Metals, Microbes and Mic – a Review of Microbiologically Influenced Corrosion
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METALS, MICROBES AND MIC – A REVIEW OF MICROBIOLOGICALLY INFLUENCED CORROSION M Critchley* & R Javaherdashti** *CSIRO Manufacturing & Infrastructure Technology Clayton VIC **Monash University Clayton VIC Australia Summary: Microbiologically influenced corrosion (MIC) is the deterioration of materials caused by the presence and activity of micro-organisms. It is a complex problem that presents huge costs to industry. This review will describe the processes and micro-organisms involved in MIC as well as detection techniques. Mitigation methods against MIC will also be addressed Keywords: Biocorrosion, biofilms, microbiologically influenced corrosion 1 INTRODUCTION Microbiologically influenced corrosion (MIC), also known as biocorrosion, is the corrosion or deterioration of a material which is initiated and/or accelerated by the activities of micro-organisms. It affects not only metals but many materials including polymers, concrete and glass. MIC can manifest as pitting corrosion, crevice corrosion, stress corrosion, selective de- alloying and generalised corrosion, depending on the environment and micro-organisms present. It is a complex process and remains one of the least understood areas of corrosion science as it falls outside the traditional disciplines of both microbiology and corrosion. MIC presents huge costs for many industries. In the oil and gas industry, MIC causes pitting corrosion of pipelines and vessels and the plugging of reservoirs. In the water industry, MIC induces pipeline corrosion, pipe blockages and the corrosion of sewer mains. In the aviation industry, MIC can cause the corrosion of aircraft fuel tanks. MIC also causes the corrosion of heat exchangers, cooling towers and fire protection systems in the power industry. A recent NACE survey estimated the direct costs of corrosion to be 3.1% of US GDP, with indirect costs at 3% US GDP. MIC is estimated to account for at least 20% of corrosion, which calculates to approximately $US 55 billion/year (1). 2 BIOFOULING MIC is initiated by the fouling of surfaces, a process which naturally occurs in many environments (2). Biofouling is the undesirable formation of deposits on a surface. Biofouling comprises of both organic and inorganic components which include micro-organisms, precipitated materials, particulates and corrosion products. The biological component occurs from the formation of biofilms, where micro-organisms accumulate on surfaces and develop complex communities within a matrix of organic polysaccharides (2). Biofilms comprise of many different micro-organisms depending on the environment, including aerobic and anaerobic bacteria, fungi, algae and protozoa. The steps involved in the formation of biofilms are shown in Figure I (2). Organic conditioning films accumulate on surfaces upon exposure to the environment, changing the surface charge and hydrophobicity. Planktonic organisms associate with surfaces, with irreversible adhesion occurring through interactions with surface structures and charges. Attachment allows microbial colonies to develop where they can secrete extracellular materials and accumulate compounds from the bulk phase. Biofouling initially occurs on a micro-scale which allows the colonisation of very small areas such as crevices, weldments and surface imperfections. The structure of biofilms is complex. Biofilms contains structural and temporal variations such as gradients in pH, oxygen concentrations (Figure II) and nutrients (2). This creates microenvironments where the activity of certain micro-organisms may be enhanced. Underneath the biofilm, chemical properties such as the pH, dissolved oxygen and nutrient concentrations may be dramatically different from those in the bulk solution. This results in a shift in the open-circuit potential of passive metals in the noble direction (ennoblement). This has been well-documented for a range of metals and alloys, particularly stainless steel (3). Corrosion & Prevention 2004 Paper 037 Page 1 Biofouling causes many problems for industrial systems. One of the most important problems is it increases the retention time and allows the proliferation of micro-organisms within an environment where they may not normally accumulate. Biofouling is an important contributor to microbial corrosion, however, it is important to note that MIC can also occur from suspended, unattached micro-organisms present in the planktonic phase. STEPS IN BIOFILM FORMATION BIOFILM FORMATION ATTACHMENT GROWTH & ATTACHMENT SURFACE COLONISATION CONDITIONING Figure I. Steps involved in biofilm formation (Critchley 2001) BULK LIQUID PHASE O2 AEROBIC HETEROTROPHIC BIOFILM ANAEROBIC HETEROTROPHIC ACTIVITY OBLIGATE ANAEROBES METAL Figure II. Spatial