Journal of Ecological Engineering Received: 2019.03.

24
Revised: 2019.04.21
Volume 20, Issue 6, June 2019, pages 90–96 Accepted: 2019.05.06
Available online: 2019.05.20
https://doi.org/10.12911/22998993/108697

Understanding the Synergic Corrosion Issues with Regard

to the Water Treatment Station

Renata Włodarczyk1*, Klaudiusz Majek2

1
Institute of Advanced Energy Technologies, Faculty of Infrastructure and Environment, Czestochowa
University of Technology, ul. Brzeznicka 60A, 42-200 Czestochowa, Poland
2
Comprehensive Implementation of Municipal and Industrial Investments – Instal Warszawa S.A. Capital
Group Seen Holding Sp. z o.o., ul. Siennicka 29, 04-394 Warszawa
* Corresponding author’s e-mail: [email protected]

ABSTRACT
The paper presents the examples of damage of elements caused by incorrect assessment of pipeline work condi-
tions. The presented damage cases resulted in the need to replace pipelines. This work is an analysis pertaining to
the impact of chemical and microbiological synergy of corrosion on stainless steel pipelines. The paper investi-
gates the corrosion mechanisms that may occur under normal operating conditions at each water treatment station,
and the methods of counteracting the corrosion were indicated. The analysis of the corrosion mechanisms was
formulated taking into account the design stage, – the correctness of the steel grade choice by the designer, the
stage of implementation – the most common implementation errors, and the operational stage – optimization of
the technological system work and the effects of the introduced changes. The analysis was carried out at a water
treatment plant in Poland with a maximum flow of 20,000 m3 a day-1, which draws raw water from deep water
intakes and from a surface intake. The treatment technology includes an aeration system (aeration) and a two-stage
treatment process using sand and carbon filters. The disinfection process and prophylaxis in the water treatment
plant is based on the use of chlorine gas.

Keywords: chlorination, corrosion microbiology, pitting corrosion, synergy effect, water treatment station

INTRODUCTION Degradation of materials causes changes in

the tightness and durability of pipelines. The con-
The requirements to maintain water parame- cept of corrosion, in a broad sense, means the de-
ters for consumption and to reduce water produc- struction of material as a result of its interaction
tion costs, enforce the use of additional products with the surrounding environment [Suslov, 2001].
to speed up the treatment process [GE Power & This phenomenon involves undesirable processes
Water., 1997–2012]. Shortening the treatment of material destruction as a result of chemical or
process by applying the treatment technology with physicochemical environmental impacts that re-
simultaneous chemical support, results in faster duce the usable properties of pipelines. The op-
wear of pipelines and devices. During the opera- eration of the environment causes the material to
tion of the installation, there are frequent changes change from a metallic to an ionic state.
in the conditions, which leads to mechanical and
chemical changes in the materials [Hilbert et al. Corrosion processes classification
2010]. In order to effectively counteract any deg-
radation processes, each type of pipeline or de- The corrosive destruction processes are gen-
vice should be tested in order to understand the erally very complex and overlap. For this reason,
role of particular factors and their impact on the there are many possibilities to classify this phe-
corrosion processes in a given environment. nomenon. The classification of corrosive damage

