Thermodynamic models were used to correlate experimental and field data for the

concentrations of copper (Cu), anions, and cations in drinking water with Cu-containing

scales on the inner walls of pipes. This study focused special attention on the aging processes

of these scales. Precipitation and dissolution were predicted to be the main aging causes for

Cu scales present on the inner walls of pipes. When data were grouped by the solid that

controls solubility, the average 8-h stagnant Cu concentration in drinking water was found to

decrease linearly with average pipe age. For these average values, langite was the most

soluble and youngest film, followed in both solubility and age by cupric hydroxide, azurite,

brochantite, malachite,

Aging and tenorite. The more

stable solidsmalachite

copper pipes
and tenoritewere 8 and

16 times less soluble,

of respectively, than the

most soluble solid,

langite. Scales usually

by drinking water contained more than one

compound, a finding that

was attributed to temperature changes, variability of water composition, long stagnation

periods, and aging. During the aging process, parts of a young scale surface area may be

covered and blocked for further reaction by a precipitate. During long stagnation periods, such

factors as changes in pH, oxygen, and carbon dioxide concentrations and precipitation of

calcium solids may induce a different Cu compound precipitate.

A
mple evidence has shown that a wide range of copper (Cu)-containing com-
pounds grow in the form of scales or films on the inner walls of copper
pipes used for drinking water distribution (Schock et al, 1995; Adeloju &
Hughes, 1988; Cruse et al, 1988; Mattson, 1988; Moss & Potter, 1984;
Potter, 1969; Ives & Rawson, 1962a). This growth takes place through-
out the lifetime of the pipe.
The most common Cu compounds found on pipe walls are cuprite (Cu2O),
tenorite (CuO), malachite [Cu2(CO3)(OH)2], langite [Cu4(OH)6SO4H2O], ata-
camite [Cu2(OH)3Cl], brochantite [Cu4(SO4)(OH)6], azurite [2CuCO3Cu(OH)2],

BY GUSTAVO E. LAGOS, CLAUDIA A. CUADRADO, AND M. VICTORIA LETELIER

94 NOVEMBER 2001 | JOURNAL AWWA | PEER-REVIEWED | LAGOS ET AL 2001 American Water Works Association
 FIGURE 1 Cu loading kinetics into water and diffusion curve for
pipe 1.3 cm in diameter

Dissolved Cu, 1999 Diffusion

Total Cu, 1998 Total Cu, 1999

and cupric hydroxide [Cu(OH)2] (Schock et al, 1995;
Edwards et al, 1994; Taylor & Cannington, 1993; Ade-
loju & Hughes, 1988; Cruse et al, 1988; Mattson, 1988;
Moss & Potter, 1984; Wilhelm et al, 1982; Potter, 1969).
Cuprite is commonly formed by an electrochemical
reaction between Cu metal and drinking water (Callot
et al, 1978; Ives & Rawson, 1962b). Under appropriate
conditions of potential and pH, other Cu compounds,
mainly malachite and tenorite, may be formed in equi-
librium with cuprite (Bockris et al, 1981).
These Cu compounds may also be formed by precip-
itation from solution or by substitution of oxygen by an
anion (Ives & Rawson, 1962b). Dissolution of Cu scales
is the main mechanism by which Cu is liberated to drink-
ing water (Schock et al, 1995). Chemical thermodynamic
equations have been successfully used to model this
process.
This study used thermodynamic models (Schecher &
McAvoy, 1998) to correlate experimental and field data
for the concentrations of Cu, anions, and cations in drink-
ing water with Cu-containing scales built on the inner
walls of pipes. The authors paid special attention to the
aging processes of the scales.
MATERIALS AND METHODS
This research focused primarily on three measure-
ments or analyses: (1) characterization of the inner films
from samples of pipe  30 years old taken from selected
locations in Santiago, Chile, (2) short-time copper pipe
coupon aging experiments, and (3) characterization of
Santiago drinking water at home taps.
Characterization of inner films from old pipe samples.
Pipes 3040 years in age were selected from three Santi-
ago locations for X-ray diffraction (XRD) and optical
TABLE 1 Short-term aging for new pipes in water of various pH
pH 6.5 pH 7.0
Langite = 4.1 mg/L* Atacamite = 1.8 mg/L*
Atacamite = 3.83 mg/L Cupric hydroxide = 2.43 mg/L
Cuprite = 5.7 mg/L Cuprite = 1.9 mg/L
Malachite and langite = Malachite and hydrated cupric
3.9 mg/L hydroxide = 1.9 mg/L
*Predicted by MINEQL+; temperature = 15oC
Predicted by MINEQL+; temperature = 20.2oC
Solid measured by X-ray diffraction (XRD); age = 46 days; measured stagnant copper concentration
indicated
Solid measured by XRD; age = 69 days; measured stagnant copper concentration indicated
Concentration/Maximum Concentration
1.0
0.8
0.6
0.4
0.2
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Stagnation Timeh
Cucopper
microscopy characterization. The premises of the locations
were being refurbished, and samples of their copper pipe
systems were made available. The aim of the measure-
ments was to establish a correspondence between the
inner films identified in old copper pipes and thermody-
namic equilibrium predictions using a selected number
of Cu compounds and water of equal composition to
that measured in the old pipe locations.
Pipe coupons of 50100 cm in length were obtained
from the sites. Coupons were dried and cut in 1  1 cm
sections for XRD analysis. The XRD instrument* had a
copper cathode tube of 40 kV and 30 mA. A commercial
software and the database PDF-2 (the database con-
taining the 20 angle [2 theta angle] and intensity of dif-
ferent solid compounds) were used to identify compounds
present in samples. For optical microscopy characteriza-
tion, the internal surfaces of the pipes were scraped, and
the collected powder was mixed with liquids of similar
refraction index. Optical microscopy was carried out
with transmitted light in a polariz-
ing microscope with up to 1,000
magnification.
Water taken from the premises
pH 8.0
was characterized by measuring the
following variables: in situ pH, in
Atacamite = 0.24 mg/L*
situ temperature, and the concen-
Atacamite = 0.18 mg/L
trations of calcium (Ca), bicarbon-
Solids not detected by
XRD = 0.66 mg/L
ate (HCO3), sulfate (SO4), chloride
Solids not detected by
(Cl), and total running water (1
XRD = 0.55 mg/L min) Cu. The methods used for the
*Siemens D-5000, Bruker AXS Inc., Madi-
son, Wis.
Diffract-at, Bruker AXS Inc., Madison,
Wis.
Nikon, Nikon Corp., Melville, N.Y.

