Corrosion Science 52 (2010) 1927–1938

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

A comprehensive investigation of copper pitting corrosion in a drinking water

distribution system
Darren A. Lytle a,*, Mallikarjuna N. Nadagouda b
a
US Environmental Protection Agency, ORD, NRMRL, WSWRD, USA
b
Pegasus Technical Services, 46 E. Hollister Street, Cincinnati, OH 45219, USA

a r t i c l e i n f o a b s t r a c t

Article history: Copper pitting is a complicated corrosion process for which exact causes and solutions are often uncer-
Received 24 July 2009 tain. This paper presents the findings of a comprehensive investigation of a cold water copper pitting cor-
Accepted 6 February 2010 rosion problem in a drinking water distribution system, including a refined process for preparing
Available online 24 February 2010
exhumed copper pipes for solids analysis. The investigation produced detailed structural, morphological
and elemental details of copper pitting that strongly corroborated previous observations and theoretical
Keywords: models, and revealed new findings. For example, cross-sections revealed three components: the cap,
A. Copper
characterized by two basic copper sulfate minerals; the cuprite membrane; and the pit containing cuprite
B. Solid analysis
C. Drinking water distribution system
crystals, and chloride.
C. Pitting corrosion Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction on the surface of copper pipes is a very complex phenomenon that

Localized, or pitting, corrosion is a major cause of household
copper drinking water pipe failure and, as a result, the subject of
many studies on the relationship between pitting corrosion and
water quality [1–5].
The cost of repairs resulting from pinhole leaks can be extensive
for property owners. Additionally, pinhole leaks may go unde-
tected behind walls or in basements for months, providing an envi-
ronment for growth of mildew and mold. Many homeowners pay
the high cost to replace their entire plumbing system to avoid
damage caused by leaks from copper pitting.
Copper corrosion is the result of the loss of solid copper metal to
solution. This occurs when electrons are lost by the base metal, and
the solid phase is transformed into soluble, dissolved cuprous (Cu+)
and/or cupric (Cu2+) ions. During metal corrosion in drinking
water, chemical oxidation occurs at anodes where electrons are re-
leased. Alternately, chemical reduction (the gain of the electrons)
occurs at the cathode.
Pitting corrosion describes the case where corrosion is localized
and copper metal is lost at small, fixed anode points. Eventually,
this attack penetrates the pipe wall. The relatively large surround-
ing surface of the pipe surface serves as the cathode. Since the elec-
tron acceptors in drinking water are chlorine (or other disinfectant
residual) and/or oxygen, the rate of corrosion is sensitive to the
concentrations of both of these oxidizing agents. Pitting corrosion
* Corresponding author. Tel.: +1 5135697432; fax: +1 5135697892.
E-mail addresses: lytle.darren@epa.gov, nnmalli@yahoo.com (D.A. Lytle).
potentially involves many initiating factors including microbial
activity, copper material imperfections, excess carbonaceous man-
ufacturing residues on the pipe surface, water chemistry, stray cur-
rents, soldering flux, and other variables within a given
distribution system. Fully understanding this process is still a chal-
lenge to researchers despite the numerous studies that have been
conducted on the subject of copper corrosion [6–15]. Such studies
have highlighted and reviewed the influence of water-quality
parameters (e.g., pH, temperature, oxygen, alkalinity, chloride, sul-
fate, phosphate, and organic matter) [16–19] and operating condi-
tions (e.g., stagnation time and pipe age) [20–22] on copper release
into drinking water from copper pipes. Effort has been made to
gain insight into the formation of solid by-products during the cor-
rosion of copper pipes, as solid-solution interactions are a key fac-
tor controlling the fate of soluble metals and metalloids in water
[17,23,24]. Despite past research, pitting corrosion of copper
plumbing in water is still poorly understood, unpredictable and
difficult to remediate. Furthermore, most previous work has been
based on bench- and pilot-scale tests under conditions not neces-
sarily representative of real drinking water distribution systems,
rather than full-scale investigations.
This paper presents and discusses an analysis of copper pipes
removed from the drinking water plumbing of homes in an Ohio
community because they failed due to pitting corrosion and the
ensuing investigation. The suite of analyses used represents a
broad, comprehensive approach to studying pinhole leak cases that
considers a variety of parameters including: water quality; field
observations; pilot testing; geochemistry, solid, and surface

