Beruflich Dokumente
Kultur Dokumente
Microbiologically
Influenced
Corrosion
Volume 2
John G. Stoecker II
Editor
NACE International
The Corrosion Society
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
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CONTENTS
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
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
FIGURE 1.1
Conceptual model of stratified biofilm.
(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
FIGURE 1.4
(a) Possible reactions under tubercles created by metal-depositing bacteria and (b) specific hydrolysis reactions that
produce acidity under tubercles.
(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
Limited Interpretation of
Cell Numbers
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
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
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.)
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
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
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.
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
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
Acknowledgments
References
Proceedings of the 12th International Corrosion and R.J. Watkinson (New York, NY: Wiley, 1987),
Congress (Houston, TX: NACE, 1993). pp. 57-62.
6. Pu B. Little, J.S. Puh, P.A. Wagner, and W.L. 20. M. Stranger-Johannessen, “Fungal Corrosion of
Bradley, “The Effects of Biofouling on Graphite/ the Steel Interior of a Ship’s Holds,” in Biode-
Epoxy Composites,” J. Compos. Technol. Res. 20, terioration 6, eds. S. Barry and D.R. Houghton
1(1998): 59-67. (CAB Int. Mycological Inst., 1986), pp. 218-
7. A.J. Sedriks, MP 33, 2(1994): 56. 223.
8. P.A. Wagner, R.I. Ray, B.J. Little, and W.C. Tucker, 21. J. Jones-Meehan, K.L. Vasanth, R.K. Conrad, B.
MP 33, 4(1994): 46. Little, and R. Ray, “Corrosion Resistance of Sev-
9. T.E. Ford, P.C. Searson, T. Harris, and R. Mitchell, eral Conductive Caulks and Sealants from Marine
J. Electrochem. SOC.,137(1990): 1175. Field Tests and Laboratory Studies with Marine,
10. J.M. Jones, M. Walch, and F.B. Mansfeld, “Micro- Mixed Communities Containing Sulfate Reducing
bial and Electrochemical Studies of Coated Steel Bacteria ,” Int ernat io nal Symposium on Mic robio Iog-
Exposed to Mixed Microbial Communities,” COR- ically Influenced Corrosion (MIC) Testing (Miami,
ROSION/91, paper no. 108 (Houston, TX: NACE, FL: American Society for Testing and Materials,
1991). 1994).
11. J.P. Pendrys, J. Electrochem. SOC., 136(1989): 22. F. Mansfeld, H. Xiao, L.T. Han, C.C. Lee, C. Chen,
113C. J. Jones-Meehan, and B. Little, “Evaluation of Coat-
12. P. Wagner, R. Ray, K. Hart, B. Little, W. Bradley, ing Degradation for Polymer Coated Steel Exposed
and P.-L. Chiou, “Microbial Degradation of Stressed to Seawater,” CORROSION/96, paper no. 659
Fiber Reinforced Polymeric Composites,” CORRO- (Houston, TX: NACE, 1996).
SION/95, paper no. 200 (Houston, TX: NACE, 23. B.J. Little, P.A. Wagner, K.R. Hart, and R.I. Ray,
1995). “Spatial Relationships Between Bacteria and Lo-
13. J.-D. Gu, T.E. Ford, K.E.G. Thorp, and R. Mitchell, calized Corrosion,” CORROSION/96, paper no. 278
“Microbial Deterioration of Fiber Reinforced Com- (Houston, TX: NACE, 1996).
posite Materials,” Proceedings of the International 24. B. Little, R. Ray, P. Wagner, J. Jones-Meehan, C.
Conference on Microbially Influenced Corrosion, Lee, and F. Mansfeld Spatial Relationships Be-
P. Angel1 et al., eds. (Houston, TX: NACE, 1995) tween Marine Bacteria and Localized Corrosion,”
p. 25/1. Biofouling X(2000): X.
