Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron

Abinash Agrawal, William J. Ferguson, Bruce O. Gardner, John A. Christ, Joel Z. Bandstra, Paul Tratnyek

Research output: Contribution to journalArticle

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Abstract

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (≈10-2 M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K1/2). The decrease in Vm/K1/2 with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

Original languageEnglish (US)
Pages (from-to)4326-4333
Number of pages8
JournalEnvironmental Science and Technology
Volume36
Issue number20
DOIs
StatePublished - Oct 15 2002

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Trichloroethanes
Dechlorination
Carbonates
dechlorination
Iron
carbonate
iron
kinetics
Kinetics
Precipitates
corrosion
Groundwater
Corrosion
groundwater
rust disease
siderite
ethane
Batch reactors
Ethane
Pitting

ASJC Scopus subject areas

  • Environmental Engineering
  • Environmental Science(all)
  • Environmental Chemistry

Cite this

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron. / Agrawal, Abinash; Ferguson, William J.; Gardner, Bruce O.; Christ, John A.; Bandstra, Joel Z.; Tratnyek, Paul.

In: Environmental Science and Technology, Vol. 36, No. 20, 15.10.2002, p. 4326-4333.

Research output: Contribution to journalArticle

Agrawal, Abinash ; Ferguson, William J. ; Gardner, Bruce O. ; Christ, John A. ; Bandstra, Joel Z. ; Tratnyek, Paul. / Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron. In: Environmental Science and Technology. 2002 ; Vol. 36, No. 20. pp. 4326-4333.
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