Abiotic Reduction of Chlorate by Fe(II) Minerals: Implications for Occurrence and Transformation of Oxy-Chlorine Species on Earth and Mars

Maeghan Brundrett, Weile Yan, Maria C. Velazquez, Balaji Rao, W. Andrew Jackson

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Recent investigations have reported a widespread occurrence of chlorate (ClO3-) and perchlorate (ClO4-) throughout the solar system, including terrestrial arid environments. ClO3- and ClO4- are deposited/accumulated at an approximate equal molar ratio, with some exceptions, such as the Antarctica Dry Valley soils (MDV) and perhaps Martian surface material, where ClO4- is the dominate ClOx- species. All known ClO4- production mechanisms produce molar ratios of ClO3-/ClO4- equal to or much greater than 1, suggesting that reduced ratios may be due to post-depositional mechanism(s). The objective of this study was to investigate potential iron-mediated abiotic reduction of ClO3-, similar to transformation mechanisms reported for nitrate (NO3-) by Fe(II) minerals. Three types of Fe(II)-containing minerals, wüstite (FeO), siderite (FeCO3), and sulfate green rust (GRSO42-), were investigated in completely mixed batch reactors as potential ClO3- reductants at a range of pH (4-9) and iron mineral concentrations (1-10 g/L). ClO3- was stoichiometrically reduced to chloride (Cl-) by wüstite, siderite, and green rust, but no transformation occurred by dissolved Fe(II). Wüstite and green rust reduced NO3- but not by siderite. When both NO3- and ClO3- are reduced simultaneously, ClO3- is reduced preferentially to NO3-, although the effect is somewhat concentration-dependent. An increased background salt concentration (NaCl) increased ClO3- reduction but decreased NO3-. The stability of ClO3- and subsequent impacts on the ratio of ClO3-/ClO4- in the environment have implications for understanding the cycling of oxyanions and stability of iron minerals, and related to this, the ratio of ClO4- and ClO3- may be an indicator of the past availability of free water. On Mars, these reactions may help to explain the unusually high concentrations of ClO4- compared to ClO3- and NO3-.

Original languageEnglish
Pages (from-to)700-710
Number of pages11
JournalACS Earth and Space Chemistry
Volume3
Issue number5
DOIs
StatePublished - May 16 2019

Keywords

  • (per)chlorate
  • Antarctica Dry Valleys
  • Martian soil chemistry
  • green rust
  • nitrate
  • reduction
  • siderite
  • wüstite

Fingerprint Dive into the research topics of 'Abiotic Reduction of Chlorate by Fe(II) Minerals: Implications for Occurrence and Transformation of Oxy-Chlorine Species on Earth and Mars'. Together they form a unique fingerprint.

Cite this