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.02.013
1928 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938
analysis; and a refined experimental methodology. Copper pipes
were analyzed using a variety of techniques, including X-ray dif-
fraction (XRD), scanning electron microscopy (SEM), and energy
dispersive spectroscopy (EDS). Analysis results provide useful in-
sight into our understanding of the mechanism(s) that lead to
the initiation and propagation of pitting corrosion that eventually
leads to pinhole leaks, and improve details regarding the chemical
and physical nature of copper pitting corrosion. The detailed re-
sults suggest a new benchmark in methodology for obtaining
greater understanding of the anatomy of pitting corrosion attack
on household drinking water copper pipes. Finally, the results
should be helpful in developing treatment strategies to address
copper pitting problems.
2. Materials and methods
Copper pipe sections examined in this study were provided by
seven homeowners living in a southwest Ohio community who
were replacing the pipes due to signs of pinhole leaks, such as visual
external corrosion deposits and water leaks. When possible, copper
pipe sections were photographed in situ prior to removal, and
plumbing details including the relative position of the removed
section(s) were documented. The investigators removed the pipe
sections or were present during removal of nearly all pipes, and
transported them to the US Environmental Protection Agency
(EPA) research center in Cincinnati, Ohio. In some cases, copper
pipes were transported under tap water to best preserve properties
including scale surface features and examine biofilm activity.
Pipe sections were labeled with identification numbers, logged,
and photographed. Pipes were then cut axially with a band saw.
Corrosion by-products that dislodged during cutting were collected
for analysis. The internal surface of each pipe section was photo-
graphed with a digital camera. Images were taken using a stereomi-
croscope with a 10 to 63 range of magnification. Some sites of
localized corrosion were dissected for further analysis using a
modified dental pick. Removed solids (e.g., pit cap, solids within
the pit, and other pit components) were collected for analysis and
documentation. Regions of ‘‘uniform” corrosion or deposits and
other noteworthy features were also photographed and analyzed.
Areas of assumed localized corrosion were encapsulated in an
epoxy resin to maintain the pit structure prior to corrosion analysis.
Copper pipe samples were cut into 2.54 cm sections using pipe tub-
ing cutters and placed into plastic molds. A two-part thermosetting
epoxy resin (low viscosity Buehler EPO-THINÒ) was prepared
according to the manufacturer’s specifications and poured into the
mold to encapsulate the pipe samples. The molds were placed into
a Buehler Vacuum Impregnation apparatus to remove air bubbles
from the resin and ensure good penetration into the porous pit
cap. Samples were cured for 24 h, removed from the molds, and then
cut using a Buehler IsoMetÒ 1000 low speed precision saw equipped
with a diamond blade. 2-Propanediol was used as a lubricant during
preparation to prevent water interference with the pit structure.
The samples were polished with a Buehler MetaServÒ 2000 Grin-
der/Polisher using 180 grit sand paper and a TEXMETÒ polishing
cloth with 1 lm diamond polishing paste. The cross section of the
polished area was examined using a stereomicroscope and a SEM.
Solids were analyzed using a variety of approaches, including
XRD, SEM, and EDS. XRD analysis was used to determine the com-
position of crystalline solid phases. Samples were prepared for XRD
analysis by grinding the solids with an agate mortar and pestle to
pass through a 200-mesh (75 lm) sieve. When sample quantity
was limited, ground samples were suspended in deionized water
and vacuum filtered onto a 0.45 lm polypropylene filter to pro-
duce a uniformly dispersed sample. The filter was mounted on
Plexiglas with spray adhesive, and placed directly onto the XRD
holder mount. A Scintag XDS-2000 diffractometer with a copper
X-ray tube was used to identify crystalline phases within the
ground solid samples at the EPA’s AWBERC facility in Cincinnati,
Ohio. The tube was operated at 35 or 40 kV and 40 mA. Scans were
typically performed over a 2-theta range between 5° and 90° with
a step of 0.02°, and a 2-second hold time. Pattern analysis was per-
formed using the MDI Jade XRD pattern processing computer soft-
ware in conjunction with the ICDD PDF-2 2002 database, following
ASTM procedures [25].
SEM was used to perform high magnification structural charac-
terization of pipe solids, including epoxy encapsulated sections. Sol-
ids were either placed directly into the instrument or a region of
interest was cut to fit into the sample chamber. EDS was used to pro-
vide elemental characterization of the solids at point locations of
elemental mapping regions. Sections of small tubercles were
mounted on 12 mm-diameter aluminum studs with double-sided
carbon tape. Samples were coated with carbon for EDS analysis
and gold for imaging. SEM images and EDS analyses were obtained
using a JEOL 5300 LV scanning electron microscope (Peabody, MA)
with an attached Oxford Instruments EDS (Concord, MA).
3. Results
Study results are based on observations from seven homes from
which copper pipes were provided by six homeowners. Three of
the pipes were maintained under water until analysis.
3.1. Nature of pinhole leak problem
Homeowners or investigators made the following general
observations of pinhole leaks:
1. Leaks were only observed in cold water plumbing of the study
homes. Water utility staff indicated leaks in hot water plumbing
have been reported in the community, but such reports were
relatively uncommon.
2. Most pinhole leaks were identified in horizontal plumbing runs.
However, this observation may be biased because the majority
of exposed pipes were mounted horizontally between floor
joists in unfinished basements where pipes could be easily
inspected and removed (i.e., majority of vertical pipes were hid-
den behind walls on upper floors).
3. Pinhole leaks were identified on all pipe orientations (e.g., top,
bottom or sides of the pipe).
4. Pinhole leaks appeared to be concentrated in the first approxi-
