Evidence for biological activity in mineralization of secondary sulphate deposits in a basaltic environment: implications for the search for life in the Martian subsurface

2013 ◽  
Vol 12 (4) ◽  
pp. 357-368 ◽  
Author(s):  
C. Doc Richardson ◽  
Nancy W. Hinman ◽  
Jill R. Scott

AbstractEvidence of microbial activity associated with mineralization of secondary Na-sulphate minerals (thenardite, mirabilite) in the basaltic subsurface of Craters of the Moon National Monument (COM), Idaho were examined by scanning electron microscopy, X-ray diffraction, laser desorption Fourier transform ion cyclotron resonance mass spectrometry (LD-FTICR-MS), Fourier transform infrared spectroscopy (FTIR) and isotope ratio mass spectrometry. Peaks suggestive of bio/organic compounds were observed in the secondary Na-sulphate deposits by LD-FTICR-MS. FTIR provided additional evidence for the presence of bio/organic compounds. Sulphur fractionation was explored to assist in determining if microbes may play a role in oxidizing sulphur. The presence of bio/organic compounds associated with Na-sulphate deposits, along with the necessity of oxidizing reduced sulphur to sulphate, suggests that biological activity may be involved in the formation of these secondary minerals. The secondary Na-sulphate minerals probably form from the overlying basalt through leached sodium ions and sulphate ions produced by bio-oxidation of Fe-sulphide minerals. Since the COM basalts are one of the most comparable terrestrial analogues for their Martian counterparts, the occurrence of biological activity in the formation of sulphate minerals at COM has direct implications for the search for life on Mars. In addition, the presence of caves on Mars suggests the importance of these environments as possible locations for growth and preservation of microbial activity. Therefore, understanding the physiochemical pathways of abiotic and biotic mineralization in the COM subsurface and similar basaltic settings has direct implications for the search for extinct or extant life on Mars.

Holzforschung ◽  
2019 ◽  
Vol 73 (11) ◽  
pp. 975-985 ◽  
Author(s):  
Maomao Zhang ◽  
Guangjie Zhao ◽  
Juan Guo ◽  
Alex C. Wiedenhoeft ◽  
Charles C. Liu ◽  
...  

Abstract Timber genus identification based on the anatomical features of wood is well established in botany. However, species-level wood identification is not always possible based on traditional wood morphology techniques alone. To compensate for the deficiencies of traditional methods, direct analysis in real time coupled to Fourier transform ion cyclotron resonance mass spectrometry (DART-FTICR-MS) was used to obtain the mass spectral fingerprints of different timber species. Using heartwood samples of two morphologically similar species, Pterocarpus santalinus and Pterocarpus tinctorius, subjected to different treatments, i.e. solvent extractions and powdered samples as well as air-dried samples and samples dried at low and high temperatures, we observed distinct chemical signatures for the wood samples from the two species, enabling rapid species-level identification when multivariate statistical analysis was adopted. The supervised orthogonal partial least squares discriminant analysis (OPLS-DA) models for samples subjected to different treatments all exhibited accurate differentiation performance of the explained fraction of variance of classes (R2Y = 0.936–0.987) and the cross-validated fraction of variance of classes (Q2 = 0.857–0.949). Compared with solvent types and the physical form of the sample, the drying treatment method had a greater impact on the chemical fingerprint from DART-FTICR-MS. Air-dried wood chips were the optimal samples for the DART-FTICR-MS method coupled with statistical analysis.


FACETS ◽  
2017 ◽  
Vol 2 (1) ◽  
pp. 461-475 ◽  
Author(s):  
Yulin Qi ◽  
Ruoji Luo ◽  
Wolfgang Schrader ◽  
Dietrich A. Volmer

Lignin is the second most abundant natural biopolymer and potentially a valuable alternative energy source for conventional fossil fuels. In this study, Fourier-transform ion cyclotron resonance-mass spectrometry (FTICR-MS) in conjunction with phase correction was applied to study photooxidation products of lignin using a 7 Tesla (T) mass spectrometer. The application of 7 T FTICR-MS has often been inadequate for the analysis of complex natural organic matter because of insufficient resolving power as compared with high-field FTICR, which led to incorrect assignments of elemental formulae and discontinuous plots in graphical and statistical analyses. Here, the application of phase correction to the FTICR mass spectra of lignin oxidation products greatly improved the spectral quality, and thus, readily permitted characterization of photooxidation processes of lignin compounds under simulated solar radiation conditions.


