Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001

Implications for oxidants and organics

Samuel P. Kounaves, Brandi L. Carrier, Glen O'Neil, Shannon T. Stroble, Mark W. Claire

Research output: Contribution to journalArticleResearchpeer-review

71 Citations (Scopus)

Abstract

The results from the Viking mission in the mid 1970s provided evidence that the martian surface contained oxidants responsible for destroying organic compounds. In 2008 the Phoenix Wet Chemistry Lab (WCL) found perchlorate (ClO4-) in three soil samples at concentrations from 0.5 to 0.7wt%. The detection of chloromethane (CH3Cl) and dichloromethane (CH2Cl2) by the Viking pyrolysis gas chromatograph-mass spectrometer (GC-MS) may have been a result of ClO4- at that site oxidizing either terrestrial organic contaminates or, if present, indigenous organics. Recently, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) Curiosity directly measured the presence of CH3Cl, CH2Cl2 and, along with measurements of HCl and oxygen, indirectly indicate the presence of ClO4 However, except for Phoenix, no other direct measurement of the ClO4- anion in martian soil or rock has been made. We report here ion chromatographic (IC) and isotopic analyses of a unique sawdust portion of the martian meteorite EETA79001 that show the presence by mass of 0.6±0.1ppm ClO4-, 1.4±0.1ppm ClO3-, and 16±0.2ppm NO3- at a quantity and location within the meteorite that is difficult to reconcile with terrestrial contamination. The sawdust sample consists of basaltic material with a minor salt-rich inclusion in a mass ratio of ~300:1, thus the salts may be 300 times more concentrated within the inclusion than the whole sample. The molar ratios of NO3-:ClO4- and Cl-:ClO4-, are very different for EETA79001 at ~40:1 and 15:1, respectively, than the Antarctic soils and ice near where the meteorite was recovered at ~10,000:1 and 5000:1, respectively. In addition, the isotope ratios for EETA79001 with δ15N=-10.48±0.32‰ and δ18O=+51.61±0.74‰ are significantly different from that of the nearby Miller Range blue ice with δ15N=+102.80±0.14‰ and δ18O=+43.11±0.64‰. This difference is notable, because if the meteorite had been contaminated with nitrate from the blue ice, the δ15N values should be the same. More importantly, the δ15N is similar to the uncontaminated Tissint Mars meteorite with δ15N=-4.5‰. These findings suggest a martian origin of the ClO4-, ClO3- and NO3- in EETA79001, and in conjunction with previous discoveries, support the hypothesis that they are present and ubiquitous on Mars. The presence of ClO3- in EETA79001 suggests the accompanying presence of other highly oxidizing oxychlorines such as ClO2- or ClO-, produced both by UV oxidation of Cl- and γ- and X-ray radiolysis of ClO4 Since such intermediary species may contribute to oxidization of organic compounds, only highly refractory and/or well-protected organics are likely to survive. The global presence of ClO4-, ClO3-, and NO3-, has broad implications for the planet-wide water cycle, formation of brines, human habitability, organics, and life.

Original languageEnglish
Pages (from-to)206-213
Number of pages8
JournalIcarus
Volume229
DOIs
StatePublished - 1 Feb 2014

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chlorates
perchlorate
meteorites
perchlorates
oxidant
meteorite
mars
nitrates
Mars
nitrate
Phoenix (AZ)
soils
ice
organic compounds
organic compound
inclusions
habitability
SNC meteorites
salts
salt

