Julia Garrelfs

Corrosion of Iron by Sulfate-Reducing Bacteria: New Views of an Old Problem

ABSTRACT About a century ago, researchers first recognized a connection between the activity of environmental microorganisms and cases of anaerobic iron corrosion. Since then, such microbially influenced corrosion (MIC) has gained prominence and its technical and economic implications are now widely recognized. Under anoxic conditions (e.g., in oil and gas pipelines), sulfate-reducing bacteria (SRB) are commonly considered the main culprits of MIC. This perception largely stems from three recurrent observations. First, anoxic sulfate-rich environments (e.g., anoxic seawater) are particularly corrosive. Second, SRB and their characteristic corrosion product iron sulfide are ubiquitously associated with anaerobic corrosion damage, and third, no other physiological group produces comparably severe corrosion damage in laboratory-grown pure cultures. However, there remain many open questions as to the underlying mechanisms and their relative contributions to corrosion. On the one hand, SRB damage iron constructions indirectly through a corrosive chemical agent, hydrogen sulfide, formed by the organisms as a dissimilatory product from sulfate reduction with organic compounds or hydrogen (“chemical microbially influenced corrosion”; CMIC). On the other hand, certain SRB can also attack iron via withdrawal of electrons (“electrical microbially influenced corrosion”; EMIC), viz., directly by metabolic coupling. Corrosion of iron by SRB is typically associated with the formation of iron sulfides (FeS) which, paradoxically, may reduce corrosion in some cases while they increase it in others. This brief review traces the historical twists in the perception of SRB-induced corrosion, considering the presently most plausible explanations as well as possible early misconceptions in the understanding of severe corrosion in anoxic, sulfate-rich environments.

Marine sulfate-reducing bacteria cause serious corrosion of iron under electroconductive biogenic mineral crust.

Iron (Fe0) corrosion in anoxic environments (e.g. inside pipelines), a process entailing considerable economic costs, is largely influenced by microorganisms, in particular sulfate-reducing bacteria (SRB). The process is characterized by formation of black crusts and metal pitting. The mechanism is usually explained by the corrosiveness of formed H2S, and scavenge of ‘cathodic’ H2 from chemical reaction of Fe0 with H2O. Here we studied peculiar marine SRB that grew lithotrophically with metallic iron as the only electron donor. They degraded up to 72% of iron coupons (10 mm × 10 mm × 1 mm) within five months, which is a technologically highly relevant corrosion rate (0.7 mm Fe0 year−1), while conventional H2-scavenging control strains were not corrosive. The black, hard mineral crust (FeS, FeCO3, Mg/CaCO3) deposited on the corroding metal exhibited electrical conductivity (50 S m−1). This was sufficient to explain the corrosion rate by electron flow from the metal (4Fe0 → 4Fe2+ + 8e−) through semiconductive sulfides to the crust-colonizing cells reducing sulfate (8e− + SO42− + 9H+ → HS− + 4H2O). Hence, anaerobic microbial iron corrosion obviously bypasses H2 rather than depends on it. SRB with such corrosive potential were revealed at naturally high numbers at a coastal marine sediment site. Iron coupons buried there were corroded and covered by the characteristic mineral crust. It is speculated that anaerobic biocorrosion is due to the promiscuous use of an ecophysiologically relevant catabolic trait for uptake of external electrons from abiotic or biotic sources in sediments.

Selective microbial electrosynthesis of methane by a pure culture of a marine lithoautotrophic archaeon

Reduction of carbon dioxide to methane by microorganisms attached to electrodes is a promising process in terms of renewable energy storage strategies. However the efficient and specific electrosynthesis of methane by methanogenic archaea on cathodes needs fundamental investigations of the electron transfer mechanisms at the microbe-electrode interface without the addition of artificial electron mediators. Using well-defined electrochemical techniques directly coupled to gas chromatography and surface analysis by scanning electron microscopy, it is shown that a pure culture of the marine lithoautotrophic Methanobacterium-like archaeon strain IM1 is capable to utilize electrons from graphite cathodes for a highly selective production of methane, without hydrogen serving as a cathode-generated electron carrier. Microbial electrosynthesis of methane with cultures of strain IM1 is achieved at a set potential of -0.4V vs. SHE and is characterized by a coulomb efficiency of 80%, with rates reaching 350 nmol d(-1) cm(-2) after 23 days of incubation. Moreover, potential step measurements reveal a biologically catalyzed hydrogen production at potentials more positive than abiotic hydrogen evolution on graphite, indicating that an excessive supply of electrons to strain IM1 results in proton reduction rather than in a further increase of methane production.