World Environmental and Water Resources Congress 2007: Restoring Our Natural Habitat © 2007 ASCE

1 AN INVESTIGATION OF COPPER PITTING CORROSION AND PINHOLE

2 LEAKS
3
4 by
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6 Darren A. Lytle1 and Michael R. Schock
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8 U.S. Environmental Protection Agency, ORD, NRMRL, WSWRD

9 26 W. Martin Luther King Dr.
10 Cincinnati, Ohio 45268
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13 ________________________________________________________________________
14 INTRODUCTION
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16 Localized corrosion of copper pipes, or "pitting" corrosion, is a major cause of
17 household plumbing failure. In relatively short periods of time after installing copper
18 plumbing, copper pitting can lead to pipe failure in the form of pinhole leaks. The cost of
19 plumbing repair and the associated expenses of repairing water damaged materials can be
20 excessive for property owners. Additionally, pinhole leaks may go undetected in walls or
21 basements for months, providing an environment for the growth of mildew and mold.
22 Many homeowners elect to replace their entire plumbing system to avoid the hassle of
23 continually repairing damage caused by copper pitting although this may only offer a
24 short-term solution before pinhole leaks in the new plumbing occur.
25 Pitting corrosion of copper plumbing materials in water is poorly understood
26 despite a number of studies (Lucey 1967; Kasul 1993; Edwards 1994; Edwards 1994;
27 Duthil 1996; Harrison 2004; Marshall 2005) on the topic in recent years. Pit initiation
28 has been associated with microbial activity, copper material imperfections, excess
29 carbonaceous manufacturing residues on the pipe surface, water chemistry, stray currents,
30 soldering flux, and others. A number of water chemistry parameters have been
31 postulated to be responsible for the initiation and propagation of pitting corrosion. The
32 parameters include pH, alkalinity or dissolved inorganic carbon (DIC), chloride, organic
33 carbon, chlorine, aluminum, silica, sulfide and sulfate.

1
Corresponding author, U.S. Environmental Protection Agency, 26 W. Martin Luther King Dr.,
Cincinnati, Ohio 45268, phone 513-569-7432, fax 513-569-7892, lytle.darren@epa.gov

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 World Environmental and Water Resources Congress 2007: Restoring Our Natural Habitat © 2007 ASCE

1 The objective of this study was to systematically investigate the impact of water
2 pH, chloride, sulfate, alkalinity, and orthophosphate on the nature of copper corrosion
3 (i.e., localized and uniform) under a relatively controlled environment.
4
5 MATERIALS AND METHODS
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6
7 Experimental systems were designed, constructed, and operated by United States
8 Environmental Protection Agency’s (USEPA’s) Water Supply and Water Resources
9 Division (WSWRD) in the early 1990’s to study the impact of water chemistry on Cu(II)
10 equilibrium solubility in water (see details in Schock 1995) (Figure 1). Copper pipe
11 recirculation experiments specifically have been performed to examine the effect of pH,
12 silica, orthophosphate, sulfate, dissolved inorganic carbon (DIC), and other parameters on
13 Cu (II) solubility in water in a controlled environment.
14 The pH was measured using a series of benchtop pH/ISE meters under computer
15 control to report stability. Measurements of pH used a closed-system technique with
16 repetitive re-equilibrations following the technique of Schock et al. (1990). The pH
17 instrument was standardized daily using a two or three-point calibration with pH 4, 7 and
18 10 high precision standard solutions (Whatman, Hillsboro, OR or Ricca). Dissolved
19 oxygen (DO) was measured with a Hach Company (Loveland, CO) Model DO175
20 dissolved oxygen meter and a Model 50180 dissolved oxygen probe. Total phosphorous,
21 silicon, calcium, sulfur (sulfate), and copper were measured with a Thermo Jarrel Ash
22 (Franklin, MA) 61E® purged inductively coupled argon plasma spectrometer (ICAPS).
23 Chloride was analyzed using an automated potentiometric titration approach (Standard
24 Methods4500-Cl-D) (APHA-AWWA-WEF 1995). Free chlorine was analyzed
25 according to the Hach DPD colorimetric method (APHA-AWWA-WEF 1995).
26 Dissolved inorganic carbon (DIC) was analyzed by a coulometric procedure on a UIC
27 Model 5011 CO2 coulometer (Joliet, IL) with Model 50 acidification module, operated
28 under computer control, equivalent to ASTM D513-02 Method (B). Enhancements in
29 sample gas stripping and sample handling were implemented to improve analytical speed
30 and accuracy.

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 World Environmental and Water Resources Congress 2007: Restoring Our Natural Habitat © 2007 ASCE

