Date Available

10-28-2014

Year of Publication

2013

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Agriculture, Food and Environment

Department/School/Program

Plant and Soil Sciences

First Advisor

Dr. Christopher J. Matocha

Abstract

Under iron (Fe3+)-reducing conditions where aqueous Fe2+ and unreduced solid Fe3+-oxides commonly coexist, soil Fe2+ oxidation has been shown to be coupled with nitrate (NO3-) reduction. One possible secondary reaction is the involvement of NO3- and nitrite (NO2-) with Fe-oxide minerals found in many natural environments. Yet, spectroscopic measurements and kinetic data on reactivity of NO3- and NO2- with Fe-containing oxide minerals such as goethite (a-FeOOH), and magnetite (Fe3O­4) are not found in the literature. The reactivity of goethite and magnetite with NO3- and NO2- was studied over a range of environmentally relevant pH conditions (5.5-7.5) with and without added Fe2+(aq) under anoxic conditions. Laboratory experiments were conducted using stirred batch experiments and reaction products were analyzed using ion chromatography (IC), gas chromatography (GC), ultraviolet visible near infrared spectroscopy (UV-VIS-NIR), x-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer, and Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Nitrate removal by goethite and magnetite was much slower when compared with NO2-. There was a pH-dependence in the reduction of NO2-, and the initial rate of NO2- removal was nearly 2 and 8 times faster at pH 5.5 than at pH 7.5 by magnetite and goethite, respectively. Nitric oxide (NO) and nitrous oxide (N2O) were identified as products when NO2- has reacted with magnetite, whereas N2O is the major reaction product in the experiment with goethite. In comparison to experiments containing magnetite or goethite alone, addition of Fe2+ greatly accelerated the NO2- removal rate. Wet chemical experiments combined with the Mössbauer study reveals that NO2- reduction to NO and subsequently to N2O by magnetite occurs via a heterogeneous electron transfer process. ATR-FTIR and diffuse reflectance spectroscopy (DRS) results from the studies with goethite indicate that NO2- was removed from solution by adsorption in a surface complex involving the oxygen atoms, and a portion of the nitrite is reduced to NO and N2O.

This study suggests that under anaerobic conditions soil and sediments that contain goethite, magnetite, and other Fe3+-oxides can catalyze abiotic NO2- reduction and the kinetics data from this study can be used to predict the NO2- removal under such conditions.

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