IRON PIPE corrosion IN DISTRIBUTION SYSTEMS

Author(s): LAURIE S. MCNEIILL and MARC EDWARDS

Source: Journal (American Water Works Association), Vol. 93, No. 7 (JULY 2001), pp. 88-100
Published by: American Water Works Association
Stable URL: http://www.jstor.org/stable/41297605
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distribution systems

BY LAURIE

IRON

IN

PIPE

MMARi^S rHF,RBULfSOF
Si
AlMSS?300 ?m^EViWED
TOTHE
ARTICLES
RELEVANT
water mnrn.

A^DA Rf-V^W
OFWtfcHAL
?M*>UUT|0HS
OFUPCOMING
REGULATIONS
FORIRON
CORROSION
IS ALSOINCLUDED.

AND MARC EDWARDS

corrosion

DISTRIBUTION

REVIEW
THISLITERATURE

ummz

S. MCNEILL

SYSTEMS

potablewaterformore
pipeshavebeenusedto transport
than500 years(Gedge,1992), and ironpipecorrosionhas beena
problemforjust as long. AWWAestimatesthatit will cost US
waterutilities
$325 billionoverthenext20 yearsto upgradewater
east-iron
distribution
(AWWA,1999). ThisAWWAvalueis basedon
systems
of$77.2 billionforservice
theUS Environmental
Protection
Agencyestimate
linesoverthenext
and replacement
oftransmission
and distribution
system
ofdistribution
20 years(Davieset al, 1997). The majority
systempipesare
iron
ductile
iron
of
iron
material:
cast
(22%), andsteel(5%)
(38%),
composed
1997
of
the
100
AWWAResearch
a
(AWWA,1996). Moreover,
survey
largest
Foundation(AWWARF)memberutilitiesfoundthat"the mostcommon
distribution
systemproblemis corrosionofcast-ironpipe" (Bray,1997).
on ironcorrosionis quite large,most
Althoughthe bodyof literature
withthe
conditionsinconsistent
studieswereconductedat experimental
oil and
brine
environment
water
distribution
solutions,
(e.g.,
potable
system
The
or
acidic
conditions, veryhightemperatures). goal
gas pipelines,highly
theresultsofseveralhundredpeerofthisliterature
reviewis to summarize
waterindustry.
reviewedarticlesrelevantto thedrinking
Corrosionof ironpipesin a distribution
systemcan cause threedistinct
oxidationto solubleiron
butrelatedproblems.
First,
pipemassis lostthrough
as largetuberscale.Second,thescalecan accumulate
speciesor iron-bearing
clesthatincreasehead loss and decreasewatercapacity.Finally,therelease
to thewaterdecreases
of solubleor particulate
ironcorrosionby-products
itsaestheticqualityand oftenleadsto consumercomplaintsof "redwater"
mustbe concernedwithall threeof these
at thetap. The waterindustry
aspectsofcorrosion.

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distribution systems

and
includepH, alkalinity,
buffer
intensity.
Role of pH. In the pH
range7 to 9, bothweight
loss (Stumm,1960) and
degree of tuberculation
(Stumm,1960; Larson &
Skold,1958b; Rice, 1947)
were found to generally
increase with increasing
pH. In contrast,by-product releasewas decreased
at higherpH (Hidmiet al,
1994). Again,thisis consistentwithincreasedcorrosion by-productsbeing
intothescale
incorporated
layer.However,one study
foundthatbothweightloss
and
iron concentration
andcanhaveseveral
different
Iron
corrosion
isanextremely
manifestations,
complex
process
decreased
as pH was raised
as shown
inthisiron
oneofwhich
istuberculation
pipe.
from8.5 to 9.2 (Kashinkuntiet al, 1999).
Alkalinity.Increasing
IRONCORROSION
MANIFESTS
studysaw decreasedironby-product alkalinitygenerallyleads to lower
ITSELFIN DIFFERENT
WAYS
releaseat higherpH (Hidmi et al,
etal, 1999;
weightloss (Kashinkunti
Ironcorrosion
isan extremely
couldbe
com- 1994).Although
bothresults
6c
Hedberg Johansson,1987) and
of
the
Because
variof
corrosionrate (Kashinkuntiet al,
plexprocess.
large
explainedbygreater
incorporation
in
distribution
condicorrosion
into
the
scale
1999; Raad et al, 1998). Also,fewer
ability
system
by-products
a
factor
be
at
from
a
customer
tions, particular
may
higher
pH,
utility
perspective
complaintsof red water
criticalin one systembut relatively theformer
result
is "bad" whereasthe were receivedwhen the alkalinity
unimportantin another system. latteris "good." Thus, thisreview was maintained at highervalues
corrosion
itself
hasseveral carefully
whichaspectofiron (Horsleyet al, 1998).
tracked
Moreover,
different
was studied(corrosion
manifestations
and can be
corrosion
Bufferintensity.
rate,
Higher buffer
evaluatedin manyways. Previous scaleformation,
and ironby-product intensityis oftenassociated with
studieson ironpipe corrosionhave
thetwo
release).Table 1 providesa general increased
alkalinity,
although
focusedon different
of
iron
overview
of
the
effects
of
are
not
aspects
expected
parameters
exactlyequivacorrosion.
Theseincludepipedegra- variousfactors
on corrosion.
Thecat- lent.However,theireffecton iron
dation(measured
loss,oxy- egoriesof "beneficial"and "detri- corrosionseemsto be similar.Sevbyweight
or
corrosion
cur- mental"areusedto describe
howthe eralstudiesfoundthatthemaximum
genconsumption,
scale
formation
effect
would
be
rent),
(measuredby
perceived
bythewater weightloss forcast-ironsamples
headlossorscaledeposition),
andby- utility
or consumer.
Further
explana- occurred at the minimumbuffer
release(measured
inthe intensity(pH 8.4) presumablybeareprovided
product
byironcon- tionandreferences
sections.
causehigherbuffer
attenucentration,
color,staining,
turbidity, following
intensity
or numberof customer
atespH changesfromcorrosion
reaccomplaints).
to compare SEVERAL
WATERQUALITY
tionsat anodic and cathodicareas
Thus,it can be difficult
conclusions
ortheories
fromdifferent PARAMETERS
(Clement&: Schock,1998; Van Der
studies.
Forexample,
onestudyfound INFLUENCE
CORROSION
Merwe,1988; PisiganJr.& Singley,
thatheadlossincreased
withincreasthat 1987; Stumm,1960). However,one
Keywaterqualityparameters
corrosion studyfoundthe opposite effect
ingpH (Rice,1947),whereasanother are expectedto influence
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TABLE1

