Richard I. Ray

Neutrophilic Iron-Oxidizing “Zetaproteobacteria” and Mild Steel Corrosion in Nearshore Marine Environments

ABSTRACT Microbiologically influenced corrosion (MIC) of mild steel in seawater is an expensive and enduring problem. Little attention has been paid to the role of neutrophilic, lithotrophic, iron-oxidizing bacteria (FeOB) in MIC. The goal of this study was to determine if marine FeOB related to Mariprofundus are involved in this process. To examine this, field incubations and laboratory microcosm experiments were conducted. Mild steel samples incubated in nearshore environments were colonized by marine FeOB, as evidenced by the presence of helical iron-encrusted stalks diagnostic of the FeOB Mariprofundus ferrooxydans, a member of the candidate class “Zetaproteobacteria.” Furthermore, Mariprofundus-like cells were enriched from MIC biofilms. The presence of Zetaproteobacteria was confirmed using a Zetaproteobacteria-specific small-subunit (SSU) rRNA gene primer set to amplify sequences related to M. ferrooxydans from both enrichments and in situ samples of MIC biofilms. Temporal in situ incubation studies showed a qualitative increase in stalk distribution on mild steel, suggesting progressive colonization by stalk-forming FeOB. We also isolated a novel FeOB, designated Mariprofundus sp. strain GSB2, from an iron oxide mat in a salt marsh. Strain GSB2 enhanced uniform corrosion from mild steel in laboratory microcosm experiments conducted over 4 days. Iron concentrations (including precipitates) in the medium were used as a measure of corrosion. The corrosion in biotic samples (7.4 ± 0.1 mM) was significantly higher than that in abiotic controls (5.0 ± 0.1 mM). These results have important implications for the role of FeOB in corrosion of steel in nearshore and estuarine environments. In addition, this work shows that the global distribution of Zetaproteobacteria is far greater than previously thought.

Relationship Between Corrosion and the Biological Sulfur Cycle: A Review

Abstract Sulfur and sulfur compounds can produce pitting, crevice corrosion, dealloying, stress corrosion cracking, and stress-oriented hydrogen-induced cracking of susceptible metals and alloys. E...

Biodegradation of composite materials

Fiber-reinforced polymer composites were examined for susceptibility to microbiologically-influenced degradation. Composites, resins, and fibers were exposed to sulfur/iron-oxidizing, calcareous-depositing, ammonium-producing, hydrogen-producing, and sulfate-reducing bacteria (SRB) in batch culture. Surfaces were uniformly colonized by all physiological types of bacteria; however, the microbes preferentially colonized surface anomalies including scratches and fiber disruptions. Epoxy and vinyl ester neat resins, carbon fibers, and epoxy composites were not adversely affected by the microbial species. SRB degraded the organic surfactant on glass fibers. Hydrogen-producing bacteria appeared to disrupt bonding between fibers and vinyl ester resin and to penetrate the resin at the interface. Acoustic emission testing demonstrated reduction of tensile strength in a stressed carbon fiber-reinforced epoxy composite after exposure to SRB.

A review of 'green' strategies to prevent or mitigate microbiologically influenced corrosion.

Abstract Two approaches to control microbiologically influenced corrosion (MIC) have been developed that do not require the use of biocides. These strategies include the following: i) use of biofilms to inhibit or prevent corrosion, and ii) manipulation (removal or addition) of an electron acceptor, (e.g. oxygen, sulphate or nitrate) to influence the microbial population. In both approaches the composition of the microbial community is affected by small perturbations in the environment (e.g. temperature, nutrient concentration and flow) and the response of microorganisms cannot be predicted with certainty. The following sections will review the literature on the effectiveness of these environmentally friendly, “green,” strategies for controlling MIC.

Spatial relationships between marine bacteria and localized corrosion on polymer coated steel

Diagnosis of microbiologically influenced corrosion on iron‐containing substrata exposed in marine environments cannot be based solely on spatial relationships between large accumulations of bacterial cells and iron corrosion products. Experiments were designed to evaluate the relationship between marine bacteria and localized corrosion on coated mild steel. The distribution of bacteria was strongly influenced by the presence of iron corrosion products independent of coating combinations. In the presence of cathodic protection, coating defects were filled with calcareous deposits and few bacterial cells. The results demonstrate that bacteria are preferentially attracted to iron corrosion products in coating defects and that attraction is more influential than topography in determining the spatial distribution of bacterial cells.

