You are on page 1of 67

Biological Treatment of Microbial

Corrosion: Opportunities and


Challenges - eBook PDF
Visit to download the full and correct content document:
https://ebooksecure.com/download/biological-treatment-of-microbial-corrosion-opport
unities-and-challenges-ebook-pdf/
Biological Treatment
of Microbial Corrosion
Opportunities and Challenges
REZA JAVAHERDASHTI, PhD
Director
ParsCorrosion
Perth, Australia

KIANA ALASVAND, PhD


ParsCorrosion
Perth, Australia

]
BIOLOGICAL TREATMENT OF MICROBIAL CORROSION ISBN: 978-0-12-816108-1
Copyright Ó 2019 Elsevier Inc. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic or
mechanical, including photocopying, recording, or any information storage and retrieval system, without
permission in writing from the publisher. Details on how to seek permission, further information about
the Publisher’s permissions policies and our arrangements with organizations such as the Copyright
Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/
permissions.

This book and the individual contributions contained in it are protected under copyright by the Publisher
(other than as may be noted herein).

Notices

Practitioners and researchers must always rely on their own experience and knowledge in evaluating
and using any information, methods, compounds or experiments described herein. Because of rapid
advances in the medical sciences, in particular, independent verification of diagnoses and drug
dosages should be made. To the fullest extent of the law, no responsibility is assumed by Elsevier,
authors, editors or contributors for any injury and/or damage to persons or property as a matter of
products liability, negligence or otherwise, or from any use or operation of any methods, products,
instructions, or ideas contained in the material herein.

Publisher: Matthew Deans


Acquisition Editor: Christina Gifford
Editorial Project Manager: Peter Adamson
Production Project Manager: Kiruthika Govindaraju
Cover Designer: Alan Studholme

3251 Riverport Lane


St. Louis, Missouri 63043
Preface

Corrosion, in general, and microbial corrosion (MIC), in These two terms are meant to add more meaning to what
particular, are very significant issues that do harm to industry does with regard to recognition, treatment, and
human-made assets and structures. Industry-wise, it is monitoring of microbial corrosion.
almost all industries that suffer from MIC and may In addition to the above innovations in this book, we
include oil and gas, pipeline, water and waste water believe that the main innovation is still in its title: so far
treatment, chemical plants, ports and jetties, ships, to in all industries, MIC has been tried to be controlled by
name a few. the aid of mechanical-physical (for example, coatings or
It may sound surprising to the reader that although pigging), electrical (cathodic protection), and chemical
MIC is so recognized, there are professionals who take it (use of biocides) means. This book will talk about a
lightly and simply think that by the ways they have been possibility that there can exist yet another means that is
using so far, it is possible to cure and control MIC. biological. In other words, how bacteria against bacteria
Apart from a few exemplary universities and research can be used to control MIC.
institutes that have largely contributed to filling the gap We do hope that with these innovative points in this
between industry and academia with respect to MIC book, our readers from engineers to researchers will find
research and engineering, a majority of technological it very useful, practical, and question-making. If after
thinktanksdand therefore researchersdare not yet reading this book, the reader has come up with some
aware of MIC and how such a complex phenomena questions to be answered in his/her head, we believe that
must be addressed and even predicted properly: if we we have reached our goals.
accept that softwares are based on mathematical The structure of the book is that it has two sections in
models, lack of specifically prepared softwares for MIC six chapters. The first section that contains three chapters
is itself a good indication of how poorly mathematics has been authored by Dr. Reza Javaherdashti. The second
has been used to look at this forgotten corrosion pro- section that contains three chapters has been written and
cess. To tackle this weakness, we have suggested a prepared by Dr. Kiana Alasvand.
mathematical model based on fuzzy logic that we We would like to dedicate this book to our beloved
previously used with success for corrosion-related ones, Helya and Hannah Javaherdashti, Tahmoures
bacteria (CRB) to predict their corrosive actions. This Alasvand, and Mahin Soleimani.
modeling now aims to highlight how pathogenic Let us close this chapter with a verse from a great man,
bacteria can also be treated likewise. the Iranian mathematician, astronomer, and poet, Omar
In addition to being intrinsically complex because of Khayyam who said:
accommodating various interactions between living
things and nonliving things, microbial corrosion also
suffers from inadequate and sometimes wrong termi-
nology that has been in use for decades in its literature:
an example of wrong terms used in MIC studies is the
term “biofilm,” we have suggested the term “Temenos” Never did I give up from learning/ To me remained unrevealed
for that and we have explained our reasons for this
rarely secrets of the Universe Spent I seventy-two years of my life
suggestion although we have still used “biofilm” in
in thinking/ what I got as a result was that I knew nothing
majority of the material given in this book.
In this book, following focusing on “corrosion con- Reza Javaherdashti, PhD
trol” and “corrosion prevention,” for the first time, we Kiana Alasvand, PhD
coined the terms “Zugzwang Effect” and “Myth Effect”
and explained their importance especially from a
microbial corrosion management point of view.

v
Contents

1 Why Corrosion and Particularly Microbial MIC as an Electrochemical Process, 25


Corrosion Are Important?, 1 Diversity of Organisms Involved in Microbial
The Definition of Engineering Importance as a Corrosion, 26
Function of “Risk” and “Cost”, 1 Suitable Environment for MIC to Occur, 27
What are the Risks and Costs of Corrosion and Biofilm, A True Concept With a Wrong
Microbial Corrosion, 2 Name, 27
Economical Costs, 2 Introducing Some Bacteria That Are Related to
Ecologic Costs, 3 Corrosion (Corrosion-Related
How can Risks, Defined as a Function of Bacteria ¼ CRB), 30
Likelihood and Consequences, be Related to Sulfate-Reducing Bacteria, 32
Microbial Corrosion?, 6 Iron-Oxidizing Bacteria, 33
References, 9 Iron-Reducing Bacteria, 34
Acid-Producing BacteriadNonorganic
2 A Brief Introduction to Corrosion Producers, 34
Engineering, 11 Acid-Producing BacteriadOrganic Acid
Introduction, 11 Producers, 34
The Thermodynamics of Corrosion and Its Possible Role of Magnetic Bacteria in Inducing
Importance in Dealing With It in Industries, 11 Corrosion, 35
Some Basic Concepts of Corrosion, 15 Use of Mathematics in Microbiology: Fuzzy
Essentialities for Corrosion, 15 Modeling for Distinguishing CRB and
Pathogenic Bacteria, 36
“Series” and “Parallel” Corrosion Process
Patterns, 16 Eight Fundamental Assumptions, 37
A Combination of a Concrete Slab and a Steel General Methodology, 37
Rod, 16 CRB Fuzzy Modeling, 38
How is Corrosion Treated?, 17 Defining Membership Function for CRB, 38
Application of Cathodic Protection Methods, 18 PB Fuzzy Modeling, 39
Materials Selection, 19 Physicoelectrostatic Factors, 40
Application of Coatings, 20 Mechanical Factors, 40
Design Factor, 21 Fuzzy Composite Functions for PB, 41
Chemical Treatment, 22 Discussion, 41
Closing Remarks, 23 Summary, 42
References, 24 How Is MIC Recognized? A Short Review of
Culture-Dependent and Culture-Independent
Methods and Their Pros and Cons, 42
3 An Introduction to Microbial
Culture-Dependent Methods, 42
Corrosion, 25
Culture-Independent Methods, 45
How Are Microbial Corrosion, in Terms of Being an
Electrochemical Process, and Microbiology “Zugzwang Effect” in MIC, 46
Related?, 25 “Myths Effect” in Recognition and Treatment
What Is MIC and What Are the Four Basic of MIC, 52
Characteristics of It?, 25 Javaherdashti Model for CM-MIC, 55

vii
viii CONTENTS

Closing Remarks, 67 Corrosion Inhibition by Predatory Bacteria, 101


References, 67 Corrosion Inhibition by Predatory Phages, 107
Corrosion Inhibition by Nitrate-Reducing
4 An Introduction to Microbiology for Bacteria, 113
Nonmicrobiologists, 71 Corrosion Inhibition by Regenerative Biofilm, 116
Introduction, 71 Corrosion Inhibition Through the Removal of
Cell and Macromolecules, 71 Corrosive Agents, 118
Amino Acids, 71 Corrosion Inhibition Through a Protective
Fatty Acids, 73 Layer, 119
Monosaccharides (or Simple Sugar), 74 Corrosion Inhibition Through Antimicrobial
Nucleotide, 74 Producing Biofilm, 119
Classification of Organisms, 78 Corrosion Inhibition With Biologically Produced
Corrosion Inhibitor, 120
Bacterial Cell Architecture, 81
Corrosion Inhibition With Biosurfactant, 120
Appendages, 81
Corrosion Inhibition by Biosynthesized
Cell Envelope, 83
Nanoparticles, 122
Cytoplasmic Region, 85
Corrosion Inhibition by Hydrophobic Biofilm, 123
Microbial Genetic Material, 86
Corrosion Inhibition by Microbial Antifreeze
Microbial Metabolism, 86
Protein, 125
Reproduction of Microorganism, 87
Inhibition of Corrosion by Targeting Signaling
Microbial Growth, 88 Molecule, 127
Dormancy in Bacteria, 89 Corrosion Inhibition by Quorum Sensing
Physical and Chemical Requirement for Bacterial Inhibitors, 127
Growth, 89 Inhibition of Corrosion by Targeting
Bacterial Signaling Pathways, 90 c-di-GMP, 130
Quorum-Sensing Signaling, 90 Corrosion Inhibition by Microbial Footprint, 130
Cyclic Dinucleotide Signaling, 91 Corrosion Inhibition by Microbial Cell Surface
Bacterial Locomotion, 91 Display, 132
Biofilm, 92 References, 133
Inhibition of Microbes, 93
Microbial Interaction, 94 6 Future Perspective of Biological
References, 96 Inhibition of Corrosion, 145
References, 148
5 Biologic Treatment of Corrosion, 101
Introduction, 101
Corrosion Inhibition by Predatory INDEX, 151
Microorganisms, 101
CHAPTER 1

Why Corrosion and Particularly


Microbial Corrosion Are Important?

THE DEFINITION OF ENGINEERING When it comes to corrosion, we, as H.H. Uhlig


IMPORTANCE AS A FUNCTION OF did, can categorize corrosion losses as below:
“RISK” AND “COST” 1. Waste of energy and materials
Anything can be specified with two variables: its 2. Economical loss
importance (the role that it plays in our lives) a. Direct loss
and the cost of being at this status. A rather trivial b. Indirect loss
example could be our pets: the role that these i. Shutdown
lovely creatures may play in the lives of many of ii. Loss of efficiency
us is hard to deny. On the other hand, the cost iii. Product contamination
for looking after them is a figure that many iv. Overdesign
won’t (can’t) afford. Of course here we don’t We will very briefly just touch economic-
mean economy for keeping a pet, I am sure ecologic aspects of corrosion loss. However, this
many of us have experienced the rather bitter is not to be understood that other aspects of corro-
feeling when we have read “No Dogs Allowed” sion loss can be ignored. Take, for example, the
signs or even the trauma that may be felt when a overdesign that will be imposed to compensate
loved pet is not with us anymore. All these can for corrosion.
make something, from a pet to corrosion, become Assume that we have a 32-inch pipeline with a
important for us. length of 10 km. If the thickness of the pipe is
However, the importance of anything is rather 5 mm, the internal volume of the pipe will be
a relative measure: something that may be impor- 5064.0 m3. However, if we could manage to
tant for someone may not be important for decrease this overdesign to 3 mm, the internal
another person. Engineering importance, on the volume will be increased to 5114.0 m3, in other
other hand, is another story. In fact, engineering words the internal volume will be increased by
importance because of its very nature cannot more than 90%.
vary from person to person. It has a clear, mathe- The above shows that the overdesigning to be
matical definition that can be stated as below: protected against corrosion is not an engineering
Engineering Importance ¼ Cost  Risk solution. In addition to decreasing the useful
volume of the pipe, overdesigning can indirectly
Each of these terms has its own nonvarying,
add up more into the pollution: overdesign as a
definitive meaning as we shall explain below in
measure of protection against corrosion will add
a moment. However, we have to add a very signif-
into the “embedded energy” (EmE). Embedded
icant point here too: if engineering importance of
energy is defined as “the energy consumed by all of
something is important, no excuse is acceptable
the processes associated with the production of a struc-
for ignoring it. Although this statement may
ture from the acquisition of natural resources to product
sound obvious, our real life experience shows
delivery.”2 Therefore, when we do overdesign, we
that in many cases in industries, the engineering
are augmenting the energy required to make the
importance of corrosion is taken not with the
part (in our example, the 10-km, 32-inch pipe).
gravity it deserves.
Biological Treatment of Microbial Corrosion. https://doi.org/10.1016/B978-0-12-816108-1.00001-X
Copyright © 2019 Elsevier Inc. All rights reserved. 1
2 Biological Treatment of Microbial Corrosion

This augmented energy will consume up more en- investment will start to become economically
ergy from extraction and refining of the metal to feasible. All physical assets we have in industry
melting and shaping and deformation. Just are exposed to the elements and thus will go
multiply this figure by the total length of pipelines through a process known by economists as
used around the world and those that are “erosion”: the value of your initial investment
designed not to pose any corrosion risk by will depreciate by many factors such as “wear
applying overdesign. and tear.” If we can assume a certain rate of annual
The example above can be taken as a stand- depreciation/wear and tear for a physical asset,
alone case of how corrosion can affect our lives then it will be possible to also calculate from
and energy sources. Below, we will briefly intro- what point in time the asset will start to become
duce some economic-ecologic disadvantages of economically feasible (this point in time is the
corrosion. “break-even point”).
However, there are at least two shortcomings in
such economical considerations:
WHAT ARE THE RISKS AND COSTS OF
1. Wear and teardas the name also impliesdcan
CORROSION AND MICROBIAL
only contain physical forms of corrosion such
CORROSION
as but not limited to erosion-corrosion or
We will start with what we mean by “cost” in the
perhaps rusting (in iron and steel alloys). The
definition of engineering importance. In the
term is not inclusive of chemical, electro-
context of this chapter, cost will mean anything
chemical, and biologic factors that can affect
that will increase the likelihood of creating a haz-
corrosion and bring it to the final stage of
ard to our investment. When we build a power
having lost its mechanical integrity and
plant or a refinery, for example, we do it by
strength.
considering if this investment is feasible enough 2. Although the depreciation rate may be
for us. In other words, we study the items required
assumed certain, constant value for each year,
to ensure us that we are not “wasting our money.”
as it is not considering the wider concept of
One important parameter here is the cost that is
corrosion, the actual depreciation rates to be
imposed on our investmentdthat is, the power
imposed on the material will be much higher
plant or refinery or pipeline grid we make. The
than what is expected on the paper. The main
cost here can be categorized into two sets: the
reason behind intensifying deprecation rates is
intrinsic costs associated with the pass of time
corrosion.
and effect of elements on our investment (that
can roughly be addressed as “depreciation” factor) Having said the above, it is now evident that as
and the costs that our investment may impose on long as there is no mutual understanding between
the surrounding environment (ecologic costs). We corrosion experts and economists, what is being
will describe the depreciation under “economic reported as “cost of corrosion” must be taken as
costs,” bearing in mind that depreciation in its the very minimum values that could have been
very financial meaning does not include corrosion surveyed and calculated.
properly, as we will discuss it below. What is very interesting about the countries
mentioned in Table 1.1 is that by proper manage-
Economical Costs ment of cost of corrosion, they have managed to
Whenever we do an investment, we are also lower this cost. Perhaps the most striking example
obliged to think how long this investment will in this regard will be Kuwait: in 1995 the cost of
last. Especially if the investment is in a physical corrosion has been 5.2% of its GDP. This cost of
form (for instance, building up a power plant, a corrosion had actually been inherited from
refinery, or the like), we are also interested to another study that had been done for this country
know how long we can expect this investment in 1987, yielding the same figure of 5.2% GDP for
will last as well as after what period in time, this the cost of corrosion.3 However, by seriously
CHAPTER 1 Why Corrosion and Particularly Microbial Corrosion Are Important? 3

TABLE 1.1
Ecologic Costs
Cost of Corrosion as a Percentage of Gross To understand the link between MIC and environ-
National Product (GNP) or Gross Domestic ment, one has to first understand the link between
Product (GDP)1 (used with permission) corrosion and environment because without
appreciating the existence of such a link, there
Percentage will no meaning in mentioning the ecologic
of the GNP importance of MIC. First, we have to define
Country Year Cost (%)
what we mean by “corrosion effect” and “corro-
USA 1949 USD 2.1 sion impact”.2
$5.5 billion • Corrosion effects address those natural causes
West 1969 USD $6 billion 3 of corrosion that can be expressed by
Germany corrosion-related terminology and within a
UK 1971 £1365 billion 3.5 corrosion-related context.
pounds • Corrosion impacts will address those natural
Australia 1972 AUD 3.5 results of corrosion that can be expressed in a
$900 million quantitative way in terms of economical costs
and measurable ecologic/community risks.
Australia 1974 AUD 1.5
$470 million To understand the interaction between corro-
Japan 1977 USD 1.8 sion and environment, we will define two types
$9.2 billion of ecologic impacts of corrosion2:
USA 1978 USD 4.5(GDP) 1. Impacts concerning the corrosion of a partic-
$70 billion ular system in a given industry (corrosion of
Australia 1983 AUD $2 billion 1.5
system impacts [CSIs])
2. Impacts concerning use of corrosion counter-
Kuwait 1995 USD $1 billion 5.2(GDP) measures on a given system in a given industry
USA 1998 USD 3.1(GDP) (counter-corrosion impacts [CCIs])
$276 billion
As an example, although in a particular case of
Japan 1999 3.9 trillion Yen 0.77 (Uhlig),
a pipeline explosion, the effect could be stress
(Uhlig), 1.02 (Hoar)
5.3 trillion Yen corrosion cracking (SCC), the impacts could range
(Hoar) from the high cost of material and labor to serious
ecologic dimensions such as leakage of the toxic
9.7 trillion Yen 1.88 (input/
fluid in the pipeline into the surrounding environ-
(input/output) output)
ments, thus causing pollution.
One important aspect of CSIs is the algorithm
working on lowering this cost, another study on by which this impact can be evaluated. The evalu-
the cost of corrosion in Kuwait in 2011 revealed ation procedure (algorithm) for CSIs is as follows:
that this cost had been decreased to the splendid 1. A materials approach toward the system of
figure of 1.7% GDP.3 Now, if we consider that interest. In other words, what are the materials
the cost of MIC is normally 20%4 to 40%5 of from which the system has been
the total cost of corrosion, then it is easy to calcu- manufactured.
late the share of cost because of MIC in a country’s 2. Standards that have been used in
economy. Javaherdashti6 has reviewed some manufacturing and corrosion management of
examples of MIC costs in various industries and the system such as materials selection, hydro-
countries. testing, coating selection criteria, etc.
4 Biological Treatment of Microbial Corrosion

