This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
Abstract Biomolecules, methylamine and alanine, found associated with natural jarosite samples pe... more Abstract Biomolecules, methylamine and alanine, found associated with natural jarosite samples peaked the interest of astrobiologists and planetary geologists. How the biomolecules are associated with jarosite remains unclear although the mechanism could ...
With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these mineral... more With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of bio/organic signatures. This study further investigates the ability of thenardite (Na2SO4) to effectively facilitate the ionization and identification of aromatic amino acids (phenylalanine, tyrosine and tryptophan) using a technique called geomatrix-assisted laser desorption/ionization in conjunction with a Fourier transform ion cyclotron resonance mass spectrometry. This technique is based on the ability of a mineral host to facilitate desorption and ionization of bio/organic molecules for detection. Spectra obtained from each aromatic amino acid alone and in combination with thenardite show differences in ionization mechanism and fragmentation patterns. These differences are due to chemical and structural differences between the aromatic side chains of their respective amino acid. Tyrosine and tryptophan when combined with ...
With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent stu... more With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of biosignatures. On Earth, biotic and biotic processes can assist in the formation and deposition of these minerals. A primary objective of these studies is the detection of bio/organic compounds that may be associated with the mineral. These biosignatures would imply biological involvement during mineral formation. The following research presents a series of natural and synthetic investigations to determine if biological activity is associated with Na-sulfate mineralization, and if these minerals can assist in detecting bio/organic compounds. Evidence for biological activity associated with the formation of Na-sulfate deposits in the basaltic subsurface of Craters of the Moon National Monument, Idaho was examined by laser desorption Fourier transform mass spectrometry (LD-FTMS), infrared spectroscopy and...
A proposed project in the Northern Territory, Australia currently has a partially developed open ... more A proposed project in the Northern Territory, Australia currently has a partially developed open pit that has lled with water and must be partially dewatered before the future operations can begin. e water quality of the pit lake is poor and predictive modeling of the future ultimate pit shell suggest that during operations and in post closure, the pit walls will be a source of acid rock drainage and metal leaching (ARD/ ML), resulting in the need to treat water collected within the pit. To allow discharge of the water being removed from the existing pit lake, in pit treatment using micronized lime was considered with the goal of raising the lake water pH to greater than 7.0 and precipitating key metals from solution. In-pit micronized lime addition began at this site in 2012, to allow dewatering of the pit and to move the project toward operations. e in-pit micronized lime treatment has been successful in producing circum-neutral water with decreased metals concentrations, which ha...
Robust, unequivocal evidence of biosignatures in extraterrestrial and ancient terrestrial materia... more Robust, unequivocal evidence of biosignatures in extraterrestrial and ancient terrestrial materials would have a profound impact on current understanding of the origins of life. In the search for signs of life, it is imperative to target minerals that are most likely to preserve and yield evidence of biological or organic compounds in order to design criteria for remotely operated instrumentation and optimize return sample missions. Laser desorption Fourier transform mass spectrometry (LD-FTMS) has been used to detect various biological and organic compounds associated with different minerals. For natural samples, LD-FTMS requires no sample preparation and offers high sensitivity to acquire spectra with a single laser shot for heterogeneously distributed biosignatures. Some organics compounds (i.e., polyaromatic hydrocarbons) self-ionize and are easily detected, but most biological and organic compounds require ionization assistance. Therefore, we are exploring how well different mi...
Pit lake modeling can be complex due to the need to consider the water/rock interactions with the... more Pit lake modeling can be complex due to the need to consider the water/rock interactions with the lithology exposed on the final pit walls and with any backfill material. Taking a systematic and iterative approach to pit lake modeling will ensure the proper level of detail and more accurate predictive results are generated. Developing a pit lake model in a stepwise method (conceptual model to “general” system representation to a detailed spatially representative statistically based model) allows for the model to be aligned with the level of detail of the data and the complexity of the scenario.
Terrestrial thermal environments can serve as analogs for subsurface environments in the search f... more Terrestrial thermal environments can serve as analogs for subsurface environments in the search for life because they regularly host microbial communities, which may leave behind biosignatures. This study focused on an acid-sulfate hydrothermal site as an analog for a potentially habitable environment on Mars. A weathered boulder in the thermal area was dissected, revealing an interior marked with disconnected horizons of differently colored materials, very low pH, and increasing temperature. The mineralogy comprised weathering products from andesite (kaolinite, quartz, clinoptilolite) along with sulfate salts (alunite, jarosite, tschermigite, and copiapite) formed by oxidation of sulfide and ferrous iron. Characterization of organic matter in this boulder and several soil samples yielded interesting but surprising results. Both mass spectrometry and Raman spectroscopy identified organic compounds in portions of the soils and the boulder. Jarosite-associated samples showed more nume...
Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ma... more Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform mass spectrometer (FTMS) has been employed to determine how well bio/organic molecules associated with the mineral thenardite (Na2SO4) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C2H4NO2 at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition of C18H39O7Na . A natural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination was estimated to be 3 parts...
Building an accurate and defensible model describing the geochemical character of water that coll... more Building an accurate and defensible model describing the geochemical character of water that collects in a pit lake after the cessation of surface mining activities involves integrating geochemical, hydrologic, and climatologic data with the lithologic units of the area surrounding the ultimate pit surface (UPS). Such a total system approach often involves developing a coarse regional groundwater model framework which is then refined into a finer-scaled localised groundwater model in the area of the pit. The groundwater model results are integrated with a detailed geologic and geochemical model of the UPS, the chemistry of the groundwater, and other factors such as climatic conditions and surface run-off. The total system approach considers temporal as well as spatial variability. GIS methods coupled to finite element (Feflow), or finite difference (Modflow) groundwater flow models allows to apportion the interaction of groundwater model nodes with geologic nodes on and adjacent to ...
Recently, the prebiotic amino acid glycine has been found associated with natural jarosite sample... more Recently, the prebiotic amino acid glycine has been found associated with natural jarosite samples from locations around the world. Since the discovery of jarosite on Mars, extensive research focuses on linking this mineral group with possible detection of biosignatures in the geologic record on Earth and Mars. Multiple analytical methods, including extraction and mass spectrometry techniques, have identified glycine and other biomolecules in jarosite samples. The jarosite end members jarosite (sensu stricto-potassium jarosite), natrojarosite (sodium jarosite), and ammoniojarosite (ammonium jarosite) have different thermodynamic stabilities, decompose at different rates, and have potentially different susceptibilities to substitution. The relationship between the thermodynamic stability of the jarosite end members and the effect that glycine has on the thermal decomposition behavior of each end member was investigated using thermal gravimetric analysis. Introducing glycine into the synthesis procedure (75 ppm) of the potassium, sodium, and ammonium jarosite end member has elucidated the effects that glycine has on the thermal stability of the mineral group. Potassium jarosite appears to be the least susceptible to the effects of glycine, with the sodium and ammonium end members showing marked changes in thermal decomposition behavior and decomposition rates. These results suggest that the sodium and ammonium jarosites are more suitable targets for identifying signs of prebiotic or biotic activity on Mars and Earth than the potassium jarosites. These results have implications for current in situ investigations of the martian surface and future sample return missions.
Secondary deposits associated with the basaltic caves of Craters of the Moon National Monument (C... more Secondary deposits associated with the basaltic caves of Craters of the Moon National Monument (COM) in southern Idaho were examined using X-ray powder diffraction, X-ray fluorescence spectrometry, Fourier transform infrared spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The secondary mineral assemblages are dominated by Na-sulfate minerals (thenardite, mirabilite) with a small fraction of the deposits containing minor
Evidence of microbial activity associated with mineralization of secondary Na-sulphate minerals (... more Evidence 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-...
The ability to detect carbon signatures that can be linked to complex, possibly biogenic, organic... more The ability to detect carbon signatures that can be linked to complex, possibly biogenic, organic molecules is imperative in research into the origin and distribution of life in our solar system particularly when used in conjunction with inorganic, mineralogical, and isotopic signatures that ...
... Jill R. Scott, 1* J. Michelle Kotler, 2 Nancy W. Hinman, 2 Beizhan Yan, 3 Daphne L. Stoner, 3... more ... Jill R. Scott, 1* J. Michelle Kotler, 2 Nancy W. Hinman, 2 Beizhan Yan, 3 Daphne L. Stoner, 3 and C. Doc Richardson 2 1 Idaho National Laboratory, Idaho Falls, ID 83415 2 University of Montana, Missoula, MT, 59812 3 University of IdahoIdaho Falls, ID 83404 ...
With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent stu... more With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of biosignatures. On Earth, biotic and biotic processes can assist in the formation and ...
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
Abstract Biomolecules, methylamine and alanine, found associated with natural jarosite samples pe... more Abstract Biomolecules, methylamine and alanine, found associated with natural jarosite samples peaked the interest of astrobiologists and planetary geologists. How the biomolecules are associated with jarosite remains unclear although the mechanism could ...