2001 American Water Works Association LAGOS ET AL | PEER-REVIEWED | JOURNAL AWWA | NOVEMBER 2001 95
TABLE 2 Composition of Santiago, Chile, water*

Standard 10th 50th 90th

n Parameter Mean Deviation Percentile Percentile Percentile

217 pH in situ 7.9 0.28 7.6 7.9 8.2

217 Temperature in situoC 13.8 1.66 11.6 13.9 15.8
217 Dissolved oxygen in situmg/L 9.54 1.46 7.8 10 10.8
217 Stagnation timeh 7.84 1.83 6 7.6 10.1
217 Total stagnant coppermg/L 0.104 0.147 0.016 0.056 0.242
217 Dissolved stagnant coppermg/L 0.084 0.119 0.012 0.048 0.202
217 Standardized dissolved stagnant coppermg/L 0.086 0.121 0.012 0.049 0.205
217 Total copper in running watermg/L 0.024 0.03 0.005 0.015 0.053
217 Dissolved copper in running watermg/L 0.019 0.023 0.004 0.012 0.041
217 Calciummg/L 73.3 35.87 33 71.5 105
217 Magnesiummg/L 9.3 6.61 4.2 8 11.5
217 Hardnessmg/L as CaCO3 221.1 110.1 103.8 212.2 300.3
217 Bicarbonatemg/L as CaCO3 83.5 35.86 56 78 108
217 Sulfatemg/L 133.7 65.66 40.2 140 220.4
217 Chloridemg/L 100.9 52.06 22.6 106 163
214 Leadmg/L 0.005 0.005 0.0005 0.003 0.011
212 Nickelmg/L 0.014 0.01 0.005 0.011 0.027
214 Ironmg/L 0.257 0.081 0.174 0.248 0.365
214 Zincmg/L 0.024 0.028 0.005 0.014 0.059
217 ConductivityS/cm 779.4 317.4 303.6 820 1,133.4
207 Pipe ageyears 18.8 12.82 2.6 20 35
1,222 Total pipe lengthm (ft) 13.4 (44) 13.02 (43) 4 (13) 10 (33) 25 (82)

*Modified from Lagos et al (1999)