ofexpected
effects
ofvarious
factors
oniron
corrosion
Summary

Potential
Effect
On. . .*
Factor
pHincrease
increase
Alkalinity
Buffer
increase
intensity
Dissolved
increase
oxygen
Kuch
reaction
Calcite
scale
Siderite
scale
Green
rust
scale
index
Langelier

Corrosion
Rate
+
+
+
+
+
Should
not
beused

+
+
?

By-product
ScaleBuildup Release
+
+
?
?

?
+
?
+
Should
not
Should
not
beused
beused

Larson
index
increase
Disinfectant
residual
increase
inhibitors
Phosphate
Silicates
Pipeageincrease
Water
increase
velocity
time
increase
Stagnation
Microbial
activity
?
increase
Temperature
Dissolved
?
copper
Natural
matter
+
+
organic
"Free
carbon
dioxide"
?
*+- beneficial
- mixed
?- not
detrimental
known
effect,
effect,
results,

weightlossforironcouponsin stag- In these equations, (s) denotes a

nantwaterincreasedwithincreasing solid precipitate.
buffer
can
(Sanderet al, 1996).
Thus,oxygenconcentration
intensity
havevarying
on ironcorrosion.
effects
DISSOLVEDOXYGEN
As expected, the corrosion rate
(DO) PLAYS
ROLEIN CORROSION
increases
withincreasing
DO (Gedge,
DO is an important
electron
several
studies
found
accep- 1992),although
torin thecorrosionofmetalliciron:
thatironreleasedecreased
withhigher
DO duringstagnation(Sarinet al,
+
+
etal, 1998). Effects
on
2000; Beckett
Fe(mctai)0.5O2 H2O
Fe+2+ 2OHiron
concentration
and
tuberculation
(1)
on thetype
maybe mixeddepending
DO can also playa role in theoxiof scale formed.Higherturbidity
(a
dationofferrous
iron(Fe+2)or iron surrogate
forironconcentration)
was
seenatloweroxygen
saturation
scales,forexample:
(Hulsmann et al, 1986), but it is also
Fe+2+ 0.2502 + 0.5H20 + 20Hreportedthatwaterfreeof DO will
<>
nottuberculate
(2)
(Baylis,1953). DO is
Fe(OH)3(s)
also responsibleforthe abilityof
ions,including
buffering
phosphates,
<
to inhibitcorrosion(Stumm,1960;
3FeC03(v)+ 0.502 > Fe304^
+ 3C02
(3)
Cartledge,1959; Pryor& Cohen,
inwaterwithDO
1951).Forexample,
< 1 mg/L,
solutionswithphosphates
<
(4)
hada higher
corrosion
ratecompared
4Fe304^ + 02 6Fe203^

withwaterswithno phosphates;in
waterwith1-6 mg/LDO, thistrend
was reversed
(Uhligetal, 1955).
KUCHMECHANISM
PROMOTESCORROSION
IN LOWDO CONDITIONS
In theabsenceofoxygen,
itis possibleforpreviously
depositedferric
scale(lepidocrosite,
7-FeOOH) to act
as anelectron
ThisKuchreacacceptor.
tionproducesferrous
ironandallows
thecorrosion
reaction
tocontinue
even
afterDO is depleted(AWWARF&
DVGW,1996; Kuch,1988):
+ 2FeOOH(scale)
+ 2H+
Fe(metal)
<>3Fe+2+ 40H-

(5)

A recentstudy(Sarinetal, 2000)
foundthatironcorrosionstillproceeded underanaerobicconditions
despitethe lack of lepidocrositein
the iron scale, indicatingthat the
Kuch mechanismis not the only
mechanism
ofironreleasein deoxywaters.
genated
SCALECOMPOSEDOFMANY
COMPOUNDS
The rateof corrosionof theiron
metalhas littlerelationshipto the
amountof iron thatactuallygoes
intothewater,primarily
becauseof
the depositionof oxidized iron or
othercompoundsinto a scale that
servesas a largereservoir
of corrosion by-products.
Ironscale is typicallycomposedofmanycompounds
andis thusveryheterogeneous
(Table
2). Thisscalelayermayprovidepassivation(protection)
the
bylimiting
diffusion
ofoxygento themetalsurfaceand slowingthecorrosionreaction. However,the scale will also
contributeiron to the water.This
includesboth soluble speciesfrom
scaledissolution
as wellas scaleparticlesthatdetachfromthesurface.
itis difficult
to model
Unfortunately,