mately 100 feet of plumbing entering the home. This observa-
tion may also be biased because more water in the home
flows through these pipes. In this study, pipe diameter was typ-
ically 1.9 cm entering the home, and reduced to 1.3 cm in the
basement. The majority of pinhole leaks were observed in the
1.9 cm copper pipe; however, in at least one case, leaks
appeared first in the 1.9 cm pipe and developed later in the
1.3 cm pipe. One homeowner closely observed the gradual
migration of newly formed pinhole leaks away from the entry
location in the basement with time.
5. Typically, the homeowner noticed signs of pinhole leaks
approximately 4–6 years after the installation of plumbing in
the home.
6. Major leaks, including those causing significant property dam-
age, were not reported; however, the rate of dripping was
excessive enough to cause staining of ceiling tiles in one of
the homes studied.
7. In most homes, it was observed that new pinhole leaks initially
dripped water at a very slow rate (Fig. 1a). Over the following
several months, blue–green corrosion deposits formed over
 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938
Fig. 1. Examples of damage to the external copper pipe wall as a result of pinhole
leaks. (a) Pinhole leak prior to corrosion deposit build-up from home in test
community, (b and c) Pinhole leak with observable corrosion deposits built up over
time.
the pinhole on the external pipe surface (Fig. 1b and c). Evapo-
ration of pit solution (water most likely containing elevated
chloride levels and having a low pH) and/or external pipe corro-
sion caused by the pit solution lead to the formation of the
deposits. The establishment of the external corrosion deposits
corresponded to a gradual decrease in the rate of dripping
and typically led to the ‘‘sealing” of pinholes. After the leaks
stopped, the corrosion deposit remained moist in appearance
and to the touch. Interestingly, removing the external deposits
(e.g., with steel wool) caused pinhole leaking to resume, sug-
gesting that the sealing mechanism was external to the pipe.
3.2. Water treatment and distribution
The ‘‘test community” (a large, rapidly growing suburban
county with many new subdivisions, industrial parks, and shop-
ping centers) receives the majority of its drinking water from an
older, industrial-based neighboring city (‘‘source community”).
The source water is lime-softened ground water, treated at one
1929
of two facilities. The source community uses chlorine dioxide
(0.10–0.37 mg/L as reported in the city’s 2003 consumers’ water
quality report) as the primary disinfectant. Sodium hypochlorite
is used to boost chlorine disinfectant residual at the location where
water enters the test community’s distribution system. The test
community’s distribution system has approximately 400 miles of
cast and ductile iron, and cement-lined water mains. Neither com-
munity has been in violation of the EPA’s Lead and Copper Rule
[26–28], nor have other distribution system corrosion-related
problems been reported (such as blue water related to copper
by-product release). The source community has no history of wide-
spread copper pinhole leaks, although there have been undocu-
mented reports of problems in new construction areas (based on
personal communication between investigator and water utility
staff), while the test community has had a history of pitting prob-
lems since the early 1990s.
3.3. Water quality
The finished groundwater is moderately hard and has a rela-
tively high pH. The source community detects chlorite, a by-prod-
uct of chlorine dioxide, on entry into the water distribution system,
and also measures it at distant sample locations. There was little
difference in water chemistry between the source and test commu-
nities based on flushed distribution system samples collected from
homes (Table 1). Cold and hot water samples were collected from a
kitchen faucet in one of the homes in the test community after the
water had been flushed for several minutes. The water was moder-
ately hard, with a high pH, and low alkalinity and total inorganic
carbon (TIC) (Table 1). The Larson’s ratio for the water was low,
suggesting the water was aggressive toward the corrosion of steel
and cast iron piping. Langelier and CCPP calcium carbonate satura-
tion indices are positive, indicating that the water has a tendency
to precipitate calcium carbonate. Both hot and cold waters from
the test community had similar chemistries with respect to hard-
ness, silica, alkalinity, TIC, and sodium. Both also had significant
and similar amounts of chlorite, chlorate, chloride, and sulfate.
The primary differences between the hot and cold waters were
pH, temperature, and the amount of dissolved oxygen.
3.4. Pipe surface deposits
A white- to cream-colored material (sometimes with a tint of
blue–green) was observed on the interior surface of most pipe sec-
tions in this study (Fig. 2a and c). The extent of coverage and tex-
ture varied. In some areas the material was relatively thick and
uniform, in others the material was splotchy, and in other areas
there was little evidence of the material. The texture of the mate-
rial, when present, was often streaky and rippled as if the motion of
flowing water shaped the surface texture. Signs of pitting corrosion
were not typically evident in areas where the material was uni-
formly deposited (Fig. 2c, top pipe half). In many cases, however,
the solid did appear to be more concentrated on the pit caps
(Fig. 2d). The white material was not obvious when the pipe was
wet (Fig. 2b), but became more apparent after the pipe was al-
lowed to air dry (Fig. 2c).
EDS analysis of the white material showed a mixture of ele-
ments, most notably silicon (15.8% by weight in one instance)
and oxygen. Copper (Cu) was present as well as detectable
amounts of magnesium (1.3% Mg), aluminum (2% Al), calcium
(3.6% Ca), and iron (0.7% Fe). XRD analysis of the material showed
the presence of magnesium-substituted calcite (Ca1–xMgxCO3) and
cuprite (CuO2). No crystalline Cu(II) mineral phases were identified
by XRD analysis in this part of the pipe surface (areas excluding
locations of pitting corrosion). If Cu(II) solids were present, they
were non-crystalline or present at undetectable concentrations.
1930 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938