Number of samples considered for each variable
CaCO3calcium carbonate

analyses of chemical variables are described elsewhere
(Lagos et al, 1999).
Short-time copper pipe coupon aging experiments. These
experiments, like those conducted on the old pipe inner
films, were carried out to establish a correspondence with
thermodynamic equilibrium predictions. The copper pipe
coupons were subjected to short-time aging (69 days), using
a procedure similar to that reported by Edwards et al (1996).
Copper tubes 2 cm in diameter and 50 cm in length were
prepared. A rubber stopper was placed at one end of the
Changes in temperature and variability of the
led to precipitation of
coupon, the coupon was filled completely with tap water,
and a second rubber stopper was placed on the other end
of the coupon. Coupons were then placed horizontally on
a rack and maintained there for two days. Water was sam-
pled and changed to provide dissolved oxygen, which is
depleted using the corrosiondissolution process.
Over the course of 13 measurements, the mean com-
position of the tap water in the laboratory was as fol-
lows: in situ pH of 7.8, in situ temperature of 20.2oC, 100
mg/L Ca, 8.8 mg/L magnesium (Mg), 191.5 mg/L SO4,
78.5 mg/L Cl, hardness of 285 mg/L as calcium car-
bonate (CaCO3), and alkalinity of 98.8 mg/L as CaCO3.
Tap water was adjusted to three different pH values (6.5,
7.0, and 8.0) using nitric acid or sodium hydroxide.
The pipe used in these experiments was deoxidized
and dephosphorized hard copper piping, manufactured in
Chile. The fabrication process included the preheating at
900oC of ingots 132 cm in length and 30 cm in diameter.
These were then passed
through a milling machine
water composition for pickling. The resulting
d i f f e r e n t c o m p o u n d s . strips were drawn to final
size. No carbon film was
expected to be present in the
off-the-shelf pipes, and XRD measurements of off-the-
shelf pipes did not show the presence of such films.
Characterization of Santiago drinking water at home taps.
The chemical variable survey (CVS) of drinking water
was conducted in 1997 at the same time as a survey of
pipe systems. The CVS was carried out on a representa-
tive sample of the Santiago population as described by
Lagos et al (1999) and included such parameters as pipe

96 NOVEMBER 2001 | JOURNAL AWWA | PEER-REVIEWED | LAGOS ET AL

2001 American Water Works Association
 material, length, age, leaks, and
water composition. The surveys TABLE 3 Cu* loading kinetics and water composition
objectives were (1) to elaborate an
exposure model for Cu in drinking Year