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distribution systems

this scale behavior.The scales are

oftenpoorlycrystallized
and heterogeneous,makingsolubilitypredictionsverycomplex;evenifsolubility
was understood,thewatermay be
undersaturated
becauseofkineticor
masstransfer
limitations.
Particulate
detachmentmechanismsare also
complicated,dependingon factors
such as scale durability
and adherence,watervelocity,and temperaturechanges.
is a comClearly,scaleformation
plicatedprocessthatdependson a
ofphysicalandchemicalconvariety
ditionsin each particularsystem.
However,severalwell-knowntypes
ofscalearepostulatedto affectiron
corrosion.
Calciumcarbonate.Precipitation
of a thinlayerofprotective
calcium
carbonate(presumably
calcite)was
theearliest
proposedmethodforconiron
corrosion,and it was
trolling
popularthroughat leastthe1980s.
Many articleshave been dedicated
to extolling
thevirtuesofcalcitelayers (Flentje,1961; Stumm,1960;
Larson, 1960; Stumm, 1959;
Stumm, 1957; Larson & Skold,
1957; Stumm,1956; Baylis,1926;
Tillmans& Heublein, 1912), and
many others detail methods to
achievea perfect
layerof protective
calcite(see nextsection).However,
fewarticles
everdemonstrated
a beneficialroleforcalcitein controlling
ironcorrosion.
Siderite.The sideritemodelpostulatesthattheformation
ofreduced
iron species, especially siderite
(FeC03), providesa moreprotective
scalethanoxidizedferric
scalessuch
as goethite(FeOOH) or hematite
& DVGW,1996;
(Fe203)(AWWARF
Sontheimer
et al, 1981). Sideritehas
been found in many iron scales
(Smithet al, 1997; Fiksdal, 1995;
Mishraet al, 1992; Feigenbaumet
et al, 1978b;
al, 1978a; Feigenbaum

"Redwater,"
which
iscausedbytherelease
ofsoluble
orparticulate
iron
corrosion
to
the
can
result
in
customer
by-products water,
complaints.

Stumm,1960; Baylis,1926). Howto note a disever,it is interesting

in studsiderite
crepancyregarding
ies of pure iron in high-carbonate
solutions(notdrinking
water).Two
suchstudiesconcludedthatsiderite
was thekeyto forming
a protective
scale (Simpson& Melendres,1996;
Blenginoet al, 1995). However,two
otherswithsimilarconditions
found
that the formation of siderite
destroyedthe protectivenatureof
otherironoxide films(Valentiniet
al, 1985; Ikedaet al, 1984).
Greenrust."Green rust" is the
genericname given to iron combothferrous
and
poundscontaining
ferric
iron,as wellas otherionssuch
as carbonate,chloride,and sulfate
(Genin et al, 1998; Simon et al,
1997). Greenrustshavebeenidenti-

fiedinthecorrosion
on iron
products
and steel (Tuovinen et al, 1980;
McGill et al, 1976), and theymay
act similarly
to sideriteand forma
film(AWWARF&
denseprotective
DVGW, 1996).
CORROSION
INDEXES
DO NOTSOLVEPROBLEMS
Calcite indexes. The Langelier
index(Merrill& Sanks,1979; Merrill Sanks,1978; Merrill& Sanks,
1977a;Merrill& Sanks,1977b;Langelier,1936) (also calledthesaturationindex[SI]) has beenimproperly
applied as the cure-allmethodfor
solvingcorrosionproblemssinceit
was first
proposedin 1936.Although
thismethodwas successfulat some
it was by no meansa uniutilities,
versalmethodforcontrolling
corro-

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distribution systems

sion. To his credit,Langeliernever

intendedtheindexto be usedin this
mannerand evenpointedoutitslimitationin certainwaters(Langelier,
1946). Several otherstudies also
foundthattheSI had no correlation
withcorrosionrate (PisiganJr.&
1987; Pironetal, 1986; SinSingley,
gley,1981; Larson 6c Sollo, 1967;
Stumm,1960). Despite proposed
modifications
to theLangelierindex
(PisiganJr.6c Singley,1985a; Pisigan Jr.6c Singley,1985b; Schock,
usebymany
1984) and itscontinued
theAWWAmanualon corutilities,
rosion states, "In light of much
the
empiricalevidencecontradicting
connection
betweentheLI
presumed
this
index]and corrosion,
[Langelier
practice should be abandoned"
(AWWARF6c DVGW, 1996). Likewise,othercalciteindexesthathave
beenproposedhaveonlylimiteduse
in corrosioncontrol.These indexes
includethe Ryznarindex (Ryznar,
index(Millette
1944),aggressiveness
etal, 1980),momentary
excess(Dye,
force
index
1958), driving
(Rossum
6c Merrill,1983), and calciumcarbonateprecipitation
potential(Merrill& Sanks,1978; Merrill6c Sanks,
1977a; Merrill6c Sanks,1977b).See
Rossum & Merrill (1983) for a
reviewof all indexes.
Larsonindex.The studiesof Larson (Larson,1975; Larson& Skold,
1958a;Larson6c Skold,1957) found
thattheratioofchlorideand sulfate
to bicarbonatewas important,as
expressedin theLarsonindex:
. , = 2[S04] + [C1]
- - v6'
Larsonindex
[HC03]
A higherindexindicatesa more
corrosive
water.Severalstudiesqualitativelyconfirmedthese results
tested
(althoughtheyneverdirectly
theaccuracyoftheLarsonindex)by

reportingthat increasedchloride
(Veleva et al, 1998; Hedberg 6c
Johansson,1987) and sulfate(Veleva et al, 1998; Riddick, 1944)
caused increased weight loss.
Anotherarticleproposed thatthe
presenceofsulfateor chlorideinthe
waterleads to ironchlorideand/or
iron sulfatecomplexesin the iron
scale thatincreaseferrousirondiffusion,causingincreasedironconcentrations(Elzenga et al, 1987).
However,severalotherstudiesfound
that
effects,
contradictory
including
sulfateinhibitsdissolutionof iron
oxides,leadingto lower ironconcentrations
(Bondiettiet al, 1993),
thepresenceof sulfateand chloride
caused a moreprotectivescale on
steel surfaces(Feigenbaumet al,
1978a), and thatsulfateand chlorideconcentrations
had no effect
on
loss
of
cast
iron
Der
(Van
weight
Merwe,1988; Pironet al, 1986).