The white material on many pit caps contained relatively high

Larson’s
amounts (12.6% in one instance) of silicon (Si) based on EDS anal-

Ratio*
ysis, and was consistent with the uniform layer in composition.

0.2

0.2

0.2

0.5
0.3

4 ) using WaterPro2002, CopyrightÓ96-02 Schott software. Published by ChemSW , Inc. Computed using and ionic strength of 120 mg/L an temperature of 23 °C when not provided.
The material was often more concentrated at or near the pits. Upon
close examination of the pipe surfaces, varying sizes of concen-
Temp.,

na 0.3
22.7

50.0

50.0
trated particles of the same composition were found (Fig. 3). When

na
na
°C

the solids were removed, there were often signs of localized corro-
sion beneath the solids. Observations did not indicate whether the
Oxygen,

material was present prior to pit initiation or deposited after pit-

mg/L
5.6

3.1

3.1

na
na
na
ting corrosion was established.
TIC, mg

3.5. Pit structure

C/L
8.8

8.1

8.1

12
16
13

Areas of pitting corrosion were identified by small mounds of

blue–green corrosion deposits, distributed randomly across the
8.22
8.80

8.30

8.30

9.09
pH

na

majority of the pipe surface. Corrosion occurred below the mounds

and was observed at various stages of development leading up to
TALK, mg/L

the establishment of a pinhole leak. The features of localized cop-

CaCO3

per corrosion observed in this case study are best illustrated by the
51
39

38

38

77
54

stereomicrography of the cross section of a ‘‘typical” copper pit

(Fig. 4). The corroded pit structure is consistent with past models
Free Cl2/L

[29], and can be separated into three distinct internal structural

CaCO3

features: pit cap, perforated pit membrane, and pit. Pits that have
1.19

0.47
0.48

0.30

0.30

na

fully penetrated the copper pipe wall exhibited noteworthy exter-

nal features as well.
ClO3,
lg/L
156

152

152

na
na
na

3.5.1. Pit cap

Blue–green pit caps covered the pit and corroding copper pipe
ClO2,
lg/L
349

328

328

na
na
na

walls (Fig. 4). Pit caps varied in size and were as large as 4–
6 mm in diameter and 3 mm thick in some cases. Although signif-
mg CaCO3
Hardness,

icant in size, pit caps were not large enough to obstruct water flow.
The cap consisted of two distinctly colored mineral layers: an
Ò
187

187

148
151
150
180

‘‘outer”, aqua blue mineral layer (typically situated nearest to flow-

ing water or bulk water boundary), and an ‘‘inner”, green mineral
mg/L
SiO2,

layer (Fig. 4). XRD analysis indicated that the cap was primarily
5.5
6.3
10

10

10

10

composed of two basic copper sulfate minerals: dominantly bro-

chantite [Cu4(OH)6(SO4)] and the likely presence of posnjakite
mg/L
SO4,

125

125
120

[Cu4(OH)6(SO4)H2O](Fig. 5). The hydrated mineral posnjakite is

77

80
80

aqua in color, and brochantite is emerald green. Posnjakite tended

Ortho-

to be located at the cap-water interface. The state of hydration and

PO4/L

0.19
0.26

relative location suggests that the posnjakite layers may be newer.

nd

nd

nd

na

Magnification of the cap material using SEM and EDS analyses re-
PO4/L

vealed areas of well-defined crystals (Fig. 6c) having content of 54%

Total

0.49
0.15
0.50
nd

nd

nd

Cu, 39% O, and 6.5% S by weight. The crystal morphology and ele-
mental composition of the mineral in these particular areas are
mg/L

most consistent with posnjakite. No other copper mineral phases

Na,

39
33

33

33

28
39

(e.g., malachite, tenorite, etc.) were identified by XRD in the pit cap.
Water quality of test community and two neighboring communities.

