Biogenic sulfide corrosion

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Biogenic sulfide corrosion is a bacterially mediated process of forming hydrogen sulfide gas and the subsequent conversion to sulfuric acid that attacks concrete and steel within wastewater environments. The hydrogen sulfide gas is biochemically oxidized in the presence of moisture to form sulfuric acid. The effect of sulfuric acid on concrete and steel surfaces exposed to severe wastewater environments can be devastating. [1] In the USA alone, corrosion is causing sewer asset losses estimated at $14 billion per year. [2] This cost is expected to increase as the aging infrastructure continues to fail. [3]

Contents

Environment

Corrosion may occur where stale sewage generates hydrogen sulfide gas into an atmosphere containing oxygen gas and high relative humidity. There must be an underlying anaerobic aquatic habitat containing sulfates and an overlying aerobic aquatic habitat separated by a gas phase containing both oxygen and hydrogen sulfide at concentrations in excess of 2 ppm. [4]

Conversion of sulfate to hydrogen sulfide

Fresh domestic sewage entering a wastewater collection system contains proteins including organic sulfur compounds oxidizable to sulfates (SO2−
4) and may contain inorganic sulfates. [5] Dissolved oxygen is depleted as bacteria begin to catabolize organic material in sewage. In the absence of dissolved oxygen and nitrates, sulfates are reduced to hydrogen sulfide (H2S) as an alternative source of oxygen for catabolizing organic waste by sulfate reducing bacteria (SRB), identified primarily from the obligate anaerobic species Desulfovibrio . [4]

Hydrogen sulfide production depends on various physicochemical, topographic and hydraulic parameters [6] such as:

Conversion of hydrogen sulfide to sulfuric acid H2SO4

Some hydrogen sulfide gas diffuses into the headspace environment above the wastewater. Moisture evaporated from warm sewage may condense on unsubmerged walls of sewers, and is likely to hang in partially formed droplets from the horizontal crown of the sewer. As a portion of the hydrogen sulfide gas and oxygen gas from the air above the sewage dissolves into these stationary droplets, they become a habitat for sulfur oxidizing bacteria (SOB), of the genus Acidithiobacillus . Colonies of these aerobic bacteria metabolize the hydrogen sulfide gas to sulfuric acid. [4]

Corrosion

Sulfuric acid produced by microorganisms will interact with the surface of the structure material. For ordinary Portland cement, it reacts with the calcium hydroxide in concrete to form calcium sulfate. This change simultaneously destroys the polymeric nature of calcium hydroxide and substitutes a larger molecule into the matrix causing pressure and spalling of the adjacent concrete and aggregate particles. [7] The weakened crown may then collapse under heavy overburden loads. [8] Even within a well-designed sewer network, a rule of thumb in the industry suggests that 5% of the total length may/will suffer from biogenic corrosion. In these specific areas, biogenic sulfide corrosion can deteriorate metal or several millimeters per year of concrete (see Table).

SourceThickness loss

(in mm/year)

Material type
US EPA, 1991 [9] 2.5 – 10Concrete
Morton et al., 1991 [10] 2.7Concrete
Mori et al., 1992 [11] 4.3 – 4.7Concrete
Ismail et al., 1993 [12] 2 – 4Mortar
Davis, 1998 [13] 3.1Concrete
Monteny et al., 2001 [14] 1.0 – 1.3Mortar
Vincke et al., 2002 [15] 1.1 – 1.8Concrete

For calcium aluminate cements, processes are completely different because they are based on another chemical composition. At least three different mechanisms contribute to the better resistance to biogenic corrosion: [16]

A mortar made of calcium aluminate cement combined with calcium aluminate aggregates, i.e. a 100% calcium aluminate material, will last much longer as aggregates can also limit microorganisms’ growth and inhibits the acid generation at the source itself.

Prevention

There are several options to address biogenic sulfide corrosion problems: impairing H2S formation, venting out the H2S or using materials resistant to biogenic corrosion. For example, sewage flows more rapidly through steeper gradient sewers reducing time available for hydrogen sulfide generation. Likewise, removing sludge and sediments from the bottom of the pipes reduces the amount of anoxic areas responsible for sulfate reducing bacteria growth. Providing good ventilation of sewers can reduce atmospheric concentrations of hydrogen sulfide gas and may dry exposed sewer crowns, but this may create odor issues with neighbors around the venting shafts. Three other efficient methods can be used involving continuous operation of mechanical equipment: chemical reactant like calcium nitrate can be continuously added in the sewerage water to impair the H2S formation, an active ventilation through odor treatment units to remove H2S, or an injection of compressed air in pressurized mains to avoid the anaerobic condition to develop. In sewerage areas where biogenic sulfide corrosion is expected, acid resistant materials like calcium aluminate cements, PVC or vitrified clay pipe may be substituted to ordinary concrete or steel sewers.