colloidal range (Hatch 6c Rice,

laterdiscovered
1939). Researchers
thatthesephosphatescould sometimesprevent
ironcorrosionand red
waterproblems.
Condensedchain
Polyphosphates.
phosphates, known generallyas
werethefirst
polyphosphates,
phosto be usedincorphoruscompounds
rosioncontrol.The originalpolyphosphate, known as sodium
hexametaphosphate,glassyphosphate,or metaphosphate
glass,had
the approximatechemicalformula
Na22P20O61. Numerous studies
foundthatpolyphosphate
couldpreventcorrosionand/orcontrolred
water (Facey & Smith, 1995;
Williams, 1990; Huang, 1980;
McCauley,1960a;McCauley,1960b;
Hamilton6c Flentje,1958; IlligJr.,
1957; Larson, 1957; Uhlig et al,
1955; Lamb & Eliassen, 1954;
Parham6c Tod, 1953; Hatch,1952;
Raistrick,
1952; Barbee,1947; Rice,
DISINFECTANT
RESIDUALSCAN
1947; Cohen, 1946; Pallo, 1946;
INCREASECORROSION
RATES
Hatch6c Rice,1945a;Hatch6c Rice,
In general,disinfectant
residuals 1945b; Hatch 6c Rice, 1940). Corincreasecorrosionrates(PisiganJr. rosionprevention
andredwatercon6c Singley,
et
trol
in
are
fact
two
1987; Hoyt al, 1979).
verydifferent
pheMonochloraminewas foundto be
but
this
distinctionwas
nomena,
lessaggressive
thanfreechlorine
overlookedinthesestud(Tre- sometimes
week et al, 1985). However,if the ies.Manyreported
beneficial
results
corrosionis microbiallyinduced, forcorrosionare simplybecauseof
stabilization
ofironparticles,
higherdisinfectantresidualsmay
causing
decreasecorrosion(LeChevallieret
a decreasein thevisualobservation
of "redwater."This led researchers
al, 1993).
to claimthatironby-product
release
PHOSPHATE
INHIBITORS
had decreased,when in realitythe
PLAYA MIXEDROLE
ironconcentration
and eventhecorinhibitors
have
rosionratemighthaveincreased.
Phosphate-based
beenadded to drinking
watersince
The theory
ofpolyphosphate
cortheearly1900s.Phosphates
werefirst rosionprevention,
ifdiscussedat all
usedto prevent
excessivecalcitepre- inthesearticles,
varieswidely.Some
researchersclaimedthatthe polycipitation(Hoover 6c Rice, 1939).
The mechanismof this "threshold phosphateadsorbedonto the iron
treatment"was thoughtto be the
surfaceto forma protectivefilm
(Hatch6c Rice,1945b). Otherstudsorptiononto calcium carbonate
nuclei,whichpreventedthecalcite ies have stressedtheimportanceof
fromgrowingoutsideofthe calciumin polyphosphate
effectivecrystals

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distribution systems

Pirnie,1998; Williams,1990; Wagner Kuch, 1984; Swayze,1983;

