia andTetrahymena pyriformis

DNA amounts have been determined in the micronuclei and macronuclei of 8 strains ofParamecium aurelia and 6 strains ofTetrahymena pyriformis. In the case ofTetrahymena a distribution of values for the amount of DNA in the macronuclei of all the strains was observed but the lowest values were approximately the same, viz. 1.17×10⁻¹¹ g. There are two groups of strains in relation to micronuclear DNA values ofTetrahymena, one giving an average of 0.36×10⁻¹² g and the other 0.815×10⁻¹² g. The ratio of MIC/MAC DNA varies in the two groups.Paramecium again has a range of macronuclear values within each stock—lowest value 2.51×10⁻¹⁰ g—and the micronuclear values are similar in all stocks—approximately 0.613×10⁻¹² g. The ratio of MIC/MAC DNA is similar in each stock.—The haploid genome values calculated from these data show excellent agreement with the values obtained by DNA renaturation studies. Supported by a Research Grant B/SR/8276 from the Science Research Council. The Vickers densitometer was purchased with a grant from the Medical Research Council.     

Inhibition of galectin-3 mediated cellular interactions by pectic polysaccharides from dietary sources

Pectic polysaccharides from dietary sources such as Decalepis hamiltonii—swallow root (SRPP), Hemidesmus indicus (HPP), Nigella sativa—black cumin (BCPP), Andrographis serpyllifolia—(APP), Zingiber officinale—ginger (GRPP) and, citrus pectin (CPP) were examined for galectin inhibitory activity. Inhibition of (a) galectin-3 of MDA-MB-231 cells induced hemagglutination of red blood cells; (b) galectin-3 mediated interaction between normal/metastatic human buccal cells (NBC)/(MBC) and; (c) invasion of MDA-MB-231 and MBC in the invasive chamber was assessed. Results indicated that SRPP inhibited hemagglutination at Minimum Inhibitory Concentration (MIC) of 1.86 μg ml⁻¹ equivalent of carbohydrate as apposed to those of BCPP (130 μg ml⁻¹), APP (40 μg ml⁻¹), HPP (40 μg ml⁻¹) and CPP (25 μg ml⁻¹). GRPP even at concentration >1–6 mg ml⁻¹ did not inhibit agglutination. Also SRPP showed ∼15 and 2 fold potent anti hemagglutination activity relative to that of galectin-3 specific sugars—galactose (MIC-27.1 μg ml⁻¹) and lactose (MIC-4.16 μg ml⁻¹) respectively. Further, SRPP at 10 μg ml⁻¹ inhibited agglutination of NBC by galectin-3 of MDA-MB-231 cells. Modified swallow root pectic polysaccharide (MSRPP) of 50 kDa retained anti hemagglutination activity (MIC of 1.03 μg ml⁻¹) and inhibited MDA-MB-231 and MBC invasion by 73 and 50% with an IC₅₀ of 136 and 200 μg ml⁻¹ respectively. Both SRPP and MSRPP induced apoptosis up to 80% at 100 μg ml⁻¹ concentration by activating ∼2 and 8 folds of Caspase-3 activity. Sugar composition analysis and its correlation with the galectin inhibitory property indicated that pectic polysaccharides with higher arabinose and galactose content—arabinogalactan inhibited hemagglutination significantly.     

Propagation of a surface microwave along the afterglow plasma column of a high-current pulsed discharge

It is demonstrated experimentally that the lifetime of the afterglow plasma of a high-current pulsed discharge in a dielectric tube filled with a mixture of argon with saturated mercury vapor is longer than 1 ms. Such a long lifetime, during which the electron density decreases from 10¹⁴ to 10¹² cm⁻³, is explained by the chemi-ionization of mercury vapor by long-lived metastable argon atoms. During this time, the afterglow plasma can serve as a microwave waveguide for a weakly damped low-noise E ₀-type axisymmetric surface mode, which allows one to use it for transmission of signals in the centimeter wavelength range.     