The role of biomineralization in microbiologically influenced corrosion

Synthetic iron oxides (goethite, α-FeO·OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

An assessment of alternative diesel fuels: microbiological contamination and corrosion under storage conditions

Experiments were designed to evaluate the nature and extent of microbial contamination and the potential for microbiologically influenced corrosion of alloys exposed in a conventional high sulfur diesel (L100) and alternative fuels, including 100% biodiesel (B100), ultra-low sulfur diesel (ULSD) and blends of ULSD and B100 (B5 and B20). In experiments with additions of distilled water, all fuels supported biofilm formation. Changes in the water pH did not correlate with observations related to corrosion. In all exposures, aluminum 5052 was susceptible to pitting while stainless steel 304L exhibited passive behavior. Carbon steel exhibited uniform corrosion in ULSD and L100, and passive behavior in B5, B20, and B100.

The role of bacteria in pit propagation of carbon steel

Pit propagation in carbon steel exposed to a phosphate‐containing electrolyte required either stagnant conditions or microbial colonization of anodic regions. A scanning vibrating electrode (SVE) was used to resolve formation and inactivation of anodic and cathodic sites on carbon steel. In sterile, continuously aerated medium, pits initiated and repassivated, while in the absence of aeration, pits initiated and propagated. Pit propagation was also observed in continuously aerated medium inoculated with a heterotrophic bacterium, originally isolated from a corrosion tubercle formed on a steel pipe in a fresh water environment. Autoradiography of bacteria following uptake of 14C‐acetate into cellular material in combination with SVE analysis demonstrated that sites of anodic activity coincided with sites of bacterial activity. Prelabeled bacteria also preferentially attached to corrosion products over the anodic sites. Confocal laser scanning microscopy demonstrated that attraction to anodic sites did not depend on bacterial viability and was not specific for iron as a substratum. The results suggest that bacteria may preferentially attach to the corrosion products formed over corrosion pits. The biofilms over these anodic sites may create stagnant conditions within corrosion pits that result in pit propagation.

Sulphide production and corrosion in seawaters during exposure to FAME diesel

Experiments were designed to evaluate the corrosion-related consequences of storing/transporting fatty acid methyl ester (FAME) alternative diesel fuel in contact with natural seawater. Coastal Key West, FL (KW), and Persian Gulf (PG) seawaters, representing an oligotrophic and a more organic- and inorganic mineral-rich environment, respectively, were used in 60 day incubations with unprotected carbon steel. The original microflora of the two seawaters were similar with respect to major taxonomic groups but with markedly different species. After exposure to FAME diesel, the microflora of the waters changed substantially, with Clostridiales (Firmicutes) becoming dominant in both. Despite low numbers of sulphate-reducing bacteria in the original waters and after FAME diesel exposure, sulphide levels and corrosion increased markedly due to microbial sulphide production. Corrosion morphology was in the form of isolated pits surrounded by an intact, passive surface with the deepest pits associated with the fuel/seawater interface in the KW exposure. In the presence of FAME diesel, the highest corrosion rates measured by linear polarization occurred in the KW exposure correlating with significantly higher concentrations of sulphur and chlorine (presumed sulphide and chloride, respectively) in the corrosion products.

Evaluation of Deoxygenation as a Corrosion Control Measure for Ballast Tanks

Abstract Field experiments designed to evaluate deoxygenation of natural seawater as a corrosion control measure for unprotected carbon steel seawater ballast tanks demonstrated decreased corrosion in hypoxic (<0.2 ppm O2) seawater using linear polarization measurements. They also demonstrated the difficulty of maintaining hypoxic seawater. Using a gas mixture it was possible to displace dissolved oxygen. However, aerobic respiration and corrosion reactions consumed oxygen and produced totally anaerobic conditions within the first days of hypoxia. When gaskets and seals failed, oxygen was inadvertently introduced. The impact of oxygen ingress on corrosion depends on the amount of oxygen in the system at the time oxygen is introduced. Carbon steel exposed to cycles of hypoxic seawater and oxygenated atmosphere had higher corrosion rates than coupons exposed to cycles of either consistently aerobic or deoxygenated conditions.