Keywords

  • Astrobiology
  • Mars
  • Mars, surface
  • Meteorites
  • Regoliths

Cite this

Kounaves, Samuel P. ; Carrier, Brandi L. ; O'Neil, Glen ; Stroble, Shannon T. ; Claire, Mark W. / Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001 : Implications for oxidants and organics. In: Icarus. 2014 ; Vol. 229. pp. 206-213.
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abstract = "The results from the Viking mission in the mid 1970s provided evidence that the martian surface contained oxidants responsible for destroying organic compounds. In 2008 the Phoenix Wet Chemistry Lab (WCL) found perchlorate (ClO4-) in three soil samples at concentrations from 0.5 to 0.7wt{\%}. The detection of chloromethane (CH3Cl) and dichloromethane (CH2Cl2) by the Viking pyrolysis gas chromatograph-mass spectrometer (GC-MS) may have been a result of ClO4- at that site oxidizing either terrestrial organic contaminates or, if present, indigenous organics. Recently, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) Curiosity directly measured the presence of CH3Cl, CH2Cl2 and, along with measurements of HCl and oxygen, indirectly indicate the presence of ClO4 However, except for Phoenix, no other direct measurement of the ClO4- anion in martian soil or rock has been made. We report here ion chromatographic (IC) and isotopic analyses of a unique sawdust portion of the martian meteorite EETA79001 that show the presence by mass of 0.6±0.1ppm ClO4-, 1.4±0.1ppm ClO3-, and 16±0.2ppm NO3- at a quantity and location within the meteorite that is difficult to reconcile with terrestrial contamination. The sawdust sample consists of basaltic material with a minor salt-rich inclusion in a mass ratio of ~300:1, thus the salts may be 300 times more concentrated within the inclusion than the whole sample. The molar ratios of NO3-:ClO4- and Cl-:ClO4-, are very different for EETA79001 at ~40:1 and 15:1, respectively, than the Antarctic soils and ice near where the meteorite was recovered at ~10,000:1 and 5000:1, respectively. In addition, the isotope ratios for EETA79001 with δ15N=-10.48±0.32‰ and δ18O=+51.61±0.74‰ are significantly different from that of the nearby Miller Range blue ice with δ15N=+102.80±0.14‰ and δ18O=+43.11±0.64‰. This difference is notable, because if the meteorite had been contaminated with nitrate from the blue ice, the δ15N values should be the same. More importantly, the δ15N is similar to the uncontaminated Tissint Mars meteorite with δ15N=-4.5‰. These findings suggest a martian origin of the ClO4-, ClO3- and NO3- in EETA79001, and in conjunction with previous discoveries, support the hypothesis that they are present and ubiquitous on Mars. The presence of ClO3- in EETA79001 suggests the accompanying presence of other highly oxidizing oxychlorines such as ClO2- or ClO-, produced both by UV oxidation of Cl- and γ- and X-ray radiolysis of ClO4 Since such intermediary species may contribute to oxidization of organic compounds, only highly refractory and/or well-protected organics are likely to survive. The global presence of ClO4-, ClO3-, and NO3-, has broad implications for the planet-wide water cycle, formation of brines, human habitability, organics, and life.",
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Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001 : Implications for oxidants and organics. / Kounaves, Samuel P.; Carrier, Brandi L.; O'Neil, Glen; Stroble, Shannon T.; Claire, Mark W.

In: Icarus, Vol. 229, 01.02.2014, p. 206-213.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001

T2 - Implications for oxidants and organics

AU - Kounaves, Samuel P.

AU - Carrier, Brandi L.

AU - O'Neil, Glen

AU - Stroble, Shannon T.

AU - Claire, Mark W.