3. Possible corrosion mechanisms and scenarios a hydrant, that is to say, a fire water ring.a To eval-
that may be expected in the system of interest. uate corrosion of system impacts (CSIs) algo-
In this regard, the three factors below must be rithm, we will follow the following steps:
taken into consideration: 1. What is the material of the ring? If it is a
a. The manufacturing standards and proced- nonmetallic material such as composite ma-
ures for making the system. For instance, terials, then the risk of corrosion is highly un-
the welding or hydrotest procedures that likely. However, if it is made of a metallic
may have been applied. material such as carbon steel, then the risk of
b. Corrosion management measures, corrosion will exist. Although it is not an en-
whether the system is under cathodic gineering practice to make these rings from
protection, whether coating has been stainless steel or titanium alloys, by making
applied etc., and whether they have been these materials the manufacturing material of
applied in accordance with the standards the ring, the risk of corrosion, and MIC would
and codes. An example is that although be highly reduced.
welding may have been applied, but it has 2. If the ring has welded parts is also a question to
not been in accordance with the relevant be answered. Fire water rings neither are not
codes. short pipes nor are seamless. Therefore, they
c. The working conditions dictated by the can always be classified as welded steels. They
industry. are not internally coated nor are subjected to
4. All possible corrosion scenarios (whether hydrotesting. Therefore, the only standards
series or parallel corrosion scenarios) must be that must be taken into consideration will be
thought of and listed. codes and standards related to welding and
Although in next chapters we will explain more postwelding treatment.
3. a. Is the welding applied in the way it was
what we mean by “series” and “parallel” corrosion
supposed to be? Precommissioning in-
scenarios, it is essential to touch the basis here
spections as well as inspections applied
briefly about these two important concepts. It is
because of failures may prove to be good
because without having a sound understanding
means to answer to this question. Bear in
about the possible corrosion mechanism and/or
mind that from an ecologic-corrosion point
scenarios in a corrosion system, it is too hard (if
of view, the main guideline for the opera-
not impossible) to be able to define the possible
root cause of the failure that may have resulted tors will be “prevention” and then
“control” of the pollution.
in a leaking “incident” that, because of its environ-
b. Is the ring under any cathodic protection?
mentally destructive nature, has been turned into
Does it have any lining? Is the water treated
an “accident.”
with biocides based on a presurvey, the
Under natural, normal working conditions, it is
result of which have shown the CRB/CRAb
very rare to face with corrosion cases in a given
that may have been present in the water? Is
system where only one specific corrosion process
there a routine procedure by which pa-
is the main trouble-making issue. The point is
that there are competing corrosion possibilities rameters such as TDS (total dissolved
solids) as well as the number and type of
that because of many reasons one may appear to
the CRB and CRA are being monitored?
be the cardinal process. This will not exclude the
possibility of other corrosion processes, and there-
fore we have to take care of knowing all possible a
A more detailed corrosion management approach for a
corrosion processes that can be assumed to exist fire water ring is to be presented in Chapter 3 to explain
in the given system of interest. “Javaherdashti corrosion management model.”
Let us try to superimpose the four steps b
In the following chapters, we will explain what we
mentioned above about CSIs for a given system mean by CRB (corrosion-related bacteria) and CRA
of interest. Suppose that the system of interest is (corrosion-related Archaea).
CHAPTER 1 Why Corrosion and Particularly Microbial Corrosion Are Important? 5

c. The working conditions of the fire water are thus giving rise to CCIs (¼ countercorrosion
that it is most of the time stagnant and at impacts). For example, even seeming “green”
ambient temperatures. The flow rate of the countercorrosion practices such as cathodic pro-
water is less than 1.5 m/s most of the time. tection could have detrimental impacts on
4. There can exist several corrosion scenarios that environment.7
in essence could be under deposit corrosion Fig. 1.1 schematically describes the interrela-
caused by the differential aeration cells, tion ship between CSJs and CCIs2:
galvanic corrosion between the parent material Fig. 1.2 shows discharge of hydrotest water8 as
and the weld, and MIC. Of these corrosion reported to one of us (Javaherdashti) into the
scenarios, MIC will be the most important one open seas. The water with a darker color that is be-
that can contribute to underdeposit corrosion ing discharged from through a pipe contains CRB
as a series of corrosion scenario (by producing as well as toxic gases such as hydrogen sulfide. The
more biofilm, more anaerobic/aerobic spots water had been left as a result of hydrotest in the
may be created, leading into intensified pipe for some months. The dark water and why
underdeposit corrosion. With the same token, it had been formed is a subject of “corrosion ef-
MIC can act as a parallel corrosion scenario to fects” because to understand why the seawater
the galvanic corrosion that may be expected: that had been used as the hydrotest water had
the anode/cathode thus produced by inap- become so corrosive, one needs to know the
propriate materials and within the conductive main corrosion scenarios that govern posthydrot-
water that will be acting as an electrolyte will est corrosion and also that why MIC is the prevail-
continue to affect the seriousness of corrosion; ing one. On the other hand, as this water that
meanwhile, MIC is proceeding with its own enters into the sea does have contaminating
mechanisms). agents in it, the water is also a case of CSI: this
contamination in the discharged water could
As seen from the above, the CSIs of the fire wa-
have detrimental impacts on the ecology of the
ter ring can be evaluated in this way. The counter-
sea, even if it is local. This means that because of
measures that can be applied to control corrosion
the corrosion thus generated, an impact has
could themselves have environmental impacts,

Corrosion Effects: Corrosion Impacts:


Technical Explanations using Economical Costs and measureable
Corrosion Terminology Ecological/community Risks

CSI CCI
Environmental Impacts due to the Environmental Impacts due to anti-
corrosion of a system of interest corrosion measures

FIG. 1.1 How CSI and CCI are connected to expand the meaning of corrosion impact.
6 Biological Treatment of Microbial Corrosion

FIG. 1.2 Discharge of hydrotest water (dark water from the pipe) into the open sea (collection of
Dr. Reza Javaherdashti).

been created that has the potential of inducing How can Risks, Defined as a Function of
risks of ecologic nature to the marine ecosystem. Likelihood and Consequences, be
However, the hydrotest water also contained a Related to Microbial Corrosion?
cocktail of chemicals (corrosion inhibitors, bio- A very common source of industrial managers not
cides, oxygen scavengers) whose environmental being able to see that MIC disaster coming is to
impacts were not surveyed and studied during mix up “likelihood of MIC” with “risk of MIC”.
the time Dr. Javaherdashti was working as a corro- The main reason for this, our years of experience
sion consultant to this project. This means that the with various industries around the world, is that
hydrotest water could also have the capability for although risk is a well-known concept in HSE
being called as CCI, as we don’t know about how (health, safety, and environment), it is not a
the chemical cocktail could have had adverse im- familiar matter to corrosion professionals so
pacts on the ecology. much so that they have not been able to properly
The example shown in Fig. 1.2 can clearly show communicate this with their managers. Although
that a case could have various aspects when we accept that there can be exceptions to the
looked at from different viewpoints, and therefore rule and many of these exceptions may indeed
corrosion and environment could be tightly be too evident to deny, we can see it from the
entangled issues that it could not be easy to sepa- never-ending list of incidents that could otherwise
rate them from each other. Another example of be simply prevented or to a large extent
possible ecologic impacts of corrosion has been controlled, similar to those reported.10 To start
given elsewhere.9 Javaherdashti6 has reported with, it will be good if we look at the main struc-
cases where MIC has been identified as the main ture of a risk matrix (Fig. 1.3):
cause of the catastrophe. However, we want to There are three elements in a risk matrix that
once again emphasize on the fact that evaluation must be taken into consideration:
of ecologic aspects of corrosion especially MIC is a. The element of likelihood
a multidisciplinary task and it requires a well- b. The element of consequences
documented approach. Just reporting that such c. The element of risk classification
and such disaster happened because of MIC is
not making that use. What makes it count is to “Likelihood” is the main task of a corrosion en-
define the cause and effect and try to concentrate gineer: he has to assess if a corrosion (and for that
on corrosion effects as well as corrosion impacts matter, an MIC) hazard is nearby, and if yes, how
in these cases. close it is. Normally, one way of saying “how close
CHAPTER 1 Why Corrosion and Particularly Microbial Corrosion Are Important? 7

FIG. 1.3 How a risk matrix may look like.

the corrosion danger is” will be by applying corro- the time being it is sufficient to just say that the
sion assessment and monitoring techniques. One assumption of existing a “uniformly corroding
way of doing it is, that is, by placing a metallic environment” is not necessarily true everywhere
coupon of the same material of the system of in- and in most cases of corrosion, and particularly
terest in the actual working conditions and in the cases of MIC, the majority of corrosion
observing that how much of its initial weight morphology resembles localized corrosion in the
will be lost because of corrosion in a given time form of local miniscule holes (i.e., pitting) that
length. This method is addressed as “weight loss will later coalescent to form larger pits or even
corrosion rate assessment”. This is a mimic of cracks and by lowering the effective surface to
the actual corrosion scenarios in action and re- carry the load, the mechanical stability of the ma-
ports the output as a function of mass loss and terial will decline, leading into failure. The data
time, a measure that is reported as “corrosion from weight loss study are not of any use as indi-
rate.” To demonstrate how corrosion rate can be vidual data, it is the trend they make that will give
a useful tool in this context, we can think of a us the information we will need to make a judg-
pipeline whose thickness is, say, 2 mm. If weight ment about how a system is responding to the
loss measurements came up with a corrosion threat of corrosion. In other words, if the collec-
rate of 1 mm/year, this means that, on the tion of data points will make an ever-increasing
average, it can be expected to lose 50% of the trend, that may be the start of the end. Fig. 1.4
thickness of the pipe in 1 year and provided that will schematically show the possible situations
no rehabilitating measures are provided, the that may exist in an imaginary system of interest
whole pipe within 2 years of operation. for monitoring corrosion in it:
Although these techniques (and other tech- Although the likelihood can be measured
niques that are widely available in corrosion engi- quantitatively in the literature of corrosion as we
neering to mimic corrosion and give estimations mentioned above with the example of weigh
about the so-called “remaining life” of the struc- loss method, the consequences may be inter-
ture”) are all in use in industries nowadays, we preted as of limited knowledge to a field, corro-
have to be very cautious about their limitations sion engineer. In fact, what can be seen in
too. For instance, the assumption behind using practice is that the corrosion engineer can estimate
coupons in weight loss studies is that the corrosive the immediate outcome of a potential corrosion
environment will be corroding the material in a hazard such as leakage from a pipe that may cause
uniform manner (uniform corrosion) rather production delay or even explosion. The assess-
than accelerating corrosion at one spot (localized ment of the aftermath issues, that is, the extent
corrosion). We will briefly explain uniform and of CSIs, often remains uncategorized and non-
localized corrosion in the next chapter but for quantified to a corrosion engineer working in a
8 Biological Treatment of Microbial Corrosion

clear understanding of these consequences (both


CSI and CCI impacts), although a corrosion has
done his job as a corrosion engineer, as a member
of the greater society of people living in a commu-
nity, he has an unfinished business. The readers of
this book should not think that in the developed
countries, all measures against CSI and CCI are
taken. This is largely true but not the whole pic-
ture. We are mainly concerned about the
decision-making minds and positions that are
only busy with keeping their production high no
FIG. 1.4 Two imaginary corrosion rates vs. time for a
weightless assessment pattern: the dashed line matter the cost (Fig. 1.5).
shows that during the test duration, corrosion is The risk, as we mentioned earlier, is how the
almost predictable within a certain fluctuating margin; likelihood and the consequences factors intercon-
however, the bold line shows that the corrosion rate is nect and act. In other words, a high risk may be a
ever increasing. What is to be seen here is that in both product of an unlikely likelihood and a very major
cases, it is not the absolute values of corrosion rate consequence. An in-depth survey of the causes of
but the trend they make that is of importance. many MIC-related disasters can show us that the
risk and the likelihood had been mixed up and
refinery or a power plant. Not that this particular that resulted in the problem. This mix-up can
individual is not concerned about the possible take various shapes, for example, just because bio-
impacts on the environment that a corrosion cides had been applied or just because corrosion
effect may cause, but that simply it has not been monitoring has not resulted in any particular
defined for him. “sudden change,” it is assumed that corrosion in
We don’t want to spend too much time on the the form of MIC does not exist. Here we want to
consequences of corrosion (and for that matter, explain a firsthand experience that one of us
MIC) here, but we have to advise that without a (Javaherdashti) had in one of his site visits to a

FIG. 1.5 We don’t want such mentalities and mind-sets. We are sure that not only within this
company but also other internationally reputable companies there are strict rules and policies to
take care of our environment, but considering that a pill could be the direct result of corrosion
(corrosion effect) and could have various, detrimental impacts (CSI), it is necessary to consider
corrosion and its risk very seriously. (Source: http://www.vancouversun.com/./KinderþMor./
9793673/story.html.)
CHAPTER 1 Why Corrosion and Particularly Microbial Corrosion Are Important? 9

very reputable petrochemical complex: when we serious issues and aftermath none of which was
were called to this complex, the operators were taken seriously by the top management until a
only concerned about the leakages they were get- serious problem arises.
ting in their fire water (hydrant) systems. As a mat- In the next chapter, we will talk about corro-
ter of fact, they did have such leakages and we did sion as much as required to understand the mech-
observe them. We also noticed that the complex anisms of MIC.
was using wet cooling towers to cool off the steam
later to be used for electricity generation. We
asked if they have had any MIC problem with REFERENCES
this water and their answer was negative. When 1. Hou B, Li X, Ma X, et al. The Cost of Corrosion
we insisted on understanding why they are of in China. www.nature.com/npjmatdeg. Published
on-line, 25 July 2017.
this opinion, they replied that they had an MIC
2. Javaherdashti R, Nikraz H. A Global Warning on
monitoring system in place for monitoring the
Corrosions and Environment: A New Look at Existing
likelihood of MIC in their cooling towers. The Technical and Managerial Strategies and Tactics.
monitoring system was in essence consisting of a Germany: VDM; 2010.
series of glass loops within which there were car- 3. Koch G, Varney J, Thompson N, Moghissi O,
bon steel coupons. The loops were filled with Gould M, Payer J. International Measures of Preven-
the water that was coming from the towers, and tion, Application, and Economics of Corrosion Technol-
the assumption was that if the water is contami- ogies Studies (IMPACT). USA: NACE International;
nated with the CRB, then biofilm must be March 2016.
observed on the coupons. The assumption did 4. Flemming H-C. In: Heitz E, Flemming H-C,
sound right though. The issue was that they had Sand W, eds. Economical and Technical Overview in
Microbially Influenced Corrosion of Materials. Berlin,
not been observing any biofilm of considerable
Heidelberg, Germany: Springer-Verlag; 1996.
size formed. Therefore, they were assuming that
5. Parthipan P, Narenkumar J, Elumalai P, et al. Neem
no seeing biofilm on their coupons was a good extract as a green inhibitor for microbiologically
reason to assume that no MIC threat (risk) of influenced corrosion of carbon steel API 5LX in a
considerable value was present. We also have hypersaline environments. J Mol Liq. 2017;240:
to mention that although the company that 121e127.
had made and installed the monitoring system 6. Javaherdashti R, Nwaoha C, Tan H. Corrosion and
had advised the operators to remove the cou- Materials in Oil and Gas Industries. USA: CRC
pons every 45 days, because of production sched- Press/Taylor&Francis; 2013.
ules, the production management was only 7. Rousseau C, Baraud F, Leleyter L, Gil O. Cathodic
allowing them to do the monitoring period for protection by zinc sacrificial anodes: impact on ma-
rine sediment metallic contamination. J Hazard
3 weeks (!) and not 45 days. When these opera-
Mater. 2009;167:953e958.
tors tool an MIC workshop, they realized a simple
8. Javaherdashti R, Akvan F. Hydrostatic Testing, Corrosion,
yet detrimental error in their MIC monitoring and Microbiologically Influenced Corrosion a Field Manual
procedure: they were installing the coupons on for Control and Prevention. USA: CRC Press; 2017.
a vertical position instead of a horizontal posi- 9. https://www.linkedin.com/pulse/note-link-between-
tion! By a vertically positioned coupon, the grav- corrosion-management-environment-reza-javaher
itation force will be one of the major factors not dashti.
allowing any deposit, let alone biofilm, form. As 10. Kletz T. What Went Wrong? Case Histories of Process
seen here, the assessment of the risk based on Plant Disasters. 4th ed. Gulf Professional Publish-
wrong likelihood calculations could have very ing; 1999.
CHAPTER 2