water and (2) to enable prediction Parameter 1998 1999

of the measured dissolved stagnant
pH 7.6 7.4
Cu concentrations using thermody-
TemperatureoC 12.4 16.1
namic equilibrium calculations.
Stagnant (8-h) total copper (Cu) concentrationmg/L 0.241 0.224
The CVS included the following
Running water total Cu concentrationmg/L 0.022 0.006
variables: soluble and total Cu con-
Stagnant (8-h) dissolved Cu concentrationmg/L 0.168
centrations measured after stagna-
Running water dissolved Cu concentrationmg/L 0.0055
tion at the kitchen tap, soluble and
Bicarbonatemg/L as calcium carbonate 80 60
total Cu concentrations in running
Calciummg/L 89.4 84.5
water (1 min), Mg, Ca, carbonate,
Chloridemg/L 118 102
HCO3, SO4, Cl, lead, iron, nickel,
Sulfatemg/L 220.8 173
zinc, pH, and conductivity. Field mea-
*Cucopper
surements were also carried out for Measurements from Santiago, Chile, home with pipes six years in age
temperature, dissolved oxygen, pH,
and location of the house in univer- TABLE 4 Reactions and constants for copper compounds*
sal transverse Mercator coordinates.
Three samples were taken in each log K
homeone for maximum Cu and Reaction Constant (25oC, I = 0)
two for other water composition Cu+2 + 2H2O Cu(OH)2(ac) + 2H+ K1 16.24
variables, including minimum Cu. Cu+2 + CO32 CuCO3(ac) K2 6.73
The methods used for sampling, Cu+2 + H+ + CO32 CuHCO3+ K3 13
sample transport, storage, chemical HCO3 CO32 + H+ K4 10.33
analysis, and quality assurance/qual- Cu+ + 2Cl CuCl2 K5 5.5
ity control (QA/QC) procedures are Cu+ + 3Cl CuCl32 K6 5.8
described in Lagos et al (1999). Cu2O(s) + 2H+ 2Cu+ + H2O Ksp cuprite 1.55
Information about physical para- Cu4(OH)6SO4H2O2(s) + 6H+ 4Cu+2 + SO42 + 7H2O Ksp langite 16.79
meters related to copper pipes (e.g., 2CuCO3 Cu(OH)2(s) + 2H+ 3Cu+2 + 2CO3 + 2H2O Ksp azurite 16.92
pipe age and length) was obtained Cu4(OH)6SO4(s) + 6H+ 4Cu+2 + SO42 + 6H2O Ksp brochantite 15.34
as part of a consumption habit CuCO3Cu(OH)2(s) + 2H+ 2Cu+2 + CO32 + 2H2O Ksp malachite 5.18
exposure survey conducted during CuO(s) + 2H+ Cu+ + H2O Ksp tenorite 7.62
199798 in a larger but also repre-
*Constants (except K1) are from MINEQL+ thermodynamic database.
sentative sample of the population Iionic strength
Paulson & Kester (1980)
of Santiago. Information about pipe
age was added later after it was real-
ized that the precise age in years
was required for pipes that the initial survey had specified Cl, and a running water (1-min) concentration of 0.039
only as older than six years. mg/L Cu. Stagnant (8-h) Cu concentration measurements
The survey sampled a total of 250 homes. However, the for this site could not be carried out because the sample
study considered only 217 homes because 19 homes had was not large enough.
part of their water distribution network made of materi- In a pipe sample (estimated age = 40 years) from a com-
als other than copper, five homes had pipes of unknown mercial location, a greenish film was observed visually,
age, and in nine homes sampled, SO4, Cl, Mg, or Ca malachite was detected via XRD and optical microscopy,
concentration measurements failed QA/QC criteria (Lagos and clays and silicates were detected with optical
et al, 1999). microscopy. A second sample from the same location
showed a dark scale. Brochantite and quartz were detected
EXPERIMENTAL RESULTS with XRD; quartz, sericitic feldespates, clays, malachite, and
Pipe films. In a pipe sample (estimated age = 30 years) possibly atacamite were detected with optical microscopy.
from the Catholic University (Santiago) Chemical Engi- The water came from two wells, one for each sample. On
neering Department, XRD and optical microscopy average, the water showed a pH of 8.2, 42.3 mg/L Ca,
detected cuprite, calcite, and hydrated silicates in the 97.8 mg/L HCO3, 7.2 mg/L SO4, 15.1 mg/L Cl, and a
pipes noncolored scale. The water had a pH of 7.8, 157 running water (1-min) concentration of 0.020 mg/L Cu.
mg/L Ca , 130.3 mg/L HCO3, 357 mg/L SO4, 271 mg/L Stagnant (8-h) Cu concentration measurements for this

2001 American Water Works Association LAGOS ET AL | PEER-REVIEWED | JOURNAL AWWA | NOVEMBER 2001 97
TABLE 5 Correlation coefficients for measured and estimated dissolved Cu* concentration

Standard Mean Minimum Maximum

Mean Deviation, Minimum Maximum Stagnant Stagnant Stagnant
Pipe Pipe Pipe Pipe Dissolved Dissolved Dissolved
Age Age Age Age Cu Standard Cu Cu Correlation
n1 years years years years n2 mg/L Deviation mg/L mg/L Coefficient

Malachite 51 21 11.7 1 48 53 0.047 0.033 0.006 0.187 0.85

Tenorite 69 20 13.5 0.25 50 70 0.022 0.009 0.003 0.173 0.83
Cupric hydroxide 10 17 9.7 0.25 26 11 0.182 0.156 0.034 0.538 0.94
Azurite 31 18 12.6 0.25 46 33 0.139 0.058 0.058 0.284 0.84
Brochantite 36 19 13 0.75 48 39 0.088 0.078 0.017 0.404 0.95
Langite 10 5 4.9 0.25 15 11 0.412 0.270 0.163 1.15 0.91
*Cucopper
n1number of cases, age
n2number of cases, stagnant dissolved Cu
between measured and predicted dissolved Cu concentrations

site could not be carried out because the pipe diameter
was 5 cm, and diffusion limitations yielded only ~38% of
the equilibrium dissolution concentration after 8 h.
In a pipe sample (estimated age = 30 years) from a
storage tank of a local hospital, a scale with green and
white stains was observed, cuprite was detected with XRD,
and fibrous aciculate monoclinic malachite was detected
with optical microscopy. The water had a pH of 7.8, 112.7
mg/L Ca, 74 mg/L HCO3, 17.8 mg/L SO4, 136 mg/L Cl,
and a running water (1-min) concentration of 0.010 mg/L
Malachite was detected by XRD for pH 6.5 and 7.0
after 69 days of aging. Under certain conditions of water
composition and temperature, malachite can be formed
as a precipitate after dissolution of langite. At pH 6.5,
when the scale was initially composed of either langite or
atacamite, the software predicted that both malachite
and tenorite precipitate when earlier scales were dissolv-
ing. At pH 7.0, when the scale was initially composed of
atacamite, both malachite and tenorite were predicted to
precipitate. At this pH, when the scale was composed of

During long stagnation periods, changes in pH , oxygen , and carbon dioxide concentration
and precipitation of calcium solids may induce a different copper compound precipitate.

