Biogenic sulfide corrosion

From Wikipedia, the free encyclopedia

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 around $14 billion per year.[2] This cost is expected to increase as the
aging infrastructure continues to fail.[3]

Contents
1 Environment

o 1.1 Conversion of sulfate SO42 to hydrogen sulfide H2S

o 1.2 Conversion of hydrogen sulfide to sulfuric acid H2SO4

2 Corrosion

3 Prevention

4 See also

5 References

6 Notes

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 SO42 to hydrogen sulfide H2S

Fresh domestic sewage entering a wastewater collection system contains proteins including
organic sulfur compounds oxidizable to sulfates 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 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

Sewage oxygen concentration. The threshold is 0.1 mg.l1; above this value, sulfides
produced in sludge and sediments are oxidized by oxygen; below this value, sulfides are
emitted in the gaseous phase.

Temperature. The higher the temperature, the faster the kinetics of H2S production.

Sewage pH. It must be included between 5.5 and 9 with an optimum at 7.5-8.

Sulfate concentration.

Nutrients concentration, associated to the biochemical oxygen demand.

Conception of the sewerage As H2S is formed only in anaerobic conditions, slow flow
and long retention time gives more time to aerobic bacteria to consume all available
dissolved oxygen in water, creating anaerobic conditions. The flatter the land, the less
slope can be given to the sewer network, and this favors slower flow and more pumping
stations (where retention time is generally longer)

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
See also: Sulfidation

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).

Thickness loss
Source Material type
(in mm.y1)

US EPA, 1991[9] 2.5 10 Concrete

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]

The first barrier is the larger acid neutralizing capacity of calcium aluminate cements vs.
ordinary Portland Cement; one gram of calcium aluminate cement can neutralize around
40% more acid than a gram of ordinary Portland Cement. For a given production of acid
by the biofilm, a calcium aluminate cement concrete will last longer.

The second barrier is due to the precipitation, when the surficial pH gets below 10, of a
layer of alumina gel (AH3 in cement chemistry notation). AH3 is a stable compound
down to a pH of 4 and it will form an acid-resistant barrier as long as the surface pH is
not lowered below 3-4 by the bacterial activity.

The third barrier is the bacteriostatic effect locally activated when the surface reaches pH
values less than 3-4. At this level, the alumina gel is no longer stable and will dissolve,
liberating aluminum ions. These ions will accumulate in the thin biofilm. Once the
concentration reaches 300-500 ppm, it will produce a bacteriostatic effect on bacteria
metabolism. In other word, bacteria will stop oxidizing the sulfur from H2S to produce
acid, and the pH will stop decreasing.

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 strength the compromised concrete structure (See Raven
Lining Systems).