A Brief Introduction to Corrosion


Engineering

INTRODUCTION electrochemically. As we will see in the next sec-


In this chapter, we will briefly introduce the tions of this chapter, electrochemical corrosion
fundamental concepts that are necessary to does need some underlying elements to be pre-
understand electrochemical corrosion, which is sent for it to happen. One of these elements is
the basis of any corrosion studies required for having a conductive path for the flow of elec-
studying MIC. trons. None of the nonmetals we named above
do have such criteria. In fact, because of their
very electronic structure, no electron flow of the
THE THERMODYNAMICS OF same we observe in metals can be thought of
CORROSION AND ITS IMPORTANCE IN for nonmetals.
DEALING WITH IT IN INDUSTRIES Therefore, nonmetals do not corrode simply
The very word “corrosion” comes from a Latin because they cannot. They degrade and deteriorate
word that originally means “bitten away.” In that if we really want to distinguish it from
many other languages, the terminology used to electrochemical corrosion, deterioration and
address corrosion is either a “dialect alteration” degradation are rather physical processes in which
of the English word (e.g., corrosion in Spanish) no electron/ion exchange can be expected.
or even if equivalents are used (e.g., in Persian Corrosion is important not just with regard to
or in Arabic ), they both would bring the what we already mentioned in the “Introduction”
same concept to their readers: bitten away. chapter but in the sense that it is, to a large
There are a few confusions about corrosion. extent, “unavoidable” but “controllable.” In
These confusions do not just come from the this chapter, we will deal with two main ques-
electrochemistry involved but even in daily tions: why is corrosion unavoidable and why it
addressing of the terminology these confusions is controllable.
arise. Two of very famous of these confusions The story of corrosion starts with the way that
are about rusting and corrosion of nonmetals. civilization started to know the use of metals.
Many peopledeven professional engineersd Metals are all “hidden” in their ores. One has to
mistake corrosion with rusting: in fact, all types find a way to take them out or, more scientifically
of rusting are corrosion but not all types of corro- speaking, extract them. But have we ever
sion are rusting. In more precise terms, if ferrous wondered why it is so?
alloys (for instance, steels) undergo corrosion, Metals, like any other material, have been
we can call it an example of rusting. It is more composed of atoms. These atoms have certain
accurate if we say copper or aluminum corrodes number of electrons that will make them,
and not rusts. altogether, being iron, copper, silver, or any other
The second confusion in addressing non- metal. Under normal conditions, these atoms are
metals and their so-called “corrosion” is a little all at minimum level of energy. In other words,
bit more confusing. Nonmetals such as polymers, they are at rest within their ores. That is why you
concrete, glass, composites, and the like cannot will never see or expect metals to “ooze out”
corrode. Or better to say, they cannot corrode from their ores. We have to apply energy to extract
Biological Treatment of Microbial Corrosion. https://doi.org/10.1016/B978-0-12-816108-1.00002-1
Copyright © 2019 Elsevier Inc. All rights reserved. 11
12 Biological Treatment of Microbial Corrosion

FIG. 2.1 The life cycle of iron from birth (extracted from its ore) to death (Corrosion).

them. When we do take them out from their 2. However, we can find ways to slow down
“comfort zone,” we are in fact putting more corrosion or control it. In other words, we can
energy to them and make them unrest by provide the conditions by which the process of
injection of electrons during extractive metallurgy “electron throw out” gets slower. We can
processes (Fig. 2.1). actually slow down corrosion by such magni-
The cycle, as shown in Fig. 2.1, is self- tude that, from a practical point of view, it will
explanatory: the metal is extracted; during the get many years to survive. This is the reason we
extractive metallurgy processes; it receives extra say corrosion is “controllable.”
electrons, and therefore, its excitation level, i.e., We would like to expand and explain the
Gibbs free energy, is highly increased. The net result importance of the two points we mentioned
is that to retain to its original low energy level, the above in more detail.
metal starts to, literally speaking, throw away these 1. Regarding the point that corrosion cannot
extra electrons. This process, otherwise being called stop: we know from many encounters we
corrosion, helps metal to reduce its excitation level have been having with industry that unless
and get back to its original low-excitation level. the client is well educated about
However, this will have its own toll on the metal the thermodynamics involved in corrosion, as
too: the metal will notdfrom an engineering point soon as they hear that you cannot stop
of viewdthe original material but rather deposits corrosion, they would take as a clear sign of
that in essence are the same as what was originally your inability and noncompetence and would
embracing the metal in its ore: the metal will turn disqualify you as a corrosion consultant. It is
into red rust (iron hydroxide) or black rust (iron comprehended that one cannot bend the truth
sulfide) or iron carbonate, etc. These all were the for the sake of getting a job; however, the harsh
companions of the metal when it was still “not reality out thered in many cases out, there is
born” and was in its ore. as we just pictured. Corrosion can be brought
The importance of understanding this process under control, but even this will not guarantee
has at least two advantages: that without a continuous maintenance and
1. There is no way to stop corrosion. It is because monitoring, corrosion would be defeated.
corrosion is a thermodynamically favorable However, maintenance and inspection are not
process. In other words, as long as we extract necessarily the same things: inspection must be
metals out of their ores, we have to also accept an ongoing, continuous procedure, whereas
that corrosion is “unavoidable.” maintenance is an intermittent action in time,
CHAPTER 2 A Brief Introduction to Corrosion Engineering 13

FIG. 2.2 Schematic representation between the asset’s states (FSS, pseudo-FSS, and
Zugzwang effect state) with maintenance and inspection. Black dot presents FSS, whereas red
and blue dots present pseudo-FSS and Zugzwang effect states (not to scale).

equating it with repair. It is quite imaginable Fig. 2.2. Fig. 2.3 shows an example of an asset
for a corrosion engineer to be engaged in that has arrived at Zugzwang effect state:
inspection all the time but when the situation Fig. 2.2 simply emphasizes upon the fact that
becomes critical gets involved in maintenance. the longer an equipment/asset remains in
If an asset is its ideal form of workability action/service; it will need more maintenance
(workworthy or fit-for-service ¼ FFS), it will and more frequently inspection.
not need any repairmen activity; however, it 2. Slowing down corrosion: This is a very impor-
will still need inspection because as soon as it tant issue because as long as we know no stop
arrives into service, it will be exposed to wear to corrosion can be achieved, the only alterna-
and tear and corrosion. This deviation from tive will be finding effective means to decelerate
FFS state, which we call pseudo-FFS, will still it. A very important issue here, however, is
allow using the equipment, but this time the to distinguish between corrosion control,
vulnerability of the asset will obviously corrosion prevention, and corrosion stop.
increase. This will enhance the likelihood for a. When an asset is put into service and is
maintenance that can be done at prearranged being used, we face with an issue that is
schedules, but yet inspection will keep its already done and little can we do about it.
continuous need for applying. This procedure In other words, when we are facing with
will continue until the equipment, if not being corrosion in a plant that has been going for
inspected and maintenance is not being some years since its establishment, it means
properly done, will develop shutdown periods that we are dealing with equipment that
(nonscheduled overhauls) and will arrive at a have been designed and manufactured and
state that we call as “Zugzwang effect” state: at the manuals that have been given to run
this state, either it is economically not feasible those equipment. We cannot just pop in
to conduct repairs or even if repairs are being and say that to manage corrosion, it is
made, as long as the root cause of failures has necessary for the operators to change or
not been recognized, overall well-being of the modify the process parameters
asset is always under question. These states (design, process temperature, process
and their relationship to inspection and pressure, process chemistry (for instance,
maintenance can schematically be shown as in the designed pH), materials). By changing
14 Biological Treatment of Microbial Corrosion

preestablished conditions, the only way by


which corrosion can be managed will be
controlling corrosion by applying the
known procedures, standards, and the like.
For instance, although the pH of the pro-
cess is designated at, say 4dwhich based
on corrosion potential may be leading to
corrosive conditions (consult with the
related Pourbaix diagram)dwe can still
use addition of corrosion inhibitors or
applying specific coatings or even go for
materials selection (provided that it will be
justified) without trying to change the pH
of the process. Corrosion control strategies
will suit equipment and assets at plants,
which have been running for some years,
in other words, a brownfield project.
b. Corrosion prevention, however, is another
story: it can be applied into a Greenfield
project. When a plant is still at design stage
and perhaps early stages of construction, it
is possible to design and apply strategies
with the general aim of preventing corro-
sion. Here what we mean by corrosion
prevention is to reduce corrosion rates to
such low values that practically they can be
FIG. 2.3 An example of Zugzwang effect on a
taken as almost-zero rates. It is at this stage
concrete wall. This wall was part of a cooling tower
structure that was directly facing the salt spray from that by applying proper plans and
seaside. The concrete has been damaged very badly. In precautions, corrosion prevention may
this figure, most probably two parallel corrosion become possible. Examples of such
processes have started the deterioration process: the precautions may be as follows: performing
salt spray has affected the integrity of the concrete, hydrotest in such a way that will not be
whereas the moisture ingress has caused corrosion of leading into posthydrotest corrosion
the steel bar. The steel bar has gone through rusting so (MIC), conducting preferring OPEX (oper-
that the corrosion products thus produced have ation cost) over CAPEX (Capital expenses)
mechanically damaged the concrete layer, therefore when it comes to corrosion prevention,
letting more moisture and salt ingress and consequently
giving care not to have too many dead legs
further deterioration. The asset is in Zugzwang effect
and zones in pipelines, emphasizing upon
state because any applied repair is doomed to fall off as
long as no solution for the salt spray and moisture flow speed rate rather than flow volume
ingress has been thought about as a root cause solution. rate (in other words, to have meter per
(From Dr. Reza Javaherdashti Collection.) second values for the fluid in parallel to
having liters per second), and the like.
Corrosion prevention is the main step in
each (let alone all) of these process pa- dealing with corrosion from a practical
rameters, chances are that the whole pro- point of view for making corrosion rates
cess would be affected (probably adversely) almost-zero. For corrosion control, corro-
just to manage corrosion. No manager sion rates are to be always lower
would buy that. However, under these than certain KPIs set by standards and
CHAPTER 2 A Brief Introduction to Corrosion Engineering 15

regulations, whereas for corrosion preven- be called the “cathode.” This simple description
tion, those standard values are almost should not confuse our readers that the electrons
automatically achieved. that leave the anode will “swim away” from it
c. Corrosion stop is an imaginary, ideal state of and find their rescue on the cathode. In fact, these
the service life of the asset in which the corro- electrons will need a metallic path to be able to
sion rates are indeed zero. As we mentioned reach the cathode, and this metallic path is the
earlier about the thermodynamics involved metal surface itself. The ions that are produced
in corrosion, achieving corrosion stop is via anodic reactions (that is, the reactions that
thermodynamically impossible and there- will give off electrons) and cathodic reactions
fore it can only be taken as a fantasy. (electron-gaining reactions) as a result of electron
In the following section, we will explain some release and gain will be traveling through the
technicalities related to corrosion with more water (that we will refer to it as electrolyte).
details. From the above, it may follow the following:
1. For corrosion to start, one has to have at least two
SOME BASIC CONCEPTS OF metals, which are in contact via the electrolyte
CORROSION 2. These metals must be in such a way arranged to
Our main focus here will be on electrochemical sit that will have different potentials (capabil-
corrosion. The main reasons for focusing on ities for losing and gaining electrons)
electrochemical corrosion are as follows: 3. During corrosion process, the electrons lost by
1. The main medium in which electrochemical the anode will be traveling to the cathode via a
corrosion takes place is water. metallic path, whereas the ions thus produced
2. Water is also the essential medium for bacteria (positively charged ions ¼ cations, and nega-
to live in and survive. tively charged ions ¼ anions) will be traveling
Therefore, if there is no water, one can safely via the electrolyte toward cathode and anode,
assume that neither electrochemical corrosion respectively.
nor microbial corrosion would bother anybody! The process is simply shown in Fig. 2.4.
The reality, however, is that as long as we are However, from the above, we can also
living on the earth, there is no way to exclude conclude the following:
water. This water can either be an essential part a. Without an electrolyte or a metallic path, no
of a process (e.g., water and waste water treat- corrosion is expected to happen.
ment) or production-support system (cooling b. Corrosion cannot take place on nonmetals.
systems) or entrained water that is normally Conclusion (a) is obvious: if we omit either
found with fluids such as oil and gas and at electrolyte or the metallic path, the circuit will be
low-lying points of pipelines will be collected to incomplete. In other ways, there will be no travel
form small-size ponds. path for electrons and ions. This will explain why
Therefore, from now on, in this book, when it is essential to do “coating”dwe will get back to
we use the term “corrosion,” we will mean it later in this chapter. Conclusion (b) is even
“electrochemical corrosion” unless advised. more critical: it explains that plastics, composites,
and the like do not corrode. Their failure mecha-
ESSENTIALITIES FOR CORROSION nism, whatever it is and we will not focus on it
Simply put, when metals of different characteris- here, cannot be referred to as corrosion simply
tics (such as, but not limited to, their ease of because no electron exchange can be expected to
release or gain electrons) are brought together in take place even if there can exist an electrolyte.
a watery medium, the metal higher tendency for Also, as the careful readers have noticed in
losing electrons will start to corrode. This metal Fig. 2.4, the way we have described the essential-
is scientifically and technically referred to as the ities of corrosion differs somewhat from what
“anode.” Its counterpart at the other end of that can be found in classical corrosion and
the system that will receive these electrons will electrochemistry books. In these books, four
16 Biological Treatment of Microbial Corrosion

FIG. 2.5 An example of series corrosion processes.

FIG. 2.4 Essentialities of corrosion in terms of


electrodes (anode/cathode) and the electrolyte (the A COMBINATION OF A CONCRETE SLAB
ion transfer medium). AND A STEEL ROD
Assume that a steel rod has been placed inside a
concrete slab. The concrete is not healthy in the
sense that it has developed several pores and
elements are described to sustain a corrosion
cracks of different sizes and orientations. In this
process: anode, cathode, electrolyte, and a
example, if water ingress takes place through the
metallic path. We have omitted the condition
pores and cracks on the slab, this will reach
for a metallic path as in our understanding of
into the inner section of the rod, thus rusting it.
real life conditions under which corrosion occurs
Obviously, the more the water ingress takes place,
that it does occur when a metallic path is
the higher the likelihood for the inner part of the
available. Thus, we see no need to reemphasize
rod inside the slab to corrode. Why do we call it an
upon an evident fact!
example of a series corrosion process? The rusting
of the rod is being enhanced by the water ingress
“SERIES” AND “PARALLEL” through the concrete pores. In other words, if
CORROSION PROCESS PATTERNS deterioration of concrete that has resulted in the
We may remember from our high school physics formation of the cracks is stopped (so that no
about how we can have two combinations of pores and cracks are developed), then the rusting
electric circuits and how they would affect the of the inner section of the rod will also be stopped.
total output current as well as the resistance. A practical use of formulating the situation as such
Those combinations were “parallel” and “series” is that instead of focusing on the rusting of the rod
combinations. We can use those in our discussion per se and trying to find a solution for it, it is
too. advised to find a solution to control the pores in
It is possible that sometimes two or more the concrete slab via mitigation of the concrete
corrosion processes happen to occur in such a deterioration.
way that they may enhance each other. This is Now assume that we have done no special
what we refer to as “series corrosion processes.” treatment on the slab yet so that it still developing
An example is as shown in Fig. 2.5: pores and cracks in it. However, we have coated
CHAPTER 2 A Brief Introduction to Corrosion Engineering 17

the inner section of the rod with a material, which HOW IS CORROSION TREATED?
is resistant to corrosion; for example, we have Naturally, a big concern for those industries
wrapped a polymer around it so that it will not involved in dealing with corrosion is how to reduce
allow the water that has been engrossed via the its detrimental effects. Over the years, many strate-
pores and cracks on the slab surface to reach on gies and tactics have been developed that can be
the surface of the steel rod inside the slab. generally categorized as electrical measures,
Obviously, this will solve the problem of corro- physical barriers measures, chemical measures, as
sion of the rod inside the slab. Yet, there is another well as materials and design measures. In other
scenario, which is going on in “parallel”: the up- words, in fact, it is possible to categorize these
per section of the rod is still exposed to atmo- measures as the main methods by which corrosion
sphere and this will make it even easier for to can be controlled (remember, corrosion cannot be
corrode. In this situation, the corrosion of the outer stopped because of its thermodynamical nature; it
section of the rod and the deterioration of the con- can only be controlled):
crete slab are two corrosion/deterioration processes 1. Application of cathodic protection (CP) and to
that do not depend on each other, and therefore, a lesser extent anodic protection (AP) methods
they happen independently, an example of “paral- 2. Materials Selection
lel corrosion processes.” The practical moral of the 3. Application of coatings
story is that if you cure and fix the deterioration 4. Design factor
problem of the concrete slab, you cannot expect it 5. Chemical treatment
to have any effect of the corrosion of the outer Although CP and AP are electrical measures,
section of the rod and vice versa. application of coatings can be regarded as creating
Understanding different corrosion scenarios as physical measures against corrosion (removing
such could be of great help: the possible galvanic contact between electrolyte and anode/cathode as
interaction between the iron sulfide film well as physically separating anode and cathode
produced by sulfate-reducing bacteria and overall from each other so that anode and cathode will
MIC thus occurring can be taken as an example of not “see” each other). Likewise, application of
series corrosion processes (the more the FeS chemicals such as corrosion inhibitors, biocides,
produced by SRB, the more intense the galvanic and the like is an example of chemical treatment.
corrosion effect). Another example could be the We will discuss materials selection and design
link between the number of acid-producing factor in required length in the following sections.
bacteria and the overall corrosion rate: the higher There are two points here that are worth of be-
the number of APB, the higher the expected ing considered: the first point is that based on the
corrosion rates. An example of parallel corrosion complexity of the corrosion system (the system in
processes with MIC is that in the same petrochem- which corrosion is occurring), it may be required
ical complex, the fire water ring and cooling tower to use all of the abovementioned five corrosion
of the base load power plant of the complex both management measures. For instance, for a buried
corrode via MIC but have no dependence on each pipeline, to cover for its external corrosion (that
other. occurs due to its exposure to the soil environment),
The immediate results for treatment strategies both CP and coating will be applied. To manage
as in given examples above are stop MIC to stop the issues of internal corrosion, chemical treatment
the galvanic effect and in the petrochemical application is a must. Also, based on the severity of
complex spend budget on the management of corrosion and cost justifications, it may be possible
MIC in both the units separately. Understanding to change the material of the pipe (this could, for
corrosion as such will decrease a lot of unneces- example, be switching from carbon steel to
sary expenditures of financial as well as man composite or polymeric materials). Design factor
power resources. is also very important in the sense that potential
18 Biological Treatment of Microbial Corrosion

Therefore, what we will discuss here is a short


introduction to each of the five factors above
without trying to go through the details. The
reason is, obviously, that our readers should
Elevation (m)

expect this chapter and the next chapter (microbial


corrosion) to be only taken as introductions to
corrosion and microbial corrosions precise enough
to understand the significance of why biological
biocidal treatment of microbial corrosion is
necessary.
Distance (Km)
APPLICATION OF CATHODIC
FIG. 2.6 A typical (subsea) pipeline topography PROTECTION METHODS
scheme where elevation is recorded as a function of To understand CP, it is necessary to get back to the
distance from a given fixed point (e.g., a pumping
basics of corrosion, anodic and cathodic reactions.
house). (Photo: from Dr. R. Javaherdashti collection.)
We said earlier that it is via losing electrons by
anodic reactions and receiving them by cathodic
for microbial corrosion will increase if the pipe reactions that corrosion current is created. In other
happens to have “too many” branches such that words, if electrons cannot be lost or, alternatively,
likelihood of fluid stagnation would increase. Yet can be fed back to the reaction, then theoretically
another factor that may be related to increasing no corrosion can be expected. The first possibility,
the likelihood of corrosion (in both microbial that is, not losing electrons, is impossible. The
and nonmicrobial forms) is the topography of reason is that because of the thermodynamics of
pipeline laying (Fig. 2.6): corrosion, metals in their fabricated forms, which,
As it can be seen in Fig. 2.6, pipelines in reality by the way, is how we use them in our everyday
are not laid up on straight lines: they pass over lives, cannot stop losing electrons. However, the
hills and have their own topographical ups and other way round is possible: if we feed the lost
downs. Although it may not seem directly linked electrons back to their ions so that they can again
with what we may have in mind from design, become atoms, then no corrosion will happen in
topographical situation of a given pipeline can essence. This “giving back the electrons” is the
intensively increase the likelihood of corrosion basic rule applied in CP practices. The electron
(especially in the form of internal corrosion). In give-back can be done via two methods: injecting
Fig. 2.6, low points of the topographical map electrons from an outside source (for example,
where, owing to low elevations, the line will face a rectifier) or letting another metal, which in com-
points where fluid stagnation becomes quite likely parison with our main structures to be protected is
are also the points at which the risk of both of less value, corrode faster. In the latter case, what
microbial corrosion and nonmicrobial corrosion happens is that by letting the other metal corrode,
(that is, purely electrochemical corrosion that an extra source of electrons is produced so that the
does not involve direct or indirect involvement of required pool of electrons, which will be necessary
corrosion-related bacteria and archaea) will highly to let the “electron give-back process” complete,
increase. will be provided (Fig. 2.7).
We would like to once again remind the reader Fig. 2.8 shows an example of CP by sacrificial
that the main topic of this book is corrosion as anode in practice; in this figure, the same steel
related to living organism, that is to say microbial bar has been put into the same corrosive environ-
corrosion, and one of the ways by which microbial ments (salt water simulating sea water) at the
corrosion can be addressed is by application of same time. The main difference is that in the
certain chemicals, including biological biocides left-hand side jar, there is a sacrificial anode
(to be discussed briefly later in this chapter). attached to the rebar, whereas the right-hand
CHAPTER 2 A Brief Introduction to Corrosion Engineering 19

FIG. 2.7 A schematic summary of what cathodic protection in essence is and its different two
methods of application.

