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A Practical Manual on

Microbiologically
Influenced
Corrosion
Volume 2

John G. Stoecker II
Editor
NACE International
The Corrosion Society

0 1993, 2001 by NACE International


Second Edition 2001. All rights reserved.

Library of Congress Catalog Number 93-85751

ISBN 1-877914-56-8 (Volume 1)


ISBN 1-57590-113-7 (Volume 2)

Printed in the United States of America. All rights reserved. This book, or parts thereof, may not be reproduced in
any form without permission of the copyright owners.

Neither NACE International, its officers, directors, or members thereof accept any responsibility for the use of the
methods and materials discussed herein. The information is advisory only and the use of the materials and methods
is solely at the risk of the user.

Cover Art Clockwise from Top Right: Figure 9.4, Figure 4.1, Figure 11.33, and Figure 4.6.
Cover Design by Michele Sandusky, NACE Graphics Department, and Techbooks.

NACE Press
Director of Publications: Jeff Littleton
Manager of NACE Press: Neil Vaughan

NACE International
The Corrosion Society
1440 South Creek Drive
Houston. Texas 77084
CONTENTS

About the Editor ....................................................................................... v


Tasks and Acknowledgments. ....................................................................... vii
Glossary ............................................................................................... ix

1. Introduction
9. Little, R. Ray, and S. Dexter.. .......................................................... 1.1
2. Fungal-Influenced Corrosion of Metals in Humid Environments
B. Little and R. Ray ....................................................................... .2.1
3. Biodegradation of Nonmetallic Engineering Materials
9. Little, R. RaH and P Wagner........................................................... 3.1
4. The Biodeterioration of Building Materials
C. Saiz-Jimenez.. ......................................................................... .4.1
5. Microbiologically Influenced Corrosion in Fire Protection Sprinkler Systems
D.H. Pope and R.M. Pope ................................................................ .5.1
6. MIC in Underground Environments: External Corrosion
in the Gas Pipeline Industry
Part I
TR. Jack.. .................................................................................. 6.1
Part II - Microbiologically Influenced Corrosion of Internal Aspects of Natural Gas
Industry Pipelines and Associated Equipment: Mechanisms, Diagnosis,
and Mitigation
D.H. Pope ................................................................................. 6.13
Part Ill - A Case Study-Microbially Induced Organic Acid Attack
in a Natural Gas Gathering System
J. W Dusseault and J.H. Schulz.. ....................................................... 6.27
7. MIC in the Power Industry
G.J. Licina ................................................................................. .7.1
Color Plate Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CP.1

iii
i\i Contents

8. MIC in the Waste Treatment Industries


J.B. Soebbing. .............................................................................. 8.1
9. Treatment for the Mitigation of MIC
R. W Lutey .................................................................................. 9.1
10. Techniques for MIC Monitoring
T.P Zintel, G.J. Licina, and T.R. Jack ................................................... 10.1
11. MIC Case Histories
Compiled by H.A. Videla, ................................................................ 11.l
CS-3 Marine Microbial Corrosion
1.B. Beech, S.A. Campbell, and EC. Walsh..................................... 11.3
CS-4 The Detection and Mitigation of MIC
T.E. Cloete, PJ. Allison, and W I .J. Poulton., .................................. 1 1 -15
MM-3 Microbiologically Influenced Corrosion in Geothermal Fields in Mexico
B. Valdez Salas, L. Rioseco de la Peha, G. Hernandez-Duque Delgadillo,
and N. Rosas Gonzalez ........................................................ 1 1.21
S-I Microbial Corrosion of Cultural Heritage Stoneworks
C. Saiz-Jimenez and X. Ariho .................................................. 11.25
SS-13 Localized Corrosion of Stainless Steel Milk Sterilizers
H.A. Videla....................................................................... 11.35
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1
CHAPTER 1

Introduction
By B. Little, R,Ray,and S, Dexter

Corrosion associated with microorganisms conditions but also takes place in humid atmo-
has been recognized for over 50 years, and yet spheres. One chapter is devoted to the role of
the study of microbiologically influenced corrosion fungi in atmospheric corrosion'and coating deteri-
(MIC) is a relatively new, multidisciplinary field oration.
in which there has been a continuum of inno- The variety of environments and industries
vations and contributions. A Practical Manual on in which MIC is encountered and controlled has
Microbiologically Influenced Corrosion Volume 2 inevitably led to some contradictions in recom-
edited by John Stoecker is a compilation of pa- mendations for mitigation from one situation to
pers by internationally recognized authorities in another. The reader should note that such con-
the field of MIC, including contributing authors from tradictions can be found between the recommen-
Argentina, Mexico, Spain, England, Canada, and dations for treatment in several of the chapters
the United States. The primary purpose of Vol- in this volume. Sometimes materials or methods
ume 2 is to document the incidence of MIC and recommended for controlling MIC in one indus-
the control measures in industries, environments, try may be specifically identified as not working
and materials not covered in Volume 1. Volume 2 well in another. This may be due to obvious or
includes chapters or case histories from the food even slight changes in chemical or physical op-
processing, fire protection, waste treatment, and erating conditions between the two industries. In
natural gas industries. There are also chapters on other cases the particular constraints in one in-
nonmetallic materials affected by MIC, including dustry may cause the most effective control tech-
polymer-coated metals, masonry building materi- nologies to be rejected in favor of ones considered
als, heritage stoneworks, fiber-reinforced compos- less effective or even ineffective in another. Thus,
ites, paints, caulks, and sealants. the reader should be careful in taking the recom-
Secondary objectives for Volume 2 are to up- mendations for MIC control from one industry and
date the information from Volume 1 in areas where applying them to another without a thorough analy-
significant new information is available and to sis of detailed operating conditions. Nevertheless,
present additional case histories. In this regard it is hoped that the methods for recognizing, mon-
chapters are presented on MIC in the electric itoring, and controlling MIC presented in this vol-
power and marine industries, as well as informa- ume will result in cross-fertilization of ideas to the
tion on MIC monitoring and mitigation, including benefit of all.
chemical treatments and biocides. Color plates are Since Volume 1' was published three major
included as an aid for plant personnel in recogniz- developments have contributed to our understand-
ing the signs of MIC. ing of MIC: (1) a redefinition of biofilm architecture,
Several chapters demonstrate the diverse en- ( 2 ) the realization that MIC of metals can best be
vironments in which MIC can be a problem as well understood as biomineralization, and (3) the limi-
as the diversity of causative organisms. MIC is tation to interpretation of cell numbers determined
not limited to aqueous corrosion under submerged by microscopy or microbiological testing.

1.1
1.2 Introduction

BULK WATER FeZt


MnZt

FIGURE 1.1
Conceptual model of stratified biofilm.

Biofilm Architecture of confocal laser scanning microscopy it became


apparent that multi- and single species biofilms
form complex structures containing voids, chan-
In aquatic environments, microbial cells attach
nels, cavities, pores, and filaments, with cells ar-
to solids. "Immobilized cells grow, reproduce and
ranged in clusters (Figure 1.2). Such complex
produce extracellular polymers which frequently structures have been reported in a wide vari-
extend from the cell forming a tangled matrix
ety of biofilms including methanogenic films from
of fibers which provide structure to the assem-
fixed-bed reactors,' aerobic films from wastewa-
blage termed a biofilm."2 The most devastating ter plant^,^,^ nitrifying biofilms,1° and pure culture
MIC takes place in the presence of microbial con-
biofilms of Vibrio parahaemolyticus' and Pseu-
sortia in which many physiological types of bac- dornonas aeruginosa. Lewandowski et al.
te r ia , including s uIfate-reducing bacteria (SR B) ,
further refined the model by demonstrating an
acid-producing bacteria, metal-oxidizing bacteria,
intricate interplay between hydrodynamics and
and metal-reducing bacteria (MRB), interact in
viscoelastic biopolymers leading to formation of
complex ways within the structure of b i ~ f i l m s . ~ , ~"streamers" and characteristic biofilm matrix os-
When images were limited to those produced by
cillation. The new conceptual model assumes an
light and electron microscopy, biofilms most often inherent biofilm heterogeneity and constitutes the
appeared to be composed of bacterial cells en- foundation for studying biofilm structure and its
closed in an exopolymeric substance (EPS) ma-
consequences, including MIC.
trix of uniform thickness and consistency (Figure
1.1). Conceptual and numerical models treated
biofilms as layers of matrix material within which Biomineralization
bacterial cells were randomly distributed, and
these models appeared to be predictive of reac- Microorganisms influence corrosion of met-
tion rates in b i o r e a ~ t o r s .However,
~,~ with the use als by both forming and dissolving minerals.14
Introduction 1.3

Biomineralization that results in mineral deposition


on a metal surface can shift the corrosion potential
in either a positive or negative direction, depend-
ing on the nature of the mineral. Manganese oxide
biodeposition on stainless steel surfaces exposed
in fresh water forces a shift in the positive, more no-
ble direction, moving the corrosion potential to the
pitting potential and potentially making some stain-
less steels more vulnerable to pitting and crevice
corrosion (Figure 1.3a,b,c).15 Iron oxide forma-
tion/deposition by microorganisms can initiate a
sequence of events that results in underdeposit
FIGURE 1.2 corrosion of susceptible metals (Figure 1 .4a,b).16
Updated model of a biofilm showing microbial micro- In the absence of oxygen, the metabolic ac-
colonies and interstitial voids filled with water. Arrows tivity of SRB causes accumulation of hydrogen
indicate convective flow. (From Lewandowski et aI.l3) sulfide near metal surfaces. This is particularly

(c) 0.5

0.4
1

0.3
h

>
3 0.2
Y
w 0.1

-0.1

-0.2 '
0
I
100
I

200
I
300
I

400 500
time ( h )

FIGURE 1.3
Annular deposits on stainless steel after 13-day exposure to fresh water. (a) Reflected light micrograph, (b) SEM micro-
graph, and ( c ) €, vs. time for 31 6-L stainless steel coupons during manganese oxide deposition in fresh river water.
(From Dickinson and L e w a n d o w ~ k i . ' ~ )
1.4 Introduction

(b)
uM2' t 2H2O -+ M (OH),

HYDROLYSIS REACTION
t 2Ht

EQUILIBRIUM pH

Fez+t 2Hz0 $ Fe(OH)2 t 2Ht pH = 6.64 - 112 log aFeZt

C+'t 3H20 Cr(OH)3 t 3H + pH = 1.53 - 1/3 log aC?+

Ni2' t 2H20 Ni(0H)z t 2H' pH = 6.5 - 1/2 log aN,2'

MnZt t 2H20 Mn(OH)z t 2Ht pH = 7.66 - 112 log aMnzt

FIGURE 1.4
(a) Possible reactions under tubercles created by metal-depositing bacteria and (b) specific hydrolysis reactions that
produce acidity under tubercles.

evident when metal surfaces are covered with


3500 I 1 biofilms (Figure 1.5).17 The concentration of sul-
3000 - 0 DISSOLVED OXYGEN fide is highest near the metal surface. Bioprecip-
f?
2
a
2500 - A SULFIDE itated sulfides stimulate the cathodic reaction so
g 2000 - m o H that sulfide formation on metal surfaces moves
'E
I 1500 the corrosion potential in a negative, more active
w direction, resulting in accelerated corrosion of
g 1000
some metals and alloys. The corrosion rate of
500
G iron in the presence of hydrogen sulfide is accel-
n o erated by the formation of iron sulfide minerals.
-500 Once electrical contact is established, mild steel
-1 0 1 2 3 4 5 6
behaves as an anode and electron transfer oc-
DISSOLVED OXYGEN CONCENTRATION (mglL)
curs through the iron sulfide. At low ferrous ion
concentrations, adherent and temporarily protec-
-9 -8 -7 4 -5 -4 -3 -2 -1
tive films of iron sulfides are formed on the steel
LOG OF TOTAL SULFIDE CONCENTRATION (mol/L)
surface with a consequent reduction in corrosion
FIGURE 1.5 rate. High rates of SRB-induced corrosion of mild
Concentration profiles of sulfide, oxygen, and p H in a steel are maintained only in high concentrations of
biofilm on mild steel. (From Lee et al.") ferrous ion.17
Introduction 1.5

(a) Thick sulfide-rich scale less for corrosion protection. In the presence of
/
turbulence, the loosely adherent sulfide film is re-
Corrosion
moved, exposing a fresh copper surface to react
Thin
subscale
product
-_.-_.
with sulfide ions. For these reasons, turbulence-
Metal induced corrosion and sulfide attack of copper
alloys cannot easily be decoupled. In the pres-
ence of oxygen, the possible corrosion reactions
Thick scale containing sulfide, in a copper sulfide system are extremely complex
partially converted sulfide, and oxide
/ because of the large number of stable copper sul-
fides, their differing electrical conductivities, and
catalytic effects . Transform at io ns between s uI-
fides or of sulfides to oxides result in changes
in volume that weaken the attachment scale and
oxide subscale, leading to spalling. Bared areas
repassivate forming cuprous oxide.
Biomineral dissolution reactions remove pas-
sive layers or force mineral replacement reactions
that lead to further dissolution. Biofilm formation of
copper alloys often results in selective dealloying
as zinc is incorporated in corrosion products.22
Dissimilatory iron and/or manganese reduction oc-
curs in several microorganisms, including anaer-
obic and facultative aerobic bacteria. MRB use
Mn(lV) and Fe(lll) oxides as the terminal electron
acceptors in anaerobic respiration, thereby con-
verting solid metal oxides to soluble metal ions.
Inhibitor and competition experiments suggest that
Mn(lV) and Fe(lll) are efficient electron acceptors
FIGURE 1.6 similar to nitrate in redox ability and are capable of
(a) Schematic of thick, sulfide-rich scale on copper alloy outcompeting electron acceptors of lower poten-
(top) and disruption of sulfide film (bottom, from Syrett tial, such as sulfate or carbon dioxide.23 Obuekwe
1981 ”) and (b) encrustations of copper sulfide on bac-
et al.24 evaluated corrosion of mild steel under
terial cells.
conditions of simultaneous formation of ferrous
and sulfide ions. They reported extensive pitting
The impact of sulfides on the corrosion of cop- when both processes were active. When only sul-
per alloys has received considerable attention, in- fide was produced, initial corrosion rates increased
cluding published reports documenting localized but later declined due to formation of a protective
corrosion of copper alloys by SRB in estuarine FeS film. High amounts of soluble iron prevent
environments.18 A porous layer of cuprous sulfide formation of protective sulfide layers on ferrous
with the general stoichiometry C U ~ - ~ 0S < , x<1 metals.
forms in the presence of sulfide ions.lg Copper Microorganisms within biofilms are capable
ions migrate through the layer, react with more of maintaining environments at biofilm/surface
sulfide, and produce a thick, black scale (Figure interfaces that are radically different from the
1.6a,b). It has been argued that if the copper sul- bulk in terms of pH, dissolved oxygen, and other
fide layer were djurelite, the sulfide layer would be organic and inorganic species.25 In some cases,
protective.20 Even if such a sulfide film were tech- these interfacial conditions could not be main-
nically passivating, the mechanical stability of the tained in the bulk medium at room temperature
film is so poor that copper sulfide films are use- near atmospheric pressure. As a consequence,
1.6 Introduction

microorganisms within biofilms produce minerals


and mineral replacement reactions that are not
predicted by thermodynamic arguments based
on the chemistry of the bulk medium.26 For
that reason, minerals within corrosion products
can often be used as fingerprints for MIC. For
example, even though the region of stability
predicted for mackinawite (tetragonal Fel - x S )
using stability diagrams is wholly outside the
region defined by surface water Eh/pH condi-
tions (Figure 1.7), excluding waters influenced by
peat bogs, coal mines, volcanic activity, and indus-
trial effluents, mackinawite is easily produced from
iron and iron oxides in surface waters by consor-
tia of microorganisms that include SRB. The pres-
ence of mackinawite in corrosion products formed
in shallow-water environments, with the exclusions
previously delineated, is proof that corrosion was
S RB-induced .27

Limited Interpretation of
Cell Numbers

Because the diagnosis of MIC can be contro-


versial, it is extremely important that interpretation
of spatial relationships between microorganisms
and corrosion products be cautiously interpreted.
Until recently, a standard procedure for evaluat-
ing MIC has been the enumeration of specific
types of microorganisms, particularly SRB, either FIGURE 1.7
in bulk liquids or in surface deposits, using a Iron stability diagram: water without chloride ions; to-
liquid medium. Growth media tend to be strain- tal sulfide 1OV2 M. Parallelograms superimposed on the
specific and a single incubation temperature is diagram are bounded by the highest and lowest pH Val-
ues commonly found in natural fresh and saline surface
further selective. The problem with all techniques
waters. The upper portion of the hatched area applies to
that attempt to quantify specific populations within
waters less than 10 m from the surface; the lower portion
biofilms is their overinterpretation to confirm or re- (oppositely hatched) represents waters at depths greater
fute the possibility of MIC. Little et a1.28 recently than 10 m. Conditions in the upper hatched parallelo-
demonstrated that anodic and cathodic polariza- gram represent those readily achieved in stagnant wa-
tions influence the numbers and types of bacteria ters. The lower portion indicates conditions not found in
associated with surfaces. In the case of anodic po- near-su rface environments.
larization, large numbers of marine bacteria were
found in association with iron corrosion products could be easily misinterpreted. Dexter29 cited a
resulting from abiotic mechanisms. The organisms case in which corrosion products surrounding a
had not caused the corrosion, but their numbers pit on an aluminum sample immersed in seawater
and spatial relationship with the corrosion products were more densely colonized by bacteria than the
Introduction 1.7

surrounding surface, but there was no evidence galvanic3’ and crevice38corrosion. All can be pro-
that bacteria had caused the attack. Franklin duced by abiotic reactions and have a similar ap-
et reported that bacterial cells were associ- pearance whether or not they were influenced by
ated with anodic regions on carbon steel detected m i c r o ~ r g a n i s m s .Cause
~~ and effect need to be
using scanning vibrating electrode microscopy. proven using evidence from complementary tech-
They were cautious not to interpret their data to niques before the most effective mitigation mea-
indicate that the cells caused the anodic sites. sures can be specified.
They did observe that once bacteria were asso-
ciated with anodic regions those areas remained
anodic for the duration of the experiments. Anodic Acknowledgments
sites not associated with bacteria were transient.
Little et aL3’ made similar observations of the spa-
tial relationships between Oceanospiri//umand an- The work for this chapter was performed un-
odic regions on copper surfaces. De Sanchez and der NRL Program Element 0601 153N and is NRL
Schiffrin3* demonstrated chemotaxis of a marine Contribution Number NRL/BA/7333-97-0001.
Pseudomonas induced by transiton metal ion con-
centration gradients from corroding copper and ti-
tanium surfaces. References
In the case of cathodic polarization, several in-
vestigators have made the observation that SRB 1. G. Kobrin, ed., A Practical Manual on Microbiolog-
are attracted to cathodically polarized surfaces in ically Influenced Corrosion (Houston, TX: NACE,
the absence of corrosion. Angel1 et al.33and Licina 1993).
et al.34 independently developed techniques for 2. W.G. Characklis and K.C. Marshall, “Biofilms: A Ba-
measuring currents sustained by bacteria. Both sis for an Interdisciplinary Approach,” in Biofilms,
techniques require cathodic polarizations and eds. W.G. Characklis and K.C. Marshall (New York,
Licina et al.34 stated that polarization “encour- NY: Wiley, 1990), p. 4.
aged biofilm formation.” Neither group has specif- 3. D.H. Pope, D.J. Duquette, P.C. Wayner, and A.H.
ically addressed differences in the microflora re- Johannes, Microbiologically Influenced Corrosion:
A State of the Art Review (Columbus, OH: Mate-
sulting from the polarization. Gomez de Saravia
rials Technology Institute of the Chemical Process
et and Videla et al.36 demonstrated that Industries, 1984).
cathodic polarization in a seawater medium in- 4. B. Little, P. Wagner, and F. Mansfeld, “Microbiolog-
creased numbers of SRB and decreased numbers ically Influenced Corrosion of Metals and Alloys,”
of aerobic bacteria on carbon steel surfaces rel- Int. Mat. Rev. 36, 6(1991): 253-272.
ative to unpolarized controls. They hypothesized 5. 0. Wanner and W. Gujer, “A Multi-Species Biofilm
that preferential increases or decreases in cell Model,” Biotech. Bioeng. 28(1986): 314-328.
types were due to differences in cell isoelectric 6. B.E. Rittmann and J.A. Manem, “Development
points. and Experimental Evaluation of a Steady-State,
In summary, reliable test methods for identi- MuItispecies Biof iIm ModeI,” Biot ec hnoI. Bioeng.
fying or predicting MIC cannot be based on en- 39(1992): 914-922.
numeration of organisms or their spatial relation- 7. R.W. Robinson, D.E. Akin, R.A. Nordstedt, M.
Thomas, and H.C. Aldrich, “Light and Electron
ship to corrosion products. There is no correlation
Microscopic Examinations of Methane-Producing
between numbers and types of cells and localized Biofilms from Anaerobic Fixed-Bed Reactors,” Appl.
corrosion. Moreover, MIC does not have a sin- Environ. Microbiol. 48(1984): 127-1 36.
gle diagnostic manifestation. The presence and 8. T. Eighmy, D. Maratea, and P.L. Bishop, “Electron
metabolic activities of bacteria heterogeneously Microscopic Examination of Wastewater Biofilm
colonizing metal surfaces can produce pitting, un- Formation and Structural Components,” Appl. Env-
derdeposit corrosion, dealloying, and enhanced iron. Microbiol. 45(1983): 1921-1931.
1.8 Introduction

9. W.N. Mack, J.P. Mack, and A.O. Ackerson, “Micro- Europ. J. Appl. Microbiol. Biotechnol. 1O(1980):
bial Film Development in Trickling Filters,” Microb. 261-274.
EcoI. 2(1975): 21 5-31 6. 21. P.H. Ribbe, ed., Sulfide Mineralogy (Washington,
10. S. Kugaprasatham, H. Nagaoka, and S. Ohgaki, DC: Mineralogical Society of America, 1976).
“Effect of Turbulence on Nitrifying Biofilms at Non- 22. B. Little and P. Wagner, “Impact of Alloying Ele-
Limiting Substrate Conditions,” Water Res. 26, ments on Microbiologically Influenced Corrosion,”
12(1992): 1629-1 638. MP 32, 9(1993): 65-68.
11. J.R. Lawrence, D.R. Korber, B.D. Hoyle, J.W. 23. C. Myers and K.H. Nealson, “Bacterial Manganese
Costerton, and D.E. Caldwell, “Optical Sectioning of Reduction and Growth with Manganese Oxide as
Microbial Biofilms,” J. Bacteriol. 173(1991):6558- the Sole Electron Acceptor,” Science 240(1988):
6567. 1319-1 321.
12. P.S. Stewart, B.M. Peyton, W.J. Drury, and 24. (2.0. Obuekwe, D.W.S. Westlake, J.A. Plambeck,
R. Murga, “Quantitative Observations of Hetero- and F.D. Cook, “Corrosion of Mild Steel in Cultures
geneities in Pseudomonas aeruginosa Biofilms,” of Ferric Iron Reducing Bacterium Isolated from
Appl. Environ. Microbiol. 59, l(1993):327-329. Crude Oil. I. Polarization Characteristics,” Corro-
13. Z. Lewandowski, P. Stoodley, and S. Altobelli, sion 37, 8(1981):461-467.
“Experimental and Conceptual Studies on Mass 25. Z. Lewandowski, S.A. Altobelli, and E. Fukushima,
Transport in Biofilms,” Water Sci. Technol. “NMR and Microelectrode Studies of Hydrodynam-
31 (1 995): 153-1 62. ics and Kinetics in Biofilrns,” Biotechnol. Prog.
14. B. Little, P. Wagner, K. Hart, R. Ray, D. Lavoie, 9(1 993): 40-45.
K. Nealson, and C. Aguilar, “The Role of Biorniner- 26. M.B. McNeil and B.J. Little, “Corrosion Mechanisms
alization in Microbiologically Influenced Corrosion,” for Copper and Silver Objects in Near-Surface En-
Biodeterioration 9(1998): 1-1 0. vironments,” J. Amer. Inst. Conserv. 31, 3(1992):
15. W.H. Dickinson and Z. Lewandowski, “Manganese 355-3 66.
Biofouling and the Corrosion Behavior of Stainless 27. M.B. McNeil and B.J. Little, “Mackinawite Formation
Steel,” Biofouling 1O(1996): 79-93. During Microbial Corrosion,” Corrosion 46,7(1990):
16. B. Little, P. Wagner, and F. Mansfeld, “Microbiolog- 599-600.
ically Influenced Corrosion of Metals and Alloys,” 28. B.J. Little, P.A. Wagner, K.R. Hart, and R.I. Ray,
Int. Mat. Rev. 36, 6(1991): 253-272. “Spatial Relationships Between Bacteria and Lo-
17. W. Lee, Z. Lewandowski, M. Morrison, W.G. calized Corrosion,” CORROSION/96, paper no. 278
Characklis, R. Avci, and P.H. Nielsen, “Corrosion (Houston, TX: NACE, 1996).
of Mild Steel Underneath aerobic Biofilms con- 29. S.C. Dexter, “Role of Microfouling Organisms in Ma-
taining Sulfate-Reducing Bacteria-Part II: At High rine Corrosion,” Biofouling, 7(1993): 97-1 27.
Dissolved Oxygen Concentration,” Biofouling 7 30. M.J. Franklin, D.C. White, and H.S. Isaacs, “Pit-
(1993):217-239. ting Corrosion by Bacteria on Carbon Steel,
18. B. Little, P. Wagner, J. Jacobus, and L. Janus, “Eval- Determined by the Scanning Vibrating Elec-
uation of Microbiologically Induced Corrosion in an trode Technique,” Corros. Sci. 32, 9(1991): 945-
Estuary,” Estuaries 12, 3(1989): 138-1 41. 952.
19. B.C. Syrett, “Accelerated Corrosion of Copper in 31. B. Little, P. Wagner, P. Angel, and D. White, “Cor-
Flowing Pure Water Contaminated with Oxygen relation Between Anodic Areas and Oceanospiril-
and Sulfide,” Corrosion 33(1977): 257-262; “The lum Biofilms on Copper,” Int. Biodet. Biodegrad. 37,
Mechanism of Accelerated Corrosion of Copper- 3-4( 1996): 159-1 62.
Nickel Alloys in Sulfide Polluted Seawater,” COR- 32. S.R. De Sanchez and D.J. Sciffrin, “Bacterial
ROSION/80, paper no. 33 (Houston, TX: NACE, Chemo-Atractant of Metal Ions from Dissolving
1980; “The Mechanism of Accelerated Corrosion Electrode Surfaces,” J. Electroanal. Chem. 403
of Copper-Nickel Alloys in Sulphide-Polluted Sea- (1996): 39-45.
water”, Corros. Sci. 21 (1981): 187-209. 33. P. Angel, J.-S. Luo, and D.C. White, “Studies of the
20. I. Nilsson, S. Ohlson, L. Haggstrom, N. Molin, Reproducible Pitting of 304 Stainless Steel by a
and K. Mosbach, “Denitrification of Water Us- Consortium Containing Sulphate-Reducing Bacte-
i ng ImmobiIized Pseudomonas denitrificans Cel Is,” ria,” Proceedings of the 1995 International Confer-
Introduction 1,9

ence on Microbially Influenced Corrosion (Houstan; 36. H.A. Videla, S.G. Gornez de Saravia, and M. de
TX: NACE and American Welding Society, 1995), Mele, “Early Stages of Bacterial Biofilm and Ca-
pp. 1/1-1/10. thodic Protection Interactions in Marine Environ-
34. G.J. Licina, G. Nekoksa, and R.L. Howard, “An ments,” Proceedings of the 12th International Cor-
Electrochemical Method for On-Line Monitoring rosion Congress, (Houston, TX: NACE, 1993),
of Biofilm Activity in Cooling Water Using the pp. 3687-3695.
BloGEORGE- probe,” in Microbially Influenced 37. S.C. Dexter and J. P. LaFontaine, “Effect of Natural
Corrosion Testing, eds. J.R. Kearns and B.J. Marine Biofilrns on Galvanic Corrosion,” Corrosion,
Little, ASTM STP 1232 (Philadelphia, PA: ASTM, 54, ll(1998):851-861.
1994), pp. 118-1 27. 38. H.J. Zhang and S.C. Dexter, “Effect of Biofilms
35. S.G. Gomez de Saravia, M.F.L. de Mele, and on Crevice Corrosion of Stainless Steel in
H.A. Videla, “Interacciones de Biopeliculas Bacte- Coastal Seawater,” Corrosion 51 1 (1995): 56-
rianas y Compuestos lnorganicos Sobre Aceros 66.
Protegidos Catodicamente,” in 5th Congreso 39. J.G. Stoecker, “Microbiological Influence and Elec-
Ibero-americano de Corrosion y Proteccion, ed. trochemical Types of Corrosion: Back to Basics,”
D. Grandosa (La Laguna, Tenerife, lslas Canarias, CORROSION/94, paper no. 259 (Houston, TX:
Spain, 1995), pp. 201-202. NACE, 1994).
CHAPTER 2

Fungal-Influenced Corrosion of Metals


in Humid Environments
By B, Little and R, Ray

Introduction films; sonar diaphragm coatings; map coatings;


paints; metals; crude oil; fuel oil; jet fuel; kerosene;
greases; waxes; lubricants; adhesives; asphalt;
The availability of water influences the dis- hydraulic fluids; rain repellents; textiles (cotton
tribution and growth of microorganisms. Water and wool); vinyl jackets; leather shoes; feathers
availability can be expressed as water activity (a,) and down; natural and synthetic rubber; optical
with values ranging from 0 to 1 .O. Microbial growth instruments; mechanical, electronic, and electric
has been documented over a range of a, from 0.60 equipment (radar, radio, flight instruments, wire
to 0.998.’ Fungi are the most dessicant-resistant strain gauges, helicopter rotors); hammocks;
microorganisms and can remain active down to tape; thermal insulation; brick masonry and
a, = 0.6 whereas few bacteria remain active at a, concrete; medicines; and museum valuables.
values below 0.9.2 Fungi are nonphotosynthetic Most documented cases of fungal-induced biode-
organisms, having a vegetative structure known terioration involve materials other than metals or
as a hypha, the outgrowth of a single microscopic metals exposed in aquatic or fluid environments.
reproductive cell or spore. A mass of threadlike For example, despite the extensive database
hyphae make up a mycelium (Figure 2.1).3 Mycelia that has been developed on biodeterioration and
are capable of almost indefinite growth in the pres- biocides, fungi remain a modern problem for
ence of adequate moisture and nutrients so that production, transportation, storage, and use of
fungi often reach macroscopic dimensions. Yeasts hydrocarbon fuels contaminated with even small
are fungi that multiply by forming buds instead amounts of water as documented by Videla5
of mycelia. Fungi are ubiquitous in atmospheric and Stranger-Johannessen8 reported
and aquatic environments where they assimilate deterioration of the epoxy resin coating of ship
organic material and produce organic acids holds filled with molasses, fatty oils, and other fluid
including oxalic, lactic, acetic, and citric. Spores, cargoes. She also confirmed fungal degradation
the nonvegetative dormant stage, can survive of polyurethane cable sheathing in the marine
long periods of unfavorable growth conditions, e n ~ i r o n m e n t There
.~ are fewer documented case
e.g., drought and starvation. When conditions for histories of fungal-influenced corrosion of metals
growth are favorable, spores germinate.4 in humid atmospheric conditions. Geesey’O dis-
Biodeterioration due to fungi has been doc- cussed the potential corrosion problem for metal
umented for the following: cellulosic materials containers selected for storage of nuclear waste
(paper, composition board, and wood); communi- in terrestrial environments. The following are
cation wire; cable splices; telephone cable; cable documented case histories of fungal-influenced
sheaths; photographic film; polyvinyl chloride corrosion of metals in humid environments.

2.1
2.2 Fungal-Influenced Corrosion of Metals in Humid Environments

FIGURE 2.1
Growth stages of filamentous fungi. (See color plates.)

FIGURE 2.2
(a) Wooden spool on which wire rope was stored. Pieces of paper are attached to rim edges. (b) Inside surface of
wooden spool. White deposits are the result of fungal growth. (See color plates.)
Funaal-InfluencedCorrosion of Metals in Humid Environments 2.3

Wire Rope

Between May 1992 and February 1993, cor-


rosion inspection statistics were compiled for 117
spools of wire rope used in military applications.”
Five of 58 highlines stored indoors showed some
sign of corrosion whereas 42 of the 59 spools
stored outdoors were unsuitable for use because
of localized corrosion. Time in storage was not
a factor. The one-inch carbon steel wire ropes
used in military applications are prepared with
six individual strands around an independent wire
core coated with a thick maintenance grease and
threaded onto wooden spools (Figure 2.2a) that
are wrapped in brown paper and black plastic prior

FIGURE 2.4
(a) Wire rope that had been in contact with wood and
PDA inoculated with Aspergillus niger. Rope rolled aside
to show localized corrosion after contact with agar or
wood (3X). (b) Light micrograph of localized corrosion
associated with fungi (40X). (See color plates.)

to storage. Wire rope may be stored for weeks


to months before being used. Any visible sign of
corrosion means that the rope cannot be used for
its intended purpose. Fungal growth was observed
on interiors of some wooden spools stored out-
doors (Figure 2.2b) and corrosion was most se-
vere on wraps of wire in direct contact with the
wooden spool flanges. There were numerous re-
ports of a musty odor associated with spools when
plastic packaging was removed. Aspergillus niger
and Penicillium sp. were isolated from wooden
spool flanges (Figure 2.3a,b). Isolates could not
FIGURE 2.3 be maintained on the protective grease (i.e., these
(a), (b) Micrographs of fungi associated with wooden fungi could not break down the maintenance
spool. coating to obtain nutrients). Instead fungi growing
2.4 Fungal-InfluencedCorrosion of Metals in Humid Environments

on wood produced copious amounts of CO2. The


pH of condensate monitored using a microelec-
trode with a tip diameter of 2.4 mm (Microelec-
trodes Inc., Londonderry, NH) was consistently
below 5.0. The acidic condensate dissolved the
maintenance grease and produced localized cor-
rosion (Figure 2.4a,b).
Laboratory data and field statistics implicated
the practice of storing carbon steel highlines in
humid conditions wrapped in plastic with microbi-
ologically influenced corrosion. The replacement
of plastic wrapping with paper packaging and re-
design of wooden spool flanges to include slats
FIGURE 2.5 one-half inch apart to promote ventilation are
Interior of H-53 helicopter with luxurious fungal growth currently being evaluated as control
on polyurethane paint. (See color plates.)

FIGURE 2.6
( a ) Aureobasidiurn sp. colonizing polyurethane paint taken from H-53 helicopter. (bj 3 X magnification of (a). (c) ESEM
micrograph of Aureobasidiurn sp. on polyurethane paint. (dj Aureobasidiurn sp. on underside of polyurethane paint
chip (40X). (See color plates.)
Fungal-InfluencedCorrosion of Metals in Humid Environments 2,5

measures. One-hundred and forty-three new high-


lines manufactured in exactly the same way as
previously described are being monitored. Six of
seven spools wrapped in plastic and stored out-
doors showed signs of localized corrosion after
two months. There have been no reports of
localized corrosion of redesigned spools stored
outdoors where plastic wrap was eliminated.

Microfungal Degradation
of Painted Surfaces

Ship Holds
FIGURE 2.7
Stranger-Johannesseni2 reported that ship Fungal-induced corrosion of bare 2024 T-6 aluminum
holds carrying cereals, woods, and other dry (40x1. (See color plates.)
cargoes were severely corroded within months.
Heavy pitting and reduced thickness of the steel
all interior surfaces, including primer-coated and
plate were observed. Viable fungi were cultured
polyurethane-coated 2024 T-6 aluminum, fiber-
from the corrosion products. Originally the holds
glass structural members, caulking, synthetic fab-
had been coated with a chlorinated rubber paint.
rics, wiring, and air-conditioning ducts. Concen-
Laboratory tests demonstrated that fungal isolates
tration of organisms did depend on the availability
grew on the coating without any additional nu-
of nutrients and water. Fungi were more numer-
trients. Fungal growth caused blistering and dis-
ous in low areas and occluded spaces hold-
bonding within 10 days.
ing water or hydraulic fluid. Fungi appear to
be able to use hydraulic fluid and lanolin as
Military Helicopters sources of nutrients, but neither appears to be
the source of the fungi. The topcoat of a piece
Numerous reports document fungal growth of peeling paint was uniformly colonized by fungi
in passenger compartments of in-service aircraft (Figure 2.6a-d). Environmental scanning electron
coated with polyurethane paint (Figure 2.5). A microscopy (ESEM) was used to demonstrate that
report by Lavoie and Little13 documented the the fungus penetrated the coating and caused dis-
following eight fungal genera associated with bonding between topcoat and primer. Glossy fin-
H-53 aircraft: Pestalotia, Trichoderma, Epicoc- ish polyurethane fouled more readily than did the
cum, Phoma, Stemphylium, Hormodendrum (also same formulation with a flat finish. Aged paint
known as Cladosporium), Penicillium, and Aure- fouled more rapidly than new coatings. Labora-
obasidium. At least one of the isolates can degrade tory tests demonstrated that in the presence of hy-
paint14 and other studies report that fungi of the draulic fluid or lanolin, most of the isolates caused
same class are capable of causing deterioration of localized corrosion of bare 2024 T-6 aluminum
polyester-based urethane coatings currently used (Figure 2.7).
on interiors of military helicopter^.^^^'^ Bacteria
and fungi were cultured from all surfaces of all plat-
forms. Representative culture plates indicated that Conclusions
several fungal species were collocated. Distribu-
tion of organisms was not limited to standing water The possibility of fungal-influenced corrosion
or fluids. Organisms were cultured from virtually of metals in humid environments has enormous
2,6 Fungal-InfluencedCorrosion of Metals in Humid Environments

economic consequences. In relative humidities of Corrosion Congress (Houston TX: NACE, 1993),
60% or greater with adequate nutrients, fungi can p. 3773.
thrive and produce acidic by-products that cause 7. R.C. Salvarezza and H.A. Videla, “Microbiolog-
corrosion of bare metals and disbonding of coat- ical Corrosion in Fuel Storage Tanks. Part 1:
ings on coated metals. Anodic Behaviour. Acta Cien. Venezol. 35(1984):
244-247.
8. M. Stranger-Johannessen, “Microbial Deteriora-
tion of Corrosion Protective Coatings,” in Microbial
Acknowledgments Problems in the Offshore Oil Industry (New York:
Wiley, 1986), pp. 57-61.
This work was supported by the Office of 9. M. Stranger-Johannessen, “The Role of Microor-
Naval Research, Program Element 601 153N and ganisms in the Blistering and Debonding of Corro-
Wright Patterson U S . Air Force Base, Program s io n Protective Organic Coatings ,” in Proceedings
Element 631 12F. It is NRL Contribution Number of the XVIlIth FATlPEC Congress (Venezia, Italy:
NRUBN7303-99-000 1. 1986), VOI. 3, pp. 1-13.
10. G. Geesey, ed. G. Cragnolino, “Review of the
Potential for Microbially Influenced Corrosion of
High-Level Nuclear Waste Containers, prepared for
References Nuclear Regulatory Commission Contract NRC-02-
88-005 (San Antonio, TX: NRC, 1993).
1. D.A.A. Mossel and M. Ingram, “The Physiology of 11. B. Little, R. Ray, K. Hart, and I? Wagner, “Fungal
the Microbial Spoilage of Foods,” J. Appl. Bacteriol. Induced Corrosion of Wire Rope in Humid Atmo-
18(1955): 232-268. spheric Conditions,” CORROSION/95, paper no.
2. H.G. Schegel and H.W. Jannasch, “Prokaryotes 190 (Houston, TX: NACE, 1995).
and their Habitats,” in The Prokaryotes: A Hand- 12. M. Stranger-Johannessen “Fungal Corrosion of the
book on Habitats, Isolation, and Identification of Steel Interior of a Ship’s Holds,” in Biodeterioration
Bacteria, eds. M.P. Starr, H. Stolp, H.G. Truper, A. 6, eds. S. Barry and D. R. Houghton (CAB Int. My-
Balows, and H.G. Schegel (New York: Springer- cological Inst., 1986), pp. 218-223.
Verlag, 1986), p. 52. 13. D. Lavoie and B. Little, “Fungal Contamination Of
3. H.L. Barnett, lllustrated Genera of Imperfect Fungi, H-53 Aircraft,” Naval Research Laboratory Memo-
2nd ed. (Minneapolis, MN: Burgess, 1965). randum Report NRL/MR/733-96-7725, 1996.
4. J.E. Smith and D.R. Berry, An Introduction to 14. R. Zabel and F. Terracina, “The Role of Aureobasid-
Biochemistry of Fungal Development (New York: ium pullulans in the Disfigurement of Latex Paints,”
Academic, 1974), p. 85. Dev. Ind. Microbiol. 21 (1980): 179-1 90.
5. H. Videla, ”The Action of Cladosporium resinae 15. W. Cook, J. Cameron, J. Bell, and S. Huang,
growth on the Electrochemical Behavior of Alu- “Scanning Electron Microscope Visualization of
minum,” in Proceedings of the lnternational Confer- Biodegradation of Polycaprolactones by Fungi,”
ence on Biologically Induced Corrosion (Houston, J. Polym. Sci. Lett. 19(1981): 159-165.
TX: NACE, 1986), p. 215. 16. D. Wales and B. Sager, “The Mechanism of
6. B.M. Rosales, A. Puebla, and D. Cabral, ”Role of Polyurethane Biodeterioration,” in Biodeterioration
the Metal Uptake by the Mycelium of the Fungus and Biodegradation of Plastics and Polymers, ed.
Hormoconis resinae in the MIC of Aluminum Al- K.J. Seal, Occasional Publications No. 1 (Kew, UK:
loys,” in Proceedings of the 12th lnternational Biodeterioration Society, 1985), pp. 56-65.
CHAPTER 3

Biodegradation of Nonmetallic
Engineering Materials
By B, Little, R.I. Ray, and P, W a g n e r

Int roduction Fungi are the most widespread and destruc-


tive group of microorganisms encountered in
biodegradation of materials. Fungi are aerobic,
All engineering materials become colonized by
nonphotosynthetic organisms with a vegetative
bacteria and fungi within hours after exposure in
structure known as a hypha that is the outgrowth
natural waters and in many atmospheric environ-
of a single microscopic reproductive cell or spore.
ments. Microorganisms grow and produce a vis-
Mycelia, masses of hyphae, are capable of al-
coelastic layer or biofilm. Most naturally occurring
most indefinite growth in the presence of adequate
biofilms contain a consortia of microorganisms
moisture and nutrients so that fungi often reach
with varied oxygen and nutritional requirements.
macroscopic dimensions. Fungi are ubiquitous
Additionally, nutritional needs of one species may
in atmospheric and aquatic environments where
be provided by other members of the community.
they assimilate organic material and produce or-
The environment at the biofilm/material interface
ganic acids including oxalic, lactic, acetic, and
is radically different from the bulk medium in terms
citric. Additionally, fungi produce carbon dioxide,
of pH, dissolved oxygen, and organic and inor-
which reacts with water to form carbonic acid.
ganic species. Biodegradation due to the activities
Fungal spores are widely distributed, and they tol-
of bacteria and fungi has been documented for
erate extreme ranges of temperature, pH, and hu-
nonmetallic materials including cellulosics (paper, midity. Fungi cause esthetic degradation via direct
wood), fabric (cotton, wool, rayon), vinyl textiles,
surface attachment in addition to loss of mechani-
leathers, greases and lubricants, rubber, coatings
cal properties due to enzymatic activities and pro-
(e.g., for electronics and structural applications),
duction of aggressive organic acid metabolites.
and architectural products including masonry and
This chapter will present recent studies and
concrete.
examples of biodegradation of nonmetallic engi-
Bacteria can tolerate a wide range of envi-
neering materials. Additional architectural materi-
ronmental conditions including extremes of pH
als are discussed elsewhere in this book.
and temperature. They vary in oxygen require-
ments from obligately aerobic to obligately anaer-
obic. Heterotrophic bacteria derive energy from a
large range of organic molecules while autotrophic Polymeric Materials
bacteria oxidize inorganic compounds as energy
sources. Bacterial production of gases, organic/ Until recently, little attention has been paid to
inorganic acids, and sulfides, as well as the for- environmental degradation of polymeric materials
mation of concentration cells, results in biodegra- because of the assumption that polymers would
dation of nonmetallic materials. not suffer the corrosion, biofouling, or deterioration

3.1
3.2 Biodegradationof Nonmetallic Engineering Materials

found in conventional materials. It is now recog- ment strength with low density. Resin matrices
nized that polymeric materials are subject to many provide load transmission and energy dissipation.
kinds of environmental degradation resulting in Fiber-resin interface bonding is essential for com-
loss of flexibility, elasticity, and strength due to frac- posite integrity.
ture, disbonding, or delamination. Possible mech- In laboratory experiments bacterial cultures
anisms for microbial degradation of polymeric ma- were chosen, to represent specific degrada-
terials include: direct attack by acids or enzymes, tion mechanisms for worst-case exposures of
blistering due to gas evolution, enhanced cracking FRPC coupons (2.5 x 2.5 x 0.6 ~ m ) Cultures . ~
due to calcareous deposits and gas evolution, and included Thiobacillus ferroxidans, a su Ifur/iron-
polymer destabilization by concentrated chlorides oxidizing bacter i um ; Pseudomonas fluorescens,
and sulfides. Fungal-induced black pitting (mildew) a calcareous-depositing bacterium originally
and pink staining have been reported in the tex- isolated from polIuted seawater; Lactococcus
tile and paint industries.’ Enzymatic attack of poly- lactis subsp. lactis, ATCC #19435, an ammonium-
meric plasticizers in flexible vinyls was related to producing bacterium ; Clostridium acetobutylicum,
loss of elasticity and increased brittleness. Fungal ATCC #824, a bacterium previously shown to pro-
attack of polyester polyurethanes has also been duce copious amounts of hydrogen from fermenta-
reported2 tion of s ~ g a r s and
; ~ a mixed facuItative/anaerobic
Organic additives including plasticizers, fillers, marine culture containing sulfate-reducing
and stabilizers, many of the ester type, may bacteria (SRB) originally isolated from corroded
provide nutrients for microbial growth and ulti- carbon steel in marine service.10 Two FRPCs-a
mate d e g r a d a t i ~ n .Polymeric
~ materials are sub- carbon fiber (T-300) reinforced epoxy and a
ject to degradation from moisture intrusion and glass (S-2) and carbon (T-300) reinforced vinyl
osmotic b l i ~ t e r i n g .Both
~ may be influenced by ester-were exposed to all microbiological cul-
biofilms. Weight change measurements suggest tures for 161 days. Additionally, carbon fibers,
that biofilms may act as a diffusion barrier for wa- glass fibers, vinyl ester, and epoxy resins were
ter, retarding moisture ~ p t a k e . ~ , ~ individually exposed for 90 days to SRB and
hydrogen-producing bacteria. Glass fibers had
Fiber-Reinforced Polymeric been treated with an organofunctional silane
Composites (FRPCs) surfactant to promote adhesion between the resin
and fibers and to facilitate handling.
FRPCs are commonly used in atmospheric Neither the epoxy nor the vinyl ester com-
and aquatic environments to replace conventional posites were adversely affected by calcareous-
materials in structural applications. Evaluations of depositing or ammonium-producing bacteria.
FRPCs in marine heat exchangers, condensers, There was no evidence of attack of resins, and
pumps, shipboard structures, and deep-sea appli- fibers remained embedded within both matrices.
cations are ~ n g o i n g Fiberglass-reinforced
.~ plas- Composites exposed to sulfur/iron-oxidizing bac-
tics are in use as piping and pipe linings and teria were covered with crystalline deposits con-
as protective claddings over metals and con- taining iron and sulfur in addition to microbial cells.
crete. Performance advantages include increased All surfaces exposed to SRB were black due to the
strength to weight ratio, hardness, wear and corro- deposition of iron sulfides. No damage to the epoxy
sion resistance, and stiffness and improved creep composite, epoxy neat resin, or carbon fibers could
behavior. Modifications during fabrication, includ- be attributed to the presence and activities of SRB
ing the altering of thermal properties and configu- and hydrogen-producing bacteria.
rations, can be tailored for specific applications. Glass fibers (Figure 3.la) exposed to SRB
Fibers, resins, and the fiber-resin interface lost all rigidity after a 90-day exposure so that the
have differing susceptibilities to biodegradation. weave pattern was no longer evident (Figure 3.1 b).
Fibers, usually glass or carbon, provide reinforce- Control glass fibers remained rigid and maintained
Biodegradation of Nonmetallic Engineering Materials 3.3