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can be made on the basis of the nature of changes the mechanical properties of the metal, mainly
that the metal surface undergoes or on the basis of in the structures the strength of which depends
the physical and mechanical changes of metal and on the strength of the weakest cross-section. The
alloy properties [Suslov, 2001]. In general, the temperature rise is a factor favoring the rate of
mechanisms of corrosive processes are classified formation of local corrosion.
as resulting from the chemical, electrochemical, Pitting corrosion is a dangerous phenomenon
mechanical factors (erosion, cavitation) and the occurring in installations (see Figure 1.). The cor-
microbiological factors. rosion points, so-called pits, occur in the form of
The chemical corrosion is the destruction of local metal losses often reaching deep into the
metals and alloys as a result of oxidation reac- material with relatively small spots on the surface
tions. The material degradation process runs dry [Alfonsson et al., 2012; Cantor et al. 2000]. The
without the use of electrolyte [Cutler, 2003]. In the conditions that are conducive to its occurrence
case of electrochemical corrosion, two processes include: moisture (or condensation) and oxygen,
occur simultaneously: oxidation, i.e. dissolution as well as the presence in the chloride environ-
of metals and reduction, i.e. hydrogen evolution, ment. Pits arise as a result of initiating the anodic
oxygen reduction, metal separation, etc. Depend- reaction through activating ions and cathodic re-
ing on the environment in which the material is action in the presence of oxidizing agents. The
used, a distinction is made between: corrosion in a bottom of the pitting is an anode and the disso-
moist environment (in sea water, atmosphere, cor- lution of the metal takes place there. The pitting
rosion in soil), in molten salts and gas corrosion environment is a cathode and oxygen reduction
(low temperature and high temperature). takes place there. The rate of dissolution of the
An important criterion for the division of cor- metal in the anode is very high, as a consequence
rosive damage is their nature and course. In this of which deep perforation and even penetration
case, it is referred to as general corrosion, which of thin-walled elements, without a greater loss of
covers the entire surface of the metal and local metal outside the attacked place occurs in a very
corrosion, which causes the destruction of only short time. Pipe corrosion threatens by all pres-
certain places on the surface of metal elements, sure flow elements of pipelines, especially during
leaving other intact areas [Avery et al., 1999; Ma- water stops in pipelines.
meng et al. 2011]. General corrosion can occur
as uniform corrosion – it spreads on the metal Degradation mechanism of installation
surface at the same rate, causing the same loss in the water treatment station
of wall thickness. The local corrosion is another
type, involving local areas characterized by the Among the degradation processes of pipe-
selective destruction of certain alloy constituents. line elements, in addition to the combination of
Its measure is the size and density of the distri- the phenomena described above, creep associated
bution of corrosive foci. Even corrosion is the with plastic deformation as a result of elevated
least dangerous type of corrosion, provided that temperature and almost constant stress and fre-
the rate of corrosive dissolution of the metal does quent pressure change play a dominant role in
not exceed the standards specified in the scale of degradation processes [Suslov, 2001, Cutler,
resistance of metals. If the thickness of the metal 2003]. The result of this process is permanent de-
is sufficient, even corrosion has a small effect on formation of the pipeline element causing irrepa-
reducing the mechanical strength of the structure rable internal damage in the form of voids, mac-
(compression, stretching). This type of corrosion ro- and microcracks. The elements of pipelines
is dangerous when the pipeline components in- that operate without appropriate supports and fas-
volve bending or twisting, because the layers tenings for the destruction process are significant-
subjected to the heaviest loads are destroyed. It ly affected by fatigue, characterized by stresses
occurs in critical elements: weld spots, pipeline causing the yield point to be exceeded; resulting
diameter reduction, knees and tees. Localized in the destruction of material; in this case, the fre-
corrosion occurs in many varieties, showing signs quency of cyclic loads is low. Fatigue damages
of both gas and electrochemical corrosion [Cut- cause a discontinuity of the trans- and intercrys-
ler, 2003]. It may have a different degree of un- talline structure in the form of a network of cracks
evenness. Localized corrosion is more dangerous and developing main cracks. When the aggressive
than even corrosion, because it strongly affects agent and external or internal mechanical stresses

