Sulphate-reducing

Aqueous environments will range from very thin condensed films of moisture to bulk solutions, and will include natural environments such as the atmosphere, natural waters, soils, body fluids, etc. as well as chemicals and food products. However, since environments are dealt with fully in Chapter 2, this discussion will be confined to simple chemical solutions, whose behaviour can be more readily interpreted in terms of fundamental physicochemical principles, and additional factors will have to be considered in interpreting the behaviour of metals in more complex environments. For example, iron will corrode rapidly in oxygenated water, but only very slowly when oxygen is absent however, in an anaerobic water containing sulphate-reducing bacteria, rapid corrosion occurs, and the mechanism of the process clearly involves the specific action of the bacteria see Section 2.6). 

Hydrogen sulphide This is produced by the putrefaction of organic sulphur compounds or by the action of sulphate-reducing bacteria in anaerobic conditions (e.g. in polluted river estuaries). It is fairly rapidly oxidised to SOj and concentrations are considerably lower than those of (Table 2.6). Nevertheless it is responsible for the tarnishing of copper and silver at normal atmospheric concentrations. 

Oxidation-reduction potential Because of the interest in bacterial corrosion under anaerobic conditions, the oxidation-reduction situation in the soil was suggested as an indication of expected corrosion rates. The work of Starkey and Wight , McVey , and others led to the development and testing of the so-called redox probe. The probe with platinum electrodes and copper sulphate reference cells has been described as difficult to clean. Hence, results are difficult to reproduce. At the present time this procedure does not seem adapted to use in field tests. Of more importance is the fact that the data obtained by the redox method simply indicate anaerobic situations in the soil. Such data would be effective in predicting anaerobic corrosion by sulphate-reducing bacteria, but would fail to give any information regarding other types of corrosion. 

Measurement of some of these parameters identifies the risk of a particular type of corrosion, for example pH measurements assess the risk of acid attack and redox potential measurements is used to assess the suitability of the soil for microbiological corrosion, a low redox potential indicates that the soil is anaerobic and favourable for the life cycle of anaerobic bacteria such as to sulphate-reducing bacteria. Other measurements are more general, resistivity measurements being the most widely quoted. However, as yet no single parameter has been identified which can confidently be expected to assess the corrosion risk of a given soil. It is therefore common practice to measure several parameters and make an assessment from the results. 

Corrosion of iron and steel, especially in anaerobic conditions such as waterlogged soils, is usually caused by sulphate-reducing bacteria of which the genus Desulphovibrio is the most commonly occuring. The presence of organic materials such as acetate often stimulates these organisms reducing... 

This is a simplified treatment but it serves to illustrate the electrochemical nature of rusting and the essential parts played by moisture and oxygen. The kinetics of the process are influenced by a number of factors, which will be discussed later. Although the presence of oxygen is usually essential, severe corrosion may occur under anaerobic conditions in the presence of sulphate-reducing bacteria Desulphovibrio desulphuricans) which are present in soils and water. The anodic reaction is the same, i.e. the formation of ferrous ions. The cathodic reaction is complex but it results in the reduction of inorganic sulphates to sulphides and the eventual formation of rust and ferrous sulphide (FeS). 

Bacterial activity often plays a major part in determining the corrosion of buried steel. This is particularly so in waterlogged clays and similar soils, where no atmospheric oxygen is present as such. If these soils contain sulphates, e.g. gypsum and the necessary traces of nutrients, corrosion can occur under anaerobic conditions in the presence of sulphate-reducing bacteria. One of the final products is iron sulphide, and the presence of this is characteristic of attack by sulphate-reducing bacteria, which are frequently present (see Section 2.6). 

While well-aerated near-neutral waters are normally much more corrosive than poorly-aerated waters, waters with near zero oxygen contents may cause high rates of corrosion if active sulphate-reducing bacteria, which can act as very efficient depolarising agents, are present. A corrosion rate of 1 5 mm/y has been observed on cast iron exposed to such a water. 

The presence of active sulphate-reducing bacteria usually results in graphitic corrosion and this has led to a useful method of diagnosing this cause of corrosion. The leaching out of iron from the graphitic residue which is responsible for the characteristic appearance of this type of corrosion leads to an enriched carbon, silicon and phosphorus content in the residue as compared with the original content of these elements in the cast iron. Sulphur is usually lost to some extent but when active sulphate-reducing bacteria are present, this loss is offset by the accumulation of ferrous sulphide in the residue with a consequent increase in the sulphur content of the residue out... 

Table 3.44 Increase in sulphur content of graphitic corrosion residue due to the presence of active sulphate-reducing bacteria...