- BACTERIA
CELLS

- DlSBONDlNG

FIGURE 3.2
Hydrogen-producing bacteria at disrupted interfaces be-
tween fibers and vinyl ester resin.

the original weave pattern after exposure to sterile


culture medium (Figure 3 . 1 ~ )There
. was no direct
attack on the glass. Fibers are not usually directly
degraded by microorganisms, although Pendrys’
reported that p-55 graphite fibers were attacked
by a mixed culture of Pseudomonas aeruginosa
and Acinetobacfer calcoaceticus, common soil
isolates.
Hydrogen-producing bacteria appeared to dis-
rupt bonding between fibers and vinyl ester resin
(Figure 3.2). Disruption may have been due to gas
formation.
The impact of SRB on the tensile strength
of stressed FRPC was evaluated using acoustic
emission (AE). Flat rectangular lengths of a car-
bon fiber reinforced epoxy resin composite (6 ply,
unidirectional fiber volume 50%) were prepared
and assembled in three- and four-point bends at
controlled strains.12 After seven months bacteria
and/or sulfide crystals were preferentially concen-
trated along fiber-resin interfaces and in superfi-
cial surface scratches (Figures 3.3 and 3.4). AE
testing suggested a 10% loss in tensile strength
as the result of microbial exposures.
Gu et reported fungal degradation of
carbon-reinforced epoxy, carbon-reinforced
bismaleimide, and glass-reinforced fluorinated
polyimide composites due to hyphae penetration
into resin interiors. Electrochemical impedance
spectroscopy was used to demonstrate increas-
FIGURE 3.1 ing permeability over 8 months exposure to a
Glass fibers (2X) (a) unexposed, (b)exposed to SRB in cul- naturally occurring fungal culture, containing
ture medium, and (c) exposed to sterile culture medium. Aspergillus versicolorand a Chaetomium species.
3.4 Biodegradation of Nonmetallic Engineering Materials

There are numerous references to deteriora-


tion of coatings and linings in fuel tanks. Premature
failures were accompanied by heavy microbio-
logical growth.15-17 Spatial relationships between
microorganisms and blisters have received con-
siderable attention. One assumption had been
that microorganisms must penetrate the coating to
cause loss of adhesion and blistering. Stranger-
Johannessen and Norgaard18 observed that
FIGURE 3.3 microbial metabolites attacked the surface of coat-
Bacteria and crystals preferentially distributed along ings containing zinc chromate and zinc phos-
fiber-resin interfaces and surface anomaly. phate exposed in humid environments, changing
chemical and physical properties without coat-
The authors concluded that microorganisms may ing penetration. The degree of blistering was re-
derive energy from resins and fiber sizings. lated to the amount of growth. In their studies,
blister-substratum interfaces were usually dry, and
Polymeric Coatings when fluid was present it was often sterile or
contained microorganisms that would not induce
Moisture- and chemical-resistant polymeric coating degradation.
coatings and linings are used to protect underly- Epoxy resin coatings have been reported to
ing metals against corrosion. The coatings may be fail after nine months of service when used to coat
based on acrylonitrile, oleoresins, polyurethane, ship holding tanks for molasses, fatty oils, and
polyamide, vinyl, epoxy, or other resins. Coat- other fluid cargoes. Two spore-forming bacilli iso-
ing performance is influenced by composition, lated from the failures caused blistering in newly
thickness, continuity, adhesion to the metal sub- coated surfaces after one week.lg Similarly, ship
stratum, and resistance to microbial degradation. holds carrying cereals, wood, and other dry cargo
Bacteria and fungi can produce acids and en- became severely corroded after months of service
zymes that cause degradation. Polyesters and due to the activities of unidentified fungi on the
polyester polyurethane coatings can be vulnera- chlorinated rubber coating, causing disbonding.20
ble to microbial attack by enzymatic hydrolysis of Breaches in the coatings expose metal sub-
the ester segment.14 Microbial production of acids strata to further attack. Jones et aLiO described
and enzymes may result in selective leaching of breaches in nylon, epoxy, and polyurethane coat-
coating components with increased ion transport ings over steel exposed to mixed marine com-
and porosity. munities of anaerobic and facultative bacteria, in-
cluding SRB. Additionally, epoxy, but not nylon,
coatings showed pinpoint holes, blistering, and
peeling after a one-month exposure to a non-
marine bacterial assemblage including SRB. The
authors suggested that microorganisms respon-
sible for breaching the coatings may not neces-
sarily be those that initiate localized corrosion
on the metal under the failed coating. Jones-
Meehan et aL2I demonstrated water and bacterial
intrusion under a polythioether conductive caulk
that resulted in corrosion of the underlying steel
FIGURE 3.4 (Figure 3.5a,b).
Disrupted fibers of stressed coupons colonized by Mansfeld et a1.22evaluated microbial degrada-
rn icroorgan ism. tion of coatings in both marine and atmospheric
Biodegradation of Nonmetallic Engineering Materials 3.5

of delamination. Damage functions were used


for qualitative assessment of coating deterio-
ration. Steel coupons coated with phosphate
primer, epoxy midcoat, and polyurethane topcoat
with an average thickness of 76 p m were ex-
posed for 405 days in Pacific Ocean seawater.
Blisters in the coating were typically associ-
ated with microorganisms (Figure 3.6a,b). After
exposures to a mixed culture containing SRB,
coating breaches in latex topcoats with zinc primer
and epoxy polyamide midcoat on steel were sur-
rounded by corrosion products and bacteria. Simi-
lar microbial preference for surface anomalies was
observed on alkyd-coated steel after exposure to
the same SRB culture. The association of bacteria
with blisters or corrosion products cannot be inter-
preted as microbiologically influenced corrosion.
Recent work by Little et al.2324 demonstrated that
marine bacteria and iron corrosion products are
collocated in corrosion products produced by abi-
ological corrosion mechanisms.
Gu et al.25studied fungal degradation of poly-
imide films used as insulators in electronic pack-
aging. Increased ionic permeability was observed
using EIS after a one-week exposure to a fungal
consortium largely identified as A. versicolor. Re-
FIGURE 3.5
sistance of the films dropped from 1 O8 to 1O6 ohms
(a) Conductive caulk applied to 4140 steel after 15-
month exposure to a mixed, SRB-containing culture and
cmP2,indicating significant changes in the coating
(b) microbial biofilm under the caulk on the steel surface. dielectric properties.
Lavoie and Little26 isolated fungi from thick
black deposits (Figures 3.7a,b) on oily, painted
exposures. A damage function, calculated based aluminum surfaces of military helicopter interiors.
on remotely collected EIS and electrochemi- Fungi were growing on polyester polyurethane
cal noise analysis, was confirmed visually. Each coatings, underlying aluminum. fiberglass. caulk-
damage function was directly related to an area ing. synthetic fabrics, and electronic wiring. The

FIGURE 3.6
(‘1) Latex c o,ititig breach and (b) associated bacteria after exposure to SRB-containing culture.
36 Biodegradation of Nonmetallic Engineering Materials

FIGURE 3.7
Fungal growth on polyester polyurethane coating at magnifications of (a) 6 X and (b) and (c) ESEM micrographs of fungal
spores associated with corrosion products in breaches in polyester polyurethane coating.

following nine genera were identified: Aureoba- to replace manholes, wet wells, concrete pipes,
sidium, Hormodendrum, Phoma. Alternaria, Epic- treatment facilities, and grit chambers.
occum, Penicillium, Pestalotia. Stemphylium. and Concrete is an inert aggregate, such as rock
Trichoderma. Aureobasidium is known to colonize and gravel. surrounded by a cement binder. Hy-
and discolor organic coatings.27 Fungi were physi- drated silicates and aluminates are produced in
cally associated with corrosion products formed in the reaction with water. Deterioration of concrete
scratches in the protective coating (Figure 3 . 7 ~ ) . will result when any environmental agent can
break the inorganic bonds of the cement binder.
Acids, sulfates, ammonium and magnesium
Concrete salts. alkalies, organic esters. and carbon dioxide
can destroy a binder over time. Perfettini et al.29
Concrete is used in worldwide structural appli- evaluated degradation of cement binder induced
cations because of its strength, durability, and low by metabolic products of two fungal strains,
cost. It is used for large storage tanks and pipes. Aspergillus niger and Mycelia sterila. isolated
interior linings and exterior ballast coatings for from soil samples. Portland cement was exposed
steel pipe and containers, paving and many other in direct contact to the two fungal strains for 1 1
applications. A major construction application is months. Acids produced by A. niger (gluconic and
municipal wastewater collection and treatment oxalic) dissolved the cement, increasing poro-
systems. Concrete is currently being evaluated as sity by 11.4% and reduced the bending strength
one of the barriers for protection of nuclear waste (the strength applied to three points on the
during storage. Severynz8estimates that the dete- surface that causes breakage) by 78%. Increased
rioration of concrete in wastewater collection and porosity indicates cement dissolution and permits
treatment systems is primarily due to biodegrada- penetration of biological and chemical species.
tion and that over $1 00 million are spent annually M. sterila (gluconic and malic acids) caused a
Biodegradation of Nonmetallic Engineering Materials 3.7

significant 4.2% leaching of calcium original con-


tent, an 11% increase in porosity, and a 62% loss
in bending strength. Major organic acids produced
by fungi solubilize calcium, silica, aluminum, and
iron minerals. Solubilization is related more to the
nature of the acid than to concentration.
Kulpa and Baker30 and Mansfeld et aL3’ de-
scribe the complex biodegradation process in
sewage collection systems involving aerobic and
o~--i anaerobic bacterial mediation of the sulfur cycle.
J I I I I I Under anaerobic conditions SRB reduce sulfate
to sulfide in the sewage. Hydrogen sulfide (H2S)
is released into the aerobic ,environment at the
sewer pipe crown above the sewage where it is

3 100
c
/ oxidized to sulfuric acid by sulfur-oxidizing bac-
teria, commonly Thiobacilli. As acid is produced
0 the pH level may reach a value of 2.0 or lower.
3
L Dissolution of the concrete pipe occurs as the re-
sult of corrosive action of the acid. Mansfeld et
aL3’ monitored surface pH values and corrosion
rates of embedded steel sensors to evaluate con-
crete deterioration and control measures. Linear
0 polarization techniques were used to determine
0 40 80 120 160 200 polarization resistance and cumulative corrosion
DAYS loss (INT) for sewage-flushed and control sensors
FIGURE 3.8 (Figure 3.8). Most concrete structures include
Cumulative corrosion loss ClNT for mild steel sensors steel reinforcements, which will readily corrode
embedded in concrete and exposed to a sewer bypass: if exposed as a result of concrete deterioration
(a) control sample and (b) flushed sample. (Figure 3.9a,b). Moosavi et aL3* reported that the

FIGURE 3.9
(a) Corrosion of rebar in concrete and (b) bacteria associated with corrosion product. (See color plates for 3.9a.)
3.8 Biodegradation of Nonmetallic Engineering Materials

- COLONIZATION
BACTERIAL

7
DEGRADED
ASPHALT

NON-DEGRADED
ASPHALT
-

FIGURE 3.10
Bacterial colonization and degradation of asphalt.

biogenic production of H2S by SRB could perme- strength, polyoses influence wood swelling and
ate concrete and convert the passive iron oxide shrinkage, and lignin makes the wood resistant
film on steel rebars to a nonprotective iron sulfide to pressure.34 Fungal species are the most com-
film. mon microorganisms in colonization/attack, espe-
cially in humid conditions. Bacterial attack of wood
Other Engineering Materials is known but not as common. Fungal coloniza-
tion of coatings on painted and processed woods
Aspha/f may cause ingress of moisture. Basidiomycetes
(soft rot fungi) may degrade one or more of the
Asphalt is the unrefined residue of the frac- three main wood components leading to loss of
tional distillation of petroleum crude oil and is strength and weight in addition to disfigurement
used extensively in road construction. Petroleum- (Figure 3.1 la,b,c).
degrading bacteria excrete biosurfactants that
emulsify petroleum hydrocarbons by reducing
interfacial tension between the hydrocarbons
and water. pen dry^^^ exposed asphalt for
Additional Comments
three weeks to a mixed culture (Pseudomonas,
Acinetobacter, Alcaligenes, Flavimonas, and The emphasis of this chapter has been on
Flavobacterium genera) cultivated to use asphalt the negative aspects of biodegradation of non-
as a sole carbon source. The author concluded metallics. However, biodegradation can have pos-
that resultant brittleness and flaking were limited itive effects. Synthetic polymeric composites of
mainly to the asphalt surface (Figure 3.10). The polyactide, polyglycolide, and polyhydroxybutyric
saturate and naphthalene aromatic distillation acid are designed for use as implant screws,
phases supported increased bacterial growth with pins, and plates to fix fractured bones in place.
concomitant emulsification. Biodegradable plastics reduce the number of
operations a patient must undergo.35 Biodegrad-
Wood able polymer resins compete with plastic materials
in the form of mulch films, planting containers,
Wood is one of the most commonly used hay twine, surgical stitching, medicine capsules,
engineering materials. Its main components are and composting bags.36 Biodegradable conformal
cellulose, polyoses (polysaccharides), and lignin. coating for printed boards and components can
Cellulose cell structure determines tensile be removed by microorganisms rather than toxic
Biodegradation of Nonmetallic Engineering Materials 3.9

Conclusions

Most engineering materials are ultimately sus-


ceptible to microbial deterioration. Both sus-
ceptibility and rate of degradation vary among
materials. Laboratory and field data have been
collected that document biodegradation of fiber-
reinforced polymeric composites, polymer-coated
metals, concrete, asphalt, and wood. In excep-
tional cases it is possible to estimate the percent-
age of the total degradation of a particular mate-
rial that can be attributed to microbial processes.
For example, Severyn28estimates that biodeteri-
oration of concrete in wastewater collection and
treatment systems costs approximately $1 00 mil-
lion annually. Laboratory evidence indicates that
asphalt is biodegradable at a slow rate. However,
there are no case histories that document the prob-
lem in an engineering application. In most cases
economic data related to biodegradation are not
available.

Acknowledgments

This work was supported by the Office of Naval


Research, Program Element 0601 153, the De-
fense Research Sciences Program, and is NRL
Contribution Number NRUBN7333-98-00XX.

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1357. (Portsmouth, UK: 1995).
CHAPTER 4

The Biodeteriorationof Building Materials


By C. Saiz-Jimenez

Introduction nitrogen and phosphorus. Rough or porous sur-


faces facilitate attachment of a,irborne propagules
and the accumulation of nutrients.
Throughout history humans have used the A primary colonization of chemoautotrophic
most beautiful and durable stone for monumental bacteria favors settling of heterotrophic bacteria
buildings. Beginning in the sixth century B.C., mar- and fungi. The activity of heterotrophic bacteria
ble extracted from the Pentelikon quarry became on stone is governed by the availability of suitable
a common building material. Abundant limestone organic matter. Most stones contain sufficient or-
and marble quarries enabled the ancient Greek ganic matter from deposition of airborne particles,
architects to build the Acropolis and Roman archi- dust, soil, or dead autotrophic and phototrophic
tects to build the Forum. organisms to maintain growth and activity of large
Weathering starts as soon as a stone is populations of bacteria.
extracted from a quarry or a mortar is placed in a Many building materials are prone to colon-
building. Weathering of building materials is cau- ization by organisms. Recently, biorecepfivify was
sed by natural environmental factors. Sun, frost, defined as the aptitude of a material to be
wind, rain, and so forth contribute gradually to this colonized by one or several groups of living
process in which materials are broken down into organisms without necessarily undergoing any
smaller particles and ultimately into constituent biodeterioration.* Biodeterioration implies material
minerals. degradation. Bioreceptivity tests for three different
Colonization and biodeterioration on build- materials-Carrara marble, Balegem calcarenite,
ing materials usually are linked to environmental and mortar-have been carried out. These ma-
conditions.’ The most significant parameters af- terials were previously subjected to different kinds
fecting microbial growth are represented by phys- of physical treatments, including frost-thaw cycles
ical factors, mainly moisture, temperature, and and thermal shock treatments, to induce physical
light, as well as by the chemical nature of the sub- and chemical weathering.
stratum. Only water and a minimal supply of min- After three months of incubation with the
eral salts are required for colonization by pioneer- cyanobacterium Gloeofhece sp. PCC 6909, it was
ing organisms. It is the duration of the period of observed that bioreceptivity was different for the
wetness that is crucial, rather than the frequency of three materials. Better growth and development
wetting, in predisposing a surface to colonization. of the biofilm was provided by mortar, followed
Inoculation is more rapid where there is ad- by Carrara marble, and Balegem calcarenite. The
jacent or overhanging vegetation from which mi- type of treatment apparently had no effect on the
croorganisms can be brought by wind and rain, bioreceptivity of mortar and Carrara marble to
and development is further accelerated by bird cyanobacterium. In the case of the calcarenite,
droppings, agricultural fertilizers, and pollution- growth was absent in untreated samples or sam-
derived nitrogen oxides, which introduce additional ples treated with frost-thaw cycles (frost and thaw

4.1
4.2 The Biodeteriorationof Building Materials

by air). Treatments that included water as thaw- The chemical basis for this decomposition is the
ing or cooling agents (in frost-thaw and thermal instability of carbonates in acid solution.8 There-
shock treatments, respectively) allowed the growth fore, any organism that generates organic acids
of Gloeothecesp. Therefore, in these cases physi- (bacteria, fungi, lichens, etc.) or inorganic acids
cal treatment changed the bioreceptivity of the ma- (bacteria) is capable of dissolving insoluble car-
terials to the organism owing to the action of water bonates. Even the mere metabolic generation of
on the mineral components and its mobilization. CO2 during respiration has this effect. In addi-
Guillitte and Dreesen exposed a wider range of tion, other building materials, such as granites and
materials (stones, bricks, mortars, and concrete) bricks, more resistant to biodeterioration, are used
to a nine-month period of intermittent sprinkling on for monumental constructions.
steeply inclined runoff surface^.^ The liquid con-
tained a mixture of pioneer organisms, from which Limestones and Marbles
cyanobacteria, algae, diatoms, and mosses were
successful in colonization. They demonstrated that The relatively easy workability of limestone
the bioreceptivity of building materials is highly makes it the most frequently used stone for con-
variable and is controlled primarily by their sur- struction of historic buildings and monuments.
face roughness, initial porosity, and mineralogical Limestone is mainly composed of calcium (calcite)
nature. and magnesium (dolomite) carbonates, with vary-
In contrast, air pollution modifies the chem- ing amounts of other materials, such as quartz,
ical composition of building materials in urban clay, and bioclasts. Marble is a metamorphic rock
environments, resulting in the selection of mi- formed by the recrystallization of limestone under
croorganisms with specific nutrient requirements relatively high heat and pressure. It is capable of
or with a defined metabolic ~ a p a b i l i t y .In ~ this taking a high polish and, therefore, is used for or-
context, the enrichment of stones in nitrogen namental purposes.
and sulfur compounds opens the way to sulfur- Microbiological analyses of weathered stones
and nitrifying-bacteria c o l ~ n i z a t i o nCyanobacte-
.~ have shown the presence of bacteria that utilize
ria needing sulfates for carbohydrate sheath pro- sulfur dioxide or sulfur-containing compounds, giv-
duction and balanced growth find a good niche ing rise to sulfate as a product of m e t a b o l i ~ m . ~ ~ ’ ~
in weathered stones with gypsum crusts6 Het- Bacteria can be involved in oxidation as well as
erotrophic bacteria and fungi are selected in ur- reduction of sulfur. Atlas et al. have reported that
ban environments because of the considerable in- the calcium ions obtained by release from gypsum
put of petroleum-derived compounds, from which when Desulfovibrio desulfuricans reduces sulfate
n-alkanes can be readily ~ t i l i z e d . ~ react with carbon dioxide, resulting in the formation
In this paper, colonization, growth, and deteri- of calcite.’’ Gypsum crusts on marble treated with
oration of building materials by organisms are re- a bacterial broth showed the cleaning and neomin-
viewed. eralization carried out by the bacterium, which con-
sumed a large portion of the available gypsum in
the crust.
Building Materials Heterotrophic bacteria were assumed to be re-
sponsible for a red-orange stain in Carrara marble
Some of the most frequently used building ma- decorating the faGade of the Certosa of Pavia, Italy
terials are based on carbonates (limestone, mar- (Figure 4.1). However, further studies showed that
ble, sandstone, mortar, etc.). Carbonates are an the origin of the stains was due to the presence
important reservoir of carbon on the earth’s sur- of minium (Pb304)as lead was probably used for
face, accounting for 78.5% of total carbon. Car- anchoring the marble slabs to the walls.’*
bonates in nature may be readily degraded as a Ortega-Calvo and Saiz-Jimenez reported the
direct or indirect result of microbiological activity. presence of phenanthrene-degrading bacteria
The Biodeteriorationof Building Materials 4.3

provide new avenues of attack deep inside the


crystal and a vastly increased surface area sus-
ceptible to attack by water and/or dissolved acids
in the water, such as nitric and sulfuric acids from
air pollutants.
Fungi could decompose mineral matter, but
probably only in a microhabitat when there is an
accumulation of organic matter that can be metab-
olized. In a survey on fungi isolated from building
stones, the most efficient oxalic acid-producing
fungus was Aspergillus niger.16 It is well known
that in laboratory conditions organic acids are pro-
duced by many fungal cultures. These acids may
FIGURE 4.1 play a role in mineral weathering, owing to their
Staining of marble on the Certosa of Pavia, Italy. (See ability to form complexes with cations, promoting
color plates.) the removal of the latter.18119
We must ask, “Are the organic acids produced
in the limestones of two European cathedrals under natural conditions?,” because the produc-
(Seville, Spain, and Mechelen, Belgium) as tion of large amounts of metabolic products from
demonstrated by conversion to 14C02 of [9- carbohydrates is a pathological behavior resulting
14C]phenanthrenefreshly added to the stones and directly from the influence of abnormal environ-
by isolation of bacteria capable of using phenan- mental conditions.20
threne as sole source of carbon and energy.13This Invariably, laboratory media for cultivation of
suggested that microorganisms present in build- fungi contain carbohydrates in concentrations far
ing stones are able to transform deposited atmo- exceeding those the organism would ever en-
spheric pollutants and to use them for growth. counter in nature, and to which the fungus is
It has been shown that fungi can also thrive adapted for maximum efficiency of utilization. It
on building stones14-16 and their growth may in- appears that the enzyme mechanisms normally in-
duce mechanical or chemical changes in miner- volved in complete oxidation of the carbohydrate
als. The fungi isolated from weathered stones are become saturated, and the molecules are shunted
usually ubiquitous saprophytes whose conidia are to secondary enzyme systems. Therefore, the pro-
readily distributed through the atmosphere. Most duction of organic acids in many fungal cultures
of the isolated species are commonly included in could be the consequence of a metabolic overflow
floristic listings. Aspergillus, Penicillium, and Cla- and should not be extrapolated to nature.
dosporium are among the most common airborne Although cyanobacteria (formerly blue-green
fungi and, thus, have worldwide distribution. Also, algae) and algae are organisms commonly as-
these fungi have a remarkable saprophytic and sociated with aquatic ecosystems, they also are
polysaccharide-degrading potential. widespread over terrestrial substrata. Their occur-
The in vitro fungal corrosion of limestone was rence at the surface of soils, stones, and trees, par-
studied by Koestler et a1.l’ After only five weeks ticularly in moist areas, is well known. In building
in culture the hyphae of a Trichotecium sp. pen- materials they grow in humid places, on cornices,
etrated at least 1 mm into the crystals. Species in holes and crevices, or beneath crusts, where
of Trichotecium are known to secrete oxalic acid, water is retained and evaporation is slow owing to
citric acid, and gluconic acid among other prod- protection against winds or direct sunshine. Fur-
ucts. These secretions can chemically attack the thermore, growth also may be due, for example,
dolomite or calcite, causing the observed etch- to leaking or badly sited roof guttering, to inade-
ing. The channels created by the fungus further quate drainage of flat areas, or to frequent wetting
4.4 The Biodeteriorationof Building Materials

are the major agent of soiling in exterior building


surfaces.
An unfavorable microclimate in the stone may
induce the formation of resistant algal forms, as
was observed by Pietrini et al. in marble remains
in Rome.22 This is a common mechanism in sur-
vival strategy. The reddish-orange colored patina
present on the marble was produced mainly by the
presence of cysts of Haernatoccus pluvialis. Their
formation is accompanied by a change in color
from green to red-orange owing to the production
of large quantities of cytoplasmatic carotenoids,
responsible for the color alteration.
Endolithic growth also could be considered as
a survival strategy. Saiz-Jimenez et al. found a
cryptoendolithic microbial community developed
as a green layer 1 mm below the surface of a lime-
stone from the Basilica of Tongeren, Belgium.23
This community was dominated by unicellular
cyanobacteria. Giaccone et al. found the endolithic
active borer Hyella fontana in marble statues in
Rome and attributed a role in the decay of the
stone to this c y a n o b a ~ t e r i u m . ~ ~
The aggressive action of phototrophic mi-
croorganisms in relation to the substratum where
they develop has been considered negligible by
some authors. However, apart from the unaes-
thetic appearance, evident in most of the reports
on cyanobacteria and algae on historic buildings,
FIGURE 4.2 there are few references in the literature that point
Phototrophic microorganisms on the fagade of the cathe-
to direct decay mechanisms. The Cestia pyra-
dral of Salamanca, Spain. (See color plates.)
mid in Rome presented pronounced pitting and
black stains in its walls, which were identified as
by wind-blown rain or from adjacent watercourses the effect of cyanobacterial g r o ~ t h .Hyvert~ ~ , ~re-~
(Figure 4.2). Their growth is rarely uniform, ported that algae also caused the cavities of the
frequently forming streaks that follow the areas of reliefs in Borobudur temple, Indonesia, to become
dampness. Their presence is more apparent on more p r o n ~ u n c e d .Danin
~ ~ reported weathering
the north faCades of buildings than on the south, of limestone walls and monolithic tombs up to
because the latter dry out more readily. 2,600 years old in Jerusalem, Israel, induced by
Dupuy et al. differentiated, from an ecologi- coccoid cyanobacteria.28 By decreasing the co-
cal point of view, two main groups of cyanobac- herence of stone crystals around their colonies,
teria inhabiting monuments.21The first group con- the cyanobacteria accelerate detachment of stone
tains species living under dim light and constant particles, leading to weathering at the rate of
humidity conditions. They develop sheaths and 5 pm/y. The same stone without cyanobacteria
form heavy, colored growths on interior walls in- does not weather even after hundreds of years.
side the buildings. The second group is composed Phototrophic microorganisms also may have a
of species that can stand extreme conditions, such role in the mechanical biodegradation of the stone,
as high light intensity and drought periods. They exerting considerable force through repeated
The Biodeterioration of Building Materials 4,5

FIGURE 4.3
Scanning electron micrograph of Gloeothece sp. cells
involved in the sheath.

shrinking and relaxation when they undergo cy-


cles of drying and moistening. This is mainly
attributed to the mucilage formed by the sheaths of
the cyanobacteria and algae, which adheres them
to the substratum and suffers deep changes in vol-
ume because of its water retention proper tie^.^^
The sheath allows the establishment of a self-
contained aquatic environment within which the
cells can attain adequate irradiation and gaseous
exchange. In addition, the presence of this wa-
ter reservoir with a high water potential ensures
that the cells remain essentially aquatic, thus per-
mitting the cyanobacteria and algae to overcome
drought periods. Through sheath contraction and
expansion, they can loosen stone grains, contribut-
ing to the gradual destruction of the ~ t o n e (Fig-
~ ~ ~ ~ ’
ure 4.3). In addition, the formation of cyanobacte-
rial and algal patinas results in a longer moisture FIGURE 4.4
retention at the surface of the stone, increasing the Limestone tessera from a mosaic of the Roman town of
mechanical damage produced by the freezing and Italica, Spain, covered by epilithic lichens. Before (a) and
thawing of water present in the pores of the stone. after (b) removal of the lichen thalli with hydrogen per-
Deterioration of limestones, marbles, and oxide. Extensive pitting was observed beneath the thalli.
sandstones by lichens was investigated by Saiz- (See color plates.)
Jimenez and coworker^.^^-^^ Petrographic studies
of several types of deteriorated limestones from damages (pitting) at the thallus-stone interface
the Roman mosaics of ltalica due to the action (Figure 4.4a, b). Endolithic lichens occur below the
of lichens were also reported.36 Epilithic and en- stone surface38 (Figure 4.5). It is well established
dolithic lichens colonize, penetrate, and etch the that lichens are able to withstand prolonged peri-
limestones. Epilithic lichens cover the surface of ods of desiccation, reabsorbing water and swelling
the limestone, causing mechanical and chemical quickly once it becomes available again. This is
4.6 The Biodeteriorationof Building Materials

matter, etc. allows the formation of a protosoil.


In some limestone cathedrals, the most com-
mon species were Tortula muralis, Didymodon fal-
lax, and Gymnostomum calcareum, although most
bryophytes appeared on bricks and mortar^.^^>^'
In contrast, in a tropical forest area where the
Mayan Great Jaguar Pyramid and its quarry are
located, the limestone is covered by a carpet of
mosses, up to 3 mm thick, formed by the accumu-
lation of biomass, that is green at the surface and
brown in the interior. The mosses are anchored
to the stone by rhizoids, which penetrate in depth,
forming a network. As a result, the stone, very dis-
FIGURE 4.5 integrated, shows holes from which a dense mat
Fruiting bodies of an endolithic lichen (Caloplaca sp.) of rhizoids emerge, and the area penetrated by the
emerging between calcite crystals. (See color plates.) rhizoids is completely di~aggregated.~~
Vascular plants represent the later invasion in
a plant succession. The roots cause important de-
particularly true in xerophytic species. The process terioration in the structure of the buildings (e.g.,
can result in deterioration of the stone, particularly in roofings, tiles, gutters, drains, etc.), ultimately
by successive expansion and contraction of the causing their ruin.
lichen during wetting and drying, as simple field
observation suggests that absorption of water by Suncistones
dry thalli in most lichens is a rapid process and
takes 1-2 minutes to achieve full saturation. The workability of some sandstones, as well
Lichens produce a wide range of secondary as limestone, makes it one of the most frequently
metabolites often referred to as lichen acids. Most used stone for construction. Sandstones are com-
of these are aromatic with orsellinic acid and its posed of consolidated sand in which the grains of
homologues as the principal structural unit, con- quartz and feldspar are cemented by four common
densed as di-, tri-, and tetracyclic compounds. cements: silica, calcite, limonite, and clay min-
Syers and lskandar demonstrated that orcinol and erals. Silica-cemented sandstones may resem-
p-orcinol depsides and depsidones are sufficiently ble quartzites (metamorphosed sandstones) in its
soluble in water to function as metal-complexing high hardness, strength, and resistance to decay.
agents in stone eat he ring.^^ Lecanoric acid Sandstone cemented by limonite is soft to work.
formed a reddish-yellow complex when it was al- Tiano et al. studied 50 samples of deteriorated
lowed to react with biotite, and significant amounts sandstones from buildings of the historic center
of Ca, Mg, Fe, and Al were released from silicates of F l ~ r e n c eMicrobiological
.~ analysis showed the
by solution of lichen acids. In addition, oxalic acid presence of autotrophic bacteria of the genus
is recognized as an active lichen metabolite in the Thiobacillus, which utilize sulfur and thiosulfates
weathering of carbonate rocks in nature. Calcium as sources of energy and which give rise to sul-
oxalate was encountered as patinas on limestone fate as a product of metabolism. The facultative
and marble statues as a consequence of the pres- chemolithotrophs species Thiobacillus novellus
ence of lichens, which provided the acid required and Th. intermedius were isolated by Gugliandolo
to form o x a I a t e ~ . ~ ~ ~ ~ ~ and Maugeri from gypsum and concrete sub-
The growth of bryophytes on marbles is rare strata in the church of s. Maria degli Alemanni, in
and usually confined to crevices or holes where Messina, Italy.1° Sulfur and nitrifying bacteria have
accumulation of dust, sand, water, dead organic been linked to deterioration of concrete and are
The Biodeteriorationof Building Materials 4.7

thus capable, by their biological activity, of generat- was well metabolized by 70% of the analyzed
ing the same acids that may be present in acid rain. bacteria.
Meincke et al. isolated nitrifying bacteria from Most heterotrophic bacteria are able to use
German sandstone monument^.^ The popula- various organic compounds as a source of carbon
tion analysis indicated that the most abundant and energy for growth. Tayler and May reported
ammonia-oxidizing bacteria in the sandstones that the quantitative and qualitative nature of the
belongs to the genus Nifrosovibrio, although heterotrophic bacterial population on sandstone
other ammonia-oxidizing bacteria of the genera varies seasonally and can be related to moisture
Nifrosomonas and Nitrosospira we re detectable. and temperature changes associated with a tem-
Nifrobacter was the only detectable genus of the perate climate.45 The potential of these popula-
nitrite-oxidizers. Both groups of nitrifying bacteria tions to cause damage to sandstone also varies
live endolithically in the sandstone of different with season. In this respect, Lewis et al. suggested
monuments. The pH tolerance of Nifrosovibrio that bacteria on stone can be extremely versa-
and its resistance to high concentrations of salts tile and could maintain their activity during nutri-
might contribute substantially to the selective ent perturbations, operating at low nutrient levels
enrichment of Nifrosovibrio in the sandstone of and utilizing what the environment has to offer.46
the monuments. The bacteria of this genus acidify As a consequence, bacterial populations may be
their environment by excretion of nitrous acid and able to maintain their involvement in the process of
thus participate in the acidic attack on calcitic stone deterioration during periods of nutrient flux.
sandstone. Bock et al. identified a new species, Petersen et al. found that Penicillium, Phoma,
Nitrobacfer vulgaris, isolated from stone from the and Exophiala species colonized most examined
Cologne cathedral .43 German sandstone monuments.47 Furthermore,
Baumgartner et al. demonstrated that stone they stressed the biodeteriorating activities of
materials from the surface of buildings generally the genera Cladosporium, Penicillium, and Tricho-
release significant quantities of NO into the derma, which were the most abundant on the mon-
~ ~ production of NO must be
a t m ~ s p h e r e .The uments investigated. The principal genera isolated
due to the chemolithotrophic nitrifiers present in from weathered sandstone from the cathedral of
large numbers at the surface of building stones. Salamanca, Spain, were Penicillium, Phoma, Cla-
The ammonium-oxidizing as well as the nitrite- dosporium, Trichoderma, and Fusarium and an
oxidizing nitrifiers have been shown to produce association between fungi and algae was also
NO and N20. The nitrifiers need ammonium, found.
which most likely is supplied by wet and dry An endol it hic filamentous cyanobacterium
deposition of atmospheric NH:, a major pollutant (Phormidium sp.) was found growing under black
in the urban atmosphere, rapidly deposited onto sulfated crusts developed on calcarenite in the
stone surfaces. cathedral of Seville, Spain.48 Ortega-Calvo et al.
Warscheid et al. identified chemoorgan- proved that under laboratory conditions, the gyp-
otrophic bacteria from the uppermost layers sum present in black crusts covering calcaren-
of sandstones of German monuments.’ It was ites from the cathedral of Seville, Spain, can be
shown that most of the isolated bacteria used used as a source of sulfur by the cyanobac-
a wide range of different carbohydrates, amino terium Gloeofhecesp.6The sulfate released to the
acids, fatty acids, and hydrocarbons. About medium due to gypsum dissolution was progres-
40% of the strains analyzed were shown to be sively incorporated into the carbohydrate sheath
potential acid producers, whereas the capability and used for balanced growth. Black crusts de-
of manganese and iron oxidation was only spo- posited in Petri dishes with only the addition of
radically found in the bacteria living on the stone. distilled water doubled the biomass in four weeks
Kerosene, as a representative mixture of different when inoculated with Gloeofhece sp., showing
hydrocarbons detectable in polluted atmospheres, that growth can be produced in natural conditions
4.8 The Biodeteriorationof Building Materials

and that the mineral content of the crusts is


enough to support cyanobacterial development.
Observations of a wide range of monuments
in different enviromental conditions indicate
that black crust covering building stones sup-
ports considerable colonization of phototrophic
microorganism^,^^ which suggests that gypsum
might play a role in the cyanobacterial colonization
of blackened monuments in urban enviroments.
Cathedrals present a rich variety of lichen com-
munities that form continuous white to dark patinas
on the stones. The communities vary according to
the type of stone, the orientation, or the climato-
logical conditions. Colonization of sandstones by
lichens is helped by the contribution of the organic
matter from bird droppings, giving rise to char-
acteristic ornithocoprophilous communities. Saiz-
Jimenez described the production of cracks and
detachment of a thin layer of about 1-2 mm of cal-
carenite from the belfry (the Giralda) of the cathe-
dral of Seville by the lichen Lecania e r y ~ i b eTo .~~
this layer was anchored the lichen thallus.
Gorgoni et al. studied the deterioration induced
by lichens in the biocalcarenite of the Greek Si-
cilian colony of Selinunte, Italy.50The most com-
mon species were Dirina massiliensis, Verrucaria
nigrescens, Lecanora pruinosa, and Caloplaca au-
ranfia. The main effects produced were a strong
corrosion, sometimes with the production of cal- FIGURE 4.6
cium oxalates and, after the lichens have died, the Walls of the cathedral of Salamanca, Spain, with disperse
disintegration of surfaces. lichen thalli. (See color plates.)
The sandstones of the cathedral of Sala-
manca usually are weathered by atmospheric
agents, an effect more visible in the pinnacles probably suffered longer periods of dessication by
and balustrades of the high naves. They normally sunlight, showed the presence of cyanobacteria.
are stained by stork droppings and, consequently, The higher humidity of the sandstone allowed
colonized by ornithocoprophilous lichens, from the development of more complex microbial
which Ramalina capitafa and R. digifellata, with communities, including bacteria and fungi.
fruticose thalli, are a b ~ n d a n t . ~In’ vertical areas Warscheid et al. investigated the biodeteri-
free of droppings the absence of lichens is oration of Brazilian churches constructed with
significant, and only occasional small, disperse quartzites and soapstone and the Aachen cathe-
lichen thalli are found (Figure 4.6). Proliferation of dral, in Germany, constructed with sandstone^.^'
algae is so heavy in these areas that continuous Extremely biocorrosive heterotrophic bacteria
green patinas, visible even from ground level, were isolated from Brazilian stones, but on
are formed. A detailed species distribution was German sandstones fungi and nitrifying bacteria
reported.49 Sandstone, at the ground level, predominated. The extent of biodeterioration was
showed a complete absence of cyanobacteria influenced by the physical and chemical properties
while sandstone situated 50 meters up, which of the stone, where alkaline soapstone was more
The Biodeteriorationof Buildinq Materials 4.9

affected by biogenic attack than quartzite and


quartzitic sandstones. The climatic conditions in
Brazil (high humidity and temperature) favored the
metabolic activity of heterotrophic bacteria while
German sandstones were more affected by air pol-
lution. Mainly lichens were found on soapstone,
and bryophytes were common in the quartzites.

Granites
These rocks consist of feldspars and quartz
with varying amounts of other minerals, such as
micas, and with all mineral constituents visible to
the naked eye. They are dense and range in grain
size from fine to granular. Porosity and permeabil-
ity are usually low, and granite has high resistance FIGURE 4.7
to weathering and corrosion. Feldspar crystal with bacterial colonization.
Biodeterioration of granite is relatively insignif-
icant compared with limestones and sandstones. not only of the hyphae but often of associated
This results from its lower pH and its low solubility. communities of bacteria and algae, also could
Bell et al. stated that attack on minerals in granite be observed (Figure 4.7). Scanning electron mi-
by microorganisms mainly includes uptake of min- croscopy showed a clear discontinuity between
eral elements by absorption, production of acids, thallus and granite (Figure 4.8),but several evenly
physical disruption of minerals, and mineral alter- distributed pits of some 4-5 pm, corresponding to
ation through increased time of wetness.52 hyphae penetration, served as attachment mech-
Weed et al. reported that bacteria and fungi anism through an active penetration process.
are able to concentrate and incorporate P, Ca, The granites from the cathedral of Toledo,
Fe, and K into the cell walls; these are needed Spain, usually do not show extensive colonization
for their mineral nutrition, thus transforming micas
into vermic~lite.’~ Duff et al. showed that bacte-
ria inhabiting granite produced ketoglutaric acid,
which is capable of solubilizing silicates and phos-
phate minerals quite successfully, and that micro-
bial reduction of iron can transform biotite into
ver micuI ite.53
Ortega-Calvo et al. identified three cyanobac-
teria: Plectonema boryanum, Plectonema sp., and
Phormidium tenue, and four chlorophyta: Chlorella
homosphaera, Klebsormidium flaccidum, Muriella
terrestris, and Stichococcus bacillaris in the gran-
ites from the cathedral of Toledo, Spain.49 How-
ever, they found a higher number of species in the
adjacent mortars, which allow a higher degree of
water retention.
Arifio and Saiz-Jimenez studied the interac-
tion between the lichen Rhizocarpon geograph- FIGURE 4.8
icum and granite.54In some pores or microfissures Thallus of Rhizocarpon geographicurn on granite sur-
beneath the lichen thallus, important proliferation, face.
Next Page

4.10 The Biodeteriorationof Building Materials

by bryophytes or vascular plants, except in very


specific places as the result of microclimate con-
ditions. The greater part of the supporting lichen
flora is formed by species having crustose thalli,
including some with endolithic thalli, so that the
deterioration (seen as mechanical disintegration
of the particles) is greater than in the case of tiles
and flagstones from the same building. The most
common species belong to the genera Aspicilia,
Candelariella, and Lecanora with crustose thalli.
Physcia, with foliose thalli, appear only rarely.37
Ascaso et al. observed the generation of new
minerals by the action of lichens.55 Rhizocar-
pon geographicurn was able to generate hal-
FIGURE 4.9
loysite from feldspars and goethite from granite.
Terracotta colonized by cyanobacteria and algae o n
The lichen also attacked the edges of biotite.
the Pardon Gate, cathedral of Seville, Spain. (See color
Parmelia conspersa produced halloysite, kaolinite, plates.)
and amorphous silica from granite and feldspars.
It also was shown that lichenic acids were able to
complex with metalic cations from granite and with which Synechococcus sp. and Pseudoanabaena
their primary minerals. sp. were isolated. Scanning electron microscopy
of the underside of glaze pieces revealed heavy
Bricks and Terracotta colonization of Synechococcus sp.
The terracottas of the Pardon Gate of the
Fired bricks and terracotta are manufactured cathedral of Seville, Spain, showed an important
from mixtures of clay (mainly montmorillonite and colonization by microalgae, including 10 cyano-
illite types) and sand (quartz type). The vitrifica- bacteria, 12 chlorophyta, 1 xanthophyta, and 2
tion and strengh of the brick depend on the tem- bacillariophyta. The species most abundant and
perature reached during firing and the composi- frequently isolated were Nosfoc puncfiforrne,
tion of the mixture. The higher the temperature is, Phormidiurn fenue, Plecfonerna boryanum,
the stronger is the Bricks have an excel- Klebsorrnidium flaccidurn, and Muriella ferresfris.
lent resistance to the elements and are practically These communities are responsible for the green
insensitive to the action of atmospheric pollution. color of the terracotta statues and develop as
Although bricks usually are a very resistant ma- epilithic-forming biofilms (Figure 4.9) or are chas-
terial (deterioration of bricks results from freez- molithic in cracks or fissures. In some cases the
ing and salt crystallization) most of the problems communities were mixed with mosses, lichens,
are caused by soluble salts whose action is more and fungi. All cyanobacteria except one and K.
marked when the material is defe~tive.~’ flaccidurn developed mucilaginous sheaths that
Biodeterioration processes of bricks have retained dust, terracotta particles, and some
barely been studied. Palmer cites the example seeds. The seeds were able to germinate, and
of the Schleswig Cathedral, built with alternat- a considerable growth of vascular plants was
ing rows of glazed and unglazed bricks, a typi- observed (Figure 4.10).
cal architectural style in northern Germany.58 In
the past century, the glaze has been almost com- Mortars
pletely lost from many bricks while others near
and beneath the windows are undecayed. This By definition, a mortar is a mixture of sand
deterioration was related to the high microbial grains joined together by a binder (lime, cement,
biomass of phototrophic microorganisms, from etc.) of plastic consistency, traditionally used as
CHAPTER 5

Microbiologically Influenced Corrosion


in Fire Protection Sprinkler Systems
By D.H, Pope and R.M. Pope

Abstract and most often do, differ in various locations in a


FPS, in various geographic areas, and in different
phases of the MIC process.
Microbiologically influenced corrosion (MIC)
has emerged in the past several years as a
major cause of problems in fire protection sprin- Examples of MIC in FPS
kler systems (FPS). These problems include fail-
ures of FPS components due to corrosion (usually
Figure 5.1 presents examples of MIC in wet,
pinhole leaks), plugging of system components
dry, steel, and copper FPS from different locations
(including sprinkler heads) by biological growths
in the United States.
and corrosion products, and reduced flow capac-
ity due to the presence of deposits on the interior
diameter of the FPS piping. In this paper, a sum- MIC and MIC Control in FPS Is
mary of the cases that have been seen thus far
is presented. These cases have involved various Different in Many Respects from
types of FPS, materials, and geographic locations. MIC in Other Facilities
Methods for diagnosis, treatment, and monitoring
of MIC in FPS are discussed. MIC in FPS is similar in many respects to MIC
in other facilities in that it can occur in aerobic
and anaerobic regions, can involve almost any
Definition of MIC alloy (except titanium), involves communities of mi-
crobes, and is most often seen as underdeposit pit-
Microbiologically influenced corrosion (MIC) is ting corrosion. However, MIC in FPS differs from
corrosion affected by the presence or activities MIC in other systems in several critical aspects.
of microorganism^.(^-^) MIC almost always occurs Many of the differences are explained, in
concurrently with, and is virtually impossible to part, by how FPS are constructed and operated.
separate from, other corrosion mechanisrns.(l3) Figure 5.2 is a generic diagram showing the com-
This is due, in large part, to the fact that microbes ponents in a typical FPS. It is important to note that
help create conditions under which other corro- the piping at the inlet to the FPS is larger in diam-
sion mechanisms (e.g., crevice corrosion, oxygen eter than the cross-mains. The internal diameters
concentration cell corrosion, underdeposit corro- of the branch lines and pipes directly coupled to
sion, and acid attack corrosion) can occur.(13) MIC sprinkler heads are even smaller. This makes me-
can change the form, appearance, and rate of cor- chanical cleaning of the pipe very difficult.
rosion from that normally associated with other A FPS can be operated as a wet system, which
corrosion mechanisms. These characteristics can, contains water most of the time, but through which
5.1
5.2 MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems

FIGURE 5.1
Examples of MIC in FPS. (a) Discrete deposits (nodules) and deposits in steel wet FPS pipe. (b) Galvanized wet steel
FPS pipe showing heavier deposition and pitting on bottom of pipe. (c) Pit in copper wet FPS pipe. (d) Deposits in
galvanized steel dry FPS pipe. (e) Pinhole leak in galvanized steel dry FPS pipe. (See color plates.)
Microbiologically Influenced Corrosion in Fire Protection Sprinkler Systems 5.3

FIGURE 5.2
Diagram of an automatic sprinkler system.

