Graduate Thesis Or Dissertation
 

The non-enzymatic formation of nitric oxide from soil and clay systems

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  • Prevailing concepts relating to the non-enzymatic gaseous loss of nitrite from soil are thought to be inadequate as regards to the mechanisms involved. The conventional explanation for nitric oxide formation i.e., the acid decomposition of nitrite, is held to be insufficient in substrates of only mild or slight acidity. A criticism is presented wherein it is maintained that certain past practices in methodology have created rather than eliminated confusion. Positive suggestions are proposed which may help to eliminate confusion in future experiments. Evidence was obtained from soil and clay systems which attest to a mechanism of loss whereby nitrite may react with certain metals to yield nitric oxide as a primary gaseous product. A conventional half-cell reaction is presented wherein a transition-like metal is oxidized and nitrite is reduced to nitric oxide with the formation of water. It is implied that hydrogen ions may be necessary--acid conditions favor the reduced state of the metals which is a more active state with respect to the formation of nitric oxide--for such reactions, but that they are not sufficient in substrates of only mild acidity. An apparent corollary to this study is that the very conditions which favor classical denitrification from nitrate also favor metal-nitrite reactions. Under such conditions both nitrate and the metals involved would be expected to undergo reduction resulting in an increased possibility for nitric oxide formation. This possibility places in question the status of nitric oxide as a direct biochemical intermediate in the microbial formation of nitrogen gas. It is suggested that a mechanism involving transition -like metals may account for significant losses of mineral nitrogen from field soils capable of accumulating nitrite under conditions of moderate or slight acidity.
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