recent
conHuang,1980).Moreover,
Name
Chemical
Formula
Oxidation
State
Iron
cernsabout zinc loadingto wasteII
waterplantshas somewhatcurtailed
Ferrous
hydroxide
Fe(OH)2
Ferric
III
the usage of thesezinc phosphates
hydroxide
Fe(OH)3
Wustite
II
FeO
(AWWARF&cDVGW, 1996).
Goethite
III
a-FeOOH
Othermechanisms.
Severalother
III
effects
are
Akaganeite
p-FeOOH
phosphate
traditionally
III
inthecontextofpipe
notconsidered
Lepidocrosite
-y-FeOOH
Hematite
III
corrosion.Phosphatesorptionmay
a-Fe203
III
restabilizeiron scales as colloids
Maghemite
7-Fe203
IIandIII
Magnetite
Fe304
(Hazel, 1942). A recentstudyfound
(Fe0-Fe203)
Ferric
III
thatorthophosphate
reducedthesize
oxyhydroxide
FeOx(OH)3_2x
Siderite
II
and increasedthesurfacechargeof
FeC03
Iron
III
iron colloids (Lytle & Snoeyink,
hydroxycarbonate Fex(0H)y(C03)z
"Green
rust"
IIandIII
2000). Polyphosphate has been
Fe(lll)x1Fe(ll)x2(0H)y(C03,S04)z
Vivianite
II
shown to induce ligand-promoted
Fe3(P04)2
-8H20
III
dissolution
ofironoxides,leadingto
Strengite
FeP04
Schrebersite
Notknown
in water
Fe4P
higherironconcentrations
(althoughveryhighphosphateconcentrationsmay actually cause a
decreasein ironconcentration
[Lin
ness(Kamrathetal, 1993; Rangelet
revert
to orthophosphate &c Benjamin,1990]). Orthophosphosphates
with time (Green, 1950), so the
al, 1992; Bailey,1980; Huang,1980;
phatecan eitherinhibitor enhance
resultsofmanypolyphosphate
stud- ligand-promoted
dissolution
Murray, 1970; Kleber, 1965;
dependiescouldbe confounded
McCauley,1960a;McCauley,1960b;
bythepres- ing on pH (Deng & Stumm,1994;
enceof orthophosphate.
Bondiettiet al, 1993). OrthophosUhliget al, 1955; Parham& Tod,
Bimetallic
In the phate also dramaticallydecreases
(zinc)phosphate.
1953; Hatch,1952; Raistrick,
1952;
Green,1950; Barbee,1947; Hatch
1960s,manufacturers
beganblending reductivedissolutionof ironoxides
& Rice, 1945a; Hatch 6c Rice,
and
polyphosphates orthophosphates (Biberet al, 1994).
1945b; Hazel, 1942; Hatch& Rice, with5-25% zincto formbimetallic
1939). Thisis believedto be because phosphates,claimingeitherthatthe SILICATESDISPERSE
of formation
of a thincalcitelayer presenceof zinc acceleratedpoly- IRONPARTICLES
made protectiveby the adsorption phosphatefilmformation
or thata
Silicatecompounds
werefirst
used
of polyphosphateions (MorrisJr., zinc orthophosphateor zinc poly- as a coagulationaid becauseoftheir
1967; McCauley,1960a; McCauley, phosphatefilmwas superiorto reg- abilityto adsorbontoparticlesand
ular phosphatefilmsforinhibiting decreasesurfacecharge(Stummet
1960b; Raistrick, 1952; Evans,
Other
studies
have
stressed
corrosion.
These compoundswere
1946).
al, 1967; Baylis,1937). Thesepropthe importanceof flowconditions reported
to decreasecorrosioncom- ertiesweresoon appliedto sequeson the efficacyof polyphosphate pared withregularpolyphosphates tration(dispersion)ofironparticles
action(see latersection).
or orthophosphates
in distribution
(Bancroft,
1988;
(Schocketal,
systems
Unlike
Mullen
Robinson
et
Orthophosphate. polyphos- Swayze,1983; Bailey,1980;
1998;
al, 1992; Broware added
&: Ritter,1980; Mullen & Ritter, manetal, 1989; Dart& Foley,1972;
phates,orthophosphates
forscale formation
butnotforiron 1974; Murray,1970; Powerset al,
Dart & Foley,1970). An earlystudy
1966; Kleber,1965). However,sev- (Riddick,1944) foundthatnatural
sequestration(Wagner,1992; Beneralstudiesfoundno benefit
ofzinc
silicapresentin thewaterwas conjamin et al, 1990; Boffardi,1988;
in therelatively
Wagner &c Kuch, 1984; Huang,
phosphatescomparedwithregular centrated
protective
1980; Pryor&c Cohen, 1951). One
phosphates(McNeill & Edwards, ironscale.Additionofsilicate-based
oftenoverlookedfactis thatpoly- 2000; Volk et al, 2000; Malcolm
inhibitorshas also been foundto
TABLE2

Selected
iron
solids

MCNEILL
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distribution systems

The role of biological activity in a water pipe can be mixed but is generally considered
to be detrimental to most aspects of iron corrosion.
reduceironcorrosionrate(Rompre
et al, 1999; Raad et al, 1998; Williams, 1990). Finally,silicatesare
reportedto decreasethe oxidation
of ferrousironbecauseferrousiron
diffusion
throughthesilicatefilmis
slowerthanthrough
ironoxidescale
&
(Hadad Pizzo, 1992).
Silicatesappearto forma self-limitingfilmon thecorrodedironsurface thatwill break down if silica
dosingis stopped.It has beenproposedthatthemetalmustalreadybe
somewhat
corrodedbecausetheprotectivefilmmustconsistof ferric
oxide and silicate (AWWARF &
ironmust
DVGW, 1996); similarly,
be oxidizedinorderto be sequestered
by the silicate(Schocket al, 1998;
Robinsonetal, 1992; Dart & Foley,
1972). Additionofsilicatescan also
raisethepH, whichis generally
beneficialtowardironcorrosion.Silicatesare naturallypresentin many
watersand mayhaveeffects
similar
to thoseof added silicateinhibitors.
PIPEAGECANDRAMATICALLY
AFFECTCORROSION
The lengthof timethepipe has
beenageddramatically
affects
itscorrosion. In general,both iron concentration
and therateofcorrosion
withtimewhena pipeis first
increase
exposedto water,butbothare then
reducedas thescalebuilds
gradually
up. However,the location of this
"cross-over"
pointvarieswidelywith
waterqualityand otherconditions.
MIXEDRESULTSAVAILABLE
ON EFFECTOFWATER
VELOCITY
Thereare verymixedresultsfor
the effectof flow velocity (see
Eliassenetal (1956) andPallo(1946)