14. B. Mitton, T.E. Ford, E. LaPointe, and R. Mitchell, 25. J.-D. Gu, T.E. Ford, K.E.G. Thorp, and R. Mitchell,
“Biodegradation of Complex Polymeric Coatings,” “Microbial Degradation of Polymeric Materials,” in
CORROSION/93, paper no. 296 (Houston, TX: Proceedings of the Tri-Service Conference on Cor-
NACE, 1993). rosion (Orlando, FL: 1994), p. 291.
15. J.J. Reynolds, M.G. Crum, and H.G. Hedrick, “Stud- 26. D.M. Lavoie and B.J. Little, “Fungal Contamina-
ies on the Microbiological Degradation of Aircraft tion of H-53 Aircraft,” Naval Research Labora-
Fuel Tank Foatings,” Develop. Indust. Microbiol. tory Memorandum Report NRL/MR/733-96-7725,
8(1967): 260-266. 1996.
16. H. Becker and H. Gross, “Beschadigung von Tank- 27. R.A. Zabel and F. Terracina, Dev. Ind. Microbiol. 21
innenbeschichtungen durch Mikroorganism,” Farbe (1980): 179.
und Lack, 77(1971): 533-539. 28. G. Severyn, “Concrete Protection Systems for
17. R.N. Miller, W.C. Herron, A.G. Krigrens, J.L. Repair of Deteriorated Infrastructures from MIC,”
Cameron, and B.M. Terry, Microorganisms Cause in Microbially Influenced Corrosion and Biodete-
Corrosion in Aircraft Fuel Tanks,” Mater. Protec. rioration, eds. N.J. Dowling, M.W. Mittleman, and
3(1964): 60-67. J.C. Danko (Knoxville, TN: Univ. Tennessee, 1991),
18. M. Stranger-Johannessen and E. Norgaard, Int. pp. 6-23.
Biodeterior. 27( 1991): 157. 29. J.V. Perfettini, E. Revertegat, and N. Langomazino,
19. M. Stranger-Johannessen, “Microbial problems in Experientia 47(1991): 527.
the Offshore Oil Oli Industry,” Proceedings of an 30. C.F. Kulpa and C.J. Baker, “Involvement of Sulfur-
International Conference organized by the Insti- Oxidizing Bacteria in Concrete Deterioration,” in
tute of Petroleum Microbiology Committee, held in Microbially Influenced Corrosion and Biodeterio-
Aberdeen, April 1986, eds. E.C. Hill, J.L. Shennan, ration, eds. N.J. Dowling, M.W. Mittleman, and
Biodegradation of Nonmetallic Engineering Materials 3.1 1
J.C. Danko (Knoxville, TN: Univ. Tennessee, 1991), 34. European Federation of Corrosion, Microbiologi-
4-7. cal Degradation of Materials-and Methods of Pro-
31. F. Mansfeld, H. Shih, A. Postyn, J. Devinny, R. tection (London: The Institute of Materials, 1992),
Islander, and C.L. Chin, “Corrosion Monitoring p. 37.
and Control in Concrete Sewer Pipes,” CORRO- 35. P. Tormala, “Biodegradable Plastics for Use in Im-
SION/90, paper no. 113 (Houston, TX: NACE, plants,” Biomed. Mater. Feb.(l993): 2.
1990). 36. D.E. Beach, R. Boyd, and N.D. Uri, “Expanding
32. A.N. Moosavi, J.L. Dawson, and R.A. King, “The Biodegradable Polymer Resin Use: Assessing the
Effect of Sulphate-Reducing Bacteria on the Cor- Aggregate Impact on the US Economy,”Appl. Math.
rosion of Reinforced Concrete,” in Biologically In- Model. 20(1996): 388-398.
duced Corrosion, ed. S.C. Dexter (Houston, TX: 37. H.P. Molitoris, “Decomposition of Plastics in the
NACE, 1986) p. 291. Sea,” in Proceedings of the 9th International
33. J.P. Pendrys, Appl. Environ. Microbiol. 55(1989): Congress on Marine Corrosion and Fouling
1357. (Portsmouth, UK: 1995).