1 The impact of water chemistry on the nature of copper corrosion was assessed
2 using a number of solids analysis approaches including scanning electron microscopy, x-
3 ray diffraction analysis and stereomicroscopic imaging.
4
5 RESULTS
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6 The findings of this work showed that pitting corrosion of copper plumbing was
7 favored in waters having low chlorine concentration and DIC (5 and 10 mg C/L, and
8 possibly at 25 mg C/L), and a high pH of 9 water in the presence of chloride. For
9 example copper pipes from experiments conducted at pH 9 (low chlorine, 23 to 28 mg
10 Cl/L, 10 to 11 mg C/L DIC, 23oC) were dominantly black in appearance with small
11 mounds of white and green to blue-green colored corrosion deposits (mounds only noted
12 in higher pH conditions). The mounds were typically oblong in shape with the widest
13 dimension in the direction of water flow. The longest dimension approached 10 mm or
14 more in some cases. Although mounds of corrosion deposits observed at pH 9 (DIC = 10
15 mg/L) were similar in appearance to pit “caps” associated with localized corrosion, these
16 observations alone are not enough to conclude that pitting corrosion was actively
17 occurring in the pH 9 test waters. To provide additional information, pipe sections from
18 pH 9 experiments were cut into smaller segments that were several inches long and
19 solidified in an epoxy resin. When hardened, the mounted pipe sections were cut with a
20 diamond saw and polished to expose cross section areas where corrosion by-product
21 mounds were identified. Stereomicroscope images of the polished cross sections clearly
22 showed that localized corrosion and pipe wall degradation was occurring below the
23 corrosion deposit mounds (now appropriately referred to as pit caps). Figure 2 shows
24 two cross-section stereomicrographs of corroded copper below the pit cap. The thickness
25 of the pit caps varied; some pit caps were as thick as a millimeter. In many cases, the pit
26 cap appeared to extend into the pit itself. Pitting attack penetration was as deep as 0.2
27 mm, or approximately 28 percent, of the copper pipe wall. The pits were shaped like a
28 bowl with the widest diameter at the cap:pit interface. Macroscale analysis of pipe cross
29 sections clearly showed localized attacks that were below the corrosion mounds had
30 taken place after only 99 days. Pitting corrosion was not observed at pH 6.5, 7 and was
31 evident at pH 8 only when higher chlorine levels were maintained. Sulfate was not

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1 necessary to develop pitting corrosion; however, it did impact the composition of the
2 corrosion by-products associated with pitting corrosion. Only chloride was in contact
3 with the copper metal surface at the point of degradation (anode) suggesting the ion’s
4 presence was necessary for pit propagation. Increasing the DIC to 50 mg C/L or adding 3
5 mg PO4/L orthophosphate (Figure 3) prevented the initiation of pitting corrosion at pH 9.
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7 ACKNOWLEDGMENTS
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9 The authors wish to thank Barbara Francis, Paul Ringhand, Keith Kelty, Jerry
10 Bashe, and Steve Harmon from the U.S. Environmental Protection Agency (USEPA), for
11 water quality and solids analysis, and Steve Harmon and Charles Button (University of
12 Cincinnati) for operating the experimental systems. We also would like to thank Christy
13 Muhlen (USEPA) and Adam Worrell (University of Cincinnati) for their assistance in
14 data analysis, and Kathrine McCullough with Miami (Ohio) University for her review of
15 the manuscript.
16 Any opinions expressed in this paper are those of the author(s) and do not,
17 necessarily, reflect the official positions and policies of the USEPA. Any mention of
18 products or trade names does not constitute recommendation for use by the USEPA.
19
20
21 REFERENCES
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23 APHA-AWWA-WEF. 1995 Standard Methods for the Examination of Water and
24 Wastewater. Washington, DC, American Public Health Association.
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26 Duthil, J.-P., Mankowski, G. and Giusti, A. 1996 “The Synergetic Effect of Chloride and
27 Sulphate on Pitting Corrosion of Copper.” Corrosion Science 38(10): 1839-1849.
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29 Edwards, M., Ferguson, J. F. and Reiber, S. H. 1994 “On the Pitting Corrosion of
30 Copper.” Journal of the American Water Works Association 86(7): 74-90.
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32 Edwards, M., Meyer, T. and Rehring, J. 1994 “Effect of Selected Anions on Copper
33 Corrosion Rates.” Journal of the American Water Works Association 86(12): 73-
34 81.
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1 Harrison, D. B., Nicholas, D. M. and Evans, G. M. 2004 “Pitting Corrosion of Copper

2 Tubes in Soft Waters: Corrosion Mechanism.” JAWWA 96(11): 67-76.
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4 Kasul, D. B. and Heldt, L. A. 1993 Characterization of Pitting Corrosion of Copper Pipe
5 Carrying Municipal Water. NACE Corrosion/93, Houston, TX.
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7 Lucey, V. F. 1967 “Mechanisms of Pitting Corrosion of Copper in Supply Waters.” Br.
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8 Corros. Jour. 2: 175-187.

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10 Marshall, B. and Edwards, M. 2005 Copper Pinhole Leak Development in the Presence
11 of Al(OH)3 and Chlorine. AWWA Annual Conference, San Francisco, CA,.
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13 Schock, M. R., Lytle, D. A. and Clement, J. A. 1995 Effect of pH, DIC, Orthophosphate
14 and Sulfate on Drinking Water Cuprosolvency. Cincinnati, OH, Office of
15 Research and Development.
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36 FIGURE 1. Photograph of experimental pilot-scale copper recirculation system.
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42 FIGURE 2. Stereomicroscope images of the cross sections of corrosion by-
43 product mounds and degree of localized corrosion attack on the
44 interior surfaces of copper pipes exposed to: (a) 0 mg SO4/L, and
45 (b) 5 mg SO4/L, at pH 9.
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 World Environmental and Water Resources Congress 2007: Restoring Our Natural Habitat © 2007 ASCE

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17 FIGURE 3. Photograph of the interior surfaces of copper pipes exposed to 2.9
18 to 3 mg/L orthophosphate at different pH values (10 mg C/L DIC).
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