FIG. 2.8 The story of two jars!, the left-hand side with CP and the right-hand side without CP.
Except sacrificial anode CP, all other conditions for the two jars are identical.

side jar does not have it. As clearly seen from the subjected to further (physical) metallurgical
figure, the jar with CP has remained pristine, processes. In these processes, it is tried to induce
whereas the one without it has already corroded various chemical and mechanical properties into
(¼rusted) and therefore will soon be losing its the same metal to make several types of alloys
mechanical integrity. out of it. For example, by increasing the carbon
content of “iron,” you will come up with cast
MATERIALS SELECTION iron, whereas by decreasing its content, you will
What is actually meant by material selection is in get steel, also known as plain carbon steel. Now
fact the measures by which a material (alloy) is if we add up “some” chromium and molybdenum
preferred over another one. After metals are into it, you will get the so-called stainless steel.
extracted from their “nonmetallic shell,” they are By increasing chromium content, you will get
20 Biological Treatment of Microbial Corrosion

different classes of stainless steels, such as stainless wrong angle of impact to the internal wall of the
steel 304, stainless steel 316, stainless steel 2205, pipe that was actually acting as a hammer, eroding
and so on. But the “art” does not stop here! You away bits and pieces of the pipe with itself.
can reduce the carbon content in stainless steel
316 and this time you will get 316L (L designated
that it has low carbon). The possibilities could be APPLICATION OF COATINGS
endless. However, in addition to the physical, Getting back again to the basics of electrochemical
mechanical, and chemical properties of a material corrosion, as seen from Fig. 2.2, the main three
that can make it a good choice, there is also factors in sustaining any electrochemical corrosion
the importance of the cost (CAPEX¼capital process are anode, cathode, and electrolyte.
expenses). A certain material (e.g., titanium) can Therefore, if by any means we can prevent these
certainly have superior properties materials-wise threedor at least one of themdfrom “seeing”
over any type of stainless steel; however, costwise each other, then corrosion is expected to be
titanium is a very expensive material. Thus unless controlled/stopped. This is the main feature of
we have to, we prefer not to use titanium. This is a coatings: they prevent the electrolyte from seeing
very important factor in the selection of thee right either electrodes (i.e., anode and cathode) as well
material. It is so important that a good number as each electrode from seeing the other one.
of corrosion failures happen because of wrong For coating to act as required, it must be
materials selection just because the material to intact and must also have no scratches or holes
be selected was simply “more expensive” and (holiday-free coatings). This is important because
therefore the contractor would choose the less otherwise corrosion will be enhanced at the
expensive option. holidays and discontinuities. This can be schemat-
Another example could also be the wrong ically represented in Fig. 2.9.
combination of right materials. In other words, As seen from Fig. 2.9, when the material has
while the materials selected for the intended coating, it has the least corrosion rate (the speed
service could be suitable regarding their corrosion at which corrosion happens is the minimum).
resistance, their combination could be disastrous: When it has no coating, it goes through corrosion
a major petrochemical operator in one of the but by time, the corrosion products are
major players of petrochemical products countries accumulated and they themselves act as coating,
in the Middle East experienced a bitter corrosion- thus reducing corrosion. However, if it has a
related catastrophe in their plant in August 2010 damaged coating, then it will experience the high-
that, in addition to the plant being out of service est corrosion rates although again because of the
for at least 50 days, also cost the lives of five of accumulation effect of corrosion products, the
the personnel. corrosion rate will drop eventually. These labora-
In addition to careless operation, not observing tory findings clearly show that if it were in a
standards, and other factors, the pipe whose natural system where the corrosion products
rupture resulted in the disaster was in fact a big could have been washed off from the surface
“battery” sold to this petrochemical unit. The and therefore new, fresh surfaces could have
pipe itself was made from stainless steel, whereas been exposed to the corrosive environment, then
the rings around it to keep it secure were all much higher corrosion rates than either coated
carbon steel. This combination of dissimilar or uncoated surfaces could have been expected
metals creates a dangerous combination known from a damaged coated material.
as “galvanic corrosion.” Our reader must be reminded, however early
The pipe also had a corrosion-enhancing yet, that the accumulation of bacterial cells,
mechanism in addition to having another corro- otherwise known as biofilm, can actually act like
sion mechanism that was operative from inside: a damaged coating: this is why they are entitled
the fluid inside had been flowing with such a to accelerate corrosion in most cases.
CHAPTER 2 A Brief Introduction to Corrosion Engineering 21

Corrosion rate 2
(mg/dm^2)
1.8

1.6

1.4

1.2

1
Uncoated 0.8

0.6
Coated
0.4

Scrached 0.2
Coating
0
24 48 72 96
Time(h)

FIG. 2.9 (Left) Corrosion rates of coated, uncoated, and coating with damage of carbon steel
coupons in simulated seawater. (Right) The damaged paint on a metallic bridge column,
progressive corrosion due to damaged coating (paint), has severed corrosion. (Both figures from
Dr. R.Javaherdashti Collection.)

DESIGN FACTOR with a composite one. By eliminating the anode,


Design factor is the only anticorrosion measure no corrosion ever happened again. Figures below
that, instead of using a technology (electrical for also show some examples of design factor in
CP, metallurgical for material selection, chemical accelerating or increasing the likelihood of corro-
for coating and chemical treatment), uses no sion. It is a very important factor in controlling
particular technology. It is relying on the fact that corrosion from the start. In fact, if there is any
certain geometries and/or practices can enhance measure that can be designated as “corrosion
corrosion, and thus by applying a simple change, preventive,” it is the design factor.
one can easily get rid of the costs and risks Fig. 2.10 shows two examples where the design
involved. Reminding our readers of galvanic factor has been neglected. Most of the time, it is
corrosion that, among other factors, can also this negligence that can result in very serious
happen because of dissimilar metals being coupled corrosion and leakage issues. In industry, the
together, we want to give a case history here. important role of design and its significant role
In a power plant, the valve on a stainless steel in the prevention of corrosion is not taken as
pipe had been made of carbon steel. The dissimilar serious as it should. In the upper picture of
metals also had the small anode/large cathode Fig. 2.10, it can be seen that the applied paint
ratio combination, leading into the valve being has been so poorly applied that it has added
extensively corroded and being replaced almost more corrosion issues to the pipe, which is already
every 2 months or so. The design from the begin- being corroded at the place of pipe supports. The
ning was not right, so to fix the problem what picture below can easily pose a risk should any
engineers did was to replace the carbon steel valve issue beyond expectation happens; for example,
22 Biological Treatment of Microbial Corrosion

be faced with resistance from operators that would


change the design thoroughly.

CHEMICAL TREATMENT
Chemical treatment of corrosion is a very wide-
spread way of treatment. In fact, whereas in oil
and gas industries it is quite common to see corro-
sion control measures such as CP, coating, mate-
rials selection as well as chemical treatment, in
thermal power plants, for example, it is chemical
treatment that can be taken as the most frequent
way of treatment of corrosion (CP is not used in
main power plants equipment). In addition,
chemical treatment is one of the corrosion treat-
ment options that has a considerable market size
worldwide. Not only is this market including oil
and gas, but also power plants, water treatment
plants, and the like. The relative size of the world
corrosion inhibitor market is seen in Fig. 2.11.
This figure clearly shows that the main players
such as North America, China, and Western
FIG. 2.10 (Above) In addition to poor quality of the Europe are the main sectors in which these
paint, corrosion has started from where the pipe is chemicals are applied.
sitting on its support. With a simple design of the Corrosion inhibitors are those chemicals that
support, this corrosion could have been prevented. affect anodic, cathodic, or both types of reactions
(Below) The welds are not continuous; therefore, a in such a way that the overall corrosion rate is
nonstandard spot welding has been applied. lowered considerably. This in turn would affect
Corrosion has already started at one of the spots. the severity of corrosion should either or both
reactions control the rate of corrosion. In addition
to inhibitors, there are other chemicals that can
if the internal pressure of the vessel shown in the also serve to control corrosion. These have been
picture suddenly increases, the spot welds may schematically shown in Fig. 2.12. Just briefly
not be expected to resist in a feasible way. Also, it
South Japan
is seen in the picture that signs of corrosion have
America
already started at one of the spot welds. Africa/
A rather “worrying” aspect of design factor may Middle East North
appear when corrosion control becomes a require- America
ment: in an already-established plant, it is almost Central/Eastern
impossible to think of adding or removing a Europe
process parameter such as design. This is despite
the fact that, in practice, many industries do Other Asia/
Oceania
apply rather small modifications to their already-
established assets. These small modifications do
not count as they are not meant to change the China
Western
overall design. In Fig. 2.2 (the below figure), chang- Europe
ing welding into continuous welding does not
FIG. 2.11 World consumption of corrosion inhibitors
affect the overall design of the part that is being
in 2008. (After P.Rajeev, A.O. Surendranathan,
used in the process. Those design factors would Ch.S.N. Murthy-2012, used with permission.)
CHAPTER 2 A Brief Introduction to Corrosion Engineering 23

FIG. 2.12 Classification of chemical treatment methods applicable to corrosion cases.

said, we would like to say that the way oxygen any reason there is a leakage of the fluid from
scavengers serve to control corrosion is by within the pipe outside, then the biocide leaked
excluding it from the system. Let us not forget into the nearby ecology has actually been itself a
that oxygen will act as a cathodic reaction part of the natural environment once. This
facilitator so that if it is removed, even if electrons would mean that in the event of leakage, much
are liberated, there will be no reception site for less harmful chemicals than synthetic biocides
them. Thus, the whole issue of corrosion will would have contaminated into the environment.
collapse. However, as long as microbial corrosion As per the main topic of this book, we will
is concerned, it is the chemicals collectively study biocides in detail. In the second section of
known as “biocide”dliterally meaning, killer of this book, biological biocides (bacteria against
the living thingdthat can help controlling the bacteria) will be discussed. It is, however,
severity of microbial corrosion. As seen from very important to note that to understand why
the figure, in a rough yet right-to-the-point way, biocides are useful, we have to know for what
biocides can be divided into three categories: mechanism of corrosion they are applicable.
the so-called “green” biocides that are environ- This means that without a knowledge about
mentally friendly and made up of formulations microbial corrosion, however brief but right-to-
that are compatible with the environment, the-point), it will be useless discussing biocides.
then the biocides to which we refer as “natural,” In the next section, we will introduce into
and we mean any herbs, trees and their microbial corrosion so much that is needed to
branches, flowers, roots, leaves, etc. that can justify why biocides would be needed and, even
kill microorganisms, such as bacteria. A good more importantly, why biological biocidesd
example of natural biocides is neem tree whose seemingly an oxymorondmust be studied
antibacterial properties have been proven by in much more detail so that they become as
many researches around the world. In our commercially available and widespread applicable
judgment, all natural biocides are also green as their synthetic counterpart do.
biocides but not vice versa. In other words, we
believe that natural biocides (and also corrosion
inhibitors, although we have not shown in the CLOSING REMARKS
figure) are compatible with the environment In this chapter, we showed that although
per se obviously because they aredor once corrosion is indeed a serious business, it is still
they have beenda part of the nature themselves. curable should it is recognized and treated on
We may choose the essence or extract of such time and monitored constantly. Corrosion cannot
and such leaf and use it as a biocide in, say, be avoided but controlled, this is a very important
the process of combating against microbial point that we will get back to it with more details
corrosion in a pipeline. The deal is that if for when we are discussing the “Zugzwang effect.”
24 Biological Treatment of Microbial Corrosion

A significant piece of corrosion management is that can have a general knowledge nature for the
to define the problem correctly and in its readers and can be addressed as “For further readings”:
correct context. This means that without a good
recognition, it is impossible to find the right treat- • For a general reading about corrosion and
ment. This may sound too evident but in reality, its electrochemistry, the following can be
it is not as such, at least in cases we have seen suggested although the interested reader can
during our 20 years of field experience around find many more:
the world! It is so unfortunate to see that • R. Javaherdashti, “Microbiologically Influ-
in many industries around the world, it is the enced Corrosion-An Engineering Insight”,
likelihood of corrosion, which is the main focus Springer, second Edition, 2017.
of managers and not the risk (we discussed the • P.R. Ruberg, “Handbook of Corrosion
difference between these two earlier in this book). Engineering”, McGraw-Hill Education, 2012.
In the next chapter, we will look at the • Z. Ahmad, “Principles of Corrosion
main topic of this book, that is, microbiologically Engineering and Corrosion Control”,
influenced corrosion (MIC) in more detail. As we Butterworth-Heinemann, 2006.
have indicated several times, this book is not • E. Mattson, “Basic Corrosion Technology
about the mechanisms by which MIC occurs or for scientists and engineers”, Ellis Horwood
the details of how it is treated and monitored. Publishers, 1989.
This book undertakes to use the next chapter to • There are numerous references on biocides,
show the readers how significant and complex oxygen scavengers, and biocides. We took
MIC could be and how the way it is recognized Fig. 2.8 from the reference below:
is vastly different from all other corrosion • P. Rajeev, A.O. Surendranathan, Ch.S.N.
processes: no other corrosion processes except Murthy and entitled "Corrosion mitigation
MIC use the recognition parameters and tools for of the oil well steels using organic
identification of planktonic and sessile bacteria. inhibitors-a review" as published in The
In addition to recognition, there is also another Journal of materials and Environmental
matter that within the context of our book is Sciences, Vol. 3, No. 5 pp.856e869, 2012.
only unique to MIC: in addition to application • About natural corrosion inhibitors, the
of CP, use of coatings and chemical and other following can be suggested:
five forms of controlling corrosion that we dis- • Abdallah, M. (2004), “Guar gum as corrosion
cussed above in required length, there is an option inhibitor for carbon steel in sulfuric acid
of using bacteria against bacteria (biological treat- solutions”, Portugaliae Electrochimica Acta,
ment of MIC) that is the main topic of this book. Vol. 22, pp. 161e75.
• Abdel-Gaber, A.M., Abd-EL-Nabey, B.A.,
Sidahmed, I.M., El-Zayaday, A.M. and
REFERENCES Saadawy, M. (2006), “Inhibitive action of
In this section, we rather discussed about matters that in
some plant extracts on the corrosion of steel
essence belong to the general body of knowledge of
corrosion. Therefore we prefer instead of introducing
in acidic media”, Corrosion Science, Vol.
individual references here, just name some resources 48, pp. 2765e79.
CHAPTER 3

An Introduction to Microbial Corrosion

HOW ARE MICROBIAL CORROSION, will suffice for both MIC and electrochemical
IN TERMS OF BEING AN corrosion to find their suitable environment to
ELECTROCHEMICAL PROCESS, carry on.
AND MICROBIOLOGY RELATED?
As we mentioned earlier, for electrochemical
corrosion to occur, it is necessary to have a
WHAT IS MIC AND WHAT ARE THE FOUR
BASIC CHARACTERISTICS OF IT?
medium through which ions can be transferred.
This medium, the electrolyte, has to be conduc- Microbial corrosion can be defined, and as a mat-
tive. The best option will then be water. It is water ter of fact “is defined,” in various ways by various
that, because of its conductivity, can play the role researchers. No matter how you define it, MIC has
of an excellent electrolyte should it contain the three features that appear as common in all of
necessary electrical charges that would act like an these definitions1:
electrolyte. The meaning of this is that water per 1. MIC is an electrochemical process.
se cannot be an electrolyte and it has to have 2. Microorganisms are capable of affecting the
certain properties to make it the best nominee extent, severity, and course of corrosion.
for being an electrolyte. 3. In addition to the presence of microorganisms,
It follows then that if somehow we manage to nutrients and water must also be present and
make water out of its ions (the so-called demin- available to let MIC commence and continue.
eralized water or, for short, demini water), then In addition to the three items above, we
although we could have anode, cathode, and a want to add one more item too.
metallic path that would let the electrons pass, 4. The central concept of MIC is biofilm and its
because of having a poor or rather nonconduc- formation mechanism. However, the term
tive water, electrochemical corrosion will not biofilm is itself misleading!
occur. This is exactly what happens in reality: We will briefly explain each of the four items in
the water to be used in many precise industry necessary length below, bearing in mind that what
applications is made demini water so that the is being represented is just the tip of the iceberg.
likelihood of corrosion will be expected to
decrease. On the other hand, waters like MIC as an Electrochemical Process
seawater, for instance, are highly conductive We have repeatedly mentioned here that MIC is
because of their dissolved salts and therefore indeed a known corrosion process that in origin
very good electrolytes. it is electrochemical. In other words, MIC is not
It may also be a strike of luck that bacteria also a “type” of corrosion. In fact, the fact that MIC is
prefer water for living. It is through this medium not a type of corrosion has also been indicated
that bacteria can give/take their necessary chemi- and emphasized upon in “Detection, Testing,
cals and it is in this medium that their food is and Evaluation of Microbiologically Influenced
found in the best possible form they can digest. Corrosion (MIC) on External Surfaces of; Buried
When we talk about water, we do not necessarily Pipelines; NACE Standard TM0106-2006.” We
mean a body of water, even the moisture in the believe that this clear and straightforward
soil or in a natural gas stream within a pipeline emphasis upon MIC not being a type of corrosion