Evaluation of the microbial diversity in a horizontal-flow anaerobic immobilized biomass reactor treating linear alkylbenzene sulfonate

The purpose of this work was to assess the degradation of linear alkylbenzene sulfonate (LAS) in a horizontal-flow anaerobic immobilized biomass (HAIB) reactor. The reactor was filled with polyurethane foam where the sludge from a sanitary sewage treatment was immobilized. The hydraulic detention time (HDT) used in the experiments was of 12 h. The reactor was fed with synthetic substrate (410 mg l⁻¹ of meat extract, 115 mg l⁻¹ of starch, 80 mg l⁻¹ of saccharose, 320 mg l⁻¹ of sodium bicarbonate and 5 ml l⁻¹ of salt solution) in the following stages of operation: SI—synthetic substrate, SII—synthetic substrate with 7 mg l⁻¹ of LAS, SIII—synthetic substrate with 14 mg l⁻¹ of LAS and SIV—synthetic substrate containing yeast extract (substituting meat extract) and 14 mg l⁻¹ of LAS, without starch. At the end of the experiment (313 days) a degradation of ∼35% of LAS was achieved. The higher the concentration of LAS, the greater the amount of foam for its adsorption. This is necessary because the isotherm of LAS adsorption in the foam is linear for the studied concentrations (2 to 50 mg l⁻¹). Microscopic analyses of the biofilm revealed diverse microbial morphologies, while Denaturing Gradient Gel Eletrophoresis (DGGE) profiling showed variations in the population of total bacteria and sulphate-reducing bacteria (SRB). The 16S rRNA gene sequencing and phylogenetic analyses revealed that the members of the order Clostridiales were the major components of the bacterial community in the last reactor operation step.     

The impact of melaphene on the expression of chloroplastic chaperone protein HSP70B and photosynthetic pigments in cells of <Emphasis Type="Italic">Chlamydomonas reinhardtii</Emphasis>

The effects of growth regulator of the new generation—melamine salt of bis(oxymethyl)phosphine acid (melaphene)—on culture growth, pigment and protein content, and the induction of protective chloroplastic chaperone HSP70B in Chlamydomonas reinhardtii CW15 cells were studied. Melaphene exhibited 10–30% growth inhibition at 10⁻⁹–10⁻²% concentration. At 10⁻⁹–10⁻⁴% of melaphene electrophoretic concentration, the pattern of cellular proteins was similar to the control. The alterations in protein content of algae cells were detected only at 10⁻²% concentration. The content of chlorophyll and carotenoids in melaphene-treated cells was 17–40% lower than in the control. Melaphene at 10⁻⁹–10⁻²% concentration inhibited HSP70B induction by 39–43% compared to untreated cells. The potential mechanism of melaphene effect might involve its influence on nuclear gene expression.     

Distribution of phytoplankton community in Kotor Bay (south-eastern Adriatic Sea)

The goal of this paper was to explain variability of phytoplankton in a shallow coastal area in relation to physico-chemical parameters. Temporal variability and composition of phytoplankton were investigated in the Kotor Bay, a small bay located in the south-eastern part of the Adriatic Sea. Samplings were performed weekly from February 2008 to January 2009 at one station in the inner part of the Kotor Bay, at five depths (0 m, 2 m, 5 m, 10 m, 15 m). Phosphates, nitrites and nitrates ranged from values under the level of detection to the maximum values of 1.54, 1.53 and 23.91 μmol l⁻¹, respectively. The phytoplankton biomass — represented by chlorophyll a concentration — ranged from 0.12 to 6.78 mg m⁻³, reaching a maximum in summer. Diatoms were present throughout the whole sampling period, reaching the highest abundance in March (3.42×10⁵ cells l⁻¹at surface). The peak of dinoflagellates in July (2.2×10⁶ cells l⁻¹ at surface) was due to a single species, Prorocentrum micans. The toxic dinoflagellate Dinophysis fortii occurred at a concentration of 2140 cells l⁻¹ in May. The present results of phytoplankton assemblages and distribution provide valuable information for this part of the south-eastern Adriatic Sea where data is currently absent.     

Sources of Nitrogen to the Riparian Zone of a Desert Stream: Implications for Riparian Vegetation and Nitrogen Retention