Cu. A laboratory experiment replicated the water com-
position at the hospital site and measured the stagnant
(8-h) dissolved Cu concentration at 0.041 mg/L. Software
A* (Schecher & McAvoy, 1998) was used to predict the
presence of malachite for this Cu concentration, a finding
that was confirmed by optical microscopy.
Short-time aging experiments. In short-time aging exper-
iments carried out in the laboratory, XRD detected the
presence of cuprite after 46 days, and langite, malachite,
and hydrated cupric hydroxide [Cu(OH)2H2O] after 69
days (Table 1).
The experiments were conducted November
1997January 1998 at an average tap water tempera-
ture of 20.2oC; the Santiago survey indicated that the
average tap water temperature in the winter was 13.8oC.
Thermodynamic predictions suggest that different com-
pounds can be formed during the winter and summer in
the same water composition. For the 69-day aging period,
predictions agreed with XRD measurements at temper-
atures of 20.2oC for water of pH 7.0 and 15oC for water
of pH 6.5. XRD did not detect any compounds for water
of pH 8.0.
cupric hydroxide, malachite, brochantite, and atacamite
were predicted to precipitate simultaneously.
CVS results. Table 2 shows the mean, the standard devi-
ation, and the 10th, 50th, and 90th percentile values for
Santiago water composition and other relevant parameters,
e.g., stagnation time, stagnant Cu concentration, pipe age,
and pipe length. The concentrations measured for Ca,
Mg, HCO3, SO4, Cl, and metals (except Cu) corre-
sponded to those measured for running water samples.
Stagnant and equilibrium concentrations. Stagnant Cu
concentrations can differ from equilibrium Cu concen-
trations, as shown by other research (Nielsen & Yding,
1997; Meyer, 1996). The loading kinetics of Cu into
water was measured in 1998 and 1999 in a Santiago
apartment with pipe that was six years in age (Figure 1).
Water composition is shown in Table 3. Cu dissolution
kinetics were controlled by the diffusion (Van den Hoven
& Van Eekeren, 1988) of Cu from the 1.3-cm diameter
pipe wall to the center of the pipe.
*MINEQL+, version 4.0 for Windows, Environmental Research Soft-
ware, Hallowell, Maine

98 NOVEMBER 2001 | JOURNAL AWWA | PEER-REVIEWED | LAGOS ET AL 2001 American Water Works Association
 FIGURE 2 Solubility versus pH for seven copper-based FIGURE 3 Dissolved Cu versus HCO3 concentration
compounds for brochantite in equilibrium with water

Tenorite Brochantite Eq 5: pH = 7.92; sulfate = 141.3 mg/L

0.45
Malachite Langite
0.40

Dissolved Cumg/L
Cupric hydroxide Cuprite
Azurite 0.35
1 0.30
2 0.25
Average pH
3 in Santiago water 0.20
4 0.15
Log CuM

5 0.10
6 0.05
7 0
8 50 100 150 200 250
9 HCO3mg/L as CaCO3
10 CaCO3calcium carbonate, Cucopper, HCO3bicarbonate
5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5
pH Line predicted by Eq 5.

Predicted by MINEQL+ at the average temperature

and water composition for the Santiago chemical
variable survey
FIGURE 5 Dissolved Cu versus pH for tenorite in equilibrium
with water

FIGURE 4 Dissolved Cu versus HCO3 concentration for langite

in equilibrium with water
Eq 3: HCO3 = 72 mg/L
0.200
Eq 6: pH = 7.88; sulfate = 184 mg/L
1.4
Dissolved Cumg/L

0.150
1.2
Dissolved Cumg/L

1.0
0.100
0.8

0.6 0.050
0.4

0.2 0.000
7 7.5 8 8.5
0
50 100 150 200 250 300 pH
HCO3mg/L as CaCO3
Line predicted by Eq 3; HCO3bicarbonate, Cucopper
CaCO3calcium carbonate, Cucopper, HCO3bicarbonate
Line predicted by Eq 6.