CHAPTER 4
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
FIGURE 4.3
Scanning electron micrograph of Gloeothece sp. cells
involved in the sheath.
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
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
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
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.
Please include any additional information that you think would be useful
CHAPTER 6
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
!
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
-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
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
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)
(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
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
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)
6.13
6.14 Microbiologically Influenced Corrosion of Internal Aspects
Crevice Anode
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
I
I
Liquid S s m p l e
Solid Samples (Soil.
Corrosion Productrr.
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
7.1
7.2 MIC in the Power Industry
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
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 7.12
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)
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
Mitigation Approaches
~~
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-
1. G. Kobrin, ed., A Practical Manual on Microbiolog-
ments, or, in many cases, complete system re-
ically lnfluenced Corrosion, Vol. 1 (Houston, TX:
placement. These more extensive treatments have NACE, 1993).
been required when a thick biofilm and MIC con- 2. S.W. Borenstein and G.J. Licina, “Avoid MIC-
dition have been allowed to progress unchecked. Related Problems in Nuclear Cooling Systems,”
Simple and reliable techniques for monitoring Power June (1990).
biofilm activity that permit an accurate and early 3. Mic robio IogicalIy Induced Corrosion of Co nt ai n-
“
indication of biofilm formation provide a means to ment Service Water System,” IE Information Notice
improve MIC control, while reducing costs and de- No. 85-30 (United States Nuclear Regulatory Com-
creasing environmental impacts. On-line methods mission Office of Inspection and Enforcement, April
permit the system operator to take mitigation ac- 19, 1985).
tions before a damaging biofilm becomes estab- 4. “Microbiologically Influenced Corrosion (MIC),”
lished while using the optimum treatment regimen. SER 73-84 (Institute of Nuclear Power Operations
Significant Event Report, 1984).
Cleaning, both by mechanical and chemical
5. “Service Water System Problems Affecting Safety-
methods, and on-line and off-line approaches have Related Equipment,” Generic Letter 89-13 (United
been used as an effective and necessary part of States Nuclear Regulatory Commission, July 18,
MIC mitigation procedures.’ 1,34,35 Off-line meth- 1989).
ods are effective; however, the additional down- 6.“Microbiologically Induced Corrosion of Emergency
time associated with the cleaning procedure is Diesel Generator Service Water Piping,” NRC In-
costly. On-line cleaning, using sponge balls or formation Notice No. 94-79 (United States Nuclear
brushes for heat exchanger tubing, or chemical Regulatory Commission Office of Inspection and
methods, has also been successfully applied to Enforcement, November 23, 1994).
plant equipment.35 7. S.C. Dexter, ed., Biologically Induced Corrosion
The use of corrosion-resistant alloys seems to (Houston, TX: NACE, 1986).
be the “treatment” of choice for severely MIC dam- 8. N.J. Dowling, M.W. Mittleman, and J.C. Danko,
eds., Microbially lnfluenced Corrosion (Houston,
aged systems.36 Replacement of lined or coated TX: AWS and NACE, 1991).
carbon steel with 6% Mo stainless steels or car- 9. 1995 International Conference on Microbially Influ-
bon steels lined with high molybdenum nickel- enced Corrosion (Houston, TX: AWS and NACE,
based alloys is expensive.* These highly alloyed 1995).
materials, used in conjunction with increased at- 10. D.H. Pope, D. Duquette, D.C. Wayner, and A.H.
tention to microbiological controls, offer a margin Johannes, “Microbiologically Influenced Corrosion:
against lapses in other mitigation approaches. The A State of the Art Review,” MTI Publ. No. 13
7.12 MIC in the Power Industry
(Columbus, OH: Materials Technology Institute of Plant Safety,” NSAC-148 (Nuclear Safety Analysis
the Chemical Process Industries, 1984). Center/Electric Power Research Institute, May,
11. D.H. Pope, “A Study of Microbiologically Influenced 1990).
Corrosion in Nuclear Power Plants and a Practi- 23. M. Bibb and K.W. Hartman, “Bacterial Corrosion,”
cal Guide for Countermeasures,” EPRl NP-4582 Corros. Coat. South Africa October (1984): 12-
(Palo Alto, CA: Electric Power Research Institute, 29.