Riparian zones effectively remove nitrogen (N) from water flowing through riparian soils, particularly in agricultural watersheds. The mechanism of N removal is still unclear, especially the role of vegetation. Uptake and denitrification are the two most commonly studied mechanisms. Retention of groundwater N by plant uptake is often inferred from measurements of N in net incremental biomass. However, this assumes other sources of N are not contributing to the N demand of plants. The purpose of this work was to investigate the relative importance of three sources of available N to riparian trees in a desert stream—input in stream water during floods, input during baseflow, and mineralization of N from soil organic matter. Two approaches were used; a mass balance approach in which the mass of available N from each source was estimated, and a correlational approach in which indexes of each source were compared to leaf N for individual willow trees. Total N from all sources was 396 kg ha⁻¹ y⁻¹, with 172 kg ha⁻¹ y⁻¹ from mineralization, 214 kg ha⁻¹ y⁻¹ from the stream during baseflow, and 9.6 kg ha⁻¹ y⁻¹ from floods. Leaf N was significantly related to N mineralization rates and flood inputs; it was not related to baseflow inputs. We conclude that mineralization is a major source of available N for willow trees, subsidized by input of N from floods. Baseflow inputs are most likely removed by rapid denitrification at the stream–riparian edge, while higher rates of flood supply exceed the capacity of this “filter.” Received 18 January 2001; accepted 15 June 2001.     

Ultrahigh charging of dust grains by the beam−plasma method for creating a compact neutron source

Generation of high-voltage high-current electron beams in a low-pressure (P = 0.1–1 Torr) gas discharge is studied experimentally as a function of the discharge voltage and the sort and pressure of the plasma-forming gas. The density of the plasma formed by a high-current electron beam is measured. Experiments on ultrahigh charging of targets exposed to a pulsed electron beam with an energy of up to 25 keV, an electron current density of higher than 1 A/cm², a pulse duration of up to 1 μs, and a repetition rate of up to 1 kHz are described. A numerical model of ultrahigh charging of dust grains exposed to a high-energy electron beam is developed. The formation of high-energy positive ions in the field of negatively charged plane and spherical targets is calculated. The calculations performed for a pulse-periodic mode demonstrate the possibility of achieving neutron yields of higher than 10⁶ s^–1 cm^–2 in the case of a plane target and about 10⁹ s^–1 in the case of 10³ spherical targets, each with a radius of 250 μm.     

Acetylene reduction (N2-fixation) by Enterobacteriaceae isolated from industrial wastewaters and biological treatment systems

Summary Acetylene reducing (N₂-fixing) Entero-bacteriaceae have been isolated from activated sludge plants treating waste from the paper and food industries (10³ to 10⁶ cells per ml) and from composting plants handling forest waste (10⁵ to 10⁶ cells per g wet weight). Detailed studies on se-lected strains of all taxa showed that: (1) pure cul-tures were able to utilize a range of carbohy-drates, polyols, amino acids and carboxylic acids as sole sources of carbon (2) high levels of nitro-genase were attained during growth with a range of carbon substrates: highest levels (12—66 n mole C₂H₄.min⁻¹.mg protein⁻¹) were found for glucose and sucrose, variable levels for polyols, and lower levels for citrate and fumarate (1—23 n mole C₂H₄.min⁻¹.mg protein⁻¹) (3) organic ni-trogen compounds which were utilized as sole sources of nitrogen did not generally repress the synthesis of nitrogenase, although low levels were found for some strains during growth with glu-cosamine. Samples from a laboratory model acti-vated sludge system showed a mean rate of acety-lene reduction corresponding to the fixation of 26 μg N.h⁻¹.1⁻¹, and direct analysis of the in-fluent and effluent waters and sludge showed a net increase in nitrogen. These observations corre-lated with the presence of a population of N₂-fix-ing Enterobacteriaceae of ca. 10⁵ cells per ml and pure strains isolated from the system had a mean nitrogenase specific activity of 88 n mole C₂H₄.min⁻¹.mg protein⁻¹. It is therefore con-cluded that endogenous N₂-fixing Enterobacteria-ceae contained in some kinds of industrial waste-waters could successfully be used to diminish the addition of combined nitrogen to activated sludge treatment plants.     

Femtosecond stage of electron transfer in reaction centers of the triple mutant SL178K/GM203D/LM214H of <Emphasis Type="Italic">Rhodobacter sphaeroides</Emphasis>