water is not normally circulated. This creates prob- components more difficult. Also, most FPS are lo-
lems for controlling corrosion, scale, and microbes cated in areas where leaks could expose person-
since it is virtually impossible to regularly deliver nel to waters containing treatment chemicals. Fur-
treatment chemicals to all parts of the FPS. Alter- thermore, many FPS receive water directly from
natively, a FPS can be operated as a dry system. In potable water systems, the suppliers of which
theory, a dry FPS contains water only when pur- are understandably reluctant to approve treatment
posefully introduced during hydrotesting, inspec- chemicals in the FPS that might leak back into the
tor’s tests, or in case of a fire. The dry system potable water systems. These characteristics of
has several problems. First, water-based treat- FPS make traditional approaches to treatment of
ment chemicals cannot be maintained in the FPS MIC and other forms of corrosion very difficult.
most of the time since most of the FPS is “dry.”
Second, these systems never actually operate in
a totally dry state because water is introduced Summary of Information from MIC
during inspector’s tests. Finally, dry FPS are al- Cases Studied Thus Far
most never thoroughly dried, leaving some resid-
ual water, dirt, etc. in portions (most often low
The information obtained from the investiga-
points) of the piping.
tion of over 200 cases of MIC in FPS supports the
While most FPS are made of carbon steel,
following conclusions:
a significant number utilize galvanized or copper
pipe. Fittings are often cast materials, and sprin-
1. MIC in FPS is almost always associ-
kler heads are often nickel coated or made of
ated with discrete deposits (tubercles
brass. Problems in diagnosis and treatment of FPS
or nodules). Failures are most often
are created by the presence of a variety of these
due to pinhole leaks.
materials, including iron or steel, cast iron, brass,
copper, plastics, rubber seals, etc., making selec- 2. Deposit formation and MIC can occur
tion of treatment chemicals compatible with FPS in all parts of the FPS (underground
5.4 MicrobioloaicallvInfluenced Corrosion in Fire Protection Sprinkler Systems

supply, storage tanks, risers, mains, son, it is recommended that when FPS
branch lines, couplings, and sprinkler piping is installed, the weld be placed
heads). It is probable that most parts on the top.
of the FPS are colonized by bac-
5. There seems to be no preferential at-
teria and that some deposition oc-
tack of MIC at the weld region or other
curs in these areas. However, in dead
worked areas such as grooves. How-
legs (smaller cross-mains and branch
ever, some of these areas may have
lines) the microbiological, deposition,
less wall thickness than other regions,
and corrosion processes often slow
often causing leaks to appear in these
down because of the lack of nutri-
areas first.
ents and reactants. Water, oxygen, and
dissolved organic and inorganic ma- 6. Thinner schedule pipe may show signs
terials are critical to these processes (Len,leaks) of MIC earlier than thicker
since the major source of materials schedule piping; however, neither are
for continued deposit formation is the immune to MIC.
water, not the metal being corroded.
7. The smelly, black “sulfurous” material
This is supported by the finding that
recovered with many samples from
the most severe deposition and cor-
branch lines and sprinkler heads is
rosion is almost always seen in areas
composed primarily of residual cutting
, in periodic contact with water contain-
oils, iron hydroxides, iron oxides, and
ing some oxygen (i.e., the risers and
other materials. These materials are, in
mains). These areas receive untreated
fact, almost always low in sulfide con-
make-up water containing microbes,
tent and are not, in most cases, formed
nutrients, and oxygen when inspector’s
by sulfate-reducing bacteria (SRB) ac-
tests of the system are performed (this
tivity.
may be done bi-weekly, monthly, or
quarterly). Even in those cases where 8 . MIC involves communities of bacteria
the damage is seen in the smaller and is not caused by just one type (e.g.,
branch lines, corrosion has usually SRB) of bacteria. MIC in FPS has usu-
been greatly accelerated after the sys- ally been found to be more extensive
tem has been emptied and refilled as and severe in portions that routinely
the result of repairs or renovation of the come into contact with new water and
system. oxygen (i.e., riser and mains). MIC is
caused by communities of microorgan-
3. Metal loss is confined to the area under
isms working together to produce con-
the deposits and is usually in the form
ditions under which biofilms and de-
of pits. In some cases (especially those
posits can be formed and corrosion can
with larger deposits), the MIC corrosion
occur. These microbes include:
sites may appear grossly as relatively
shallow areas of metal loss. However, Aerobic bacteria that require
closer inspection usually reveals that oxygen to live. Aerobes are very
these areas are composed of multiple important in forming biofilms and
corrosion pits. discrete deposits (nodules and
tubercles).
4. MIC is usually most severe or ad-
vanced where the most and largest Low-nutrient bacteria (LNB) that
deposits accumulate (generally along grow in conditions of low organic
the bottom of the pipe). For this rea- foodstuffs (e.g., potable water).
MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems 5.5

LNB are generally aerobic bac- 13. MIC can plug sprinkler heads, leading
teria and are very important in to failure of the heads to activate and
the processes of biofouling, de- deliver water to control a fire.
posit formation, and corrosion. In
14. MIC can possibly “glue” sprinkler head
FPS, they are generally found in
components together to the extent that
larger numbers than other micro-
they may not operate properly.
bial groups.
15. MIC may cause changes in rubber
lron-related bacteria (IRB) that
components such as gaskets and 0-
precipitate iron compounds
rings, causing them to weep small
through a variety of metabolic
amounts of water to the outside of the
processes. These bacteria are
piping, often resulting iri severe corro-
largely responsible for forming
sion on the outside of the pipe.
discrete deposits (nodules and
tubercles) on surfaces. 16. Each FPS must be studied and treated
individually, as each has its own unique
Acid-producing bacteria (APB)
features.
that produce organic acids. Or-
ganic acids are very important
factors in the initiation of MIC. In the process of investigating and treating cases
of MIC in FPS, we have studied and tested nu-
Sulfate-reducing bacteria (SRB) merous methods for diagnosis and treatment. The
that produce sulfides. Sulfides following guidelines and methods have proven to
and SRB can be important in be the most practical for dealing with MIC in FPS
MIC, but they should not be used and attempt to accommodate the differences be-
as the sole indication of MIC. tween the different systems.
9. Microbes capable of causing MIC are
present in virtually all ground and sur- Diagnosis of MIC in FPS
face waters, soils, dust, etc. There-
fore, they can enter the FPS during
construction. They will also be in wa- Test samples from the FPS for viable bacteria
ters used to hydrotest, fill, or make-up of the types most often involved in MIC of FPS (see
to the FPS, unless these waters are item 8 , above). Also determine pH, dissolved oxy-
treated sufficiently to kill all MIC mi- gen, total iron, hardness, and free residual chlo-
rine. Tests should be done on water samples from
crobes. These microbes are, in many
the make-up to the system (riser or main) and at
cases, not killed by the disinfection pro-
the end of a branch line or inspector’s test valve.
cess applied by the water supplier.
Since each FPS is unique, each system must be
10. MIC can occur in any geographic tested for MIC. If the tests show the presence of
area in North America and probably any type of MIC bacteria, it is probable that the
throughout the world. FPS has MIC. Greater numbers and variety of
microbes increase likelihood of MIC.
11. MIC can affect most, if not all, materials
found in FPS. If a diagnosis of probable MIC is made visu-
ally inspect the interior of the riser(s) cross mains
12. MIC deposits can cause reduced flow and branch lines for deposits (nodules and tuber-
capacity in the FPS and, therefore, pre- cles) and underdeposit pitting corrosion, which are
vent the FPS from performing its func- strong indicators of MIC. Also determine chemical
tion of containing or putting out a fire. nature of deposits.
5.6 Microbiologicallyinfluenced Corrosion in Fire Protection Sprinkler Systems

Treatment of MIC in FPS We have developed the FPS Questionnaire,


~~ ~ _ _ ~ ~
located on the following page, as an aid in gather-
ing data necessary to diagnose and treat MIC in
If deposits and/or corrosion are present, the FPS. A detailed mitigation plan should be prepared
FPS should be rehabilitated by flushing with dis- before any work is started.
infectant or other cleaning chemicals, it should be
chemically cleaned to remove the deposits, or the
pipe should be replaced. The rehabilitation method Monitoring MIC in FPS
chosen should depend upon an analysis of the
extent to which MIC is present and on risk-benefit The FPS should be tested immediately af-
analysis. ter the treatment device is installed and regu-
After rehabilitation, the FPS should be disin- larly thereafter for viable bacteria and chemical
fected and a device installed on the make-up to parameters, including levels of treatment chemi-
disinfect all water entering the FPS (during fill, cals, to confirm that disinfection is being achieved.
inspector’s tests, or flow tests, or due to pres- FPS operations, treatments, and treatment levels
sure fluctuations or jockey pump operations). This should be reviewed at least once a year and when-
prevents MIC from recurring. The choice of dis- ever changes to the FPS are contemplated. This
infectants and use of other treatment chemicals will ensure that treatment continues to be ade-
will depend on the type of FPS, water chemistry, quate to prevent MIC in the FPS.
materials contained in the FPS, and regulations
pertaining to FPS in your area.
If deposits and corrosion are absent in both References
the riser and branch lines, the FPS should be dis-
infected and a device installed on the make-up 1. D.H. Pope, D.J. Duquette, D.C. Wayner, Jr., and
to disinfect all water entering the FPS (during fill, A. H. Johannes, Microbiologically Influenced Corro-
inspector’s tests, or flow tests, or due to pressure sion: A State of the Art Review (Columbus, OH: Ma-
fluctuations or jockey pump operations). This pre- terials Technology Institute of the Chemical Process
vents MIC from developing in the FPS. Again, the Industries, 1984).
2. D.H. Pope, “State-of-the-Art Report on Monitoring,
choice of disinfectants and use of other treatment
Prevention and Mitigation of Microbiologically Influ-
chemicals will depend on the type of FPS, water enced Corrosion in the Natural Gas Industry,” Topical
chemistry, materials contained in the FPS, and Report GRI-92/0382 (Chicago, IL: Gas Research In-
regulations pertaining to FPS in your area. stitute, 1992).
All new FPS should be cleaned and treated 3. G. Kobrin, ed., A Practical Manual on Microbiolog-
with effective biocides and oxygen consuming ically Influenced Corrosion (Houston, TX: NACE,
chemicals to prevent occurrence of MIC. 1993).
MicrobiologicallyInfluenced Corrosion in Fire Protection Sprinkler Systems 5,7

FPS QUESTIONNAIRE
This FPS QUESTIONNAIRE is a tool for assembling information necessary to recommend proper treatment for your FPS. Provide
as much information as possible. Fill out a separate questionnalre for each FPS.

It is assumed that you followed the directions in BTl’s “GUIDE TO DIAGNOSIS AND TREATMENT OF MIC IN FPS” to obtain data
allowing a diagnosis of MIC in your FPS. It is also assumed that you used MICkitTMFPS test kits to determine bacteria and chemical
parameters and that you or BTI inspected pipe from your FPS to confirm that it has MIC.

1. Client name
2. Namellocation of FPS
3. Type of facility or facilities served by FPS
4. Size of facility or facilities served by FPS
5. Number of buildings served by FPS
6. Number of years since FPS installed
7. Pipe material (e.g., black iron, steel (stainless,
galvanized, etc.), copper, etc.)
8. Pipe schedule
9. Valve materials (e.g., brass, cast iron, etc.)
10. Sprinkler head materials (e.g., brass)
11. Other metallic components
12. Rubber components (types and materials)
13. Plastic components (types and materials)
14. System construction (e.g., welded, screwed,
grooved, slip, socket, or others)
15. Type system (wet, dry, deluge, or others)
16. Volume of water storage tank (gal) feeding FPS
17. Volume of underground (gal) feeding FPS
18. Number of FPS “systems” fed by underground
19. Backflow preventor present (yesho)
20. Volume of each FPS (gal) to be treated
21. Roof design density
22. Sprinkler coverage (square feet)
23. Maximum flow rate (gpm) and pressure (psi)
of water into FPS from fire pump or city supply
24. Jockey pump rating (gpmlpsi)
25. Source of water (e.g., potable from supplier,
treated well water, untreated water, etc.) used
to fill and make up to the FPS
26. Water treatment performed prior to entering
FPS, other than that done by water supplier
27. Chemical composition of deposits in FPS
28. Chemical compostion of cleaning solution(s)
andlor flushing solutions, if any, used or to be
used in FPS

A diagram of the entire FPS is very useful in deciding where to apply treatment.

Results obtalned using MICkitTMFPS-SCREEN :

26. Locations in FPS where samples taken


27. Type of bacteria (LNB, APB, IRB, SRB) found
28. pH
29. Dissolved oxygen
30. Hardness level
31. Total iron
32. Free residual chlorine

Please include any additional information that you think would be useful
CHAPTER 6

MIC in Underground Environments:


External Corrosion in the Gas
Pipeline Industry
By T.R. Jack

Introduction 3. using effective tools to identify locations


of immediate concern,
Gas transmission systems developed over 4. selectively rehabilitating affected sec-
the past half century now carry much of the tions or taking mitigative action to re-
world’s energy conveniently and cheaply from duce risk, and
source to market over great distances. These 5. setting a schedule for future actions
systems consist of buried large-diameter carbon as part of an ongoing maintenance
steel pipe transporting clean, dry gas at high scheme.
pressures. The line pipe is typically protected with
a surface coating, which prevents direct contact This article focuses on the role played by micro-
of the external soil environment with the steel organisms in initiating external corrosion and on
surface, and by cathodic protection (CP) systems, the management of microbiologically influenced
which maintain a negative charge on the steel corrosion (MIC) on gas pipeline systems. This
and prevent its dissolution in corrosion processes article will not detail ways to recognize and
wherever the steel is exposed. characterize MIC sites. A major research pro-
External corrosion is a key threat to the on- gram sponsored by the Gas Research Institute
going integrity of gas transmission lines. Con- (GRI) has provided a state-of-the-art review of
sequences of a major pipeline rupture include monitoring methods along with practical field
issues of public safety and environmental dam- guides for this p ~ r p o s e Commercial
. ~ ~ ~ ~ ~ assay
age as well as the economic losses associated kits suitable for field use are readily available for
with system failure. To manage the risks posed, some of the more important bacteria involved in
a proactive approach to integrity management is MIC,2~3~4 and ongoing research is looking at ways
desirable. Overall, any proactive integrity manage- to characterize mixed populations by new deoxyri-
ment plan is based on a sequence of steps carried bonucleic acid (DNA) probe technique^.^^^
out in a more or less formal way. While details vary
depending on the unique featires of each system
the general process involves:
Setting the Stage
1. understanding the nature of the threat
posed,
Pipeline coatings bonded to the steel surface
2. assigning priority based on risk to parts of the pipe provide an impermeable barrier of high
of the system, electrical resistance. This effectively isolates the
6.1
6.2 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

(A) Degraded Coating: (B) Shielding Disbondment:


CP Penetrates Coating CP Limited Access
SOIL SOIL

FIGURE 6.1
Principal Modes of Coating Failure: (a) Degraded coating: The coating loses integrity, becomes permeable, hardens, and
cracks to allow CP access to steel surface. (b)Shielding disbondment: The coating remains impermeable and electrically
insulating. CP penetration into disbondment is limited by conductivity of water trapped under disbondment.

steel from the surrounding environment. Where materials that foster microbial growth. Despite this
the coating is properly applied and remains in- warning most of the early coating systems did
tact, external corrosion is effectively prevented; support microbial growth and suffered damage in
however, application problems and subsequent consequence as susceptible coating components
degradation during service can compromise coat- were biodegraded. From the point of view of in-
ing performance. Microorganisms play a role in the tegrity management, two basic failure modes can
in-service degradation of coatings. be distinguished (Figure 6.1). In one mode the
Microorganisms are naturally present in soil coating degrades in place, losing its ability to in-
environments. Conditions in the backfilled ditch sulate the pipe from its external environment. In
around pipelines can promote microbial activity. In this failure mode, cathodic protection can reach the
cold and temperate climates, the warm gas flow- underlying steel surface and protect the pipe from
ing through the system elevates the temperature corrosion (Figure 6.la). Early asphalt and coal tar
around the pipe, promoting biological activity. Mi- coating systems typically failed in this way. The
crobial populations depend on a number of factors, second mode of coating failure occurs where an
including soil moisture levels and nutrient avail- inert, durable coating retaining its insulating prop-
ability. The backfill around the pipe is often more erties pulls away from the pipe surface to create
permeable to air and water and this provides en- a disbondment capable of shielding the underly-
hanced levels of nutrients to microbial colonies in ing steel surface from cathodic protection (Figure
the soil next to the pipe. In the past, before top soil 6.lb). This is a more serious failure mode. Al-
and surface debris were segregated and handled though many kinds of coatings have been used
separately during construction, organic material in pipeline protection, asphalt enamel and tape
was often interred with the backfill, and its decay wrap coatings are discussed here to illustrate the
promoted microbial activity around the pipe.’ Fi- characteristics of the two basic kinds of coating
nally, coating components and other construction failure. These coatings have been chosen to pro-
materials can themselves be a source of nutrients vide examples because of their widespread ap-
for a microbial community. plication in the pipeline industry and because a
As early as 1939, Bunker8 emphasized the great deal of information is available on their per-
undesirability of employing coatings containing formance.
MIC in UndergroundEnvironments: External Corrosion in the Gas Pipeline Industry 6.3

1.4 - retained a high level of electrical resistance, 10


"E megaohms, while an uncracked specimen from an
si

!
w 1.0
adjacent area of coating, which had degraded and
separated from the steel surface, showed less than
10% of this resistance for the same size speci-
Z
0.8. men measured in the same way. An even more
w
' degraded coating in which fine cracks had devel-

1
3
0.6.

0.4
oped as the coating hardened and became brit-
tle showed a resistance of only 1 kiloohm. Pre-
sumably, continued cracking would ultimately have
led to a complete loss of insulating ability. These
u 0.2.
changes in electrical properties reflect changes in
1965 1970 1975 1980 1985 1990 1995
the composition of the coating, as water leaching
and biodegradation remove susceptible hydrocar-
YEAR bon components over time.
FIGURE 6.2 The involvement of various microorganisms in
Increase in current density required to sustain cathodic coating degradation or MIC can be documented
protection on an asphalt enamel pipeline over time. in a variety of ways. An effective traditional ap-
proach is to use the Most Probable Number tech-
nique based on simple growth tests in which a
Coating Degradation selective growth medium is inoculated with var-
ious dilutions of a field sample. The extent of
The petroleum asphalt and coal tar based coat- growth in the dilution series reflects the num-
ing systems used in the 1940s and 1950s degrade ber of viable bacteria in the original sample that
in place, losing their insulating qualities and their were able to grow in the specific test medium
adherence to the steel surface. Microorganisms used. Samples of degraded asphalt coating from
can be involved in this degradation, especially in the line described above were found to host a
the case of asphalt coatings. Phenols in coal tar mixed population of hydrocarbon-degrading bac-
coatings tend to discourage microbial growth.' teria, acid-producing bacteria (APB), and sulfate-
Excavations carried out on a 30-year-old reducing bacteria (SRB). In contrast, in samples
NPS16 pipeline with an asphalt enamel coating of adjacent ditch soil, hydrocarbon-degradingbac-
provide examples of what to expect for this mode teria and APB were not detected at all while
of coating failure. Figure 6.2 illustrates the ongo- SRB counts were a thousand-fold less than those
ing loss of coating integrity on this line. In the fig- associated with the degraded coating. The loss
ure, the progressive failure of the coating is evident of coating components can be seen by compar-
from the ever-increasing current density needed ing the infrared spectra of intact and degraded
to maintain an acceptable level of cathodic protec- material.
tion in the associated impressed current CP sys- Degradation of the coating does not necessar-
tem. As the coating failed, more and more steel ily represent a threat to pipeline integrity. The loss
surface became accessible to cathodic protection. of electrical resistance and increased permeability
Over time the number of anode beds needed to of the coating allows cathodic protection to reach
support the CP system had to be substantially in- the underlying steel surface, especially where
creased to maintain adequate levels of protection. the salinity of local groundwater provides an
Samples of asphalt enamel taken from exca- electrolyte of good conductivity. Effective cathodic
vations on this line reflect this change in insulat- protection reduces protons in aqueous solution
ing ability. For example, a sample from a strongly to cathodic hydrogen on the steel surface. This
bonded area of intact coating on this pipeline process increases the pH of the aqueous phase
6.4 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

next to the pipe and can coincidentally concen- by the potential (IR) drop through the electrolyte.
trate bicarbonate and carbonate salts under the For long disbondments, much of the steel surface
coating. One site excavated in a sodium sulfate exposed by separation of the coating remains at
salt seep showed trapped waters of pH 10 or a freely corroding potential. Because CP cannot
more and extensive deposits of crystalline ther- penetrate these disbondments, they fail to show
monatrite (Na2C03-HZO) in dried-out areas under up as potential dips in normal pipe to soil poten-
nonadherent degraded asphalt coating. In these tial surveys or in other holiday detection methods
conditions, microbial growth is discouraged and normally used to find missing coating without ex-
corrosion cannot proceed. Thus, MIC is not a cavation. Often the first indication of a problem is
threat. Historically, the relatively good perfor- a leak or rupture. The most susceptible locations
mance of asphalt coated lines confirms that loss are those in which a low conductivity groundwater
of coating integrity need not result in corrosion is present.
where adequate CP levels are maintained. While the polymers used to form tape coat-
Where effective cathodic protection is not ings (polyethylene, polypropylene, polyvinyl chlo-
maintained, MIC can occur. One such situation is ride) remain inert to microbial attack by virtue of the
found where soil dries out locally around the pipe large size of the polyolefin molecules,10other coat-
to give a high resistance barrier to CP while leaving ing components are susceptible to loss and alter-
sufficient water trapped in and under the degraded ation. Adhesives and primers that fix the tape to the
coating to support corrosion. These sites occur in pipe surface are particular targets for biodegrada-
relatively well drained areas exposed to periodic tion. Table 6.1 shows that these components rather
water fluxes. than the tape itself provide the nutrients for micro-
This kind of coating failure can be monitored bial activity (in this case the reduction of sulfate to
generally for a facility by tracking the current de- sulfide by anaerobic sulfate-reducing bacteria).' '
mand in the associated impressed current CP sys- A mixed microbial community is involved in break-
tem as shown in Figure 6.2. Affected spots can be ing down the complex organics in the adhesive
identified by holiday detection methods and short- to feed the SRB. In Figure 6.3, a piece of coat-
interval pipe to soil potential surveys. Locations ing from the field is exposed to a pure culture of
showing bad coating and poor CP potentials are SRB previously obtained from a pipeline corrosion
candidates for MIC failures. site. A burst of sulfide production results but then
the process stops as suitable nutrients already
present in the degraded adhesive and primer are
Shielding Disbondments
Plastic tape coating systems, which appeared
in the 1960s, provided a durable coating with high TABLE 6.1
electrical resistance and excellent insulating abil- 35S-SulfateReduction to Sulfide(A)
ities. Unfortunately, where these tapes separate 35S-Sulfide
from the pipe surface, a shielding disbondment can Incubation Time (counts per
result (Figure 6.1 b). Medium (days) minute)
In this scenario, penetration of protective ca- Mineral Salts Medium 7 1275
thodic protection potentials under the disbonded (MSM) 15 1445
coating depends strongly on the conductivity of Polyolefin Tape in MSM 7 4704
the water trapped in the pocket under the sepa- (adhesive removed) 15 3264
rated coating. Algorithms have been developed to Adhesives from Tape in 7 501,535
MSM 15 1,593,310
determine the degree of CP penetrati~n.~ Where
groundwater is very fresh and has low conductivity (A) By seven-day-old cultures of sulfate-reducing bacteria (Desulfovibrio vulgaris var.
vulgaris NClB 8303) grown anaerobically on tape coating components from a field
(1 mS/cm), protective potentials are limited to a few corrosion site."
centimeters from the opening of the disbondment
MIC In Underground Environments: External Corrosion in the Gas Pipeline Industry 6.5

2.8 with an increased current demand.' 1913 Where the


? current density available is not sufficient to meet

-6
rn
2.4

I
I
I this increased current demand, protective CP po-
tentials will be lost.
There is evidence that biodegradation of the
@t3 I
adhesive promotes disbondment of tape coating
from the pipe surface. Lab studies15 have shown
T-d 2.0
5 that tape wrap systems are especially susceptible
W I to loss of adhesion on exposure to wet biologically
z
0 I active soil. Figure 6.4 shows the loss of adhesion
p 1.6 of a polyethylene tape coating around a holiday
I
exposed to various environments for 20 weeks.
n I After exposure the specimens were subjected to
O 1.2 I a cathodic disbondment test16 to assess changes
E I in the tenacity of bonding of the coating to the
a steel surface. Exposure to a wet biologically active
E 0.8 clay soil had more impact on coating adhesion
5
v)
than exposure to a water control treated with
antibiotic. This suggests that soil organisms play
a role in reducing the adhesion of such coating
0.4 systems in service. Field observations indicate
that microbial effects can occur in the adhe-
sive layer even where the surrounding coating
appears well bonded and intact. Pressurized
20 40 60 80 100 bubbles of gas (Figure 6.5) found between layers
DAYS of tape wrap as well as under the coating in
FIGURE 6.3 a field excavation were obviously of microbial
Microbial reduction of groundwater sulfate to sulfide on origin. The composition of the trapped gas was
disbonded tape coating samples incubated anaerobically that expected for a mixed anaerobic population
with a pure culture of sulfate-reducing bacteria (SRB) and including methanogens: methane, 64-8970;
with a mixed culture containing SRB. carbon dioxide, 11-34%; nitrogen, 9-1 9%; and

1
Polyethylene Tape
exhausted (Figure 6.3). The SRB are not able to 40 r
attack complex organics present in the adhesive. 335
Repeating the experiment with a mixed popula- 30
tion of bacteria maintained in the lab on field coat- c
25
-a
l
1
ing samples gives a different result (Figure 6.3). In g 2o
this case sulfide production is sustained as other 4 15 Extruded Polyethylene
organisms continue to break down the coating ad- 4 10
E

hesive and feed the SRB the nutrients needed to Li5


sustain sulfide production. 0
The iron (11) sulfides ultimately produced by WATER CLAY WATER CLAY WATER CLAY

this microbial community are a family of unusual FIGURE 6.4


materials,12 many of which display interesting Cathodic disbondment of coatings16 around holidays
electrical properties. These become involved in after exposure to microbially active clay soil for 20
corrosion cells (as will be described presently) but +
weeks compared to exposure to water antibiotic as the
can also challenge the cathodic protection system control.
6.6 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

FIGURE 6.5
Pressurized bubbles of gas in the adhesive between coating layers on a tape-wrapped pipeline. (See color plates.)

hydrogen, 0.2-1.2%. Such observations clearly separates from the pipe surface to allow access of
demonstrate that microbial growth can occur in a low conductivity groundwater to the steel surface
the adhesive layer of a tape coating system with can create a shielding disbondment. For example,
evident damage to coating adhesion (Figure 6.5). shielding disbondments can be found under as-
While polyethylene or polypropylene tapes phalt coatings where coating degradation has not
remain intact indefinitely in an underground envi- proceeded to the point where CP can penetrate the
ronment even when disbonded from the pipe sur- coating to reach steel surface prior to separation of
face, polyvinyl chloride (PVC) may lose its integrity the coating from the pipe. Shielding disbondments
over time through biodegradation. The proper- provide the opportunity for MIC, especially where
ties of PVC are adjusted to meet the needs of the coating components feed microbial growth.
coating applications by inclusion of plasticizers.
These are typically phthalates, which constitute
50% or more of a pipeline tape coating. Although
the polymer itself remains inert to degradation Understanding the
in an underground application, the plasticizers Corrosion Threat
may be lost by a variety of mechanisms, includ-
ing bi0degradation.l’ This results in embrittlement Unprotected Steel
and cracking. Where this occurs over time, the
coating loses its ability to form a shielding disbond- The corrosion of unprotected steel in soil is
ment; however, field observations18 indicate that relatively well understood as a combination of
this degradation is not sufficiently rapid to avoid chemical and microbiological processes. Simple
corrosion problems. chemical corrosion depends on the presence of
Shielding disbondments are not confined to an aggressive agent, which provides the oxidizing
tape coating systems. In priniciple, any coating that power needed to convert iron in the steel to ionic
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry 6.7

form, and on the presence of an electrolyte, which OALVANlC BACTERIAL


supports the electrochemical processes leading COUPLE ENHANCEMENT
to metal loss. In general piping exposed to oxy-
gen and groundwater under conditions of neutral
pH will corrode to form iron (Ill) oxides at a mod-
est rate. Decreasing pH below 4 leads to rapidly
accelerated corrosion as acid becomes the ag-
gressive agent and corrosion products dissolve
readily to expose fresh steel surface to attack.lg
Increasing the salinity of the water in contact with
the steel surface increases corrosion rates by
improving the efficiency of the corrosion cell.
Overall Reaction:
These simple chemical considerations suggest
that corrosion under anaerobic conditions at near 8H' + 4Fe +S042- + "FeS" + We2++ 4H20
neutral pH should be modest, but this is not the
case. FIGURE 6.6
In the 193Os, severe corrosion rates were Schematic diagram of the mechanism of corrosion in
found in such circumstance^.^^^^ Water mains in a steel/FeS/SRB corrosion cell. The galvanic couple be-
black water logged soils in Holland had to be re- tween steel and iron sulfide is created and probably sus-
tained by SRB removing electrons from the iron sulfide
placed every two or three years. These biologi-
matrix as a source of reducing power.
cally active soils were found to contain SRB, a
group of anaerobic organisms that reduce ground-
water sulfate to sulfide as part of their essential
metabolism. Microbially generated black iron sul- predicting corrosion risk for unprotected steel in
fide precipitates are very aggressive toward steel. soil. These are shown in Table 6.2.
The mechanism involved is now usually described In this scheme, aerobic soils with low conduc-
as a galvanic couple formed between iron sulfide tivity groundwater are deemed relatively benign
and steel,21which is created and sustained by mi- while anaerobic soils are considered more aggres-
crobial action14 as shown in Figure 6.6. Corrosion sive presumably due to the potential for anaerobic
rates of 0.2 mm/year and penetration rates greater SRB to set up corrosion cells (Figure 6.6). Re-
than 0.7 mm/year have been reported in field18 duced soil resistivity is taken as more aggressive.
and lab14studies, but the actual corrosion rate is
a function of the iron sulfide content of the matrix in
contact with the steel s ~ r f a c e . ' ~Soils
~ ' ~with high TABLE 6.2
clay content, which retain water saturation and pro- Soil Aggressivity Model(A)
mote anaerobic conditions at pipe depth, are es-
pecially conducive to this scenario. Criterion Aggressive Nonaggressive
In general the relative importance assigned Resistivity (ohms-cm) t2000 >2000
to these simple chemical and microbial corrosion and/or
mechanisms is supported by early schemes for de- Oxidation Reduction ~0.400 >0.400
Potential (at pH 7, or ~0.430if clay or >0.430 if clay
termining soil aggressivity. These schemes used
measurable soil parameters taken at pipe depth to v WE))
Borderline Cases to >20 <20
assess the threat of corrosion damage in various Be Resolved by
locations. One such scheme developed by Booth Water Content ("A)
et al. in the 1970s was based on the extensive
(A) Based on average values of soil resistivity, redox potential, and water content
collection of soil information over dozens of field of the soil at pipe depth.22,23Because soil readings varied in some sites over
time, predictions in this model were based on the average of as many readings as
Correlations of observations to actual possible for each site.
corrosion damage established a set of criteria for
6.8 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

Increased conductivity of both soil and ground- protected pipeline systems in western Canada.
water makes conditions more aggressive as this The primary corrosion scenarios correspond to
provides a better electrolyte to support a more mechanisms that underlie simple soil aggressivity
efficient corrosion cell. The degree of soil wa- models. The secondary transformations represent
ter saturation is taken as a secondary parameter cases where transitions occur between aerobic
for prioritizing locations, with other factors being and anaerobic conditions in the field. These are
equal. not adequately represented in the schemes such
Such schemes are in principle useful for as- as the one shown in Table 6.2.
signing the likelihood of unprotected steel in The various scenarios shown in Table 6.3 can
a given location suffering significant corrosion be identified by analysis of corrosion products
damage. Appropriate soil probes have been taken from field site^.^^^^^ In general, X-ray diffrac-
designed for the convenient collection of the tion (XRD) can be used to identify crystalline prod-
needed data.24 The information gained can be ucts that are diagnostic for the various scenarios
used for risk assessment and for identification shown. In some situations, microbially produced
of locations needing high-priority attention in an iron sulfides are amorphous and cannot be seen
integrity management plan. Unfortunately, the by XRD. In this case simple qualitative chemi-
simple model shown in Table 6.2 breaks down cal analysis3 or energy dispersive X-ray analysis
when applied to operating pipeline systems with (EDXA) can be used to detect telltale sulfides. Us-
protective coatings and under cathodic protection. ing corrosion products to assign the mechanism of
attack is convenient, and it has the advantage that
Protected Steel organisms do not have to be numerous and active
at the time of excavation for one to recognize an
For pipelines under cathodic protection, the MIC scenario.
dependence of aggressivity on the soil resistivity The most severe corrosion scenarios found
factor as shown in Table 6.2 is reversed. The sim- to date (Table 6.3) all involve sulfides produced
ple model predicts that more corrosion will occur by microbial action.14 The steelhron sulfide/SRB
with lower soil resistivity but the opposite is true for corrosion cell is a feature of anaerobic conditions
cathodically protected pipelines. Here better elec- but can be considerably worsened by the occa-
trical conductivity in the groundwater leads to more sional incursion of oxygen as shown in laboratory
effective CP for steel exposed by: studies (Figure 6.7). These corrosion cells are
extremely difficult to oxidize thoroughly and they
missing coating in “holidays” or “jeeps,” revert readily to the original corrosion rate when
anaerobic conditions return.26 Conversion of an
degraded coating that has lost its insu-
aerobic corrosion cell that has produced iron (Ill)
lating ability, or
oxides as its corrosion products to an anaerobic
shielding disbondments. scheme with active SRB leads to the production of
unique iron (11) sulfides in the microbially sustained
Even MIC involving the steeI/iron sulfide/SRB corrosion mechanism. These sulfides are more
corrosion cell shown in Figure 6.6 is arrested aggressive in nonbiological studies of the galvanic
by cathodic protection potentials of -950 mV couple formed between steel and iron sulfides
(CU/CUSO4). ’ than the mackinawite precipitated in the simple
In the real world, swings between aerobic primary SRB scenario.21 This suggests that the
and anaerobic conditions at a single location secondary transformation of an aerobic corrosion
lead to mixed corrosion scenarios, some of which site to an anaerobic SRB one may be a more
give surprisingly severe corrosion rates. Table 6.3 severe corrosion scenario than shown in the table.
summarizes the six common corrosion scenarios The importance of at least two secondary
found in almost 200 corrosion excavations on transformations as severe corrosion scenarios
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry 6.9

TABLE 6.3
Corrosion ScenariodA)

Frequency Diagnostic Corrosion Rates


Scenario (W Corrosion Products (mm/year)
PrimarycB)
Aerobic 3 iron oxides: lepidocrosite, 0.03 to 0.2
maghemite, magnetite,
hematite, goethite
Anaerobic 29 iron carbonate: siderite 0.01
Anaerobic + SRB 27 iron sulfides: 0.2 (general)
amorphous "FeS:' 0.7 (pitting)
mackinawite, greigite
Secondary(c)
Anaerobic becomes aerobic 21 +
iron oxides siderite 0.03to 0.2
underneath
Aerobic becomes anaerobic + SRB 3 marcasite, pyrite 0.2 (general)
0.7 (pitting)
or more?
Anaerobic + SRB becomes aerobic 17 elemental sulfur, iron 1 to 5(D)
oxides, siderite

(A) Deduced from corrosion product analysis based on excavation of corrosion sites on pipelines in western Canada.'4,25
(B) A primary scenario is one that occurs under one set of conditions.
(c) A secondary scenario is one in which the original scenario changes to a second scenario.
(D) Extreme rates may be related to very aggressive short-lived intermediates (such as sulfur) and may not be sustained.

suggests that the simple criterion for soil oxi- locations showing either a sustained anaerobic na-
dation reduction potentials (ORP) shown in the ture (consistent with Table 6.2) or showing periodic
soil aggressivity model, Table 6.2 is inade- swings between anaerobic and aerobic conditions.
quate. Worst-case scenarios can be expected for

Other MIC Scenarios


0.07
2 0.06
v Although SRB are important agents for MIC,
2 0.05
3 0.04 they are not found at all external corrosion sites
5 0.03t
.* cornsion Rate = o 11 mm/yr I \ on pipeline systems. An extensive survey of field
0 0.02 sites carried out in a Gas Research Institute project
0.01
0
on MIC found that many sites did not contain
0 50 100 150 zoo these organisms.' Other mechanisms for MIC
p2

Time (Days) have been suggested. Notable observations were


FIGURE 6.7
made with respect to the concentration of organic
Weight-loss experiment under anaerobic conditions with acid anions found in corrosion deposits' and an
steel exposed to wet clay soil rich in SRB and iron sul- assay was developed to enumerate the sort of mi-
fide/iron carbonate corrosion products. A period of air croorganisms involved. A fingerprint for the micro-
exposure in the middle of the experiment greatly en- scopic metal damage in the bottoms of corrosion
hances corrosion rates. Return to anaerobic conditions pits associated with microbial involvement was de-
restores the original scenario. scribed as diagnostic for MIC sites. Techniques for
6.10 MIC in Underaround Environments: External Corrosion in t h e Gas Pipeline Industry

generally assessing field sites for MIC along with performance to date has been very good in terms
tools to do so, which came out of this program, of the frequency of corrosion failures.
have been described e l ~ e w h e r e In
. ~the
~ ~ context
of this discussion, these other MIC scenarios rep-
resent situations where external pipeline corrosion Integrity Management
is aggravated by involvement of bacteria other than
SRB. In terms of integrity management, the possi- Microorganisms are important to consider in
bility of MIC in sites without iron sulfide suggests pipeline integrity management as agents of coat-
that corrosion scenarios may be more severe than ing degradation and disbondment as well as MIC.
expected on the basis of simple chemical stud- For MIC or any other external corrosion mecha-
ies of corrosion rates for scenarios without SRB in nism to proceed, both the mating and CP system
Table 6.3. More needs to be known of these other have to be rendered ineffective.
scenarios and where they occur before further For steel surfaces exposed by missing or de-
implications can be drawn. graded coatings, adequate cathodic protection can
MIC may be aggravated by the presence of forestall and mitigate corrosion damage. Monitor-
chloride anions. Laboratory studies show that a ing the current density required to maintain ade-
synergy exists between pitting of stainless steels quate CP potentials in pipe to soil potential sur-
and corrosion by SRB.27 In the field a general veys along the right of way can identify degraded
correlation is seen between the chloride content coating problems. Installation of new anode beds
of corrosion products and the severity of damage or increasing current output for existing ones can
seen in corrosion pits on pipelines.’I2 This sug- maintain the integrity of the system where the coat-
gests that chloride levels in a groundwater may ul- ing ultimately degrades to lose its electrical resis-
timately be linked to enhanced corrosion damage tance. Close interval surveys and holiday detec-
in future predictive models for soil site aggressiv- tion techniques are useful to help pinpoint potential
ity. Preliminary lab experiments and available liter- trouble spots.
ature suggest that chloride concentrations above Shielding disbondments offer an insidious op-
about 150 ppm merit attention. portunity for MIC and other external corrosion
problems. These do not show up in pipe to soil po-
tential surveys where groundwater salinities are
Newer Coatings too low to allow penetration of CP under the
disbonded coating. Low-conductivity groundwater
The two basic types of coating failure de- (<4 mS/cm) combined with very anaerobic condi-
scribed here have been illustrated using avail- tions (-300 mV Cu/CuSO4 or less) or conditions
able information on asphalt and tape coated lines. that vary between anaerobic and aerobic provide
Newer coating systems employing a wide range of worst-case conditions for corrosion damage. For
materials and application technologies have been tape coatings that tend to form shielding disbond-
in service less time and their modes of failure are ments, wet soils with a high clay content (>20%)
yet to be understood fully. In general, newer coat- in freshwater locations have proven particularly
ings such as factory applied fusion bond epoxy prone to MIC involving SRB and iron sulfide.
powder technologies, extruded polyethylenes, At present, shielding disbondments cannot be
and combination coatings involving intimately identified by any kind of surface survey. Moni-
bonded layers of fusion bond epoxy (FBE) and toring is confined to the use of intelligent tools
polyolefins promise superior performance and for In Line Inspection (ILI). Identification of ex-
potentially lower life-cycle costs. Certainly, initial ternal metal loss allows excavation and repair of
evaluations suggest that they will be less sus- specific locations representing high risk. Analy-
ceptible to disbondment (Figure 6.4),and field sis of corrosion products in excavated sites and
MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry 6.11

a knowledge of the external environmental fac- References


tors that foster various corrosion scenarios along
the right of way can be used to assign the worst-
case corrosion rates for locations not excavated. 1. D.H. Pope, “Microbiologically Influenced Corrosion
in the Natural Gas Industry,” Gas Research Insti-
These predicted corrosion rates can be used to tute, Topical Report GRI-92/0469 (Chicago, IL: Gas
set an interval for future ILI runs. As subse- Research Institute [GRI], 1992).
quent ILI data become available, the progress 2. D.H. Pope, “State-of-the-Art Report on Monitoring,
of corrosion damage at specific sites can be Prevention and Mitigation of Microbiologically Influ-
tracked and the ongoing maintenance program enced Corrosion in the Natural Gas Industry,” Gas
refined. Research Institute, Topical Report GRI-92/0382
(Chicago, IL: GRI, 1992).
3. “Microbiologically Influenced Corrosion (MIC):
Future Needs Methods of Detection in the Field,” Gas Research
Institute, GRI Report no. 88/0113 (Chicago,lL: GRI,
1991).
Use of newer coating systems offers the 4. P.J.B. Scott and M. Davies, MP 28, 5(1992): 64.
promise of improved performance, but past history 5. G.A. Voordouw, Y Shen, C.S. Harrington, C.S.
suggests that careful analysis of failure modes in- Telang, T.R. Jack, and D.W.S. Westlake, Appl. En-
cluding testing for susceptibility to microbial degra- viron. Microbiol. 59(1993): 4104.
dation be carried out as part of coating qualification 6. G.A. Voordouw, A.J. Telang, T.R. Jack, J. Fought,
tests. P.M. Fedorak, and D.W.S. Westlake, “ldentifica-
tion of Sulfate-Reducing Bacteria by Hydrogenase
For existing systems, complete rehabilitation
Gene Probes and Reverse Sample Genome Prob-
by extensive excavation and recoating is extremely ing,” in Applications of Molecular Biology in Envi-
costly. Improved integrity management methods ronmental Chemistry, eds. R.A. Minear, A.M. Ford,
must be developed to locate and repair specific L.L. Needham, and N.J. Karch (Boca Raton, FL:
locations of special susceptibility, high risk, or im- Lewis Publishers, 1995).
pending failure. Ideally, ways must be found to ex- 7. B. Davis, Petroleum Microbiology (New York, NY:
tend this approach by soil probe measurements Elsevier, 1967), pp. 403-439.
and surface survey techniques to lines not acces- 8. J. Bunker, J. SOC.Chem. Ind. 58(1939): 93.
sible to ILI. 9. T.R. Jack, G.Van Boven, M.J. Wilmott, R.L.
The outstanding needs to achieve this aim Sutherby, and R.G. Worthingham, MP 33,8(1994):
include: 17.
10. J.E. Potts, R.A. Clendinning, W.B. Ackart, and W.D.
Niegisch, “The Biodegradability of Synthetic Poly-
a way to locate shielding disbondments
mers,” in Polymers and Ecological Problems, ed. J.
without ILI or excavation, Guillet (New York, Plenum, 1973), pa71,
a better understanding of the mecha- 11. T.R. Jack and R.G. Worthingham, in Biologically
nisms of MIC not involving SRB, Induced Corrosion, ed. S.C. Dexter (Houston, TX:
NACE, 1986), p. 339.
reliable correlations between measur- 12. J.S. Smith and J.D.A. Miller, Brit. Corros. J. 10, 3
able environmental parameters in the soil (1975): 136.
around a pipe and the likelihood of cor- 13. T.R. Jack, R.G. Worthingham, and F.G. Ferris, in
rosion under adjacent degraded and dis- Microbially Influenced Corrosion and Biodeteriora-
bonded coatings, and tion, eds. N.J. Dowling, M.W. Mittelman, and J.C.
Danko (Houston, TX: NACE, 1990), pp. 4-19.
tools to make the necessary measure- 14. T.R. Jack, M.J. Wilmott, R.L. Sutherby, and R.G.
ments by surface survey without excava- Worthingham, “External Corrosion of Line Pipe-A
tion. Summary of Research Activities Performed Since
6.12 MIC in Underground Environments: External Corrosion in the Gas Pipeline Industry

1983,”CORROSION/95, paper no. 354 (Houston, 22. G.H. Booth, A.W. Cooper, and P.M. Cooper, Brit.
TX: NACE, 1995). Corros. J. 2,May (1 967):109.
15.T.R. Jack, G. Van Boven, M. Wilmott, and R.G. 23. G.H. Booth, A.W. Cooper, and A.K. Tiller, Brit. Cor-
Worthingham, “Evaluation of Coating Performance ros. J. 2,May (1 967):1 16.
After Exposure to Biologically Active Soils,” COR- 24. M. Wilmott, T.R. Jack, J. Geerligs, J. Sutherby, R.L.
ROSION/95, paper no. 353 (Houston, TX: NACE, Diakow, and B. Dupuis, Oil Gas J. 93, 14(1995):
1 995). 54*
16.Canadian Standards Association, CSA 2 245.20- 25. T.R. Jack, M.J. Wilmott, and R.L. Sutherby, MP 31,
M92,clause 12.9. ll(1995):19.
17. E.S. Pankhurst, J. Oil Colour Chem. Assoc. 56 26. T.R. Jack, M. Wilmott, J. Stockdale, G. Van Boven,
(1973):373. R.G. Worthingham, and R.L. Sutherby, “Corrosion
18. R.G. Worthingham, T.R. Jack, and V. Ward, in Consequences of Secondary Oxidation of Micro-
Biologically Induced Corrosion, ed. S.C. Dexter bial Corrosion Scenarios” in Proceedings of the
(Houston, TX: NACE, 1986),p. 330. 1995 InternationalConference on Microbially Influ-
19. W. Whitman, R. Russell, and V. Altieri, Ind. Eng. enced Corrosion, held May 8-1 0, 1995 (Houston,
Chem. 16(1924):665. TX: NACE, 1995),p. 28/1.
20. C.A.H. Von Wohlzogen Kuhr and L.S. Van der Vlugt, 27. T.S. Gendron, R.D. Cleland, and P.A. Lavoie, in
Water (The Hague), 18(1934):147. Microbially Influenced Corrosion and Biodeteriora-
21. R.A. King and J.D.A. Miller, Anti Corrosion August tion, eds. N.J. Dowling, M.W. Mittelman, and J.C.
(1 977):9. Danko (Houston, TX: NACE, 1990),p. 2-1.
CHAPTER 6 (PARTII)

Microbiologically Influenced Corrosion of


Internal Aspects of Natural Gas Industry
Pipelines and Associated Equipment:
Mechanisms, Diagnosis, and Mitigation
By D.H. Pope

