Chemical Mapping of Proterozoic Organic Matter at Sub-Micron Spatial Resolution

We have used a NanoSIMS ion microprobe to map sub-micron-scale distributions of carbon, nitrogen, sulfur, silicon, and oxygen in organic microfossils and laminae from the approximately 0.85 Ga Bitter Springs Formation of Australia. The data provide clues about the original chemistry of the microfossils, the silicification process, and biosignatures of specific microorganisms and microbial communities. Chemical maps of fossil unicells and filaments reveal distinct wall-and sheath-like structures enriched in C, N and S, consistent with their accepted biological origin. Surprisingly, organic laminae, previously considered to be amorphous, also exhibit filamentous and apparently compressed spheroidal structures defined by strong enrichments in C, N and S. By analogy to data from the well-preserved microfossils, these structures are interpreted as being of biological origin, most likely representing densely packed remnants of microbial mats. Because the preponderance of organic matter in Precambrian sediments is similarly "amorphous," our findings open a large body of generally neglected material to in situ structural, chemical, and isotopic study. Our results also offer new criteria for assessing biogenicity of problematic kerogenous materials and thus can be applied to assessments of poorly preserved or fragmentary organic residues in early Archean sediments and any that might occur in meteorites or other extraterrestrial samples

NanoSIMS opens a New Window for Deciphering Organic Matter in Terrestrial and Extraterrestrial Samples

Recognition of the earliest morphological or chemical evidence of terrestrial life has proved to be challenging, as organic matter in ancient rocks is commonly fragmentary and difficult to distinguish from abiotically-produced materials (Schopf, 1993; Van Zuilen et al., 2002; Altermann & Kazmierczak, 2003; Cady et al., 2003; Brasier et al., 2002, 2004, 2005; Hofmann, 2004; Skrzypczak et al., 2004, 2005). Yet, the ability to identify remnants of earliest life is critical to our understanding of the timing of life's origin on earth, the nature of earliest terrestrial life, and recognition of potential remnants of microbial life that might occur in extraterrestrial materials. The search for earliest life on Earth now extends to early Archean organic remains; these tend to be very poorly preserved and considerably more difficult to interpret than the delicately permineralized microfossils known from many Proterozoic deposits. Thus, recent efforts have been directed toward finding biosignatures that can help distinguish fragmentary remnants of ancient microbes from either pseudofossils or abiotic organic materials that may have formed hydrothermally or in extraterrestrial processes (House et al., 2000; Boyce et al., 2001; Kudryavtsev et al., 2001; Schopf, 2002; Schopf et al., 2002, 2005a,b; Cady et al., 2003; Garc a-Ruiz et al., 2003; Hofmann, 2004; Brasier et al., 2005; Rushdi and Simoneit, 2005; Skrzypczak et al., 2005). An exciting area of biosignature research involves the developing technology of NanoSIMS. NanoSIMS is secondary ion mass spectrometry (SIMS) for ultrafine feature, elemental and isotopic analysis. Its resolution approaches 0.05 micrometers for element mapping, which is 10-50 times finer than that attainable with conventional SIMS or electron microprobes. Consequently, NanoSIMS has the potential to reveal previously unknown, chemical and structural characteristics of organic matter preserved in geologic materials. Robert et al. (2005) were the first to combine NanoSIMS element maps with optical microscopic imagery in an effort to develop a new method for assessing biogenicity. They showed that the ability to simultaneously map the distribution of organic elements [such as carbon (C), nitrogen (N), and sulfur (S)] and compare those element distributions with optically recognizable, cellularly preserved fossils could provide significant new insights into the origin of organic materials in ancient sediments. This chapter details a recent NanoSIMS study which was designed to acquire new data relevant to establishing critical biosignatures (Oehler et al., 2006a-c). In this study, NanoSIMS was used to characterize element distributions of spheroidal and filamentous microfossils and associated organic laminae in chert from the approx. 0.85 billion year old (Ga) Bitter Springs Formation of Australia. Previous work established preservation of a diverse microbiota in the Bitter Springs Formation (Schopf, 1968; Schopf and Blacic, 1971), and there is no dispute within the scientific community regarding the biogenicity of any of the Bitter Springs structures evaluated in this new study. Thus, the NanoSIMS results described below provide new insight into - and can be used as a guide for assessing - the origin of less well understood organic materials that may occur in early Archean samples and in meteorites or other extraterrestrial samples