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act simultaneously, stress corrosion occurs. Inter- Erosive destruction of the material is caused
nal stresses can be caused by bending, welding by the dynamic interaction of solid particles on
or assembly of additional elements. This type of the solid surface [Alfonsson et al., 2012]. In the
corrosion occurs in critical elements, i.e.: pipeline process of erosion, the size of the destruction de-
connection points, dosing points, assembly points pends, to a large extent, on the nature of the car-
of the measuring apparatus. rier’s motion and its speed, on the shape and size
Another type of corrosion, encountered in of the particles, on the temperature, the environ-
sanitary installations is intercrystalline corro- ment and chemical composition and the proper-
sion. It propagates along grains and proceeds at ties of eroded metal, i.e. hardness, abrasion resist-
a relatively high speed, to a considerable depth ance, ductility structure. The type of destruction
[Cantor et al. 2000], decreasing the durability and depends on the angle of impact of the destructive
ductility of the metal. It is related to the phenom- particles on the surface. The maximum metal loss
enon involving formation of chromium carbides corresponds to 40°, regardless of the speed of the
at the grain boundaries and with the impoverish- jet. When tangentially attacking a destroyed sur-
ment of the border areas of grains into chromium. face, it is destroyed by slip – destructive particles
This results in an aggressive corrosive environ- act on the material by sliding or rolling on it. The
ment or “hatching” individual grains from the erosion can be caused by the turbidity of the raw
steel surface, thereby reducing the thickness of water and the bed particles emitted during the
the walls, or violating the coherence between par- flushing of the filters during hydraulic or pneu-
ticular grains without visible external signs, [5] matic transport [Little et al. 2006]. The hydraulic
Cutler, 2003. It results not only from the inter- fitting installed on the pipelines but also the places
granular corrosion in the metal itself, but mainly where the pipeline route changes, i.e., tees, knees
in its plastic or mechanical treatment aimed at and reductions, are the most exposed to the erosive
giving the material a certain specialized shape. impact of these elements. The erosive destruction
Then, the gradual disappearance of the passive is often a secondary effect, for example, associ-
film occurs in the gaps in which the film cannot ated with a damaged drainage in the riverbed.
regenerate due to impeded aeration and inhibited
oxygen supply. It forms in the gaps and construc- Corrosion hazard resulting from the use
tion cavities, under seals, heads of bolts and riv- of chlorine in water treatment station
ets, under sediments and scale, and in all kinds of
cracks. The type of material destruction occurring In water treatment stations, disinfecting pro-
in pipelines is erosion (Fig. 1). cesses are carried out to to eliminate the bacteria

Fig. 1. Types of corrosion damage occurring in water installations

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and other microorganisms present in the water and 8.5, the hydrolysis reaction proceeds within a
and to ensure microbiological water purity in few seconds and is irreversible. Chlorine acid (I)
the distribution network. Chlorination has a dis- is a weak acid and partially dissociates to form a
infecting role and serves to destroy the bacteria hydrogen cation and hypochlorite anion, accord-
and other microorganisms present in the water ing to equation 2:
and to provide microbiological water purity in HOCl → H+ + OCl- (2)
the distribution network [GE Power & Water.,
1997–2012]. The process should be carried out so Chlorine in the form of HOCl and OCl-
that the disinfectant remains in the water, protect- known as free chlorine, has a strong bactericidal
ing it from secondary infection in the distribution effect, similar to the atomic oxygen emitted by
network. The chlorine demand (parameter deter- chloric acid decomposition, equation 3:
mining the purity of water) is the difference be-
HOCl → HCl + O (3)
tween the amount added to water and the amount
of free chlorine remaining after a certain time. The resistace of stainless steel to pitting or
Nominally, it is the smallest amount of chlorine crevice corrosion depends on the concentration
free Cl2 mg added to 1 dm3 of water at 20°C, of chlorides in water [Moore, 2001; Borenstein,
which gives 0.1 mg/dm3 of residual chlorine af- 1994; Suban et al. 2010]. Installations in net-
ter 30 minutes of contact with water. The chlorine works are usually made of 1.4301 (304), 1.4307
should be added to the water in such an amount (304L), and 1.4404 (316L) steel types. These
that after covering the demand, the remaining free steels usually do not cause any corrosion prob-
chlorine after a 30-minute contact with water was lems if the chloride content is low (see Table 1).
0.1 mg / dm3 of water. According to Hilbert et al. Stainless steels are considered to be a useful con-
(2010), 304L steel (1.4307) can be used for free struction material for drinking water pipelines
chlorine content up to 2 ppm (2 mg/dm3), while up to a chloride concentration of 200 ppm, while
316L steel (1.4404) – for 5 ppm in raw water. the steels of 316 grade, up to a concentration of
The raw water in the water treatment plant has around 1000 ppm. At higher chloride concentra-
a pH of about 7.5. After introducing chlorine gas, tions, the risk of local pitting corrosion (or fissure
the pH stays within the range of 7.3–7.8. Both the corrosion) increases, especially if welds do not
chlorine content and pH are within the limits ad- have full penetration. Pitting and crevice corro-
opted for drinking water. Normally accepted pH of sion sometimes occur in the water containing a
drinking water ranges from 6 to 8.5. The pH fluc- small concentration of chlorides if the chlorides
tuations usually do not affect the operation of stain- promote microbial corrosion. 316L steel with
less steels, although local low values, for example better corrosion resistance is used when deposits
in the gaps, are an indicator of the increased corro- and higher concentrations of chlorine are present.
sion rate. Specialists believe that it is necessary to These stainless steels are stable if the clean water
maintain a chlorine concentration of 0.5 mg/dm3 to flow rate is 0.5 to 0.6 m s-1 [Suban et al. 2010].
effectively act on microorganisms. Such a flow or greater is desirable, because then
In pure water, chlorine reacts with wa- there are no conditions for the formation of sedi-
ter and immediately hydrolyses to chlorine (I) ments, biofilms and the development of microbial
(HOCl) and hydrochloric acid (HCl) according to corrosion. For raw water, a flow rate of 1 m s-1 or
equation 1 [Cutler, 2003]: 1.5 m s-1 is effective to limit the bacterial growth.
Cl2+ H2O → HOCl + HCl (1) The 304 grade steel is used for the drinking wa-
ter containing 50 mg dm-3 chlorides [Hilbert et
As a result of chlorination, the pH decreases al. 2009, Tuhtill et al. 1998], 316 grade steel in
and metal chlorides are formed. Between pH 6.5 the water containing up to 250 mg dm-3 chlorides