Introduction available that will give the reader an introduction


to these topics and provide specific references to
particular situations that are beyond the scope of
Microbiologically influenced corrosion (MIC) this chapter.(l-lO)
processes are those forms of corrosion that are MIC has been described for almost all pipeline
influenced by the presence and activities of mi- metals and alloys, except t i t a n i ~ m . ( ~ l ~Mi-
-~~~)
croorganisms. Microbiologically influenced corro- crobiologically influenced deterioration of other
sion usually acts in concert with other corrosion pipeline materials such as cement, concrete, and
mechanisms and may, at times, appear to be un- linings and coatings, although not strictly speaking
der deposit acid attack, crevice corrosion, oxygen- corrosion events, represent serious problems to
concentration-cell corrosion, ion-concentration- pipeline operator^(^^^^^^' l) (see also Chapter 6,
cell corrosion, or carbon-dioxide corrosion. In its Part I, this volume).
most severe form MIC can lead to highly local- MIC-related failures can be diagnosed by test-
ized metal loss and premature system failure. The ing for microbiological and chemical constituents
problem-causing microbes may be present, di- at the corrosion site and evaluating these data
rectly influencing the local corrosion rates, for only with the results of metallurgical tests and opera-
a portion of the overall corrosion process, a fact tional information. In the opinion of the author there
that led to the current terminology microbiology in- is no single biological, chemical, or metallurgical
fluenced corrosion, as opposed to the older refer- factor upon which a diagnosis should be made
ences to microbiologically inducedcorrosion, bac- (e.g., presence, absence, or numbers of sulfate-
terialcorrosion, or biocorrosion. It is very important reducing bacteria or the biochemical activity levels
to realize that the presence of active microbes in a of these organisms, or presence of certain forms of
system does not dictate that MIC is occurring, but iron sulfide (mackinawite). Rather, all of the avail-
it does indicate the potential for its occurrence. able information should be taken together to form
MIC has been documented in a wide variety of an opinion and to determine whether the influence
pipelines, including, but not limited to, those trans- of the microbes was principally in the past or is
porting potable water, sewage, natural gas, liquid continuing at the time of the investigation. Early
hydrocarbons, production chemicals (e.g., soaps, detection of MIC and continued monitoring of cor-
acids), and cooling waters. Several reviews are rosion rates, including maximum pitting rates, are

6.13
6.14 Microbiologically Influenced Corrosion of Internal Aspects

necessary if MIC is to be brought and kept under Mechanisms of MIC


control.
Treatment of MIC can be accomplished using
a wide variety of methods. These should be ap- The classic mechanism for MIC of steel and
plied to a given system only after careful testing iron was proposed by von Wolzgen Kuhr in 1934.
of effectiveness in that particular location, consid- The mechanism was based on the idea that
eration of compatibility with system materials and the rate-limiting step in corrosion is the dissoci-
other treatment chemicals, safety, environmental ation of hydrogen from the cathodic site. Some
issues, and cost. (hydrogenase-positive) strains of SRB consume
These various aspects of MIC diagnosis, mon- hydrogen and thus “depolarize” the cathode and
itoring, and treatment are discussed in further de- accelerate the corrosion process. Although the
tail in the following sections of this chapter, with cathodic-depolarization mechanism may be a con-
examples given to illustrate the main points. Since tributing factor in MIC, it is rarely seen as the sole
this chapter deals primarily with internal MIC of gas mechanism for corrosion in laboratory-controlled
pipelines, the reader is referred to other sources and industrial environments.
(e.g., References 2 and 3) for comprehensive in- Figures 6.8 through 6.13 illustrate a model in
formation on MIC and its occurrence on a wide which microbial colonization can lead to a corro-
variety of industrial metals and alloys. References sion site and examples from field sites of each ma-
2 through 11 provide case histories and more de- jor phase in the development of a MIC site. The
tailed information on MIC mechanisms, detection concept is based on the formation of an occluded
methods, and mitigation strategies than can be spot on the surface of the metal, which, in the pres-
provided in this chapter. ence of an electrolyte, creates anodidcathodic re-
lationships between the occluded area and sur-
rounding metal. Phase 1 (Figure 6.8), the initial
attachment of microbes to the surface, may be
Microbes Involved in MIC related to preexisting corrosion, metallurgical fac-
tors (welds, inclusions, etc.), or other local con-
ditions. The local chemical-electrochemical envi-
Most types of microbes occurring naturally in
ronment is also an important factor for microbial
waters or soils have the potential to participate in
attachment and colony development. Figure 6.9
MIC of some type of metal or alloy.(1~3~4~10~1
Micro-
shows the surface of carbon steel exposed to
biologically influenced corrosion of pipelines has
tap water for 3 days and demonstrates Phase I
been documented as involving aerobic, anaerobic,
slime-forming, acid-producing, sulfate-reducing,
nitrate-reducing, iron-oxidizing, and iron-reducing
bacteria. Within each of these general physiolog- < J
ical groups are hundreds of individual species of
bacteria. It is important to recognize that MIC is
C Bacteria
Adsorbed Nutrients
almost always due to the presence and action of
microbial communities containing many different
types of microbes. The composition of the com-
munity may change with each stage in the devel- -
Metallurgical Feature Desirable to Bacteria
opment of the MIC site and from one specific lo-
cation to another. Contrary to popular belief, MIC
is rarely due to the activities of any single group
of organisms such as sulfate-reducing bacteria FIGURE 6.8
(SRB). Phase 1. Microbial attachment.
Microbiologically Influenced Corrosion of Internal Aspects 6,15

to become chemically dissimilar to the surround-


ing surface. As the community matures, interde-
pendencies continue to develop between the in-
dividual community members. For example, the
organic acids produced by acid-producing bac-
teria (APB) provide nutrients for other microbes
including SRB. Most microbes use only the an-
ionic part of the organic acids; thus their con-
sumption results in a buildup of protons, leading to
lower pH in the corrosion site developing under the
community. The lower pH tends to attract anions
(CI- >> SO, > OH-) into the occluded area, which
can add to the corrosivity of the environment and
FIGURE 6.9 stimulate the biochemical actidties of certain types
FITC-stained MIC community on carbon steel exposed of microbes. These conditions under the commu-
to city water for 8 days. (See color plates.) nity lead to occluded corrosion. Thus, character-
istically, Phase 2 involves a fixed community over
an area of occluded corrosion, acidic conditions in
colonization. Note the patchy nature of the colo- the occluded region, accumulation of chloride and
nization. other anions, and aggregation of these materials
Phase 2 (Figure 6.10) shows the development with corrosion products into the beginnings of what
of a discrete and well-developed microbial commu- will eventually be recognized as discrete deposits
nity, fixed to the metal, which creates an occluded (also called nodules or tubercles). Figure 6.1 1 is a
area that may be relatively anodic to the surround- picture of a well-developed, Phase 2 MIC site.
ing area. The communities often produce sticky Phase 3 (Figure 6.12) involves the formation of
polymers that retain organic and inorganic mat- a mature nodule, or tubercle, over a well-defined
ter and aid in the occlusion process. The contin- pit. At this stage, the pH in the active pit region is
ued buildup of material in and over the community often less than 4. Owing to the low pH, most of
allows the conditions inside and under the com-
munity (i.e., oxygen level, ion concentration, pH)

Microbial Community (Calls, Polymer and Corrosion products)

Crevice Anode

It is suspected that the pH in the crevice


region is above 4 during this phase

FIGURE 6.10 FIGURE 6.11


Phase 2. Microbial community development and initia- Internal diameter of gas pipeline showing Phase 2 of a
tion of crevice corrosion under fixed anode. MIC site. (See color plates.)
6.16 Microbiologically Influenced Corrosion of Internal Aspects

Anlona (CL ,SO ,,

It is thought that most of the nodule is corrosion product -


live bacteria are present in crust of nodule

FIGURE 6.1 2
Phase 3. Nodule formed over well-defined pit. FIGURE 6.1 3(b)
Copper-nickel (90/10) tubing showing mature discrete
deposits. Severe pitting was seen under most deposits.
(See color plates.)
the viable microbes are now in the crust of the
tubercle, rather than in the pit. The corrosion
process now takes the form of underdeposit acid 3 nodules on various metals and alloys. All of
attack and is driven (rate controlled) chemically these showed severe, localized pitting under the
rather than as a direct result of microbial coloniza- nodules.
tion. Thus, the corrosion process would continue
even in the absence of the microbes. Therefore,
when the problem is in the advanced stages, Detection of MIC
simple chemical treatment to kill microbes will not
solve the corrosion problem, but rather, mechan- A variety of methods have been used or pro-
ical and/or chemical cleaning and treatment are posed for use in detection and diagnosis of MIC
required. Figure 6.13 is a composite of Phase and for on-line monitoring of MIC. A review of

FIGURE 6.1 3(a) FIGURE 6.1 3(c)


Phase 3. MIC nodule on a sucker rod from an oil well, 304 Stainless steel piping showing mature nodules es-
showing layers of corrosion product. Layer at bottom of pecially at weld and heat-affected zone. Goblet-shaped
pit is very rich in chloride. (See color plates.) pits were observed under the nodules. (See color plates.)
Microbiologically Influenced Corrosion of Internal Aspects 6.17

I
I
Liquid S s m p l e
Solid Samples (Soil.
Corrosion Productrr.

Collect in Sterile Place i n Sterile


D e i o n i z e d W star
Container and Makc Slurry

Analysis Kit

Fixativr Bottl0
c ~ . ~ formalin
.. or Analyses
glutorrldohydo)

-
Imolrtion of
Spociflc Micro-
Anorobic Bacteria Orgrni8mr
A n r l y om
for soluble
Aoid-produoing B sotaria Cb-m foal
S P E O f i c M
I
Sulfate-roducing B acteria
I
I Iron-related Bacteria I
I Low Nutrient Bacteria I
NitribdNitrato
Motabolizing Bacteria

FIGURE 6.14
Liquid and solid samples.

these methods, specific to the pipeline industry, The samples must also be processed carefully to
was done in which the advantages and disadvan- avoid killing microbes of importance to a proper
tages of each were d i s c ~ s s e dThe
. ~ following is a diagnosis. A generalized scheme for sample col-
discussion of the methods that have proven use- lection and processing for a variety of samples (liq-
ful to the author and co-workers in research and uids, soils, corrosion products) is shown in Figure
consulting work on pipelines, including those used 6.14. A more detailed discussion of each proce-
in several research programs performed for the dure is given in Reference 8.
Materials Technology Institute, the Gas Research Microscopic examination of samples can be
Institute (GRI), the Electric Power Research Insti- done on site or on samples properly preserved at
tute (EPRI), water distribution systems, fire protec- the time of collection. The sample can be observed
tion systems, oil pipelines, and a variety of private using a light microscope or an epifluorescence mi-
industries. croscope after staining with a fluorescent dye that
Viable culture of microbes in samples can be will attach specifically to biological materials. Spe-
done to determine the types and numbers of mi- cific types of microbes in samples can be detected
crobes present in samples. These tests are simple using fluorescently labeled antibody probes. A
and quantitative, and can be used to detect very generalized diagram for such procedures is given
low levels (1 cell) of bacteria, if performed using in Figure 6.15.These microscopic techniques re-
quality media and done according to the appro- quire the use of a relatively expensive microscope
priate procedures. Viable culture tests should be and a trained observer. However, such an observer
done immediately after collection of the sample. can gain considerable useful information regarding
6.18 Microbiologically Influenced Corrosion of Internal Aspects

1;kks
I
n

prepared on-site in PBS-Formalin


with MIC. If the chemical results indicate MIC, it
should be confirmed by microbial culture along
’ c , m

1 Small volume spotted onto slide


with consideration of the conditions at the site.
Tests for chemical species such as sulfide and
ferrous iron and for pH should be done immedi-
Heat fixed
ately after sample collection; otherwise significant
Stained with FlTC or changes may occur in these materials, leading to
fluorescent antibody
false results.
Viewed using epifluorescence
The physical characteristics of the corrosion
site can also be of use in diagnosing MIC. In car-
bon steel, the degradation often takes the form of
FIGURE 6.15(a) hemispherical, cup-like pits within pits or scooped-
Procedure for total microscopic count using fluorescent out pits. Also, microbial colonization may follow
stain for biological material and epifluorescent micro- manganese-sulfide inclusions that are “strung out”
scope. (See color plates.) in the process of rolling carbon steel, which re-
sults in a type of material loss that resembles tun-
neling. In stainless steels the pits are usually as-
the numbers and types of microbes in the sample, sociated with the weld, heat affected zone, or an
their physiological status, and their relationship to
area where the material has been deformed. Sub-
the corrosion site or products. surface, goblet-shaped pits are usually observed
Chemical characterization of corrosion prod-
in stainless steels. Other patterns are characteris-
ucts and bulk fluids is also important in the diag-
tic of MIC in aluminum alloys, copper alloys, and
nosis of MIC. The presence of metals in the ap- nickel alloys. The metallurgical characterization of
proximate ratio of the degraded alloy indicates a the suspect MIC site should be done in the field,
corrosion product as opposed to a product of de- if possible. Guidelines for metallurgical examina-
position. However, in MIC of stainless steels, the tion have been published in field guides for the
nickel content in the corrosion product is normally investigation of MIC in pipelines for a variety of
lower than in the alloy (“denickelfication”). The industries 7-9)
presence of ferrous iron and sulfide in pitted re- Finally, the physical and chemical characteris-
gions, in conjunction with lower pH, is consistent
tics of the affected system should be considered in
the diagnosis. For example, microbial activity, and
- SRB the previously described electrochemical mecha-
0 - non-SRB nisms, require water to be present in the corrosion
Cells from PBS-forrnalin heat site at least periodically; therefore, MIC historically
fixed to microscopic slide
occurs in places within systems where water can
Rabbit anti-SRB antibody accumulate. Other factors, such as system tem-
added to slide & allowed to
react
perature, should be considered to determine if MIC
is feasible.
Goat anti-rabbit second
antibody labeled with FlTC
allowed to react with rabbit
anti-SRB
Monitoring for MIC
Viewed using epifluorescence Monitoring for MIC is a topic discussed by
imicroscopy
several authors with various points of view and
FIGURE 6.15(b) with different experiences. It should be pointed
Procedure for enumeration of specific bacteria using flu- out that monitoring in laboratory settings and in
orescently labeled antibodies. (See color plates.) actual pipelines is quite different. The author and
Next Page

Microbiologically Influenced Corrosion of Internal Aspects 6.19

colleagues involved in research and testing for MIC Physical Methods


in a wide variety of industrial settings have con-
cluded that a monitoring program for internal cor- Pigging, which physically cleans the internal
rosion should include consideration of as many of surfaces of the pipeline, is very effective for mit-
the following factors as possible. igating MIC when performed regularly and may
System conditions including the presence of be enhanced with a cleaning agent (e.g., alcohol),
water, nutrients, and other chemical constituents corrosion inhibitor, and/or biocide. Pigging disturbs
(e.g., pH, akalinity, chloride, sulfate, sulfide), vi- the corrosion sites and removes water, microbes,
able microbes (in liquids and on metal surfaces), corrosion products, and food for microbes. It also
and operational conditions should be determined allows treatment chemicals access to the area of
as precisely as possible. It is critical that some di- active corrosion in the pits, where the corrosion
rect measurement of general and localized (pitting) process and/or bacterial activity may be more ef-
corrosion also be used. The most reliable results fectively integrated.
in the author’s studies have come from the use of
coupons that are analyzed for colonization, gener- Chemical Methods
alized corrosion rates, and maximum pitting rates
(by performing microscopic pit analyses). It is ab- Corrosion inhibitors and biocides can be of use
solutely critical that coupons used in monitoring be in mitigating MIC as well as in preventing MIC from
of the same metallurgy and surface condition as becoming established. However, it is imperative
the pipe. Polished coupons, in our experience, will that treatments be tested on actual samples from
rarely be colonized or corroded in the same way the sites to be treated to determine whether the
or to the extent as mill-finished coupons. It is also treatment regime will work and to avoid over- or
crucial that the coupons be located in areas that undertreating. Details of field tests and methods
have conditions conducive to the development of of testing mitigation measures are contained in
MIC (i.e., the worst-case conditions for the pipeline References 8 and 10. Significant incompatibilities
under consideration). Coupons used for MIC mon- can exist between corrosion and scale inhibitors
itoring should be removed and processed imme- and some biocides (see Table 6.4 for examples).
diately using culture and microscopic examination These must be checked before chemical treat-
for microbes and corrosion (details can be found ment is implemented in the actual facility. Chem-
in Reference 8). An attempt must be made to cor- ical treatments can be used with great success,
relate the presence and activities of microbes to economy, and minimal risk to the environment and
corrosion, since the simple presence of microbes personnel if the principles of targeted treatment
in a sample is rarely suff icient to prove MIC involve- and optimization are followed. This requires find-
ment in the corrosion events at the site. ing the location of the microbes, water, etc. and
eliminating them as close to the source as possi-
ble with the minimum amount of biocide or corro-
sion inhibitor necessary to do the job. This must
Mitigation of MIC be accompanied by aggressive follow-up monitor-
~ ~~~

ing to make sure that the treatment is continuing


Mitigation of internal MIC must be done af- to work.
ter careful monitoring and consideration of the
local situation; otherwise considerable time and Some Examples
money can be spent performing unnecessary or
ineffective treatment of the pipeline. A much more An example of targeted treatment is shown in
detailed discussion of mitigation methods, their Figures 6.16-6.18. An offshore production, gath-
application, and monitoring of treatment success ering, and transmission system had suffered from
is contained in Reference 8. MIC. After performing system-wide microbiological
CHAPTER 7

MIC in the Power Industry


By GJ,Licina

Introduction and mitigation activities. Whenever plants must


be shut down for cleaning or repairs, the costs
of replacement power canbe extremely high. For
Microbiologically influenced corrosion (MIC) example, downtime for large nuclear units is of-
has compromised the structural integrity of pip- ten of the order of $1,000,000 per day. Similarly,
ing and numerous components in nuclear and repairs and replacements of service water sys-
fossil-fueled power plants. Cooling water and ser-
tems, part of the infrastructure of a power plant,
vice water systems in these plants have been
can be costly. Several large nuclear units have
designed with minimal corrosion allowances-a
repaired or refurbished their service water sys-
reasonable approach for corrosion resistant ma-
tems. Full system replacement costs are of the or-
terials exposed to environments that would nor-
der of $30,000,000 per unit; partial replacements
mally be considered benign. Microbial influences
or weld overlay repairs cost $100,000 or more.2
can cause localized corrosion, often at rates one Costs for biocide treatment include the cost of the
or more orders of magnitude greater than the ex-
treatment chemical(s), delivery systems, monitor-
pected general corrosion rates, for copper-based
ing, discharge permits, and training. The annual
alloys, carbon steels, and stainless steels. The flow cost of mitigation can be $1,000,000.
capabilities of some carbon steel lines have also Microbiologically influenced corrosion in nu-
been affected as massive quantities of corrosion
clear plants has been the subject of commu-
products and deposits have seriously reduced the niques from regulatory agencies and industry
pipe diameters, in some cases leading to complete organizations.= NACE International, the Chem-
blockage.
ica! Processing Industry, and the Electric Power
Microbiologically influenced corrosion, the in-
Research Institute (EPRI) have sponsored a num-
teraction of biological activity with corrosion pro-
ber of publications on MIC in nuclear plants and
cesses, is a significant cause of degradation of fossil-fired plants7-15
piping and heat transfer surfaces in such cool-
ing water systems. MIC can produce through-wall
penetration of piping and heat exchanger tubing Competing Requirements
as localized corrosion, at rates 10 to 1000 times
more rapid than those normally encountered. As Economic pressures force plant operators to
noted in A Practical Manual on Microbiologically continually maintain or improve plant availability.
lnfluenced Corrosion,' MIC has been observed in Unplanned downtime, the result of MIC or other
essentially all raw waters including soft and hard degradation mechanisms, cannot be tolerated.
fresh waters, brackish waters, and seawater. Those same economic pressures dictate strict
The impact of MIC on the operating and main- controls on the costs of mitigation activities. Thus,
tenance costs of power plants can be significant. plant operators must maintain improved levels of
Those costs include costs of replacement power, MIC control at lower operating cost, often with
increased inspection, repairs and replacements, less staff. In addition, restrictions on effluents are

7.1
7.2 MIC in the Power Industry

continually tightening. These factors make plant Once-Through


maintenance an increasingly challenging job.
Water treatments to mitigate MIC and biofilms ------ -
are expensive in terms of chemical delivery intake
systems, training, permits, and the chemicals
Plant Optional
themselves. Environmental requirements on dis- Heat Cooling
Tower
charges have become increasingly restrictive.
Over-treatment of water thus carries a double
penalty as the cost of the chemical is high and as-
Discharge
sociated penalties for excessive discharge ensue.
The propensity for MIC and biofouling in nuclear
and fossil plants and the costs of repairs indi-
cates the importance of improved biofilm monitor- Corrosion and Corrosion Control
ing methods. COOLING SYSTEM DESIGN
Open Recirculating
Background
The primary process water in power plants, the
boiler water in fossil-fired units or reactor coolant Makeup
system water in nuclear units, is virtually always a Water

treated water that starts from a high-purity dem- I -' '-1 Air Condenser
ineralized water, to which specific chemicals are J
added for the control of deposition and corrosion.
When the plant is in operation, the boiler water wn
or reactor cooling water also is boiled or raised to
a very high temperature (>25OoC) at which mi-
Closed Recirculating
crobes will not flourish and will typically be de-
stroyed. While MIC has been shown to occur in
high-purity waters,38 the overwhelming majority
of MIC incidents in power plants have been re- I
ported for cooling waters, both treated and un-
treated.
Cooling water loops may be open, where the
cooling water loop and the ultimate heat sink
are continuously exchanging fluid, or closed,
where only a small fraction of water, typically
treated water, is added to the closed cooling
water loop. Open loops are further subdivided
Q Generator

FIGURE 7.1
Heat
Exchanger
To Heat

Schematic illustrations of typical cooling systems.


as recirculating (e.g., with cooling towers) or
once-through. Several examples are provided in
Figure 7.1. All of these system designs have been ods since large quantities of treatment chemical
subject to MIC damage.7~10~12~13~15 Closed loops must be used, with the associated cost and envi-
offer the advantage that they can be continuously ronmental ~ 0 n c e r n s . l ~
treated with biocides, corrosion inhibitors, and de- Power plant fire protection systems may be
posit control chemicals. Once-through systems closed systems, much like fire protection sys-
are the most difficult to control by chemical meth- tems in buildings or on ships, but are often
MIC in the Power Industry 7.3

interconnected with service water systems or other day for smaller units and more than $1,000,000
plant auxiliary systems. Unlike most other build- per day for large units. In addition, the costs of re-
ings, however, power plants must test their fire pro- pairs to components in a nuclear plant are high.
tection systems regularly. In most cases, fire pro- For example, one utility has spent more than
tection system waters are untreated. MIC in fire $55,000,000, including the costs of replacement
protection systems is much more common when power, replacement tube bundles, and inspection,
the system experiences intermittent flow condi- on critical heat exchangers that were degraded by
tions than when the systems remain closed and MC2’
experience flow infrequentIy.16 Key words that describe the design philosophy
A number of failures in power plants and for nuclear plants are “diverse and redundant.” The
other industries have been attributed to MIC, re- safe shutdown of the plant, via diverse, indepen-
sulting from microorganisms introduced during dent systems, must be assured for an extremely
h y d r ~ t e s t i n g . ~ As ~ ~the
~ ~ fabrication
’ ~ ~ ~ ~ ~of’ ~a broad set of conditions. The diverse and redun-
system or a portion of a plant is completed, the dant approach permits the plant to be shut down
structural integrity of the systems is verified by safely, even if a key component or system fails or is
pressurizing the system to a pressure in excess unavailable for service as a result of maintenance
of the system’s design pressure. Most often, such or other activity. This same approach requires that
tests are done with water available at the time. numerous systems simply sit idly in wet lay-up, in
Rarely has that water been treated to remove po- anticipation of a time when they might be needed
tentially harmful microbes. Often, the system is left to provide emergency cooling, to remove residual
full or partially full of the hydrotest water for months heat after a normal shutdown, or to cool equip-
or years, until the system is ready for operation. ment that operates intermittently. This type of de-
In that period, MIC can dramatically degrade the sign requires extremely large and complex piping
system, such that it fails on start-up. Similar effects systems. Each component or system also has its
have occurred during long shutdowns.20 redundant or parallel backup system to provide for
The focus on MIC in the power industry has the safe shutdown of the plant. This redundancy
been on nuclear plants. The focus is likely to re- adds to the size and complexity of the piping sys-
main there because of tems and guarantees that a number of systems
will be kept full under stagnant or near-stagnant
the enormous costs of downtime, conditions. Periodic testing of the numerous par-
allel or standby systems is required to assure that
design philosophy, the system will provide the required flow if and
potential safety implications of failures when it may be needed. These long periods of
and public sensitivity to any and all wet lay-up, interrupted by short periods of flow and
degradations at nuclear facilities, and the introduction of new and fresh water, provide a
nearly ideal situation for biofilms to form on struc-
limiting conditions of operation (LCOs). tural materials and for MIC to degrade the system’s
integrity.
Nuclear plants are typically large, base-loaded Safety-related components in nuclear facili-
units that provide utilities with a steady supply of ties are those components that have a direct im-
clean power. Shutdown of a large nuclear unit, par- pact on the safe shutdown of the plant. Such
ticularly an unplanned shutdown, requires that the safety-related systems are generally designed and
utility must replace that large quantity of electric built to more restrictive standards and use more
power with electricity generated from older, less corrosion-resistant materials to ensure their relia-
efficient, higher pollution units, or purchase the bility. Virtually all components in nuclear facilities
power from other sources. The costs of downtime have some safety function, such as lube oil coolers
for nuclear units are of the order of $300,000 per for pumps that support safety-related equipment.
7,4 MIC in t h e Power Industry

Failure of even non-safety-related equipment can demonstrations. The enormous time pressures ex-
ultimately lead to the degradation of safety-related erted by LCOs and stringent requirements for re-
equipment that would have a measurable influence porting events in nuclear units may also yield a
on plant shutdown.22 The public’s typical percep- smaller number of MIC diagnoses reported for fos-
tion is that any failure in a nuclear facility is related sil plants. When corrosion damage is observed in
to safety. The nuclear industry is appropriately sen- noncritical systems in a fossil plant, the damage
sitive to that perception. is repaired and the system brought back into ser-
A part of the nuclear design philosophy is the vice. In a nuclear unit, removing that same system
limiting condition of operation (LCO) that is asso- from service may not be nearly as simple. When
ciated with many of the components in a nuclear degradation is observed, considerable resources
plant, including components that may be degraded are brought into play to diagnose the problem and
by MIC. The LCO requires that the component not correct it.
be out of service longer than a predefined time;
otherwise, the plant must be shut down. Failures
of piping or components or the discovery of unex- Materials
pected fouling that requires an action can initiate
an LCO. The visibility and impact of MIC or other Steels and Cast Irons
forms of degradation is greater for a nuclear unit,
where the repair must be completed in a short pe- Steels and cast iron are most often used for
riod of time. In other types of power plants, de- piping, vessels, structures, and tanks. In addition
graded components are simply cut out and re- to concerns with MIC and other forms of corrosion
placed when convenient or are left in a degraded on internal surfaces, these components, especially
condition and monitored to track the progress of large-diameter pipes, are often buried, resulting in
the degradation. concerns with MIC and other attack on external
A number of examples of MIC in nuclear facil- surfaces, as described in the chapter of this vol-
ities have been reported. Several of them will be ume by T.R. Jack that deals with MIC in under-
described in greater detail in the section on Mate- ground applications.
rials. Piping and vessels that contain or deliver cool-
Several examples of MIC have also been re- ing water or fire protection system water are sub-
ported for fossil-fired p l a n t ~ . Bibb, ~ - report-
~ ~ ~ ~ ~ject~ to~ general
~ corrosion, localized corrosion, and
ing on experience with MIC in the power genera- tuberculation, with serious pitting attack under
tion industry in South A f r i ~ a , ’ ~noted
~ * ~that larger some tubercles. While the presence of tubercles
plants appeared more susceptible to MIC failures does not signal the presence of MIC, tubercles on
because of the delays between hydrotest and steel or cast iron can indicate that MIC is occur-
operation. She also noted apparent correlations ring beneath the tubercle. The underdeposit en-
between MIC and the nutrient levels in surface wa- vironment dictates whether MIC has occurred or
ters (e.g., from chemical fertilizers) and with poorer will occur. These systems will almost always be
water quality (e.g., accompanying drought). Fos- built with a corrosion allowance to account for the
sil plants probably report MIC failures less often expected wall thinning due to general corrosion.
than do nuclear facilities for several reasons. In Figures 7.2 through 7.6 provide several examples
general, the turnaround times from construction of the MIC attack that has been found in such ma-
and hydrotest to operation is less, leaving less op- terials and systems.
portunity for extended or poor wet lay-up. Further, In some situations, the attack under tubercles
far fewer systems in fossil units are as suscepti- may be minor; however, the growth of the large
ble as their counterparts in nuclear units, which tubercles can reduce the effective cross section of
are kept in wet lay-up conditions over the major- piping to the point that the fluid-carrying capacity
ity of their lives, coupled with periodic operability of the pipe is seriously decreased.
MIC in t h e Power Industry 7.5

FIGURE 7.4
FIGURE 7.2 Attack at carbon steel welds on service water piping from
MIC of carbon steel fire protection system piping. (Pho- a nuclear plant.
tograph provided courtesy of Buckman Laboratories in-
ternational, inc.) (See color plates.)
flow is intermittent (Figure 7.7). During the pe-
riods of stagnation, especially with untreated or
Copper A /loys inadequately treated waters, biofilms containing
sulfate-reducing bacteria can become established
Copper alloys are often used for heat ex-
and the protective oxide film on the copper is
changer tubing and sometimes for piping and
enriched in the sulfides that were produced by
other components depending upon the salinity of
the SRB. When the system is subsequently sub-
the water. Despite copper’s reputation for toxicity,
jected to flowing, oxygenated water, the sulfide-
copper alloys are not immune to MIC, especially
modified film is dissolved and rapid corrosion
when long periods of stagnation are involved or
occurs. Essentially all of the copper-based alloys
are subject to this form of degradation by water

FIGURE 7.3
Attack at carbon steel welds on service water piping from FIGURE 7.5
a nuclear plant. (See color plates.) MIC of carbon steel at a nuclear plant. (See color plates.)
7.6 MIC in the Power Industry

FIGURE 7.6 FIGURE,7.8


MIC of carbon steel at a nuclear plant. (See color plates.) MIC of stainless steel weldments, showing pre-service
failure from a fossil-fired plant. (See color plates.)

flow over a sulfide-degraded, hence nonprotective,


film. location of MIC attack, other parts of the welded
structure, including heat-affected zones and heat
Stainless Steels tint, have also been subject to MIC. Kearns,
Borenstein, Buchanan, and others have demon-
Stainless steels are generally used as raw wa- strated that the creation of local anodic sites (e.g.,
ter piping for “essential” or “safety-related” cool- heat tint) or surface roughness in the weld filler
ing water systems in fossil-fired or nuclear plants. has a dramatic effect on the initiation of MlC.24-26
Stainless steels may also be used in heat exchang- In some welds, preferential attack of the ferrite
ers in such systems. MIC of these corrosion re- phase is observed. In other welds, the austenite
sistant alloys in apparently benign raw water en- phase is preferentially attacked. In a test program
vironments has been the subject of industry and at a power plant, Borenstein showed that the ferrite
regulatory scrutiny.
Weldments have been by far the most MIC-
susceptible areas of stainless steel systems
(Figures 7.8-7.1 3). While the duplex microstruc-
ture of the weld metal has been the most frequent

FIGURE 7.7 FIGURE 7.9


M I C of 90-10 copper-nickel stator cooler. (See color MIC of stainless steel weldments, showing pre-service
plates.) failure from a fossil-fired plant. (See color plates.)
MIC in the Power Industry 7.7

FIGURE 7.12
MIC in stainless steel weldments. (From Chung et
(See color plates.)
FIGURE 7.10
MIC in stainless steel weldments at a nuclear plant.
of Borenstein. In some cases, preferential attack
content of the weld metal had no significant effect of ferrite and preferential attack of austenite oc-
on its MIC s~sceptibility.~~ She also showed that, curred in different locations in the same weld
in a single length of pipe, one weld might experi- (Figures 7.14-7.17).
ence preferential attack of the ferrite while a dif- Heat-affected zones from stainless steel weld-
ferent weld in the same length of pipe exhibited ments also appear to exhibit an increased sus-
attack of the austenite. Chung and his colleagues ceptibility to MIC (Figures 7.18 and 7.19). The
performed a very careful microstructural analy- severe intergranular attack at welds in thin-wall
sis of MIC-degraded stainless steel weldments stainless steel pipes at the H. B. Robinson plant
from power plants.28Their results confirmed those (Figure 7.19) was identified as MIC.29 Sensitiza-
tion has not appeared to play a significant role in

FIGURE 7.13
FIGURE 7.11 MIC in stainless steel weldments. (From Chung et
MIC in stainless steel weldments at a nuclear plant. (See color plates.)
7.8 MIC in the Power Industry

FIGURE 7.14
MIC in stainless steel weldments. (From Chung et al.28)

MIC susceptibility. There appears to be no differ-


ence between low-carbon ("L")grades and normal
composition stainless steels.
Despite the greater propensity for MIC in weld-
ments, some MIC failures in stainless steels have
occurred in wrought materials, completely inde-
pendent of any welding (Figure 7.20).20
FIGURE 7.16
MIC in stainless steel weldments: preferential attack of
ferrite. (From Chung et

Oxygen appears to have played a significant


role in MIC failures in stainless steels in the power
industry. Systems that have experienced fairly con-
tinuous low flow or intermittent flow (e.g., during
periodic operability demonstrations of standby
equipment) appear to be more susceptible than
systems that flow continuously at higher flow ve-
locities (>2m/s) or systems that are essentially
stagnant. Several test systems, each designed to
simulate a specific plant cooling water system,
have shown that much of the corrosion damage
during periods of flow follow extended periods of
tag nation.^^ During the stagnant periods them-
selves, little or no corrosion occurs, despite the
FIGURE 7.15 formation of an active biofilm replete with anaer-
MIC in stainless steel weldments. (From Chung et al.28) obes, including SRB.
MIC in the Power Industry 7.9

FIGURE 7.19
MIC attack at heat-affected zone of a stainless steel weld-
ment in a nuclear plant.

FIGURE 7.1 7
MIC in stainless steel weldments: preferential attack of
austenite. (From Chung et a1.28)

FIGURE 7.1 8
MIC attack at heat-affected zone of a stainless steel weld- FIGURE 7.20
ment in a fossil plant. (See color plates.) MIC attack on heat exchanger tube. (See color plates.)
7.10 MIC in t h e Power Industry

Nickel-Based Alloys and Other


Corrosion-Resistant Materials
Nickel-based alloys or high molybdenum stain-
less steels are often selected as replacements for
stainless steels that have not provided the desired
degree of corrosion resistance. In general, this ap-
proach has proven to be justified. In at least one
case, however, critical heat exchangers, tubed with
nickel-based alloys (e.g., UNS N08800) have failed
as a result of MIC (Figure 7.21).31-33Unlike most
power industry heat exchangers, the cooling water
(lake water) is on the tube outer diameter. Silt, cal-
cium carbonate scale, and microbiological foulants
all collect on the tubes and at tube-tube support
plate crevices. Because of the design, cleaning
of the units is virtually impossible. The microbio-
logical fouling effectively “glues” the silt and other
nonbiological foulants together, producing more
effective differential aeration cells. The SRB ac-
tivity also produces sulfides that influence initi-
ation and growth of pits. On-line monitoring of
test systems that simulate these heat exchang-
ers has shown that corrosion activity is essentially
nonexistent during stagnant periods and is great-
est when flow is initiated. When oxygen is intro-
duced, the biogenically produced sulfides and the
oxygen interact to produce pitting, even in these
highly pitting resistant alloys.

Mitigation Approaches
~~

Water treatment, using biocides, biodisper-


FIGURE 7.21
sants, etc., is the most common approach for con- MIC of Alloy NO8800 heat exchanger tube.
trol or prevention of MIC. Biocide treatment is
primarily a preventive measure unless biofilms ac-
tually participate in the corrosion process. Both ox-
idizing and nonoxidizing biocides are commonly etrating power of the treatment and its ability to
used. Chlorine, chlorine compounds, and bromine remove biomass and other deposits have been
compounds remain the most common approaches shown to provide a reliable approach to control of
for microbiological control in the power industry. MIC in the power industry.
Nonoxidizing biocides, such as glutaraldehyde, Concerns with both MIC and fouling in
quaternary amines, and dodecyl guanidine, are power plant equipment have led to alternative
being used more often, especially in closed sys- approaches to mitigation. One such approach,
tems. Water treatments that combine biocides, targeted chlorination, treats a group of heat ex-
dispersants, and other agents to increase the pen- changer tubes with a high dosage of biocide for a
MIC in the Power Industry 7.1 1

relatively short period of time. That high concen- more highly alloyed materials have shown a great
tration of biocide is sufficiently diluted by mixing resistance to MIC. Of the commercial alloys, only
with the effluent from the other tubes in the heat titanium has shown an apparent i m m ~ n i t y . ’ ~ , ~ ~
exchanger that the concentration of chlorine in the The feasibility of other approaches, such as
total effluent is less than plant and regulatory lim- brief thermal treatments to “sterilize” surfaces or
its. During the targeted treatment, the tubes see the use of acoustic methods, has been demon-
a sufficiently high concentration of chlorine to ef- strated on a small scale; however, these ap-
fect a kill of the biofilm. Several approaches to tar- proaches have not yet been adopted for routine
geted treatments have been adopted on a plant plant application. The primary advantage of such
scale. methods is that they offer the opportunity for mi-
Although preventive treatments (e.g., biocide crobiological control with no effluents.
and biodispersant chemicals, delivery systems, ef-
fluent permits) are expensive, they are far more
economical than remedial MIC control methods, References
which will include mechanical and chemical clean-
ing, more extensive water treatment, thermal treat-
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ical Cleaning at River Bend Gets Results,” COR- EPRl Service Water System Corrosion Seminar
ROSION/94, Paper no. 251 (Houston, TX: NACE, (Palo Alto, CA: Electric Power Research Institute,
1994). 1992), pp. 281-294.
35. R.W. Lutey and G.A. Lozier, “On-line Chem- 38. J.G. Stoecker and D.H. Pope, “Study of Biological
ical Cleaning for Once-through Service Water Corrosion in High Temperature Demineralized Wa-
System,” EPRl Service Water System Reliability ter,” MP 25( 1986): 56-58.
CHAPTER 8

MIC in the Waste Treatment Industries


By J.B. Soebbing

Introduction anticipated to increase with the expanded applica-


tion of new and existing biological waste treatment
processes.
Corrosion failures in biological waste treatment
processes from microbiologically influenced corro-
sion (MIC) have not been widely publicized. Infor-
mation appears limited to several case histories.’ s2 Industrial and Municipal
The small number of failures reported for such pro- Wastewater Treatment
cesses probably is attributed to the lack of recog-
nition of MIC as a potential source and the lower
priority of corrosion prevention compared to the Industrial and municipal waste water often is
overall importance of the process itself. treated or cleaned in a series of physical, biolog-
Biological waste treatment processes are natu- ical, and chemical processes prior to discharge
rally conducive to MIC. These processes rely on back into local rivers, lakes, and oceans. The bi-
dense concentrations of microorganisms, inclu- ological processes, often called secondary treat-
ding those commonly associated with MIC, to ment, utilize microorganisms to remove carbona-
effectively reduce or consume the wastes. Simi- ceous organic matter and correspondingly reduce
larly, environmental conditions are monitored and the biological oxygen demand (BOD) of the waste
maintained to enhance the activity and prolifera- water. They also may include nitrification and nu-
tion of the desired microorganisms. trient removal.
One biological treatment process commonly
used in wastewater treatment is the return-
Overview of Biological Waste activated sludge process. In this process, waste
water containing organic waste and recycled, set-
Treatment Processes tled sludge, called return activated sludge (RAS),
from settling tanks are continuously fed to an ae-
An increasing number of industries are de- ration basin. Within the aeration basin, they are
riving significant benefits by using biological pro- mixed and aerated with a suspended, aerobic
cesses to treat wastes. Traditionally, biological microbiologic mass. The combined liquid com-
waste treatment processes have been used for the monly is called mixed l i q ~ o rIn
. ~time, the aerobic
ablution of industrial and municipal waste water. microorganisms decompose the organic wastes
However, in recent years they also are being suc- to carbon dioxide, water, some stable compounds,
cessfully used for the remediation of hazardous and additional microorganism^.^ When the mixed
waste spills and the enhanced reclamation of pre- liquor reaches a specified age, it passes to a
cious metals from mining waste piles. settling tank, where effluent is separated from the
Without the dissemination of information on settled sludge (including microorganism^).^ Part
MIC and the implementation of preventative mea- of the settled sludge is recycled (RAS) to the aera-
sures, the occurrence of failures of this type is tion basin to maintain the desired concentration of
8.1
8.2 MIC in the Waste Treatment Industries

FIGURE 8.1 FIGURE 8.2


Flocculating and settling activated sludge with hetero- Bacillus subtilis and Sphaerotilis natans in activated
trophic bacteria and protozoa (2000x1. (See color plates.) sludge (2000X). (See color plates.)

microorganisms, and a portion is wasted (waste- Submerged components constructed of materials


activated s l ~ d g e ) .Thus,
~ the return of living without inherent resistance or adequate protection
microorganisms to the aeration basin is necessary measures in other wastewater treatment facilities
to sustain this biological waste treatment process. could experience similar MIC attack.
The mixed liquor-activated sludge typically
contains largely heterotrophic microorganisms
and, to a lesser extent, autotrophic b a ~ t e r i a . ~ Hazardous Waste Bioremediation
The heterotrophic microorganisms include bacte-
ria, protozoa, fungi, and multicellular organisms. Bioremediation has been successfully used
The types of waste and the process operation sig- on contaminated soils, groundwater, beaches and
nificantly influence the predominant species of mi- shorelines, and on slicks on open waters. In
croorganisms present. Figures 8.1 and 8.2 show these processes either packaged or naturally oc-
flocculating and settling-activated sludge with pro- curring microorganisms are used. For hydrocar-
tozoa and heterotrophic bacteria. bon wastes, the microbes bond to contaminant
The microorganisms of such processes have molecules and exude enzymes that yield their
been shown to cause MIC on submerged metal breakdown. Subsequently, the microorganisms
surfaces. Both carbon steel and stainless steel absorb and further digest the reduced molecules,
(UNS S30400) components within an aeration thus decreasing the contaminant concentration.
basin of one plant experienced rapid failure from Bacterial genera commonly used for bioremedia-
MIC.’ The interiors of carbon steel piping without tion of hydrocarbon contaminants include Pseu-
adequate coatings have experienced through-wall dornonas and Bacillus. Oxygen, nutrients, and
penetrations from MIC attack in several plants.* biological catalysts frequently are added to the
Figures 8.3 and 8.4 show tubercle mounds cov- processes to accelerate microorganism activity.6
ered by a biofilm and a resultant deep, rounded Bioremediation processes for contami-
pit beneath a removed tubercle, respectively. nated soils include “land farming” and “in situ
MIC in the Waste Treatment Industries 8.3

microorganisms to complete the necessary re-


mediation. This technique uses few metallic and
nonmetallic components and, therefore, generally
would not be expected to exhibit significant MIC.
In situ bioremediation is used to remediate
both contaminated soils and groundwater “in
place.” In this process, numerous holes are drilled
to the contaminated zones, and solutions for the
enhancement of existing microorganisms or so-
lutions of select microorganisms are injected to
complete remediation. In situ bioremediation has
the potential for MIC-related failures on buried and
submerged components. The piping and screens
of injection, monitoring, and pumping wells, as well
as the sheet piling of barrier walls at clean-up sites,
are candidates for attack.
FIGURE 8.3
The potential for MIC attack also exists when
Tubercles beneath the biofilm appear as mounds at ap-
in situ bioremediation is utilized to treat hydrocar-
proximately 3 and 5 o’clock on the pipe wall. (See color bon contaminants in flooded utility manholes. In
plates.) this submerged environment, MIC would be of con-
cern to both metallic and nonmetallic surfaces of
electrical and mechanical equipment.
bioremediation.” In land farming, the contaminated
soils are excavated and placed in piles or spread
across the ground. The removed soils are regu-
larly wetted and tilled following enhancement of the
Biocatalyzed Leaching of Precious
existing microorganisms or the addition of select Metals from Waste Ores

Microorganisms are used to catalyze bio-


oxidation of low-grade, hard-to-treat sulfidic pre-
cious metal ores. The method currently is being
used by several gold producers to separate gold
from base-metal s ~ l f i d e s . ~
One such process used by a mining company
utilizes Thiobacillus ferroxidans to strip iron and
sulfur from low-grade gold ore in waste piles8
The result is a more concentrated ore that can be
economically recovered using conventional tech-
nologies. An additional benefit of the biological
treatment process is the acceleration of the natural
oxidation of the waste ore. The accelerated oxida-
tion causes a steady flow of sulfuric acid runoff
that is more efficiently collected and treated and
more promptly yields an environmentally inert ore
that can be stockpiled for future processing. Dur-
FIGURE 8.4 ing past operations, the oxidation rate of waste ore
Deep, rounded pit identified beneath a removed yielded a slow, inconsistent production of waste
tubercle. (See color plates.) sulfuric acid.
8.4 MIC in the Waste Treatment Industries

Prevention of MIC configuration and agitation can minimize this oc-


currence. Agitation of fluids within vessels can be
The experiences of diverse industries have completed using either diffused air or mechanical
provided numerous methods for the prevention methods.
and mitigation of MIC. However, as discussed Stagnant areas also can occur within piping
shortly, many mitigation methods are not appli- systems with dead legs or within an idle or re-
cable to or have significant limitations in biologi- dundant pump. Dead legs should be avoided dur-
cal waste treatment processes. Therefore, initial ing design, and where found in existing systems
prevention is the key to the avoidance of MIC they should be isolated, flushed, and dried. Dur-
in such processes. Methods for initial prevention ing the operation of process pumps, one pump, a
include: redundant unit, commonly remains idle. The flu-
ids within the idle pump and its associated suction
proper system design, and discharge piping are stagnant. The installation
of a small-diameter, continuous-flowing bypass
utilization of resistant materials, header is one method for eliminating this stag-
correct fabrication, installation, and test- nant condition. Two methods for reducing the stag-
ing, and nant period include cycling the pumps so that
each pump has equal idle time and shortening
cathodic protection. the pump cycling time to minimize the actual idle
duration.
Proper Design While it is commonly recognized that veloc-
ity affects the thickness and density of resultant
Proper design requires measures to eliminate
biofilms, it has little effect on the overall attachment
or reduce the occurrence of crevices, regions of
of microorganisms to exposed surfaces. However,
stagnation, and locations of low velocity. The de-
at greater fluid velocities, there is less tendency
sign of vessels, piping, and associated equipment
for solids to settle out. Minimizing the settlement
with these precautions is recommended to prevent
of solids can reduce the potential for MIC attack.
the settling and accumulation of solids on surfaces
Therefore, it is commonly recommended that the
susceptible to MIC attack.
velocity in piping systems be approximately 3 to
Crevices often can be eliminated by redesign-
5 ft/s (0.9 to 1.5 m/s). Caution is warranted for
ing the component to entirely eliminate the crevice
some piping materials with velocities exceeding
or to widen and smooth the crevice opening. Simi-
5 ft/s (1.5 m/s) because other forms of corrosion,
larly, they can be avoided by specifying the follow-
such as erosion-corrosion, may occur.
ing:
Figure 8.5 shows a thick biofilm on the inte-
rior walls of steel pipe conveying RAS with relati-
0 joining materials by welding rather than
vely low velocity, 0.75 to 1.5 ft/s (0.23 to 0.46 m/s).
bolting or coupling,
This piping system has experienced nume-
0 welding seams completely rather than in- rous through-wall penetrations from MIC attack.
term itt ent Iy,
0 filling crevices with sealant or caulk, and Utilization of Resistant Materials
0 welding components using double-butt The use of resistant materials is another
or double-lap joints rather than single- method of preventing MIC in biological waste
butt or single-lap joints. treatment processes. The identification of suit-
able materials includes researching the perfor-
Stagnant areas can exist in process vessels mance of materials successfully used in similar
without sufficient fluid movement. Proper vessel environments and, as necessary, in situ testing of
MIC in the Waste Treatment Industries 8.5

FIGURE 8.5 FIGURE 8.6


Thick biofilm on the interior of RAS piping. (See color Small pinhole-type pit and nonuniform coal tar epoxy lin-
plates.) ing on the interior of the pipe sample. (See color plates.)