relationships of micro-organisms within an established biofilm (Critchley 2001) 3 MICRO-ORGANISMS IMPLICATED IN MIC Micro-organisms can be classified in many ways including their cellular structure, morphology, source of energy and oxygen requirements (4). Numerous micro-organisms have been implicated in MIC, the most common are described briefly below: Corrosion & Prevention 2004 Paper 037 Page 2 3.1 Sulphate reducing bacteria Sulphate reducing bacteria (SRBs) are naturally found in the environment in soil and surface waters. They are anaerobic, growing under very low oxygen or completely oxygen depleted conditions (5). The optimum conditions for their growth are temperatures of 25 to 35°C and a pH range of 6 to 9.5 (5). Some species of SRBs are thermophilic (ie. Desulfotomaculum) and can survive at temperatures up to 60°C. SRBs use hydrogen, alcohols, lactates and acetates as sources of energy. SRBs contain the hydrogenase enzyme which enables them to utilise hydrogen from the environment. For SRBs to flourish, sulphate concentrations of at least 50 to 100 ppm are required (5). SRBs reduce sulphates to sulphides which react with metals to produce metal sulphides. Corrosion by SRBs is usually detected by the hydrogen sulphide odour, blackening of waters or the presence of black coloured deposits (Plate 1). Common species of sulphate reducing bacteria include Desulphovibrio and Desulphotomaculum. Plate I. Corrosion cause by sulphate reducing bacteria (source unknown) 3.2 Iron oxidising bacteria Iron oxidising bacteria require the oxidation of Fe2+ to Fe3+ to produce energy for metabolism (6). Common species of iron oxidising bacteria include Gallionella, Sphaerotilus, Siderocapsa and Crenothrix. They generally grow in filamentous clumps and can be visually detected by microscopy by the presence of a twisted helical/sheath that are excreted by the cells and encrust them with their growth (Plate 2). For this reason, corrosion by iron bacteria often manifests as tubercles (7). Chloride ions can accumulate within these tubercles, which combine with corrosion products to produce ferric chloride. Ferric chloride is extremely corrosive to stainless steel (7). Tubercles additionally allow the development of anaerobic conditions and can lead to the growth of SRBs (7). Iron oxidising bacteria prefer pH ranges from neutral to acidic, oxygen concentrations from 0 to saturated and temperatures up to 90°C. Bacteria that oxidise manganese have also been identified and implicated in the corrosion of stainless steel (8). In contrast to this, there are bacteria that can accumulate iron and manganese which also have been associated with corrosion (9). Corrosion & Prevention 2004 Paper 037 Page 3 Plate II. SEM image of iron bacteria showing precipitated iron (Critchley 2003) 3.3 Acid producing bacteria Acid producing bacteria (APBs) generate acidic by-products with their metabolism that is corrosive to many materials. Clostridium spp. have been shown to produce acetic acids with fermentation and has been extensively isolated from industrial water systems (10). More importantly, bacteria which oxidise sulphur or sulphides including Thiobacillus and Beggiatoa can produce up to 10% sulphuric acid solutions (11). These bacteria have been widely implicated in the corrosion of reinforced concrete structures. Sulphur oxidisers are acid tolerant and are typical of microbes found in acid mine drainage systems. Sulphur oxidising bacteria are almost always found with SRBs, existing synergistically cycling sulphur. Biofilms allow the existence of both organisms due to the existence of microenvironments within its structure, where localised conditions are controlled. 3.4 Fungi Certain species of fungi are corrosive, mainly through the production of acids with metabolism. Hormoconis or Cladosporium resinae is a fungus notorious for corrosion in aluminium fuel systems (Plate 3)(12). It has presented major problems for the aviation industry as its growth in fuel systems causes significant corrosion and also operational problems such as errors in fuel gauging and filter blockages. Fungi have also been implicated in the corrosion of glass and more recently, compact discs (13). Fungi produce spores which enables them to survive environmental extremes only to regenerate when conditions are favourable. This makes the eradication of fungi extremely difficult. Other fungi that have been associated with corrosion include Aspergillus spp. (14) 3.5 Heterotrophic slime forming bacteria Heterotrophic bacteria are aerobic and use organic carbon as a nutrient source. They are commonly found in the environment particularly within biofilms. Many can produce copious amounts of exopolysaccharides or slime which causes many operational problems as well as corrosion (15). Polysaccharides can contain acidic groups which directly