Table 1. Resistance of stainless steels in water depending on the concentration of chlorides

Chloride content Stainless steel
<200 ppm 1.4301 (304), 1.4307 (304L), 1.4404 (316L)
200 – 1000 ppm 1.4404 (316L), (duplex 2205)
1000 – 3600 ppm 1.4462 (duplex 2205), super duplex, superaustenitic 6% Mo
>3600 ppm i woda morska 6% Mo superaustenitic , super duplex
[Cutler 2003, Alfonsson et al. 2012]

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[Borenstein, 2002]. There is no doubt that the include: Gallionella, Sphaerotilus, Pseudomonas,
chloride content is the most important indicator Desulphovibrio, Desulphotomaculum [Little et
of steel selection, due to the pitting and crevice al. 2011]. Bacteria act under sediments of metal
corrosion, with the mechanism of both types of oxides and hydroxides in biovarials. Bacteria are
corrosion being very similar. Table 1 presents adsorbed on metal, where they quickly reproduce
types of stainless steels showing durability for and form an organic biofilm. In the outer part of
specific limits of chlorides concentration in water the biofilm, they consume oxygen completely in
at ambient temperatures, if there is no microbio- the oxidation of soluble metal ions to form insolu-
logical corrosion [Little et al. 2007, Little et al. ble oxides and hydroxides, which accumulate as
2012, Mathiesen et al. 2008]. sediments and coatings of bacterial clusters. Very
small anodes are formed in which a very fast cor-
Risk of microbial corrosion rosion process occurs with the participation of mi-
grating chlorides into the pits.
Natural water taken from deep wells con-
tains various types of microorganisms that form Effect of chemical and microbiological synergy
biofilms on metals and accelerate the corrosion of corrosion of stainless steel pipelines
of stainless steels. Chlorination destroys micro-
organisms; therefore, it is to prevent microbial Microbial corrosion occurs in drinking water
corrosion. The water pipes made of 304 and 316 distribution systems in the areas where the level
grade steel may undergo bacterial corrosion if the of residual chlorine, even in short periods of time,
water flows slowly or when there is no flow. Many falls below the level required for the destruction
factors cause the conditions under which metal of corrosive microorganisms. According to [Can-
alloys undergo microbial corrosion [Mathiesen tor et al. 2000], chlorine should be introduced
2008, Kobrin, 1998]. These include, first of all, the into the water in an amount sufficient to obtain a
water flow rate and the surface roughness of the concentration of 25 mg dm-3, and after 12 hours,
pipelines. Under normal flow conditions, bacteria check that the concentration did not drop below
do not attack smooth stainless steel. In stagnant 15 mg dm-3. If the concentration is smaller, the
water, the colonies of bacteria form local clus- disinfection process should be repeated. A high
ters and develop quickly, especially in the area chlorine concentration of approx. 25 ppm for dis-
of ​​welds, where welding discolorations have not infection purposes can only be used for 24 hours
been removed. If there is insufficient flow in the without adversely affecting stainless steel, after
water, there are conditions for the formation of a which chlorine must be thoroughly rinsed [Op-
biofilm containing microorganisms on the surface erational Guidelines and Code of Practice for
of the steel, an aggressive environment for stain- Stainless Steel Products in Water Supply, 2002].
less steels, differing from the water in pH, oxygen, The microbial corrosion takes place particularly
organic and inorganic substances. Under micro- intensively under stagnant water conditions, in
fossil corrosion, microbiological corrosion takes the presence of thick dark layers of metal oxides
place at high velocities in the biofilm, because formed during welding if the oxygen content in
there is no oxygen supply and no sufficient water the inert gas is too high. Corrosive bacteria usu-
flow. Under the conditions of limited aeration, the ally form colonies in the area of welds.
​​
amount of anaerobic bacteria that reduce sulfate to Iron and manganese hydroxides precipitate as
sulphides increases. Chlorides and sulfides react a result of steel oxidation. This process intensi-
with the stainless steel substrate creating pitting in fies the presence of Gallionellia bacteria, provok-
the existing micro-grids [Moreno et al. 2011]. The ing the synergy effect [Little et al. 2011, Little et
metabolism products formed in biofilms (inorgan- al. 2012, Mathiesen et al. 2008]. Under aerobic
ic and organic acids, sulfides, hydrogen sulphide, conditions, yellow or red-brown iron compounds
CO2 and others) cause a rapid pitting corrosion such as hematite Fe2O3 lepidokrokit y-FeOOH
of stainless steel leading to perforation. Corro- and α-FeOOH goitite and manganese oxides like
sion rate at the border of the biofilm is 100 times Mn3O4 are formed in the biofilm. It is difficult to
greater than that of a corrosive reaction under nor- rule out the formation of black Mn2O3 oxide or
mal conditions. Most metal alloys, except for ti- gray-black MnO2 as a result of the action of met-
tanium, are strongly attacked [Suban et al. 2010]. al oxidizing bacteria, as shown schematically in
In the case of stainless steels, corrosive bacteria Figure 2. In pits or their vicinity in the anaerobic