Smaller pit caps were often covered by the white material de-
mg/L
Mg,

11
27

28

28

24
13

scribed earlier (Fig. 2d). SEM–EDS analysis indicated that these

caps contained copper, oxygen, magnesium, aluminum, and sili-
mg/L

con. This material was often absent from larger pits. Close exami-
4.5
3.8

4.1

4.1

4.4
na
K,

nation of the pit cap revealed several other important features that
may be difficult to appreciate as presented in Fig. 4 under the ste-
mg/L

75
64

65

65

45
72
Cl,

reomicroscope, but which become apparent when closely exam-

ined (Fig. 6).
mg/L

Calculated as (alkalinity/Cl+SO2
Ca,

42
27

28

28

26
39

1. The caps were relatively porous and had hollow centers in

many cases (Figs. 4 and 6).
Community 2, cold water
Community 2, hot water

2. Some large pit caps had holes in the top (Fig. 6a). It can be spec-
Test community home

Test community home

Test community home

Site 1, cold water

ulated that the holes served as a vent for gases released during
Site 1, hot water

Site 1, hot water

the corrosion process or resulted from a ‘‘cave-in” of the hollow

na, not available.
nd, not detected.
Community 1

region.
3. Another interesting feature of the pit cap was what appears to
Sample

be relatively large pieces (>1 mm long in many cases) of pure

Table 1

metallic copper (Fig. 7), as determined by microscopic and

EDS analyses. This copper commonly appeared near or in the
*
 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938 1931

Fig. 2. Examples of internal appearance of cold water copper pipes and relatively uniform deposit appearance: (a) thick deposits with no pits, (b) whitish deposits not
observable on wet pipes, (c) whitish deposits observable on dry pipes, (d) magnified image of pit cap deposit.

center of the hollow pit cap region. The most reasonable expla-
nation for the observation was a sample preparation artifact.
However, the observation was typical and, upon close examina-
tion, arguably part of the cap. Therefore, the possibility that the
copper pieces in the cap were in some way associated with pit
development should not be totally ruled out.
3.5.2. Perforated pit membrane
The typical perforated pit membrane was sandwiched between
the pit cap and the pit (Figs. 4 and 7). The membrane was brittle,
thin (approximately 50–75 lm in thickness), porous, and non-con-
tinuous in the region covering the pit (Fig. 8). Perforations or holes
in the membrane were as large as 1 mm across, and when viewed
under SEM magnification, the crystal contents of the pit below
were revealed. The pit membrane appeared to be an extension of
a relatively thin, uniform solid that extended around the entire
internal pipe surface.
Under close SEM examination, the membrane appeared to con-
sist of two layers (Fig. 8b). The top layer appeared smooth and was
largely comprised of copper, oxygen, and sulfur, the latter of which
suggests the remnants of the sulfur-rich pit cap. Below the top
layer was a second, relatively rough layer, largely made of copper,
oxygen, and smaller but significant amounts of silicon and chlo-
rine. The presence of silicon and chlorine could be important in
the development and propagation of copper pits, and will be dis-
cussed later in more detail.
While there was not enough material present for XRD analysis,
given the ratio of copper to oxygen (based on EDS analysis) and the
maroon color, it is reasonable to assume that the membrane is
cuprite (Cu2O). The membrane appeared to be degraded from the
pit outward (Fig. 9).
3.5.3. The pit
The pit (Figs. 4 and 7) included the corroding region below the
pit membrane and cap, and represented the zone where the local-
ized corrosion occurred and penetrated into the pipe wall. Pits
were generally bowl-shaped, with the largest diameter (5–6 mm)
adjacent to the internal pipe wall. Pits were filled with large,
loosely packed, individual, maroon-colored crystals (Fig. 10), and
identified as cuprite by XRD analysis. When dry, the contents of
larger pits could be emptied and analyzed; cuprite crystals from

Fig. 3. Stereomicrographs of randomly deposited particles of varying sizes (a–h), and accompanying underlying pipe surface (all stereomicrographs taken at same
magnification).
1932 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938

Fig. 4. General appearance and structural features of a copper pit.

these pits were very well-formed and cubic in shape (Fig. 10). Gi-
ven the degree of crystal definition, the solution and crystal growth
conditions (i.e., Eh and pH) under which this cuprite formed were
ideal.
SEM imaging and EDS elemental mapping analysis also revealed
another important feature of the pit. Chlorine (most likely in the
form of chloride) was concentrated across the floor of a pit that
had not fully penetrated the pipe (Figs. 11–13, Table 2), and was
particularly concentrated in small cracks and imperfections on
the surface near the surface of the pit. This observation suggests
Fig. 6. Features of the pit cap: (a) top of cap, (b) underside of cap, and (c) scanning
high importance for chloride in the propagation of the pits and ac- electron micrography of cap crystals.
tive corrosion of the copper pipe wall.
Pits that grew to form a pinhole exhibited slightly different
internal features. In addition to cuprite crystals, these pits con- that the material consisted of one or both of the Cu(II) sulfate min-
tained green corrosion deposits concentrated near the pit-pipe erals (brochantite and/or posnjakite) previously identified in the
wall interface (Figs. 4 and 7 and supporting information). Insuffi- pit cap. Interestingly, chlorine (chloride) was absent and presum-
cient amounts of this material were available for identification ably drawn out of the pit with the leaking water where it was asso-
by XRD analysis, but SEM imaging coupled with EDS elemental ciated with the external corrosion by-products (Fig. 12d). Also,
analysis (see Figs. 12 and 13, Table 2) revealed that the green mate- sulfate appeared to have displaced chloride in the pit, perhaps
rial was dominated by sulfur and copper (not shown), suggesting due to being drawn down from the sulfate-rich cap region

Fig. 5. XRD pattern of the pit cap obtained from test community.
 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938 1933

Fig. 7. Large copper particle observed in the pit cap (EDS analysis).

