Molecular Biosignatures

Life, as we know it, is based on carbon chemistry operating in an aqueous environment. Living organisms process chemicals, make copies of themselves, are autonomous and evolve in concert with the environment. All these characteristics are driven by, and operate through, carbon chemistry. The carbon chemistry of living systems is an exact branch of science and we have detailed knowledge of the basic metabolic and reproductive machinery of living organisms. We can recognise the residual biochemicals long after life has expired and otherwise lost most life-defining features. Carbon chemistry provides a tool for identifying extant and extinct life on Earth and, potentially, throughout the Universe. In recognizing that certain distinctive compounds isolable from living systems had related fossil derivatives, organic geochemists coined the term biological marker compound or biomarker (e.g. Eglinton et al. in Science 145:263–264, 1964) to describe them. In this terminology, biomarkers are metabolites or biochemicals by which we can identify particular kinds of living organisms as well as the molecular fossil derivatives by which we identify defunct counterparts. The terms biomarker and molecular biosignature are synonymous. A defining characteristic of terrestrial life is its metabolic versatility and adaptability and it is reasonable to expect that this is universal. Different physiologies operate for carbon acquisition, the garnering of energy and the storage and processing of information. As well as having a range of metabolisms, organisms build biomass suited to specific physical environments, habitats and their ecological imperatives. This overall ‘metabolic diversity’ manifests itself in an enormous variety of accompanying product molecules (i.e. natural products). The whole field of organic chemistry grew from their study and now provides tools to link metabolism (i.e. physiology) to the occurrence of biomarkers specific to, and diagnostic for, particular kinds of metabolism. Another characteristic of living things, also likely to be pervasive, is that an enormous diversity of large molecules are built from a relatively small subset of universal precursors. These include the four bases of DNA, 20 amino acids of proteins and two kinds of lipid building blocks. Third, life exploits the specificity inherent in the spatial, that is, the three-dimensional qualities of organic chemicals (stereochemistry). These characteristics then lead to some readily identifiable and measurable generic attributes that would be diagnostic as biosignatures. Measurable attributes of molecular biosignatures include:

1. Enantiomeric excess
2. Diastereoisomeric preference
3. Structural isomer preference
4. Repeating constitutional sub-units or atomic ratios
5. Systematic isotopic ordering at molecular and intramolecular levels
6. Uneven distribution patterns or clusters (e.g. C-number, concentration, δ ¹³C) of structurally related compounds.

In this paper we address details of the chemical and biosynthetic basis for these features, which largely arise as a consequence of construction from small, recurring sub-units. We also address how these attributes might become altered during diagenesis and planetary processing. Finally, we discuss the instrumental techniques and further developments needed to detect them.