2019 ◽  
Vol 19 (22) ◽  
pp. 13945-13956 ◽  
Author(s):  
Min Cui ◽  
Cheng Li ◽  
Yingjun Chen ◽  
Fan Zhang ◽  
Jun Li ◽  
...  

Abstract. The molecular compositions of polar organic compounds (POCs) in particles emitted from various vessels and excavators were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and possible molecular structures of POCs were proposed. POCs were extracted with purified water and sorted by elemental composition into three groups: CHO, CHON, and S-containing compounds (CHONS and CHOS). The results show the following. (i) CHO (accounting for 49 % of total POCs in terms of peak response) was the most abundant group for all tested off-road engines, followed by CHON (33 %) and CHOS (35 %) for diesel and HFO (heavy-fuel-oil)-fueled off-road engines. (ii) The abundance and structure of the CHON group in water extracts were different in terms of engine type and load. The relative peak response of CHON was the highest for excavator emissions in working mode, compared to the idling and moving modes. Furthermore, dinitrophenol and methyl dinitrophenol were potentially the most abundant emission species for high-rated speed excavators, while nitronaphthol and methyl nitronaphthol were more important for low-rated speed vessels. (iii) The composition and structure of the S-containing compounds were directly influenced by fuel oil characteristics (sulfur content and aromatic ring), with more condensed aromatic rings in the S-containing compounds proposed in HFO-fueled vessel emissions. More abundant aliphatic chains were inferred in diesel equipment emissions. Overall, higher fractions of condensed hydrocarbons and aromatic rings in POCs emitted from vessels using HFO cause strong optical absorption capacity. Different structures in POCs could provide a direction for qualitative and quantitative analysis of organic compounds as tracers to distinguish these emissions from diesel or HFO-fueled off-road engines.


2020 ◽  
Vol 92 (9) ◽  
pp. 1447-1467
Author(s):  
Alexander Zherebker ◽  
Sunghwan Kim ◽  
Philippe Schmitt-Kopplin ◽  
Robert G. M. Spencer ◽  
Oliver Lechtenfeld ◽  
...  

AbstractInterlaboratory comparison on the determination of the molecular composition of humic substances (HS) was undertaken in the framework of IUPAC project 2016-015-2-600. The analysis was conducted using high resolution mass spectrometry, nominally, Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with electrospray ionization. Six samples of HS from freshwater, soil, and leonardite were used for this study, including one sample of humic acids (HA) from coal (leonardite), two samples of soil HA (the sod-podzolic soil and chernozem), two samples of soil fulvic acids (FA) (the sod-podzolic soil and chernozem), and one sample of freshwater humic acids (the Suwannee River). The samples were analyzed on five different FTICR MS instruments using the routine conditions applied in each participating laboratory. The results were collected as mass lists, which were further assigned formulae for the determination of molecular composition. The similarity of the obtained data was evaluated using appropriate statistical metrics. The results have shown that direct comparison of discrete stoichiometries assigned to the mass lists obtained by the different laboratories yielded poor results with low values of the Jaccard similarity score – not exceeding 0.56 (not more than 56 % of the similar peaks). The least similarity was observed for the aromatics-rich HA samples from leonardite (coal) and the chernozem soil, which might be connected to difficulties in their ionization. The reliable similarity among the data obtained in this intercomparison study was achieved only by transforming a singular point (stoichiometry) in van Krevelen diagram into a sizeable pixel (a number of closely located stoichiometries), which can be calculated from the population density distribution. The conclusion was made that, so far, these are descriptors of occupation density distribution, which provide the metrics compliant with the data quality requirements, such as the reproducibility of the data measurements on different instruments.


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