Existing structures that have extensive exposure to biogenic corrosion such as sewer manholes and pump station wet wells can be rehabilitated. Rehabilitation can be done with materials such as a structural epoxy coating, this epoxy is designed to be both acid resistant and strengthen the compromised concrete structure.

See also

Related Research Articles

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Hydrogen sulfide is a chemical compound with the formula H2S. It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. Swedish chemist Carl Wilhelm Scheele is credited with having discovered the chemical composition of purified hydrogen sulfide in 1777.

<span class="mw-page-title-main">Sewerage</span> Infrastructure that conveys sewage or surface runoff using sewers

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Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH−) are the conjugate acids of sulfide.

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<i>Acidithiobacillus</i> Genus of bacteria

Acidithiobacillus is a genus of the Acidithiobacillia in the phylum "Pseudomonadota". This genus includes ten species of acidophilic microorganisms capable of sulfur and/or iron oxidation: Acidithiobacillus albertensis, Acidithiobacillus caldus, Acidithiobacillus cuprithermicus, Acidithiobacillus ferrianus, Acidithiobacillus ferridurans, Acidithiobacillus ferriphilus, Acidithiobacillus ferrivorans, Acidithiobacillus ferrooxidans, Acidithiobacillus sulfuriphilus, and Acidithiobacillus thiooxidans.A. ferooxidans is the most widely studied of the genus, but A. caldus and A. thiooxidans are also significant in research. Like all "Pseudomonadota", Acidithiobacillus spp. are Gram-negative and non-spore forming. They also play a significant role in the generation of acid mine drainage; a major global environmental challenge within the mining industry. Some species of Acidithiobacillus are utilized in bioleaching and biomining. A portion of the genes that support the survival of these bacteria in acidic environments are presumed to have been obtained by horizontal gene transfer.

<span class="mw-page-title-main">Sulfate-reducing microorganism</span> Microorganisms that "breathe" sulfates

Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria (SRB) and sulfate-reducing archaea (SRA), both of which can perform anaerobic respiration utilizing sulfate (SO2−
4) as terminal electron acceptor, reducing it to hydrogen sulfide (H2S). Therefore, these sulfidogenic microorganisms "breathe" sulfate rather than molecular oxygen (O2), which is the terminal electron acceptor reduced to water (H2O) in aerobic respiration.

<span class="mw-page-title-main">Sewer gas</span>

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Sulfur-reducing bacteria are microorganisms able to reduce elemental sulfur (S0) to hydrogen sulfide (H2S). These microbes use inorganic sulfur compounds as electron acceptors to sustain several activities such as respiration, conserving energy and growth, in absence of oxygen. The final product of these processes, sulfide, has a considerable influence on the chemistry of the environment and, in addition, is used as electron donor for a large variety of microbial metabolisms. Several types of bacteria and many non-methanogenic archaea can reduce sulfur. Microbial sulfur reduction was already shown in early studies, which highlighted the first proof of S0 reduction in a vibrioid bacterium from mud, with sulfur as electron acceptor and H
2 as electron donor. The first pure cultured species of sulfur-reducing bacteria, Desulfuromonas acetoxidans, was discovered in 1976 and described by Pfennig Norbert and Biebel Hanno as an anaerobic sulfur-reducing and acetate-oxidizing bacterium, not able to reduce sulfate. Only few taxa are true sulfur-reducing bacteria, using sulfur reduction as the only or main catabolic reaction. Normally, they couple this reaction with the oxidation of acetate, succinate or other organic compounds. In general, sulfate-reducing bacteria are able to use both sulfate and elemental sulfur as electron acceptors. Thanks to its abundancy and thermodynamic stability, sulfate is the most studied electron acceptor for anaerobic respiration that involves sulfur compounds. Elemental sulfur, however, is very abundant and important, especially in deep-sea hydrothermal vents, hot springs and other extreme environments, making its isolation more difficult. Some bacteria – such as Proteus, Campylobacter, Pseudomonas and Salmonella – have the ability to reduce sulfur, but can also use oxygen and other terminal electron acceptors.