The British Non-Ferrous Metals Research Association carried out two series of tests, the results of which have been given by Gilbert and Gilbert and Porter these are summarised in Table 4.12. In the first series tough pitch copper tubes were exposed at seven sites for periods of up to 10 years. The two most corrosive soils were a wet acid peat (pH 4-2) and a moist acid clay (pH 4-6). In these two soils there was no evidence that the rate of corrosion was decreasing with duration of exposure. In the second series phosphorus-deoxidised copper tube and sheet was exposed at five sites for five years. Severe corrosion occurred only in cinders (pH 7 1). In these tests sulphides were found in the corrosion products on some specimens and the presence of sulphate-reducing bacteria at some sites was proved. It is not clear, however, to what extent the activity of these bacteria is a factor accelerating corrosion of copper. 

Patches of conductive lead sulphide can be formed on lead in the presence of sewage. This can result in the flow of a large corrosion current . Sulphate-reducing bacteria in soils can produce metal sulphides and H2S, which results in the formation of deep pits containing a black mass of lead sulphide . Other micro-organisms may also be involved in the corrosion of lead in soil . 

General corrosion damage was the cause of failure of an A1 alloy welded pipe assembly in an aircraft bowser which was attacked by a deicing-fluid — water mixture at small weld defects . Selective attack has been reported in welded cupro-nickel subjected to estuarine and seawater environments . It was the consequence of the combination of alloy element segregation in the weld metal and the action of sulphate reducing bacteria (SRB). Sulphide-coated Cu-enriched areas were cathodic relative to the adjacent Ni-rich areas where, in the latter, the sulphides were being continuously removed by the turbulence. Sulphite ions seemed to act as a mild inhibitor. 

The most widely accepted criterion for protection of steel at room temperature (the protection potential) in aerobic conditions is - 0 - 85 V with respect to a Cu/CuSOa reference electrode. In anaerobic conditions -0-95 V (vs. Cu/CuSOa) is the preferred protection potential because of the possible presence of active sulphate-reducing bacteria (SRB). 

Soil supporting active sulphate-reducing bacteria 451-9... 

Other tests to determine bacterial-notably sulphate reducing-activity, soil resistivity, pH, redox potential, etc., will provide valuable data to supplement the results obtained with test specimens. A useful account of some of these was given in Reference 336 and they are also discussed in Sections 2.6 and 10.7. A scheme for assessment of corrosivity of soils based on some of the above parameters has been given by Tiller . 

Postgate, J. R. Sulphate Reducing Bacteria 2nd ed. Cambridge University... 

Parkes RJ, GR Gibson, I Mueller-Harvey, WJ Buckingham, RA Herbert (1989) Determination of the substrates for sulphate-reducing bacteria within marine and estuarine sediments with different rates of sulphate reduction. J Gen Microbiol 135 175-187. 

Galushko A, D Minz, B Schink, F Widdel (1999) Anaerobic degradation of naphthalene by a pure culture of a novel type of marine sulphate-reducing bacterium. Environ Microbiol 1 415-420. 

Some bacteria can give products a rancid smell others can impart the "sweet" odour of dirty drains by the production of certain pyrazine derivatives. Other bacteria, known as sulphate reducers, for example Desulphovibrio desulphuricans, are able, under anaerobic conditions, to utilise oxygen from sulphates leading ultimately to the formation of hydrogen sulphide. Opperman and Goll (1984) in their study of contaminated emulsion paints concluded that more than a quarter were infected with these and other anaerobic organisms. 

Such growth of sulphate reducing bacteria is responsible for the most commonly noticed malodour associated with emulsion paint spoilage. Hydrogen sulphide levels in paint have never been shown to have reached toxic concentrations, but even very small... 

Formation of insoluble sulphides from H2S production by sulphate reducing bacteria can bring about blackening of products (Figure 11) and some bacteria such as Serratia and Flavobacteria species and yeasts, including Rhodotorula can give pink or yellow discolorations. Other bacteria such as the Pseudomonads can produce fluorescent pigments. 

Olson, G.J.H., Dockins, W.C., McFeters, G.A., and Iverson, W.P., Sulphate-reducing and methanogenic bacteria from deep aquifers in Montana, Geomicrobial. J., 2, 327-340, 1981. 

Togo CA, Mutambanengwe CCZ, Whiteley CG (2008) Decolourization and degradation of textile dyes using a sulphate reducing bacteria (SRB) - biodigester microflora co-culture. Afr J Biotechnol 7(2) 114-121... 

Pitcher MC, Beatty ER, Cummings JH The contribution of sulphate reducing bacteria and 5-aminosalicylic acid to faecal sulphide in patients with ulcerative colitis. Gut 2000 46 64-72. 

Cervantes FJ, Enriquez JE, Petatan EG et al (2007) Biogenic sulphide plays a major role on the riboflavin-mediated decolourisation of azo dyes under sulphate-reducing conditions. Chemosphere 68 1082-1089... 

Diniz PE, Lopes AT, Lino AR (2002) Anaerobic reduction of a sulfonated azo dye Congo Red by sulphate reducing bacteria. Appl Biochem Biotechnol 97 147-163... 

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