Biological Treatment of Microbial Corrosion. https://doi.org/10.1016/B978-0-12-816108-1.00003-3


Copyright © 2019 Elsevier Inc. All rights reserved. 25
26 Biological Treatment of Microbial Corrosion

but a rather a corrosion process that can be that microbial corrosion, as it implies that both
explained within the known framework of corro- micro- and macroorganisms can get involved in
sion control measure already used for controlling the process of corrosion. Fig. 3.1A shows an
electrochemical corrosion is of great practical example of when macroorganisms (that is, the
importance: this way it can become possible for organisms that can be observed with naked eye)
the industry experts as well as researchers to try could be involved in the deterioration process. In
to find ways by which treatment of MIC could this figure, it can be seen that at least three
be achievable. It is also in this regard that theories corrosion mechanisms are in action: the uniform
such as EMIC can be better understood where bac- corrosion of the above water line section of the col-
teria due to direct electron pick-up from metal will umn, probably because of the marine atmosphere,
become itself a living cathode and therefore could the tidal zone corrosion where the zone is affected
increase the rate of corrosion to very high values. by high-oxygen and low-oxygen conditions at low
To summarize, in order to understand MIC, one tide and high tide, as well as the biofouling of the
has to know two scientific majors: microbiology marine creatures that have been stuck on the
and electrochemical corrosion. column. We said at least three mechanisms but
we do not confine it to that number. In cases as
Diversity of Organisms Involved in such, one thing that is of significant importance
Microbial Corrosion for advising a feasible corrosion management pro-
In fact, an alternative name for MIC is bio- gram is to realize if these corrosion mechanisms
corrosion. This, in our opinion, is more convenient are functioning in series or in parallel. A good

B
FIG. 3.1 (A) An example of marine organism stuck on the tidal zone of a steel column. Their main
contribution to corrosion could be via establishing differential aeration cells. (B) MIC or not MIC?
(Photo: Dr. R.Javaherdashti’s collection.)
CHAPTER 3 An Introduction to Microbial Corrosion 27

mitigation program will have to revolve around question that comes to mind is that how one
this priority to be successful. can talk about the possibility of MIC if no analyt-
Therefore, it is not just microorganisms such as ical method has been applied to show the
bacteria and/or archaea that can contribute to existence of any bacteria, let alone sulfate-
corrosion. The practical importance of this can reducing bacteria? Although we do not open up
be that, when on offshore platforms, one gets the discussion that even mere existence of CRB
stringers clogged by marine creatures (a process (such as but not limited to SRB) is not a
known as biofouling), if one knows that it is convincing reason to make us believe the case is
through the formation of biofilm that serves as a indeed MIC.
“sticky tape” to larger marine life to let them We hope the example above has served to show
grow on it, then it will make sense to first try to our readers that in real-life industry practices, they
control biofilm formation instead of spending may not even be that much concerned about the
large sums of money on dealing with controlling rather obvious basic requirement of existence of
biofouling. bacteria to confirm that the case might be MIC-
related.
Suitable Environment for MIC to Occur Another important condition for sustaining
MIC cannot take place if the following three basic MIC is existence of nutrients in the environment.
requirements are not met: What we mean by nutrients are chemicals such
• Corrosion-related bacteria (CRB) as phosphorus, carbon, hydrogen, and the like.
• Nutrients
• Water/water-containing environment Biofilm, A True Concept With a Wrong
Let us first start with CRB. It may sound Name
obvious but one will be amazed to see how Perhaps the most important, and in a way, the
frequently people address a corrosion case as to central concept of MIC is the concept of biofilm.
be microbial (even without checking it out) just It is essential because by forming biofilm, a great
because they have seen something that might deal of corrosion will be expected to happen
have had some resemblance with some features and one can conclude that MIC and biofilm
of MIC as they have read or overheard. A real formation are closely related.2
case history as such is as follows. The term “biofilm” has been coined in 1978,3
As a corrosion expert, we are receiving many and it can be defined as “‘matrix-enclosed bacte-
requests over a week in which people send the rial populations’ adherent to each other and/or
photos of the failed parts along with some process to surfaces or interfaces.”4 To understand the
parameters that in their minds are important for concept of biofilm formation, we must under-
us to know and then ask if the type of corro- stand the “states” at which bacteria can exist.
sion/failure could have been an example of As long as bacteria can find food in the nearby
MIC! An example of such is seen in Fig. 3.1B. bulk solution, they will prefer to swim around. In
An inquirer sent us the pictures shown in this state, they can be called as “freely swimming”
Fig. 3.1B. He said that the figures belonged to a or planktonic. However, if the food falls down
part of a pipe used in upstream gas and oil indus- under its weight on surfaces and stays there and
try. The fluid inside that passes through the pipe bacteria “sense” that the food for them is not in
contains 3% hydrogen sulfide and 5% carbon the bulk but rather can be reached on surfaces,
dioxide along with methane. The temperature is then they will drive down onto these surfaces
120 C and the pH is 5.5. Very severe corrosion and through a very sophisticated mechanism,
has been observed, and inside the pipe, a rather details of which are still unknown to us, settle
thick, black deposit has also been observed. The themselves on these surfaces, and become
inquiry was whether the cause of corrosion could “motionless” or sessile bacteria. It is these sessile
be MIC by sulfate-reducing bacteria! (Perhaps bacteria that make up the so-called biofilm and,
based on the color of the deposits!) The first through various mechanisms,5 can contribute to
28 Biological Treatment of Microbial Corrosion

(1) (2)

(4)
(3)

(5) (6)

FIG. 3.2 Steps involved in biofilm buildup (construction) and deconstruction and how this
process contributes to corrosion in form of pitting. (From Javaherdashti R. Corrosion and
biofilm. In: Kanematsu H, Barry DM, eds. Biofilm and Materials Science. Springer; 2015.)

corrosion, one of these mechanisms by which


corrosion can be enhanced can be through forma-
tion of spots of low and high oxygen partial pres-
sure adjacent to each other. This can be even more
enhanced by the formation of yet another form of
electrochemical cells known as ion concentration
cells. These formation processes of electrochemi-
cal cells would make biofilm into a rather “aggres-
sive” entity that would increase the likelihood of
corrosion. It may, however, be good to know
FIG. 3.3 Differential aeration cell and ion concen-
that there is a certain time lag between the time
tration cell mechanisms as operative on a biofilm-
that biofilms form and the time they start to
metal system. Relative size differences of the arrows
become aggressive that in the case of filtered and represent the corresponding oxygen partial pressures.
unfiltered seawater may differ from weeks to When via cathodic reactions atomic metal (M) is
months.6 Fig. 3.2 schematically shows biofilm for- oxidized, it will liberate enough positively charged ions
mation stages and how it can facilitate corrosion (cations, Mþ) to shift the charge balance to yield ion
via, for instance, establishing differential aeration concentration difference. In either case, pitting under
electrochemical cells. Fig. 3.3 schematically shows the biofilm is inevitable. (From Javaherdashti R.
the way adjacent high- and low-oxygen spots can Corrosion and biofilm. In: Kanematsu H, Barry DM,
be formed. eds. Biofilm and Materials Science. Springer; 2015.)
CHAPTER 3 An Introduction to Microbial Corrosion 29

There is also another important issue about be exerted on smaller surfaces. The end result
biofilm that will make them a very confusing issue will be local increase in the stress that can well
especially when it comes to industrial practices: pass the yield strength of the material and thus
biofilms, because of their the ever-changing struc- cause its failure.
ture, can easily become the focal point of all types In soil, there are no freely swimming bacteria of
of microorganisms, not all of which are neces- course, in those environments the bacteria would
sarily CRB. Some of these biofilm guests could move by mechanisms such as gliding and twitch-
well be potentially pathogenic bacteria (e.g., ing;7 however, the end result will still be biofilm
Legionella) that over time could pose a serious formation by the bacteria that are successful in
threat to the surroundings. We will get back to adhering themselves onto the metallic surface.
this issue later in this chapter, but we want to However, one may wonder we call the concept
put emphasis on the fact that by letting biofilm of biofilm right but its name wrong? We have two
grow and sustain, we are actually letting not reasons for that:
only the risk of MIC to become more serious but 1. Biofilm is not a film at all in the sense that it
also the possible issues with pathogenic bacteria’s may imply a rather uniform tape covered over
sustained growth and spreading over. Biofilm the material. In fact, biofilm has rather a pat-
control, then, is an issue to be handled by both chy shape nature, and that is why, it can
corrosion department and HSE (health, safety, accommodate several ions or allows the
and environment). passage of gases or creates spots of different
We are not going to describe each step shown oxygen partial pressure. As a matter of fact, it is
in Fig. 3.2, as we have done this before in required these openness characteristics of biofilm that
length before. However, it is necessary to say that, allows it to be corrosive, if it were uniform and
as can be seen from the figure, especially in stages tight, it could have been taken as a rather
3 and 4, as long as the biofilm is managed to stay useful internal coating and thus slow down or
on the metallic surface, this may not expose a even stop corrosion.
threat. It is true that the coverage of biofilm is 2. Not all biofilm material is organic and bio-
not uniform and we can still get some formations logical, based on the dry weight of biofilm;
of electrochemical cells; however, it is also impor- the nonorganic content of biofilm is around
tant to see that these cells could be quite small in 60%e70% of its dry weight.8
size and may actually not show a significant threat Based on the above, we think it is now time to
to the mechanical integrity of the metallic part of find another alternative name for “biofilm.” What
the asset. It is possible to think that even if small- we can suggest is “Temenos,” the Greek term,
size perforations are formed, these will be filled by sέmεno2, for “a sacred enclosure or precinct.” The
corrosion products that themselves are the result reason we are suggesting Temenos instead of bio-
of formation of other corrosion processes or the film is obviously because under-biofilm and
adjacent corrosion sites. This way, the anodes outside-of-biofilm could have very different con-
may be blinded by being filled with these prod- ditions, from the chemicals involved to the oxy-
ucts. However, the large-scale problem starts gen concentration. It is as if when “biofilm”
when the biofilm patches are removed or shifted forms, that part of the system will become func-
in a significant shifting process as shown in stage tionally isolateda from the rest of the system.
5. This can easily be leading into stage 6 where Although the bulk solution could be oxygenated,
owing to formation of various electrochemical the underbiofilm patches could be rather identi-
cells such as differential aeration cells (adjacent fied with anaerobic pockets or the concentration
sites with different oxygen partial pressures), of certain ions (such as chlorides) could be well
pitting and perforation will become a dominant above their concentrations in the bulk. All these
process. The “holes” thus produced during this
process and as a result of it will serve to enhance a
The word “Temenos” is derived from the Greek
crack formations, and therefore, local forces will
“temeno” that means “to cut off.”
30 Biological Treatment of Microbial Corrosion

will make biofilm to act as an enclosure that has stated in section 9, article 9.1. of “NACE standard
its own characteristics. TM0212-2012-Standard Test method: Detection,
Temenos or biofilm, what has been found Testing and Evaluation of Microbiologically Influenced
about these ever-changing structures, is that they Corrosion on Internal Surfaces of Pipelines” that
do contain various kinds of bacteria. As a matter verbatim reads “mere detecting viable microorganism
of fact, there are many types of bacteria/archaea in liquid or solid samples associated with internal corro-
that can be classified as to be related to MIC. sion does not necessarily prove that MIC has occurred.”
Below we will just briefly describe some of However, we want to look at this matter from
them. This must not be taken in any way that another angle point, the pre- and proceeding
the CRB (this abbreviation is defined below) are corrosion process. When there is more than one
just limited to the bacteria listed below, nor is it corrosion process involved, it is always possible
to be understood that we will review these bacte- to think of these competing corrosion processes
ria per se. In other words, we will list and briefly as being in series or in parallel (Fig. 3.4).
explain these bacteria from the standpoint of the What is meant here is that sometimes corrosion
role they are playing in MIC scenarios. processes may serve to enhance (or perhaps slow
down) each other and sometimes each can go its
own way without virtually having any effects on
INTRODUCING SOME BACTERIA the other one. Understanding series and parallel
THAT ARE RELATED TO CORROSION corrosion series could have invaluable practical
(CORROSION-RELATED importance: the reason is that if corrosion pro-
BACTERIA [ CRB) cesses are acting in accordance with series model,
The reader may wonder why we are not referring then by controlling one, it is quite likely to be able
to these bacteria as “corrosive” and we rather to control the other. An example is the so-called
prefer to address them as “corrosion-related bacte- reinforced concrete corrosion. In this instance,
ria,” or briefly, CRB. Isn’t it true that these bacteria the moisture that penetrates through concrete
will always cause enhancement of corrosion and via its surface cracks will find its way to the core
the mere existence of them in a system must set of the reinforced concrete metallic phase, which
an alarm to the operators? The short answer is is the steel bar. Therefore, the steel is affected
“not necessarily”! Let us explain this a little bit and rusted, and as a result of corrosion, by-
more but we need to answer to two questions products and the pressure exerted by them on
that are in fact “hidden” in the expectation that the concrete (that owing to its certain crystal struc-
the so-called “corrosive bacteria” is probably a ture cannot withstand tensile stresses and thus
better and more correct way of addressing these cracks), more cracks are created. These additional
bacteria than “corrosion-related bacteria”: cracks will then serve as extra corridors for mois-
1. Isn’t it true that if you have these bacteria ture entrance, and loss of mechanical integrity
hanging around in your system, they are the happens and thus more enhanced rusting, and
“Cassandra” of corrosion? this cycle repeats itself till complete and spalling
2. Isn’t it true that these bacteria always accelerate will become inevitable. In this particular example,
corrosion as measured by corrosion rates? rusting of the reinforced steel bar and concrete
Let us focus first on question (1): spalling are in series: if it is not for rusting, no
As we have shown in one of our research extra cracks will occur and therefore no further
studies,9 even if CRB are present in the system as corrosion would be expected. It is followed then
long as we have done our corrosion management by either waterproofing the concrete from outside
homework well and efficient, the risk of MIC will or coating the reinforced steel bar or replacing the
be nil. This is a finding that is also being steel bar with a nonrusting material (e.g., compos-
supported by practice too; in other words, mere ite bars), the spalling and total loss of mechanical
existence of microorganism does not necessarily integrity of the concrete structure will be
mean that the case is MIC. This has been clearly controlled.
CHAPTER 3 An Introduction to Microbial Corrosion 31

Working/commissioning
conditions and/or CORROSION
material’s features CORROSION
leading to corrosion

CORROSION CORROSION

Working/commissioning
conditions and/or
material’s features
leading to corrosion

CORROSION CORROSION

FIG. 3.4 “Series” and “parallel” corrosion processes.10

Based on the above, it is now easy to anticipate explain belowdthere is no general agreement as
what parallel corrosion process could mean; in being “totally corrosive.” For instance, experi-
this model, two or more corrosion processes ments by Rodríguez et al.,11 on the effect of SRB
would be proceeding, which are essentially inde- on stainless 304, lead these investigators to
pendent from each other, and thus, treatment of conclude that SRB were actually protecting metal
one does not necessarily mean that the overall from corrosion. In this context, Liu et al.12 studied
corrosion problem has been resolved simply the possible effect of SRB on carbon steel X 80,
because other competing corrosion reactions will where by increasing the biofilm coverage, MIC
still be in action. resistance of the metal increased. With regard to
Now, getting back to the core question we possible corrosion inhibition effects of IRB under
asked earlier, we can look at MIC as a corrosion certain conditions, researchers have done many
process that in many cases would appear in a par- research studies,13,14 and in addition to personal
allel pattern and therefore there can be other experimenting that IRB could indeed reduce
competing corrosion reactions that could become corrosion, we have addressed a good collection
more active and more aggressively corrosive of it in our work.15
compared with MIC alone. So, the short answer The end result of the above is that neither mere
to question (1) is that mere existence of CRB existence of bacteria can be taken as a proof of
may not be taken as a potential threat and there- MIC nor are all the bacteria involved indeed “cor-
fore not all the time having these bacteria is a rosive.” Based on the above, we will use the term
signal of “bad luck” of MIC. “CRB” to put even more emphasis on the involve-
Question (2) is even more delicate as it implies ment of bacteria in corrosion, which is not always
that under, practically speaking, all conditions, a threatening issue.
the bacteria that have been known to be involved There is a wide range of bacteria/archaea that
in corrosion will actually accelerate it. This is not could be taken as CRB and CRA (corrosion-
conclusive. In fact, contrary to what it may seem, related archaea). Table 3.1 represents schemati-
even about SRB (sulfate-reducing bacteria) and cally some bacteria/archaea that could be
IRB (iron-reducing bacteria)dthat we will potentially classified as CRB/CRA.
32 Biological Treatment of Microbial Corrosion

TABLE 3.1
A Schematic Presentation of CRB/CRA Based on the Work by Al-Abbas et al.16
General heterotrophic Thiosulfate-oxidizing Acetogenic bacteria Slime-forming bacteria
bacteria/archaea bacteria (TOB)
Acid-producing Methanogens Nitrate-reducing Sulfur-oxidizing
bacteria/archaea bacteria/archaea bacteria/archaea
Sulfate-reducing Nitrite-reducing, Thiosulfate-reducing Thiosulfate-reducing
bacteria/archaea sulfur-oxidizing bacteria bacteria (TRB) archaea (TRA)
(NR-SOB)