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<span class="mw-page-title-main">Calcium aluminate cements</span> Rapidly setting hydraulic cements

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<span class="mw-page-title-main">Concrete degradation</span> Damage to concrete affecting its mechanical strength and its durability

Concrete degradation may have many different causes. Concrete is mostly damaged by the corrosion of reinforcement bars due to the carbonatation of hardened cement paste or chloride attack under wet conditions. Chemical damages are caused by the formation of expansive products produced by various chemical reactions, by aggressive chemical species present in groundwater and seawater, or by microorganisms. Other damaging processes can also involve calcium leaching by water infiltration and different physical phenomena initiating cracks formation and propagation. All these detrimental processes and damaging agents adversely affects the concrete mechanical strength and its durability.

Sulfur concrete, sometimes named thioconcrete or sulfurcrete, is a composite construction material, composed mainly of sulfur and aggregate. Cement and water, important compounds in normal concrete, are not part of sulfur concrete. The concrete is heated above the melting point of elemental sulfur at ca. 140 °C (284 °F) in a ratio of between 12% and 25% sulfur, the rest being aggregate.

Cement hydration and strength development mainly depend on two silicate phases: tricalcium silicate (C3S) (alite), and dicalcium silicate (C2S) (belite). Upon hydration, the main reaction products are calcium silicate hydrates (C-S-H) and calcium hydroxide Ca(OH)2, written as CH in the cement chemist notation. C-S-H is the phase playing the role of the glue in the cement hardened paste and responsible of its cohesion. Cement also contains two aluminate phases: C3A and C4AF, respectively the tricalcium aluminate and the tetracalcium aluminoferrite. C3A hydration products are AFm, calcium aluminoferrite monosulfate, and ettringite, a calcium aluminoferrite trisulfate (AFt). C4AF hydrates as hydrogarnet and ferrous ettringite.

References

Notes

  1. ↑ O’Dea, Vaughn, “Understanding Biogenic Sulfide Corrosion,”MP (November 2007), pp. 36-39.
  2. ↑ Brongers et al., 2002
  3. ↑ Sydney et al., 1996; US EPA, 1991
  4. 1 2 3 Sawyer&McCarty p.461&462
  5. ↑ Metcalf & Eddy p.259
  6. ↑ US EPA, 1985
  7. ↑ USDI pp.9&10
  8. ↑ Hammer p.58
  9. ↑ United States Environmental Protection Agency, 1991. Hydrogen Sulphide Corrosion in Wastewater Collection and Treatment Systems (Technical Report)
  10. ↑ Morton R.L., Yanko W.A., Grahom D.W., Arnold R.G. (1991) Relationship between metal concentrations and crown corrosion in Los Angeles County sewers. Research Journal of Water Pollution Control Federation, 63, 789–798.
  11. ↑ Mori T., Nonaka T., Tazaki K., Koga M., Hikosaka Y., Noda S. (1992) Interactions of nutrients, moisture, and pH on microbial corrosion of concrete sewer pipes. Water Research, 26, 29–37.
  12. ↑ Ismail N., Nonaka T., Noda S., Mori T. (1993) Effect of carbonation on microbial corrosion of concrete. Journal of Construction Management and Engineering, 20, 133-138.
  13. ↑ Davis J.L. (1998) Characterization and modeling of microbially induced corrosion of concrete sewer pipes. Ph.D. Dissertation, University of Houston, Houston, TX.
  14. ↑ Monteny J., De Belie N., Vincke E., Verstraete W., Taerwe L. (2001) Chemical and microbiological tests to simulate sulfuric acid corrosion of polymer-modified concrete. Cement and Concrete Research, 31, 1359-1365.
  15. ↑ Vincke E., Van Wanseele E., Monteny J., Beeldens A., De Belie N., Taerwe L., Van Gemert D., Verstraete W. (2002) Influence of polymer addition on biogenic sulfuric acid attack. International Biodeterioration and Biodegradation, 49, 283-292.
  16. ↑ Herisson J., Van Hullebusch E., Gueguen Minerbe M., Chaussadent T. (2014) Biogenic corrosion mechanism: study of parameters explaining calcium aluminate cement durability. CAC 2014 – International Conference on Calcium Aluminates, May 2014, France. 12 p.

Pomeroy's report contains errors in the equation: the pipeline slope (S, p. 8) is quoted as m/100m, but should be m/m. This introduces a factor of 10 underestimate in the calculation of the 'Z factor', used to indicate if there is a risk of sulphide-induced corrosion, if the published units are used. The web link is to the revised 1992 edition, which contains the units error - the 1976 edition has the correct units.

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