With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these mineral... more With the discovery of Na-sulphate minerals on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of bio/organic signatures. This study further investigates the ability of thenardite (Na2SO4) to effectively facilitate the ionization and identification of aromatic amino acids (phenylalanine, tyrosine and tryptophan) using a technique called geomatrix-assisted laser desorption/ionization in conjunction with a Fourier transform ion cyclotron resonance mass spectrometry. This technique is based on the ability of a mineral host to facilitate desorption and ionization of bio/organic molecules for detection. Spectra obtained from each aromatic amino acid alone and in combination with thenardite show differences in ionization mechanism and fragmentation patterns. These differences are due to chemical and structural differences between the aromatic side chains of their respective amino acid. Tyrosine and tryptophan when combined with ...
With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent stu... more With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of biosignatures. On Earth, biotic and biotic processes can assist in the formation and deposition of these minerals. A primary objective of these studies is the detection of bio/organic compounds that may be associated with the mineral. These biosignatures would imply biological involvement during mineral formation. The following research presents a series of natural and synthetic investigations to determine if biological activity is associated with Na-sulfate mineralization, and if these minerals can assist in detecting bio/organic compounds. Evidence for biological activity associated with the formation of Na-sulfate deposits in the basaltic subsurface of Craters of the Moon National Monument, Idaho was examined by laser desorption Fourier transform mass spectrometry (LD-FTMS), infrared spectroscopy and...
A proposed project in the Northern Territory, Australia currently has a partially developed open ... more A proposed project in the Northern Territory, Australia currently has a partially developed open pit that has lled with water and must be partially dewatered before the future operations can begin. e water quality of the pit lake is poor and predictive modeling of the future ultimate pit shell suggest that during operations and in post closure, the pit walls will be a source of acid rock drainage and metal leaching (ARD/ ML), resulting in the need to treat water collected within the pit. To allow discharge of the water being removed from the existing pit lake, in pit treatment using micronized lime was considered with the goal of raising the lake water pH to greater than 7.0 and precipitating key metals from solution. In-pit micronized lime addition began at this site in 2012, to allow dewatering of the pit and to move the project toward operations. e in-pit micronized lime treatment has been successful in producing circum-neutral water with decreased metals concentrations, which ha...
Robust, unequivocal evidence of biosignatures in extraterrestrial and ancient terrestrial materia... more Robust, unequivocal evidence of biosignatures in extraterrestrial and ancient terrestrial materials would have a profound impact on current understanding of the origins of life. In the search for signs of life, it is imperative to target minerals that are most likely to preserve and yield evidence of biological or organic compounds in order to design criteria for remotely operated instrumentation and optimize return sample missions. Laser desorption Fourier transform mass spectrometry (LD-FTMS) has been used to detect various biological and organic compounds associated with different minerals. For natural samples, LD-FTMS requires no sample preparation and offers high sensitivity to acquire spectra with a single laser shot for heterogeneously distributed biosignatures. Some organics compounds (i.e., polyaromatic hydrocarbons) self-ionize and are easily detected, but most biological and organic compounds require ionization assistance. Therefore, we are exploring how well different mi...
Pit lake modeling can be complex due to the need to consider the water/rock interactions with the... more Pit lake modeling can be complex due to the need to consider the water/rock interactions with the lithology exposed on the final pit walls and with any backfill material. Taking a systematic and iterative approach to pit lake modeling will ensure the proper level of detail and more accurate predictive results are generated. Developing a pit lake model in a stepwise method (conceptual model to “general” system representation to a detailed spatially representative statistically based model) allows for the model to be aligned with the level of detail of the data and the complexity of the scenario.
Terrestrial thermal environments can serve as analogs for subsurface environments in the search f... more Terrestrial thermal environments can serve as analogs for subsurface environments in the search for life because they regularly host microbial communities, which may leave behind biosignatures. This study focused on an acid-sulfate hydrothermal site as an analog for a potentially habitable environment on Mars. A weathered boulder in the thermal area was dissected, revealing an interior marked with disconnected horizons of differently colored materials, very low pH, and increasing temperature. The mineralogy comprised weathering products from andesite (kaolinite, quartz, clinoptilolite) along with sulfate salts (alunite, jarosite, tschermigite, and copiapite) formed by oxidation of sulfide and ferrous iron. Characterization of organic matter in this boulder and several soil samples yielded interesting but surprising results. Both mass spectrometry and Raman spectroscopy identified organic compounds in portions of the soils and the boulder. Jarosite-associated samples showed more nume...
Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform ma... more Geomatrix-assisted laser desorption/ionization (GALDI) in conjunction with a Fourier transform mass spectrometer (FTMS) has been employed to determine how well bio/organic molecules associated with the mineral thenardite (Na2SO4) can be detected. GALDI is based on the ability of the mineral host to assist desorption and ionization of bio/organic molecules without additional sample preparation. When glycine was mixed with thenardite, glycine was deprotonated to produce C2H4NO2 at m/z 74.025. The combination of stearic acid with thenardite produced a complex cluster ion at m/z 390.258 in the negative mode, which was assigned a composition of C18H39O7Na . A natural sample of thenardite from Searles Lake in California also produced a peak at m/z 390.260. The bio/organic signatures in both the laboratory-based and natural samples were heterogeneously dispersed as revealed by chemical imaging. The detection limits for the stearic acid and thenardite combination was estimated to be 3 parts...
Building an accurate and defensible model describing the geochemical character of water that coll... more Building an accurate and defensible model describing the geochemical character of water that collects in a pit lake after the cessation of surface mining activities involves integrating geochemical, hydrologic, and climatologic data with the lithologic units of the area surrounding the ultimate pit surface (UPS). Such a total system approach often involves developing a coarse regional groundwater model framework which is then refined into a finer-scaled localised groundwater model in the area of the pit. The groundwater model results are integrated with a detailed geologic and geochemical model of the UPS, the chemistry of the groundwater, and other factors such as climatic conditions and surface run-off. The total system approach considers temporal as well as spatial variability. GIS methods coupled to finite element (Feflow), or finite difference (Modflow) groundwater flow models allows to apportion the interaction of groundwater model nodes with geologic nodes on and adjacent to ...
Recently, the prebiotic amino acid glycine has been found associated with natural jarosite sample... more Recently, the prebiotic amino acid glycine has been found associated with natural jarosite samples from locations around the world. Since the discovery of jarosite on Mars, extensive research focuses on linking this mineral group with possible detection of biosignatures in the geologic record on Earth and Mars. Multiple analytical methods, including extraction and mass spectrometry techniques, have identified glycine and other biomolecules in jarosite samples. The jarosite end members jarosite (sensu stricto-potassium jarosite), natrojarosite (sodium jarosite), and ammoniojarosite (ammonium jarosite) have different thermodynamic stabilities, decompose at different rates, and have potentially different susceptibilities to substitution. The relationship between the thermodynamic stability of the jarosite end members and the effect that glycine has on the thermal decomposition behavior of each end member was investigated using thermal gravimetric analysis. Introducing glycine into the synthesis procedure (75 ppm) of the potassium, sodium, and ammonium jarosite end member has elucidated the effects that glycine has on the thermal stability of the mineral group. Potassium jarosite appears to be the least susceptible to the effects of glycine, with the sodium and ammonium end members showing marked changes in thermal decomposition behavior and decomposition rates. These results suggest that the sodium and ammonium jarosites are more suitable targets for identifying signs of prebiotic or biotic activity on Mars and Earth than the potassium jarosites. These results have implications for current in situ investigations of the martian surface and future sample return missions.
Secondary deposits associated with the basaltic caves of Craters of the Moon National Monument (C... more Secondary deposits associated with the basaltic caves of Craters of the Moon National Monument (COM) in southern Idaho were examined using X-ray powder diffraction, X-ray fluorescence spectrometry, Fourier transform infrared spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The secondary mineral assemblages are dominated by Na-sulfate minerals (thenardite, mirabilite) with a small fraction of the deposits containing minor
Evidence of microbial activity associated with mineralization of secondary Na-sulphate minerals (... more Evidence 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-...
The ability to detect carbon signatures that can be linked to complex, possibly biogenic, organic... more The ability to detect carbon signatures that can be linked to complex, possibly biogenic, organic molecules is imperative in research into the origin and distribution of life in our solar system particularly when used in conjunction with inorganic, mineralogical, and isotopic signatures that ...
... Jill R. Scott, 1* J. Michelle Kotler, 2 Nancy W. Hinman, 2 Beizhan Yan, 3 Daphne L. Stoner, 3... more ... Jill R. Scott, 1* J. Michelle Kotler, 2 Nancy W. Hinman, 2 Beizhan Yan, 3 Daphne L. Stoner, 3 and C. Doc Richardson 2 1 Idaho National Laboratory, Idaho Falls, ID 83415 2 University of Montana, Missoula, MT, 59812 3 University of IdahoIdaho Falls, ID 83404 ...
With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent stu... more With the discovery of Na-sulfate minerals (thenardite, mirabilite) on Mars and Europa, recent studies using these minerals have focused on their ability to assist in the detection of biosignatures. On Earth, biotic and biotic processes can assist in the formation and ...
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