Biofilms And General Mechanisms In Biocorrosion
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1 Lecture 35 Biofilms And General Mechanisms In Biocorrosion Keywords: Biofilms, Structural Materials, Sulfate Reducing Bacteria Biofilms on metals and alloys can cause several engineering problems. [ ] Heat transfer reduction leading to energy loss. Reduction in mass and fluid transfer (water, oil, gas pipelines). Structural breakdowns. Enhanced fuel and operating costs. Several mechanisms and models have been proposed to understand biofilm formation. Growth of aerobic bacteria utilize oxygen at the metal-solution interface generating an anaerobic environment. Anaerobic bacteria such as SRB can subsequently grow in the anaerobic environment. Bacterial synergy lead to the formation and growth of a heterogeneous biofilm consisting of a mixture of aerobes and anaerobes. MIC of some structural metals and alloys. Copper and copper alloys: They are commonly used in heat exchangers, pumps, and condensers. Copper-nickel alloys, brasses, aluminium bronzes and admiralty brasses are used in sea water applications. SRBs in sea water environments can cause localised corrosion of these alloys. Extra-cellular polymers and biofilms created by microorganisms can lead to corrosion of copper-base alloys through differential aeration and selective dissolution. Pitting, dezincification and ammonia cracking of brasses and bronzes can be caused by organisms. Sulphate-reducing bacteria can generate tubercles (sulphide-rich scales) on copper alloys. In spite of copper toxicity, copper and copper alloys are not free from biofouling. 1
2 Steels. Tubercle formation with pitting beneath the scales can occur in steel pipes and tubes, due to microbial action. Aerobic bacteria such as Gallionella, Leptothrix and Acidithiobacillus can oxidize iron, leading to deposition of ferric oxyhydroxides. The above organisms can also cause corrosion through formation of slimes, oxidation of iron and sulphides and generation of acidic metabolites. Iron oxidising bacteria oxidize ferrous ions to less soluble ferric oxides, leading to the formation of insoluble tubercles. Steel water pipes are amenable to such attack. Massive tubercle formation inside steel pipes, block fluid flow and can cause extensive pitting, and crevices. Stainless steels. Stainless steels find numerous applications in marine and other industrial environments. Iron oxidising and depositing bacteria induce pitting corrosion of stainless steels especially adjacent to weldments. SRB can bring about corrosion of stainless steels, duplex steels and molybdenum steels. Slimes formed by bacteria can initiate pits in stainless steels in marine environments. Destruction of passive films on stainless steels can be caused by reducing environments created by anaerobic bacteria. Nickel-based alloys. Monels and inconels are susceptible to microbial corrosion. Nickel-based alloys used in power plants corrode due to microbial action in marine environments. Aluminium and its alloys. Protective passive oxide films present on aluminium and its alloys could be broken and destroyed by microbial action. Aluminium alloys used in aircraft and fuel storage tanks are susceptible MIC in the presence of hydrocarbons. Production of organic and inorganic acids by bacteria and fungi lead to pitting and intergranular corrosion of aluminium and alloys. Aluminium-magnesium alloys used in marine applications are susceptible to pitting, intergranular corrosion, exfoliation and stress corrosion in the presence of aerobic and anaerobic microorganisms. Aircraft fuel tanks and marine structures made of aluminium and its alloys are corroded by microorganisms such as Pseudomonas, Leptothrix, Sulphate Reducing Bacteria and fungi. The fungus, Cladosporium resinae grow and multiply using kerosene or paraffins as carbon sources. MIC failure of aircraft fuel tanks is well established. 2
3 The following microorganisms had been isolated from an aircraft tank sludge. Titanium. Bacillus, Aerobacter aerogenes. Pseudomonas aeruginosa. Cladosporium Aspergillus, Clostridium, Desulfovibrio, Fusarium, Penicillium. Titanium is amenable to biofouling. SRBs and acid-producing bacteria create conditions that destabilize passive films. Titanium and its alloys used in marine environments are susceptible to biofouling and biofilm formation in the presence of manganese and iron oxidising bacteria and sulfate reducing halophiles. Surface passive films on titanium could be disrupted in the presence of anaerobes, leading to potential ennoblement and susceptibility to pitting. MIC due to Sulphate Reducing Bacteria (SRB) Microorganisms relevant to MIC possess the following general characteristics: Extremophiles (tolerant to wide range of metal concentrations, acidity, temperature, pressure, oxygen gradients) Fast reproduction and growth. Adhesion to metal substrates and colonisation. Ubiquitous and omnipotent Small size (few micrometers) Sessile or motile Existence of consortia and synergy Production of organic and inorganic acids, alkalis, chelating agents and extracellular polymeric substances such as proteins and polysaccharides. Can oxidize or reduce metals and ions. 3