Chemical mapping of proterozoic organic matter at submicron spatial resolution

A NanoSIMS ion microprobe was used to map the submicron-scale distributions of carbon, nitrogen, sulfur, silicon, and oxygen in organic microfossils and laminae in a thin section of the similar to 0.85 billion year old Bitter Springs Formation of Australia. The data provide clues about the original chemistry of the microfossils, the silicification process, and the biosignatures of specific microorganisms and microbial communities. Chemical maps of fossil unicells and filaments revealed distinct wall- and sheath-like structures enriched in C, N, and S, consistent with their accepted biological origin. Surprisingly, organic laminae, previously considered to be amorphous, also exhibited filamentous and apparently compressed spheroidal structures defined by strong enrichments in C, N, and S. By analogy to NanoSIMS data from the well-preserved microfossils, these structures were interpreted as being of biological origin, most likely representing densely packed remnants of microbial mats. Given that the preponderance of organic matter in Precambrian sediments is similarly "amorphous," our findings indicate that a re-evaluation of ancient specimens via in situ structural, chemical, and isotopic study is warranted. Our analyses have led us to propose new criteria for assessing the biogenicity of problematic kerogenous materials, and, thus, these criteria can be applied to assessments of poorly preserved or fragmentary organic residues in early Archean sediments and any that might occur in meteorites or other extraterrestrial samples

NanoSIMS Reveals New Structural and Elemental Signatures of Early Life

The young technology of NanoSIMS is unlocking new information from organic matter in ancient sediments. We have used this technique to characterize sub-micron scale element composition of Proterozoic organics that are clearly biogenic as a guide for interpreting problematic structures in terrestrial or extraterrestrial samples. We used the NanoSIMS 50 of the National Museum of Natural History in Paris to map carbon, nitrogen (as CN), and sulfur in organic structures from the approximately 0.8 Ga Bitter Springs Formation. We analyzed spheroidal and filamentous microfossils as well as organic laminae that appeared amorphous by optical and scanning electron microscopy. In clear-cut microfossils, a coincidence between optical images and NanoSIMS element maps suggests a biological origin for the mapped carbon, sulfur, and nitrogen; this conclusion is supported by high resolution NanoSIMS maps showing identical spatial distributions of C, CN and S. High resolution images also demonstrate distinctive nano structure of the filaments and spheroids. In the amorphous laminae, NanoSIMS reveals morphologies reminiscent of compressed microfossils. Distinct CN/C ratios of the spheroids, filaments, and laminae may reflect their biological precursors (cell walls, cyanobacterial sheaths, and microbial communities/biofilms, respectively). Similar amorphous laminae comprise a preponderance of the organic matter in many Precambrian deposits. Thus it is possible that NanoSIMS will provide fresh insight into a large body of previously uninterpretable material. Additionally, NanoSIMS analysis may establish new biosignatures that will be helpful for assessing the origin and biogenicity of controversial Archean structures and any organic materials that may occur in Martian or other extraterrestrial samples

Kaolinite dating from Acrisol and Ferralsol: A new key to understanding the landscape evolution in NW Amazonia (Brazil)

