Carbon Steel Corrosion Induced by Sulfate-Reducing Bacteria: A Review of Electrochemical Mechanisms and Pathways in Biofilms
Abstract
:1. Introduction
2. Mechanism of SRB-Induced Metal Corrosion
2.1. Corrosion of Carbon Steel
2.1.1. The Cathodic Depolarization Theory (CDT)
2.1.2. Acid Metabolite Corrosion Theory
2.1.3. The Biocatalytic Cathodic Sulfate Reduction Mechanism (BCSR)
2.2. Corrosion of Cu, Zn
3. Effect of Extracellular Polymers
3.1. EPS Affects MIC
3.1.1. Suppression of MIC
3.1.2. Promotion of MIC
3.2. EPS Affects EET
3.2.1. EPS Influences DET
3.2.2. EPS Influences MET
4. MIC and MFC
- MIC is now an important branch of metals research. Xu et al. [11] classified MIC into two main categories based on the type of anaerobic metabolism and electron transport: I MIC and II MIC. I MIC refers to the fact that the underlying biofilm close to the metal surface, due to the lack of a carbon source, directly uses the metal (e.g., Fe0) as an electron donor to obtain energy [16]. Since the electrons released from metal anodization cannot “swim” as freely as the ions in solution, the electrons must pass through the biofilm on the surface of the iron [27] and then cross the cell membrane into the cytoplasm, reducing the intracellular electron acceptor and releasing the energy. The SRB metal corrosion mechanism of both the CDT and BCSR involves I MIC. II MIC is caused by corrosive metabolites secreted by microorganisms, including protons and (undissociated) organic acids [11]. These oxidants do not require the involvement of biofilms or biocatalysis, with direct extracellular elimination of electrons from the metal anode. The biofilms can act as a diffusion barrier, maintaining high local metabolite concentrations and causing severe localized metal corrosion. H2S corrosion released by SRB metabolism is II MIC [15].
- The concept of EET is adapted from MFC. An MFC refers to the technology that uses biofilm as a catalyst to directly convert the chemical energy generated by oxidizing organic substances into bioelectric energy [54]. When microorganisms with the ability to produce electricity participate in MFC, the direction of EET is directed outward from the cell to the extracellular electrodes (e.g., insoluble Fe (III), Mn (III), Mn (IV), and other oxides [55,56]), which means that electrons released from the oxidation of organic carbon are transported from the cytoplasm to the metal oxide cathode outside the cell. When there is a localized lack of an organic carbon source as an electron donor within the cells of an electroproducing microorganism, this causes EET reversal, resulting in MIC. Xu et al. [57] compared Desulfovibrio vulgaris with different degrees of MIC caused by carbon-source starvation in media with different carbon contents. Bacteria grown on C1018 carbon steel sheets in the ATCC 1249 medium versus the medium with 90% and 99% reduced organic carbon were found to have the most severe metal corrosion caused by biofilm in the case of starved, but not completely starved, carbon sources. Clauwaert et al. [58] and Huang et al. [59] designed the MFC with a biocathode instead of an oxygen cathode. In this case, electrons are released from the anode into the extracellular environment and enter the biofilm covering the surface of the biocathode before being transferred across the cell wall into the cathode biofilm cells, and the direction of electron transfer from the cathode biofilm to the cathode is the same as in MIC. Therefore, electron transfer in biofilm is often reversible, and the electrochemical mechanism and electron transfer mode in MIC is the same as that in the biocathode of MFC, and the mechanism of how extracellular electrons are imported into the intracellular cell through biofilm can be explored based on the microbial export electron pathway [14,15,16].
4.1. Electrical Direct Contact Transmission: Shewanella oneidenis MR-1
4.2. Conductive Bacterial Hair Proteins or Nanowires: Geobacter sulfurreducens
4.3. Electron Shuttling Based on Soluble Electron Mediators: Flavins and Phenazines
5. Electron Transfer in the Corrosion of SRB Microbial Carbon Steel
5.1. Electron Transfer in EPS
5.2. Electron Transfer in the Periplasm from the Outer to the Inner Cell Membrane
5.3. Electron Transfer in SRB Cells
6. Conclusions
- The bioinduced mineralization occurring in EPS can effectively inhibit metal corrosion, providing new ideas for corrosion protection and the development of new, natural green corrosion inhibitors. The biomineralization induced by SRB will form MeS/MeCO3 mineral precipitates on the cell surface, but how the changes in its own physiological and metabolic activities specifically induce the occurrence of extracellular mineralization needs to be further explored experimentally.
- Currently, there are more studies on extracellular electron transfer in MFC, and the transfer mechanism where electrons undergo single-step tunneling in the range of 15.5 Å and undergo long-range jumps driven by redox gradients expands the quantum mechanical perspective for probing electron transfer at the bioenergetics level. The elucidation of the mode, mechanism, and pathway of extracellular electron transfer occurring in MIC, on the other hand, only originates from the inference of reversible processes and lacks substantial and more direct experimental evidence.
- The identification of the types of cytochromes or other electron carriers involved in electron transfer and their roles in the various types of cytochromes present in the EPS layer, extracellular membrane, periplasm, and intracellular membrane during the corrosion of carbon steel induced by SRB still requires further experimental investigation. Molecular tools such as gene mutation, proteomics analysis, and metabolomics studies may play an important role in the identification of key components.
- The actual corrosion environment is often more complex, whether or how temperature, pH, anions, symbiotic bacteria, etc., affect the corrosion process of SRB carbon steel. Further understanding and discussion are needed to determine whether the electrochemical mechanism and pathway of SRB corrosion on other metal materials, such as carbon steel materials of different concentrations, other alloys and so on, occurring in biofilms are consistent, and whether the corrosion mechanism is the same.
Author Contributions
Funding
Conflicts of Interest
Appendix A
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Liu, N.; Qiu, L.; Qiu, L. Carbon Steel Corrosion Induced by Sulfate-Reducing Bacteria: A Review of Electrochemical Mechanisms and Pathways in Biofilms. Coatings 2024, 14, 1105. https://doi.org/10.3390/coatings14091105
Liu N, Qiu L, Qiu L. Carbon Steel Corrosion Induced by Sulfate-Reducing Bacteria: A Review of Electrochemical Mechanisms and Pathways in Biofilms. Coatings. 2024; 14(9):1105. https://doi.org/10.3390/coatings14091105
Chicago/Turabian StyleLiu, Na, Lina Qiu, and Lijuan Qiu. 2024. "Carbon Steel Corrosion Induced by Sulfate-Reducing Bacteria: A Review of Electrochemical Mechanisms and Pathways in Biofilms" Coatings 14, no. 9: 1105. https://doi.org/10.3390/coatings14091105