candidate materials. Prior to finalizing the material Similarly, the pigments and resins of some of
selection, the influence of the methods of fabrica- the organic coating systems actually can serve as
tion, installation, and testing on the potential for a food source for some bacteria, thus enhancing
MIC in the completed system also would require their growth and yielding progressive degradation
consideration. Resistant material alternatives in- of the organic lining systemUgSome asphalt coat-
clude the use of protective linings, nonmetallic ma- ings, for example, experience more rapid degrada-
terials, and upgraded metallic alloys. tion in environments containing microorganisms.
The application of protective organic linings, Polyamide-cured epoxies also are reported to be
such as coal tar epoxies that are amine-cured or consumed by bacteria common to wastewater
contain phenols, to the surfaces of ferrous metals treatment environments.1° Again, epoxies that are
is one recognized method for preventing or retard- amine-cured or contain phenols have been shown
ing corrosion, including MIC, for biological waste to have increased resistance and provide satis-
treatment processes. These paint materials have factory performance for most exposures. Alter-
been used successfully on carbon steel, ductile nately, some coating systems incorporate fillers
iron, and cast iron in many industrial and munic- or biocides that increase their resistance to such
ipal wastewater treatment facilities. However, the microorganism^.^
performance of these paint materials is strongly The long-term durability of such lining systems
dependent on their composition and long-term also is a concern. The breakdown of the lining
durability as well as on their pinhole-free applica- system would allow rapid, localized corrosion by
tion and final testing prior to service. MIC at these locations. Similar results can occur
Carbon steel piping with poorly applied coal tar if pinholes or other anomalies exist in the lining
epoxy linings has experienced numerous through- following application and are not repaired prior to
wall penetrations in several wastewater treatment placement into service.’
facilities.2 Figure 8.6 shows small pinhole-type pits Cement or cement mortar is another protective
in poorly applied coal tar epoxy lining on an interior coating material that can prevent MIC on underly-
pipe wal I. ing ferrous metals in fully submerged conditions.
8.6 MIC in the Waste Treatment Industries

The protection afforded by this coating material is FRP has been shown to be resistant to bacteria
attributed to its natural alkalinity, with pH values of representing several degradation mechanisms.16
10 and above, and to the isolation of metal surfaces Alternately, glass-reinforcing fibers could be used
from the environment containing the microorga- rather than carbon fibers, provided fabrication
nisms. The natural alkalinity of the cement may methods are used to prevent exposure of the
slow or stifle the activity of some strains of sulfate- glass fibers to the process fluids since some
reducing bacteria (SRB) on or immediately ad- microbes have been shown to cause degradation
jacent to this lining with pH values greater than of the organic surfactants applied to the exterior of
10.51.~ glass fibers.16
Alternately, nonsubmerged, concrete, and While many upgraded or exotic metallic alloys
metal surfaces of wastewater collection and treat- have increased general corrosion resistance, they
ment systems can experience aggressive attacks are not necessarily immune to MIC. The failure of
attributed to sulfuric acid. In this process, sulfur stainless steels and other alloys by MIC is well doc-
compounds in the wastewater are reduced by umented. The failure of type 303 (UNS S30300)
anaerobic bacteria to sulfides, including hydrogen and 304 (UNS S30400) stainless steel piping and
sulfide and other compounds. Hydrogen sulfide supports from MIC has been reported for an in-
is released to gas space above the wastewater dustrial wastewater treatment facility.’ Thus, up-
and dissolves in the moisture on these surfaces. graded or exotic metallic alloys are not recom-
In turn, it is oxidized by aerobic bacteria, such mended for biological waste treatment processes
as Thiobacillus, to form sulfuric acid which without bench test results that show sufficient re-
causes corrosion. Although performance reports sistance and, thus, extended service life to justify
can vary sharply, systems commonly used to the increased expense.
protect against these conditions include thick film, Table 8.1 summarizes materials recommended
reinforced-epoxy or polyurethane linings or acid for the prevention of MIC in biological waste treat-
resistant, potassium silicate cement ment processes.
While MIC is known to cause degradation of
some plastics and plastic composite^,^ several Correct Fabrication, Installation,
are reported to be resistant to MIC and can be and Testing
used to prevent its occurrence in biological waste
treatment processes. In general, increased resis- Fabrication, installation, and testing can influ-
tance to MIC for plastic products is achieved with ence the performance of otherwise resistant mate-
increased polymer chain cross-linking. One plastic rials. Adequate cleaning and surface preparation
material reported to be “unaffected by bacteria or prior to lining application and subsequent holiday
fungi or does not promote or support algae or bac- testing and repairs are necessary for successful
teria growth” is extra high molecular weight, high- coating systems. Similarly, seal welding using pro-
density polyethylene (EHMW-HDPE).l5 Other cedures that eliminate crevices caused by under-
plastics, such as polyvinyl chloride (PVC) and cuts and spatter is essential. Other measures in-
chlorinated polyvinyl chloride (CPVC), when highly dicated in the earlier Proper Design section also
polymerized and formulated without additives sen- are necessary.
sitive to microbial attack, also can be used in such In some industrial facilities, hydrostatic test-
environments. ing of equipment and piping (particularly stain-
Another nonmetallic material, a plastic com- less steel ones) with waters contaminated with mi-
posite, also is reported to be resistant to MIC croorganisms has caused extensive damage from
attack when constructed of select materials. One MIC. The equipment and piping systems of bio-
such plastic composite is fiber-reinforced plastic logical waste treatment facilities could experience
(FRP) with epoxy resin and carbon fibers. This similar failures because of MIC-laden hydrotesting
MIC in the Waste Treatment Industries 8.7

TABLE 8.1
Materials for Biological Waste Treatment Processes

Nonmetallic F
Plastic Extra high molecular weight, high density polyethylene (EHMW-HDPE)
Rigid polyvinyl chloride (PVC)(A)
Rigid chlorinated polyvinyl chloride (CPVC)(A)
Fiber-Reinforced Plastic Epoxy resin-carbon fiber
Epoxy resin-glass fiber (B)
Concrete (Nonsubmerged) Various types with thick film, reinforced epoxycD)or polyurethane linings
Various types with acid resistant, potasium silicate cement linings
Metallic F
Carbon Steel with Protective Various grades with cement cover or cement mortar liningcc)
Linings Various grades with coal tar linings(C),(D)
Ductile Iron Various grades with cement cover or cement mortar lining(c)
with Protective Linings Various grades with coal tar linings(C),(D)
Stainless Steel Type 304 (S30400)-Not recommended without demonstrated resistance(E)
Type 316 (S31600)-Not recommended without demonstrated resistance(E)
Others-Not recommended without demonstrated resistance(E)

(A) Highly polymerized grades without additives that are sensitive to microbial attack.
Fabrication methods are required to prevent exposure of glass fibers to environment.
(c)Cathodic protection may be desired where practical to supplement resistance in submerged or buried environments.
(O) Epoxy formulations should be the amine-cured type or contain phenols in submerged or buried environments.
(E) MIC resistance proven by identical service or on-site testing is recommended prior to full-scale service; some failures identified.
(F) Environment is submerged except where noted otherwise.

without taking precautions, such as immediate coatings and a -0.95 V minimum structure-to-
draining and drying following t e ~ t i n g Numerous
.~ wastewater potential (Cu/CuSO4) is achieved.
other options for hydrotesting are available, de- It can be used to protect submerged metal
pending on the materials of construction, type of surfaces of primary clarifiers, aeration basins,
test water (e.g., chlorinated, demineralized, etc.) and settling tanks of wastewater treatment facili-
and its disposal requirements, and funding. Each ties. However, because the amount of turbulence
location should be evaluated and approached on and the oxygen content of wastewater in aeration
a case-by-case basis. basins can vary by plant and by treatment objec-
tives, field testing is recommended prior to the de-
Cathodic Protection sign and installation of such systems.
The application of cathodic protection is not
For more than 40 years, cathodic protection recommended for the interiors of RAS piping, as
has been used successfully in many industries shown corroded herein. It is not considered practi-
to preclude corrosion, including MIC, on metal cal for the interiors of these pipes because of flow
surfaces in buried and submerged environments. disruption and excessively high current require-
Similarly, it can be applied to some biological treat- ments.
ment processes for the initial prevention of MIC in The application of cathodic protection to sheet
which the current requirement for protection is at- pile barrier walls and wells at in situ remediation
tainable and the installation of anodes is feasible. sites is achievable. In contrast, it is not consi-
Success in these environments is most com- dered applicable to surfaces exposed to sulfuric
monly achieved when cathodic protection is used acid waste discharge from biocatalyzed leaching
to supplement the protection afforded by protective at mining operations.
8.8 MIC in the Waste Treatment Industries

Mitigation of MIC for the following reasons:

They could kill or inhibit the activity of mi-


For most industries, the mitigation of MIC fol-
croorganisms essential to the process.
lowing its identification can be achieved by the ap-
plication of one or more of these measures: They likely would be cost-prohibitive be-
cause most of the processes are consid-
internal cleaning (mechanical or chemi- ered once-through systems.
cal), The duration of benefit may be limited be-
chemical treatments (disinfection, water cause the processes contain high con-
treatments, corrosion inhibitors, etc.), centrations of microorganisms that could
be capable of reestablishing conditions
biocide treatments, and
(biofilms, bulk fluid, etc.) conducive to
cathodic p r o t e c t i ~ n . ~ , ’ MIC.

With exception of cathodic protection, most of Many of the treatment chemicals could
these otherwise successful methods have either require additional treatment for their re-
limited benefit or would be detrimental to the es- moval from discharge streams or could
sential microorganisms or potentially yield other yield additional contamination to be re-
waste or contamination concerns. mediated.
Their accessibility to microorganisms ac-
Internal Cleaning tually causing the MIC may be greatly
limited by existing biofilms or corrosion
Cleaning the interiors of process tankage nodules.
and pipe surfaces removes corrosion products,
Some may be detrimental to existing,
debris, and developed biofilms. However, neither
protective linings.
mechanical nor chemical cleaning is expected
to provide long-term benefits for biological waste
treatment processes. Following cleaning and
Biocide Treatmenfs
return to service, freshly exposed surfaces again For the purpose of this discussion, the chem-
would be exposed to processes with dense icals used to kill microorganisms (biocides) or
concentrations of microorganisms. One source to inhibit the growth of microorganisms (biostats)
indicated that a biofilm could reestablish itself in are grouped herein as biocide treatments. These
as little as 72 hours in such an environment17 and chemicals are used widely to mitigate MIC in other
the detrimental effects of MIC could recommence. industries. Similar to chemical treatments, biocide-
type treatments are not considered applicable to
Chemical Treatments biological waste treatment processes for the rea-
sons listed previously.
Chemical treatments are used in other indus-
tries to clean and disinfect systems, treat wa- Cathodic Protection
ter to enhance biocide performance, or to inhibit
corrosion where MIC has been identified. These As noted herein before, cathodic protection
treatments are applied in slug or continuous feed can be an effective method for initially prevent-
arrangements or both. ing MIC on submerged or buried metal surfaces
These treatments generally are not considered in biological waste treatment processes. However,
applicable to biological waste treatment processes once detected, MIC in these environments is often
MIC in the Waste Treatment Industries 8,9

accompanied by mounds, tubercles, and corrosion removal from discharge streams, cause additional
deposits that can shield underlying surfaces from contamination to be remediated, provide benefits
cathodic protection. for a very short duration, or be cost-prohibitive
The recommended corrective action prior to because of the once-through nature of some of the
the application of cathodic protection in such in- processes. The key to avoidance of MIC in these
stances includes completely cleaning the sur- processes is initial prevention through proper
faces, fully opening pits, preparing surfaces by system design, utilization of resistant materials or
abrasive blasting, and applying protective linings. protective coatings, the correct fabrication, instal-
Similar to the use of cathodic protection for the lation, and testing of exposed components and
initial prevention of MIC, its use for the mitigation application of cathodic protection where suitable.
of MIC is usually suited to
References
submerged metal surfaces and equip-
ment of most primary clarifiers and set-
tling basins, and some aeration basins of 1. G. Kobrin and R. Strong, ‘Case 5-Corrosion in a
wastewater treatment facilities; and Waste Water Treatment Tank,” MP 20(1981): 46.
2. J. Soebbing and R. Yolo, “Microbiologically Influ-
buried sheet pile barrier walls and wells enced Corr0s ion Wastewater Treatment PIants,”
at hazardous waste, in situ remediation CORROSION/95, paper no. 214 (Houston, TX:
sites. NACE, 1995).
3. G. Tchobanoglous, Wastewater Engineering: Treat-
It is unlikely to be suitable for metal surfaces ex- ment, Disposal, Reuse, 2nd ed. (Boston, MA:
Metcalf & Eddy, 1979), pp. 393-432.
posed to sulfuric acid waste discharge from bio-
4. P. Vesilind and J. Peirce, Environmental Engineer-
catalyzed leaching at mining operations, and the ing (Ann Arbor, MI: Ann Arbor Science, 1982), pp.
interiors of RAS piping and exposed metal sur- 170, 171, and 270.
faces of highly turbulent aeration basins in waste- 5. R. Noyes, ed., Unit Operations in Environmen-
water treatment facilities. tal Engineering (Park Ridge, NJ: Noyes, 1994),
pp. 10-12.
Summary 6. “Basic Bio remediat io n Concepts ,” Co r porate
~ ~~
Brochure (Bonita Springs, FL: Oettco Products
Corp).
Although corrosion failures in biological waste 7. “Cyanide-Free Biocatalyzed Leaching of Gold and
treatment processes from MIC have not been Silver Ore,” Corporate Brochure (Bonita Springs,
widely publicized, they can and have been docu- FL: Oettco Products Corp).
mented. The dense concentrations of microorgan- 8. M. Charlier, “Newmont Mining Bets on Bugs to
isms and the preservation of process conditions Boost Gold Reserves,” The Wall Street Journal,
to enhance their activity and reproduction in the January 30, 1995, p. B4.
processes yield conditions naturally conducive to 9. G. Kobrin, ed., A Practical Manual on Micro-
MIC. biologically Influenced Corrosion (Houston, TX:
NACE, 1993) pp. 13, 101-1 21.
Many methods commonly used to mitigate MIC
10. C. Munger, Corrosion Prevention by Protective
in other industries, including biocide and chemical Coatings (Houston, TX: NACE, 1984), p. 506.
treatments and mechanical and chemical clean- 1 1. S. Borenstein, Microbiologically Influenced Corro-
ing, as well as others, are not generally applicable sion Handbook (New York: Industrial Press, 1994),
to biological treatment processes. These methods pp. 221-265.
could kill or inhibit the activity of microorganisms 12. J. Soebbing, et al., “Rehabilitating Water and
essential to the continuation and effectiveness of Wastewater Treatment PIant ,” J. Protect. Coatings
the process, require additional treatment for their Linings 13 (1996): 54-64.
8.10 MIC in the Waste Treatment Industries

13. A. Cunningham, “Corrosion Protection in Sewage A01 ,” Corporate Brochures (Richardson, TX:
Treatment Plants,” J. Protect. Coatings Linings 13 Phillips Driscopipe).
(1996): 66-74. 16. P. Wagner, et al., “Microbiologically Influenced
14. J. Redner, et al., “Evaluating Protective Coatings Degradation of Fiber Reinforced Polymer Compos-
for Concrete Exposed to Sulfide Generation in ites,” CORROSION/94, paper no. 255 (Houston,
Wastewater Treatment Facilities: An Update,” J. TX: NACE, 1994).
Protect. Coatings Linings December (1994): 50- 17. D. Blackwood, et al., “Novel Sensors for On-Site
61. Detection of MIC,” CORROSION/94, paper no. 254
15. “9-92 A17, 820-91, 1089-91 A17, and 1091-91 (Houston, TX: NACE, 1994).
CHAPTER 9

Treatment for the Mitigation of MIC


By R. W. Lufey

Introduction Prevention of MIC

It is widely accepted that overcoming or mit- Sysfem Design


igating MIC is difficult, time consuming, and
expensive.' Therefore, it would be logical to as- System design, whether it is the redesign of an
sume that preventing MIC from being initially es- existing system or original design of a new plant or
tablished should be a top priority. At the present system components, must incorporate sound en-
time, increased awareness of the potential prob- gineering concepts for total corrosion control, in-
lems associated with MIC has made prevention a cluding MIC. Design considerations for corrosion
high priority consideration in the strategy used to control overlap several other areas of considera-
treat cooling water systems. A totally coordinated tion. Items to be coordinated into the total system
water treatment program should include elements design include preconstruction, construction and
to prevent MIC. pre-operational phases, hydrostatic testing, ope-
Once the corrosion situation has been identi- rational phases, and preventive m a i n t e n a n ~ e . ~ , ~
fied as MIC several decisions must be made about Important factors within each of these items
how to deal with the corrosion. In most cases, are:
these decisions lead to a program of mitigation
or the elimination of the MIC, or at least prevent- source water chemistry (including pH,
ing it from being a contributor to putting the sys- salinity, hardness, levels of suspended
tem out of operation. It must be noted that there solids or turbidity, organic contamina-
are some situations where mitigation is neither tion),
practical nor possible. Under those circumstances, typical temperature ranges,
the alternatives are to replace the system com-
ponents and implement a program to prevent flow rates (including the increase or dec-
MIC from recurring or to simply allow the condi- rease of flow rates within a process line),
tion to continue until 'an alternative can be imple- and
mented. type of operation (continuous, intermit-
Most specialists agree that depending on the tent, stagnant, once-through vs. circula-
system and the degree of severity of the MIC, tion, closed-loop circulation, buried pipe,
state-of-the-art technology provides some means underwater, imbedded in concrete,
of mitigating most existing MIC conditions. The etc.).
procedures are typically situation specific, but
there are certain guidelines that can be used to Original system design and redesign must include
increase the probability of a successful mitigation provisions for accessibility for cleaning and for
program in a majority of cases.* These procedures water treatment. Neither of these considerations
are discussed in the following sections. should be handled as an afterthought.

9.1
9.2 Treatment for the Mitigation of MIC

Stagnant or low flow conditions provide opti- System design also should include the devel-
mum environments for the growth of microorgan- opment of a totally coordinated water treatment
isms and subsequent corrosion. These conditions program, which includes control of scale, deposits,
also make it more difficult to use traditional mi- and microorganisms. The design must provide fa-
croorganism control procedures. Where possible, cilities to implement the water treatment program
the system design should provide control of the in the most effective manner possible. Included
flow velocity to a range that will be a limiting fac- with these facilities should be equipment to moni-
tor to the growth of MIC microflora. Generally, this tor the control parameters used in the water treat-
would involve a lower limit on flow velocity to the ment program and to detect any variation from the
extent that suspended solids will remain in the bulk criteria on which the water treatment program is
water stream. Continuous flow is preferred to inter- based.
mittent flow conditions. Dead-leg and bypass cir- Designing processes to provide the capability
cuits should be avoided wherever possible. When of on-line cleaning of isolated components that are
they are required and when standby components particularly susceptible to biofouling or MIC must
are part of the system, the system design should be considered, especially when there are no other
include provisions for drains, traps, recycle circuits, alternatives to prevent potential problems.
monitoring equipment, and the capability to per- Serious consideration of the use of closed-
mit periodic draining and cleaning when necessary loop design should be made for processes with a
without interrupting the operation of the s y ~ t e m . ~ , ~high susceptibility to MIC and with serious conse-
Detailed designs should consider local sites quence of failure. In a closed-loop system, ingress
likely to create optimum environments for the of contaminants can more readily be controlled,
growth of microorganisms. When possible, the de- and chemical treatment is less restricted by envi-
sign of these sites should be changed. For ex- ronmental effluent limits. This approach, although
ample, crevices generated by weld-backing rings initially more capital-intensive, may prove to be the
may act as a means to trap accumulations of most economical approach for preventing MIC for
organic and inorganic deposit-forming materials. safety-related systems or critical components in
This can be eliminated with proper design. Provi- the long run.
sions should be made for circulating water period- There are certain design considerations that
ically or flushing the system in those components should be included in fire safety water systems for
that typically remain stagnant for long periods of purposes of preventing MIC. These include elimi-
time (e.g., fire safety water systems). Side-stream nating the use of hydrant water, which will reduce
filtration and in-line filters and screens should be the need for adding makeup water to the system;
included in the design when it is known that the including in the design a makeup water reservoir
water flow will contain high levels of suspended that facilitates chemical treatment of the system;
solids. Provisions must be made to purge the ac- designing the capability to purge suspended solids
cumulations of suspended solids from the system from the bulk water via bypass circulation and side-
when it is not possible to prevent their existence. stream filtration; and designing facilities to monitor
Planned maintenance and routine housekeep- and test the system for potential or existing MIC.
ing procedures should be developed, and the
system design should include considerations of ef- Materials of Construction
fective implementation of this type of preventive
maintenance. System design should consider the In the past, selection of construction materials
need for periodic removal of deposits by physical or was frequently done without direct consideration
mechanical cleaning. This involves providing ac- of preventing MIC. Other criteria, including initial
cess ports for the insertion of pigs, air-bumping, cost of materials, were given higher priority. It has
sand-jetting, or high-pressure water spray (hydro- only recently been accepted that prevention of MIC
laz i ng) equi pment . is a top priority item. It was believed that in many
Treatment for the Mitiaation of MIC 9.3

systems, MIC could be controlled through proper be well planned and coordinated with both oper-
water treatment, such as the use of biocides, dis- ational and maintenance projects, and with plant
persants, and corrosion inhibitors. This was and personnel responsible for these activities. The pri-
may still be true, particularly in closed-loop mary objective of the cleaning project is to pre-
and recirculating systems. However, in open-loop vent or minimize the existence of an environment
and once-through systems, such as raw water or at any point in the system that supports the growth
service water systems, chemical treatment alone of MIC microflora and to condition the surfaces of
is not adequate to prevent MIC. It very often proves the system in such a way that sessile growth of mi-
to be uneconomical and very difficult because of croorganisms is restricted. When this objective is
the increased limitations on water treatment by en- achieved, other preventive measures can readily
vironmental restrictions. Consequently, especially and effectively inhibit MIC.
in once-through systems, proper selection of ma- Maintenance cleaning programs must be well
terials of construction as related to MIC has be- planned with attention to detail to ensure the suc-
come more i m p ~ r t a n t . ~ cess of the program. It is important to define what
types of deposits are involved. Cleaning trials prior
Maintenance Cleaning to establishment of a routine procedure provide es-
sential information. The planning should involve all
When addressing the question of preventing disciplines and organizations responsible for the
MIC, the first factor that must be considered is operation and maintenance of the system. The
good housekeeping and cleanliness. Even though planned procedure should define each of the es-
MIC can occur in environments free of sludge, de- sential stages of the cleaning. However, the pro-
posits, and foulants, basic microbiological control cedure should be flexible to the degree that it can
technology stresses the need to maintain the sys- be modified as the conditions require.
tem and specific components in a condition as free Routine cleaning becomes necessary as a
of sludge, deposits, and foulants as possible. Prac- means for preventing MIC when procedures to
tical experience has shown that this can be done prevent fouling and deposition are inadequate. In
only when there is a commitment to routine main- some situations, the operating conditions may be
tenance cleaning. This commitment to cleaning on too severe to be manageable with typical practical
a routine basis is no different than committing to preventive measures, and the only alternative is
changing the oil in an automobile on a mileage or routine cleaning.
calendar schedule. System or component clean-
ing is typically done only when heat transfer effi- Mechanical Cleaning
ciency or flow rates become a limiting factor in the The selection of a method should consider the
operation of the system. In safety-related cooling cleaning objectives, as well as the function of the
water systems, the decision to clean most likely re- component being cleaned. Generally, it is most
sults from the necessity to maintain heat rejection practical to carry out mechanical cleaning projects
capabilities for the design basis accident condition. on individual sites or components rather than
This philosophy must be modified to the extent consider system-wide cleaning. In some cases,
that the decision to perform routine maintenance mechanical cleaning is done prior to chemical
is based on preventing MIC. cleaning. Routine mechanical cleaning methods
Cleaning programs may involve a mechani- (Table 9.1) have been designed for individual sites
cal procedure, a chemical treatment procedure, or components, including piping systems, tanks,
or some combination of these. There are several and heat exchangers. Both on-line and off-line
cleaning methods and alternatives to consider. methods may be considered. On-line mechanical
The selection of a routine cleaning procedure re- cleaning most often is considered as a preventive
quires consideration of technical, economic, and method. However, off-line procedures may offer
practical factors. Routine cleaning projects must alternative preventive methods.
9.4 Treatment for the Mitiaation of MIC

TABLE 9.1
Mechanical Cleaning Alternatives

Heat Exchangers Piping Systems Tankage


Batch or recirculation sponge balls High-pressure water lance High-pressure water lance
Scrapers High velocity and reverse velocity flushes Drain and flush
Brushes Sand jetting High-pressure air lance
High-pressure water lance Pigging methods Sand jetting
Component side-stream filtration Side-stream filtration
Air bumping

When evaluating the effectiveness of mecha- materials of construction and service


nical methods, it is expected that these will main- function of the system or component to
tain the required heat transfer and specified flow be cleaned,
rates and prevent the establishment of sessile mi-
on-line vs. off-line cleaning, and
crobiological growth and existence of favorable
MIC environments. It cannot be assumed that the interaction with routine water treatment
procedure is totally effective. Therefore, it is es- program.
sential that the uniformity of cleaning be monitored
because underdeposit corrosion, galvanic effects, As with mechanical cleaning, the decision to im-
and MIC may be promoted by nonuniform or in- plement a cleaning project is usually based on
effective mechanical cleaning. Depending on the the need to maintain the design level of sys-
specific cleaning method(s) used, inspection of tem performance in heat transfer and flow velo-
the system or component should be made before city. Practical experience has taught industry that
and after the cleaning procedure. Where possible, preventive chemical cleaning is also an effective
photographic records are useful in assessing the method for preventing localized corrosion, inclu-
effectiveness of the cleaning program when the ding MIC.
procedure extends over a long period of time. Some of the most common chemical cleaning
agents may be classified according to the charac-
Chemical Cleaning teristics of the materials to be removed as listed in
The success of a routine chemical cleaning Table 9.2.
program and the number of problems encountered Selection of the chemical cleaning agent
in the execution of it reflect the adequacy of plan- must take into consideration the applicability to
ning. This emphasis on planning is not intended the particular materials to be removed and the
to imply that chemical cleanings are extremely dif- compatibility with materials of construction. It must
ficult to plan and carry out. It is simply to point be emphasized that chemical cleaning processes
out that a technically sound chemical cleaning pro- used as a routine measure for preventing MIC
gram can be most effectively performed when the must be passive, nonaggressive procedures.
proper procedures are f ~ l l o w e d . ~ , ~ Uniform metal loss, even at moderate levels,
There are several chemical cleaning alterna- is generally not a primary concern with routine
tives that can be considered. They can be classi- chemical cleaning . However, metal rep recipitat ion
fied according to the following criteria: must be avoided and, when necessary, combina-
tions of chemical cleaning agents, which include
chemical characteristics of the contami- chelating agents, can be employed. Additional
nants to be controlled or removed, considerations in selecting a chemical cleaning
Treatment for the Mitigation of MIC 9.5

Makeup Water
TABLE 9.2
Common Chemical Cleaning Agents Major considerations in the selection of the
makeup water source include the function of the
Scale and Metal Oxides3 system, the volume of makeup water required, and
Ammoniated citric acid Citric acid the design and operation of the system. Makeup
Phosphonatesiphosphorous acid Polyacrylic water sources are primarily surface sources such
acidisalts as lakes, reservoirs, and rivers or ground wa-
NaEDTA HEDTA
Hydrochloric acid Phosphoric acid
ter (wells). However, there is an increasing trend
Sulfamic acid Sulfuric acid to consider the use of treated waste water as a
Ammonium bifluoride/ HEDP makeup water source. The selection of makeup
hydrofluoric acid Oxalic acid water is now influenced by environmental impact
Organic Deposits considerations of how and where the blowdown or
Oxidizing agents (CIz, Brp, Polymeric ionic discharge of water from the system is being done.
NaMn04, Na202,0 3 ,C102) dispersants The quality of the makeup water is a pri-
Nonoxidizing biocides Alkaline detergents mary consideration for the potential of MIC occur-
(NaOH, polyphosphates, Organic Solvents ring in the system. Recognizing the importance
NaHS03, NaZCO3)
Non-ionic penetrantidispersants Non-ionic alkyl of preventing MIC, one must make every effort to
(dimethylamides of fatty acids) surfactants select high-quality makeup water. The important
quality criteria include: low organic content; essen-
tially no soluble iron and minimum suspended iron;
minimum microflora and fauna; minimum turbi-
procedure include: industrial safety and handling, dity and suspended solids; minimum dissolved or
waste treatment and disposal, environmental dispersed gases, including H2S, NH3, 0 2 , C02;
issues, temperature limitations, compatibility with and essentially no hydrocarbons such as oils and
water treatment programs, cost, and corrosion greases.
control. When there is no alternative to using a makeup
water source of low quality such as with waste-
water makeup, consideration must be given to pro-
Water Source viding capabilities for pretreatment and the routine
In many cases, few options relative to the wa- implementation of a water treatment program de-
ter source are available. Very often pretreatment, signed to prevent the establishment of a MIC con-
other than simple filtration, aeration, and sedimen- dition. Pretreatment procedures are based on the
tation, is not practical because of the large vol- characteristics of the specific water. These proce-
umes involved. While the microbiological activity dures include:
occurring in raw water leading to MIC has been
well documented, it 'is less recognized that the
use of deionized water or condensate may not eli- full-stream filtration,
minate microbiological activity that results in MIC
ion exchange/zeolite softening,
failures. Design modifications to provide closed-
loop or recirculation systems offer an extension anionic/cationic resin ion removal,
of water treatment capability. This, in effect, re-
aeration,
duces the volume of water requiring treatment
and also provides a means of internal water treat- degasification,
ment. This also permits the quality of the wa-
nitrate/phosphate removal,
ter to be upgraded and reduces the potential
for MIC. side-stream filtration,
9.6 Treatment for the Mitigation of MIC

lime-soda softening, a number of positions herein. However, it needs


to be stressed here that the prevention of MIC
coagulation/flocculation clarification,
is dependent not only on controlling the growth
bio-oxidation, and of those microorganisms involved with MIC but
also on the operation of the system free of cor-
oil-water separation/emulsion breaking
rosion problems, scale and deposits problems,
Hydrostatic Test Water and maintenance problems that can, to some
degree, be controlled through water treatment
Special emphasis should be given to the selec- procedures.
tion of hydrostatic testing water. There are numer- A water treatment program focused on pre-
ous case histories illustrating the severe MIC prob- venting MIC must consist of three components.
lems that can result from ignoring the quality of the The first is an optimized routine maintenance
water used for hydrostatic tests and other preoper- chemical treatment to control microbiological prob-
ational activities. The water sources for hydrostatic lems, deposits, and corrosion. The second com-
tests are not necessarily limited by plant or com- ponent is a contingency treatment program that
ponent design. Therefore, very few excuses exist
is used only when the operating conditions of the
for using makeup water with an undesirable quality
system change suddenly to the degree that the
that would contribute to potential MIC. maintenance treatment will not prevent the ini-
Quality factors that are important for hydro- tiation of MIC. The contingency treatment must
static testing are the same as those listed above
be implemented immediately when the conditions
for operational makeup waters. If the available change rather than waiting until the problem gets
sources are not of adequate quality, provisions for
out of control. The third component is to plan and
treatment should be made. Treatment of hydro-
implement a proactive maintenance program. This
static test water is discussed in detail later in this would include scheduled on-line cleaning (me-
section. chanical and/or chemical) and other normal com-
ponent maintenance.
Preventive Maintenance
Control of Microorganisms
Water Treatment
In the recent past, the application of biocides
Changing or modifying the inorganic chemistry to water for preservice use, hydrostatic tests, and
of the system water has not proven to be of pri- wet lay-up was rarely considered. The routine use
mary importance in preventing MIC. Some of the of treatment chemicals for the prevention of mi-
alternatives investigated included pH adjustment, crobiological problems, including MIC, was either
sulfate ion removal, iron sequestration, phosphate an afterthought, or something that required consi-
removal, and hardness ion removal. The use of tra- derable persuasion to implement. The concept of
ditional chemicalcorrosion inhibitors such as chro- providing an insurance factor (optimized mainte-
mates, phosphates, molybdates, zinc, and azoles nance treatment) against MIC problems was not
has not been effective in preventing MIC. widely accepted. Very often, the use of corro-
Nevertheless, considerable progress has been sion inhibitors and deposit inhibitors received top
made during the past few years in the technol- priority when dealing with preventive water treat-
ogy of chemically treating water to prevent MIC. ment. Under present-day requirements, it is, with-
This progress encompasses both makeup water out exception, necessary to give first consideration
pretreatment and routine maintenance treatment to procedures required to prevent microbiological
of the system water. The concept of a totally co- problems. A definite commitment for the responsi-
ordinated treatment program represents a major bility of microorganism control must be made and
part of that progress. The factors important to a system of accountability established as part of
the existence of MIC have been discussed from the procedure to prevent MIC.
Treatment for the Mitigation of MIC 9.7

It also must be recognized that, without an ef- 5.0 ppm of oxidizing agents are used to control
fective microbiological control program in effect, or eradicate biofouling, but generally these are not
all other efforts to prevent corrosion and deposit used as a preventive procedure for controlling MIC.
problems will be seriously limited. The concept of Present environmental regulations related to dis-
applying biocides on a routine basis to prevent charge limits place some restrictions on the con-
MIC is based on the capability of the treatment centration of TRO allowed in plant effluent. If the
to maintain the population of the problem-causing MIC microflora reach a exponential growth phase,
microorganisms at a low level where the rate of re- treatment of the bulk water with oxidizing agents
production is no greater than the death rate. Prac- will not be adequate to prevent the establishment
tical experience has shown it is not economically of MIC. It usually is not possible to apply sufficient
possible to sterilize a system to the extent that no oxidant to meet the organic chemical demand with-
MIC organisms exist in the environment, especially out contributing significantly to accelerated gen-
when there is a persistent source of microorgan- eral and pitting corrosion rates and also exceeding
isms (inoculum) being introduced into the system. the effluent discharge limits. Oxidizing agents are
However, it is possible to keep the population un- not effective in penetrating sessile colonies of MIC
der control to the extent that MIC is prevented microorganisms, even at high dosage levels.
when the biocide (a treatment that kills existing Ozone and hydrogen peroxide have greater
microorganisms) is used as part of the total wa- oxidizing potential than chlorine at levels of prac-
ter treatment program. The application of a biostat tical use. For this reason, these materials may be
(a treatment that eliminates or limits microorgan- more efficient in penetrating existing colonies of
ism reproduction) may function in closed-loop sys- sessile MIC microorganisms. There are, however,
tems where an inoculum source does not persist a number of factors that limit the effectiveness of
and there is no limit on maintaining the concentra- ozone or peroxide for routine use as a preven-
tion of the biostat in the treated watere819 tive treatment for MIC. These factors include cost
Chlorine as well as other oxidizing agents, considerations, methods of application, personnel
such as bromine compounds, ozone, or hydrogen safety regulations, and compatibility with materials
peroxide, have been used for microorganism con- of construction and other components of a coordi-
trol in many industries for years. However, there nated water treatment program.
is no standard application procedure or specific When circumstances prohibit the routine use
accepted level of chlorination used for preventing of oxidizing agents for preventing MIC, alternatives
MIC. Practical experience has shown that, at a pH that can be considered include the use of nonox-
less than 7.8, chlorine treatment of once-through idizing biocides. There are many organic, nonox-
and circulating water systems will provide an ef- idizing compounds that are capable of controlling
fective degree of control of MIC microorganisms in the growth of MIC microorganisms in industrial
the bulk water, that is, if the water is free of exces- process water systems. Very often, it is necessary
sive organic contaminants, suspended solids, and to test the efficacy of these compounds under ac-
other dechlorinating substances. At a pH greater tual operating conditions to establish the most ap-
than 7.8, bromine compounds or chlorine dioxide propriate material and the most practical means
may be more effective than chlorine. Above pH 8.5, of applying it. Generally, the cost of treatment with
none of the oxidant materials should be relied upon nonoxidizing biocides is greater than with oxidizing
alone to provide consistent prevention of MIC. agents. However, when oxidants cannot be used,
A total residual oxidant (TRO) of 0.2 to 0.5 ppm the increased cost of treatment with nonoxidizing
appears to be the typical concentration required biocides is justified on the basis that the economic
to provide microorganism control applied contin- losses due to MIC far exceed the cost of even the
uously in severe situations or during as short as nonoxidizing biocides .
1 to 2 hours per 24 hours in less severe situa- In addition to efficacy and cost of the nonoxi-
tions. Intermittent or slug dosages greater than dizing biocides, the environmental impact factors
9.8 Treatment for the Mitigation of MIC

must be considered. As with chlorine and other ox- etrate the colony. Some of the penetrants are
idants, there are effluent discharge limitations re- hydrophobic to the extent that afilm forms on metal
lated to the use of nonoxidizing organic biocides. surfaces making the surfaces less susceptible to
Most of the nonoxidizing biocides in current use the deposition of biomass and sessile colonies
and registered with the EPA are designed to associated with MIC. Thus the use of penetrant-
be nonpersistent in the environment. That is to biodispersants offers an important alternative for
say, they degrade rapidly at use concentrations consideration in preventing MIC. The possibility
into nontoxic or nonobjectionable substances. Be- exists that future technological advances will lead
cause of this fact, most materials can be used with- to the use of nontoxic, low-cost, noncorrosive
out concern when the effluent is discharged to a materials classified as penetrant-biodispersants
conventional industrial wastewater treatment facil- as replacements for the traditional approach of
ity. This makes the use of nonoxidizing biocides using oxidizing or nonoxidizing biocides.
practical in open recirculating systems, closed-
loop systems, and hydrostatic testing procedures. Control of Suspended Solids
At use concentrations, most nonoxidizing bio- Current technology approaches the control of
cides are compatible with typical materials of suspended solids in two ways. The first is to
construction and do not contribute to corrosion. prevent suspended solids from entering or being
Nonoxid izing biocides have Iimited appl icabi Iit y formed in the system. The second approach is to
for preventing MIC in once-through systems where prevent the existence of suspended solids from
the water is discharged directly to regulated causing problems in the system either by remov-
receiving waters and where large volumes of ing them by filtration, bleed, or flushing, dissolving
water must be treated for extended periods of them, or by treating the system with chemicals,
time. such as dispersants and deflocculation agents.
The intermittent use (alternation treatment) of No single procedure has proved to be entirely ef-
nonoxidizing biocides, in conjunction with chlorine, fective. Based on the importance of controlling
bromine, or other oxidants, is another alternative suspended solids as a factor in preventing MIC,
that can be considered. This procedure provides system-specific programs must be developed in
potential cost savings over the use of nonoxidizing coordination with all elements of operation to pre-
biocides alone. It also offers potential mechanisms vent the accumulation of deposits in the ~ y s t e m . ~ , ~
for overcoming specific environmental limitations A specific program may involve a combination
associated with the use of either type of material. of the use of chemical water treatment and me-
Recent technology has been developed that chanical or operational modifications. These pro-
deals with the use of penetrant-biodispersants in grams must include consideration of pretreatment
conjunction with both oxidizing and nonoxidizing of makeup water, selection of makeup water, rou-
biocides.’O~’l Chemically, these materials are tine cleaning and maintenance, system design,
composed of nontoxic organic compounds with and most importantly the coordination of each
penetrating and dispersing properties. Their use in component of the total water treatment program
mitigating existing MIC has been important. How- with all others.
ever, the benefits of their use as routine compo-
nents of a preventive treatment program is becom- Control of Scale and Deposits
ing more widely recognized. Continuous low-level The existence of scale and other deposits in
application of the penetrant-biodispersant enables the system has equal significance to each of the
sessile colonies of the MIC microorganisms to other factors discussed in relation to preventing
be penetrated by the biocide, which is typically MIC.3,4 Present-day technology provides the ca-
used at lower dosages with greater effectiveness. pability of controlling scale and deposits in two
The penetrant-biodispersant inhibits the biomass ways. The first is by removal of ions or suspended
produced by the microorganisms from becoming solids before the water is added to the system.
so massive that oxidizing biocides cannot pen- The second is to leave the materials in the water
Treatment for the Mitiaation of MIC 9.9

and treat it chemically or mechanically in a way to particularly susceptible to degradation by nitric


prevent scale or deposit formation. acid-producing bacteria. Phosphate-based in-
The availability of scale inhibitors, such as hibitors can readily be metabolized by specific
phosphonic acid derivatives, specific chelants, an- bacteria, with the end result being more favorable
ionic polymeric dispersants, and deflocculation environments for MIC.
agents, has provided adequate means of control- Cathodic protection (CP) has proven to be ef-
ling scale and deposits in most closed-loop and fective in preventing nonmicrobiological corrosion
open-recirculation systems. However, these types in a number of applications. There are a few re-
of chemical treatments have limited application in ported cases where CP may have provided pro-
once-through systems, which have a high poten- tection against MIC. These possible successes
tial for scale and deposit problems. Practical ex- have prompted further research on the subject, al-
perience has shown that scale and deposit control though, the technology has not been developed
in once-through systems can best be achieved by to the extent that cathodic inhibition can be relied
mechanical means. Compatibility of specific scale upon to prevent MIC in a wide range of applica-
and deposits inhibitors with biocides and corrosion tions. It is evident that not much is known about
inhibitors must be considered when included as the microbiological effects on CP effectiveness or
part of the total water treatment program. if MIC can actually be controlled consistently by
CP methods. However, CP in conjunction with a
Control of Corrosion good non-metallic lining such as epoxy-coal tar or
MIC is an electrochemical corrosion process. epoxy-fiberglass has a proven track record for cor-
However, the traditional approaches used to con- rosion prevention in buried pipelines, wastewater
trol nonmicrobiological corrosion have not proved treatment vessels, and other applications.
to be effective in controlling MIC.3,4 Water treat-
ment corrosion inhibitors are generally ineffective
for the routine treatment under conditions where Prevention of MIC in
MIC would occur. Indirectly, they do prove use- Specific Systems
ful as preventive measures only when the growth
of microorganisms is controlled by a biocide or Fire-Safety Water Systems
other means. For most water treatment corrosion Fire-safety water systems require specific con-
inhibitors to be effective, the chemical must be able sideration regarding the prevention of MIC.12 Very
to contact the metal surfaces and anodically or ca- often, the makeup water sources are the same raw
thodically retard the half-reaction controlling corro- water sources as used in the open-loop cooling
sion. Uncontrolled growth of microorganisms often water systems. This water characteristically is high
prevents this from occurring. Some chemical in- in microbiological activity and often contains sub-
hibitors, including chromates, benzothiazoles, and stantial organic contaminants. Suspended solids
hydrazine, have a degree of biocidal activity. How- may exist at levels that would contribute to the
ever, at the dosages used for corrosion inhibition, accumulation of sludge under the stagnant con-
these substances cannot be relied upon to prevent ditions of wet standby operation. These conditions
the occurrence of MIC. contribute to microbiological activity and a high po-
The corrosion inhibitors suggested for use in tential for MIC. Prevention of MIC is particularly im-
wet lay-up and hydrostatic testing conditions of- portant in fire-safety water systems because the
ten supplement the addition of a biocide in these alternative of mitigating a MIC problem once it has
applications, and they can contribute to prevent- been established is difficult.
ing MIC. It should be restated, however, that cor- Cleaning a system for mitigation purposes is
rosion inhibitors can be degraded or inactivated often not practical because of system design.
by microbiological growth, including growth of System flushing may be possible, but flush-
some microorganisms associated with MIC. Nitrite ing can accelerate corrosion by introducing oxy-
borate inhibitors used in closed-loop systems are genated water into a system containing hydrogen
9.10 Treatment for the Mitigation of MIC

sulfide and metal sulfides. Nonaggressive chemi- Closed-Loop Systems


cal cleaning of the entire system immediately prior Closed-loop cooling water systems are sus-
to putting it into service is the first and most im- ceptible to microbiological contamination and
portant step in preventing MIC in fire-safety water subsequent MIC. However, cleaning is usually
systems. When the system is clean at start-up, considered only when a need exists to restore heat
subsequent efforts to prevent MIC will be more transfer efficiency or when flow rates are restricted
effective. A discussion of MIC in fire-safety water by the formation of sludge and deposits in the sys-
systems is presented in Chapter 6. tem. Like open-cooling water systems, the incen-
Selecting the best possible makeup water tive for routine cleaning may be increased when
source is the next step. Once the makeup wa- prevention of MIC is considered.
ter source has been determined, a microbiological Safety-related closed-loop systems of mixed
control treatment program, based on the treatment metallurgy should not be routinely chemically
of the makeup water with nonoxidizing biocides cleaned with aggressive cleaning compounds.
and biostats with efficacy against both aerobic Typically, these systems can be cleaned on a rou-
and anaerobic MIC microflora, should be im- tine basis by on-line procedures when the sys-
plemented. Biologically inert organic film-forming tem design includes side-stream filtration. When
inhibitors and pH adjustment can be used to sup- filtration is not available, flushing of the system by
plement the effect of the persistent biocide and/or “makeup and bleed” operations can be used. This
biostat treatment. In some situations, it may be procedure requires the implementation of an ef-
advisable to incorporate a chemical oxygen sca- fective water treatment program, which includes
venger as part of the chemical treatment program. nonoxidizing biocides, dispersants, and appropri-
It has been proposed that oxygen control may ate corrosion inhibitor^.'^
be the most important control parameter since Periodic treatment of the system with slug
it addresses all corrosion mechanisms, inclu- treatments of chemicals that sequester metal ions
ding MIC. can be used to provide some degree of clean-
Microbiological surveys of the fire-safety water ing. Strong oxidizing agents generally are not
systems should be made at least once per quar- used for closed-loop cleaning simply because
ter to ensure that the chemical treatment program they increase the potential for electrochemical
is functioning. Dead-end sites should be sampled corrosion. Certain oxygen scavengers, such as
and tested for the presence of sulfate-reducing hydrazine, appear to provide some degree of bio-
bacteria and other microorganisms that may con- static activity and also function to inhibit corrosion.
tribute to MIC. Chemical analysis of the water
should be made monthly, monitoring the pH and
residual concentrations of the treatment chem- High-Purity Water Systems
icals, including the oxygen scavenger, if used. There are a number of high-purity systems
When any of the.control parameters are not within that may experience potential MIC. The methods
specifications, immediate steps should be taken to for cleaning these systems may include mechani-
correct the situation. When an increase in turbid- cal and chemical procedures, either off-line or on-
ity or suspended solids is observed, bypass side- line. High-pressure water lancing has been suc-
stream filtration, or other alternatives, should be cessful where access is available. The biomass
instituted to purge the solids from the system. and other deposits can be satisfactorily removed.
Every effort should be made to reduce the However, the application of a nonoxidizing biocide
need for introducing oxygenated water into the may be needed to prevent the need for immediate
system once it has been put into service. All recleaning.
makeup water added to the system must be Oxidizing agents are often considered for
chemically treated to maintain the required treat- chemically cleaning high-purity water systems,
ment chemical residuals. inasmuch as both biocidal and cleaning effects are
Treatment for the Mitigation of MIC 9.11

obtained. Oxidants such as hydrogen peroxide do ages and lay-up, this may not be possible. Depend-
not introduce additional contaminating solids into ing on the length of time involved for the outage
the system when used for cleaning. The compat- or lay-up, several alternative procedures are avail-
ibility of the oxidants with the materials of con- able to implement prevention of MIC.
struction of the system must be considered before The first is appropriate for use with an “as is”
use. For example, hydrogen peroxide may cause lay-up. A selection is made of a persistent bio-
problems with some nonmetallic seal and gasket cide treatment, such as polymeric quaternary ni-
materials. Cleaning with oxidants may not be en- trogen or glutaraldehyde compounds, that can be
tirely effective if the oxidant does not penetrate into added to the process immediately prior to the shut-
the materials to be removed. The use of a non- down. Addition is made in a manner to ensure
ionic penetrant-dispersant provides some means that the treatment materials are adequately dis-
of overcoming this limitation. tributed throughout the system to be shut down.
In most cases, the biocide material used for rou-
Prevention of MIC Under Specific tine preventive treatment would not be appropriate
for use with outages or lay-up because of a short
Operating Conditions
half-life. When assessing biocide persistency, the
Outages and Wet Lay-Up half-life of the biocide at prevailing pH and temper-
Scheduled outages and wet lay-up periods re- ature conditions during the outage or lay-up must
quire special attention when developing a program be considered. The dosage levels of the biocide
for preventing MIC. It is important that specific at- should be based on the half-life of the biocide and
tention be directed to preventing the uncontrolled the time anticipated between applications or the
growth of microorganisms when environmental duration of the lay-up.
conditions are substantially different from those Another alternative is to drain the process,
during operation of the system. flush the system with water treated with shock
The most significant difference encountered dosages of a quick kill biocide with a very short
with outages and during lay-ups is that the rou- half-life such as hydrogen peroxide, and refill the
tine procedure for biocide treatment during oper- system with water treated with biostatic chemi-
ation is not implemented. When this occurs, the cals including oxygen scavengers and corrosion
parameters used to specify the biocide treatment inhibitors, such as sodium sulfite or hydrazine.
to be used during operation are no longer relevant. This alternative requires frequent monitoring of
An entirely new set of parameters are needed to the treated water during the outage or lay-up and
prevent MIC during periods when the process is provisions to make supplemental additions, if re-
not in operation. The basic fundamentals of bio- quired, during the shutdown.
cide application are quite pertinent to outage and A third alternative would be to expand on
lay-up situations. However, two further consider- the routine preventive treatment used during sys-
ations must be taken’ into account: the half-life of tem operation, assuming a nonoxidizing biocide
the biocide and whether the water is stagnant or has been used. Use of oxidizing biocides for this
flowing. application would be less effective because of
their short persistence and potential for increasing
Half-life of the Biocide at Existing pH and Tempera- corrosion. This option is dependent on the spe-
ture. Little consideration is given to the hydrolysis cific components of the system and the capabil-
rate or persistence of the biocide used when the ity for periodic circulation or bleed and makeup
system is in operation. In fact, most of the nonoxi- procedures. Approximately one week prior to the
dizing biocides are selected because of their very outage or lay-up, the maintenance dosage of the
short half-life or rapid hydrolysis rate. During oper- biocide is increased three- to five-fold. Immediately
ating conditions, biocide application can be made before shutdown, a slug addition of the biocide is
on a routine and frequent schedule. During out- made at the maximum dosage allowed under EPA
9.12 Treatment for the Mitigation of MIC

registrations, based on the volume of the water in selected has an adequate half-life at the alkaline
the system. pH, it probably will function well as a biostat at a pH
Depending on the system and the biocide greater than 10.0. The polyquaternary ammonium
used, a periodic circulation cycle should be initi- compounds generally fit into this category and
ated. If this is not possible, a bleed and makeup are recommended for use as a biostat at high pH
procedure is implemented where 10% of the vol- conditions.
ume of water in the system is bled per month. The Consideration must be given to the effect of the
makeup water added to replace the bleed should high pH on the various materials of construction in
be treated with the biocide at the same dosage the specific components of the system. It is not
made with the slug treatment. This alternative can recommended that aluminum, copper, or copper
be used with short-term (6 to 16 weeks) “as is” alloys be exposed to pH above 9.0 for extended
lay-up and wet lay-up situations. It provides the periods. This may be modified somewhat by in-
advantage of not being required to drain, dispose cluding azole anodic inhibitors as part of the pH
of the water, and refill the system before putting it adjustment procedures. Buffered borate salts may
back into operation. be a suitable alternate corrosion inhibitor in certain
situations. Before the decision is made to consider
Stagnant vs. Flowing Water. Assuming it is not this alternative, a plan for draining and discharg-
possible to have the system drained and dried ing the treated water at the end of the outage or
during the outage or lay-up, provisions concern- lay-up must be made. In some cases, this may be
ing water flow must be considered. If design engi- an important limiting factor.
neering originally made water circulation possible, Prior to putting the system into operation after
then it should, by all means, be circulated at least a wet lay-up or outage, the system should be thor-
once per 1 to 4 weeks for a period long enough to oughly inspected to ensure that the potential for
provide a 3 to 4 times turnover of the component MIC is minimal.
vol ume.
Care should be taken not to entrain air in the Preoperational and Hydrostatic Periods
circulating water. The system should be at maxi-
There is limited factual documentation avail-
mum volume of water. Often during lay-up or out-
able to substantiate the claim that MIC often is
ages, parts of the system drain to less than full
established during preoperational phases of plant
volume levels. The flow velocity should be at or
construction or during the preconditioning and hy-
above design rates to help move and transport any
drostatic testing phases when water is first intro-
sediment or sludge that may have settled out dur-
duced into the system. However, past experiences
ing a stagnant period. Periodic sampling of the wa-
of the MIC specialists certainly have confirmed
ter should be made before and after a flow period.
that this period is critical when considering pro-
Any change in the pH, turbidity, or dissolved iron
cedures for preventing MIC. It is the purpose of
level may indicate that further remedial steps to
this discussion to point out those factors that are
prevent MIC may be necessary. Sampling of stag-
known to contribute to the MIC potential and those
nant water may not provide sufficient information
factors that may help to prevent MIC during pre-
to indicate whether or not MIC exists.
operational and hydrostatic t e ~ t i n g . ~
When it is not possible to drain and dry the sys-
tem, another alternative may be considered. The Preoperational Construction Phase. From the ini-
pH of the water can be raised to a level greater tiation of construction, through hydrostatic testing,
than 10.0. This will reduce the metabolic activity of and into the operation phase, good housekeep-
most of the microorganisms involved with MIC. Re- ing and cleanliness are critical to the prevention of
member, however, that the pH adjustment will not MIC. This has been emphasized earlier. Keeping
kill them. Most of the nonoxidizing biocides have components dry and free of contact with stagnant
less efficacy at alkaline pHs. However, if the one water during this period is equally as important.
Treatment for the Mitigation of MIC 9,13