We are not claiming that in a given biofilm sound. SRB may be found everywhere from
environment, one can find all these CRB/CRA at soil18 to seawater.19
the same time and in the same location. However, These bacteria are expected to induce very high
from the types given in the table, it must be corrosion rates that in some case have been as
obvious to the reader that although corrosion high 10 mm per year.20 These bacteria are so
per se is a confusing issue, MIC can make it even exotic to researchers, maybe because they are
more complex and confusing in terms of inducing anaerobic (do not require oxygen for their
various types of life forms that can be accommo- growth) in an all-oxygen demanding environment
dated there and the role they can play in affecting like the earth. Since the time it was tried to explain
corrosion. In addition to that, we want to once their corrosive effects in terms of involving con-
more remind our readers that biofilms are not cepts of electrochemistry (the so-called classic the-
necessarily all composed of organic matter and ory), many rival theories have emerged to explain
the inorganic matter thatdespecially in rather the unusually too high corrosion rates generated
nonclean industrial systemsdcan be accumu- by SRB. A collection of these theories is given in
lated; it can itself have huge detrimental effects Table 3.2.
on enhancing corrosion. Below we will briefly As it can be seen from Table 3.2, the rather
touch some CRB from a corrosion point of view. recent opinion census among experts is the last
The reason we have selected these CRB is not one: this recent theorydabbreviated as EMIC
because they are very important CRB but simply that stands for electrical microbiologically influ-
because they have been appearing more enced corrosiondstates that SRB can directly
frequently in MIC-related descriptions of failures. take up the electron that needs through nanosized
tubes thatdlike a straw in a fizzy drinkdwill be
Sulfate-Reducing Bacteria used to transfer electrons from metal to the bacte-
SRB are most probably the most notorious type of ria, sulfur-oxidizing bacteria. This can be schemat-
CRB known to industry. However, this is in fact ically shown in Fig. 3.5.
one of the “myths” of MIC repeatedly put for- With very rough terms, we can simplify explain
warded by self-declared MIC experts. Sulfate- what is seen in Fig. 3.5 as the following: SRB will
reducing bacteria (SRB) that grow aerobically be steeled onto the metal and produce back-
(no oxygen) are known for their capability of colored iron sulfate deposits on the metal. The
reducing sulfate (SOe24) to sulfide (S2) where, procedure is that SRB will, literally speaking,
in the absence of metallic ions such as iron, they grow on nanotubes that will assist them in taking
produce H2S gas17 and, with ferrous ion, iron sul- electrons directly to themselves via conductive
fide is generated. The “black rust” iron sulfide con- metal and sulfate film. By doing so, bacteria
sumes the iron that was necessary to keep the will, practically speaking, become a cathode and
original steel structure mechanically strong and the metal an anode. This will induce very high
CHAPTER 3 An Introduction to Microbial Corrosion 33

TABLE 3.2
A Summary of Theories Put Forwarded So far for Explaining the Corrosive Effect of SRB
Classical Theory (VonWolzogen Kuhr Other Theories:
and Van der Vlugt, 1934):
• According to this explanation, the • Galvanic corrosion between the iron sulfide film
bacteria use the cathodic hydrogen and underlying steel (Stümper, 1923)
through consumption by an enzyme • Mixed effect of hydrogenase and the FeS-Steel
called hydrogenase galvanic effect (Miller and King, 1971)
• Thus, main probable effect of SRB • Replacing FeS with hydrogen sulfide as the
on corroding metal is the removal of cathodic reactant (Costello, mid-1970s)
hydrogen from the metal surface by • The existence of a corrosive volatile phosphorous
means of hydrogenase and metabolite leading to observed high corrosion
catalyzing the reversible activation (Iverson, 1998)
of hydrogen • Direct interaction of SRB and the metal to facilitate
direct electron pick-up (Hang et al., 2003)

electron

electron

FIG. 3.5 How Can EMIC Take Place?

corrosion rates that will eventually cause acceler- Iron-Oxidizing Bacteria


ated corrosion of the part. IOB utilize ferrous iron Feþ2 as a source of energy
The smart reader will notice that in Table 3.2, and are characterized by the deposition of ferric
we have not closed the list of theories that can Feþ3 hydroxide. A common example of IOB is
be suggested. The main reason is that just by look- the Gallionella sp. These bacteria will oxidize
ing how these theories have been evolved, one can ferrous to ferric and therefore this will make the
deduce that sooner or later new theories will initial “food” for IRB (see below). In addition,
emerge that maybe like EMIC are not just new we should not forget that oxidation of iron and
theories but as an example of the fifth level of converting iron atom into its ionic form (ferrous)
innovation as per TRIZ,b a ground-breaking para- is in fact itself an anodic reaction (that is, corro-
digm in the literature of MIC. sion). Therefore, these bacteria will in fact
enhance corrosion by this way too. Fig. 3.6 shows
an example of IOB:
b
TRIZ is the abbreviation of the Russian term “tfprj>
rfzfoj> jipbrftatfm:sljy iaeay” that can be trans- Iron-oxidizing bacteria are not just a member
lated as “the theory of inventive problem solving.” of CRB in its negative sense: these bacteria can
34 Biological Treatment of Microbial Corrosion

gram of soil. It must be reminded that as IRB


are both chemoheterotrophic (organic com-
pounds are the source of energy for them) and
facultative anaerobes, their numbers within
the soil’s surface layer are higher than deeper
levels especially if the soil is rich in organic
matter at the surface level. As a result, in case
their numbers in soil are reported, the depth of
sampling for the organic carbon content must
also be recorded.
3. Incorporation (assimilation) of iron into pro-
teins containing, for instance, iron-sulfur: IRB
are capable of making the environment suitable
for SRB. In a mixed population of microor-
FIG. 3.6 An example of iron-oxidizing bacteria ganisms in a biofilm, as oxygen is consumed,
(ferrooxidans) grown on chalcopyrite.15
the redox (reduction-oxidation) potential starts
to decrease so that nitrate, then manganic and
have very useful applications in mining and ferric ion, and the sulfate are reduced.
particularly in a method that is called “bio-
leaching1” that is applied to extract copper from Acid-Producing BacteriadNonorganic
its ore when routine chemical treatment methods Producers
are not feasible to be applied. Sulfur-oxidizing bacteria (SOB): SOB are a family
of bacteria that require oxygen for their growth
Iron-Reducing Bacteria (aerobic bacteria). SOB can produce sulfuric acid
In simple terms, the way by which IRB can with very low pH values down to one even.22 A
contribute to corrosion, and thus MIC, is that they type of these bacteria known as colorless SOB pro-
convert (reduce) insoluble ferric iron into soluble duces sulfuric acid by either of the reactions given
ferrous ion. Although ferric ion can assist in gener- below23:
ating protective films against corrosion, ferrous ion H2 S þ 2O2 /H2 SO4
will be dissolved easily and fresh surface will be pre-
or
sented to the corrosive environment surrounding
2S0 þ 3O2 þ 2H2 O/2H2 SO4
the material.21 How can IRB be pivotal to MIC?
The following could be some mechanisms by Colorless SOB can be found everywhere in the
which IRB can contribute to corrosion15: nature and be isolated from almost every aquatic
1. Availability of iron: Iron is not very soluble but system. A genus of SOB known as Thiobacillus
if it is reduced to ferrous iron (which is solu- errooxidans is capable of producing 10% concen-
ble), the organic compounds can stabilize iron trated sulfuric acid with pH less than 2.5.22,23
by chelation where, later on, that iron can
“liberate” itself from the organic matter and Acid-Producing BacteriadOrganic Acid
precipitate as iron. Producers
2. IRB are a very important part of the soil Clostridia:
microbial community, as most of the IRB are Clostridia are perhaps the most dangerous of
facultative anaerobes; thus if oxygen is avail- CRB about which we still do not know that
able, they will prefer it for their growth while much except that:
maintaining also their capability of growth 1. Like SRB, these bacteria are also anaerobic.
under anaerobic conditions too. It is estimated 2. There are contradicting reports about these
that in the surface layer of soil, on the average, bacteria and their impact on corrosion.
the number of IRB could be as 106 cells per 3. They can cause very serious diseases.
CHAPTER 3 An Introduction to Microbial Corrosion 35

The mechanism by which Clostridia and their which we have not faced any official corrosion
various kinds can facilitate corrosion is mainly report! Nevertheless, we accept this risk and do
by generation of organic acids as metabolic include magnetotactic bacteria in our list of
by-products, thus lowering the pH and sustaining CRB. We believeeas we will explain belowd
corrosive conditions. These bacteria are also magnetotactic bacteria could in fact make much
known to produce ample amounts of hydrogen, contribution to corrosion even when compared
thus increasing the likelihood of hydrogen- with SRB should the conditions for the former
induced cracking (HIC). They are capable of become sustainable.
applying at least three mechanisms that, poten- Among various types of microorganisms that
tially, will enhance corrosion: can be found in nature, there is a class of bacteria
1. Enhancing anodic reactions by producing that can be collectively referred to as “magnetotac-
acids tic bacteria” or, equivalently, magnetic bacteria.
2. Facilitating hydrogen-induced cracking (HIC) These bacteria are termed magnetic because of
via hydrogen generation their ability to form nanosized magnets within
3. Constant availability of freshly corroding their “body”24 (Fig. 3.7).15
steel surface by ferric iron reduction, similar The average size of each of these nanosize mag-
to IRB nets (called a magnetosome) is about 50 nm.25
In addition to the above, Clostridium sp. have Magnetic bacteria were discovered in the mid-
been reported to be resistant to high temperatures. 1970s and they can either be aerobic or anaer-
This thermophilic feature of Clostridia can make obic.26 As magnetic bacteria are capable of
them an ideal corrosion culprit in an environment accumulating huge amounts of iron,25 it has
that is anaerobic and relatively hot as well as rich been theorized they may be an instrumental factor
in nutrients necessary to sustain Clostridia alive in inducing corrosion.15,27,28 According to
and active. Hughes,25 although up to 80% of magnetosome
These bacteria have been quoted to have consists of magnetite (Fe3O4), it can highly be
caused corrosion in systems such as subsea car- possible that other minerals of irondfor example,
bon steel pipe lines, natural gas pipelines, injec- iron sulfidesdmay also exist in some magnetic
tion systems using produced brine to displace bacteria. Javaherdashti15 proposed for the first
oil from the reservoir as well as a potential prob- time the possible role of these bacteria in corro-
lem in closed water systems that could form sion and thus the need to classify them as CRB
anaerobic environments. Clostridia are also very as well. His proposed mechanism is based on
dangerous bacteria from health-related point deduction about the possible link between MIC
of view. and magnetic bacteria based on the following
The information mentioned above along with two fundamental questions:
more detailed and updated knowledge about
Clostridia has been given elsewhere.15

Possible Role of Magnetic Bacteria in


Inducing Corrosion
So far, we talked about CRB about which there
have been enough field and research evidence
and support that we are almost certain that bacte-
ria such as SRB, SOB, IOB, and IRBdalong with
those that have been mentioned in Table .3.1ddo
have some kind of contribution to corrosion in FIG. 3.7 Schematic presentation of a magnetotactic
the form of MIC. However, the bacteria we are bacterium where the magnetosomes can be seen as
going to mention here are in fact bacteria about black beads.
36 Biological Treatment of Microbial Corrosion

1. Magnetic bacteria can accumulate iron either right or wrong. If it is right, it will get a value
approximately 20,000- to 40,000-fold over its of “1,” and if it is wrong, its value will be “0.” If we
extracellular concentration. Between 14% and say, for example, “John is 35 years old AND He is
79% by weight of the magnetosome is old,” this combines two statements of which one
magnetite (Fe3O4). If these bacteria need this is right (John is 35) and the other is wrong ([John]
much iron, from where can they get it? One is old). It seems that the combination of these two
most possible way is that these bacteria must statements by “AND” will make a wrong result:
encourage the corrosion process to accumulate John cannot be old but 35 years old. But what
as much iron ions as they can. This, in turn, about considering 35 years old as being young?
could simply mean magnetic bacteria would We know from our everyday experiences that defi-
accelerate corrosion by affecting anodic reac- nition of “young” and “not young ¼ old” is not
tion of metal dissolution. that easy. It is this very approach of “not being
2. Proposed model for magnetite biomineraliza- easy” and the uncertainty associated with it that
tion in Magnetospirillum species is that Fe(III) is makes ordinary binary logic not that useful. In
actively taken up by the bacteria and then, it is fact, instead of two fixed values of 1 and 0, we
thought to be reoxidized, resulting in magne- can talk about a range of values that can later be
tite production within the magnetosome. expressed as percentages. Let us give another
Could magnetosome formation mechanisms example that may be more self-expressing: we all
contribute to corrosion in the way that iron- know that most of the time, it is not that easy to
oxidizing bacteria do by consuming ferrous say if it will rain or not. However, using new meth-
ions? We mentioned above that IOB would odologies, one can easily hear on the weather
contribute to corrosion by uptaking ferrous forecast programs news such as “most probably
ions and oxidizing them to ferric ions. This by tomorrow we will have rain!“ What is this “most
itself is an anodic reaction that would serve to probably”? It is based on applying fuzzy logic to
increase corrosion rates. In addition to that, let meteorology where by measuring some important
us not forget that the ferric ions thus produced parameters, with a certain probability, the case of
could always find an opportunity to be weather condition for tomorrow could be
reduced by the nearby IRB. predicted. Fuzzy logic, proposed by Iranian-
The above are just some “scientific gut feeling” American scientist Lotfi Askarzadeh (Zade) in
that may or may not be true about magnetic the 1960s, is now the required theoretical basis
bacteria. We prefer to “bite the bullet” and keep for essentially any device that is branded as
magnetic bacteria on the list of CRB so far as hard- “smart.” Fuzzy logic, in simple terms, is the math-
core evidence is found that would show they were ematics of uncertainty.3
not involved in MIC in any way. Although CRB can alter the severity of corro-
sion in various ways, confusing as it is, some
CRB can be pathogenic too. For example, the
USE OF MATHEMATICS IN pathogenic role of Clostridia in Gangaria has also
MICROBIOLOGY: FUZZY MODELING been reported.29 In addition to Clostridia, Pseudo-
FOR DISTINGUISHING CRB AND monas are also a group of CRB that although
PATHOGENIC BACTERIA they can enhance corrosion by rapidly forming
biofilm under which various corrosive reactions
Mathematics is a very powerful tool that, in case
will be facilitated, they can also be a health issue
applied correctly, could create wonders. If we
in several cases.c,30.
apply mathematics in building mathematical
models, these models can then be used for, at
least, two reasons: understanding the present state c
There are a lot of publications about what fuzzy logic
of a system and predicting its future state. and fuzzy calculus are all about. We have introduced
“Ordinary” mathematics and logic relies on many of such publications in our previous works that
binary systems. In this system, a statement is we have also referenced here.
CHAPTER 3 An Introduction to Microbial Corrosion 37

It is also possible to think that there can be 3. In the context of this modeling, pathogenic
other bacteria that in their natural path of getting bacteria (PB) will mean those bacteria, which
energy are capable to induce harm to both human are contributing to human health problems via
body (pathogenic) or human-made structures infection mechanisms.
(CRB). If this is true, this will mean that for 4. PB will do the infection process by “adher-
both microbial corrosion and medical microbi- ence” onto the healthy cells and then
ology, studying of dual-functioning CRB (corro- “invasion.”
sion and disease) is a greenfield for doing 5. Although invasion includes essentially chemi-
research. This classification of bacteria into PB cal factors, many of these factors cannot be
(pathogenic bacteria) and CRB (corrosion- modeled and mathematically quantified.
related bacteria) does not necessarily mean that However, adherence does include various
all bacteria are either PB or CRB. This is certainly measurable physical as well as chemical
oversimplification and certainly not true. Howev- parameters.
er, classifying bacteria into PB and CRB simply 6. CRB, which are PB as well, are collectively
means that some CRB could also be PB and referred to as CRB-PB.
some PB could also play a role that would make 7. The fuzzy algorithm describing CRB-PB is a
them suitable to be considered as CRB. In other combination of fuzzy mode/description of
words, our classification does not apply to all CRB corrosive action via biofilm formation
bacteria species but to only those that can be and fuzzy model/description of adherence for
both CRB and PB at the same time. It will PB via infection mechanisms.
also serve us to mathematically describe the
expected behavior from these bacteria in a more General Methodology
convenient way. We will define a general set of features related to
In the past in a series of works, we have applied both biofilm formation (main assumed MIC
fuzzy logics and reasoning to successfully predict mechanism by CRB) and infection (main
the risk of MIC.31e33 Here, we will develop the assumed infection mechanism by PB). Then we
same methodology with augmenting some funda- will define some subsets related to each of these
mental elements that would enable us to define general sets. A fuzzy membership function for
mathematically what “more or less corrosive bac- each set is defined to arrive at composite function
teria” or “more or less pathogenic bacteria” would of membership functions. By defining the com-
mean. This first-ever modeling methodology will posite functions, fuzzy rules to characterize the
enable researchers in a multidisciplinary arena to environment and its important parameters are
look for new solutions and methodologies. defined. A fuzzy method known as “generaliza-
tion of compositional rule of inference” is utilized
Eight Fundamental Assumptions in this study. In this method, a fuzzy rule is trans-
The model we would like to propose for the formed into a general form of multiantecedents
assessment of the health risk associated with (inputs) and consequents (outputs). Also “Kosko
corrosion-related bacteria will be based on fuzzy decomposition method” for decomposing a fuzzy
calculations. rule and Mamdani minimum fuzzy implication
The fuzzy algorithm that we will use in our will be used. Utilizing “Mamdani minimum fuzzy
approach here is based on the following initial implication,” the minimum value of membership
conditions: functions of the given fuzzy sets is calculated.
1. Corrosion-related bacteria (CRB) do contribute Then, by “maximum-minimum technique,” first
to corrosion via biofilm formation.5 the minimum values of membership functions
2. Biofilm formation is a process that rests on a are calculated. After that, among the selected
variety of factors that can be grouped into minimum values, the maximum value is picked
physicomechanical factors and chemical up. If, in any case, the membership functions of
factors.34 some elements are equal, one of the functions is
Another random document with
no related content on Scribd:
accelerated Bodo’s resolution, though contemporary indignation
traced it to the direct agency of Satan.
843 The golden age of Franko-Jewish history continued
under Charles the Bald, son of Louis and Judith, who
numbered amongst his closest friends the Jewish physician
Zedekiah and another Jew called Judah. But the same causes
brought about similar effects. The favour shown to the Jews by
Louis’s successor excited the enmity of the pious, who found a
leader in Agobard’s successor and other bishops, and held several
councils with the object of inventing means for the curtailment of
imperial power, the exaltation of ecclesiastical authority, and the
suppression of the Jews. Again letters were addressed to the
Emperor, in which he was recommended to enforce towards the
murderers of Christ the measures which had been originated by
Constantine the Great and Theodosius the Younger, adopted by the
Spanish Visigoths and the Merovingian Kings of France, and
sanctioned by the unanimous intolerance of so many Synods in the
East and West. But these new enemies of the Jews proved no more
successful than their predecessors. Charles the Bald
877
contented himself with extorting one-tenth of their
earnings from the Jews, while his Christian subjects paid one-
eleventh. Thanks to their commercial enterprise and integrity the
“murderers of Christ” continued to prosper under the judicious
fleecing of the Carlovingians, until the partition of the empire into a
number of small states, the wane of the secular and the growth of
the spiritual power brought about a change.
899–914 Charles the Simple was induced by his love of God
and fear of the Pope to surrender all the lands and
vineyards of the Jews in the Duchy of Narbonne to the Church.
Boso, King of Burgundy and Provence, also made to the Church a
gift of the property of his Jewish subjects, and this cavalier treatment
of the wretched people continued under the first Capets, their
degradation keeping pace with the progress of Papal influence. So
deep was the suspicion now inspired by them, that when King Hugh
Capet died in 996 his Jewish physician was generally accused of
having murdered him.
A parallel evolution took place in Germany. When
965
Otto the Great wished to show his piety by endowing
the newly-built church of Magdeburg, he did so by bestowing upon it
the revenue which he derived from the Jews. Likewise Otto II.,
sixteen years later, made an offering of the Jews of Merseburg to the
local bishops. At the beginning of the eleventh century there
occurred in Germany an event which may be regarded as the
prelude to the subsequent persecutions of Judaism.
1005
The chaplain of the Duke Conrad suddenly
scandalised the Christian world by going over to the Synagogue, and
exasperated the brethren whom he had forsaken by producing a
scurrilous lampoon on Christianity. The Emperor Henry caused to be
published a reply in every respect worthy of the apostate’s pamphlet.
Six years after the Jews were driven forth from Mayence, a decree
was issued ordering the Jews of various towns to be branded, that
they might not seek refuge in baptism, and so rigorous was the
persecution that a contemporary Jewish poet commemorates it in
lugubrious songs, wherein he expresses the fear that the children of
Israel might be forced to forget the faith of their fathers. But the
alarm was premature. Though, as a general rule, traffic in goods and
in money were the only callings left open to the Jews, in some of the
German states they still possessed the rights of citizenship and were
permitted to own real estate.
Thus the first period of the mediaeval drama came to a close, as
the second was opening.
CHAPTER VII

