Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms.;Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR.;Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms.;A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled out the enzymatic catalysis of ORR and supported the catalysis by MnO2.;Sustainable redox reactions at the cathode were evaluated by monitoring the cathodic current of biofilm coated stainless steel for a year under different polarization intensities. The results showed that sustainable cathodic reactions were present in marine biofilms but their influence on the cathodic current was negligible until a potential was reached where the ORR could take place. Additionally seasonal variability was observed in the enhanced cathodic current in Delaware Bay biofilms. This was attributed to the seasonal variability of manganese in the water column.