PY - 2014/2/1

Y1 - 2014/2/1

N2 - The results from the Viking mission in the mid 1970s provided evidence that the martian surface contained oxidants responsible for destroying organic compounds. In 2008 the Phoenix Wet Chemistry Lab (WCL) found perchlorate (ClO4-) in three soil samples at concentrations from 0.5 to 0.7wt%. The detection of chloromethane (CH3Cl) and dichloromethane (CH2Cl2) by the Viking pyrolysis gas chromatograph-mass spectrometer (GC-MS) may have been a result of ClO4- at that site oxidizing either terrestrial organic contaminates or, if present, indigenous organics. Recently, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) Curiosity directly measured the presence of CH3Cl, CH2Cl2 and, along with measurements of HCl and oxygen, indirectly indicate the presence of ClO4 However, except for Phoenix, no other direct measurement of the ClO4- anion in martian soil or rock has been made. We report here ion chromatographic (IC) and isotopic analyses of a unique sawdust portion of the martian meteorite EETA79001 that show the presence by mass of 0.6±0.1ppm ClO4-, 1.4±0.1ppm ClO3-, and 16±0.2ppm NO3- at a quantity and location within the meteorite that is difficult to reconcile with terrestrial contamination. The sawdust sample consists of basaltic material with a minor salt-rich inclusion in a mass ratio of ~300:1, thus the salts may be 300 times more concentrated within the inclusion than the whole sample. The molar ratios of NO3-:ClO4- and Cl-:ClO4-, are very different for EETA79001 at ~40:1 and 15:1, respectively, than the Antarctic soils and ice near where the meteorite was recovered at ~10,000:1 and 5000:1, respectively. In addition, the isotope ratios for EETA79001 with δ15N=-10.48±0.32‰ and δ18O=+51.61±0.74‰ are significantly different from that of the nearby Miller Range blue ice with δ15N=+102.80±0.14‰ and δ18O=+43.11±0.64‰. This difference is notable, because if the meteorite had been contaminated with nitrate from the blue ice, the δ15N values should be the same. More importantly, the δ15N is similar to the uncontaminated Tissint Mars meteorite with δ15N=-4.5‰. These findings suggest a martian origin of the ClO4-, ClO3- and NO3- in EETA79001, and in conjunction with previous discoveries, support the hypothesis that they are present and ubiquitous on Mars. The presence of ClO3- in EETA79001 suggests the accompanying presence of other highly oxidizing oxychlorines such as ClO2- or ClO-, produced both by UV oxidation of Cl- and γ- and X-ray radiolysis of ClO4 Since such intermediary species may contribute to oxidization of organic compounds, only highly refractory and/or well-protected organics are likely to survive. The global presence of ClO4-, ClO3-, and NO3-, has broad implications for the planet-wide water cycle, formation of brines, human habitability, organics, and life.

AB - The results from the Viking mission in the mid 1970s provided evidence that the martian surface contained oxidants responsible for destroying organic compounds. In 2008 the Phoenix Wet Chemistry Lab (WCL) found perchlorate (ClO4-) in three soil samples at concentrations from 0.5 to 0.7wt%. The detection of chloromethane (CH3Cl) and dichloromethane (CH2Cl2) by the Viking pyrolysis gas chromatograph-mass spectrometer (GC-MS) may have been a result of ClO4- at that site oxidizing either terrestrial organic contaminates or, if present, indigenous organics. Recently, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) Curiosity directly measured the presence of CH3Cl, CH2Cl2 and, along with measurements of HCl and oxygen, indirectly indicate the presence of ClO4 However, except for Phoenix, no other direct measurement of the ClO4- anion in martian soil or rock has been made. We report here ion chromatographic (IC) and isotopic analyses of a unique sawdust portion of the martian meteorite EETA79001 that show the presence by mass of 0.6±0.1ppm ClO4-, 1.4±0.1ppm ClO3-, and 16±0.2ppm NO3- at a quantity and location within the meteorite that is difficult to reconcile with terrestrial contamination. The sawdust sample consists of basaltic material with a minor salt-rich inclusion in a mass ratio of ~300:1, thus the salts may be 300 times more concentrated within the inclusion than the whole sample. The molar ratios of NO3-:ClO4- and Cl-:ClO4-, are very different for EETA79001 at ~40:1 and 15:1, respectively, than the Antarctic soils and ice near where the meteorite was recovered at ~10,000:1 and 5000:1, respectively. In addition, the isotope ratios for EETA79001 with δ15N=-10.48±0.32‰ and δ18O=+51.61±0.74‰ are significantly different from that of the nearby Miller Range blue ice with δ15N=+102.80±0.14‰ and δ18O=+43.11±0.64‰. This difference is notable, because if the meteorite had been contaminated with nitrate from the blue ice, the δ15N values should be the same. More importantly, the δ15N is similar to the uncontaminated Tissint Mars meteorite with δ15N=-4.5‰. These findings suggest a martian origin of the ClO4-, ClO3- and NO3- in EETA79001, and in conjunction with previous discoveries, support the hypothesis that they are present and ubiquitous on Mars. The presence of ClO3- in EETA79001 suggests the accompanying presence of other highly oxidizing oxychlorines such as ClO2- or ClO-, produced both by UV oxidation of Cl- and γ- and X-ray radiolysis of ClO4 Since such intermediary species may contribute to oxidization of organic compounds, only highly refractory and/or well-protected organics are likely to survive. The global presence of ClO4-, ClO3-, and NO3-, has broad implications for the planet-wide water cycle, formation of brines, human habitability, organics, and life.

KW - Astrobiology

KW - Mars

KW - Mars, surface

KW - Meteorites

KW - Regoliths

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