fora review).It is thoughtthattwo

factors
aredominant:
increasedflow
providesmoreoxygenforthecorrosionreaction,butitcan also hasten
theprecipitation
ofa protective
layer.
For example,a studyof mildsteel
foundthattheweightloss increased
withincreasing
watervelocity
when
theDO was saturated
(Gedge,1992;
PisiganJr.& Singley,1987). However,other studies found a more
denseprotective
water
layerat higher
flowrates(Fiksdal,1995). Also, if
thevelocityis veryhigh,thewater
can scourawaytheprotective
scale.
Thereis anecdotalevidencethat
phosphateinhibitors
perform
poorly
at low flowor stagnantconditions
(Rompreet al, 1999; Larson,1957;
Cohen,1946; Hatch& Rice,1945b;
Hatch & Rice, 1940), and several
studies found that phosphate inhibitorshad no effector actually
increasedironcorrosionundersuch
conditions(McNeill & Edwards,
2000; Maddison& Gagnon,1999;
Rice,1947; Pallo, 1946).
STAGNATION
TIMEMAYINCREASE
CONCENTRATIONS
OFIRON
Ironconcentrations
wereshown
to increasewithlongerstagnation
times(Sarinet al, 2000; Beckettet
al, 1998). One study from the
Netherlands(van Rijsbergenet al,
in a cast1998) foundthatturbidity
irondistribution
system
peakeddurthe
then
in the
decreased
ing
night,
as
demand
increased
earlymorning
and stagnation
timedecreased.
BIOLOGICAL
ACTIVITY
ALSOIMPORTANT
Microorganismsare presentin
(Holdenet
manydistribution
systems

etal, 1993; De
al, 1995;LeChevallier
etal, 1992; Emdeetal,
Araujo-Jorge
1992; Smith& Emde, 1992; Victoreen,
1984;Allenetal, 1980;Lee et
al, 1980; Tuovinen et al, 1980;
O' Conneretal, 1975; Larson,1939),
andtheycan influence
ironcorrosion
in a numberof ways.Bacteriahave
beenfoundin irontubercles(Emde
et al, 1992; Smith&; Emde, 1992;
Allen et al, 1980; Tuovinenet al,
1980; Victoreen,
1974). Growthofa
bacterialbiofilmon a pipewall may
serveas a barrier
to corrosion(Abernathy&cCamper,1998; O'Conneret
can also proal, 1975), butbiofilms
ducea differential
aerationcell,leading to localizedchangesin oxygen
concentration
andelectrical
potential
in
(Lee etal, 1980). The biopolymers
thebiofilmmayalso uptakesoluble
metals(Tuovinenet al, 1980). Various bacteria
canaffect
ironspeciation
Fe+3or oxidizingferrous
byreducing
iron (Nemati & Webb, 1997;
Chapelle6c Lovley,1992; Okereke
6c Stevens
Jr.,1991; Kovalenkoetal,
1982; Denisov et al, 1981; Shair,
1975). Bacteriamay also consume
oxygen(Larson,1939), cause localized pH gradients(Tuovinenet al,
metabo1980),andproducecorrosive
litessuch as hydrogensulfide(De
etal, 1992;Tuovinenet
Araujo-Jorge
or
iron
al, 1980)
phosphide(Iverson,
1998; Hamilton,1985; Iversonetal,
1985; Iverson, 1984; Iverson 6c
Oldon,1983; Iverson,1981; Iverson,
1968). Thus, therole of biological
in a waterpipecan be mixed
activity
considered
to be detributisgenerally
mentalto mostaspectsofironcorrois
sion.In casesinwhichsuchactivity
it
is
not
that
biodominant,
surprising
cides such as chlorineeffectively

94 JULY
2001| JOURNAL
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distribution systems

reduceoverallcorrosionproblems
despitetheiroxidativeproperties.

rate,thermodynamic
propertiesof
ironscale (leadingto formationof
different
phasesorcompounds),and
TEMPERATURE'S
EFFECTS
biological activity.Moreover,hetOFTENOVERLOOKED
erogeneous iron scale formedon
oftemperature
The effect
on iron pipesmayhave largedifferences
in
corrosionis oftenoverlooked.
such
Many
physicalproperties as scaledenthatinfluence
corrosion sity(as describedbythePilling-Bedparameters
can varywithtemperature.
These
worthratio)and coefficients
oftherparametersincludeDO solubility, mal expansion (Schutze,1997). If
and
solutionproperties
thescale is exposedto temperature
(e.g.,viscosity
ionmobility),
ironoxidation gradients
ferrous
orcycling,
thesedifferences

can cause mechanicalstressesin the

scale, leadingto spallingor crack
formation.
Onlya fewstudieshaveexamined
theroleof different
in
temperatures
In
distribution
corrosion. one
system
ironsamplesheldat 13C had
study,
lower weightloss comparedwith
samples at 20C (Fiksdal, 1995).
Otherstudiesfoundlowerironconcentrations(Volk et al, 2000) and
fewercustomercomplaintsof red

J.M.
etal,1995.
Characterization
ofCorrosion
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F.H.
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AMechanism
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Mass.
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MassachuBancroft,
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NEWWA,
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Sodium
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Cohen,
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Tuberculation
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Cruse,
H.,1971.
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J.R.,
AWWA,
Baylis,
PipeCoatings
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29:9:1355.
J.R.,
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Baylis,
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Preventing
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Prevention
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J.R.,
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62:10:663.
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C.etal,1997.
USEPA's
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Jour.
Davies,
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M.A.
etal,1998.
APipeLoop
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89:12:30.
System
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SulT.C.;
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Inhibitors
Benjamin,
Bacteria
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phate-Reducing
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j
Memorias
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Cruz,
Dos
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1994.
The
Coordination
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ofAquatic
Biber,
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Afonso,
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Iron(lll)
Deng,
Reactivity
Oxyhydroxides
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ETAL| PEER-REVIEWED
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distribution systems

water (Horsleyet al, 1998) during

thecolderwinter
months.
two
Finally,
studies
saw
in
pilot-scale
peaks turet
bidity(Smith al, 1998) and metal
concentrations(MacQuarrie et al,
with
1997) thatappearedto correlate
temperature
changes.
OTHERCOMPOUNDSHAVEEFFECTS
Dissolved copper. Two studies
foundthatconcentrations
ofdissolved
copperas low as 0.01 mg/Lcatalyzed

iron corrosionrates (Cruse, 1971;

Hatch,1955).
Natural
(NOM).Sevorganicmatter
eral studies(LindJohansson,1989;
Sontheimeret al, 1981; Larson,
1966) foundthatNOM decreased
thecorrosionrateofbothgalvanized
steeland cast iron.NOM was also
foundto encouragea moreprotectivescale(Campbell& Turner,
1983)
and alter the redox chemistryby
reducingFe+3colloidsto solublefer-

rous iron (Deng Stumm,1994).

