Natural abundances of carbon isotopes in acetate from a coastal marine sediment.

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment.

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio (delta 13C) of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95%. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

Experiments on the amplification of optical activity.

By way of investigating possible mechanisms for the abiotic amplification of small enantiomeric excesses (e.e.'s) in almost racemic mixtures of amino acid enantiomers, we have undertaken a quantitative study of the base-initiated partial polymerization of leucine and valine N-carboxy-anhydride (NCA) enantiomer mixtures containing known excesses of both the R- and S-forms. Polymerization to the extent of ca. 50% of leucine NCA having an 8-70% e.e. of either the R- or S-enantiomer led to an e.e. enhancement in the polymer, which contained a 12-84% e.e. of that enantiomer which predominated in the original monomer NCA. A corresponding decrease in the e.e. of the initially predominant enantiomer was noted in the unpolymerized residue from each reaction. Polymerization to the extent of 25-50% of mixtures of valine NCA enantiomers containing a 12-13% e.e. of either R- or S-isomer led to polymers showing a 7-8% decrease in the e.e. of the initially predominant enantiomer, and to an increase of its e.e. in the unpolymerized residue. these divergent results, the latter of which is quite novel, are compared with earlier qualitative results in the literature and are discussed briefly from the viewpoint of both mechanism and the amplification of optical activity.

The radiolysis of tryptophan and leucine with 32P beta-radiation.

We have extended earlier experiments on the radiolysis of DL-tryptophan using 32 p beta-radiation to longer reaction times, observing complete destruction of the tryptophan by secondary, non-radiolytic processes. We have also undertaken the irradiation of DL-leucine with 32 P beta's at -196 degrees, achieving radiolyses to the extents of ca. 20-30%, but observing no concomittant asymmetric bias. The implications of these observations are discussed with regard to the Vester-Ulbricht mechanism for the origin of optical activity.

A model for the enantiomeric enrichment of polypeptides on the primitive earth.

A mixture of D- and L-leucine N-Carboxyanhydride (NCA) having an enantiomeric composition of 65.6% L- and 34.4% D-isomer (i.e. 31.2% enantiomeric excess (e.e)) was polymerized to the extent of 52% with sodium methoxide initiator to yield a polyleucine product the enantiomeric composition of which was 72.7% L- and 27.3% D-leucine (45.4% e.e.). This polymer was in turn partially hydrolyzed by acid, whereupon the unhydrolyzed polyleucine residue was found to have an enantiomeric composition of 77.5% L- and 22.5% D-leucine (55.0% e.e.). Thus the e.e. increase in the partial polymerization step (14.2%) and the partial hydrolysis step (9.6%) combined to total 23.8% for the overall polymerization-hydrolysis sequence. On the basis of these model experiments it is proposed that repetitive partial polymerization hydrolysis reactions, driven by environmental dry-wet cycles, might have been operative on the primitive Earth to engender the abiotic evolution of optically enriched polypeptides.

Experiments on the abiotic amplification of optical activity.

Our earlier experiments are briefly reviewed, involving the abiotic generation of optical activity by exposure of DL-amino acids to various "chiral" physical forces. The enantiomeric enrichments so obtained were low, however, and additional experiments were undertaken with the objective of abiotically enhancing such small enantiomeric excesses. D not equal to L Mixtures of leucine N-carboxy anhydride gave enantiomerically enriched polymers on partial polymerization, while valine NCA mixtures behaved oppositely. Leucine polymers were also found to hydrolyze stereoselectively, providing for additional enantiomeric enhancement. A repetitive sequence of partial polymerization-hydrolysis steps is suggested as a possible mechanism for the abiotic genesis of optically enriched polypeptides on the primitive Earth.

The radioracemization of amino acids by ionizing radiation: geochemical and cosmochemical implications.

A number of optically active amino acids, both in the solid state and as sodium or hydrochloride salts in aqueous solution, have been exposed to ionizing radiation from a 3000 Ci60Co gamma-ray source to see if radioracemization might accompany their well-known radiolysis. gamma-Ray doses causing 55--68% radiolysis of solid amino acids typically engendered 2--5% racemization, while aqueous solutions of the sodium salts of amino acids which underwent 53--66% radiolysis showed 5--11% racemization. Amino acid hydrochloride salts in aqueous solution, on the other hand, showed little or no radioracemization accompanying their radiolysis. Both radiolysis and radioracemization were roughly proportional to gamma-ray dose in the range studied (1--36 x 10(6) rads). Mechanisms for the radioracemization of amino acids in the solid state and as aqueous sodium salts are discussed, and the absence of radioracemization for aqueous hydrochloride salts is rationalized. Isovaline, a non-protein amino acid which has been isolated from the Murchison meteorite, contains no alpha-hydrogen atom and is therefore incapable of racemization via the chemical mechanisms by which ordinary amino acids racemize. Nevertheless, isovaline suffers radioracemization in the solid state to an extent comparable to that shown by ordinary amino acids, as do its sodium and hydrochloride salts in the solid state. The sodium salt of isovaline in aqueous solution, however, fails to racemize during its radiolysis. Several implications of the newly described phenomenon of radiomization are pointed out for the fields of geochemistry and cosmochemistry.