Spark Discharge Experiments Research Articles

Prebiotic thiol-catalyzed thioamide bond formation

Thioamide bonds are important intermediates in prebiotic chemistry. In cyanosulfidic prebiotic chemistry, they serve as crucial intermediates in the pathways that lead to the formation of many important biomolecules (e.g., amino acids). They can also serve as purine and pyrimidine precursors, the two classes of heterocycle employed in genetic molecules. Despite their importance, the formation of thioamide bonds from nitriles under prebiotic conditions has required large excesses of sulfide or compounds with unknown prebiotic sources. Here, we describe the thiol-catalyzed formation of thioamide bonds from nitriles. We show that the formation of the simplest of these compounds, thioformamide, forms readily in spark-discharge experiments from hydrogen cyanide, sulfide, and a methanethiol catalyst, suggesting potential accumulation on early Earth. Lastly, we demonstrate that thioformamide has a Gibbs energy of hydrolysis (ΔGr∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta G^{\\circ }_r$$\\end{document}) comparable to other energy-currencies on early Earth such as pyrophosphate and thioester bonds. Overall, our findings imply that thioamides might have been abundant on early Earth and served a variety of functions during chemical evolution.

The effect of lightning on the atmospheric chemistry of exoplanets and potential biosignatures

Context. Lightning has been suggested to play a role in triggering the occurrence of bio-ready chemical species. Future missions such as PLATO, ARIEL, HWO, and LIFE, as well as ground-based extremely large telescopes (ELTs), will carry out investigations of the atmospheres of potentially habitable exoplanets. Aims. We aim to study the effect of lightning on the atmospheric chemistry. We also consider how it affects false-positive and false-negative biosignatures and whether these effects would be observable on exo-Earth and TRAPPIST-1 planets. Methods. We utilised a combination of laboratory experiments and photochemical and radiative transfer modelling. We conducted spark discharge experiments in N2−CO2−H2 gas mixtures, representing a range of possible rocky-planet atmospheres. We investigated the production of potential lightning signatures (CO and NO), possible biosignature gases (N2O, NH3, and CH4), and important prebiotic precursors (HCN and urea). Using the measured CO and NO production rates, we conducted photochemical simulations for oxygen-rich and anoxic atmospheres for rocky planets orbiting in the habitable zones of the Sun and TRAPPIST-1 for a range of lightning flash rates. Synthetic spectra were calculated using SMART to study the atmosphere’s reflectance, along with the emission and transmission spectra. Results. Lightning enhances the spectral features of NO, NO2, and (in some cases) CO through direct production; whereas CH4 and C2H6 may be enhanced indirectly. Lightning at a flash rate slightly higher than on modern-day Earth is able to mask the ozone features of an oxygen-rich, biotic atmosphere, making it harder to detect the biosphere of such a planet. Similarly, lightning at a flash rate at least ten times higher than on modern-day Earth is also able to mask the presence of ozone in the anoxic, abiotic atmosphere of a planet orbiting a late M dwarf, reducing the potential for a false-positive life detection. Conclusions. The threshold lightning flash rates to eliminate oxygen (>0.1%) and ozone false positive biosignatures on planets orbiting ultra-cool dwarfs is up to ten times higher than the modern flash rate. This result indicates that lightning cannot always prevent these false-positive scenarios.

Isotopic constraints on lightning as a source of fixed nitrogen in Earth’s early biosphere

Bioavailable nitrogen is thought to be a requirement for the origin and sustenance of life. Before the onset of biological nitrogen fixation, abiotic pathways to fix atmospheric N2 must have been prominent to provide bioavailable nitrogen to Earth’s earliest ecosystems. Lightning has been shown to produce fixed nitrogen as nitrite and nitrate in both modern atmospheres dominated by N2 and O2 and atmospheres dominated by N2 and CO2 analogous to the Archaean Earth. However, a better understanding of the isotopic fingerprints of lightning-generated fixed nitrogen is needed to assess the role of this process on early Earth. Here we present results from spark discharge experiments in N2−CO2 and N2−O2 gas mixtures. Our experiments suggest that lightning-driven nitrogen fixation may have been similarly efficient in the Archaean atmosphere, compared with modern times. Measurements of the isotopic ratio (δ15N) of the discharge-produced nitrite and nitrate in solution show very low values of −6‰ to −15‰ after equilibration with the gas phase with a calculated endmember composition of −17‰. These results are much lower than most δ15N values documented from the sedimentary rock record, which supports the development of biological nitrogen fixation earlier than 3.2 billion years ago. However, some Paleoarchean records (3.7 billion years ago) may be consistent with lightning-derived nitrogen input, highlighting the potential role of this process for the earliest ecosystems. Spark discharge experiments suggest lightning was not the main source of bioavailable nitrogen for the established Archaean biosphere, but could have been significant for Earth’s earliest ecosystems.