4 Microorganisms relevant to MIC can be classified with respect to their functions. Iron-oxidizing /reducing bacteria. Sulfur-sulfide oxidizing bacteria. Bacteria secreting exopolymers / slime and organic acids. Manganese oxidizers / reducers Sulfate-reducing bacteria (SRB). Sulfate-reducing bacteria (SRB) bring about dissimilatory sulphate reduction to sulfides. Oil, gas and marine-based vessels and installations are seriously affected by SRB activities due to H 2 S generation. Common SRB such as Desulfovibrio, Desulfobacter and Desulfotomaculum, are capable of growing in soil, fresh water and sea-water environments and also in stagnant marshy areas. They oxidize organic substances to organic acids or CO 2, by reduction of sulfate to sulfide through anaerobic respiration. Black deposits of precipitated sulfides and H 2 S smell are indicative of SRB growth. Characteristics of some MIC-causing heterotrophs and Sulfate reducing bacteria relevant to MIC are given in Tables 35.1 and
5 Table 35.1: Some MIC causing heterotrophs Organism ph Temp 0 C Oxygen Action Affected metals Gallionella Aerobic Oxidizes ferrous and manganoustubercle formation Sphaerotilus Aerobic Oxidizes ferrous and manganous - tubercle formation Iron and steel Iron and steel S.natans Aluminium alloys Pseudomonas Aerobic Some strains can reduce Fe +++ to Fe ++ Iron and steel P.aeruginosa Aerobic Aluminium alloys Cladosparium resinae (fungi) Aerobic Produces organic acids. Aluminium alloys 5
6 Table 35.2: Characteristics of some sulfate reducing bacteria Desulfovibrio Single flagellum. Do not form spores. Hydrogenase present, ph C, anaerobic. Dt.nigrificans Hydrogenase activity variable. Growth even on pyruvate, sulphate-free media, C, ph Desulfotomaculum Peritrichous flagella, anaerobic, ph 6-8 Dt. Orientis Fat curved rods, 5 µm x 1.5 µm, Hydrogenase absent, ph 6-8, C. Dv. desulfuricans Dv. vulgaris Dv. Salexigens Curved rods (vibrios); sometimes spirilloid, Typical size 3-5 µm ph 6-8, C, Anaerobic The manner in which SRB brings about microbial corrosion need be understood with respect to: H 2 S and hydrosulfides Oxygen concentration cells Formation of insoluble metal sulfides (FeS) Cathodic depolarization (Hydrogen reduction). Metal adhesion of SRB results in generation of corrosion cells. Many hydrocarbons encountered in oil and gas exploration harbour SRB through nutrient supply. Cathodic hydrogen generation on metal surfaces promote SRB growth. Hydrogenase-positive SRB utilize hydrogen for reduction of sulfate. Bacterial scavenging of cathodically-generated hydrogen results in cathodic depolarisation enhancing anodic corrosion. Effect of SRB attachment on steel surfaces resulting in hydrogen depolarization is illustrated in Fig
7 Fig. 35.1: Model showing surface anchoring of SRB cells and cathodic depolarization. Electrochemical reations involved in microboal corrosion of steel are outlined below: Fe = Fe e (Anodic) 2H + + 2e = H 2 (Cathodic) SO H = S H 2 O (Bacterial depolarization) Fe ++ + S -- = FeS (Reaction of iron with reduced sulfide) Fe OH - = Fe (OH) 2 (Corrosion product) Net corrosion reaction can be summarized as 4 Fe + SO H 2 O = 3 Fe (OH) 2 + FeS + 2OH - The following factors promote SRB corrosion of steels Presence of hydrogenase enzyme as a catalyst for hydrogen utilization. Bacterial generation of H 2 S and formation of FeS on metal surfaces as a reaction product. Cathodic hydrogen removal leading to depolarization. Role of iron sulfide galvanically promoting iron dissolution. Possibility of galvanic couple formation involving steel (anode) and the iron sulfide (cathode) promotes corrosion. The role of bacteria as a catalyst promoting the above electrochemical reactions need be stressed. 7
8 Other factors which influence MIC in the presence of SRB are. Anodic depolarization (besides cathodic polarization). Formation of volatile phosphorus compounds promoting steel dissolution. Role of iron-binding biopolymers. Stress corrosion cracking in the presence of sulfides and hydrogen induced cracking. SRB corrosion of steel will also be influenced by the nature and structure of the sulfide films. Metal-cells-solution interface and environmental variables such as ph, ionic concentration, oxygen levels and nature of exopolymers will control the surface corrosion products. Presence of aggressive anions such as chlorides would enhance the corrosion rate. Serious corrosion problems due to SRB is reported in environments pertaining to oil, gas exploration and shipping. Serious biocorrosion problems in petroleum industries result in increased refining costs and oil souring. SRB growth in marine injection systems results in material damage besides oil and gas contamination with viable cells and reaction products. Level of SRB activity in soils and waters can be monitored through redox potential measurements. < 100 mv Severe biocorrosion possibility mv Moderate mv Very low >400 mv Almost insignificant Soil and water environments can be classified in terms of resistivity, redox potentials, ph, water content and SRB cell counts. Similarly, soil types (clayey, chalky, sandy and loamy) will have a bearing on SRB corrosion. 8
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