1986). 24. J.R. Kearns and G.E. Moller, “Reducing the
12. G.J. Licina, “Sourcebook for Microbiologically Influ- Heat Tint Effects on the Corrosion Resistance of
enced Corrosion in Nuclear Power Plants,” EPRl Austenitic Stainless Alloys,” MP May (1994): 57-
NP-5580 (Palo Alto, CA: Electric Power Research 61.
Institute, 1988). 25. J.R. Kearns and S.W. Borenstein, “Microbially In-
13. G.J. Licina, “Detection and Control-An Extension fluenced Corrosion Testing of Welded Stainless
of the Sourcebook for Microbiologically Influenced Steel Alloys for Nuclear Power Plant Service Wa-
Corrosion in Nuclear Power Plants,” EPRl NP-6815- ter Systems,” CORROSION/91, paper no. 279
D (Palo Alto, CA: Electric Power Research Institute, (Houston, TX: NACE, 1991).
1990). 26. P. Li, et. al., “Corrosion Studies of Stainless Steel
14. D.H. Pope, “Microbial Corrosion in Fossil-Fired Weldments in a Microorganism-ContainingArizona
Power Plants-A Study of Microbiologically Influ- Ground Water System,” 1995 International Confer-
enced Corrosion and a Practical Guide for Its Treat- ence on Microbially Influenced Corrosion (Houston,
ment and Prevention,” EPRl CS-5495 (Palo Alto, TX: AWS and NACE, 1995).
CA: Electric Power Research Institute, 1987). 27. S.W. Borenstein, “Microbiologically Influenced Cor-
15. G.J. Licina, “Electrochemical Aspects of Microbio- rosion Failures of Austenitic Stainless Steel Weld,”
logically Influenced Corrosion,” 1988 Proceedings MP August (1988): 62-68.
of EPRl Microbial Corrosion Workshop, ed. G.J. 28. Y. Chung, H.J. Mantle, and G.E. Lakso, “Selective
Licina, EPRl ER-6345 (Palo Alto, CA: Electric Attack in Microbiologically Influenced Corrosion of
Power Research Institute, 1989). UNS S30800 and S32100 Welds,” 1995 Interna-
16. “Program Reduces Fire Protection System Corro- tional Conference on Microbially Influenced Corro-
sion,” Power Eng. 99(1995): 21-23. sion (Houston, TX: AWS and NACE, 1995).
17. P.R. Puckorius, et. al., “Service Water System 29. C.J. Johnson, “Keep the Water Flowing to Reduce
Corrosion and Deposition Sourcebook,” EPRl TR- the Potential for MIC,” Power March (1987): 41-
103403 (Palo Alto, CA: Electric Power Research 43.
Institute, 1993). 30. A.M. Brennenstuhl and T.S. Gendron, “The Use of
18. G.J. Licina, “An Overview of Microbiologically Influ- Field Tests and Electrochemical Noise to Define
enced Corrosion in Nuclear Power Plant Systems,” Conditions for Accelerated Microbiologically Influ-
MP 28( 1989): 55-60. enced Corrosion (MIC) Testing,” in Microbiologically
19. M. Bibb, “Bacterial Corrosion in the South African lnfluenced Corrosion Testing, ASTM STP 1232,
Power Industry,” in Biologically lnduced Corro- eds. J.F. Kearns and B.J. Little (Philadelphia, PA:
sion, ed. S.C. Dexter (Houston, TX: NACE, 1986), American Society for Testing and Materials, 1994),
pp. 96-1 01. pp. 15-27.
