Craig P. Marshall

Stromatolite reef from the Early Archaean era of Australia

The 3,430-million-year-old Strelley Pool Chert (SPC) (Pilbara Craton, Australia) is a sedimentary rock formation containing laminated structures of probable biological origin (stromatolites). Determining the biogenicity of such ancient fossils is the subject of ongoing debate. However, many obstacles to interpretation of the fossils are overcome in the SPC because of the broad extent, excellent preservation and morphological variety of its stromatolitic outcrops—which provide comprehensive palaeontological information on a scale exceeding other rocks of such age. Here we present a multi-kilometre-scale palaeontological and palaeoenvironmental study of the SPC, in which we identify seven stromatolite morphotypes—many previously undiscovered—in different parts of a peritidal carbonate platform. We undertake the first morphotype-specific analysis of the structures within their palaeoenvironment and refute contemporary abiogenic hypotheses for their formation. Finally, we argue that the diversity, complexity and environmental associations of the stromatolites describe patterns that—in similar settings throughout Earths history—reflect the presence of organisms.

Organic-walled microfossils in 3.2-billion-year-old shallow-marine siliciclastic deposits.

Although the notion of an early origin and diversification of life on Earth during the Archaean eon has received increasing support in geochemical, sedimentological and palaeontological evidence, ambiguities and controversies persist regarding the biogenicity and syngeneity of the record older than Late Archaean. Non-biological processes are known to produce morphologies similar to some microfossils, and hydrothermal fluids have the potential to produce abiotic organic compounds with depleted carbon isotope values, making it difficult to establish unambiguous traces of life. Here we report the discovery of a population of large (up to about 300 μm in diameter) carbonaceous spheroidal microstructures in Mesoarchaean shales and siltstones of the Moodies Group, South Africa, the Earth’s oldest siliciclastic alluvial to tidal-estuarine deposits. These microstructures are interpreted as organic-walled microfossils on the basis of petrographic and geochemical evidence for their endogenicity and syngeneity, their carbonaceous composition, cellular morphology and ultrastructure, occurrence in populations, taphonomic features of soft wall deformation, and the geological context plausible for life, as well as a lack of abiotic explanation falsifying a biological origin. These are the oldest and largest Archaean organic-walled spheroidal microfossils reported so far. Our observations suggest that relatively large microorganisms cohabited with earlier reported benthic microbial mats in the photic zone of marginal marine siliciclastic environments 3.2 billion years ago.

A REVISION OF REDUVIASPORONITES WILSON 1962: DESCRIPTION, ILLUSTRATION, COMPARISON AND BIOLOGICAL AFFINITIES

Abstract Geochemical analyses of specimens of Reduviasporonites suggests that it is most likely of algal, rather than fungal origin. As a probable alga, Reduviasporonites is unlikely to be integral to the process of mass extinction occurring at or near the Permian‐Triassic boundary, as suggested by Visscher and other workers because it cannot have acted as a saprophytic metaboliser of dead vegetation resulting from that event. Moreover, it ranges outside the postulated time of mass extinction by at least 10 million years. Optical and electron microscopy of topotype material confirms that Reduviasporonites Wilson 1962 is the senior synonym of Chordecystia Foster 1979, and Tympanicysta Balme 1980. Moreover the type species of the last two genera, assigned in 1999 to Reduviasporonites by Elsik as R. chalastus (Foster) and R. stoschianus (Balme), are conspecific. The type species, R. catenulatus Wilson 1962, differs from R. chalastus in that its constituent cells are significantly smaller, more rounded, and h...

Understanding the Application of Raman Spectroscopy to the Detection of Traces of Life

Investigating carbonaceous microstructures and material in Earths oldest sedimentary rocks is an essential part of tracing the origins of life on our planet; furthermore, it is important for developing techniques to search for traces of life on other planets, for example, Mars. NASA and ESA are considering the adoption of miniaturized Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for fossil or extant biomolecules. Recently, Raman spectroscopy has been used to infer a biological origin of putative carbonaceous microfossils in Early Archean rocks. However, it has been demonstrated that the spectral signature obtained from kerogen (of known biological origin) is similar to spectra obtained from many poorly ordered carbonaceous materials that arise through abiotic processes. Yet there is still confusion in the literature as to whether the Raman spectroscopy of carbonaceous materials can indeed delineate a signature of ancient life. Despite the similar nature in spectra, rigorous structural interrogation between the thermal alteration products of biological and nonbiological organic materials has not been undertaken. Therefore, we propose a new way forward by investigating the second derivative, deconvolution, and chemometrics of the carbon first-order spectra to build a database of structural parameters that may yield distinguishable characteristics between biogenic and abiogenic carbonaceous material. To place Raman spectroscopy as a technique to delineate a biological origin for samples in context, we will discuss what is currently accepted as a spectral signature for life; review Raman spectroscopy of carbonaceous material; and provide a historical overview of Raman spectroscopy applied to Archean carbonaceous materials, interpretations of the origin of the ancient carbonaceous material, and a future way forward for Raman spectroscopy.

The potential of Raman spectroscopy for the analysis of diagenetically transformed carotenoids

Recently, carotenoids have received much attention as target compounds for astrobiological prospecting principally because they are a group of molecules that display unique diagnostic Raman spectra that can be assigned to organic material of unequivocal biological origin. However, no work has been performed on assessing the potential of Raman spectroscopic detection of carotenoids from fossilized microbes. Here, we report the first Raman spectra acquired from ‘perhydro’ derivatives of β-carotene and lycopene formed by hydrogenation of the polyene chain during diagenesis, resulting in much less specific fossil hydrocarbons such as β-carotane and lycopane, respectively. We propose here that diagenetically altered carotenoids formed by hydrogenation reactions during the fossilization processes also provide unique diagnostic spectra that can be interpreted as a biological signature.