Stagnant water, such as rainwater in a pipe laying solutions contain an adequate concentration of a
on the ground, open tanks containing leak-test wa- quick-kill, nonpersistent biocide proven to be effec-
ter, or site-stored components exposed to the ele- tive against MIC microorganisms at the prevailing
ments, can readily be found at every construction pH and temperatures, as well as being compati-
site. Throughout construction and also extensive ble with the pretreatment solution. Prior to moving
maintenance outages, constant attention should from the pretreatment phase to hydrostatic test-
be paid to draining off stagnant water and drying ing and start-up, the system should be examined,
the components of the system. Dirt and construc- component by component, to confirm that the pre-
tion debris should not be left in contact with materi- treatment procedures were completed.
als, particularly in the presence of moisture. If this
cannot be prevented, the components or materials Hydrostatic Testing Phase. It has been discussed
should be flushed with clean water, drained, and previously that selection of a high-purity water for
dried. Drying can be achieved by the circulation hydrostatic and leak testing is critical to the efforts
or blowing of warm air through or onto the com- of preventing MIC. There are other factors that are
ponents. In large piping systems, drying can be also important. These include how well the sys-
performed by the circulation of warm air or nitro- tem or component was cleaned prior to adding the
gen gas and the moisture content of the discharge test water. If there was residual debris in the sys-
gas monitored to ensure the desired dryness has tem, it will often be transported to a site where
been achieved. it accumulates and subsequently provides an op-
A thorough inspection of the system must be timum environment for MIC. Provisions must be
made, component by component, on a routine made to prevent this from occurring or to have
basis during the preoperational and construction the capability of purging these materials following
phase to confirm that the potential for MIC is testing.
minimal. System design is another factor that plays an
important role in the prevention of MIC during the
Pretreatment Phase. The pretreatment phase is hydrostatic testing phase. Hydrostatic testing usu-
the initial conditioning of a component or an en- ally is done in progressive stages, testing each
tire system, following initial construction or an segment of the system or individual component
extensive maintenance project. Pretreatment ac- as construction is completed. The system must be
tually is done in two steps. The first involves designed in such a way that the individual seg-
general cleaning where construction debris, dirt, ments can be drained completely and dried im-
grease, and mill scale are removed from those sur- mediately after hydrostatic testing. The segments
faces that ultimately will come in contact with the should not be allowed to stand idle even for a
process water. This cleaning should be done first few days with the test water still in them. Tanks
by mechanically removing as much foreign materi- and vessels should be completely drained after
als as possible, and then following this by a passive leak testing as well. The design of these compo-
chemical cleaning flush. nents should enable them to be completely drained
The second step is to condition the cleaned and not in a way that a few feet of water still re-
surfaces so that subsequent routine chemical mains standing in the component below the drain
treatments will be effective. In some situations, it is point.
desirable to pretreat and passivate the metal sur- Planning and scheduling the hydrostatic test-
faces with a high dosage of the corrosion inhibitor ing sequence must take into consideration how
to be used in the routine water treatment program. long the system will stand idle after hydrostatic
In other cases, it may be necessary to pretreat testing before the process is put into normal
and passivate with materials other than those to operation. Every effort should be taken to do the
be used later during operations. In every case, testing as near as possible to the time the process
however, it is recommended that the pretreatment will be put into operation. When it is known that
9.14 Treatment for the Mitigation of MIC