Numerical investigation of the spark discharge process in a crossflow

The present study numerically investigates the spark discharge process under crossflow conditions using a thermal equilibrium plasma solver that fully couples the electromagnetic physics and fluid dynamics in a computational framework. Numerical results are validated by the comparison with experimental data. The spark discharge experiment is performed in a constant volume vessel using an inductive coil ignition system for automotive applications, and the evolution of the spark channel is measured using high-speed imaging. The crossflow in the gap between the spark-plug electrodes is generated by a rotating fan with two different fan speeds, and the flow velocity across the gap is characterized by particle image velocimetry (PIV) measurement. A computational fluid dynamics (CFD) solver is employed to simulate the crossflow and provide the flow field variables (velocity, pressure, temperature) to the plasma solver. The crossflow velocity predicted in the flow simulation agrees well with the PIV data in that the non-uniform velocity profiles at monitoring points are reproduced by the CFD code. With the crossflow initialization in the plasma solver, the simulated spark discharge process from the breakdown to spark discharge matches the experimental data, including the voltage and circuit waveforms and the high-speed images of the spark channel evolution. The stretch of spark channel captured by plasma simulations agrees with the measured data. The plasma simulation reveals that the mean temperature of the spark channel is maintained at 5000 K during the discharge phase, and the temperature varies along the spark channel so that the highest value is obtained at the spark root on the center electrode. Overall, the results presented in this paper are meant to provide valuable information about the properties of the plasma generated by the spark discharge.

Mineral Grains, Dimples, and Hot Volcanic Organic Streams: Dynamic Geological Backstage of Macromolecular Evolution

The hypothesis of hot volcanic organic stream as the most probable and geologically plausible environment for abiogenic polycondensation is proposed. The primary synthesis of organic compounds is considered as result of an explosive volcanic (perhaps, meteorite-induced) eruption. The eruption was accompanied by a shock wave propagating in the primeval atmosphere and resulting in the formation of hot cloud of simple organic compounds-aldehydes, alcohols, amines, amino alcohols, nitriles, and amino acids-products, which are usually obtained under the artificial conditions in the spark-discharge experiments. The subsequent cooling of the organic cloud resulted in a gradual condensation and a serial precipitation of organic compounds (in order of decreasing boiling point values) into the liquid phase forming a hot, viscous and muddy organic stream (named "lithorheos"). That stream-even if the time of its existence was short-is considered here as a geologically plausible environment for abiogenic polycondensation. The substances successively prevailing in such a stream were cyanamide, acetamide, formamide, glycolonitrile, acetonitrile. An important role was played by mineral (especially, phosphate-containing) grains (named "lithosomes"), whose surface was modified with heterocyclic nitrogen compounds synthesized in the course of eruption. When such grains got into hot organic streams, their surface catalytic centers (named "lithozymes") played a decisive role in the emergence, facilitation and maintenance of prebiotic reactions and key processes characteristic of living systems. Owing to its cascade structure, the stream was a factor underlying the formation of mineral-polymeric aggregates (named "lithocytes") in the small natural streambed cavities (dimples)-as well as a factor of their further spread within larger geological locations which played a role of chemo-ecological niches. All three main stages of prebiotic evolution (primary organic synthesis, polycondensation, and formation of proto-cellular structures) are combined within a common dynamic geological process. We suppose macromolecular evolution had an extremely fast, "flash" start: the period from volcanic eruption to formation of lithocyte "populations" took not million years but just several tens of minutes. The scenario proposed can be verified experimentally with a three-module setup working with principles of dynamic (flow) chemistry in its core element.

Electric ignition energy evaluation and the energy distribution structure of energy released in electrostatic discharge process**Project supported by the National Natural Science Foundation of China (Grant No. 11572044) and the National Key Research and Development Program of China (Grant No. 2017YFC0804705).