THE CRUSADES

Towards the end of the eleventh century there arose in Europe a


gale of religious enthusiasm that boded no good to infidels. The
zealous temper which at an earlier period had found a congenial
pursuit in the extirpation of heathenism from Saxony, Lithuania,
Poland, and the Baltic provinces, and in the suppression of heresy
among the Vaudois, the Cathari or Albigenses, and others at a later,
was now to be diverted into a different channel. During the preceding
ages the authority of the Popes had been advancing with stealthy,
but undeviating and steady, strides. Their own industry, foresight,
and prudence laid the foundations of their political power; the piety
and the ignorance of the nations which recognised their spiritual rule
consolidated it. Every succeeding age found the Bishop of Rome in a
higher position than that occupied by his predecessors, until there
came one who was fitted to make use of the immense heritage of
authority bequeathed to him.
Gregory VII., surnamed Hildebrand, ascended St. Peter’s throne
in 1073. Though born in an obscure village and of humble
parentage, he was a person endowed by nature with all the qualities
necessary to make a successful master of men: strong and
ambitious, and possessed of an ideal, he was a stranger to fear as to
scruple. It was related of him that, whilst a lad in his father’s
workshop and ignorant of letters, he accidentally framed out of little
bits of wood the words: “His dominion shall be from one sea to the
other.” To his contemporaries the story was prophetic (we may be
content to regard it, true or not, as characteristic) of his career.
Gregory’s dream was to deliver the papacy from the secular
influence of the Emperor and to establish a theocratic Empire. This
was the guiding principle of his policy, and, though his plans were
flexible to circumstance, his purpose remained fixed. Like all great
men, Hildebrand knew that, where there is a strong will, all roads
lead to success. The first step to this end was the purification of the
Church of the corruption into which it had sunk under his depraved
predecessors, and the organisation of its soldiers under strict rules of
discipline. This was effected by the suppression of simony and the
enforcement of celibacy on the clergy. At the same time Gregory did
not neglect that which was the main object of his life: to make
Europe a vassal state to the pontifical see. The thunderbolts of
excommunication, which Gregory, the son of Bonic the carpenter,
wielded with Zeus-like majesty and impartiality, were freely hurled
against his enemies in the East and West. In the Emperor Henry IV.
the Pope met an adversary worthy of his heavenly artillery. But,
undismayed by Henry’s power, and unrestrained by considerations
of humanity, he plunged Christendom into that long-drawn strife
between the Guelf and Ghibelline factions which makes the history
of Europe for generations a melancholy tale of murder and outrage,
ending in a blood-stained triumph for St. Peter.
After having temporarily humbled Henry IV. and forced him in the
dead of winter to do penance in his shirt, the iron Pope turned his
weapons against the Jews. In 1078 he promulgated a canonical law
forbidding the hated people to hold any official post in Christendom,
and especially in Spain. Alfonso VI., King of Castile, two years later
received an Apostolic epistle congratulating him on his successes
over the Mohammedans, and admonishing him that “he must cease
to suffer the Jews to rule over the Christians, and to exercise
authority over them,” for such conduct, his Holiness affirmed, was
“the same as oppressing God’s Church and exalting Satan’s
Synagogue. To wish to please Christ’s enemies,” he added, “means
to treat Christ himself with contumely.” However, Alfonso was too
busy in the campaign against his own enemies to devote much
attention to the enemies of Christ—or of Gregory Hildebrand. None
the less, the letter marks an epoch. What hitherto was prejudice now
became law.
In Germany also the Pope’s anti-Jewish decrees met with only
partial obedience. Bishop Rudiger of Speyer granted many privileges
to the Jews of his diocese. Their Chief Rabbi enjoyed the same
judicial authority over his own community as the burgomaster over
the Christian burgesses. The Jews were allowed to buy Christian
slaves and to defend themselves against the intrusion of the mob.
For all these boons they paid three and a half pounds of gold
annually. The Emperor Henry IV., Gregory’s antagonist, confirmed
and augmented these privileges. He forbade his subjects, under
severe penalties, to compel the Jews, or their slaves, to be baptized.
In litigation between Jews and Christians the Jewish law and form of
oath were to be followed; and the former were exempted from the
ordeals of fire and water. But in spite of these favours their lot was
such as to encourage Messianic expectations. The Redeemer, a
prince of the house of David, was confidently awaited about this time
(1096) to lead the chosen people back to the Holy Land. However,
fate had other things in store for them.
It was a time when the Eastern and Western halves of mankind
agreed in regarding the conversion, or, at least, the extermination of
each other as their divinely appointed task. If the followers of
Mohammed considered it an article of faith that the propagation of
Islam at all costs was the supreme duty of every true believer, the
propagation of the belief in the divinity of Christ, or the annihilation of
those who denied it, was not less firmly held by all good Christians
as a sacred obligation. A collision between the rival creeds was
inevitable. All that was wanting was union on the part of the
Christians equal to that which characterised the Mohammedans.
This consummation was prepared by Peter the Hermit and was
brought about by the exertions of the Pope.
1095 At the great Council of Clermont Urban II.
described to the noble crowd of prelates and barons,
assembled from all parts of Western Christendom, the sufferings of
the Eastern Christians at the hands of the Saracens. With burning
eloquence, and, no doubt, considerable exaggeration, he depicted
the dark deeds of “the enemies of God”: their destruction and
desecration of Christian churches; their slaughter, torture, and
forcible conversion of Christian men, and their violation of Christian
women; and he ended with a passionate appeal to all present to
hasten to the assistance of the Holy Land, “enslaved by the godless
and calling aloud to be delivered”; promising, at the same time, a
plenary indulgence and general remission of sins to all who should
enlist under the banner of the Cross. The effect of the Pontiff’s
harangue on his chivalrous, sinful, and bigoted hearers was
stupendous. It was the first official instigation to that hatred of the
non-European and non-Christian which, however loth we may be to
acknowledge the fact, in a less furious form, still survives amongst
us. Many obeyed the summons with fervour born of pure piety; many
more saw in the enterprise a comparatively cheap means of
obtaining pardon for all their crimes, past and to come; while others
welcomed an opportunity for satisfying their adventurous
dispositions, for gaining wealth and renown, or for quenching in the
blood of foreigners that fanatical zeal which could not find its full
gratification in the butchery of fellow-countrymen.
Among such foreigners—Asiatic at once and infidel—the nearest
were the Jews. Cruelty, like its opposite, begins at home. It was
natural that the champions of the Cross should begin the vindication
of their sacred emblem by the extermination of the race which had
made so criminal a use of it. The shadow of the Old Crime once
more fell upon the hapless people, and darkened their lives.
Religious frenzy kindled the ancient feud, and greed fanned it. The
vast and motley rabble of savage peasants who, under the
command of a monk and the guidance of a goat, followed in the
wake of the knightly army, incited by the lower clergy, fell upon the
Jewish colonies which lay along their route through Central Europe
—at Rouen, on the Moselle and the Rhine, at Verdun, Trèves,
Speyer, Metz, Cologne, Mayence, Worms, Strasburg—massacring,
pillaging, raping, and baptizing, without remorse or restraint.
But the Jews, as on so many occasions before and since, so
now proved in a practical and ghastly manner that they dreaded
death less than apostasy. Many of them met bigotry with bigotry, and
cheated their assailants of both glory and gain by committing their
property, their families and themselves to destruction. Martyrdom is a
pathetic yet forcible reply to oppression. At Trèves the Jews, on
hearing that the holy army was drawing near, were so terrified that
some of them killed their own children; matrons and maidens
drowned themselves in the Moselle in order to escape baptism or
disgrace; and the rest of the community vainly implored the hard-
hearted Bishop for protection. His answer was that nothing could
save them but conversion. Thereupon the wretches hastened to be
converted. The scene must have been a perfect study in the grimly
ludicrous. The enemy was outside ready to pounce upon his prey.
The latter said to the Bishop: “Tell us quickly what to believe.” The
Bishop recited the creed, and the converts repeated it after him with
all the fervour and fluency which the fear of death can only inspire.
At Speyer the Jews stoutly refused to be baptized, and many
were, therefore, massacred. Those who succeeded in escaping
sought shelter in the palace of the Bishop, who not only protected
them, but incurred the censures of his contemporaries by ordering
the execution of some of the holy murderers. A similar tragedy was
acted at Worms, where some of the victims were temporarily saved
by the Bishop, while a few were baptized, and the rest, men and
women, committed suicide. At Mayence, they were slaughtered in
the Archbishop’s palace, where they had taken refuge, and many
murdered each other rather than betray their faith. At Cologne the
majority of the community were rescued by the good burghers and
their humane Bishop Hermann III. The Emperor Henry IV, also, on
his return from his third Italian campaign, publicly denounced the
crimes of the Crusaders, instituted proceedings against the
Archbishop of Mayence, who had shared the spoils of the Jews, and
permitted the surviving converts to return to Judaism;
1097
thereby drawing down upon himself an indignant
reproof from his own antipope, Clement III., on whose behalf he had
undertaken that expedition to Italy. For, however grateful Clement
might be to Henry, he could not conscientiously connive at his
impious interference with the designs of Providence.
1146 Similar scenes were repeated at the Second
Crusade. Pope Eugenius III. issued a Bull, announcing
that all who joined in the Holy War would be released from the
interest which they owed to the Jewish money-lenders. St. Bernard
seconded the Pope’s recruiting efforts. Peter the Venerable, Abbot of
Clugny, exerted himself by might and main to inflame King Louis VII.
of France and other noble Crusaders against the Jews: “Of what use
is it,” wrote he to the king, “to go forth to seek the enemies of
Christendom in distant lands, if the blasphemous Jews, who are
much worse than the Saracens, are permitted in our very midst to
scoff with impunity at Christ and the Sacrament?... Yet, I do not
require you to put to death these accursed beings, because it is
written ‘Do not slay them.’ God does not wish to annihilate them, but
like Cain, the Fratricide, they must be made to suffer fearful
torments, and continue reserved for greater ignominy, and to an
existence more bitter than death.” In conformity with this charitable
doctrine, the Jews of France were forced to yield their ill-gotten gains
for the service of the cause of God.
Far worse was their fate in Germany. Even the partial protection
which the citizens of the Rhineland had afforded the persecuted
people in the First Crusade was now withdrawn, and the
undisciplined mob gave the reins to the gratification of its religious
zeal and of its lust. St. Bernard endeavoured to curb the demon of
fanaticism, which his own eloquence had raised, by admonishing the
enthusiasts, with more earnestness than consistency, that “the Jews
are not to be persecuted, not to be butchered.” But his well-meant
efforts produced no other effect than to turn the fury of the mob
against himself; for a rival monk, Rudolf, had been going up and
down the Rhineland, everywhere preaching, with tears in his eyes,
that all Jews who were found by the Crusaders should be slain as
“murderers of our dear Lord”—an appeal far more acceptable to the
brutal herd of besotted hinds to whom it was addressed. The
persecution commenced at Trèves, in August, 1146, where a Jew
was seized by the Crusaders, and, on refusing to be saved by
baptism, was murdered and mutilated. Soon afterwards a Jewess at
Speyer was tortured on the rack. Many others were waylaid and
made to suffer for their constancy at Würsburg and elsewhere. From
Germany the frenzy passed into France. At Carenton, Rameru, and
Sully the Jews were hunted and massacred.
For one who, in the face of such deeds, strives to preserve his
faith in human nature, it is reassuring to note that the German
bishops exerted themselves on behalf of the miserable victims, and,
by accepting a simulated and temporary conversion, rescued many
from martyrdom. The Emperor also extended to them his protection.
But this favour was to cost the recipients dearly. Henceforth the
German Jews were regarded as the Emperor’s protégés, which
gradually came to mean the Emperor’s serfs. All they possessed,
including their families and their own persons, were the Emperor’s
chattels to be bought, sold, or pledged by him at pleasure. They
were designated “Chamber-servants” (Servi Camerae or
Kammerknechte); a servitude, however, that had the advantage of
making it the Emperor’s interest to safeguard them against
oppression, and to suffer no one to fleece them but himself.
And yet, such is the wonderful vitality of the race, the Jewish
traveller, Benjamin of Tudela, who visited the Jewry on the Rhine
only seventy years after the First, and twenty after the Second,
Crusade, describes these colonies as rich in money and culture and
hope; the brethren whom he found there as hospitable, cheerfully
alive, and awaiting the Messiah. This expectation had never been
entertained in vain. The wish had always yielded its own fulfilment.
About this time, it gave rise to David Alroy, another Redeemer
destined to delude the hapless nation for a while. He appeared in
Asia Minor, and summoned his brethren to his banner. Many gave up
all they possessed in order to respond to the call, and the
enthusiasm spread from Baghdad to East and West. But the
Messiah was excommunicated by the Synagogue, and murdered by
49
his own father-in-law while asleep. According to another version,
Alroy, when face to face with the Sultan, exclaimed: “Cut off my head
and I shall yet live.” He thus astutely exchanged prompt death for
lingering torture. Many Jews, however, continued to believe in him
for generations after his death.
The same spirit of religious mania which gave birth and
sustenance to the Crusades animated other movements, more
enduring in their results, if less romantic in their form. In 1198 the
throne of St. Peter was filled by Innocent III., a young and zealous
priest, fired with the lofty ambition to make Romanism the dominant
creed over East and West, and himself the autocrat of a united
Roman Catholic world. His genius was all but equal to this Titanic
task, and in a reign of eighteen years Innocent, favoured by the
convulsions and feuds which rent the whole of Europe, succeeded in
raising the Papacy to a pinnacle of power only dreamt of by his
predecessors, and attained by few of his successors. A worthy
spiritual descendant of Gregory VII., he made and unmade
Emperors and Kings at will, visiting the disobedience of princes upon
whole nations, or compelling them to submission by releasing their
subjects from their oath of allegiance. He exercised an absolute
sway over the conscience and the mind of contemporary
Christendom, and his pontificate was distinguished, in Gibbon’s
scathing phrase, by “the two most signal triumphs over sense and
humanity, the establishment of transubstantiation and the origin of
the Inquisition.” It was he, who by a rigorous interdict
1200
laid upon the Kingdom of France, compelled the
headstrong Philip Augustus to recall the wife whom he had
dismissed; who by the ban of excommunication forced
1208
John, King of England, to lay his crown at the feet of
his legate, and who by the execution of a like sentence
1211
against the Emperor Otho, John’s nephew, had
humbled that mighty and haughty monarch to the dust. It was under
his auspices that the Fifth Crusade was undertaken,
1203
and it was with his connivance that the forces,
ostensibly recruited for the deliverance of the holy Sepulchre from
the infidels, were employed to subjugate the Christian Empire of the
East, and thus to pave the way for the advent of the Turk.
However, these and many other triumphs notwithstanding,
Innocent’s dream of world-wide dominion could not be fully realised
while such a thing as individual conscience remained in the world,
and individual conscience could not be abolished without
persecution. Innocent was too great a despot to shrink from the
difficulties of the work; too sincere a Catholic to show any pity to
unbelief. The thirteenth century opened under evil omens for
dissenters. Immediately on his accession Innocent had demanded
the suppression of the Albigenses of Southern France, those
unfortunate forerunners of the Reformation, because they, choosing
to follow the dictates of their own conscience, refused to conform to
the practices of the Church and to comply with the commands of her
clergy. Raymund VI., Count of Toulouse, however,
1207
declined to consider the massacre of his subjects one
of his duties as a sovereign, and was excommunicated. In the
following year the Pope, seizing the pretext offered by the murder of
his legate, proclaimed an unholy war against the heretics. And so
great was the Pope’s power over the superstitious and unscrupulous
world of mediaeval Europe, that thousands volunteered to carry out
the Pontiff’s atrocious orders. Raymund, who alone among the
Christian princes had ventured to raise his voice in defence of the
persecuted, had meanwhile been stripped of his dominions, dragged
naked into the Church, scourged by the Pope’s legate, and was now
forced to lead the crusade against his own people. The harmless
population was almost exterminated by the most barbarous means,
their heresy was all but quenched in blood; and one of the most
prosperous and civilised provinces of Europe was laid waste. The
ferocity of the soldiers was eclipsed by that of the monks and priests,
great numbers of whom swelled the ranks of the butchers. On the
22nd of July, 1209, the city of Beziers was taken by storm. The
Abbot Arnold, being asked how the heretics were to be distinguished
from true believers, replied, “Slay all; God will know his own.” “We
spared,” said the same monk in his report to the Pope, “no dignity,
no sex, no age; nearly twenty thousand human beings have perished
by the sword. After that great massacre the town was plundered and
burnt, and the revenge of God seemed to rage upon it in a wonderful
manner.”
So fared European heretics within the Church. Infidels of alien
blood could hardly expect better treatment. The popular notion that
the dispersion and sufferings of the Jews were a divine punishment
for the crucifixion of Christ was raised by Innocent to the dignity of a
dogma. It followed as a logical corollary that it was the sacred duty of
Christ’s Vicar on earth to make the culprits feel the full rigour of the
sentence. After the fashion of fanatics, Innocent mistook his own
intolerance for holy enthusiasm, and, while indulging his own hatred,
he imagined that he was only hating the enemies of Heaven. It was
also currently believed that the example and the teaching of the
Jews tended to pervert their Christian neighbours, and to encourage