an extended period will occur between testing and system after pretreatment. Others will suspend
start-up, appropriate measures to reduce the po- residual debris in the test water and prevent
tential for MIC must be taken. The ideal situation it from settling out. Some penetrant-dispersants
is to drain and dry. will form a hydrophobic film on metal surfaces
Chemical treatment of the testing water pro- and provide some degree of short-term corrosion
vides some degree of assistance in preventing the inhibition.l0I1 The use of anionic polymeric disper-
initiation of MIC during hydrostatic testing, espe- sants is recommended when the test water con-
cially when the considerations mentioned earlier tains high levels of suspended solids and when the
cannot be managed to the extent needed to pre- metal surfaces of the system were not adequately
vent MIC. However, it must be reemphasized that cleaned during pretreatment. Anionic dispersants
water treatment alone should not be expected to should be used when hydrostatic testing is done
reduce the potential for MIC to zero. The water under high flow velocity and it is possible to com-
treatment program for hydrostatic testing should pletely drain and dry the system after testing. This
entail the use of biocides, penetrant-dispersants, prevents the accumulation of sludge at low flow
and/or corrosion inhibitors. sites after testing is completed.
Biocides are perhaps the most critical part of Corrosion inhibitors do not typically provide
the water treatment program. The selection of the significant benefits in preventing MIC to justify their
biocide must be based on the specific job it is ex- routine use in hydrostatic testing waters. Neverthe-
pected to do.8,9 If the quality of the makeup wa- less, there are specific situations when anodic pas-
ter is such that a substantial MIC inoculum level sivating agents, such as chromate, molybdate, or
exists, a quick-kill biocide should be applied. Typi- orthophosphate-based inhibitors, will assist in pre-
cally, a shock dosage of an oxidizing biocide, such venting corrosion of ferrous metals. Azole-based
as chlorine, bromine, peroxide, or ozone, is ap- inhibitors have been used with nonferrous metals,
propriate. If the makeup water contains high lev- such as aluminum and copper alloys. The pH ad-
els of suspended solids, including organics, oils, justment of the makeup water to a level above 10.0
and greases, or if the system was not thoroughly will reduce the potential for MIC where the system
purged of deposit and sludge materials during pre- can be maintained in a flooded condition follow-
treatment, or if the pH is higher than 7.8, then oxi- ing testing and prior to start-up. Buffered borated
dizing biocides should not be used. In any of these water may serve the same purpose under certain
situations, a quick-kill, nonoxidizing biocide is re- conditions. Where corrosion inhibitors are used, it
quired because contact time is short and high lev- is recommended that an appropriate biocide also
els of suspended solids are present. be used to ensure prevention of MIC.
A persistent biocide-biostat should be used System inspection must be done, component
when it is expected that the system cannot be com- by component, immediately before putting the sys-
pletely drained or is going to be held idle in a wet tem into operation. This is the last time remedial
condition for more than a few days. It should be procedures can be taken to correct any situations
noted that hydrostatic testing water treated with a that occurred during preoperational phases.
persistent biocide-biostat can be drained from the
system after testing and stored on site for use with
future testing. This type of biocide-biostat also pro- Mitigation of Existing MIC
~~~ ~ ~~ ~~

vides some degree of protection from MIC when


the system cannot be completely drained or the Deciding on Whether Mitigation
potential exists for residual debris in the system is a Viable Option
after pretreatment .
~ e n e ~ r ~ n f - ~ i s ~ ecomplement
r s ~ n f s the effec- When MIC has been identified as the cause
tiveness of either oxidizing or nonoxidizing bio- of the existing corrosion, it is necessary to
cides. Their use assists the penetration and/or decide whether a mitigation program is feasible
dispersion of those deposits that may exist in the or whether it will be necessary to remove and
Treatment for the Mitigation of MIC 9.15

FIGURE 9.1 FIGURE 9.3


Internal surface of carbon steel pipe that has been colo- Internal surface of carbon steel pipe and face of a
nized by iron-oxidizing bacteria forming tubercles. This gate valve located in a fire protection system. Note
condition can be mitigated by mechanical/chemical the "old" tubercles formed by iron-oxidizing bacteria
cleaning before pipe failure occurs. (See color plates.) and the "new" growth on the surface of the tubercles
demonstrated by the orange-colored deposits. (Courtesy
Russ Green.) (See color plates.)
replace the corroded component. The following is
a series of photographs that illustrate frequently
encountered MIC. They can be used as exam- when chemical cleaning after flushing may be a vi-
ples of whether mitigation is a viable option for able option. Figures 9.8,9.9, and 9.10 show condi-
eliminating the condition. tions where chemical cleaning would remove cor-
Figures 9.1 and 9.2 are examples of when rosion products and result in substantial leaking.
mechanical/chemical cleaning is a viable option. Figures 9.1 1, 9.12, and 9.13 are examples of mi-
Figures 9.3, 9.4, 9.5, 9.6, and 9.7 are examples crobiological fouling that should be mitigated by

FIGURE 9.2
Internal surface of carbon steel pipe showing exten- FIGURE 9.4
sive tuberculation caused by iron-oxidizing bacteria. The Internal surface of a carbon steel elbow covered with cor-
tubercles could be removed by mechanical/chemical rosion products and tubercles formed by iron-oxidizing
cleaning, but there may be significant pitting corrosion bacteria. Note the aggressive attack of the weldment at
underneath the tubercles. (See color plates.) the socket welds covered by tubercles. (See color plates.)
Next Page

9,16 Treatment for the Mitigation of MIC

FIGURE 9.5 FIGURE 9.7


Internal surface of carbon steel pipe showing corrosion Internal surface of carbon steel pipe at a welded flange
products and tubercles caused by iron-oxidizing bacte- colonized by iron-oxidizing bacteria. Note the black de-
ria. Note that only some of the corrosion product and tu- posits on the metal surface where the tubercle has been
bercles have been removed by chemical cleaning (lower removed. (See color plates.)
half of split pipe). (See color plates.)

penetration into the tube wall are the criteria that


chemical cleaning before significant damage by are used to determine whether replacement or mit-
MIC occurs. Figures 9.1 4 and 9.1 5 illustrate dam- igation is the most practical procedure.
age to welds on stainless steel tank walls that can-
not be mitigated by any means. Figures 9.1 6,9.17, Preprogram Planning
and 9.18 are photographs of pitting corrosion on
copper alloy materials. Pit depth or the extent of Mitigation of MIC should be considered much
in the same way as a major maintenance program.

FIGURE 9.6
Close-up view of pipe in Figure 9.5 showing the partially FIGURE 9.8
removed tubercle and the pit area beneath it. To SUC- Exterior surface of pipe shown in Figure 9.7 showing the
cessfully mitigate this MIC, the cleaning solution must through-wall penetrations of pits caused by growth of
penetrate though the deposited corrosion product. (See sulfate-reducing bacteria underneath tubercles seen in
color plates.) Figure 9.7. (See color plates.)
CHAPTER 10

Techniques for MIC Monitoring


By T.P.Zintel, G-J,Licina, and T.R. Jack

Importance The most common approach to the mitigation


of MIC is to chemically treat the water or other
fluid. Chemical costs for a large power generation
The annual costs of corrosion in industrialized facility are often on the order of one million dollars
nations have been estimated at approximately 4% per year. The toxicity of these chemicals is always
of the gross national product (GNP).’ The esti- a concern for plant personnel as well as the envi-
mated cost of corrosion in the United States is ronment. Toxicity concerns are the basis for close
on the order of 300 billion dollars per year. That scrutiny and control of effluents and chemical in-
same study estimated that at least 15% of those ventories by regulators, environmental agencies,
costs are avoidable using existing technologies. and plant and pipeline owners.
The costs for microbiologically influenced corro- Probably the second-most common approach
sion (MIC) are consistent with those estimates; to MIC mitigation is to do nothing and simply re-
however, these costs could be significantly re- place system piping or components when they fail.
duced since the control of MIC through the use Several nuclear plants have sustained extensive
of timely treatments and scheduled maintenance corrosion damage to their service water systems;
is often relatively simple. much of the damage has been the result of MIC. In
In the past twenty years, MIC has been shown many cases, extensive and expensive repairs and
to be a real and significant degradation mecha- replacements were required at costs of several mil-
nism for industrial plant materials in a wide range lion dollars per system. At least three domestic nu-
of areas, including nuclear and fossil-fueled power clear plants have completely replaced the piping in
plants, chemical processing facilities, refineries, oil their service water systems. Costs per plant aver-
and gas production and distribution systems, pulp aged 30 million dollars.
and paper industries, and t r a n ~ p o r t a t i o n . MIC
~,~ Since MIC encompasses the full range of in-
has also been a problem for the military and for teractions between microbiological activity on sur-
building plumbing and ventilation systems, as well faces and corrosion processes, controlling or elim-
as for numerous other industries and processes. inating biofilms on such surfaces can prevent MIC
Unplanned downtime, a loss in production, and a reliably and practically. The treatment of clean sur-
loss of efficiency manifest the costs of MIC, as pip- faces to keep them clean and biofilm-free is rela-
ing and equipment are crippled by the localized tively simple, using proven technologies. However,
corrosion and the costs of the various mitigation a mature biofilm, replete with copious amounts of
treatments themselves. Essentially all cooling wa- exopolymeric saccharides, entrapped silt and de-
ter and process water applications are susceptible bris, and corrosion products, serves to protect the
to MIC. Further, biological fouling, which is a pre- underlying microbes on the metal surface from
cursor to most instances of MIC, can reduce the all but the most aggressive treatments. As a re-
efficiency of heat exchangers and gas and fluid dis- sult, the treatment of biofouled surfaces is much
tribution systems, and it can interfere with water- more difficult and much more costly in terms of
based processes. downtime, the costs of the treatment, and in the
10.1
10.2 Techniques for MIC Monitoring

costs to the environment necessitated by toxic Rugged. The monitoring system must
chemical treatments or the generation of wastes. be able to withstand the normal use and
Further, heavily microbiologically fouled surfaces abuse it is likely to experience in an in-
can establish conditions that are conducive to dustrial environment.
rapid localized corrosion even after the living or-
Sensitive. The monitor must be sensi-
ganisms have been killed. Such severely pitted
tive to the onset of biofilm formation and
surfaces are almost impossible to salvage.
provide a definitive indication of biofilm
Water or fluid treatment remains the most com-
activity in real time that may be used
mon approach to the control of MIC. The costs of
to evaluate the effectiveness of bio-
such treatment include the costs of the biocide,
cide additions or other water treatments,
delivery system, and labor to install and maintain
cleaning, or other mitigation measures.
the equipment as well as the costs of the opera-
Biofilm formation on the monitor must al-
tor training and permits to store and discharge the
ways “lead” biofilm formation on heat ex-
toxic chemicals. The costs of chemical treatment
changer or piping surfaces. This degree
increase rapidly as the thickness and activity of the
of enhancement of sensitivity provided
microbiological fouling goes unchecked. Higher
by the monitor and the prototypicality of
concentrations of chemicals, the use of disper-
biofilms on monitoring probes vs. those
sants and surfactants, or the use of much more ag-
on component surfaces (the lead factor)
gressive chemical treatments are often required.
must be reasonable and quantifiable.
Monitoring to provide an early warning of the
onset of biocorrosion or biofilm formation and its Accurate. False positives or indications
activity or deactivation by the selected treatment caused by interference from other ef-
is critical to maintaining control of surface cleanli- fects such as flow, light, degree of aer-
ness when MIC prevention is still simple and inex- ation, and fouling by nonbiological de-
pensive. Many of the MIC monitoring technologies posits must be minimized. A maximum of
currently used or available are discussed in this two false positives per year is the target
chapter. rate. Lead factor can also impact accu-
racy requirements. An excessive or unre-
alistic lead factor will produce a positive
Methods indication of biofilm activity that bears lit-
tle resemblance to fouling and corrosion
MIC monitoring methods can be categorized of system components.
by the primary characteristic of the process that is
Maintainable. Probes are expected to
monitored. That is, there are techniques that mon-
become fouled in service. A minimum
itor microbiology; others detect microbiological in-
time between servicing operations of
fluences, while other methods track corrosion.
several months to several years will be
An effective MIC monitor, like any monitor,
required for most applications. Periodic
should exhibit the following characteristics:
servicing, consisting of cleaning with
readily available tools such as brushes
User Friendly. The monitor must be sim-
or abrasive tools, shall take less than one
ple to install, simple to use, and simple to
hour per probe.
interpret by system operating personnel.
At least some interpretation functions Cost Effective. The cost of the monitor
must be sufficiently developed so that the must be significantly less than the cost of
system can be interfaced to alarms and the downtime that is avoided or the treat-
controllers for chemical treatment addi- ment costs that are saved. The speed
tions or on-line cleaning systems. and accuracy of the technique are also
Techniques for MIC Monitoring 10.3

factors in the cost effectiveness of the treatment program, when in reality, attached or-
monitor. ganisms may be quite unaffected by the biocide
treatment and were able to continue their attack
on the metal surfaces.
Microbiology Biological deposits are the controlling factor
in degradation of heat transfer or initiation of
Microbes are ubiquitous; they survive a wide MIC. The monitoring approach should emphasize
variety of environmental conditions, including ex- counts, accumulation, activity, etc. of microbes on
tremes of temperature, aeration, and nutrient de- surfaces. Microbe counts in the cooling tower wa-
pravation. The interaction of microbial metabolism ter have little or no correspondence to counts and
and corrosion processes can produce localized activity on surfaces. The primary value of “bug
attack at very high rates. Monitoring techniques counts” in the water is a regular and inexpen-
that detect the presence of microbes, especially sive comparison of the effectiveness of the treat-
on metallic surfaces, can provide an early indica- ment on the most readily controlled microorgan-
tion of incipient MIC or the potential for MIC. A isms. Plots of total counts of bacteria, fungi, and
number of methods for the detection of microor- specific types of microorganisms (e.g., sulfate-
ganisms, including specific types of organisms and reducing bacteria) will show variations in organism
estimates of their numbers and activity, have been levels and reflect the level of control. Those counts
developed. of planktonic organisms should be extremely low
for any effective biocide treatment program.
Planktonic Organisms
Sessile Organisms
Free-floating bacteria are commonly referred
to as “planktonic” organisms, but depending on Microorganisms that are attached to a sur-
the type of industrial system, these may also in- face are termed “sessile” organisms. Bacteria and
clude unattached algae, diatoms, fungi, and other other microorganisms are almost always present
microorganisms present in a system’s bulk fluids. as a consortium or community of organisms, col-
In most cases, it is planktonic bacteria that are lectively referred to as a biofilm. Since MIC occurs
the focus of monitoring for MIC using microbio- directly on metal surfaces, sessile organisms are
logical detection techniques since system fluids the ones that are most representative of poten-
are generally easier to sample than metallic sur- tial problems and, therefore, are a more important
faces. Unfortunately, the levels of planktonic bac- component to monitor. Monitoring sessile organ-
teria present in the liquids are not always indicative isms either requires that the system or pipeline be
as to whether MIC will occur or, if so, to what ex- regularly opened for sampling or that accommo-
tent. At best, detection of viable planktonic bacteria dations be made in the system design to allow for
only serves as an indicator that living microorgan- regular collection or on-line tracking of attached
isms are present in a particular system. Some of organisms while the system continues to operate.
those organisms may be capable of participating in It should be pointed out, however, that the pres-
the microbial attack of the system’s materials. It is ence of viable sessile organisms does not always
generally very important that additional monitoring translate into actual attack on the metal surfaces.
methods be performed to confirm that actual cor- Again, it is a good idea to use additional methods
rosion due to microbial processes has occurred. that directly determine the presence of active MIC.
In some cases, monitoring for planktonic organ-
isms can be misleading. For example, following Direc t Inspection
biocide application, elimination or reduction of vi-
able planktonic organisms suggest to many op- Surfaces coated with slime, the presence of
erators that they have implemented a successful black iron sulfide deposits or algal growth, and
10.4 Techniaues for MIC Monitorina

odors can all indicate the presence of a microbial Growfh Assays


biofilm. The presence of microbes suspended in
the aqueous phase is usually not evident to the The most popular way to enumerate microor-
unaided eye. Very high numbers of planktonic mi- ganisms in industrial systems is through growth
crobes (>l O7 cells/ml) are needed to cloud a water assays.15 Commercial kits are widely available to
sample. This level of turbidity is very rarely seen. count different kinds of organisms that have been
To see microorganisms directly in field samples re- related to specific industrial problems. These kits
quires the use of a microscope capable of at least may be used to analyze fluid samples or solid sam-
400X magnification and preferably equipped to op- ples scraped from surfaces.
erate in a phase contrast mode. The type most commonly used in industrial ap-
Direct inspection can allow detection and plications involves a series of liquid vials. The kits
enumeration of planktonic organisms. A simple include all the tools needed to prepare the sam-
sample holder called a Petroff Hauser Counting ple and dilute it quantitatively into vials of growth
Chamber allows organisms in a known volume of medium. Different media are available to grow
water to be c o ~ n t e d Populations
.~ of greater than sulfate-reducing bacteria (SRB), acid-producing
1O6 cells/ml can be conveniently enumerated. A bacteria (APB), and general aerobic or anaero-
variety of dyes can enhance detection by staining bic bacteria. The extent of growth seen in a di-
cells with bright colors or making them fluoresce lution series after an appropriate time interval al-
under ultraviolet In some cases the re- lows estimation of the numbers of each type of
sponse of the dye can be keyed to indicate the via- bacteria present in the original sample. This ap-
bility of the cells, enabling live and dead organisms proach is called the Most Probable Number (MPN)
to be distinguished. Enumeration of less dense technique, reflecting the semiquantitative nature of
planktonic populations requires concentrating the the counts obtained. Detection limits are very low
sample. This can be conveniently done by filtering (1 to 10 cells/ml) but very high populations can
the organisms from a large volume of water and also be enumerated by extending the dilution se-
then staining and counting the cells on the filter.8 ries if needed. It is important that growth assays be
Direct inspection is less useful for sessile pop- done at the salinity and temperature of the indus-
ulations or dirty water systems where particles and trial operating system. Commercial kits are offered
debris hide the microbial cells and interfere with for different levels of salinity. In some kits, solid me-
the use of dyes by picking up stain. Hydrocarbons, dia in the form of agar stabs or dip slides are used
deposits, and coating materials commonly seen in place of liquid media in vials, but the general
in industrial systems occasionally fluoresce under approach remains similar.
ultraviolet light thereby preventing the use of flu- Commercially available kits were compared in
orescent dyes. In effect direct inspection is often a round-robin test performed by field personnel
limited to detection of microorganisms in field Sam- in 1992.16These kits provide untrained personnel
ples. This limitation along with the cost and deli- with a relatively inexpensive way to monitor vari-
cacy of the microscope has left direct inspection a ous groups of bacteria thought to be important in
lab technique. MIC over time. Changes in populations provide an
Direct inspection has been used as a research indication of emerging MIC problems or the effect
tool to investigate the arrangement of specific of biocide addition or other actions in the system.
kinds of bacteria and processes in microbial com- Despite the successful use of growth assays,
munities. Tagged antibodies can bind dyes to spe- only a small fraction of wild microorganisms ac-
cific kinds of b a ~ t e r i a . ~ -Such
’ ~ techniques can tually grow in commonly supplied artificial media.
provide insight into how microbial biofilms develop For example, less than one organism in a thousand
and influence corrosion processes, but they are of present in marine sediments can actually be grown
limited application in the routine management of by standard procedures.17 Commercial growth as-
industrial operations. says do not count all the organisms present but do
Techniques for MIC Monitoring 10.5

characterize the composition of populations gen- especially from highly reduced environments
erally associated with industrial problems. where hydrogen sulfide is present, can prove dif-
ficult to measure. Natural variations in the amount
Enzyme Assays of ATP per cell make direct correlation with cell
counts unreliable, but the assay can be used to
Enzymes are proteins that act as catalysts for monitor the general health and activity of a micro-
specific chemical reactions. An increasingly popu- bial population in an industrial system.
lar approach is the use of commercial kits to assay
the presence of enzymes specifically associated Cell Components
with organisms or processes implicated in MIC.
These assays do not depend on growth of the A general index of biomass in field samples
organisms but focus instead on the chemical re- can be obtained by classical analytical methods for
actions that a microbial community can catalyze. protein, lipopolysaccharides, or other cell compo-
Commercial products are available for determin- nents. More specific information can be obtained
ing the presence of h y d r ~ g e n a s e ' ~
or, ~sulfate
~ by analyses based on the fatty acid profile of the
reductase20,21enzymes present in many species microbial cells or on nucleic acid samples derived
of SRB. Correlation of enzyme activity with popu- from field samples.
lation counts is variable. In general these kits have Analysis of fatty acid methyl ester (FAME) pro-
a range of application that is narrower than growth- files is one of the best available ways to charac-
based assays, making it important to select a kit terize the composition of a naturally occurring mi-
with a range of response appropriate to the prob- crobial community.26-28The composition of fatty
lem under investigation. Test kits are generally a acids in cellular components can be used to finger-
little costlier and have a higher detection limit than print specific organisms. Provided pertinent pro-
growth-based assay kits; however, results can be files are known, organisms can be identified with
obtained in less than an hour compared to several c o n f i d e n ~ e .FAME
~ ~ ~ ~can
~ be used to identify
days. what organisms are present in an industrial sys-
tem, to monitor populations in the field, and to
Metabolites assess the impact of operating actions such as
biocide addition on the makeup of sessile com-
In some cases, microbial products are impli- munities. The technique involves separating fatty
cated in MIC scenarios. One example is the pre- acids from field samples and converting them
cipitation of black iron sulfides as a corrosion prod- to the corresponding methyl esters suitable for
uct by SRB in systems normally free of hydrogen gas chromatographic analysis. Commercial sys-
sulfide. The concentration of iron sulfide in corro- tems including instrumentation, procedures, and
sion products has been related to corrosion rates databases of FAME profiles for a library of known
seen in SRB-based' MIC.22 Organic acids have organisms are available.
been detected in corrosion deposits,23 implicating Nucleic acids are the blueprints for construc-
acid-producing bacteria in some MIC scenarios. tion of cell components. The sequence of nu-
An overall assessment of microbial activity cleotides in nucleic acid polymers provides a code
can be achieved by measuring the amount of for protein synthesis. The master blueprint (DNA)
adenosine triphosphate (ATP) in field samples.24 is transcribed to form working copies (RNA) spe-
This key metabolite drives many cellular reactions. cific to various cell components. Assays based on
Commercial instruments are available for field use the sequence of nucleic acids can be used to iden-
but the method is best suited to clean aerobic tify specific organisms, kinds of organisms, or the
aqueous samples. The measurement is based on presence of enzymes at a general or specific level
fluorescence that can be chemically quenched of discretion depending on the approach used. For
or blocked by particulate^.^^ Biofilm samples, example, a gene probe designed to detect [NiFe]
10.6 Techniques for MIC Monitorina

hydrogenase enzyme has been used to character- from the system being monitored is crucial to
ize SRB in oil-field production waters3’ Because ensure that subsequent laboratory tests provide
gene probes are highly targeted, a battery of dif- representative information. Biofilms in particular
ferent probes would be needed to characterize a are highly sensitive to dehydration, exposure to
microbial community broadly. air, temperature, mechanical damage, and other
A more general approach is to use the whole gross environmental changes that can occur
DNA genome as a fingerprint for the identification during removal and transport of the coupon. The
of organisms. A practical technique called Reverse steps necessary to preserve the components of
Sample Genome Probing (RSGP) allows DNA interest that may exist on the coupon should be
separated from field samples to be cross-reacted planned well in advance of coupon removal.
with standard samples prepared from organisms With special preservation and handling,
cultured from previous MIC sites.32 In effect the coupons may be examined both chemically and
method can show, in a semiquantitative manner, physically for macro- and microstructural corro-
whether any of the known organisms are present. sion effects. Chemical composition of the coupon
A problem faced by nucleic acid-based as- surface can be performed using energy disper-
says is the separation of sufficient material from sive X-ray spectroscopy (EDS) in combination
a field sample to allow analysis. A special tech- with scanning electron microscopy (SEM), trans-
nique based on the polymerase chain reaction mission electron microscopy (TEM) of replicas,
(PCR) can replicate targeted genetic material in or environmental scanning electron microscopy
a sample millions of times.33 Initial tests identified (ESEM). The distribution and relative concentra-
over 300 strains of bacteria using this ~ r 0 c e d u r - e . ~ ~tions of elements involved in the corrosion can
While the technique is extremely sensitive, the ex- also be identified in some cases, which is partic-
tent of amplification varies for nucleic acid material ularly valuable where pitting has occurred. These
from various organisms. Results are best regarded techniques are also beneficial when investigating
as qualitative. A comparison of this approach with scales and other deposits. Both optical microscopy
FAME has been published.35 and electron microscopy are useful in assessing
Analysis of cell components requires skilled the nature of corrosion attack on coupons and in
staff in an appropriately equipped laboratory, but determining the corrosion mechanism(s) present.
many such assays are available on a fee-for- The morphological characteristics of the corro-
service basis. Costs are high relative to the use sion observed on coupons can be beneficial in
of commercial kits for assaying microbial growth diagnosing the corrosion mechanism(s); however,
or enzyme activity. the interpretation of the data must also consider
the surface chemistry and microbial analysis of the
Detailed Coupon Examinations coupon and the operating environment.
Examination of coupons for microbial popula-
A great deal of information can be learned by tions can be performed either directly (which is
careful, in-depth examination of corrosion coupon destructive to surface conditions intended for sub-
surfaces using commonly available analytical sequent analyses) or indirectly, using histological
techniques. These coupons can yield far more embedding techniques to preserve and remove
information than a simple loss of weight, which the biofilm. Although fairly involved, the embed-
may be the original purpose for their installation. ding technique offers several advantages over di-
The condition of the coupon surfaces themselves, rect observation in that the biofilm and corrosion
as well as their deposits, corrosion products, products are preserved for future analysis. ESEM
and biofilms can all yield useful data to help the may also be utilized to examine biofilms on test
corrosion engineer diagnose corrosive conditions coupons; however, exopolymers and corrosion
at key locations in a pipeline or industrial sys- products often obscure the cells, making quantifi-
tem. Special handling of coupons after removal cation and identification difficult with this method.
Techniques for MIC Monitoring 10.7

FIGURE 10.1 (a)


Biofilm sampling device with removable "buttons."

A wide variety of samplers for introducing a useful indicator that a biofilm is present and
metallic surfaces of interest into the system are that action should be taken to mitigate potential
available. Examples of such sampling devices are MIC.
shown in Figures 10.1-1 0.3.
Deposition A ccurn ulation Monitors
Influence Methods for monitoring deposits can provide
an indication of the accumulation of biofilm and
The presence of a biofilm on a metallic sur- other solids on surfaces or in orifices. For exam-
face changes the local chemistry, which can mod- ple, monitoring pressure drop across an orifice
ify the local anodic and cathodic processes and provides a simple method for continuous monitor-
initiate or dramatically alter corrosion processes. ing of deposit accumulation that can be used as
In addition to the electrochemical changes that af- a method for detecting biofilm accumulation and
fect corrosion, those same biofilms can also mod- serve as a monitor for incipient MIC. The disadvan-
ify other readily measured characteristics such as tage of such a monitor is that the total deposition
pressure drop or heat transfer resistance. Moni- is tracked and that the pressure drop technique is
toring such microbiological influences can provide not specific to biofilm.
10.8 Techniques for MIC Monitoring

CPVC SAMPLE CYLINDER COVER

r GALV STEEL HANGER


/ I
314 SCH 80 C SAMPLE STUBS 11 " POLYPROPYLENE
FLANGE CONNECTION

SIDE VIEW

SAMPLE CYLINDERS
( 563'' ID)
1 1 ,-CPVC SAMPLECYLINDERCOVER

1 I,,
1625 OD
~LC P
SAMPLE TUBEV C

TUBE

SECTION "A - A SECTION "B - B"

SAMPLE STUB PLACEMENT SAMPLE CYLINDER PLACEMENT

FIGURE 10.1 (b)


Biofilm sampling tube with removable stub-type coupons. (From Don1at-1.~~)

FIGURE 10.2(a) FIGURE 10.2(b)


Biofilm sampler with removable stubs. (From Videla Close-up of biofilm sample holder. (From Videla et
et al.48) (Copyright ASTM. Reprinted with permission) (Copyright ASTM. Reprinted with permission)
Techniques for MIC Monitoring 10.9

providing an accelerated condition that is useful


to the system operator.
In a laboratory environment, Geesey used a
quartz microbalance to monitor the accumulation
of biofilm on polished surfaces.36 The technique
provides an extremely sensitive method for detect-
ing biofilms on surfaces and for tracking the growth
of those films. When used in conjunction with other
techniques, including removal and visual exami-
nation of the surfaces, the influence of the biofilm
on corrosion can be demonstrated. The technique
has not yet been demonstrated to be feasible for
operating systems, however.
Deposit accumulation monitors provide a use-
ful and rapid method for the detection of fouling;
however, used alone, they are not specific to the
accumulation of microbiological fouling that can or
will lead to MIC.

Electrochemical Methods
An electrochemical method for on-line moni-
toring of biofilm activity has been developed. This
device (Figure 10.5) was motivated by the need for
continuous monitoring of biofilm formation without
the need for excessive involvement of plant per-
sonnel. A series of stainless steel or titanium disks
FIGURE 10.3(a) are exposed to the plant environment. One set of
Photo of the tube and ring column sampler. (From von disks is polarized (relative to the other set) for a
Rege and Sand.”) short period of time each day. The electrodes are
connected through a shunt the remainder of the
time. Biofilm activity, which is also an electrochem-
Model heat exchangers also monitor total ac- ical process, is monitored by tracking changes
cumulation by continuously tracking deposition un- in the applied current (i.e., when the external po-
der carefully controlled flow and heat flux. Such tential is on) and the generated current (when the
methods (Figure 10.4) can be extremely sensi- potential is off). The onset of biofilm formation on
tive to deposit accumulation, as reflected by an the probe is indicated when either of these in-
increase in the heat transfer resistance across one dependent indicators deviates from the baseline
or more heat transfer tubes. In many applications, level (Figure 10.6). The level of biofilm activity is
the degradation of heat transfer capabilities is a also measured by the amount of variation from the
primary concern that will be monitored routinely. baseline. The applied and generated currents from
Additional information from those same monitor- a well-controlled system will be a flat line, devoid of
ing tools can provide useful information regarding any significant deviations. The design of the probe
biofilm accumulation and incipient corrosion due and results from plant exposures have been de-
to microorganisms. The presence of the heat flux scribed e l ~ e w h e r e . ~ ~ - ~ ~
can accelerate the deposition of microbes, as well Blackwood and c o - w ~ r k e r shave
~ ~ taken a
as other solids, both dissolved and suspended, slightly different electrochemical approach. They
10.10 Techniques for MIC Monitorina

sterile loop inoculated loop

ring column:

conventional sensors for


medium control

of miniaturized
sensors

valve and fining for serial


arrangement of the loops

FIGURE 10.3(b)
Scheme of a laboratory test apparatus for MIC monitoring. (From D ~ n l a and
n ~ from
~ Eul and he it^.^')

used several very small (0.12 cm2) silver elec- Coupons


trodes, plated onto platinum electrodes of the
same size, with the entire array on a ceramic sub- Traditio nal corros io n mo nito ring coupons are
strate. The silver was exposed as the metal, as most commonly referred to as “weight-loss”
AgCI, or as Ag2S. The silver and Ag2S electrode coupons since that is the measurement most
pair acts as a sulfide sensor while the silver and often associated and performed with these de-
AgCl electrode pair acts as a chloride sensor. The vices. Weight-loss coupons are fabricated from
production of sulfides or concentration of chlorides different alloys and in many different sizes and
by microbial action produces a nearly instanta- shapes to fit a variety of applications. The sur-
neous change in the potential of the electrode faces of such coupons are usually ground to
pair, providing an indication of specific microbial improve the reproducibility of weight-loss mea-
activity. surements. Coupons that are rough or have mill
scale on surfaces may only allow visual or macro-
scopic examinations (e.g., low magnification with
a stereoscope) for gross pitting. Often, only cor-
Corrosion Monitoring rosion rates are determined using weight-loss
coupons. Since MIC is most often a localized cor-
MIC is a form of localized corrosion. Standard rosion phenomenon, weight-loss measurements
and specialized corrosion monitors have been de- are typically poor indicators of even serious MIC
veloped that provide an alert that the system be- problems. The weight-loss coupon can still be
ing monitored (or an accelerated and disposable of significant value as a MIC monitor if surfaces
simulation of the system) is corroding, how it is are examined carefully for the presence of mi-
corroding, and at what rate. The corrosion monitor crobes and their viability, and by characterizing
may or may not provide information that MIC is the the numbers and depths of pits (which must be
operative form of corrosion. assumed to be due to bacterial attack, especially
Techniaues for MIC Monitoring 10.11

\ Series Connection /
Install piping in position shown

0 316'' 81 Union
@ * 316'' Steam Strainer
@ * 3i6" Impulse Steam Trap
@ 316'' x 6 BI Nipple
@ 112'' x 6 81 Nipple
@ V2" Tee Parallel Connection Shown
@ * Armored Thermometer and Well
@ 1g" x 114" BI Bushing
@ * Pressure Gauge
@ * 150 ccimim Rotameter with Valve
0 * Armored Thermometer and Well
@ * Pressure Snubber
0 * Insulation-minimum 1" Fiberglass
@ Condenser Tubes-3 Feet Long

*Steam Control Package

U.S. PATENT NO. 4,093,020

FIGURE 10.4
Model heat exchanger.

in the absence of other contributors, e.g., C02, treatments, or fabricating methods in controlling
H2S, 0 2 ) . corrosion. All of these physical coupon conditions
A variety of different coupon configurations can have some effect on surface microbiology and,
and designs are commercially available today, subsequently, on corrosion. When monitoring for
allowing the corrosion engineer to monitor corro- the presence or influence of microorganisms in
sive conditions, which may be unique to a system. corrosion, it is important to match the coupon or
For example, if crevice corrosion is a particular probe material to that of the system being moni-
concern in a pipeline because of the way field tored. Low carbon steels, for example, tend to gen-
joints were made, special coupons incorporating erate larger amounts of corrosion products than do
a similar crevice design may be used for monitor- stainless steels, which in turn impacts the biofilm
ing. Special coupons can be designed to evaluate that is formed. The surface condition of the coupon
galvanic corrosion between adjoining materials, is also an important consideration when moni-
mimic geometry and flow conditions, and evaluate toring for the effects of microbes on corrosion.
protective coatings. Coupons may also be used to The preparation and surface finish of the coupon
evaluate the effectiveness of different alloys, heat must be selected to facilitate analysis, yet permit
10.12 Techniques for MIC Monitoring

When attempting to utilize any coupon design


to monitor for MIC, the nature of microbial involve-
ment in the corrosion mechanism should not be
assumed. Microbes may facilitate corrosion initia-
tion, contribute to deposit formation, act as cata-
lysts to predominantly electrochemical corrosion,
form concentration cells, fix anodic sites, and/or
any combination of these functions. Most likely,
one “standard” exposure duration will not suffice
to reveal the true effects of microbial involvement
unless some level of experience with the system
being monitored has been acquired. Thus, when
evaluating any system for microbial contribution
to corrosion, a number of coupon exposure times
should be employed, if at all possible. As with any
type of coupon monitoring program, placement
of the coupons in a system environment repre-
sentative of where corrosion has occurred is of
the greatest importance. Prior evaluation of en-
vironmental and material conditions in locations
where corrosion is known to occur is valuable
in designing a monitoring program using special
FIGURE 10.5
Electrochemical biofilm activity probe. (From L i ~ i n a . ~ ~ )
coupons.

Galvanic Probes
attachment and colonization of bacteria. Placing
coupons in inhibitor-treated storage bags is one A number of investigators have utilized
way that the coupon surface chemistry can be pre- galvanic probes to evaluate corrosion in oil-
vented from being inadvertently affected and alter- field waters, in cooling waters, and in other
ing the representative attachment of organisms. e n v i r o n m e n t ~ . ~A~typical
~ ~ * galvanic probe (Fig-
ure 10.7) will electrically connect the material of
interest (e.g., carbon steel) to a more noble metal
Essential Equipment Cooling Water System (e.g., brass) in order to initiate corrosion on the
40
material of interest and to perpetuate conditions
30 that are conducive to continuing corrosion (e.g.,
the formation of biofilms comprised of microbes
f 20
that are attracted to anodic sites). The result is ac-
=2
U”
10 celerated corrosion of the active member in the
5
0 0

-10

-20
10/20/93 12119/93 02117/94 04118/94 06117/94 08/16/94

FIGURE 10.6
Typical data from electrochemical biofilm activity probe. FIGURE 10.7
(From Licina and N e k ~ k s a . ~ ~ ) Galvanic probe. (From Smart and P i ~ k t h a l l . ~ ~ )
Techniaues for MIC Monitorina 10,13

pair. Comparison of the performance of the gal- down on the element is electrically conductive,
vanic probe in the environment being monitored causing an apparent increase in the cross section
(where the effects of microbial action on the corro- of the exposed element. This results in a lower
sion are unknown) to the performance in a similar corrosion rate measurement, zero apparent corro-
environment, which does not have a microbiolog- sion, or even a negative reading (as an apparent
ical influence, provides insight into the probability increase in metal rather than a decrease through
that MIC is a significant contributor, rates of att- corrosive attack). Localized corrosion can produce
ack, etc. a very dramatic decrease in the cross section at
Galvanic probes are simple devices with no the point of the local attack and a measured resis-
moving parts. The polarization of the carbon steel tance that is artificially high.
from the galvanic coupling produces conditions Attempting to correlate corrosion rate mea-
that are conducive to biofilm formation on the metal surements with MIC (sessile or planktonic organ-
surfaces. It should be noted that the polarization isms) instead of determining whether actual met-
potential is not adjustable for a single probe. How- allurgical evidence of microbial attack exists could
ever, the use of a different noble member, or a potentially mislead the corrosion engineer to an
series of different probes with a variety of different incorrect diagnosis and subsequent mitigative ac-
metals, can provide a broad spectrum of corrosion tion that is unnecessary. Unless the probe is phys-
conditions. ically removed from service and the attached de-
posits are analyzed for chemical composition, or
Electrical Resistance Probes morphological characteristics of corrosion on the
probe surface are identified, correct diagnosis of
Electrical resistance (ER) probes determine the corrosion mechanism(s) will be unlikely.
metal loss by measuring the increase in resistance Even when the measured changes in electri-
of a metal specimen as its cross-sectional area cal resistance are due to corrosion, the indication
is reduced by corrosion. These probes are some- provided by the ER probe would not be specific to
times referred to as “electric coupons.” The probe MIC. Further, ER probes are typically poor for the
should be made of an alloy similar to the metal in detection of localized corrosion. It should be noted
the system and inserted into the system through that the use of specially configured resistance ele-
an access fitting. A baseline instrument reading is ments can provide a “fuse” that is very sensitive to
made after the probe is installed and a suitable localized corrosion, including MIC; however, that
time has elapsed for the probe to come to equilib- sensitivity comes at the expense of sensor life.
rium with the environment (i.e., temperature, sur-
face conditioning). At prescribed time intervals, the
instrument measures the resistance. A simple al- Linear Polarization Resistance
gorithm supplied by the manufacturer is used to
correlate the change in resistance to metal loss. Probes
Evaluating the change in resistance and metal loss
over time produces a time-wise history of metal Linear polarization resistance (LPR) probes
loss. The corrosion rate in mils per year (mpy) is measure instantaneous corrosion rates and qual-
determined as the average metal loss between any itatively measure the pitting tendency of metals
two points in time. in electrolytes. The technique involves measuring
Interpretations of the data obtained with the the current required to change the electrical poten-
electrical resistance probe are subject to the tial of a specimen corroding in a conductive fluid.
same general limitations for traditional weight-loss Both two-electrode and three-electrode linear po-
coupons. For example, deposits on the probe sur- larization probes are available for corrosion rate
face can shield the element from the corrosive en- measurements. The electrodes should be made
vironment. In some cases, iron sulfide scale laid of an alloy similar to the metal in the system. Use
10.14 Techniques for MIC Monitoring

of the linear polarization resistance technique for Electrochemic a1 lmpedance


corrosion rate measurements is limited to electri- Spectroscopy
cally conductive solutions since current must flow
from one electrode to another through the solution. Electrochemical impedance spectroscopy
Corrosion rates are determined by measuring the (EIS) is an alternating current (AC) technique
applied current required to polarize the electrodes that uses small-amplitude polarization of a test
to a small potential difference (20 mV). Users of electrode to characterize the impedance and ca-
these instruments should seek advice from the pacitance of the operative corrosion process(es).
manufacturer pertaining to instrument function in Direct current (DC) techniques such as linear
a specific system. polarization resistance rely upon determinations
As with using coupons, when attempting to of the current between sensor electrodes. That
use any probe configuration to monitor for MIC, current is affected by the total resistance between
the nature of microbial involvement in the corro- the electrodes, where the total resistance consists
sion mechanism should not be assumed. Specially of the polarization resistance (the parameter that
configured LPR probes can provide useful infor- is actually an indicator of the corrosion kinetics)
mation relative to localized corrosion mechanisms, and the solution resistance. As the solution
including MIC; however, the indicated corrosion resistance increases, the error in the apparent
is not specific to MIC. Such probes will typically polarization resistance increases. Further, as
use oversized electrodes and may incorporate nonconductive or poorly conductive films form on
crevices to facilitate microbiological growth. The surfaces, the capacitance of the film will change,
use of different levels of polarization may also en- possibly very dramatically, and the “error” in the
courage and accelerate microbiological settlement measured signal will increase. EIS examines
on the probe electrodes. both the resistive and capacitive nature of the
Whenever evaluating any system for micro- response to the small-amplitude AC polarization
bial contribution to corrosion, several monitoring by examining that response of potential and
parameters should be employed and correlated current and the phase angle between the two
to provide corroborative evidence. Many times over a range of frequencies. From an analysis of
the employment of only a single device will raise the outputs, the specifics of the overall process
more questions than the corrosion engineer can can be revealed. Silverman’s “Primer on the AC
answer. Impedance Technique”43 describes the methods
As with any monitoring program, placement involved in making the measurements and in data
of the LPR probes in a system’s environment is analysis.
of paramount importance. Typically, locations that Most often, an “equivalent circuit” for the pro-
are representative of where corrosion has oc- cess, consisting of resistors, capacitors, and in-
curred in the past or where it is predicted to be ductors, is developed as a predictive tool for the
most likely to occur in the future are the most rea- nature of the expected impedance. Many research
sonable starting points. However, when selecting activities have used EIS to characterize the in-
these monitoring sites, it must be reinforced that fluence of microbial films on c o r r o ~ i o n Most
.~~~
LPR probes require immersion in a conductive so- often, the primary parameter that was measured
lution (electrolyte) to function accurately and they was the polarization resistance. In some of those
are subject to fouling by hydrocarbons. Therefore, studies, the nature of the microbiological influence,
prior evaluations of the environment and mate- produced by changes in the diffusion characteris-
rial conditions in locations where corrosion has tics, or the charge transfer through the biofilm was
been known to occur are probably among the most characterized. For example, the steeper slope and
valuable commodities when designing an inter- greater frequency dependence of the impedance
nal corrosion monitoring program and deciding on for copper in an inoculated environment shown
monitoring technologies to use, especially when in Figure 10.8 is indicative of a greater influ-
MIC is a concern. ence of the electrochemical properties of the films
Techniques for MIC Monitoring 10.15

2 I I I I I I -50 I I I I I I

(versus a greater relative contribution from diffu- potential raw data are collected every few sec-
sion through the film in the sterile control). onds, over long periods, and analyzed using a per-
EIS work on MIC has been done in both labo- sonal computer. Analyzing the resulting transients
ratory and field The equipment, using a variety of statistical approaches can pro-
including hardware, computers, and data analy- vide insight into the controlling mechanisms of the
sis software, is expensive and the interpretation of corrosion.
the data requires considerable expertise. Still, the A major advantage of electrochemical noise
technique can be used in the field, particularly in techniques is that the testing itself is nonintrusive.
dedicated side streams. That is, no potentials are applied to force corrosion

TYPICAL EN EQUIPMENT
Electrochemical Noise
Electrochemical noise (ECN) methods monitor
and characterize small-amplitude, low-frequency,

z?-E3
and random fluctuations of the current and po-
tential of corroding electrodes that are observed
in typical corrosion processes. Most simplistically, @YOLTMETER
the current and potential fluctuations mark specific
anodic or cathodic events.
Most often, three electrodes are used as
shown in Figure 10.9. Current fluctuations be-
tween nominally identical electrodes are moni- COUNTER WORKING REFERENCE
ELECTRODE ELECTRODE ELECTRODE
tored using a zero resistance ammeter (ZRA)
while potential noise is measured between a test FIGURE 10.9
electrode and a reference electrode. Current and Typical electrochemical noise setup.
10.16 Techniques for MIC Monitoring

The dramatic increases in the mean value of


the potential and the current immediately upon
opening the valve, and the increase in both the
potential and current noise about 100 seconds
after opening the valve, provided a very dramatic
indication of the effects of the introduction of
oxygen to the system following the extended
period of stagnation. The current values from a
sterile test leg exposed to the same flow history
exhibited essentially no change when the inlet
valve was opened. The potentials in that leg did
change; however, the potential noise did not.
Although electrochemical noise methods do
l I I 111 P I ' I I
I require that an enormous amount of data be col-
lected and processed, those tasks are readily han-
dled by modern personal computers. A number of
commercial software packages are available for
real time or nearly real time analysis of the data.
The application of ECN techniques to MIC and var-
ious other corrosion processes is increasing.
ECN Data for the Sample Exposed
to Untreated Stagnant Water - Summary
Arrow Indicates when Oxygenated .
Water was Allowed to Enter the System

FIGURE 10.10 A variety of techniques are available to


Electrochemical noise results. (From Brennenstuhl and monitor MIC. The techniques include methods for
Gendr~n.~ (Copyright
~) ASTM. Reprinted with permis- monitoring numbers or types of either planktonic or
sion) sessile microorganisms, for tracking biofilm accu-
mulation (e.g., pressure drop, degradation in heat
to occur. Initiation and propagation of the corrosion transfer resistance), and for ascertaining the in-
on the test electrodes will produce natural fluctu- fluence of biofilms on surface properties (on-line
ations in the current and potential. Different forms electrochemical methods). Techniques to modify
of corrosion will have very different noise charac- and refine standard corrosion monitoring methods
teristics. Interpretation software is trainable (see, such as coupons, linear polarization resistance,
for example, Reference 47). electrochemical impedance spectroscopy, or elec-
ECN was used to monitor microbiological trochemical noise are also in use. Unfortunately,
influences on Type 304L stainless steel exposed the techniques that may be chosen to best mon-
to untreated Lake Erie water in a side-stream test itor for MIC and other corrosion are often limited
stand at a power plant. Selected electrode sets by economics, available monitoring equipment and
were exposed to slowly flowing lake water, periods analytical devices, operator expertise, system de-
of stagnation, and oxidizing biocide treatments. sign, or any other number of parameters.
The most interesting exposure involved exposing
the ECN probes to stagnant lake water conditions
for 30 days and then opening the inlet valve only Acknowledgments
(Figure 10.10). As shown, during the stagnation
period, both the potential and current noise The authors would like to thank Bruce A. Cook-
were very small, as would be expected for a ingham and Richard B. Eckert of ANR Pipeline
stainless steel exposed to deaerated conditions. Company for their contributions to this chapter.
Techniques for MIC Monitoring 10.17

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Techniques for MIC Monitoring 10.19

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CHAPTER 1 1

MIC Case Histories


Compiled b y Hector A. Videla

Microorganisms are ubiquitous, and microbiologically influenced corrosion (MIC) can be encountered
in a diversity of natural and industrial environments. MIC failures of technical equipment often occur
under more varied operational conditions than those of inorganic or abiotic corrosion. Practical cases
can help illustrate a number of situations where failure by corrosion or fouling are always due to the
interaction between microorganisms and the structural materials. In each case, the applied solution must
be tailored to particular requirements, taking into account the influencing elements. These elements
include microorganisms, materials, physicochemical characteristics of the environment, fluid dynamics,
the type of protection applied to the system, and others.
The case histories presented in this chapter were selected to cover different situations frequently
encountered in practice.

Carbon Steel (CS)


CS-3: Marine Microbial Corrosion
CS-4: The Detection and Mitigation of MIC
Note: CS-1 and CS-2 located in Volume 1
Mixed Metals (MM)
MM-3: Microbiologically Influenced Corrosion in Geothermal Fields in Mexico
Note: MM- 1 and MM-2 located in Volume 1
Stone (S)
S-1 : Microbial Corrosion of Cultural Heritage Stone Works
Stainless Steels (SS)
SS-13: Localized Corrosion of Stainless Steel Milk Sterilizers
Note: SS- 1 through SS- 12 located in Volume 1

The MIC of carbon steel in marine environments CS-3 is described in case histories involving European
harbor pilings’ internal surfaces of ships’ ballast tanks, and ships’ hull bottom plates. Although it can not
be strictly classified as a carbon steel case, the fourth case history in marine environments describes
the tin-oxide corrosion of the white-metal bearing surfaces used in the main propulsion engines of five
different vessels.
The practical aspects of detection and mitigation of the MIC of carbon steel CS-4 are illustrated by
case histories from South African industrial plants: the mechanical removal of tubercles from a pipeline
used for water transports the use of an organic wetting agent and an anionic iron-dispersing copolymer in
a fire-water system to mitigate MIC, and the use of biocides and biodispersants to control MIC in a power
station.
The MIC of carbon steel and stainless steel is described jointly with the microbial biodeterioration of
other materials such as the reinforced fiberglass and wood MM-3 that are used in the cooling towers of
geothermal power plants in Mexico.
11.1
11.2 MIC Case Histories

The two last case histories of this chapter refer to a case of localized corrosion of stainless steel and
to the biodeterioration of stone works.
The stone case history S-1 describes the biodeterioration or the discoloration of stone work by the
action of the microorganisms. It must be emphasized here that when a material (e.g., stone) has a cultural
value, a staining process or the formation of patina could affect the esthetic value of the material even in
the absence of a noticeable material decay.
The stainless steel case (SS-13) describes the localized corrosion of (UHT) milk sterilizers. In this
peculiar case history, microorganisms are not involved in the metal attack. The corrosion is due to the
combined action of biological substances from the milk (e.g., caseinates), chemical cleaning agents and
high levels of chlorides in the water. The term “biodeterioration” should be used in replacement of MIC for
stone and non-metallic materials. Conversely, MIC would be used to denote the electrochemical process
of metal dissolution initiated or accelerated by microorganisms.
Some case histories have a complete description of symptoms, analytical findings, possible mech-
anisms, and corrective measures. Others are a brief description from original cases, and include only
significant details. However, in all cases the relevant role of the microorganisms or biological factors is
highlighted.
CASE HISTORY CS-3

Marine Microbial Corrosion


By 1. B. Beech, S.A. Campbell, and F.C. Walsh

Introduction have received insufficient attention in the literature,


despite their importance. Several cases related
to each type of failure have been experienced, in
Marine conditions represent an aggressive
several ports and on various ships over the past
and unforgiving environment for the degradation
decade.
of metals used in harbor constructions and on
board vessels. The corrosion of marine engineer-
ing components and structures can arise as the
result of shortcomings in materials selection, de-
Case #1: Low Water Corrosion of
sign, or fabrication, poor choice of the protec- Constructional Steel Piling
tion technique, or inadequate maintenance and
housekeeping.’ In comparison to land-based sys- Background
tems, the failure of shipping components via cor-
rosion presents additional problems owing to the Severe corrosion and perforation of steel piling
possibility of failure at sea, restricted access for at the low water level has been reported in several
inspection of corrosion failures, and, for remedial European ports and harbors (Figures 11.1 and
work, the inconveniences and costs involved in lost 11.2). Steel sheet piles are usually produced from
sailing time or decreased speeds and the need to grade 43A and 50A carbon steel (e.g., BS 4360).
berth or dry dock the vessel when severe problems The maximum length of the pile can be rolled
exist. up to 30 m, and its thickness is typically within
Many cases of marine microbial corrosion the range 10-28 mm. Steel piles are used in
have been discovered at an advanced stage, when many types of temporary works and permanent
mechanical damage or process inefficiencies have structures such as retaining walls, river frontages,
forced hasty remedial action or it was not rea- quays, dock harbor works, or land reclamation
lized that microbial corrosion processes were and sea defense works.
causing the initiation, or propagation of attack. In The corrosion profile of steel pilings in tidal
some cases, the accelerated rate of attack on the waters has five different characteristic zones: at-
metal or its localized nature has been correctly at- mospheric, splash, tidal, permanent immersion,
tributed to a particular corrosion mechanism but and subsoil.* Corrosion mechanisms operating in
the underlying cause is not understood. Emphasis these zones are generally well understood3 and,
is often placed on rapid removal and replacement for UK harbours, the average corrosion rate of
of damaged components or structures, because each zone has been predicted4 (Figure 11.3).
of short-term commercial or strategic pressures. Recently, a large number of piling walls in
In extreme cases, the lack of diagnosis may lead quays, jetties, river embankments, and piers have
to repetitive or more serious failures. needed repair or even replacement after as lit-
Four case studies have been selected for this tle as 20 years; their effective life, according to
review. These are based on types of corrosion that estimates of normal corrosion rates in seawater
11.4 Marine Microbial Corrosion

FIGURE 11.1
General view of steel piling, showing zones affected by
low water corrosion. (See color plates.)

environments, should be greater than 50 years. In ~0.03


some cases, the rate of corrosion reached 0.5 mm Bedzone
per year, resulting in perforation of sheets of steel 9
Corrosion
welded over existing holes within six months of the
profile
installation of such repair panels.
To determine the cause of steel failure, in- FIGURE 11.3
strumentation has been installed at a UK port to Typical corrosion profile of steel piling in tidal seawater,
continuously monitor electrical potentials and gal- showing the general rates of penetration observed.
vanic current flow between steel panels mounted
at various levels on sheet piling walls (Figure 11.4).
macro-anodic and macro-cathodic regions were
This monitoring program, carried out over a pe-
initially formed, these did not persist for much
riod of one year, clearly showed that although
longer than 100-1 50 days and that after that time
there can be no viable electrochemical explana-
tion for the very severe corrosion experienced
at the low water level. Attention was then turned to
the involvement of a biological component in the
deterioration of steel pilings.

Findings
The present study was carried out in the
United Kingdom to elucidate the contribution
of biofilms to low water (tidal zone) corrosion
of steel pilings in Portsmouth Harbour. Samples of
biofilms recovered from the surface of corroding
and noncorroding areas of pilings were collected
FIGURE 11.2 and analysed microbiologically to determine the
A close-up of a particular section of steel piling, show- types and numbers of organisms present using
ing severe perforation at the low water level. (See color API identification kits and MPN counts. Char-
plates.) acterization of corrosion products accumulated
Marine Microbial Corrosion

ing parts of the piling (1 O4 or 1 O5 SRB cells cm-2)


exceeded the number of SRB detected in biofilms
removed from the noncorroding sites, by one to
two orders of magnitude.
Biofilms recovered from sites that did not ex-
hibit corrosion showed the prevalence of either
Pseudornonas or Vibrio species (typically contri-
buting to between 70% and 90% of the total spe-
cies detected) and only up to 10% SRB, whereas
biofilms collected from corroding areas contained
Low water zone a mixture of all bacterial genera with SRB being a
dominating species (up to 60%) and high levels of
either Pseudornonas or Vibrio (up to 40%).
Phase analysis of surface products by XRD
revealed differences between samples from
corroding and noncorroding sites. The former
lol Bed zone consisted largely of iron sulphides whereas the
latter showed the presence of oxyhydroxides
FIGURE 11.4 and magnetites. EDXA analysis confirmed the
Arrangement of steel test panels (approximately accumulation of relatively high levels of sulphur in
30 cm x 30 cm) in various tidal zones during a test pro-
samples taken from the corroding areas of piling.
gram of galvanic current monitoring using the zero resis-
tance ammeter technique. Samples were placed on the
These findings were in good agreement with
“outpan” (0)or “inpan” (I) regions of the piling. microbiological data, which showed a high level
of SRB (up to lo6 cells cm-2) associated with the
corroding sites.
in biofilms was carried out by energy dispersive Linear polarization resistance measurements
X-ray analysis (EDXA) and by X-ray diffraction of averaged corrosion rates revealed that the most
(XRD). Electrochemical measurements using lin- rapid failure of steel would occur in the presence
ear polarization resistance (LPR) were performed of a mixed population of SRB and Vibrio species
under laboratory conditions to determine the (1 :1 ratio). In this culture a corrosion rate of 1.4mm
corrosion rates of steel in the presence of pure per year was recorded. Rates of 0.38 mm per
and mixed microbial isolates. year and 0.30 mm per year, respectively, were ob-
The outcome of the microbiological studies re- served for steel exposed to a mixed population of
vealed that the biofilms contained diverse genera Pseudornonas and SRB (1:l ratio) and to SRB
of aerobic, facultatively anaerobic, and anaero- species. These corrosion rates were significantly
bic bacteria such as Pseudornonas, Vibrio, and higher than the rate of 0.019 mm per year mea-
sulphate-reducing bacteria (SRB), all of which sured in sterile seawater.
are known to have a role in marine corrosion of
Summary
The composition of microbial consortia var-
ied depending on the region from which sam- The overall results of this investigation, based
ples were taken. In general, higher levels of all on microbiological, electrochemical, and mate-
types of bacteria were detected in biofilms re- rial analysis, indicate that biofilms formed in tidal
covered from corroding areas of the piling, typ- zones on the surface of steel piling were likely
ically 3 x 10’ cells cm-2, compared to biofilms to contribute to the localized corrosion of the
removed from the noncorroding sites, typically structure and that the composition of microbial
3 x lo4 cells cm-* (lo2 SRB cells). The number consortia could be a key factor in determin-
of SRB present in biofilms associated with corrod- ing whether and to what extent the biocorrosion
11.6 Marine Microbial Corrosion

influences the performance of the piling material.


A more detailed treatment of microbial corrosion
of steel pilings at the low water level is provided
e l ~ e w h e r e Further
.~ studies are being carried out
on the effectiveness of (a) cathodic protection,
(b) protecting organic coatings, (c) mechanical re-
moval of the biofilm by high-pressure water jets,