20. P.R. Puckorius, “Massive Condenser Failure 31. A.M. Brennenstuhl, T.S. Gendron, and P.E. Do-
Caused by Sulfide Producing Bacteria,” MP herty, “Fouling and Corrosion of Freshwater Heat
December (1983). Exchangers,” 5th International Symposium on En-
21. A.M. Brennenstuhl and P.E. Doherty, “The Eco- vironmental Degradation of Materials in Nuclear
nomic Impact of Microbiologically Influenced Cor- Power Systems-Water Reactors, American Nu-
rosion at Ontario Hydro’s Nuclear Power Plants,” in clear Society, 1992.
Microbially lnfluenced Corrosion, eds. N.J. Dowl- 32. A.M. Brennenstuhl, T.S. Gendron, and B. Cleland,
ing, M.W. Mittleman, and J.C. Danko (Houston, TX: “Mechanism of Underdeposit Corrosion in Fresh-
AWS and NACE, 1991). water Cooled Austenitic Alloy Heat Exchangers,” In-
22. D.C. Bley, V.M. Bier, D.H. Johnson, and J.W. ternational Conference on Advances in Corrosion
Stetkar, “Service Water Systems and Nuclear and Protection, University of Manchester Institute
MIC in the Power Industry 7.13
of Science (UMIST), Manchester, United Kingdom, Improvement Seminar (Palo Alto, CA: Electric
June, 1992. Power Research Institute, 1992), pp. 75-89.
33. T.S. Gendron, R.D. Cleland, and P.A. Lavoie, 36. J.D. Redmond and C.M. Houska, “Service Water
“The Role of Chloride and SRB in Underdeposit System Materials Replacement Trends,” Service
Corrosion of Alloy 800 in Fresh Water,” in Microbially Water Systems Reliability Improvement Seminar
Influenced Corrosion, eds. N.J. Dowling, M.W. Mit- (Palo Alto, CA: Electric Power Research Institute,
tleman, and J.C. Danko (Houston, TX: AWS and 1993).
NACE, 1991). 37. A.H. Tuthill, “Survey of Microbiological Influenced
34. T.O. Brice and W.A. Glover, “Service Water Chem- Corrosion of Alloys Other Than Type 304 and 316,”
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
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
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
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
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
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
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
~~~ ~ ~~ ~~
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
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
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
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
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
SIDE VIEW
SAMPLE CYLINDERS
( 563'' ID)
1 1 ,-CPVC SAMPLECYLINDERCOVER
1 I,,
1625 OD
~LC P
SAMPLE TUBEV C
TUBE
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
ring column:
of miniaturized
sensors
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^.^')
\ 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
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
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
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
CORROSION/97, Paper no. 222 (Houston, TX: Mittleman, and J.C. Danko (Knoxville: Univ. Ten-
NACE, 1997). nessee, 1990), pp. 5-33-5-39.
40. D.J. Blackwood, J.L. deRome, D.L. Oakly, and A.M. 47. S. Reid, G.E.C. Bell, and G.L. Edgemon, ”The Use
Pritchard, “Novel Sensors for On-Line Detection of of Skewness, Kurtosis and Neural Networks for De-
MIC,” CORROSION/94, Paper no. 254 (Houston, termining Corrosion Mechanism from Electrochem-
TX: NACE, 1994). ical Noise Data,” CORROSION/98, Paper no. 176
41. U. Eul and E. Heitz, “Sensor Application for MIC (Houston, TX: NACE, 1998).
on Metals by a Mobile Monitoring Apparatus,” 1995 48. H.A. Videla, F. Bianchi, M.M.S. Freitas, C.G.
