Voltammetric (micro)electrodes for the in situ study of Fe2+ oxidation kinetics in hot springs and S2O32- production at hydrothermal vents

Katherine M. Mullaugh, George W. Luther, Shufen Ma, Tommy S. Moore, Mustafa Yücel, Erin L. Becker, Elizabeth L. Podowski, Charles R. Fisher, Robert E. Trouwborst, Beverly K. Pierson

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


We have used solid-state Au/Hg voltammetric electrodes to understand redox and biogeochemical processes in hot spring and deep sea hydrothermal environments. These electrodes are non-specific and have the capability of measuring simultaneously a suite of chemical species including several of the principal redox species involved in early diagenesis (O2, Mn 2+, Fe2+, H2S/HS-, and I -) as well as some Fe species (FeS and Fe3+) and sulfur species (Sx2- and S2O3 2-). Here we demonstrate how in situ data obtained in complex environments can be used to study specific iron and sulfur reactions and processes at (sub)millimeter to centimeter resolution and over short time scales. Examples include the oxidation of Fe2+ by O2 produced by cyanobacterial mats in Yellowstone National Park hot springs and the formation of S2O32- in diffuse flow waters from the hydrothermal vents at Lau Basin. In one example, profiles of redox species in cyanobacterial mats from Yellowstone National Park hot springs show that in the light dissolved Fe2+ is completely removed from the source waters as cyanobacterial mats produce O2 and oxidize the Fe2+. Performing kinetic experiments in the dark and light at the depth of maximum O2 production indicates that the decay of Fe 2+ follows a zero order rate law consistent with photosynthesis as the source of O2. These dynamic environments show how kinetic data can be obtained in situ and be used to understand the interactions between biology and chemistry. We know of no other analytical technique that can provide this information in both clear and turbid waters on the time scales (seconds) observed.

Original languageEnglish (US)
Pages (from-to)280-290
Number of pages11
Issue number3
StatePublished - Feb 2008

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Electrochemistry


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