and (d) replacing the existing material by low alloy
steels, to determine the most effective method, or
combination of methods, in controlling marine bio-
corrosion of steel pilings.

Case ## 2: Pitting and Perforation of


the Internal Surfaces of Ship’s
Ballast Tanks

Background
During pressure testing of a ballast tank near
the bottom of a ship, pitting and some perforation
was discovered. The damage to the 12-mm steel
hull plate was located under mud slimes in the tank
bottoms (Figure 11.5). Consultation of the vessel’s
records indicated that the corrosion probably oc-
curred within a nine-month period and that the ves-
sel had undergone constructional work to increase FIGURE 11.5
its size and load-carrying capacity. During this con- View of the underside of a ship’s hull bottom plate in a
structional work, the ship was floated in a harbor dry dock, with a corroded section removed for analysis
that was later found to have high levels of sulphate- and repair. (See color plates.)
reducing bacteria (up to 1O6 cells ~ m - ~This
) . type
of problem has been experienced by the authors a sister vessel) revealed high levels of sulphide
on seven other vessels (unpublished results). in the sludge (up to 3600 ppm) together with
significant levels of both anaerobic (103-l O5 ~ m - ~ )
Findings and aerobic (103-106 ~ m - bacteria.
~ ) In partic-
ular, active sulphate-reducing bacteria up to a
A thorough manual inspection of the tank level of 1O5 cells ~ m were- ~found via microscopic
was carried out in dry dock and sections of hull and standard microbial culture techniques. A dam-
plate were removed from the vessel for anal- aged section of hull plate is shown in Figure 11.8,
ysis (Figures 11.6 and 11.7). Sludge, mud which gives an indication of the severity of the
(Figure 11.6), and corrosion products from the pitting attack and the attendant reduction in the
pitted regions (Figure 11.7) were brought to thickness of the hull plate. EDXA analysis of a
the laboratory for rapid analysis. Damaged sec- damaged section of the steel plate showed an
tions were cut out and samples were retained for increasing sulphur content near pit bottoms
metallographic and Scanning Electron Micro- Figure 11.9a. XRD and chemical analysis demon-
scopy (SEM)/EDXA analysis. Chemical and mi- strated the presence of iron sulphides in these
crobial analysis of samples from this ship (and regions, and high levels of magnetite were also
Marine Microbial Corrosion

FIGURE 11.7
General view of the inside surface of a section of hull
plate, showing extensive pitting corrosion and crater
formation. (See color plates.)

the result of classical corrosion mechanisms.10


The analytical results revealed the presence of
high levels of SRB in mud samples and signifi-
cant sulphide ion and iron sulphide formation in
pitted regions. Damage was largely attributable
to microbially influenced corrosion, primarily due
to the presence of SRB action. The mud slimes
and sludge act as a supportive matrix for micro-
FIGURE 11.6 bial growth. The formation of localized corrosion
Photograph of the inside surface of a ship’s bottom plate
removed from the vessel, showing pitting of the steel re-
vealed by clearing away the mud film. (See color plates.)

found. Figure 11.9b provides a schematic to indi-


cate the corrosion cells that can form inside the
pits.
It was discovered that the harbor berth used
for constructional work on the vessel was located
a short distance away from the discharge from
a fish processing plant, which could provide a
high level of nutrient-rich material during ballasting
operations.

Summary FIGURE 11.8


Cross section of the hull plate, showing the reduction in
The rapidity, severity, and localized nature Of normal thickness (1 2 mm) due to microbial attack result-
this attack exceeded those expected to occur as ing in severe pitting. (See color plates.)
11.8 Marine Microbial Corrosion

8
0,5K

d
c1

0 i N W Ln W P co a 0
rl

FIGURE 11.9a
Energy dispersive X-ray analysis spectrum taken in the bottom of a pit on the surface of a steel ballast tank plate suffering
microbial corrosion under mud slimes.

cells, mainly the result of differential aeration cells, Case # 3: Tin-Oxide Corrosion of
and the existence of magnetite as an efficient ca-
thodic site for oxygen reduction were likely to have
White Metal Bearing Surfaces
contributed to the corrosion rate.
Background
Remedial Work Over the past ten years, the authors have in-
vestigated the failure of thirteen white metal faced
Damaged areas of the vessel were replated. bearings from various parts of main propulsion
A careful survey of the affected tank (and others) engines on five vessels. The majority of these
was carried out. The ballast tanks were thoroughly have been journal bearings from both diesel and
cleaned to remove mud and sludge and then re- steam turbine engines, although thrust pad sur-
coated with a nonsetting organic coating where faces have also been involved. In all cases, the
necessary. The sister vessels were also inspected. bearing failures resulted in the need for partial
Early stages of pitting corrosion were detected stripping and rebuilding of the ship’s engine. Typ-
in localized regions but cleaning, followed by in- ical examples of bearing compositions are pro-
filling and the application of protective organic vided in Table 11.1. While most of the bearing
coatings and biocide, precluded the need for re- surfaces were tin-based, several examples of lead-
plating. Where feasible, ballasting with fresh water based materials have been encountered. All of the
was recommended. bearing surfaces showed severe pitting together
low O2 concentration

I iron k d p h i d e and oxides


arising fran action of
sulphides (anodic site)
pit b o t t c h n remains
active leading t o perforation

FIGURE 11.9b
Corrosion cells that can arise under mud films and in the presence of biofilms.

with scoring wiping and other types of mechanical viscosity index, flash point, and total base num-
damage in many cases. Examples of a journal and ber) showed the oils to be suitable for further ser-
a camshaft bearing are shown in Figures 11.10 vice. However, many of the oil samples showed
and 11.12 while Figures 11.11 and 11.13 show significantly reduced demulsification properties in
more detailed photographs of pit formation on the comparison to fresh oil. Bearings A and B were 10-
surface of these bearings. cated near a water header tank, and water leakage
was observed onto the camshaft area of the en-
Findings gine. Analysis of the water showed a pH of 7.7 and
a low conductivity (250 mS cm-I) together with a
In each case analysis was made on a wide very low chloride ion level (t25ppm).
range of samples, including the lubricating oil, The surface of these bearings showed exten-
sludge from the oil purification system and water sive pitting and mechanical damage as indicated
phases, and the bearing surfaces. In all cases, in Figures 11.11 and 11.13. In addition, large sec-
analysis of the bulk lubricating oil by plasma tions of white metal had been removed. In some
emission spectroscopy (for dissolved wear metals) areas, the steel shell was exposed. Metallographic
and standard ASTMAP tests (e.g., for viscosity, and SEM observations revealed a wide range of
11.10 Marine Microbial Corrosion

~~ ~ ~ __.__ ___
TABLE 11.1
Composition of White Metal Bearing Alloys (Determined by Atomic Absorption Spectroscopy)

Percentage by Weight of Metal


Bearing Sample Tin Antimony Copper Lead Sum
Bearing A 80.3 7.7 7.5 4.6 100.1
(main camshaft)
(o.d.(A)-l1 cm)
Bearing B 15.2 7.5 0.8 75.8 99.3
(main camshaft)
(0.d. -8 cm)
Bearing C 87.0 6.8 3.6 0.9 99.3
(main engine journal)
(0.d. -20 cm)
Bearing D 88.0 7.0 3.5 0.7 99.2
(thrust pad assembly)
(Area -10 cm2)

(A)Nominaloutside diameter

sharp-sided pits, several millimeters in diameter peared to be regular and well defined. Etching and
and with depths from 1 to 60 mm (the former be- metallographic analysis revealed well-dispersed
ing the nominal lining thickness). The interface SbSn cuboids and Cu6Sn5 strands within a
between the white metal and the steel shell ap- tin-based matrix. No selective corrosion or degra-
dation of the intermetallic phases was ob-
served. A detailed SEM survey showed the pres-
ence of many pits containing intact corrosion
products. EDXA studies showed the presence of

FIGURE 11.10 FIGURE 11.11


A journal bearing, showing pitting and scoring due to Close-up of the surface of a white metal bearing, show-
the formation of hard tin oxide particles (which appear ing the formation of pits containing dark particles of tin
as darkened areas on the surface). (See color plates.) oxides. (See color plates.)
Marine Microbial Corrosion

smallest pits was confirmed by electron diffraction


(ED) measurements on fragments.
Strategic sampling of the lubricating oil system
in areas such as tank bottoms, U-tube sec-
tions, filters, and purifier bowls showed the pres-
ence of sludges and seawater-contaminated water
phases, both of these having high levels of anaer-
obic and aerobic bacteria. Both XRD and ED re-
vealed significant levels of SnO and Sn02 within
the corrosion pits.

Summary
FIGURE 11.12
A camshaft bearing, showing pitting and mechanical
The results are consistent with failure due
damage to the white metal lining. (See color plates.) to the localized formation of tin oxides via elec-
trochemical c o r r o ~ i o n . ~This
~ - ~type
~ of degra-
dation requires a conductive electrolyte phase
and a suitable cathodic reactant. In the case of
high sulphur levels in the bottom of many of the
bearings C and D, seawater contamination and
pits. In several cases, fracture cracks were seen
emulsification (assisted by the microbial presence)
emanating radially from pit recesses, as shown in provided an efficient electrolyte. Localized pock-
Figure 11.10. Several of the larger pits were
ets of water (arising from leakage into the en-
scraped and the wear products were analysed by gine) became emulsified and conductive via ther-
XRD. The results showed the presence of SnO and
mal breakdown of the oil during service. In all
Sn02 in addition to the usual phases of the lin- cases, the most obvious cathodic reactant is dis-
ing material (b-Sn, SbSn, and Cu~Sns).The pres-
solved oxygen, although the reduction of iron ox-
ence of significant amounts of tin oxides in the
ides embedded into the surface may also have
played a part. The formation of hard particles of
Sn02 results in scratching and scoring as the
bearing surface loses its essential conformabil-
ity and embedability properties. Localized stress
concentration at pit bottoms may lead to stress
cracking.

Remedial Work
For all the ships involved, steps were taken
to prevent water ingress into the lubricating oil
by leakage or condensation. Following thorough
cleaning, the bearings were relined and carefully
refitted. In the case of vessels showing signif-
icant water phases, sludge formation, and the
FIGURE 11.1 3 presence of microorganisms in the oil system,
A scanning electron micrograph of the surface of a pitted cleaning was followed by biocide treatment, im-
region on the bearing shown in Figure 11.1 2, showing proved purification procedures, and oil monitoring
fatigue cracks around the pit recesses. programs.
11.12 Marine Microbial Corrosion

Case # 4: Extensive Pitting of the


External Surface of a Ship’s Hull
Bottom Plate

Background
The immersed part of a ship’s hull on a float-
ing oil storage tanker, anchored in tropical waters,
was examined by divers and was found to be heav-
ily fouled to a thickness of up to 60 cm. The ves-
sel showed some leakage of its oil cargo and was
taken into dry dock for inspection. The hull was
cleaned and subjected to an extensive visual ob-
servation. The bottom was found to be severely FIGURE 11.15
corroded with tens of thousands of pits, each A welded region of the ship’s hull plate, showing a row
pit being approximately hemispherical in shape, of pits along the weld seam. (See color plates.)
20-25 mm deep, and filled with black material. Re-
moval of outer corrosion products and macrofoul-
ing exposed an underlying shiny metallic surface. external hull plate. Oil leakage into the sea sig-
Figure 11.14 shows a section of the hull plate when nified damage and a diver was sent down to in-
the ship was inspected in dry dock after removal spect the hull. Videos showed a comparable pat-
of all marine growth and corrosion. Figure 11-15 tern of damage to that on the first tanker but no
shows the distribution of pits along a welded seam large-scale perforations were detected. The ship’s
hull was covered with barnacles and other types
and Figure 11.16 provides an example of a perfo-
rated section of hull plate. of macrofouling such as seaweed. After clean-
A second (400,000 tonne) oil storage tanker ing, some pitting of the hull was found. A diver
was also found to show pitting corrosion of the found a macrofouled area containing 10-20 oys-
ters. Removal of these revealed some damage to

FIGURE 11.1 4 FIGURE 11.16


General view of ship’s hull, showing the extensive distri- A Perforated zone of ship’s hull Plate, showing leakage of
bution of pits over the surface. (See color plates.) seawater from the interior of the vessel. (See color plates.)
Marine Microbial Corrosion

the underlying steel but no perforations. When dis- 0.5 mm y-l in batch cultures. Additional studies
lodged, some of the oysters took the paint coat- showed a very high activity of the hydrogenase
ing with them. Holes were typically found to be enzyme, which has been implicated in microbial
18-20 mm in depth in the 25-30 mm hull plate. The corrosion of steel by SRB.15
damaged zone was filled with black (magnetite-
containing) deposits and the underlying metal was Remedial Action
very dark in appearance, with some areas being
covered by corrosion products. The following re- Extensive cleaning and replating of the hull
sults refer to the second vessel. plate was necessary. Regular inspection and me-
chanical cleaning of the macrofouled hull plate
Findings to remove biofilms, followed by coating with an
appropriate antifouling paint, was recommended.
A sample from a pit, containing water and Cathodic protection was used in the case of the
sludge, was allowed to settle and these samples second vessel, but excessive anode wear oc-
were analyzed for the presence of sulphates and curred and no beneficial effects on the corrosion
sulphides. The water was found to contain traces of rate were noted.
hydrogen sulphide and 2.28 g/dm3 sulphate (c.f.,
2.26 g dm-3 for seawater). The sludge contained
0.25% SO:- and 0.92% S2-. The water was in- Closure
fected with extremely high levels (on the order
of 1O8 cells ~ m - of ~ sulphate-reducing
) bacteria. During the investigation of microbial corro-
Aerobic bacteria were also present at a concen- sion problems, on-site observation and sampling
tration of 1o3 cells ~ m - ~ . should be followed by a wide range of chemical and
surface analysis whenever feasible. The materials
Summary analysed may include water phases, oils, sludges,
emulsions, and scale in addition to corrosion prod-
Both vessels provide examples in which a very ucts. The application of SEM, EDXA, XRD, and
aggressive local environment, caused by macro- ED techniques to localized corrosion products is
fouling, resulted in extensive pitting damage to seen to be particularly important in diagnosing the
a ship’s hull plate. The presence of high lev- type of attack via a knowledge of phase compo-
els of sulphide ions in the sludge found in the sition. The importance of X-ray techniques in this
pit, together with the extremely high numbers of context has been emphasised elsewhere.16 Docu-
sulphate-reducing bacteria present in the sam- mentation of corrosion failures provides a critically
ples taken from beneath the macrofouling layer, important source of information for the following
is indicative of active microbiological corrosion in reasons:
this region. The presence of aerobic bacteria in
the sample may have resulted in even more ag- Design engineers may recognize the
gressive conditions due to accumulation of cor- dangers and take remedial action.
rosive metabolic products such as exopolymers
Inspection and maintenance personnel
and organic and inorganic acids8 The attachment
may be alerted to the possibility of corro-
of oysters appeared to create an extremely favor-
sion and hence aggressive conditions in
able environment for the growth of SRB, as almost
similar environments on vessels may be
pure cultures of these bacteria were isolated from
treated early, avoiding severe damage.
the pit underneath the oyster.
Subsequent laboratory trials of the purified cul- Personnel involved in inspection and
tures showed this SRB strain to be highly corro- consultancy services can be made more
sive to mild steel with measured corrosion rates of aware of the likelihood of microbial
11,14 Marine Microbial Corrosion

corrosion and the attendant possibility 4. E. Marsh and D. Dulieu, British Steel Technical
of accelerated, localized attack on metal Report, SUS/R/S/952/1/92/D, 1992.
components and structures. 5. N.J.E. Dowling, J. Guezennec, and D.C. White, in
Microbial Problems in the Offshore Oil Industry,
Research workers may be stimulated eds. E.C. Hill, J.L. Shennan, and R.J. Watkinson
to investigate the complex mechanisms (Chichester, England: Wiley, 1987), pp. 27-38.
and interrelated factors involved in prac- 6. C.C. Gaylarde and J.M. Johnston, Int. Biodeterior.
tical cases of corrosion. Bull. 18(1982):111-116.
7. C.C. Gaylarde and H. Videla, Int. Biodeterior.
23(1987): 91-1 04.
Acknowledgments 8. I.B. Beech, C.W.S.Cheung, C.S.P. Chan, M.A. Hill,
R. Franco, and A.R. Lino, Int. Biodeterior. Biodeg.
34(1994) 289-303.
The authors are grateful for technical assis-
9. F.C. Walsh, W.T. Chao, S.A. Campbell, and I.B.
tance rendered by Dr. A.H. Nahle and Dr. R.A. Beech, Int. Biodeterior. Biodeg. 34(1994): 259-
Scannell (University of Southampton) and collab- 274.
orations with Dr. T. Baker (Imperial College of Sci- 10. S.A. Campbell, R.A. Scannell, and F.C. Walsh,
ence and Technology), Dr. W.T. Chao, K. Johnson “Microbially-Assisted Pitting Corrosion of Ships’
(British Steel Technical), and Prof. D.J. Schiffrin Hull Plate,” Indust. Corros. December (1989):
(University of Liverpool). Scanning electron mi- 7-1 4.
croscopy and energy dispersive X-ray analysis 11. J.B. Bryce and T.G. Roehner, Trans. I. Mar. E.
benefited from the expertise of Dr. S. Moss and 73(1961): 377-385.
P. Bond. X-ray diffraction facilities were kindly pro- 12. J.F.C. Brown and E.E. Goundry, “Bearing White
vided by R. Mortlock and Dr. M. Weller (University Metal Corrosion: An Electrochemical Explanation,”
of Southampton). BSRA Report NS 153,1967.
13. K.A. Lloyd and R.W. Wilson, “Formation of Tin
Oxide on White Metal Bearings,” Proc. I. Mech. E.,
7th Tribology Conference, 1969.
References 14. R.W. Hiley, Trans. I. Mar. E. 91(1979):52-57.
15. C.W.S. Cheung and I.B. Beech, Biofouling 9(1996):
1. S.A. Campbell and F.C. Walsh, Bull. Electrochem. 231-249.
8(1992):311-317. 16. F.C. Walsh and A.H. Nahle, “The Application of
2. H.A. Humble, Corrosion 5(1949): 292-302. X-ray Techniques to Studies of Corrosion and
3. M. Schumacher, Seawater Corrosion Handbook Protection,” Arab. J. Sci. Eng. 20(1995): 315-
(Park Ridge, NJ: Noyels Data Corp., 1979). 341.
CASE HISTORY CS-4

The Detection and Mitigation of MIC


By If,Cloete, PJ. Allison, and WI.J,Poulton

Summary Introduction

The present trend in industrial water systems is Both water consumption and discharge in
to minimize both water consumption and water dis- industrial water systems are currently minimized.
charge by recirculation. This results in the concen- The circulation of such water results in concen-
tration of dissolved and suspended substances, tration of dissolved and suspended substances,
promoting growth of waterborne microbes, and promoting the growth of waterborne microbes,
shifting the microbial community to a more copi- biofouling, and subsequent macrofouling of the
otrophic state. The accumulation of undesirable system and concomitant microbially induced
organic materials on any surface, either natural corrosion.
or man-made, is generally referred to as biofoul- A number of reviews have been published
ing with subsequent macrofouling of the system on the mechanisms of microbially induced corro-
and concomitant microbially induced corrosion sion and the organisms involved.’ The subject of
(MIC). biofilm formation has also been well covered in the
Tubercles of iron hydroxide or iron oxide literature.
caused by the growth of aerobic iron-precipitating A lack of information on practical control strate-
bacteria and anaerobic sulphate-reducing bacte- gies and case studies is appararent.
ria were removed to prevent excessive underde- Owing to the inaccessibility of sulphur-
posit corrosion. It is important to note that most reducing bacteria (SRB) beneath biofilms and tu-
of the commonly used corrosion inhibitors cannot bercles, many microbiocide treatment programs
penetrate through the tubercles to passivate the fail to control microbiologically influenced corro-
active anodic sites. sion in industrial water systems2
A number of MIC mitigation strategies were Recognition of the inability of most microbio-
employed, depending on various factors includ- cides to penetrate slime masses and tubercles
ing the system configuration, extent of pitting, and stimulated interest in compounds capable of pen-
treatment economics. etrating and dispersing such deposit^.^ Biodis-
Chemical cleaning using a combination of an- persants have been used on a continuous or in-
ionic copolymer dispersants and organic pene- termittent basis to enhance the effectiveness of
trants was an effective mitigation program that microbi~cides.~ Sessile bacterial biofilm popula-
was conducted on-line. Gradual loosening and dis- tions are dispersed or loosened from the surface
solution of iron corrosion by-products occurred, into the bulk water, thereby exposing the under-
and the metal beneath the softened and dis- deposit corrosion sites (pits) to biocide-containing
persed nodules was chemically passivated and circulating watera4
sanitized. Removal of iron oxide tubercles, which har-
Mechanical cleaning (pigging) was also em- bor sulphate-reducing bacteria (SRB), can be
ployed as a means of removing MIC nodules. achieved by a number of methods, including
11.16 The Detection and Mitigation of MIC

physical removal by “pigging,” the more aggres-


sive acid cleaning techniques, or the passivating
on-line cleaning approach using a combination of
surfactants and biocides.
The case histories presented demonstrate
successful strategies for the detection and mit-
igation of microbial corrosion in industrial water
systems.

Case Study 1 : Mechanical


Removal of MIC Tubercles by
Means of Pigging Operations
FIGURE 11.18
Pitting corrosion beneath a tubercle. (See color plates.)
Severe MIC was prevalent in a 450-mm diam-
eter 17-km long mild steel pipeline used to trans-
port water at ambient temperatures between two a series of mechanical pigging operations was
mines. The sulphate concentration of 1015 mg/l, undertaken at regular intervals over an eight-
neutral pH of 7.60, and intermittent operation of month period. The pigs comprised a flexible cellu-
the pipeline provided conditions favorable for the lar polyurethane, coated with an abrasion resistant
growth of SRB. polyurethane polymer. The flexible interior allowed
Figure 11.17 shows the density of tubercles for contraction and expansion of the pig cylinder
within the pipeline. Removal of the tubercles ex- with variations in the pipe interior. Wire brushes
posed typical pitting corrosion caused by SRB on the exterior of the pig facilitated easier removal
(Figure 11.18). of harder corrosion by-products.
Since chemical cleaning was not an option Microbiological analyses were performed on
for this system (because of excessive costs) water samples taken before and after passage
of the pig through the pipe. A marked increase
in numbers of total aerobic bacteria (TAB) (from
bacterial biofilm) and SRB was detected after the
mechanical cleaning action. Counts of TAB in the
bulk water increased from 1O4 to 1O8 colony form-
ing units/ml, and those of SRB from 2 to greater
than 100 cfu/ml after pigging.
Incorporation of a biodispersant and broad
spectrum microbiocide (comprising two different
“quick-kill” active ingredients) into the flush water
following the pig served to reduce the SRB popu-
lation and eventually resulted in a 100°/o kill of the
bacteria.
Visual inspection of the pipe interior after the
pigging operations showed that efficient removal of
the nodules and corrosion by-products had been
FIGURE 11.1 7 achieved. Figure 11.19 shows the cleaned metal
High density of tuberculation before mechanical clean- surface with “scars” where the tubercles had been
ing. (See color plates.) removed.
The Detection and Mitigation of MiC

FIGURE 11.19 FIGURE 11.21


Scars on the metal surface after mechanical cleaning Gallionella ferric hydroxide ribbon and bacterial cell
(pigging) operations. (See color plates.) (1 OOOX magnification). (See color plates.)

Samples of water were collected from the


Case Study 2: Mitigation of MIC pipes and filtered through 0.22-pm cellulose ac-
Using an Organic Wetting Agent etate filters and examined using light and scan-
ning electron microscopy. The appearance of
and an Anionic Iron-Dispersing bean-shaped bacterial cells of the iron bacterium
Copolymer Gallionella was evident.
Figures 11.20 and 11.21 show light micro-
MIC mitigation was required to prevent serious scopy photographs of the twisted iron hydroxide
impairment of a fire water system integrity caused ribbons at a magnification of 400X and 1OOOX re-
by leaking pipes. spectively. The SEM appearance is illustrated in
Figure 11.22.

FIGURE 11.20 FIGURE 11.22


Ferric hydroxide ribbons filtered from the fire hydrant Scanning electron micrograph of twisted ferric hydro-
water (400X magnification). (See color plates.) xide (SOOOX magnification).
11.18 The Detection a n d Mitiaation of MIC

FIGURE 11.24
FIGURE 11.23 Slight algal regrowth in the spray area of a cooling tower
Biofouling deposits on cooling tower packing before after nine months of biodispersanVbiocide treatment.
biodispersandbiocide treatment (A) and packing clear of (See color plates.)
biofouling deposits after three weeks of treatment (B).
(See color plates.) The mitigation strategy involved application
of an organic wetting agent and an anionic
Bacterial swabs taken from the fouled metal iron-dispersing copolymer to gradually dissolve
surface were cultured in a synthetic agar medium and disperse the bacterial nodules. Caution was
selective for Gallionella ferrugines and positive required with this approach, since too rapid a rate
growth was detected. Similarly, the presence of of chemical dispersion might lead to dislodgment
viable SRB was confirmed by culturing swabs of large pieces of corrosion by-products.
from the pitted areas in a modified Postgate/SABS Although chemical dispersion was applied
successfully, replacement of some of the piping
The results from the microbial investigation was necessary, since some of the pits had
showed that the concentration of 3-4 mg/l soluble penetrated through the pipe wall and removal of
iron (Fe2+) in the water, caused by electrochemi- the nodules removed the “protective caps” and
cal corrosion, stimulated the growth of Gallionella led to water leaks.
in the aerated system water. Tuberculation or A controlled maintenance program incorporat-
induced precipitation of iron hydroxide in turn pro- ing a microbiocide, biodispersant, and scale and
vided the anaerobic environment required for the corrosion inhibitor was recommended for ongoing
growth of SRB. treatment of the fire water system.
The Detection and Mitigation of MIC

Case Study 3: MIC Control bacteria. Biocides resulted in percentage kills of


by Biocide and Biodispersant planktonic bacteria between 83.2% and 1OO%,
with only one exception, where no change in
Treatment in Power Station the number of anaerobic bacteria occurred. The
Open Recirculating Cooling biodispersants resulted in a decrease in sessile
Water Systems aerobic bacteria numbers in 80% of the cases
and the biocides resulted in decrease in all of the
systems evaluated. Inspections revealed that the
Cooling water treatment programs were mon- biodispersant/biocide combination removed ses-
itored in the open recirculating cooling water sile microbiological deposits and aided in the pen-
systems at four fossil-fired power station^.^ Combi- etration of the biocide into inorganic deposits by
nations of three biodispersants and four biocides softening the overlying nodules. The use of combi-
were evaluated. Visual system inspections were nations of biodispersants and biocides effectively
carried out where possible. All of the dispersants controlled microbiological growth in all the cooling
resulted in increases in the numbers of planktonic

A
A

B
B

FIGURE 11.26
FIGURE 11.25 Strainer box after three weeks of biodispersanVbiocide
Strainer box before the initiation of biodispersantlbiocide treatment showing softened nodules on surface (A) and
treatment showing hard nodules on surface (A) and un- loss of black coloration in underlying pits (B). (See color
derlying pits filled with black liquid (B). (See color plates.) plates.)
11,20 The Detection a n d Mitigation of MIC

period (Figures 11.25A, B). After three weeks of


treatment, the nodules had been softened and only
half of them contained SRB (Figures 11.26A, B).
However, it was only after nine months that al-
most complete removal of the nodules and thus
mitigation of MIC occurred (Figure 11-27). This
indicated that the biodispersant was responsible
for biofouling deposit removal and mitigation of
MIC, and not the biocide. However, the use of
biocides, particularly in the “clean-up” phase of
treatment, can assist with the control of those
microorganisms dispersed into the bulk water,
where they are more susceptible to the action of
FIGURE 11.27 biocides.
Strainer box after nine months of biodispersant/biocide
treatment showing almost complete removal of nodules.
(See color plates.)
References

1. T. Ford and R. Mitchell, “The Ecology of Microbial


water systems. However, the treatment products Corrosion,” Adv. Microb. Ecol. 11(1990): 231-252.
2. T.E. Cloete, V.S. Brozel, and A. Von Holy, “Practi-
did not produce the same effects in different sys-
cal Aspects of Biofouling Control in Industrial Water
tems; therefore treatment products had to be se- Systems,” Int. Biodeterior. Biodeg. 29(1992): 299-
lected for each individual system. 341.
The visual inspections confirmed that a combi- 3. L. Jacobs, “Anionic and Nonionic Surfactants for the
nation of a biodispersant and biocides was effec- Controlling of Attached F! aeruginosa to Glass and
tive in removing biofilms, biofouling deposits, and 3CRIZ Metal Surfaces,” MSc. Thesis, University of
nodules of iron oxide, thus assisting in the miti- Pretoria, Pretoria, South Africa, 1996.
gation of MIC. After three weeks, the biofouling 4. W.I.J. Poulton, “Monitoring and Control of Biofoul-
deposits on the cooling water packing and clari- ing in Power Utility Open Recirculating Cooling Wa-
fiers were either removed or had lost their green ter Systems,” MSc. Thesis, University of Pretoria,
coloration, indicating cell death (Figure 11-23). Pretoria, South Africa, 1993.
In addition, little regrowth of algae occurred over 5. Standard Methods for the Examination of Water
and Wastewater, 15th ed. (Washington, DC: Amer-
the nine-month observation period (Figure 11-24).
ican Public Health Association, American Water
Thus the biodispersant/biocide program was effec- Works Association, Water Pollution Control Feder-
tive not only in the removal of biofouling deposits ation; 1981).
but also in preventing any reattachment. 6. SABS, “Media and Reagents for Microbiological
The softening and removal of the nodules in Tests,” Test Method 563 (South African Bureau of
the strainer boxes occurred over a longer time Standards, Pretoria, Transvaal, 1975).
Next Page

CASE HISTORY MM-3

Microbiologically Influenced Corrosion


in Geothermal Fields in Mexico
By B. Valdez Salas, L. Rioseco de la Pefia, G. Hernandez-Duque Delgadillo,
and N. Rosas Gonzalez

Introduction fiberglass structures. The temperature range was


from 40 to 98°C. Cooling towers with MIC problems
had a maximum temperature of 45"C, and at steam
In Mexico, 5% of generated electricity is
purges temperatures were above 70°C.
produced by geothermal power plants (700
Figure 11.28 shows bacterial attack on a
megawatts). The main Mexican geothermal field
stainless steel joint. Microbiological activity took
is located at Cerro Prieto, 20 km from Mexicali in
place on wooden and reinforced fiberglass
the state of Baja California.
(Figure 1129). These composite materials show
Geothermal power plants have cooling towers
a higher degree of biodeterioration.
that process large quantities of water and steam.
Our aim is to report the experimental results
This fluid commonly contains hydrogen sulfide;
of the study conducted on the inductive effect of
thus, when it enters the cooling system and con-
anaerobic bacteria on the corrosion process of
denses, optimum conditions exist to initiate local-
carbon steel supports of the cooling towers. Such
ized corrosion. Not only does the cooling water
supports are immersed in a dense sludge, which
contain dissolved inorganic salts and elemental
promotes biocorrosion.' This sludge is generated
sulfur, it also promotes the growth of bacterial
by chemical transformation of hydrogen sulfide in
colonies, which produce metabolites capable of
oxygenated waters into the inorganic sulfur inside
corroding metallic structures.
cooling towers.

Background Experimental Results

Microbiologically induced corrosion (MIC) The strains used in the study were isolated
problems in the Cerro Prieto geothermal field oc- from natural media. Samples of sludge and wa-
cur in three different zones: ter were taken from the bottom part of the cooling
tower of Cerro Prieto I in clean plastic 1 L bottles.
the exploitation zone, To obtain a more representative sample of anaer-
obic microorganisms, the sampler was immersed
the power generation zone (mainly in
1 m deep, and the bottle was filled with sludge at
condensers), and
40°C. Microbial cultures as well as isolation tech-
the cooling tower zone. niques were carried out to identify the species. The
production of hydrogen sulfide and the decrease of
Materials that were deteriorated include car- pH values were considered indicators of bacterial
bon steel, stainless steel, wooden, and reinforced metabolic processes.
CP.1

COLOR PLATES

2, Fungal-Influenced Corrosion of Metals


in Humid Environments c P.3-c P.5
3, Biodegradation of Nonmetallic Engineering Materials CPm6-CP,6
4. Biodeterioration of Building Materials CP.7-CP. 10
5 Microbiologically Influenced Corrosion
I

in Fire Protection Sprinkler Systems c P. 1-CP. 1 1


6. Part1
MIC jn Underground Environments: External
Corrosion in the Gas Pipeline Industry c P, 2-CP. 12
Part II
Microbiologically Influenced Corrosion of Internal Aspects
of Natural Gas Industry Pipelines and Associated Equipment:
Mechanisms, Diagnosis, and Mitigation CP.13-CP, 15
Part Ill
A Case Study-Microbially Induced Organic Acid
Attack in a Natural Gas Gathering System CP. 16-CP, 16
7. MIC in the Power lndustry CP.17-CP. 19
8# MIC in the Waste Treatment Industries CP,19-CP.20
9. Treatment for the Mitigation of MIC CP,2 1-CP. 24
11. cs-3
Marine Microbial Corrosion cP,25-c P.27
cs-4
The Detection and Mitigation of MIC CP028-CP,31
CP.2 COLOR PLATES

MM-3
Microbiologically Influenced Corrosion in
Geothermal fields in Mexico CP.31-CP.31
s- 1
Microbial Corrosion of Cultural Heritage Stoneworks CP.32-CPn34
COLOR PLATES - ChaDter 2 CP.3

Fungal- Influenced
Corrosion of
Metals in Humid
Environments

FIGURE 2.2 (a)


Wooden spool on which wire rope was stored.
Pieces of paper are attached to rim edges.

FIGURE 2.1
Growth stages of filamentous fungi.
CP,4 COLOR PLATES - Chapter 2

FIGURE 2.2 (b)


Inside surface of wooden spool. White deposits are
the result of fungal growth. FIGURE 2.4
(a) Wire rope that had been in contact with wood and PDA
inoculated with Aspergillus niger. Rope rolled aside to
show localized corrosion after contact with agar or wood
(3x1. (b) Light micrograph of localized corrosion associated
with fungi (40x1.

FIGURE 2.5
Interior of H-53 helicopter with luxurious fungal growth
on polyurethane paint.
COLOR PLATES - Chapter 2 CP.5

FIGURE 2.6
(a) Aureobasidiurn sp. colonizing polyurethane paint taken from H-53 helicopter. (b) 3 X magnification of (a).
(c) ESEM micrograph of Aureobasidiurn sp. on polyurethane paint. (d) Aureobasidiurn sp. on underside of
polyurethane paint chip (40X).

FIGURE 2.7
Fungal-induced corrosion of bare 2024 T-6 aluminum (40X).
CP.6 COLOR PLATES - Chapter 3

Biodegradation of
Nonmetallic
Engineering Materials

FIGURE 3.9 (a)


Corrosion of rebar in concrete.

FIGURE 3.11
(a) Deterioration of wood due to bacteria and fungi, (b) fungal
colonization (400X), and (c) staining to show bacterial penetration
of wood (1OOOX). (Courtesy of R. Lutey, Buckman Laboratories,
Memphis, TN.)
COLOR PLATES - Chapter 4 CP.7

Biodeterioration of
Building Materials

FIGURE 4.1
Staining of marble on the Certosa of Pavia, Italy.

FIGURE 4.2
Right: Phototrophic microorganisms on the facade of the cathedral
of Salamanca, Spain.

FIGURE 4.4
Limestone tessera from a mosaic of the Roman town of Italica, Spain, covered by epilithic lichens. Before (a) and
after (b) removal of the lichen thalli with hydrogen peroxide. Extensive pitting was observed beneath the thalli.
CP,8 COLOR PLATES - ChaDter 4

FIGURE 4.5
Fruiting bodies of an endolithic lichen
(Caloplaca sp.) emerging between calcite
crystals.

FIGURE 4.6
Walls of the cathedral of Salamanca, Spain, with
disperse lichen thalli.
COLOR PLATES - Chapter 4 CP.9

FIGURE 4.10
Vascular plants emerging from terracotta crevices
on the Pardon Gate, cathedral of Seville, Spain.
FIGURE 4.9
Terracotta colonized by cyanobacteria and algae on the
Pardon Gate, cathedral of Seville, Spain.

FIGURE 4.11
Deteriorated mural painting from the chapel of Castle Herberstein, Austria.
CP,lO COLOR PLATES - Chapter 4

FIGURE 4.12
Wall of the cloister of the Jeronimos
monastery, Lisbon, Portugal, colonized
by lichens.

FIGURE 4.13
Wall of the Quadrangular Mausoleum, Necropolis of
Carmona, Spain, colonized by calcifying cyanobacteria.
Next Page

COLOR PLATES - Chapter 5 CP,ll

Microbiologically Influenced
Corrosion in Fire Protection
Sprinkler Systems

FIGURE 5.1
Examples of MIC in FPS. (a) Discrete deposits (nodules) and deposits in steel wet FPS
pipe. (b) Galvanized steel wet FPS pipe showing heavier deposition and pitting on bottom
of pipe. (c) Pit in copper wet FPS pipe. (d) Deposits in galvanized steel dry FPS pipe.
(e) Pinhole leak in galvanized steel dry FPS pipe.
INDEX

Index Terms Links

Aachen cathedral, Germany 4.8


Abrasive particles 9.22
Acidity. see pH
Acid-producing bacteria (APB)
asphalt degradation 6.3
biocides and 6.22
in fire protection sprinkler systems 5.5
in gas gathering system study 6.35
growth assays 10.4
testing for 6.28 6.31
Acid rain 4.7
Acinetobacter 3.8
Acinetobacter calcoaceticus 3.3
Acinetobacter Iwoffi 4.11
Acoustic emission (AE) 3.3
Actinomycetes 4.11
Activated sludge 8.1 CP.19
Adenosine triphosphate (ATP) assays 10.5
Adhesives degradation 6.4 CP.12
Aerobic/anaerobic alternating conditions 6.8
Aerobic biofilms 1.2 6.31 CP.16
Alcaligenes 3.8
Algae
consolidant resins 11.30
marble 11.27
mortars 4.14
mosaics 11.26 CP.32
organic resins 4.15
stonework deterioration 4.5 4.8 4.10 CP.9

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Index Terms Links

Algae (cont.)
stuccoes 11.28 CP.34
ultraviolet radiation treatment 4.15
Algophase 11.31
Alloys
copper 1.5 6.16 7.5 9.12
9.16 9.19 CP.18
nickel-based 7.10
nonferrous 9.19
pH and 9.12
in wastewater treatment systems 8.6
Alternaria 3.6
Alternating current (AC) impedance
techniques 10.14
Aluminum 1.6 2.5 CP.5
Anaerobic conditions 6.7
Anionic polyelectrolytes 9.27 11.18
Anodic pitting corrosion cells 9.18
Anodic polarizations 1.6
Antimony 11.10
APB. See Acid-producing bacteria
APS reductase test 6.31
Archaea 4.12
Arthrobacter globiformis 4.11
Aspergillus 4.3
Aspergillus niger 2.3 3.6 4.3 CP.4
Aspergillus versicolor 3.3 3.5 4.12
Asphalt degradation 3.8 6.2 6.6 8.5
Aspicilia 4.10
Aspicilia contorta 11.27 CP.33
Aspicilia hoffmanii 11.27
Aureobasidium sp. 2.4 3.6 CP.5
Austenite phase 7.6 7.9 9.19
Autotrophic bacteria 3.1 4.6
Azole-based inhibitors 9.14

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Index Terms Links

Bacillariophyta 4.10
Bacillus 4.11 8.2
Bacillus sp. Algal 11.22
Bacillus subtilis 8.2 CP.19
Bacteria. See also Acid-producing bacteria; names
of individual bacteria; Sulfate- reducing bacteria
aerobic 1.2 5.4 6.31
autotrophic 3.1 4.1 4.6
in fire protection sprinkler systems 5.4
heterotrophic vs. autotrophic 3.1 4.6
iron-oxidizing 9.15 9.20 11.17 CP.21
CP.22 CP.23
iron-related 5.5
Iow-nutrient 5.4
manganese-reducing 1.5
nitrifying 1.2 4.6
wood degradation 3.8 CP.6
Baelo Claudia, Cadiz, Spain 4.13 11.28 CP.33 CP.34
Balegem calcarenite 4.1
Ballast tanks 11.6
Basidiomycetes 3.8
Basilica of Tongeren, Belgium 4.4
Bearings, white metal 11.8 CP.26 CP.27
Benzalkonium chloride 11.31
Benzothiazoles 9.9
Biocalcarenite 4.8
Biocatalyzed leaching from waste ores 8.3 8.7
Biocides
application 6.31
bioassay evaluation of 6.28
biological wastes 8.8
case studies 6.31 11.19
during chemical cIeaning 9.25

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Index Terms Links

Biocides (cont.)
combined with biodispersants 11.16 CP.29 CP.30 CP.31
compatibility with scale inhibitors 6.19
costs 10.2
effluent discharge limitations 9.8
failure of 6.27 6.30
foaming of 6.30
in gas gathering system study 6.33
glutaraldehyde 6.21
half-lives of 9.11
in hydrostatic testing water 9.14
isopropyl alcohol 6.21
for lichens and algae 11.31
maintenance 9.6
during mechanical cleaning 11.16
nonoxidizing 9.7 9.25
during outages and wet lay-up periods 9.11
pH and 9.12
power plants 7.10
quaternary amines 6.21
residual testing 6.33 6.38
stoneworks 4.15
2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine 4.15
toxicity concerns 10.1
Biocorrosion. See Microbial-induced corrosion
Biodispersants 7.11 9.27 11.15 11.18
CP.29 CP.30
Biofilms
concentration profiles in 1.4
conceptual models 1.2
copper alloys 1.5
corrosion cells under mud films 11.9
deposition accumulation monitors 10.7
direct inspection 10.3
electrochemical monitoring 10.9 10.12

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Index Terms Links

Biofilms (cont.)
fluid velocity and 8.4
hydrogen sulfide accumulation 1.4
methanogenic 1.2
pH within 1.5
sampling devices 10.7 10.12
Spools 6.30 CP.16
in waste treatment equipment 8.4 CP.20
Biofilm spools 6.30 CP.16
Biomineralization 1.2
Bioreceptivity 4.1
Bioremediation of hazardous wastes 8.2 8.7
Biostats 9.7 9.14
Biotite 4.9
Bird droppings 4.8
Bismaleimide, carbon-reinforced 3.3
Blue-green algae. See Cyanobacteria
Borate salts 9.12 9.14
Borobudur temple, Indonesia 4.4
Brazilian sandstone churches 4.8
Bricks 4.10
Bromine treatment 9.7
Bryophytes 4.6 4.9
See also Mosses
Building materials. See also Stonework corrosion
bioreceptivity 4.1
bricks and terracotta 4.10 CP.9
granites 4.9
limestones 4.2 11.26 CP.7 CP.32
CP.33
marble 4.1 11.27 CP.7
mortars 1.5 4.1 4.9 8.5
sandstones 4.6
treatment and restoration 4.14

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Index Terms Links

Caius Cestius pyramid 11.27 CP.33


Calcarenite 4.1
Calcite 4.3 4.6 4.14 11.28
CP.8
Caloplaca 4.6 11.26 CP.8 CP.32
Caloplaca aurantia 4.8
Caloplaca chalybaea 11.27 CP.33
Caloplaca citrina 11.30 CP.34
Caloplaca lactea 11.30
Camshaft bearings 11.11 CP.27
Candelariella 4.10
Carbon dioxide corrosion 6.27
Carbon fibers 3.2 8.6
Carbon steel
cooling tower supports 11.21 CP.31
gas pipelines 6.1 6.15 CP.13
internal surface of corroded piping 7.5 9.15 CP.17 CP.21
CP.22
pit shape 6.18
return activated sludge 8.2
rupture zones 11.22
type 43A 11.3
type 50A 11.3
wastewater piping 8.2 8.5 8.7 CP.20
weight-loss coupons 10.11
Carrara marble 4.1 11.27
Case studies
consolidant resins 11.30
constructional steel pilings 11.3 CP.25
geothermal fields in Mexico 11.21
marble 11.27
milk sterilizers 11.35
natural gas gathering system 6.27

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Index Terms Links

Case studies (cont.)


organic wetting agents and anionic copolymers 11.17
pigging operations 11.16
power station cooling water 11.19 CP.30 CP.31
Roman mosaics 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
ships' ballast tanks 11.6
ships' hull bottom plate 11.6 11.12 CP.25 CP.26
CP.27
tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Castle Herberstein, Austria 4.11 CP.9
Cathodic polarizations 1.7
Cathodic protection (CP)
changes in electrical properties 6.3
gas pipelines 6.1 6.10
non-metallic linings 9.9
pH changes 6.3
waste treatment processes 8.7
water conductivity 6.8
Cell components assays 10.5
Cell numbers, limited interpretation of 1.6
Cement mortar 8.5
Cerro Prieto geothermal field 11.21
Certosa of Pavia, Italy 4.2 CP.7
Cestia pyramid, Rome, Italy 4.4
Chaetomium 3.3
Chelating agents, for cleaning 9.4 9.24
Chemautotrophic bacteria 4.1
Chemical cleaning. See Cleaning, chemical
Chlorella homosphaera 4.9
Chlorella saccharophila var.saccharophila, 11.27
Chlorinated polyvinyl chloride (CPVC) 8.6
Chlorine treatments 7.10 9.7 9.25
Chlorophyta 4.10
Chromates 9.9

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Index Terms Links

Citrobacter sp. 11.22


Cladosporium 2.5 4.3 4.7
Cladosporium sphaerospermum 4.12
Clays 4.10 4.11
Cleaning
biocides during 9.25 11.16
chemical
of carbon steel piping 9.15
long-term, on-line, nonaggressive 9.4 9.26
materials of construction and 9.23
procedures 9.22
selection of chemicals 9.4 9.23
short-term, shutdown, aggressive 9.25
short-term, shutdown, nonaggressive 9.25
effluent discharge 9.20 9.24
maintenance 8.8 9.3 9.10
mechanical 6.19 6.22 9.3 9.15
9.22 11.16 CP.28
Closed-loop systems 7.2 9.2 9.5 9.10
11.19
Clostridium 4.11
Clostridium acetobutylicum, ATCC #824 3.2
Coal tar 6.2 8.5 8.7 CP.20
Coatings
cement mortar 8.5
coal tar 6.2
epoxy resin 2.1 3.2 8.5 CP.20
latex 3.5
new 6.10
plastic tape 6.2 6.4 CP.12
polymeric 3.4 8.6
Cologne cathedral, Germany 4.7
Colonization 4.1
Concrete 3.6 4.6 8.7 CP.6
Conductive caulk 3.4

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Index Terms Links

Consolidant resins 11.30


Control of MIC. See also Biocides; Mitigation of MIC
cathodic protection 6.1 6.8 6.10 8.7
9.9
corrosion inhibitors 6.20 6.30 9.9 9.14
environmental conditions control 4.15
fabrication, installation, and testing 8.6
fire protection sprinkler systems 5.4
fluid velocity 8.4 9.1 9.12
gas pipelines 6.19
maintenance and system design changes 9.28
microorganism control 9.6
postmitigation chemical treatment 9.29
prevention costs 7.11
source water 7.4 9.1 9.5 9.10
9.14
stoneworks 4.14 11.31
surfactants 6.40
system design 8.4 9.1 9.13 9.19
ultraviolet radiation 4.15
utilization of resistant materials 8.4 9.2 9.20
ventilation 2.4
welding seams 8.4
Cooling waters
bacterial species in 11.21
biocide/biodispersant treatment 11.19 CP.30 CP.31
monitoring 10.3 10.12
packing material 11.18 11.20 CP.29
recirculating systems 7.2 9.3 9.5 9.10
11.19 CP.30 CP.31
tower supports 11.22 CP.31
typical designs 7.2
Copper 5.1 9.19 11.10 CP.11
Copper alloys 1.5 6.16 7.5 9.12
9.16 9.19

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Index Terms Links

Copper-nickel tubing 6.16 CP.14 CP.24


Corrosion cells 6.7 11.9
Corrosion inhibitors 6.20 6.30 9.9 9.14
Corrosion potential 1.3
Corrosion products
analysis 6.8 6.18
austenite phase 7.6 7.9 9.19
as fingerprints for MIC 1.6 6.9
organic acid diagnosis from 6.28 CP.16
Costs of MIC 7.1 7.11 9.21 10.1
Coupon examination 10.6 10.10
CP. See Cathodic protection
Crevice corrosion 6.15 9.19 11.37
Cryptoendolithic communities 11.29
Cumulative corrosion loss (INT) 3.7
Cyanobacteria
bioreceptivity 4.1
consolidant resins 11.30
frescoes and mortars 4.13
light intensity and 4.4 4.13
mosaics 11.26
stonework deterioration 4.3 4.7 CP.9 CP.10
stuccoes 11.29 CP.34
ultraviolet radiation treatment 4.15

Delta ferrite 9.19


Denaturing gradient gel electrophoresis (DGGE) 4.11
Denickelfication 6.18
Deposition accumulation monitors 10.7
Design factors 8.4 9.1 9.13 9.19
Desulfobacter latus 11.22
Desulfovibrio 11.22
Desulfovibrio desulfuricans 4.2
Desulfovibrio vulgaris var. vulgaris NClB 8303 6.4

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Index Terms Links

Desulfuromonas acetoxidans 11.22


Diagnosis of MIC
cathodic protection current demand 6.4
chemical characterization of products 6.18
commercial assay kits 6.1
culturing 6.17 6.31
DNA probe techniques 6.1
in fire protection sprinkler systems 5.5
fluorescently labeled antibody probes 6.17 10.4 CP.18
in gas pipelines 6.13 6.16
In Line Inspection 6.10
microscopic examination 6.17 10.4 CP.14
Most Probable Number technique 6.3
Dichlorophene 4.15
Didymodon fallax 4.6
Direct current (DC) impedance techniques 10.14
Dirina massiliensis 4.8 4.12
Dispersants 7.11 9.27 11.15 11.18
CP.29
Djurelite 1.5
DNA genome assays 4.11 10.6
Dolomite 4.3

Effluent discharge 9.8 9.20 9.24


EHMW-HDPE (extra high molecular weight,
high-density polyethylene) 8.6
Electric coupons 10.13
Electrical resistance (ER) probes 10.13
Electrochemical biofilm monitoring 10.9 10.12 11.35
Electrochemical corrosion inhibitors 9.28
Electrochemical impedance spectroscopy (EIS) 3.3 10.14
Electrochemical noise (ECN) 3.5 10.15
Electron microscopy. See Scanning electron
microscopy; Transmission electron microscopy

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Index Terms Links

Energy dispersive X-ray analysis (EDXA) 6.8 10.6 11.5 11.6


11.8 11.10 11.35
Engyodontium album 4.12
Environmental scanning electron microscopy
(ESEM) 2.4 3.6 10.6
Enzymatic attack 3.2
Enzyme assays 10.5
Epicoccum 2.5 3.6
Epoxy resin coatings
bacterial degradation 3.2
fungal deterioration 2.1
polyamide-cured 8.5
in wastewater treatment piping 8.5 CP.20
Epsomite 4.12
Exophiala 4.7
Extra high molecular weight, high-density
polyethylene (EHMW-HDPE) 8.6
Extruded polyethylene 6.5

Fatty acid methyl ester (FAME) profiles 10.5


Feldspars 4.9
Fiber-reinforced plastic (FRP) 8.6
Fiber-reinforced polymeric composites (FRPCs) 3.2
Filtration of source water 9.2 9.5 9.10
Fire protection sprinkler systems (FPS)
components 5.1 5.3
diagnosis of MIC 5.5
maintenance cleaning 9.9 9.15
in power plants 7.2 7.5 CP.17
questionnaire 5.7
source water 9.2 9.10
summary of MIC cases 5.3
treatment and monitoring of MIC 5.6 9.11 11.17 CP.28
Flavirnonas 3.8

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Index Terms Links

Flavobacteriurn 3.8
Fluid velocity 8.4 9.1 9.12 9.23
Fluorescently labeled antibody probes 6.17 10.4 CP.14
Fluorinated polyimide composites 3.3
Foam application 9.24
Foaming 6.30
Forum of Baelo Claudia (Spain) 11.30 CP.34
FPS. See Fire protection sprinkler systems
Frankia 4.11
Frescoes 4.11
Frost-thaw cycles 4.1
Fuel tanks 3.4
Fungi
acidity 2.4
humid environments 2.1
military he1icopters 2.4
polymeric coatings 3.5 4.15
ship holds 2.5
stonework 4.3 4.10
structure and growth 2.1 3.1 CP.3
stuccoes 11.30
water activity and 2.1
wire rope 2.2 CP.4
Wood 3.8 CP.6
Fusariurn 4.7
Fusion bond epoxy 6.5

Gallionella 9.20 11.17 CP.29


Gallionella ferruginea 11 .18
Galvanic probes 10.12
Gas gathering systems 6.27
baseline monitoring 6.30
bioassay of potential biocides 6.28

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Index Terms Links

Gas gathering systems (cont.)


biocide application 6.31
biocide residual testing 6.33
conclusions 6.40
monitoring results 6.33
Gas pipelines, external corrosion in
coating degradation 6.3
corrosion scenarios 6.9
future needs 6.11
integrity management 6.10
modes of coating failure 6.1
newer coatings 6.10
protected steel 6.8
shielding disbondments 6.4 6.10
unprotected steel 6.6
Gas pipelines, internal corrosion in
detection 6.16
mechanisms 6.14
microbes involved 6.14
mitigation 6.19
monitoring 6.18
photographs 6.15 6.23 6.24 CP.13
CP.15
Geitleria calcarea 4.13
Gene probes 10.5
Geothermal power plants 11.21
Glass fibers 3.2 8.6
Gloeothece sp. 4.1 4.5 4.7
Glossary of terms ix
Glutaraldehyde 6.21 9.11
Goethite 6.9
Gold ore 8.3
Granites 4.9
Graphite fibers 3.3
Greigite 6.9

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Index Terms Links

Growth assays 6.3 6.31 10.4


Gymnostomum calcareum 4.6
Gypsum crusts 4.2

Haematoccus pluvialis 4.4


Halite 4.12
Halobacterium 4.12
Halococcus 4.12
Halomonas 4.11
Halophilic microorganisms 4.12
Hazardous waste bioremediation 8.2
Heat exchangers
corrosion monitoring 10.9 10.11
mechanical cleaning 9.4
photos of corrosion on 9.17 CP.23 CP.24
in the power industry 7.5 7.9 CP.19
Hematite 6.9
Heterotrophic bacteria 3.1 4.1 4.7 4.11
High-pressure water lancing 9.10
Hormodendrum 2.5 3.6
House of Neptune (Italica, Spain) 11.26 CP.32
House of the Birds (Italica, Spain) 11.26 CP.32
Hull plate corrosion 11.12 CP.25 CP.26 CP.27
Humid environments, fungal-influenced corrosion 2.1
Hydraulic fluid 2.5
Hydrazine 9.9
Hydrocarbon fuels 2.1 4.7 6.24 8.2
Hydrocarbon wastes 8.2
Hydrogenase assays 10.5 11.13
Hydrogen peroxide 4.15 9.7 9.11 9.25
Hydrogen sulfide accumulation 1.3 8.6
Hydrolazing 9.22
Hydrolysis of biocides 9.11
Hydrolysis reactions by metal-depositing bacteria 1.4

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Index Terms Links

Hydrophase 11.31
Hydrostatic testing, MIC from 7.3 8.6 9.6 9.9
9.13
Hyella fontana 4.4
Hyphae 3.1 4.9
Hypochlorite treatments 4.15 9.25

In-line filtration 9.2


In Line Inspection (ILI) 6.10
Inoculation 4.1
In situ bioremediation 8.2 8.7
INT (cumulative corrosion loss) 3.7
Iron 1.6 8.7
Iron hydroxide ribbons 11.17 CP.28 CP.29
Iron oxide deposition 1.3 1.4 9.15
Iron-oxidizing bacteria 9.15 9.20 11.17 CP.21
CP.22 CP.23
Iron-related bacteria (IRB) 5.5
Iron sulfides 6.5 10.5 10.13
See also Sulfides
lsoelectric points 1.7
lsopropyl alcohol 6.21
Italica, Spain 4.5 4.13 11.26 CP.7
CP.32

Jeronimos monastery, Lisbon, Portugal 4.13 CP.10


Jetting 9.22
Journal bearings 11.8 11.10 CP.26 CP.27

Kerosene 4.7
Ketoglutaric acid 4.9
Klebsormidium flaccidum 4.9 4.10 11.27

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Index Terms Links

Lactococcus lactis subsp. lactis, ATCC #19435 3.2


Lancing, high-pressure water 9.1
Land farming 8.2
Lanolin 2.5
Lateral corrosion 9.18
Latex coatings 3.5
LCO (limiting condition of operation) 7.4
Lead 4.2 11.10
Leak testing water. see Hydrostatic testing, MIC from
Lecania erysibe 4.8
Lecania turicensis 11.31
Lecanora 4.10
Lecanora pruinosa 4.8
Lecanoric acid 4.6
Lepidocrosite 6.9
Lichen acids 4.6 4.13
Lichens
building stone 4.5 4.8 4.14 CP.7
CP.8 CP.9
endolithic 4.5 4.14 CP.8
epilithic 4.5
frescoes and mortars 4.12 CP.10
on limestone 4.5 11.26 CP.7 CP.8
CP.32 CP.33
organic acids from 4.6 4.13
ornithocoprophilous 4.8
polyester resins 4.15
on stuccoes 11.29 CP.34
Limestones 4.2 11.26 CP.7 CP.8
CP.32
Limiting condition of operation (LCO) 7.4
Linear polarization resistance (LPR) probes 10.13 11.5
Low-nutrient bacteria (LNB) 5.4
Lubricating oils 11.9 11.11

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Mackinawite 1.6 6.9


Maghemite 6.9
Magnetite 6.9
Makeup water 9.5 9.10
See also Source water
Manganese oxide deposition 1.3
Manganese-reducing bacteria (MRB) 1.5
Marble 4.1 11.27 CP.7
Marcasite 6.9
Marine microbial corrosion
constructional steel pilings 11.3 CP.25
ships’ ballast tanks 11.6
ships’ hull bottom plate 11.6 11.12 CP.25 CP.26
CP.27
tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Mayan Great Jaguar Pyramid 4.6
Mechanical cleaning 9.3 9.15 9.22
Medical uses of biodegradation 3.8
Mesopitting 4.14
Metabolites 10.5
Metals. See also names of individual metals
biocatalyzed leaching from waste ores 8.3 8.7
biomineralization 1.2
chemical cleaning agents 9.4
fungal-influenced corrosion 2.1
reprecipitation 9.4
Methanogenic films 1.2
Mica 4.9
Microbial-induced corrosion (MIC)
assessment of 9.17
(See also Diagnosis of MIC)
beneficial uses 3.8
Costs of 7.1 9.21 10.1

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Microbial-induced corrosion (MIC) (cont.)


definition 5.1
mechanisms 6.14
monitoring (See Monitoring of MIC)
overview 6.13
pitting, general, and crevice 6.15 9.18 11.37
rate-limiting step 6.14
Microbiology influenced corrosion 6.13
See also Microbial-induced corrosion
Micrococcus 4.11
Microcolonies 1.3
Micropitting 4.14
Microscopic examination 6.17 10.4 CP.14
Mildew 3.2
Military helicopters 2.4 3.5 CP.4 CP.5
Milk sterilizers 11.35
Mineral generation 4.10
Minium 4.2
Mitigation of MIC. See also Biocides; Cleaning
Control of MIC
chemical treatments 8.8 9.3 9.6
chlorine treatments 4.15 7.10 9.7 9.25
control of microorganisms 9.6
deciding viability of 9.14
effluent discharge 9.8 9.20
evaluation of 9.14
during hydrostatic testing 7.3 8.6 9.6 9.9
9.13
identification of limitations 9.19
maintenance cleaning 8.8 9.3 9.10
microorganism control 9.6
off-line vs. on-line 9.3 9.20
during outages and wet lay-up 9.11
pigging 6.19 6.22 11.16
postmitigation chemical treatments 9.29

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Mitigation of MIC. See also Biocides; Cleaning


Control of MIC (cont.)
during preoperational construction phase 9.12
preprogram planning 9.16
during pretreatment phase 9.13
stagnant vs. flowing water 9.12
suspended solids control 9.8
use of resistant materials 8.4 9.2 9.20 CP.20
waste treatment systems 8.8
water treatment 7.10 8.8 9.3 9.5
Monitoring of MIC
assessment of severity and extent 9.17
baseline 6.30
cell components 10.5
coupon examinations 10.6
deposition accumulation monitors 10.7
direct inspection 10.3
electrical resistance probes 10.13
electrochemical impedance spectroscopy 3.3 10.14
electrochemical methods 10.9 10.12
electrochemical noise methods 10.15
enzyme assays 10.5
in fire protection sprinkler systems 5.6
galvanic probes 10.12
in gas gathering system study 6.33
gas pipelines 6.18
growth assays 10.4
linear polarization resistance probes 10.13
metabolites 10.5
method requirements 10.2
of microbes 10.3 10.13
sampling devices 10.7 10.12
Monuments. See Stonework corrosion
Mortars 1.5 4.1 4.9 8.5
Mosaics deterioration 4.13 11.25 CP.32

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Mosses 4.6 4.9 4.14 11.26


11.32 CP.32
Most Probable Number (MPN) 6.3 6.31 10.4
Muriella terrestris 4.9 4.10 11.27
Mycelia 3.1
Mycelia sterila 3.6

Natrococcus 4.12
Natronobacterium 4.12
Necropolis of Carmona, Spain 4.13 CP.10
Nickel-based alloys 7.10
Nitrifying bacteria 1.2 4.6
Nitrite borate inhibitors 9.9
Nitrobacter 4.7
Nitrobacter vulgaris 4.7
Nitrosomonas 4.7
Nitrosospira 4.7
Nitrosovibrio 4.7
Nitrous oxides 4.7
Nocardia 4.11
Nodules. See Tubercles
Nonferrous alloys 9.19
Nostoc punctiforme 4.10
Nuclear power plants. See also Power stations
competing requirements 7.1
copper alloys 7.5 CP.18
costs of repairs 7.1 10.1
mitigation 7.10
nickel-based alloys 7.10
redundancy requirements 7.2
stainless steels 7.6
steels and cast irons 7.4 7.6 CP.17
Nuclear waste storage containers 2.1 3.6
Nucleic acid assays 10.5
Nutrients, from air pollution 4.2

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Oceanospirillum 1.7
Offshore production systems 6.19
Open-loop systems 7.2 9.3 9.5
Orcinol depsides and depsidones 4.6
Organic acids
analysis of 6.31
bacterial 5.5
concrete degradation 3.6
diagnosis of 6.28
free acid forms 6.31
fungal 2.1 3.6 4.3 4.9
in gas gathering system study 6.37
lichen acids 4.6 4.13
as microbial nutrients 6.15
Organic deposits, cleaning of 9.5
Organic wetting agents 11.18
Orsellinic acid 4.6
Outages 9.11
Oxalic acid 4.5 4.8 4.13
Oxidizing agents 9.7 9.10
Oxygen
alternating aerobic/anaerobic conditions 6.8
copper sulfide corrosion 1.5
gas gathering pipe corrosion 6.28 CP.16
scavengers 9.10
stainless steels 7.8 7.1
Oysters 11.13
Ozone treatment 9.7

Palazzo Farnese, Caprarola, Italy 4.13


Pardon Gate, Seville, Spain 4.10 CP.9
Parmelia conspersa 4.10
PCR (polymerase chain reaction) 10.6

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Penetrant-biodispersants 9.8 9.14


Penicillium sp. 2.3 2.5 3.6 4.3
4.7
Pentachlorophenol 4.15
Pestalotia 2.5 3.6
Petroff Hauser Counting Chamber 10.4
Petrographic studies 4.5
pH
in biofilms 1.5
cathodic protection and 6.3
cement mortars 1.5 8.5
corrosion rates 6.7
in frescoes and mortars 4.12
hydrolysis reactions and 1.4
during hydrostatic testing 9.14
organic acid production 6.15
Phenanthrene 4.2
Phoma 2.5 3.6 4.7
Phormidium sp. 4.7
Phormidium tenue 4.9 4.10
Phosphonic acid derivatives 9.9
Phototrophic microorganisms 4.4 4.10 CP.7 CP.33
Phthalates 6.6
Physcia 4.10
Pigging 6.19 6.22 9.22 11.16
Piling corrosion, case history 11.3 CP.25
Piping systems. See also Gas pipelines, external
corrosion in; Gas pipelines,
internal corrosion in
internal surfaces of 7.5 9.15 CP.17 CP.21
CP.22 CP.23
mechanical cleaning 9.4 9.15 9.22
in nuclear plants 7.3 CP.17
steel 6.6 8.2 CP.20
sulfate-reducing bacteria 9.16
in wastewater treatment 8.2 8.5 CP.20

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Pitting
anodic corrosion cells 9.18 11.9
assessment of 9.17
ballast tanks 11.6
bearing surfaces 11.10 CP.26 CP.27
beneath tubercles 6.15 9.15 9.20
11.16 CP.14 CP.28
fire protection systems 5.2 CP.11
formation process 6.15
gas gathering systems 6.28 CP.16
heat exchangers 9.17 CP.24
hyphae penetration 4.9
mesopitting/micropitting 4.14
nuclear power plants 7.4 CP.17
pit shape 6.18
ships’hulls 11.12 CP.26 CP.27
in stonework 11.27 CP.33 CP.34
Planktonic organisms 10.3 11.19
Plasticizers 6.6
Plastics degradation 8.6
Plastic tape coatings 6.2 6.4 CP.12
Plectonema 4.9
Plectonema boryanum 4.9 4.10 11.27
Polarization resistance (LPR) probes 10.13 11.5 11.35
Polyamide-cured epoxies 8.5
Polycyclic aromatic hydrocarbons (PAHs) 4.2
Polyester polyurethanes 3.2 3.4
Polyethylene 6.5 8.6
Polyimide films 3.5
Polymerase chain reaction (PCR) 10.6
Polymeric coatings 3.4 8.6
PoIymeric materials
cross-linking in 8.6
fiber-reinforced polymeric composites 3.2
medical uses of biodegradation 3.8

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PoIymeric materials (cont.)


polymeric coatings 3.4 8.6
for treatment and restoration 4.15
Polymeric quaternary nitrogen 9.11
Polyolefin tape 6.4
Polypropylene tape 6.6
PoIyt hioet h er conductive cauIk 3.4
Polyurethane cable sheathing 2.1
Polyurethane paint 2.4 3.5 CP.4 CP.5
Polyvinyl chloride (PVC) 6.6 8.6
Portsmouth Harbour pilings 11.3
Power stations. See also Nuclear power plants
biocide and biodispersant case study 11.19 CP.30 CP.31
cleaning 7.11
copper alloys 7.5 CP.18
Costs of MIC 7.1
fire protection systems 7.2
hydrotesting 7.3
mitigation approaches 7.10
piping systems 7.3
stainless steel 7.6 CP.18
Pozzolana 4.1
A Practical Manual on Microbiologically Influenced
Corrosion 7.1
Preoperational construction phase 9.12
Pretreatment phase 9.13
Prevention of MIC. see Control of MIC
“Primer on the AC Impedance Technique” 10.14
Protozoa 8.2 CP.19
Pseudoanabaena sp. 4.10
Pseudocapsa dubia 11.27
Pseudomonas 1.7 3.8 4.11 8.2
11.5 11.22
Pseudomonas aeruginosa 1.2 3.3 11.22
Pseudomonas fluorescens 3.2

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Pseudonocardiaceae 4.11
Pyrite 6.9

Quartzite 4.9
See also Sandstones
Quaternary amines (QA) 6.21
Quaternary ammonium compounds 4.15

Ramalina capitata 4.8


Ramalina digitellata 4.8
Rate-limiting step 6.14
Rebar 3.7 CP.6
Recirculating systems 7.2 9.3 9.5 9.10
11.19 CP.30 CP.31
Redox potential 1.4 6.7
Reinforced fiberglass 11.22 CP.31
Resins
consolidant 11.30
epoxy 2.1 3.2 8.5 CP.20
organic 4.15
polyester 4.15
for treatment and restoration 4.15
Restoration, of stoneworks 4.14
Return activated sludge (RAS) 8.1 8.4 8.7
Reverse Sample Genome Probing (RSGP) 10.6
Rhizocarpon geographicum 4.9
Rhizopus sp. 11.22
Roman mosaics 4.5 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
Rupture zones 11.22

Salamanca, Spain 4.4 4.8 CP.7 CP.8


Salinity 4.12 6.7

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Sampling devices l0.7 10.12


Sandblasting 9.22
Sandstones 4.6
Santa Maria degli Alemanni, Messina, Italy 4.6
Santa Maria de la Rabida, Huelva, Spain 4.11
Sarcogyne pruinosa 11.30
Scale inhibitors 6.19 9.5 9.8
Scanning electron microscopy (SEM)
biofilms 11.22
building materials 4.5 4.9 4.14
copper alloys 1.5
cyanobacteria 4.5
environmental 2.4 3.6 10.6 CP.5
fatigue cracks 11.11
ferric hydroxide 11.17
fungi 2.3 CP.5
iron hydroxide ribbons 11.17 CP.29
lichens 11.29
stainless steel milk sterilizers 11.36
weldments 7.8
Schleswig Cathedral, Germany 4.10
Scytonema julianum 4.13
Secondary treatment 8.1
Selinunte, Italy 4.8
Sessile organisms, monitoring of 10.3
Seville, Spain 4.7
Sewage collection systems 3.7 3.9
Ships' holds 2.1 2.5 3.4 11.6
Ships' hull bottom plates 11.6 11.12 CP.25 CP.26
CP.27
Siderite 6.9
Side-stream filtration 9.2 9.10
Soapstone 4.8
Sodium hypochlorite 4.15 9.25
Sodium sulfite 9.11

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Soil, clay content in 6.7


Soil aggressivity model 6.7
Soil organisms 6.5
Soil resistivity 6.7
Source water 7.4 9.1 9.5 9.10
9.14
Sphaerotilis natans 8.2 CP.19
Sponge-ball cleaning systems 9.22
Spores 2.1
SRB. See Sulfate-reducing bacteria
Stability diagram, mackinawite 1.6
Stainless steel
chemical composition 11.37
high molybdenum 7.10
manganese oxide deposition 1.3
milk sterilizers 11.35
nickel content of corrosion products 6.18
pit shapes 6.18
polymeric coatings on 3.4
return activated sludge 8.2
sulfides and 1.4
tanks 9.16 9.18
two-phase welds 9.19
type 303 8.6
type 304 6.16 8.2 8.6
9.18 10.16 CP.24
type 316 8.7
wastewater treatment systems 8.6
weldment corrosion 7.6 CP.18 CP.24
wrought 7.8
Steel. See also Carbon steel; Stainless steel
embedded in concrete 3.7
in fire protection sprinkler systems 5.1 CP.11
galvanized 5.2 CP.11
iron sulfide galvanic couples 6.7

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Steel. See also Carbon steel; Stainless steel (cont.)


pilings 11.3 CP.25
piping 6.6 8.2 CP.20
rebar 3.7 CP.6
steel/FeS/SRB corrosion cells 6.7
Stemphylium 2.5 3.6
Stichococcus bacillaris 4.9
Stonework corrosion
bricks and terracotta 4.10 CP.9
consolidant resins 11.30
frescoes 4.11
granites 4.9
limestone 4.2 11.26 CP.7 CP.8
CP.33
marble 4.2 11.27 CP.7
mortars 4.1 4.9
remedial measures 4.14 11.31
Roman mosaics 4.5 11.25 CP.32 CP.33
Roman stuccoes 11.28 CP.34
sandstones 4.6
soapstone 4.8
Streamers 1.2
Streptomyces 4.11
Streptomyces griseus 4.11
Stuccoes deterioration 11.28 CP.34
Suffield shallow gas gathering system 6.27
Sulfate-reducing bacteria (SRB)
cathode depolarization 6.14
cement mortar coatings 8.5
concrete degradation 3.7
diagnosis 6.27 6.31 10.6
in gas gathering system study 6.35
gas pipeline degradation 6.3 6.7
growth assays 10.4
hydrogen sulfide accumulation 1.3

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Sulfate-reducing bacteria (SRB) (cont.)


limited interpretation of cell numbers 1.6
marine pilings degradation 11.5
in piping 9.16
poIymeric materials 3.2 3.4
ships' ballast tanks 11.6
Sulfate reductase 10.5
Sulfides
accumulation 1.3 8.6
bioprecipitated 1.4
black iron sulfide precipitates 6.7
detection and analysis of 6.8
iron 6.5 10.5 10.13
in wastewater treatment systems 8.6
Sulfur, elemental 6.9
Sulfuric acid, in wastewater treatment systems 8.6
Surfactants 6.40 8.6 11.18
Suspended solids control 9.8 9.10
Synechococcus sp. 4.10
Synechocystis sp. 11.27

Tanks
ballast 11.6
fuel 3.4
mechanical cleaning 9.4
stainless steel 9.16 9.18
Tape wrap coatings 6.2 6.4 CP.12
Temperature 7.9 9.1 9.23
Temple of lsis (Baelo Claudia, Spain) 11.30
Temple of Jupiter (Baelo Claudia, Spain) 11.29 CP.33 CP.34
Templete Mudejar (Spain) 11.32
Terracotta 4.10 CP.9
Tesserae deterioration 4.2 11.26 CP.7 CP.32
CP.33

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2,3,5,6- TetrachIoro-4-( methylsuIfonyl)-pyridine 4.15


Thermonatrite 6.4
Thiobacillus 4.6 8.6
Thiobacillus ferroxidans 3.2 8.3
Thiobacillus intermedius 4.6
Thiobacillus novellus 4.6
Tidal zones 11.3 CP.25
Tin-oxide corrosion of white metal bearing surfaces 11.8 CP.26 CP.27
Titanium corrosion 1.7
Toledo, Spain 4.9
Tortula muralis 4.6
Total residual oxidant (TRO) 9.7
Transmission electron microscopy (TEM) 10.6
Treatment. See Biocides; Control of MIC; Mitigation
of MIC
trichoderma 2.5 3.6 4.7
trichotecium sp. 4.3
Tubercles
carbon steel piping 9.15 CP.21 CP.22 CP.23
effects on fluid-carrying capacity 7.4
formation of 6.15
heat exchangers 9.20
nuclear power plants 7.4
pipelines 11.16 CP.28
reactions under 1.4 7.4 CP.14
removal of 11.15
Turbidity inspections 9.10 10.4
Turbulence-induced corrosion 1.5

Ultraviolet radiation 4.15


Underdeposit acid attack 6.16 6.30

Vascular plants 4.11 CP.9


Verrucaria muralis 11.31

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Verrucaria nigrescens 4.8 11.26 11.29 CP.33


Vibrio 11.5
Vibrio parahaemolyticus 1.2
Vinyl ester composites 3.2

Waste ores, biocatalyzed leaching 8.3 8.7


Waste treatment
biological waste treatment processes 8.1
cathodic protection 8.7
fabrication, intalIation, and testing 8.6
hazardous waste bioremediation 8.2
resistant materials 8.4 CP.20
system design 8.4
wastewater 3.6 3.9 8.1
Wastewater treatment systems 3.6 3.9 8.1
Water
activity 2.1
conductivity 6.7 6.10
hydrostatic testing 8.6 9.6
lancing 9.10
makeup 9.5 9.10
source 7.4 9.1 9.5 9.10
9.14
velocity 8.4 9.1 9.12 9.23
Water systems, high purity 9.10
Water treatment 9.5
Weight-loss coupons 10.6 10.10
Welded seams 7.5 8.4 8.6 9.2
9.18 CP.18 CP.24
Wet lay-up 9.11
Wetting agents 11.18
White metal, tin-oxide corrosion of 11.8 CP.26 CP.27
Wire rope corrosion 2.2 CP-4
Wood degradation 3.8 CP.6
Wooden spools 2.2 CP.3 CP.4

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Xanthophyta 4.10
X-ray diffraction (XRD) 6.8 11.5 11.6 11.11
11.13

Yeasts. 2.1

Zero resistance ammeter (ZRA) 10.15


Zinc chromate 3.4
Zinc phosphate 3.4

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