International Conference on Microbiologically In- Canales, and J.F. Wilkes, “Monitoring Biocorro-
fluenced Corrosion May (Houston, TX: American sion in Industrial Waters: A Practical Approach,”
Welding Society and NACE, 1995). in Microbiologically Influenced Corrosion Testing,
42. J.S. Smart and T. Pickthall, “A New System for On- eds. J.F. Kearns and B.J. Little, ASTM STP-1232
Line Monitoring of Internal Corrosion and Bacte- (Philadelphia, PA: American Society for Testing and
ria in Pipelines,” CORROSION/92, Paper no. 15 Materials, 1994).
(Houston, TX: NACE, 1992). 49. R.M. Donlan, “Correlation Between Sulfate Reduc-
43. D.C. Silverman, “Primer on the AC Impedance ing Bacterial Colonization and Metabolic Activity on
Technique,” in Electrochemical Techniques for Cor- Selected Metals in a Recirculating Cooling Water
rosion Engineering, eds. R.A. Baboian (Houston, System,” CORROSION/92, Paper no. 183 (Hous-
TX: NACE, 1986), pp. 73-79. ton, TX: NACE, 1992).
44. F. Mansfeld and H. Xiao, “Electrochemical Tech- 50. H. von Rege and W. Sand, “Identification and Simu-
niques for Detection of Localized Corrosion Phe- lation of MIC on Metals by a Mobile Test Apparatus,”
nomena,” in Microbiologically Influenced Corrosion 1995 International Conference on Microbially Influ-
Testing,eds. J.F. Kearns and B.J. Little, ASTM STP- enced Corrosion (Houston, TX: American Welding
1232 (Philadelphia, PA: American Society for Test- Society and NACE, 1995), p. 58.
ing and Materials, 1993), pp. 42-61. 51. B.J. Webster, D.B. Wells, and P.J. Bremer, “The In-
45. B.J. Webster and R.C. Newman, “Producing Rapid fluence of Potable Water Biofilms on Copper Cor-
Sulfate-Reducting Bacteria (SRB)-Influenced Cor- rosion,” CORROSION/96, Paper no. 294 (Houston,
rosion in the Laboratory,” in Microbiologically Influ- TX: NACE, 1996).
enced Corrosion Testing, eds. J.F. Kearns and B.J. 52. A.M. Brennenstuhl and T.S. Gendron, “The Use
Little, ASTM STP-1232 (Philadelphia, PA: Amer- of Field Tests and Electrochemical Noise to De-
ican Society for Testing and Materials, 1993), fine Conditions for Accelerated Microbiologically In-
pp. 28-41. fluenced Corrosion (MIC) Testing,” in Microbiologi-
46. F. Mansfeld and B.J. Little, “A Critical Review of cally Influenced Corrosion Testing,eds. J. F. Kearns
the Application of Electrochemical Techniques to and B.J. Little, ASTM STP-1232 (Philadelphia, PA:
the Study of MIC,” in Microbially Influenced Corro- American Society for Testing and Materials, 1993),
sion and Biodeterioration, eds. N.J. Dowling, M.W. pp. 15-27.
CHAPTER 1 1
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.
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
FIGURE 11.1
General view of steel piling, showing zones affected by
low water corrosion. (See color plates.)
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
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.)
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
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)
(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
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
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
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
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
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
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
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
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 2.1
Growth stages of filamentous fungi.
CP,4 COLOR PLATES - Chapter 2
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 3.11
(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
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
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
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
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
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
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
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
Kerosene 4.7
Ketoglutaric acid 4.9
Klebsormidium flaccidum 4.9 4.10 11.27
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
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
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
Pseudonocardiaceae 4.11
Pyrite 6.9
Quartzite 4.9
See also Sandstones
Quaternary amines (QA) 6.21
Quaternary ammonium compounds 4.15
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
Xanthophyta 4.10
X-ray diffraction (XRD) 6.8 11.5 11.6 11.11
11.13
Yeasts. 2.1