Coherent processes in an initial phase of charge transfer in reaction centers (RCs) of the triple mutant S(L178)K/G(M203)D/L(M214)H of Rhodobacter sphaeroides were investigated by difference (light — dark) absorption spectroscopy with 18 fsec time resolution. Electron transfer in the B cofactor branch is activated in this mutant, while the A-branch electron transfer is slowed in comparison with native RCs of Rba. sphaeroides. A bulk of absorption difference spectra was analyzed in the 940–1060 nm range (stimulated emission of excited bacteriochlorophyll dimer P* and absorption of bacteriochlorophyll anions B_A⁻ and β⁻, where β is a bacteriochlorophyll substituting the native bacteriopheophytin H_A) and in the 735–775 nm range (bleaching of the absorption band of the bacteriopheophytin H_B in the B-branch) in the −0.1 to 4 psec range of delays with respect to the moment of photoexcitation of P at 870 nm. Spectra were measured at 293 and 90 K. The kinetics of P* stimulated emission at 940 nm shows its decay with a time constant of ∼14 psec at 90 K and ∼18 psec at 293 K, which is accompanied by oscillations with a frequency of ∼150 cm⁻¹. A weak absorption band is found at 1018 nm that is formed ∼100 fsec after excitation of P and reflects the electron transfer from P* to β and/or B_A with accumulation of the P⁺β⁻ and/or P⁺B_A⁻ states. The kinetics of ΔA at 1018 nm contains the oscillations at ∼150 cm⁻¹ and distinct low-frequency oscillations at 20–100 cm⁻¹; also, the amplitude of the oscillations at 150 cm⁻¹ is much smaller at 293 than at 90 K. The oscillations in the kinetics of the 1018 nm band do not contain a 32 cm⁻¹ mode that is characteristic for native Rba. sphaeroides RCs having water molecule HOH55 in their structure. The ΔA kinetics at 751 nm reflects the electron transfer to HB with formation of the P⁺H_B⁻ state. The oscillatory part of this kinetics has the form of a single peak with a maximum at ∼50 fsec completely decaying at ∼200 fsec, which might reflect a reversible electron transfer to the B-branch. The results are analyzed in terms of coherent nuclear wave packet motion induced in the P* excited state by femtosecond light pulses, of an influence of the incorporated mutations on the mutual position of the energy levels of charge separated states, and of the role of water HOH55 in the dynamics of the initial electron transfer.     

Influence of Azolla management on the growth,yield of rice and soil fertility

A field experiment conducted at Central Rice Research Institute, Cuttack, during three successive seasons showed that with the 120-day-duration variety Ratna two dual crops ofAzolla pinnata R. Brown (Bangkok isolate) could be achieved 25 and 50 days after transplanting (DAT) by inoculating 2.0 t ha⁻¹ of fresh Azolla 10 and 30 DAT respectively. One basal crop of Azolla could also be grown using the same inoculum 20 days before transplanting (DBT) in fallow rice fields. The three crops of Azolla grown—once before transplanting and twice after transplanting—gave an average total biomass of 38–63 and 43–64 t ha⁻¹ fresh Azolla containing 64–90 and 76–94 kg N ha⁻¹ respectively in the square and rectangular spacings. Two crops of Azolla grown only as a dual crop, on the other hand, gave 26–39 and 29–41 t ha⁻¹ fresh Azolla which contained 44–61 and 43–59 kg N ha⁻¹ respectively. Growth and yield of rice were significantly higher in Azolla basal plus Azolla dual twice incorporated treatments than in the Azolla dual twice incorporation, Azolla basal plus 30 kg N ha⁻¹ urea and 60 kg N ha⁻¹ urea treatments. Azolla basal plus 30 kg N ha⁻¹ urea and 60 kg N ha⁻¹ urea showed similar yields but Azolla dual twice incorporation was significantly lower than those. The different spacing with same plant populations did not affect growth and yield significantly, whereas Azolla growth during dual cropping was 8.3 and 64% more in the rectangular spacing than in the square spacing in Azolla basal plus Azolla dual twice incorporation and Azolla dual twice incorporation treatments.     

Kinetics of N-substituted phenothiazines and N-substituted phenoxazines oxidation catalyzed by fungal laccases