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environment, reduced forms of iron and manga- CONCLUSIONS

nese can prevail like black wustite and magnetite
FeO and Fe3O4, or FeS [Little et al. 2006], which The direct causes of pipes corrosion include
accelerates corrosion and possibly formation of the presence of microorganisms in raw water, the
Mn3O4, which can also be black. parameters of technological water treatment pro-
Removal of raw water from deep wells, in which cesses and the performance of pipelines. Techno-
there are larger amounts of bacteria, fungi, organic logical pipelines are often exploited under complex
substances, or sulphides, is essential to eliminate conditions, in which corrosion, erosion and plastic
microbial corrosion. Maintaining a higher dose of deformation occur jointly. This results in the disap-
chlorine should prevent the growth and activity of pearance of the protective action of oxides and, as
corrosive bacteria [Borenstein 1994, Jack, 2002]. a result, accelerates the destruction of the material.
Figure 3 shows the effect of microbiologi- The local corrosion and perforations of the
cal and chemical factors, particularly chlorides installation elements from the water side are sub-
(black deposits of steel oxidation products) in jected to three pipeline assemblies in which the
good-quality welds of a 316L steel tank for drink- water is not in continuous flow:
ing water at a chloride content of 56 mg dm-3, af- •• rinsing water and air pipes directed to filters,
ter 2 years of downtime, which indicates a corro- •• water pipes after rinsing,
sion rate of about 2 mm month-1. •• treated water collector from pump tanks.

Fig. 2. Synergic effect of chemical corrosion and bacteria in water installation

Fig. 3. a) Black-brown leakage of corrosion products from the treated water pipeline, b) Black pitting
in the ridge of the weld and brown rust in the pipe cut from the pipeline of rinsing water operated
for about 1.5 years, c) water collector treated for pumps with perforation of 4 mm thick wall after a
period of about 2 years of use with black discoloration of corrosion products during perforation

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In the case of wrong choice of material, leaks 10. Hilbert L.R., Carpen L., Moller P., Fontenay F.,
occur after a few months and are most often lo- Mathiesen T., Unexpected Corrosion of Stainless
cated in the places where irregular welds edges Steel in Low Chloride Waters – Microbial Aspects,
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10085, 1998.
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Corrosion, John Wiley & Sons, 2007.
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