C. T. Adcock

Synthesis and characterization of the Mars-relevant phosphate minerals Fe- and Mg-whitlockite and merrillite and a possible mechanism that maintains charge balance during whitlockite to merrillite transformation

Abstract Merrillite [Ca9NaMg(PO4)7] occurs as a dominant primary Ca-phosphate mineral in martian meteorites and therefore presumably also on Mars. The mineral is an important phase in exploring differences in geologic processes between Earth and Mars, and also has astrobiological implications due to its potential role as a significant source of the bio-essential nutrient phosphate. Merrillite does not occur terrestrially as a discrete mineral phase, making it difficult to obtain for Mars-relevant studies. It can, however, be synthesized from a similar terrestrial mineral, whitlockite (natural or synthetic), through dehydrogenation. Here we present methods for synthesizing relatively large quantities (0.5 g or greater per batch) of coarse crystalline (75 μm+) Mg-whitlockite, Fe-whitlockite, mixed Fe/Mg-whitlockites, and from these synthesized minerals produce Mg-merrillite, ferrous and ferric Fe-merrillite, and ferrous and ferric mixed Fe/Mg-merrillite. Chemistry and atomic structures of synthesized Fe- and mixed Fe/ Mg-whitlockite and ferrous and ferric Fe- and mixed Fe/Mg- merrillite resulting from single-crystal X-ray diffraction, infrared spectroscopy, and electron microprobe analyses are presented. We also present a mechanism for maintaining charge balance during the formation of merrillite from whitlockite. Our results shed light on these mineral structures for future martian studies, and provide methods for creating coarse crystalline merrillite for use in Mars-relevant thermodynamic, kinetic, soil/dust simulant, crystallographic, astrobiological, and other studies.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.In the Gale Crater on Mars, organic matter has been detected, but in much lower concentrations than expected. Here, the authors conduct clay mineral synthesis experiments which suggest that clay minerals may rapidly form under oxidized conditions and thus explain the low organic concentrations in Gale Crater.

Modeling background radiation using geochemical data: A case study in and around Cameron, Arizona

This study compares high resolution forward models of natural gamma-ray background with that measured by high resolution aerial gamma-ray surveys. The ability to predict variations in natural background radiation levels should prove useful for those engaged in measuring anthropogenic contributions to background radiation for the purpose of emergency response and homeland security operations. The forward models are based on geologic maps and remote sensing multi-spectral imagery combined with two different sources of data: 1) bedrock geochemical data (uranium, potassium and thorium concentrations) collected from national databases, the scientific literature and private companies, and 2) the low spatial resolution NURE (National Uranium Resource Evaluation) aerial gamma-ray survey. The study area near Cameron, Arizona, is located in an arid region with minimal vegetation and, due to the presence of abandoned uranium mines, was the subject of a previous high resolution gamma-ray survey. We found that, in general, geologic map units form a good basis for predicting the geographic distribution of the gamma-ray background. Predictions of background gamma-radiation levels based on bedrock geochemical analyses were not as successful as those based on the NURE aerial survey data sorted by geologic unit. The less successful result of the bedrock geochemical model is most likely due to a number of factors including the need to take into account the evolution of soil geochemistry during chemical weathering and the influence of aeolian addition. Refinements to the forward models were made using ASTER visualizations to create subunits of similar exposure rate within the Chinle Formation, which contains multiple lithologies and by grouping alluvial units by drainage basin rather than age.

Discreditation of Bobdownsite and the Establishment of Criteria for the Identification of Minerals with Essential Monofluorophosphate (PO3F2-) [STUB]

Abstract Bobdownsite, IMA number 2008-037, was approved as a new mineral by the Commission on New Minerals, Nomenclature and Classification (CNMNC) as the fluorine end-member of the mineral whitlockite. The type locality of bobdownsite is in Big Fish River, Yukon, Canada, and bobdownsite was reported to be the first mineral with essential monofluorophosphate (PO3F2–). The type specimen of bobdownsite has been reinvestigated by electron probe microanalysis (EPMA), and our data indicate that fluorine abundances are below detection in the mineral. In addition, we conducted detailed analysis of bobdownsite from the type locality by gas chromatography isotope ratio mass spectrometry, Raman spectroscopy, EPMA, and NMR spectroscopy. These data were compared with previously published data on synthetic monofluorophosphate salts. Collectively, these data indicate that bobdownsite is indistinguishable from whitlockite with a composition along the whitlockite-merrillite solid solution. Bobdownsite is therefore discredited as a valid mineral species. An additional mineral, krásnoite, has been purported to have monofluorophosphate components in its structure, but reexamination of those data indicate that F– in krásnoite forms bonds with Al, similar to OH– bonded to Al in perhamite. Consequently, krásnoite also lacks monofluorophosphate groups, and there are currently no valid mineral species with monofluorophosphate in their structure. We recommend that any future reports of new minerals that contain essential monofluorophosphate anions be vetted by abundance measurements of fluorine, vibrational spectroscopy (both Raman and FTIR), and where paramagnetic components are permissibly low, NMR spectroscopy. Furthermore, we emphasize the importance of using synthetic compounds containing monofluorophosphate anions as a point of comparison in the identification of minerals with essential monofluorophosphate. Structural data that yield satisfactory P-F bond lengths determined by X-ray crystallography, coupled with direct chemical analyses of fluorine in a material do not constitute sufficient evidence alone to identify a new mineral with essential monofluorophosphate.