Fig. 9. SEM image of the pit cap, membrane, and pit contents.

Fig. 8. Features of the perforated pit membrane: (a) Stereomicrography of

perforated membrane and (b) scanning electron micrography of perforated pit
membrane depicting a smooth top layer atop a relatively rough inner-membrane
layer.

(Fig. 12b). This observation (i.e., the lack of chloride in a pit that
penetrated the pipe wall) could be associated with the observation
that pinholes did not grow to the point where excessive leaking
was observed.
Fig. 10. Features of the pit contents: (a) Stereomicrography of pit contents after
perforated membrane is removed, and (b) SEM of pit contents showing cubic crystal
structure. XRD analysis showed that the crystals were cuprite (CuO2).

per, chlorine and oxygen were identified as the primary elements

3.5.4. External features
in the solids. SEM and EDS analysis indicated that corrosion of
The external surfaces of copper pipes at the location of pinhole
the external pipe wall occurred below the corrosion by-products,
leaks were covered with blue, green and white corrosion by-prod-
based on the clear degradation of the external pipe wall in the area
ucts (Figs. 1b and c and 7). The solids appeared to be moist, and
(Fig. 7) which reflects the corrosive nature of the pit water.
thought to be important in stopping continued growth in pinhole
diameter and preventing major water leaks. The solids were often
the only sign to the homeowner of a corrosion problem and often 3.6. Hot water versus cold water plumbing
not recognized as a pinhole. The nature of the by-products re-
flected the water quality inside the pit, and likely formed as slowly The fact that consumers in the test community dominantly
leaking ion-rich pit water evaporated in the air. Specifically, cop- reported pinhole leaks in cold water plumbing is very important.
1934 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938

Fig. 11. Elemental make-up of materials at copper wall-pit interface: (a) carbon, (b) oxygen, (c) silicon, (d) sulfur, (e) chlorine, and (f) copper.

Fig. 12. Elemental make-up of materials in the pit cap, at copper wall-pit interface and external pipe surface: (a) cross section micrography, (b) sulfur, (c) silicon, and (d)
chlorine.

As previously noted, dissolved oxygen, temperature, and pH
were the only water-quality parameters that differed between
the source and test waters, but it was unclear how those
changes might impact pitting corrosion without examining hot
water copper pipe.
Small sections of hot water and pitted cold water pipe (both
1.9 cm in diameter) were removed from one of the test homes. A
comparison of the internal surfaces of the pipe sections revealed
obvious differences in the nature of the corrosion by-products.
The cold water pipe exhibited random locations of pitting corro-
sion and the previously described white material (Fig. 14). In con-
trast, the hot water pipe was covered with a relatively uniform,
poorly crystalline black Cu(II) oxide tenorite scale as revealed by
XRD (not shown) and SEM analysis (Fig. 15), as well as traces of
the white material. There was no indication of non-uniform corro-
sion on the surface of the scale of the hot water pipe.
 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938 1935

Fig. 13. SEM image of a typical cap.

3.7. pH of pit water

A micro-pH electrode (1.2 mm tip) was used to measure the pit

of water that exited a pinhole leak in one of the test homes.
Although the measurements were not made under ideal condi-
tions, the pH of the water that slowly passed through the pit was
5.5, supporting the conclusion that the internal solution within
the pit was much lower in pH than the bulk water inside the pipe
(pH 8.8). The acidic pH of the pit water supports the corrosive at-
tack and degradation to the inner and outer copper pipe wall noted
earlier (Fig. 7).
Fig. 14. Comparison between internal and external surfaces of copper piping from
home #1 exposed to hot water (a) external surface, (b) internal surface; and cold
water, (c) external surface, (d) internal surface.
3.8. Experiences of neighboring communities