However,NOM can complexmetal
ions (AWWARF& DVGW, 1996),
which may lead to increasediron
concentrations.
"Freecarbondioxide."
Severalstudies stressedtheimportanceof "free
carbondioxide,"whichis thesumof
carbonicacid and dissolvedcarbon
dioxide.Thesestudiesfoundthatthe
freecarbon dioxide formssurface
complexeson theironoxide,increas-

&Kovaleva,T.F.,
1981.
Effect
ofthepHandTem- Hadad,
A.S.& Pizzo,
1992.
TheEffect
ofTemperature,
Denisov,
andSiliG.V.;
Kovrov,
B.G.;
P.P.,
Humidity,
oftheMedium
ontheRate
ofOxidation
ofFe2+to
Fe3+
conContent
ontheOxidation
ofFine
Iron
Particles.
Corrosion
ofElecperature
bya
Culture
ofThiobacillus
ferrooxidans
andtheCoefficient
ofEfficiency tronic
andMagnetic
ASTM
STP1148.
ediMaterials,
(P.J.
Peterson,
ofBiosynthesis
from
Amer.
Soc.Testing
& Materials,
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Russian).
(Microbiol.), tor).
Mikrobiologiya
Philadelphia.
50:5:696.
- Red,
J.J.
&Flentje,
Colored
1958.
Water
orBlue.
Hamilton,
M.E.,
Black,
1958.
Correlation
oftheTwoPrincipal
ofCalculating
Methods
the
Water
&Sewage
105:5:188.
J.F.,
Dye,
Works,
Three
Kinds
ofAlkalinity.
Jour.
50:6:801.
AWWA,
W.A.,1985.
Bacteria
andAnaerobic
CorroHamilton,
Sulphate-reducing
Guidance
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sion.
Ann.
Review
39:195.
Edwards,
M.;Jacobs,
S.;&Dodrill,
D.,1999.
Microbiol.,
Desktop
MitigatJour.
>41/1/1/1/4,91:6:66.
ingPbandCuCorrosion
By-products.
1955.
Control
ofCouples
inWater
Hatch,
G.B.,
Developed
Systems.
R.etal,1956.
Effects
ofpHandVelocity
onCorrosion
ofSteel
11:1:15.
Eliassen,
Corrosion,
Water
Jour.
48:8:1005.
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Pipes.
1952.
Protective
Film
With
Formation
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Hatch,
G.B.,
Phosphate
1987.
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Industrial
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44:8:1
775.
C.H.J.;
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J.G.M.M.,
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by
Water
ofDifferent
Qualities.
Water
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Supply,
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Threshold
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Hatch,
0.,1945a.
&Facey,
Initial
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&Engrg.
37:8:752.
Emde,
K.M.E.;
Smith,
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ina Low-temperature
Corrosion
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With
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Quality
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andIron
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Thermodynamic
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96 JULY
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| PEER-REVIEWED
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distribution systems

of ferrousironand
ingthesolubility
thus increasingiron concentration
and corrosionrates (Sander et al,
1997; Sanderet al, 1996; Sanderet
al, 1995; Ahlberg,1995).

cipitated ferricscale is attracted

back to the pipe surfaceby magneticforce,so the amountof scale
built up depends on its magnetic
properties(Baylis,1953).

MAGNETIC
PROPERTIES
MIGHTHAVEEFFECTS
Some iron oxides, such as magnetite,are magnetic,whereas others such as hematiteare not. One
finalinteresting
theoryis thatpre-

MAY
UPCOMINGREGULATIONS
HAVEIMPACTONIRONCORROSION
faces
The drinking
waterindustry
or recently
numerous
proimpending
mulgatedregulations.Implementation of thesenew regulationsmay

changesto treatrequiresignificant
mentprocessesand finishedwater
quality,therebycreatingthepoteneffects
on ironcortialforsecondary
rosion(Siebel,1998).
Lead and CopperRule(LCR).The
LCR (USEPA, 1991), firstimplementedin 1991, requiresutilitiesto
controllead and copperlevelsin tap
water.In orderto complywiththe
LCR, most utilitieseitherchanged
waterqualityor began
theirfinished