protest and heresy. The Albigensian sect in France, already
mentioned, like the Hussite reform movement in Bohemia two
centuries later, was attributed to Jewish influence. For both these
reasons, their own infidelity and their tendency to foster infidelity in
others, the Jews ought to be crushed.
The times were propitious. In 1167 the assassination of
Raymund, Viscount of Beziers, had deprived the Jews of their
protector. His successor Roger, who favoured the
1170
Albigensian heretics, had Jewish sheriffs; but his
partiality to these two classes of enemies of Catholicism had
provoked the wrath of the Pope and led to the prince’s tragic death.
At Montpellier William VIII. and his sons excluded the Jews from the
office of Sheriff. But these restrictions were not
1178–1201
sufficient. Innocent began the attack methodically in
1205, when he wrote to Philip Augustus, King of France, complaining
of the usurious extortions of the Jews in that country, of their being
allowed to employ Christian servants and nurses, and of the fact that
Christians were not admitted to depose against Jews—things which
were contrary to the resolution of the Third Lateran Council held
under Pope Alexander III. Moreover, Innocent
1179
complained that the Jewish community of Sens had
built a new synagogue which rose to a greater height than the
neighbouring Christian church, and disturbed the service in the latter
by loud and insolent chanting; that they scoffed at Christianity, and
that they murdered Christians; and he ended by exhorting Philip
Augustus to oppress the enemies of Christ. A similar epistle was
addressed to Alfonso, King of Castile, threatening him with St.
Peter’s displeasure, should he continue to allow the Synagogue to
thrive at the expense of the Church. Three years later a pastoral
epistle to the same effect was sent to the Count of Nevers, urging
him to coerce the Jews and condemn them to serfdom, for they, “like
the fratricide Cain, are doomed to wander about the earth as
fugitives and vagabonds, and their faces must be covered with
insult.” The writer further pointed out that it is disgraceful for
Christian princes to receive Jews into their towns and villages, to
employ them as usurers in order to extort money from the Christians,
and to allow them to press wine which was used in the Lord’s
Supper.
1209 All the above exhortations were systematised by
the Council of Avignon. By the Statutes then passed
the Jews were officially pronounced as polluted and polluting. It was
decreed that “Jews and harlots should not dare to touch with their
50
hands bread or fruits exposed for sale.” The old Church law which
forbade the Jews to employ Christian servants was renewed and
enforced. The faithful were warned neither to receive services from
Jews nor to render services to them, but to avoid them as a pest. All
who had any dealings with Jews who transgressed these decrees
were threatened with excommunication. Raymund of Toulouse, the
protector of the Albigensian heretics and friend of the Jews, and all
the barons of free cities, were bound by oath to carry out the
decisions of the Council.
1211 Once more oppression from without fanned the
longing for Redemption in the hearts of the Jews. The
yearning after Zion, invigorated by Jehuda Halevi’s poetry, impelled
more than three hundred Rabbis of France and England to emigrate
to the Holy Land, where they visited the spots hallowed by the spirits
of the past, wept over the ruins of their departed glory, and built
synagogues and schools in order to keep alive the memory and the
hope of a better day.
Meanwhile the Pope did not allow the iron to cool. In 1215 a
great Œcumenical Council was convoked in Rome, under his
presidency, to complete the ruin of the Albigenses, to stimulate the
Crusades against the Saracens of Spain and Palestine, and,
generally, to promote the kingdom of God on earth. The Jews,
knowing from experience that any measures taken to that end could
not fail to redound to their detriment, hastened to send deputies to
Rome, in order to ward off the blow. But their endeavours proved
fruitless. Four out of the seventy canonical decrees passed by the
Council referred to them. The King of France, the Duke of Burgundy,
and all other princes were called upon to lend their help in reducing
the doomed people in their respective dominions to that state of
bondage which was ordained for it by the divine will, as interpreted
by theological bigotry. The Pope’s order met with general obedience.
In most European countries the Jews were forbidden to hold any
public appointment of trust, or to show themselves in the streets at
Easter. They were obliged to pay tithes to the Church that
persecuted them, and the head of each Jewish family was forced to
subscribe an annual sum at the Easter festival. They were compelled
by heavy fines and penalties to wear a yellow badge of distinction,
which in their case meant a badge of shame, and the Christians
were exhorted by their pastors not to allow their homes or their
shops to be defiled by the presence of Heaven’s enemies.
However, papal decrees and anathemas notwithstanding, self-
interest might have prevailed over religious fanaticism, and the
sovereigns who had hitherto sold their connivance to the Jews might
have continued to shield them. In fact, the Duke of Toulouse and the
barons, despite the oath which they had been obliged to take,
continued to invest the Jews with public dignities, and in Spain the
Pope’s commands were strenuously ignored. But there now came
into being a power of persecution, even more formidable than
Papacy itself. The pan-Catholic enthusiasm, which had inspired
Innocent’s anti-Jewish policy was bequeathed to two bodies of
apostles, through whose organised zeal it was destined to spread far
and wide, and, like a poisonous breath, to blight many a noble flower
in the bud. The age of stationary and corpulent monks was
succeeded by the age of lean and wandering friars. A
1223
few years after Innocent’s death were instituted the
Order of Dominic and the Order of Francis, the precursors of the
stakes and scaffolds of the Inquisition. The latter order had been
called into existence with the special object of stamping out the
Albigensian heresy. But an essential part of the mission of both
bodies was to hunt out dissent, to root out free-thought, and to
realise the bigot’s ideal of spiritual peace by means of intellectual
starvation. Uniformity was their idol, and to that idol they were
prepared to sacrifice the moral sense of mankind and the lives of
their fellow-creatures. The Jews supplied them with a splendid field
for the exercise of their missionary ardour: numerous, obstinate, rich
and unpopular, they offered a prey as tempting as it was safe. The
friars were in some ways an undoubted power for good; but the Jews
experienced none of this better side of their activity.
In 1227 a Council at Narbonne confirmed the canonical
ordinances against the Jews, and many ancient decrees of the
Merovingian kings were revived. Not only were the Jews forbidden to
take interest on money and compelled to wear the badge and to pay
taxes to the Church, but they were again prohibited from stirring
abroad during Easter. Shortly afterwards two other
1231
Councils at Rouen and Tours re-enacted and enlarged
the anti-Jewish statutes of the Council of Rome.
But the Dominicans were as subtle as they were zealous. They
felt that the citadel of Judaism which had held out for so many
centuries, could not be carried by storm. They resorted to less crude
tactics. With a patience, perseverance, and ingenuity worthy of their
high ambition, they devoted themselves to the study of the Hebrew
language and literature, their Master Raymund de Peñaforte
prevailing upon the Kings of Aragon and Castile to found special
colleges for the purpose. The Prophets of the Old Testament had
already supplied the apologists of the Church with proofs of the truth
51
of Christianity. The Talmud was now to supply them with fresh
proofs of the falsity of Judaism. From the pages of that marvellous
compilation of noble thoughts and multifarious absurdity, they culled
everything that was likely to reflect discredit on the morality or the
intelligence of their adversaries. In this campaign the Dominicans
were fortunate enough to enlist the services of renegade Jews, who,
after the fashion of renegades, strove to prove their loyalty to the
faith they embraced by a bitter persecution of the one they deserted.
One of these apostates, Nicolas Donin by name, in 1239 submitted
to Pope Gregory IX. a minute indictment of the pernicious book, and
induced him to issue Bulls to the Kings of England, Spain, and
France, as well as to the bishops in those countries, ordering a
general confiscation of the Talmud, and a public enquiry into the
charges brought against its contents. The Pope’s instructions, so far
as we know, appear to have produced no impression in the first two
kingdoms, but in France there reigned Louis IX., known to fame as
St. Louis: in mundane affairs a brave, high-minded, just and humane
prince; but not far in advance of his age in things celestial. In fact, he
possessed all the prejudices of an ordinary mediaeval knight, and
more than the superstition of an ordinary mediaeval monk. He was
sincerely convinced that the road to heaven lay through Jerusalem.
Acting on this conviction, he led the last two Crusades, and laid
down his life in the cause of Catholicism; a sacrifice which earned
him a place among the saints of the Church. Such a prince could
not, without flagrant inconsistency, ignore the Pontiff’s wishes. He,
therefore, ordered that a careful search for the suspected book
should be made throughout his dominions, that all copies should be
seized, and that a public disputation should be held, in which four
Rabbis were to take up the challenge thrown down by Donin.
The antagonists met in the precincts of the Court, and a brilliant
assembly of secular and spiritual magnates formed the audience.
Donin warmly denounced the Talmud as a farrago of blasphemy,
slander, superstition, immorality and folly, and the Rabbis defended it
as warmly as they dared. The debate, though distinguished by all the
scurrility and more than all the ferocity of a village prize-fight, seems
to have been conducted on the principle that whichever side had the
best of the argument, the Christian should win; and the Court of
Inquisitors returned a verdict accordingly. The Talmud was found
guilty of all the charges brought against it and was sentenced to the
flames. Execution was delayed for two years through bribery; but it
was carried out in 1242. Fourteen—some say four and twenty—
cartloads of Rabbinical lore and legislation fed the bonfire. The grief
of the French Jews at the loss of their sacred books was bitter, and
the most pious amongst them kept the anniversary of the cremation
52
as a day of fasting.
1263 Twenty-one years later a similar tourney took place
in Barcelona by order, and in the presence, of Jayme
I., King of Aragon. Don Jayme had borrowed from his northern
neighbours the axiom that the Jews were to be treated as royal
chattels. Moreover, his conscience was in the keeping of Raymund
de Peñaforte, the Master of the Dominicans, a great Inquisitor born
before his time. King Jayme had led an amorous and not immaculate
youth. He was, therefore, in his old age, peculiarly susceptible to his
Confessor’s admonitions. The sins of love should be atoned for by
acts of persecution. The religious freedom of the Jews should be
offered up as a sacrifice of expiation. It was the logic and the
morality of the Middle Ages.
The outcome of Jayme’s remorse was a theological contest at
the royal court of Barcelona. There again the lists were held for
Christianity by a Dominican friar of Jewish antecedents, while the
champion of Judaism was Nachmanides, famed in the annals of
Israel as the greatest philosopher, physician, theologian, and
controversialist of his age. Pablo Christiani politely endeavoured to
prove that the prophets of the Jews had predicted the advent and
recognised the divinity of Jesus. Nachmanides with equal politeness
denied that they had done anything of the kind. After five days’
refined recrimination the Court unanimously pronounced in favour of
Christianity. The books of the Jews were expurgated of all “anti-
Christian” passages, Nachmanides’s account of the controversy was
burnt publicly as blasphemous, and the author, then in his seventieth
year, banished from Spain, ended his days in Jerusalem. Pablo,
whose ambition was kindled by victory, undertook a tour through the
Iberian Peninsula and Provence, and, armed with a royal edict,
compelled the Jews to engage in religious controversies with him
and to defray the expenses of his missionary journeys.
Missions to the Jews became the fashion of the day, and the
kingdoms of the West were overrun by itinerant dialecticians seeking
whom they might convert. The Jews were forced to attend church
and to listen to sermons against their own religion. Thanks to their
long training in Rabbinical subtleties, the benighted people
sometimes proved more than a match for their assailants, and, if fair
play were not contrary to the laws of ecclesiastical warfare, they
might succeed in converting the would-be convertors. But, though
religious discussion was invited, nay, forced by the Church, it was
always on the clear understanding that the Christians might beat the
Jews, but that the Jews should under no circumstances be allowed
to beat the Christians. To prevent any misconception on the subject,
Thomas Aquinas, justly celebrated as one of the least bigoted of
theologians, and distinguished among schoolmen for his tolerance of
Judaism, gravely cautioned his readers to have no intercourse with
the Jews, unless they felt sure that their faith was proof against
reason.
In later years the work of conversion in the various countries was
entrusted by the Popes to Dominican friars and inquisitors, who
carried it on with a diligence never practised except by men
fanatically believing in the truth of their doctrines and with a
ruthlessness only possible in men too firmly persuaded of the
holiness of the end to be scrupulous about the means. These
apostles were authorised to reinforce the powers of their eloquence
by an appeal to the secular arm. Even so modern missionaries in
China have been known in time of peril to forget that an apostle
should be above earthly weapons and “to clamour for a gunboat with
53
which to ensure respect for the Gospel.”
And while disappointed theologians represented the Jew’s
loyalty to his religion as a proof of his anti-Christian tendencies,
scholars represented his aloofness as a proof of his anti-social
nature, and they both agreed in denouncing him as “an enemy of
mankind.” This lesson, to use the words of a distinguished Jewish
writer, “was dinned into the ears of the masses until the calumny
became part of the popular creed. The poets formulated the idea for
54
the gentry, the friars brought it to the folk.”
The animosity thus fomented against the Jews found frequent
opportunities of translating itself into acts of horror. In France, after
the war declared against the unfortunate people by the Church, they
lost the royal protection which they had enjoyed hitherto, and were
henceforth exposed not only to the spasmodic fury of the populace,
but also to systematic persecution on the part of bishops, barons and
towns. Bishop Odo of Paris, in 1197, forbade the Christians to have
1236
any dealings, social or commercial, with the Jews. The
Crusaders called to arms by Gregory IX. attacked the
Jewish communities of Anjou, Poitou, Bordeaux, Angoulème, and
elsewhere, and on the Jews refusing to be baptized, the holy
warriors trampled many of them, men, women and children, to death
under the hoofs of their horses, burned their synagogues, and
pillaged and sacked their private dwellings. St. Louis encouraged the
conversion of the Jews, permitting the children of baptized fathers to
be torn away from their unregenerate mothers. By a
1246
decree of the Council of Beziers the disabilities of the
Jews were once more confirmed, and the Christians were now
forbidden to call in Jewish doctors, thus depriving the Jews of the
profession which they had hitherto almost monopolised in Europe. A
few years after Pope Alexander IV., who had just
1257
established the Inquisition in France at the request of
St. Louis, issued another Bull in which the ruler of that kingdom and
other princes were again exhorted to enforce the distinctive garb
upon the Jews and to burn all copies of the Talmud. To omit minor
acts of oppression, the fanatical sect of the “Shepherds,” following
the example of the Crusaders, massacred the Jews on the Garonne
in 1320.
In Germany the sufferings of Israel were equally
1218–1250
severe. The Emperor Frederick II., despite his infidelity
and his enmity towards the Papacy, adopted the Pope’s anti-Jewish
decrees. He excluded the Jews from public offices, he censured the
Archduke of Austria for tolerating and protecting them, he enforced
the use of the badge in his Italian and Sicilian dominions, and he
oppressed them with heavy taxes, dwelling with especial satisfaction
on the dictum that the Jews were the Emperor’s serfs. In the
troublous period which followed Frederick’s death the Jews were
slain and burnt in great numbers at Weissenberg, Magdeburg, and
Erfurt, while other cities year after year witnessed wholesale
slaughter, and “Jew-roaster” became a coveted title of honour. In
addition to occasional massacre, from the end of the twelfth to the
middle of the fifteenth century the German Jews underwent eight
expulsions and confiscations of their communal property: Vienna
(1196), Mecklenburg (1225), Frankfort (1241), Brandenburg (1243),
Nuremberg (1390), Prague (1391), Heidelberg (1391), and Ratisbon
(1476).
In Switzerland the persecution commenced about the middle of
the fourteenth century, and several expulsions are recorded in the
ensuing century. In Eastern Europe the Jews suffered in Russia and
Hungary. The semi-civilised and semi-Christianized Magyars, who
had hitherto tolerated the Jews, were incited to acts of oppression by
the Western friars. Poland and Lithuania were the only European
countries where the Jews of the later Middle Ages found shelter, and
consequently both those countries received large numbers of
fugitives from the Western fields of carnage.
Credulity joined hands with bigotry. No story told of the Jews was
too extravagant for belief; no charge brought against them too trivial
for repetition, provided it afforded an excuse for persecution. Some
of the odious crimes attributed by the heathens in the early centuries
to the Christians, as a justification of their suppression, were now
revived by the Christians against the Jews. The latter were accused
of enveigling Christian children into their houses and sacrificing them
for ritual or medicinal purposes, of travestying the sacraments of the
Church, of poisoning wells and of committing all kinds of
abominations, which plainly rendered their utter extermination a
public duty. Similar charges, curiously enough, are still brought
against the Jews by the Christians of Eastern Europe, by the Jews
themselves against Hebrew converts to Islam in Turkey, and by the
Chinese against Protestant missionaries—“charges of gross
personal immorality and of kidnapping and mutilation of children,
which, however monstrous and malevolent, are not the less, but the
more serious, because they are firmly believed by the ignorant
55
audiences to whom they are addressed.” To the vulgar all that is
strange is sinister.
The free propagation of these heinous and disgusting myths
among the vulgar masses of mediaeval Europe led, as it had done in
ancient times and as it has done more recently, to a horrible
persecution of those against whom they were levelled.
1171
The Jews were ruthlessly burnt by order of Duke
Theobalt at Blois, were massacred by the populace in Languedoc
1321
and Central France, and on the plague breaking out in
the following year, they were burnt en masse—men,
women and children. A season of alternate persecution and
toleration ensued, until they were banished from Central France and

You might also like