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Reduction of nitrate to ammonium by sulphate green rust: activation energy and reaction mechanism

Published online by Cambridge University Press:  09 July 2018

H. C. B. Hansen  and
C. Bender Koch
H. C. B. Hansen
Affiliation:
Chemistry Department, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C., Denmark
C. Bender Koch
Affiliation:
Chemistry Department, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg C., Denmark
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Abstract

Iron(II)-containing minerals are potential inorganic nitrate reductants in soils and sediments. Specifically, synthetic green rust (Fe4IIFeIII2(OH)12SO4.yH2O, GR) reduces nitrate to ammonium. The reaction of GR with two different nitrate salts, NaNO3 and Ba(NO3)2, has been compared. The reaction stoichiometry and the reaction order with respect to Fe(II) in GR does not change in the examined temperature range (15-50°C) irrespective of the nitrate salt used. Activation energies of 83.9±7.6 kJ mol-1 and 90.5±6.9 kJ mol-1 have been determined for the reaction of GR with NaNO3 and Ba(NO3)2, respectively. However, for the latter reaction the rate of reaction is increased 40 times. Based on X-ray and M6ssbauer investigations, this acceleration of the reaction rates is attributed to the forced exchange of sulphate with nitrate in GR interlayers caused by precipitation of BaSO4 outside the GR particles, a reaction which does not occur in the presence of NaNO3. This difference in anion exchange behaviour is confirmed by anion exchange experiments with the redox-inactive GR-analogue, pyroaurite. A reaction model initiated by nitrate electrostatically bound at positively charged sites of GR is proposed.

Type
Research Article
Information
Clay Minerals , Volume 33 , Issue 1 , March 1998 , pp. 87 - 101
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1998

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