Home
Plumb- Kovalenko,
&Courchene,
1979.
G.J.;
Effect
ofFe3+
Ionsin
& Piskunov,
1982.
J.E.,
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V.P.,
Evaluating
T.V.;
Karavaiko,
G.I.;
Hoyt,
Kirmeyer,
71:12:720.
Problems.
Jour.
ofFerrous
Iron
ferrooxidans
atVarious
theOxidation
AWWA,
ingCorrosion
byThiobacillus
from
(translated
Russian).
(Microbiol.),
Temperatures
Mikrobiologiya
inWater
Distribfor
Corrosion
Control
1980.
D.J.-S.,
Polyphosphate
Huang,
51:1:142.
PhDdissertation,
Univ.
Columbia.
ution
Missouri,
System.
Kinetics
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of
A.,1988.
Investigations
inDis- Kuch,
Water
&
1986.
Ekkers,
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Hulsmann,
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Quality
Hettinga,
Formed
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28:3:221.
Oxide
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distribution systems

dosing phosphateinhibitors.Typical water quality adjustmentsare

raisingpH and loweringdissolved
inorganic carbon. According to
Table 1, raisingpH is detrimental
to iron corrosion rate and scale
buildupbut can reducethe release
of by-products.
Manyutilities
beganaddingphosphate inhibitorsto meetthe LCR,
oftenwithout regard to how the

inhibitorswould affectironcorroDisinfectants/Disinfection
By-prodsion.In fact,from1992 to 1994 the uctsRule(D/DBPR).
the
Implementing
percentageof large utilitiesdosing D/DBPR(USEPA,1998b) can affect
inhibitors
doubledfrom30 to 60% iron corrosionbecause of changes
(Edwards et al, 1999) and may be associated with disinfectionand
even highertoday.Althoughthese increasedorganicmatter
removal.As
can be effective discussedearlier,decreaseddisinfecphosphateinhibitors
in decreasinglead and coppercorro- tantresidualsgenerally
decreasecorsionundersomeconditions,
theycan rosionrates.However,decreaseddisalso be quitedetrimental
to ironcor- infectant residual may increase
rosion(McNeill& Edwards,2000). corrosionifitis relatedto microbial

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2001| JOURNAL
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distribution $prrn>.

activity.Many utilities may also

disinfectant
changeto a different
(e.g.,
fromchlorineto chloramine),
which
can also affectironcorrosion.
ThesecondaspectoftheD/DBPRis
therequirement
forincreased
removal
oforganic
matter
measured
(as
bytotal
carbon
[TOC]) through
organic
enhanced
orenhanced
softcoagulation
matter
is
to
ening.Organic
thought be
beneficial
forironcorrosionrateand

scale buildupbut detrimental

to byso
the
overall
effect
of
productrelease,
increasedTOC removalis unclear.
Otherpotentialeffectsof enhanced
treatmenthave been documented
Affairs
(AWWAGovernment
Office,
enhanced
1998). Briefly,
coagulation
can be associatedwithlowerpH and
andhigher
sulfate
andchloalkalinity
ride concentrations because of
increasedcoagulantdoses.Enhanced

softeningmay be associated with

higherpH, lower alkalinity,and
decreased
hardness.
toTable
According
each
of
these
factors
have
mixed
1,
may
for
iron
corrosion.
consequences
Enhanced
SurfaceWaterTreatment
Rule (ESWTR),GroundWaterRule
andTotalColiform
Rule(TCR).
(GWR)r
In contrastto theD/DBPR,theprimaryconcernforutilitiestryingto
meetthe ESWTR (USEPA, 1998a),

1966.
with Schock,
RedWater
M.R.
etal,1998.
With
Powers,
J.T.;
Cahalan,
E.M.;
Silicate
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Replacing
Polyphosphate
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Jour.
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Problems
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andSource
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distribution systems

because of compliance effortsfor andan MS degreeand a PhD, bothin

civilengineering,
new regulations.
fromtheUniversity
Colorado
at
Boulder
and Virginia
of
in
ACKNOWLEDGMENT
Institute
Polytechnic
Blacksburg,
This workwas supportedby the respectively.She is a memberof
National ScienceFoundation(NSF)
AWWA,theAmericanSocietyofCivil
undergrantBES 9796299. The opinandconclusions
orrecand the
ions,findings,
Engineers,
ommendations are those of the
National Associaauthorsand do notnecessarily
reflect
tion of Corrosion
theviewsoftheNSF.Atthetimethis
HerpreEngineers.
workwas completed,
thefirst
author
vious articleshave
was supportedby theAWWAWol- been publishedin Journal AWWA
SUMMARY
manFellowship
andtheVirginia
Tech and theJournalof Environmental
MarcEdwardsis a proIron pipe corrosionis extremely Via Foundation.
Engineering.
fessorin theDept. ofCiviland Envicomplicatedand is affected
bypracTHEAUTHORS:
ronmentalEngineeringat Virginia
ticallyeveryphysical,chemical,and ABOUT
Institute.
pro- Polytechnic
biologicalparameterin waterdistri- LaurieS. McNeillis an assistant
butionsystems.This workprovides fessorat UtahStateUniversity
, Utah
a summaryof keyfactorsthatutili- WaterResearchLab, 8200 Old Main
tiesmustevaluatein orderto miti- Hill,Logan, UT 84322-8200;e-mail Ifyouhavea comment
aboutthis
iron
corrosion
Utili<lmcneill@cc.usu.edu>.
She
has
a
BS
contact
us
at
article,
please
gate
problems.
ties should also considerpotential degreein chemicalengineering
from <journal@awwa.org>.
secondary impacts on corrosion theUniversity
ofColoradoat Boulder
GWR, or TCR (USEPA, 1989) will
be increaseddisinfection
and disinfectantresidual requirements.In
addition, the TCR may require
changesin circulationand flowpatternsin the distributionsystemin
orderto decrease"dead ends." This
may be beneficial to corrosion,
because these dead-end areas are
oftenthe source of iron corrosion
problemsbecause of low flowconditionsand decreasedDO.

on
atCarbondale,
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100 JULY
2001| JOURNAL
AWWA
ETAL
| MCNEILL
| PEER-REVIEWED

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