Multiple Generations of Carbon in the Apex Chert and Implications for Preservation of Microfossils

While the Apex chert is one of the most well-studied Archean deposits on Earth, its formation history is still not fully understood. Here, we present Raman spectroscopic data collected on the carbonaceous material (CM) present within the matrix of the Apex chert. These data, collected within a paragenetic framework, reveal two different phases of CM deposited within separate phases of quartz matrix. These multiple generations of CM illustrate the difficulty of searching for signs of life in these rocks and, by extension, in other Archean sequences.

Raman Hyperspectral Imaging of Microfossils: Potential Pitfalls

Initially, Raman spectroscopy was a specialized technique used by vibrational spectroscopists; however, due to rapid advancements in instrumentation and imaging techniques over the last few decades, Raman spectrometers are widely available at many institutions, allowing Raman spectroscopy to become a widespread analytical tool in mineralogy and other geological sciences. Hyperspectral imaging, in particular, has become popular due to the fact that Raman spectroscopy can quickly delineate crystallographic and compositional differences in 2-D and 3-D at the micron scale. Although this rapid growth of applications to the Earth sciences has provided great insight across the geological sciences, the ease of application as the instruments become increasingly automated combined with nonspecialists using this techique has resulted in the propagation of errors and misunderstandings throughout the field. For example, the literature now includes misassigned vibration modes, inappropriate spectral processing techniques, confocal depth of laser penetration incorrectly estimated into opaque crystalline solids, and a misconstrued understanding of the anisotropic nature of sp² carbons.

Hematite and carbonaceous materials in geological samples: a cautionary tale.

Over the last few decades Raman spectroscopy has been increasingly applied as an analytical tool in geoscience research. Raman spectroscopy is a powerful tool for geologists as it is non-destructive, requires little to no sample preparation, and can be undertaken in situ on various irreplaceable geological samples. Also, this technique is useful in the identification of minerals and geo-organic material. However, despite this ease of application, there are some facets of Raman spectroscopy data that can lead to erroneous interpretations. For instance, there is much confusion in the geological literature distinguishing the difference between the hematite vibrational mode at ca. 1320 cm(-1) and the disordered sp(2) carbonaceous material D band at 1340 cm(-1). Furthermore, geologists will often collect 2 spectra, one in the mineral finger print region (200-800 cm(-1)) and then a spectrum in the carbon first-order region (1000-1800 cm(-1)), rather than performing a full-region scan. This allows the misidentification of the hematite mode at 1320 cm(-1) as the D band from disordered carbonaceous material. Here we show that it is best practice for geologists to collect spectra between 200 and 1800 cm(-1) to better distinguish between hematite and disordered carbonaceous material, materials that often co-occur in geological samples.

Structure of organic matter in conodonts with different colour alteration indexes

Devonian conodont samples from the Beechwood Member of the North Vernon Limestone, IN, USA and Garra Formation Wellington, NSW, Australia with Colour Alteration Index (CAI) values of 2 and 4, respectively, were analysed using X-ray photoelectron spectroscopy (XPS), pyrolysis gas chromatography mass spectrometry (py-GC/ MS) and Fourier transform infrared emission spectroscopy (FTIRES). The results show the organic matter is different for the two conodont samples, but contrary to that predicted if only thermal processes were operating. The organic matter in the Beechwood Member conodonts appears to be reduced whereas conodonts from the Garra Formation appear to be oxidised. Pyrolysates from organic matter in the Beechwood Member conodonts are dominated by an n-alkane series of hydrocarbons from C 8 to C 19 , and simple aromatic hydrocarbons, however pyrolysates of organic matter from conodonts in the Garra Formation are dominated by nitrogen compounds and ketones. It is concluded that CAI values should be checked spectroscopically since CAI values indicating oil potential will be misleading if the organic matter is oxidised.

RAMAN SPECTROSCOPIC INVESTIGATIONS OF BURGESS SHALE–TYPE PRESERVATION: A NEW WAY FORWARD

Abstract Study of the Burgess Shale-type deposits of the Cambrian has greatly enhanced scientific understanding of early animal evolution, but as the mechanisms by which these deposits formed are still unclear, here we outline and present data from the application of a new analytical approach, Raman spectroscopy, that can be used to characterize fossils from these deposits. Although these deposits present exceptional views into a diverse, nonbiomineralized to lightly biomineralized biota, this taphonomic regime mostly disappears from the fossil record after the Cambrian, with a few notable exceptions. Numerous detailed taphonomic and chemical studies have provided significant insight into modes of fossil preservation in these deposits, although there is still significant debate regarding the preservational and diagenetic mechanisms that may be involved. Compared to previous electron microscopy-based elemental mapping approaches, which have identified the elemental components of similar fossils, Raman spectroscopy allows a determination of the chemical phases and specific mineralogy at the molecular level, as well as the thermal maturity, of these fossils. This approach therefore provides new types of data, such as hematite phase, that may prove helpful for elucidating some of the mechanisms responsible for the exceptional types of preservation found in these deposits, and potentially helps to resolve the existing taphonomic debates.