Laccase-catalyzed oxidation of N-substituted phenothiazines and N-substituted phenoxazines was investigated at pH 5.5 and 25°C. The recombinant laccase from Polyporus pinsitus (rPpL) and the laccase from Myceliophthora thermophila (rMtL) were used. The dependence of initial reaction rate on substrate concentration was analyzed by applying the laccase action scheme in which the laccase native intermediate (NI) reacts with a substrate forming reduced enzyme. The reduced laccase produces peroxide intermediate (PI) which in turn decays to the NI. The calculated constant (k_ox) values of the PI formation are (6.1±3.1)×10⁵ M⁻¹s⁻¹ for rPpL and (2.5±0.9)×10⁴ M⁻¹s⁻¹ for rMtL. The bimolecular constants of the reaction of the native intermediate with electron donor (kred) vary in the interval from 2.2×10⁵ to 2.1×10⁷ M⁻¹s⁻¹ for rPpL and from 1.3×10² to 1.8×10⁵ M^-1s⁻¹ for rMtL. The larger reactivity of rPpL in comparison to rMtL is associated with the higher redox potential of type I Cu of rPpL. The variation of k_red values for both laccases correlates with the change of the redox potential of substrates. Following outer sphere (Marcus) electron transfer mechanism the calculated activationless electron transfer rate and the apparent reorganization energy are 5.0×107 M⁻¹s⁻¹ and 0.29 eV, respectively.     

Experimental study of the spatial structure of high-energy ion sources in micropinch

Images of ion sources in the plasma of a micropinch discharge were recorded. The most intense ion source was found to be a ⩾1-mm-diameter 3-mm-long anode region. The main contribution to the images is made by single-charged ions of the plasma-forming element with energies of 10–50 keV.     

Production Of Low Molecular Weight Hydrocarbons By Volcanic Eruptions On Early Mars

Methane and other larger hydrocarbons have been proposed as possible greenhouse gases on early Mars. In this work we explore if volcanic processes may have been a source for such molecules based on theoretical and experimental considerations. Geologic evidence and numerical simulations indicate that explosive volcanism was widely distributed throughout Mars. Volcanic lightning is typically produced in such explosive volcanism. Therefore this geologic setting was studied to determine if lightning could be a source for hydrocarbons in volcanic plumes. Volcanic lightning was simulated by focusing a high-energy infrared laser beam inside of a Pyrex reactor that contained the proposed volcanic gas mixture composed of 64% CH₄, 24% H₂, 10% H₂O and 2% N₂, according to an accretion model and the nitrogen content measured in Martian meteorites. The analysis of products was performed by gas chromatography coupled to infrared and mass spectroscopy. Eleven hydrocarbons were identified among the products, of which acetylene (C₂H₂) was the most abundant. A thermochemical model was used to determine which hydrocarbons could arise only from volcanic heat. In this case, acetylene and ethylene are formed at magmatic temperatures. Our results indicate that explosive volcanism may have injected into the atmosphere of early Mars ∼6×10¹² g yr⁻¹ of acetylene, and ∼2×10¹² g yr⁻¹ of 1,3-butadiyne, both produced by volcanic lightning, ∼5×10¹¹ g yr⁻¹ of ethylene produced by volcanic heat, and 10¹³ g yr⁻¹ of methane.     

The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water

This article reports rate constants for thiol–thioester exchange (k _ex), and for acid-mediated (k _a), base-mediated (k _b), and pH-independent (k _w) hydrolysis of S-methyl thioacetate and S-phenyl 5-dimethylamino-5-oxo-thiopentanoate—model alkyl and aryl thioalkanoates, respectively—in water. Reactions such as thiol–thioester exchange or aminolysis could have generated molecular complexity on early Earth, but for thioesters to have played important roles in the origin of life, constructive reactions would have needed to compete effectively with hydrolysis under prebiotic conditions. Knowledge of the kinetics of competition between exchange and hydrolysis is also useful in the optimization of systems where exchange is used in applications such as self-assembly or reversible binding. For the alkyl thioester S-methyl thioacetate, which has been synthesized in simulated prebiotic hydrothermal vents, k _a = 1.5 × 10⁻⁵ M⁻¹ s⁻¹, k _b = 1.6 × 10⁻¹ M⁻¹ s⁻¹, and k _w = 3.6 × 10⁻⁸ s⁻¹. At pH 7 and 23°C, the half-life for hydrolysis is 155 days. The second-order rate constant for thiol–thioester exchange between S-methyl thioacetate and 2-sulfonatoethanethiolate is k _ex = 1.7 M⁻¹ s⁻¹. At pH 7 and 23°C, with [R″S(H)] = 1 mM, the half-life of the exchange reaction is 38 h. These results confirm that conditions (pH, temperature, pK _a of the thiol) exist where prebiotically relevant thioesters can survive hydrolysis in water for long periods of time and rates of thiol–thioester exchange exceed those of hydrolysis by several orders of magnitude.