International audienceFerralsols and Acrisols are major types of soils of the Amazon basin observed on various landform units comprisingplateau surfaces, incised hills at their edges and slopes. The present study focuses on an Acrisol developedon plateaus surfaces from northwest Amazonia and a Ferralsol from the convex hills of the incised plateau edges.Local geomorphologic models of weathering covers suggest that Ferralsols are younger than plateau Acrisols butthe absolute chronology of their formation is still lacking. This type of information is however critical to understandthe evolution of northwest Amazon Basin landscapes and to identify its link with major climatic andgeomorphologic events. In this article, kaolinite-rich samples from soils and saprolites belonging to a transect inthe São Gabriel da Cachoeira region (Amazon state, Brasil) are investigated. Based on their crystal-chemicalcharacters, several types of kaolinites are identified. Using a previously developed methodology based onelectron paramagnetic resonance (EPR) spectroscopy, crystallization ages are proposed for these differentkaolinites. Saprolite kaolinites are dated from 6 to 3.6 Ma in the Acrisol profile and display significantly morerecent ages (< 1 Ma) in the Ferralsol saprolite. Kaolinite from solum (soils horizons above the C horizon) displayages ranging from 2.5 to 1 Ma for both the Acrisol and Ferralsol. Three distinct weathering stages are thusunraveled by kaolinite dating. The Acrisol saprolite displays the older weathering stage preserved in the investigatedsoil sequence. It is followed by a single weathering stage leading to the formation of both soils. Thesetwo stages can be correlated to the formation of two paleosurfaces recognized at the scale of the South Americasubcontinent as the Miocene Vehlas and the Quaternary Paraguaçu surfaces, indicating that the Curicuriariprofiles evolved during periods favorable to tropical weathering surfaces development in Amazonia. The lastweathering stage corresponds to the saprolite formation in the Ferralsol profile, which is still developing underthe present Amazonian climate. This still active, late weathering stag

NanoSIMS: Insights to biogenicity and syngeneity of Archaean carbonaceous structures

NanoSIMS is a relatively new technology that is being applied to ancient carbonaceous structures to gain insight into their biogenicity and syngeneity. NanoSIMS studies of well preserved organic microfossils from the Neoproterozoic (similar to 0.8Ga) Bitter Springs Formation have established elemental distributions in undisputedly biogenic structures. Results demonstrate that sub-micron scale maps of metabolically important elements (carbon [C], nitrogen [measured as CN ion], and sulfur [S]) can be correlated with kerogenous structures identified by optical microscopy. Spatial distributions of C, CN, and S in individual microfossils are nearly identical, and variations in concentrations of these elements parallel one another. In elemental maps, C, CN, and S appear as globules, aligned to form remnant walls or sheaths of fossiliferous structures. The aligned character and parallel variation of C and CN are the strongest indicators of biogenicity

NanoSIMS Sheds Light on the Origin and Significance of Early Archean Organic Microstructures from the Pilbara of Australia

NanoSIMS was used to characterize sub-micron scale morphology and elemental composition (C, N, S, Si, O) of organic microstructures in Early Archean (3 - 3.4 Ga) charts from the Pilbara of Western Australia. Three categories of structures were analyzed: small spheroids in clusters; spindle-shaped remains; and large spheroids. All are relatively poorly preserved and occur within the chert matrix of the samples. Carbonaceous material in a secondary hydrothermal vein also was analyzed, as an example of non-indigenous organic matter. Comparisons were made of NanoSIMS characteristics of the Archean samples and those from well-preserved, biogenic microfossils in the 0.8 Ga Bitter Springs Formation. The comparisons show that the Pilbara microstructures are generally distinct from material in the hydrothermal vein but similar in morphology and elemental composition to the Bitter Springs microfossils. In addition, the Pilbara structures exhibit a spatial relationship to silicon and oxygen that seemingly reflects silica nucleation on organic surfaces; this argues that the organic frameworks of the Archean structures were present in the sediment during crystallization of the silica matrix. The structures are thus interpreted as being indigenous to the enclosing sediment. While these results are suggestive of Early Archean biogenicity and are consistent with a growing body of data suggesting that life on Earth was well established by 3 to 3.4 Ga, work is continuing to determine the N/C and 13C ratios of individual forms, and this should provide additional insight into the derivation and significance of these ancient organic remains