Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality.

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Indigeneity of organic matter in fossils: a test using stable isotope analysis of amino acid enantiomers in Quaternary mollusk shells.

Comparison of the delta 13C values of D and L enantiomers of individual amino acids was used to evaluate the presence of amino acid contaminants in Quaternary land snails. Measurements of delta 13C values of amino acid D and L enantiomers determined by combined gas chromatography, combustion, isotope-ratio mass spectrometry are reported. Conventional combustion techniques, following separation of aspartic acid and glutamic acid enantiomers by liquid chromatography, were also used to determine delta 13C as well as delta 15N values. Thoroughly cleaned samples ranging in age from 7000 to > 100,000 yr B.P. are shown to have analytically identical delta 13C values for the D and L enantiomers of each amino acid, thus confirming that the amino acids are indigenous to the shells, even in Pleistocene samples. On the other hand, partially cleaned material shows divergence of isotopic values, thus indicating the presence of amino acid contaminants and emphasizing the importance of proper cleaning procedures. This approach provides a powerful method for assessing the indigeneity of amino acids in fossils.