Miller's 1950s experiments used, besides the apparatus known in textbooks, one that generated a hot water mist in the spark flask, simulating a water vapor-rich volcanic eruption. We found the original extracts of this experiment in Miller's material and reanalyzed them. The volcanic apparatus produced a wider variety of amino acids than the classic one. Release of reduced gases in volcanic eruptions accompanied by lightning could have been common on the early Earth. Prebiotic compounds synthesized in these environments could have locally accumulated, where they could have undergone further processing.

models incorporate high partial pressures of CO2 to raise the temperature of the Earth by a greenhouse effect *Departamento de Biologı ´a Facultad de Ciencias and thus prevent the complete freezing of the oceans (Kasting, 1993). However, a frozen Earth has some ad-Universidad Nacional Auto ´noma de Mexico Apartado Postal 70-407 vantages for prebiotic chemistry (Bada et al., 1994). But again, there is no direct evidence either way. In addition, Cd Universitaria Me ´xico 04510, D.F. Mexico processes relevant to the origin of life may have taken place in environments different from the terrestrial aver-

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.

The action of an electric discharge on reduced gas mixtures such as H(2)O, CH(4) and NH(3) (or N(2)) results in the production of several biologically important organic compounds including amino acids. However, it is now generally held that the early Earth's atmosphere was likely not reducing, but was dominated by N(2) and CO(2). The synthesis of organic compounds by the action of electric discharges on neutral gas mixtures has been shown to be much less efficient. We show here that contrary to previous reports, significant amounts of amino acids are produced from neutral gas mixtures. The low yields previously reported appear to be the outcome of oxidation of the organic compounds during hydrolytic workup by nitrite and nitrate produced in the reactions. The yield of amino acids is greatly increased when oxidation inhibitors, such as ferrous iron, are added prior to hydrolysis. Organic synthesis from neutral atmospheres may have depended on the oceanic availability of oxidation inhibitors as well as on the nature of the primitive atmosphere itself. The results reported here suggest that endogenous synthesis from neutral atmospheres may be more important than previously thought.

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