Ignition energy is one of the important parameters of flammable materials, and evaluating ignition energy precisely is essential to the safety of process industry and combustion science and technology. By using electric spark discharge test system, a series of electric spark discharge experiments were conducted with the capacitor-stored energy in the range of 10 J, 100 J, and 1000 J, respectively. The evaluation method for energy consumed by electric spark, wire, and switch during capacitor discharge process has been studied respectively. The resistance of wire, switch, and plasma between electrodes has been evaluated by different methods and an optimized evaluation method has been obtained. The electric energy consumed by wire, electric switch, and electric spark-induced plasma between electrodes were obtained and the energy structure of capacitor-released energy was analyzed. The dynamic process and the characteristic parameters (the maximum power, duration of discharge process) of electric spark discharge process have been analyzed. Experimental results showed that, electric spark-consumed energy only accounts for 8%–14% of the capacitor-released energy. With the increase of capacitor-released energy, the duration of discharge process becomes longer, and the energy of plasma accounts for more in the capacitor-released energy. The power of electric spark varies with time as a damped sinusoids function and the period and the maximum value increase with the capacitor-released energy.

Quantitation of α-hydroxy acids in complex prebiotic mixtures via liquid chromatography/tandem mass spectrometry.

Spark discharge experiments, like those performed by Stanley Miller in the 1950s, generate complex, analytically challenging mixtures that contain biopolymer building blocks. Recently, α-amino acids and α-hydroxy acids (AHAs) were subjected to environmental cycling to form simple depsipeptides (peptides with both amide and ester linkages). The synthesis of AHAs under possible primordial environments must be examined to better understand this chemistry. We report a direct, quantitative method for AHAs using ultrahigh-performance liquid chromatography and triple quadrupole mass spectrometry. Hexylamine ion-pairing chromatography and selected reaction monitoring detection were combined for the rapid analysis of ten AHAs in a single run. Additionally, prebiotic simulation experiments, including the first-ever reproduction of Miller's 1958 cyanamide spark discharge experiment, were performed to evaluate AHA synthesis over a wide range of possible primitive terrestrial environments. The quantitating transition for each of the AHAs targeted in this study produced a limit of detection in the nanomolar concentration range. For most species, a linear response over a range spanning two orders of magnitude was found. The AHAs glycolic acid, lactic acid, malic acid, and α-hydroxyglutaric acid were detected in electric discharge experiments in the low micromolar concentration range. The results of this work suggest that the most abundant building blocks available for prebiotic depsipeptide synthesis would have been glycolic, lactic, malic, and α-hydroxyglutaric acids, and their corresponding amino acids, glycine, alanine, and aspartic and glutamic acids. Copyright © 2016 John Wiley & Sons, Ltd.

Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

Hydrogen peroxide is an important atmospheric component involved in various gas-phase and aqueous-phase transformation processes in the Earth’s atmosphere. A study of mass-independent 17O anomalies in H2O2 can provide additional insights into the chemistry of the modern atmosphere and, possibly, of the ancient atmosphere. Here, we report the results of laboratory experiments to study the fractionation of three oxygen isotopes (16O, 17O, and 18O) during H2O2 formation from products of water vapour dissociation. The experiments were carried out by passing an electrical discharge through a gaseous mixture of helium and water at atmospheric pressure. The effect of the presence of O2 in the gas mixture on the isotopic composition of H2O2 was also investigated. All of the experiments showed that H2O2 produced under two different conditions (with or without O2 added in the gas mixtures) was mass-independently fractionated (MIF). We found a positive MIF signal (∼1.4‰) in the no-O2 added experiments, and this signal increased to ∼2.5‰ once O2 was added (1.6% mixing ratio). We suggest that if O2 concentrations are very low, the hydroxyl radical recombination reaction is the dominant pathway for H2O2 formation and is the source of MIF in H2O2. Although H2O2 formation via a hydroxyl radical recombination process is limited in the modern atmosphere, it would be possible in the Archean atmosphere when O2 was a trace constituent, and H2O2 would be mass-independently fractionated. The anomalous 17O excess, which was observed in H2O2 produced by spark discharge experiments, may provide useful information about the radical chemistry of the ancient atmosphere and the role of H2O2 in maintaining and controlling the atmospheric composition.

An Interpretation of the Ancestral Codon from Miller's Amino Acids and Nucleotide Correlations in Modern Coding Sequences.

Purine bias, which is usually referred to as an “ancestral codon”, is known to result in short-range correlations between nucleotides in coding sequences, and it is common in all species. We demonstrate that RWY is a more appropriate pattern than the classical RNY, and purine bias (Rrr) is the product of a network of nucleotide compensations induced by functional constraints on the physicochemical properties of proteins. Through deductions from universal correlation properties, we also demonstrate that amino acids from Miller’s spark discharge experiment are compatible with functional primeval proteins at the dawn of living cell radiation on earth. These amino acids match the hydropathy and secondary structures of modern proteins.

