Thermal Stability of (Bio)Carbonates: A Potential Signature for Detecting Life on Mars?

The environmental conditions that prevail on the surface of Mars (i.e., high levels of radiation and oxidants) are not favorable for the long-term preservation of organic compounds on which all strategies for finding life on Mars have been based to date. Since life commonly produces minerals that are considered more resilient, the search for biominerals could constitute a promising alternative approach. Carbonates are major biominerals on Earth, and although they have not been detected in large amounts at the martian surface, recent observations show that they could constitute a significant part of the inorganic component in the martian soil. Previous studies have shown that calcite and aragonite produced by eukaryotes thermally decompose at temperatures 15°C lower than those of their abiotic counterparts. By using carbonate concretions formed by microorganisms, we find that natural and experimental carbonates produced by prokaryotes decompose at 28°C below their abiotic counterparts. The study of this sample set serves as a proof of concept for the differential thermal analysis approach to distinguish abiotic from bio-related carbonates. This difference in carbonate decomposition temperature can be used as a first physical evidence of life on Mars to be searched by in situ space exploration missions with the resolution and the technical constraints of the available onboard instruments.

Probing atomic scale transformation of fossil dental enamel using Fourier transform infrared and nuclear magnetic resonance spectroscopy: a case study from the Tugen Hills (Rift Gregory, Kenya).

A series of fossil tooth enamel samples was investigated by Fourier transform infrared (FTIR) spectroscopy, (13)C and (19)F magic-angle spinning nuclear magnetic resonance (MAS NMR) and scanning electron microscopy (SEM). Tooth remains were collected in Mio-Pliocene deposits of the Tugen Hills in Kenya. Significant transformations were observed in fossil enamel as a function of increasing fluorine content (up to 2.8wt.%). FTIR spectroscopy revealed a shift of the ν1 PO4 stretching band to higher frequency. The ν2 CO3 vibrational band showed a decrease in the intensity of the primary B-type carbonate signal, which was replaced by a specific band at 864cm(-1). This last band was ascribed to a specific carbonate environment in which the carbonate group is closely associated to a fluoride ion. The occurrence of this carbonate defect was consistently attested by the observation of two different fluoride signals in the (19)F NMR spectra. One main signal, at ∼-100ppm, is related to structural F ions in the apatite channel and the other, at -88ppm, corresponds to the composite defect. These spectroscopic observations can be understood as resulting from the mixture of two phases: biogenic hydroxylapatite (bioapatite) and secondary fluorapatite. SEM observations of the most altered sample confirmed the extensive replacement of the bioapatite by fluorapatite, resulting from the dissolution of the primary bioapatite followed by the precipitation of carbonate-fluorapatite. The ν2 CO3 IR bands can be efficiently used to monitor the extent of this type of bioapatite transformation during fossilization.

Validation of multimedia models assessing exposure to PAHs--the SOLEX study.

Polluted soils have become a public health problem. While population exposure to soil pollutants is generally quantified using multimedia models, their estimations have not been validated, and studies that attempted to do so are scarce. The objective of the SOLEX study was to compare the predictions of pyrene exposure levels (converted into 1 hydroxypyrene) computed by several models with the results of urinary 1-hydropyrene (1-HOP) assays among 110 employees working at three sites polluted during their past use as manufactured gas plants. Four models were used: AERIS (Canada), CalTOX (California, USA), CLEA (UK), and HESP (The Netherlands). Three occupational exposure scenarios--with office, mixed, and outdoor workers--were constructed, based upon job activities during two measurement campaigns, one in winter and one in summer. The exposure levels estimated by the four models could differ markedly (from 7 up to 80 times) according to the exposure scenario. Also, the predominant exposure routes differed according to the model (direct soil ingestion for HESP and CalTOX, inhalation for AERIS, and dermal absorption for CLEA). The predictions of CalTOX are consistent with the 1-HOP measurements for all the scenarios. For HESP, the consistency is observed for the scenarios, office and mixed, for which the pyrene level in the soil is low. AERIS and CLEA yield results that are systematically above the 1-HOP measurements. This study confirms that validation of the models is crucial and points out to the need to proceed to assess components of the models that are the most influential using appropriate statistical analysis in combination with true field data.