The water source, treatment approach and distributed water

3.9. Microbiological analysis
quality are not unique to the test community but, rather, are nearly
identical to at least two other large neighboring cities. Yet, despite
Microbiological analysis was limited to testing for the presence
the similarities, the neighboring communities do not share copper
of sulfate reducing bacteria (SRB) because they have been associ-
pinhole leak problems. For example, two neighboring cities share
ated with pitting corrosion of metals including copper [30–33].
the same groundwater aquifer source and practice lime softening
The presence/absence of SRB in water and scale samples was deter-
water treatment like the test (and source) community and, as a re-
mined using the BART™ (Droycon Bioconcepts Inc.) test according
sult, produced finished water having nearly identical quality to the
to the manufacturer’s protocol. Solid samples were scraped from
test community (Table 1, community 1 and 2). The only major dif-
wet pipe sections and re-suspended in sterile water. Heavy parti-
ference was that the two neighboring communities historically
cles were allowed to settle, and then the supernatant solution
added polyphosphate-based chemicals for corrosion control, or
was injected into the ampule and tested. Analysis was only per-
for controlling excessive deposition of calcium carbonate in their
formed on one copper pipe section and the results tested negative
filters. The resulting total phosphate concentration in a cold water
for the presence of SRB.
sample taken from a home in neighboring community #2 was
0.38 mg PO4/L. Hot and cold water copper pipes removed from
the same home had similar features and had no signs of localized 4. Discussion
pitting (Fig. 16). The pipes were covered with a relative uniform
layer of cream- to yellow-colored solids. The cold water pipe also Localized pitting has been recognized as a source of copper pipe
had streaks of a blue–green colored material across its surface. failure in home plumbing systems. Over time, pitting corrosion re-

Table 2
EDS analysis of cap at different location as shown in Fig. 13.