Energy measurement of spark discharge using different triggering methods and inductance loads

Abstract Spark discharge experiments with different nominal energy (100–1000 mJ) and inductance loads (0.024 or 1.454 mH) were carried out using different trigger methods. A Tektronix oscilloscope with a high-voltage probe and a current probe was used to record the dynamic voltage and current. The influence of inductance and trigger method on the discharge efficiency and discharge time were investigated. It was found that, when the discharge was triggered by electrode movement, the discharge efficiency ranged from 78.2% to 90.1% in case of without inductor, and ranged from 41.1% to 59.3% in case of with inductor.

Shock wave generated by high-energy electric spark discharge

Shock wave generated by electric spark discharge was studied experimentally and the shock wave energy was evaluated in this paper. A pressure measurement system was established to study the pressure field of the electric spark discharge process. A series of electric spark discharge experiments were carried out and the energy of the electric spark used in present study was in the range of 10 J, 100 J, and 1000 J, respectively. The shock wave energy released from the electric spark discharge process was calculated by using the overpressure values at different measurement points near the electric spark discharge center. The good consistency of shock wave energies calculated by pressure histories at different measuring points in the same electric spark discharge experiment illustrates the applicability of the weak shock wave theory in calculating the energy of shock wave induced by electric spark discharge process. The result showed that shock wave formed at the initial stage of electric spark discharge process, and the shock wave energy is only a little part of electric spark energy. From the analysis of the shock wave energy and electric spark energy, a good linear relationship between shock wave energy and electric spark energy was established, which make it possible to calculate shock wave energy by measuring characteristic parameters of electric spark discharge process instead of shock wave. So, the initiation energy of direct initiation of detonation can be determined easily by measuring the parameters of electric spark discharge process.

Conducting Miller-Urey Experiments

In 1953, Stanley Miller reported the production of biomolecules from simple gaseous starting materials, using an apparatus constructed to simulate the primordial Earth's atmosphere-ocean system. Miller introduced 200 ml of water, 100 mmHg of H2, 200 mmHg of CH4, and 200 mmHg of NH3 into the apparatus, then subjected this mixture, under reflux, to an electric discharge for a week, while the water was simultaneously heated. The purpose of this manuscript is to provide the reader with a general experimental protocol that can be used to conduct a Miller-Urey type spark discharge experiment, using a simplified 3 L reaction flask. Since the experiment involves exposing inflammable gases to a high voltage electric discharge, it is worth highlighting important steps that reduce the risk of explosion. The general procedures described in this work can be extrapolated to design and conduct a wide variety of electric discharge experiments simulating primitive planetary environments.

Conducting Miller-Urey Experiments

In 1953, Stanley Miller reported the production of biomolecules from simple gaseous starting materials, using an apparatus constructed to simulate the primordial Earth's atmosphere-ocean system. Miller introduced 200 ml of water, 100 mmHg of H2, 200 mmHg of CH4, and 200 mmHg of NH3 into the apparatus, then subjected this mixture, under reflux, to an electric discharge for a week, while the water was simultaneously heated. The purpose of this manuscript is to provide the reader with a general experimental protocol that can be used to conduct a Miller-Urey type spark discharge experiment, using a simplified 3 L reaction flask. Since the experiment involves exposing inflammable gases to a high voltage electric discharge, it is worth highlighting important steps that reduce the risk of explosion. The general procedures described in this work can be extrapolated to design and conduct a wide variety of electric discharge experiments simulating primitive planetary environments.

Miller-Urey and Beyond: What Have We Learned About Prebiotic Organic Synthesis Reactions in the Past 60 Years?

The synthesis of amino acids in the Miller-Urey spark-discharge experiments in the early 1950s inspired a strong interest in experimental studies of prebiotic organic chemistry that continues today. Over the years, many of the basic building blocks of life as we know it have been synthesized in the laboratory from simple ingredients, including amino acids, sugars, nucleobases, and membrane-forming lipids. Questions remain, however, concerning whether the conditions that allow synthesis of these compounds in the laboratory accurately simulate those that might have been present on the early Earth, and a closer convergence between plausible prebiotic conditions and laboratory simulations remains a challenge for experimentalists.

Research on spark discharge of floating roof tank shunt

In order to quantitatively analyze the spark discharge risk of floating roof tank shunts, the breakdown voltage of shunt has been calculated by Townsend theory, the shunt spark discharge experiment is carried out by using 1.2/50 μs impulse voltage wave, and the relationship between breakdown voltage of shunt spark discharge and air gap is analyzed. It has been indicated by theoretical analysis and experimental study that the small gap is more easily cause spark discharge than the big gap when the contact between shunt and tank shell is poor. When air gap distance is equal to 0.1 cm, average breakdown voltage is 5280 V. When the air gap distance is less than 0.3 cm, experiment data agree well with Townsend theory. Therefore, in the condition of small gap, Townsend theory can be used to calculated breakdown voltage of shunt. Finally, based on the above conclusions, improvements for avoiding the spark discharge risk of shunt of floating roof tanks have been proposed.

New insights into prebiotic chemistry from Stanley Miller's spark discharge experiments

1953 was a banner year for biological chemistry: The double helix structure of DNA was published by Watson and Crick, Sanger's group announced the first amino acid sequence of a protein (insulin) and the synthesis of key biomolecules using simulated primordial Earth conditions has demonstrated by Miller. Miller's studies in particular transformed the study of the origin of life into a respectable field of inquiry and established the basis of prebiotic chemistry, a field of research that investigates how the components of life as we know it can be formed in a variety of cosmogeochemical environments. In this review, I cover the continued advances in prebiotic syntheses that Miller's pioneering work has inspired. The main focus is on recent state-of-the-art analyses carried out on archived samples of Miller's original experiments, some of which had never before been analyzed, discovered in his laboratory material just before his death in May 2007. One experiment utilized a reducing gas mixture and an apparatus configuration (referred to here as the "volcanic" apparatus) that could represent a water-rich volcanic eruption accompanied by lightning. Another included H(2)S as a component of the reducing gas mixture. Compared to the limited number of amino acids Miller identified, these new analyses have found that over 40 different amino acids and amines were synthesized, demonstrating the potential robust formation of important biologic compounds under possible cosmogeochemical conditions. These experiments are suggested to simulate long-lived volcanic island arc systems, an environment that could have provided a stable environment for some of the processes thought to be involved in chemical evolution and the origin of life. Some of the alternatives to the Miller-based prebiotic synthesis and the "primordial soup" paradigm are evaluated in the context of their relevance under plausible planetary conditions.

The use of ascorbate as an oxidation inhibitor in prebiotic amino acid synthesis: a cautionary note.

It is generally thought that the terrestrial atmosphere at the time of the origin of life was CO(2)-rich and that organic compounds such as amino acids would not have been efficiently formed abiotically under such conditions. It has been pointed out, however, that the previously reported low yields of amino acids may have been partially due to oxidation by nitrite/nitrate during acid hydrolysis. Specifically, the yield of amino acids was found to have increased significantly (by a factor of several hundred) after acid hydrolysis with ascorbic acid as an oxidation inhibitor. However, it has not been shown that CO(2) was the carbon source for the formation of the amino acids detected after acid hydrolysis with ascorbic acid. We therefore reinvestigated the prebiotic synthesis of amino acids in a CO(2)-rich atmosphere using an isotope labeling experiment. Herein, we report that ascorbic acid does not behave as an appropriate oxidation inhibitor, because it contributes amino acid contaminants as a consequence of its reactions with the nitrogen containing species and formic acid produced during the spark discharge experiment. Thus, amino acids are not efficiently formed from a CO(2)-rich atmosphere under the conditions studied.

Enhanced Synthesis of Alkyl Amino Acids in Miller’s 1958 H2S Experiment

Stanley Miller's 1958 H(2)S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH(4)), ammonia (NH(3)), carbon dioxide (CO(2)), and hydrogen sulfide (H(2)S) produced several alkyl amino acids, including the α-, β-, and γ-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H(2)S, aspartic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H(2)S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H(2)S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

Primordial synthesis of amines and amino acids in a 1958 Miller H 2 S-rich spark discharge experiment

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H(2)S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H(2)S, CH(4), NH(3), and CO(2). A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordial environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H(2)S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H(2)S may have played an important role in prebiotic reactions in early solar system environments.

Experimental Investigation on Measurement of Spark Discharge Energy Using Integration Method

Minimum ignition energy is an important characteristics of dust cloud. Accurate determination of minimum ignition energy is significant for dust explosion prevention. According to EC 6124-2-3, when nominal energy is great than 100mJ, the spark energy is recommended to be determined by integration of voltage and current with time. However, few experimental investigations were reported on the determination of spark discharge energy using integration method. Spark discharge experiments were carried out for different nominal energies, which were ranged from 63mJ to1271mJ. Tektronix oscillograph was used to record the dynamic voltage and current between the discharge gap during spark discharge. The period characteristics of the LC discharge circuit were calculated, and experimental period agreed with theoretical periods. The ratios of discharge energies measured using integration method to the nominal energies stored in the capacitors (discharge efficiency) were investigated. It was found that, when nominal energy is in the range of 63mJ∼1271mJ, the discharge efficiency varies from 75.4% to 24.5%.