Element C O Mg Si S Cl Ca Cu
Spectrum 1 Weight% 15.3 51.2 0.55 6.51 3.02 0.36 0.18 22.9
Atomic% 24.55 61.6 0.43 4.46 1.81 0.19 0.09 6.92
Spectrum 2 Weight% 14.00 57.5 0.36 4.60 3.27 0.22 – 20.0
Atomic% 21.8 67.0 0.28 3.06 1.90 0.12 – 5.88
Spectrum 3 Weight% 30.40 60.5 – 0.70 1.72 0.15 – 6.58
Atomic% 39.0 58.2 – 0.39 0.83 0.06 – 1.59
Spectrum 4 Weight% 17.0 19.0 – 0.88 0.34 0.85 – 6.58
Atomic% 39.0 32.5 – 0.86 0.29 0.65 – 1.59
1936 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938
Fig. 15. SEM images of the internal surface of copper pipe exposed to hot water
magnified at (a) 1700, and (b) 4000.
search has led to a variety of theories regarding the initiation and
propagation of pitting corrosion, and descriptions of the physical
and mineralogical properties of the areas of attack. Despite ad-
vances, pitting corrosion of copper in water is still poorly under-
stood, and difficult to predict and remediate. Constraints are
most certainly associated with the difficulty in reproducing repre-
sentative pitting corrosion in an experimental setting in a timely
manner, though bench and pilot scale testing have been attempted.
Unfortunately, the majority of this work, and resultant theories
and conclusions, have been conducted under and based on unreal-
istic conditions instead of in-depth examinations of failing copper
pipes removed from real drinking water distribution systems. Fur-
thermore, current case study field investigations and establish-
ment of causative factors are typically limited to simple pipe
analysis and basic observations.
Future investigations on community-wide copper pinhole leaks
should include: (1) a detailed literature review; (2) examination of
in situ pitting problems (e.g., hot versus cold water, pipe configura-
tion, grounding schematics, etc.); (3) complete water chemistry
analysis and assessment; (4) bench and pilot scale work; (5) a de-
tailed solids and surface analysis; and (6) a microbiological screen-
ing. Almost as important as examining pipes that have failed is
examining those with similar physical and aqueous environments
but are not yet experiencing pitting, and investigating the experi-
ences of local communities with similar water treatment practices
and finished water qualities. Such work will illustrate the value of
considering a multi-variable investigation approach and will im-
prove our understanding of copper pitting corrosion.
Despite the detailed investigation presented here, the exact
cause of pinhole leaks in the test community and solution to their
problem are uncertain. This is typical for such investigations, as
copper pitting corrosion is too complex and poorly understood to
establish such conclusions. Nonetheless, the observations have im-
Fig. 16. Comparison between internal surfaces of copper piping removed from a
home in community 2 exposed to (a) cold water, and (b) hot water.
proved our overall understanding of copper pitting corrosion,
added to the knowledge database on the subject, and suggested
possible treatment options.
Localized copper corrosion in water has been categorized into at
least three types based on chemistry and physical features: cold
water, hot water, and soft-water [34–39]. Categorically, the pitting
corrosion observed in this work can be most closely described as
soft-water pitting. Soft-water copper pits have been described as
relatively wide and shallow with an exterior layer of bronchantite
and/or malachite covering a layer of crystalline red–brown cuprite
over the corroded copper surface [39]. The voluminous corrosion
deposits of the exterior layer are released to the water and can
potentially cause water blockage. Waters with low conductivity,
low alkalinity, and relatively high pH have been associated with
soft-water pitting and although the exact cause of pit initiation is
debatable, it is clear that such waters can be problematic and sup-
port pit propagation [40].
The features of the area of pitting corrosion attack are also gen-
erally consistent with previous theories and observations [29]. De-
tailed analysis of copper pits in this work improved details
regarding known physical and chemical properties of pitting corro-
sion. The analysis also introduced several new features, including a
hollow pit cap, holes in the cap, and the presence of two basic cop-
per–sulfate compounds in the cap. However, one of the most
important findings resulting from this study was the differences
between the internal surface of the cold water (pitted) and the
hot water (non-pitted) pipes. Cold water plumbing had little iden-
tifiable Cu(II) scale on the surface, while the hot water plumbing
was covered with a thin uniform layer of poorly crystalline tenor-
ite. The presence of tenorite on the hot water pipe is particularly
noteworthy. Copper aging theory predicts that in ideal situations,
copper solubility in the distribution system is initially controlled
by metastable and relatively soluble Cu(II) hydroxide in new
 D.A. Lytle, M.N. Nadagouda / Corrosion Science 52 (2010) 1927–1938
plumbing [41]. However, as the solid ages, it is transformed
through several possible mechanisms into the more stable and less
soluble malachite at a low pH, or into tenorite at a high pH. The hot
water pipe observations made during this investigation suggest
that water temperature impacts the rate of aging, leading to the
establishment of a relatively uniform layer of tenorite on copper
pipe. It may also be concluded that the rate of ‘‘aging,” or develop-
ment of a stable and relatively uniform Cu(II) corrosion by-product
layer on the pipe may be critical to reducing pitting corrosion.
Lastly, the observations from neighboring water systems proved
to be very informative and useful. Despite having the same water
source, treatment approach, and finished water quality, the neigh-
boring water systems have not reported copper pitting problems.
The only notable and important difference was that the neighbor-
ing systems add some form of phosphate to their waters. The
observations suggest that phosphate compounds may be impor-
tant preventing pitting corrosion of copper in some way. Although,
more research is needed.
5. Conclusions
Multiple approaches were used to investigate a community-
wide copper pitting corrosion case. Specifically, water quality, field
observations, geochemistry, solid and surface analysis and obser-
vations of similar neighboring communities were reported. The fol-
lowing conclusions were drawn:
 A refined process for encapsulating pipe sections in epoxy
improved the ability to obtain details regarding the physical
and chemical nature of copper pits.
 Copper pinhole leaks were predominantly associated with cold
water pipes, and the associated water was chlorinated and had
a high pH (ffi8.8), low alkalinity or TIC (ffi8.8 mg C/L), and signif-
icant levels of chloride (64 mg/L) and sulfate (120 mg/L).
 Copper pit structure was separated into three distinct regions:
pit cap, porous membrane and the pit. In addition to internal
features, corrosion and corrosion by-product build-up was
observed on the external pipe wall surface adjacent to pinholes.
 SEM imaging and EDS elemental mapping analysis confirmed
the presence of sulfur in the pit cap, and chlorine (most likely
in the chloride form) was concentrated at the pit floor where
the local corrosion of copper was occurring. Aluminum and silica
were non-uniformly deposited over the pipe surface.
 XRD analysis indicated that the pit cap was primarily composed
of basic copper sulfate minerals: brochantite [Cu4(OH)6(SO4)]
and posnjakite [Cu4(OH)6(SO4)H2O]; and the pit contained cupr-
ite [Cu2O] crystals.
 Hot water was not typically associated with pinhole leaks, but it
was associated with accelerated aging of uniform copper corro-
sion by-products. The thermodynamically favored copper min-
eral tenorite [CuO] was only observed on hot water copper
pipes.
 Copper pitting of household plumbing was not reported in two
neighboring communities despite having identical water
sources, and nearly identical treatment processes and finished
water qualities as the test community. The only major identifi-
able difference was that the neighboring communities added
blended phosphate compounds to their water(s).
Acknowledgements
The authors wish to thank Keith Kelty, Christy Muhlen, Brittany
Almassalkhi, from the US EPA, and Bill Kaylor and Larry Milbrandt
(Senior Environmental Employee Program) for water quality anal-
1937
ysis. The authors would also like to thank Kyle Hawkins, Joel Wil-
cox, Chris Starkey, Sacha DeVroomen Bellman, Melissa
Andreychek, Mark Weflen, Natalie L. Corzine and Dr. Jean Lutz of
Miami University (Ohio) and Robert Hyland of Pegasus Corporation
for assistance with paper review and editing.
Notice. The US Environmental Protection Agency, through its Of-
fice of Research and Development, funded and managed, or par-
tially funded and collaborated in, the research described herein.
It has been subjected to the Agency’s administrative review and
has been approved for external publication. Any opinions ex-
pressed in this paper are those of the author(s) and do not neces-
sarily reflect the views of the Agency, therefore, no official
endorsement should be inferred. Any mention of trade names or
commercial products does not constitute endorsement or recom-
mendation for use.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.corsci.2010.02.013.
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