Sampling was carried out with 250-cc bottles at the
times indicated in Figure 1, except for the 8- or 9-h stag-
nation concentrations, which corresponded to the first
measurement taken after the stagnation period. When a
sample was taken, a new volume of water with an
unknown Cu concentration filled the apartment pipe,
which may have contributed to the depression of the
kinetic curve in Figure 1. Because the pipes of Santiago
homes are mostly 1.3 cm (0.5 in.) in diameter, the exper-
iment shown in Figure 1 was used to standardize stag-
nation times obtained in the survey to 8 h.
Prediction of measured dissolved Cu concentration. The
soluble Cu concentration can be expressed as the sum of the
concentrations of the predominant soluble cupric species
Cu2+, Cu(OH)2(aq), CuCO3(aq), and CuHCO3+ (Edwards et
al, 1996). Other species (e.g., orthophosphate, SO4, Cl, and
ammonium) were not considered because their effect on the
total dissolved Cu concentration in the pH range of 78.5
was negligible (Schock et al, 1995). The reactions and con-
stants shown in Table 4 can be used to write an equation
for the equilibrium of cupric species:
Cu = [Cu2+] + K1[Cu2+][H+]2 + K2K4[Cu2+][H+]1 [HCO3]
+ K3K4[Cu2+][HCO3] (1)
Equation 2 describes the equilibrium of cuprous species:
Cu(I) = [Cu+] + K5[Cu+][Cl]2 + K6[Cu+][Cl1]3 (2)
Equations for Cu compounds. The equations for the equi-
librium between the five Cu(II) compounds shown in Table
4 and the dissolved Cu concentration at 25oC are as follows:

2001 American Water Works Association LAGOS ET AL | PEER-REVIEWED | JOURNAL AWWA | NOVEMBER 2001 99
 than the values they determined using the Cu(II) ion
FIGURE 6 Dissolved Cu concentration versus pipe age
selective electrode method.
It appears that much of the difference in log K1 val-
Malachite Azurite
ues was attributable to the characteristics of the solid-
Tenorite Brochantite
Cupric hydroxide Langite phase equilibration rather than the solution-phase
0.6 hydrolysis. Special techniques were used to prevent
Cu(II) hydroxide precipitation, Cu(II) carbonate, and
0.5
Cu(II) organic complexation (formation of other soluble
Dissolved Cumg/L

0.4
compounds such as organic complexes because of the
presence of fulvic or humic acids) during the titration.
0.3 These authors indicated that the study of Vuceta and
Morgan (1977), who determined a value closer to 13.7
0.2 for log K1, did not consider the adsorption of Cu2+ onto
the container surfaces, and this factor was found to be
0.1
significant. In the work described here, the values
employed for the equilibrium constants were those used
0
0 20 40 60 80 by Software A (Table 4), except for log K1, which used
Pipe Ageyears a value of 16.24.
Number of samples = 207; Cucopper

Tenorite
Cu = 10(7.622 pH) + (10(4.02 pH) + 10(10.292 pH)) [HCO3] (3)
Malachite
Cu = (10(2.5751.5 pH) + 10(13.665+0.5 pH)) [HCO3]0.5
+ (10(1.0250.5 pH) + 10(5.2451.5 pH)) [HCO3]0.5
Brochantite
Cu = (10(3.8351.5 pH) + 10(12.405+0.5 pH) + (10(0.2350.5 pH)
+ 10(6.5051.5 pH)) [HCO3]) [SO42]0.25
Langite
Cu = (10(4.19751.5 pH) + 10(12.0425+0.5 pH) + (10(0.59750.5 pH)
+ 10(6.86751.5 pH)) [HCO3]) [SO42]0.25
Azurite
Cu = (10(1.2474/3 pH) + 10(14.993+2/3 pH)) [HCO3]2/3
+ (10(2.3531/3 pH) + 10(3.9174/3 pH)) [HCO3]1/3
Predictions of Cu concentration using these equations
were strongly dependent on equilibrium constant val-
ues. For the most part, the literature contains different
values for one equilibrium constant. For instance, Schock
et al (1995) discuss values for log K1 ranging from 13.7
to < 17.3. Experimental work by Paulson and Kester
(1980) led to a value for log K1 of 16.24 and suggested
that their research provided the first consistent mea-
surements for K1. These authors observed that the values
of K1 obtained through the Cu(OH)2(S) solubility method
(Gubeli et al, 1970) were two orders of magnitude greater
PIPE AGING
Electrochemical theory predicts that cuprite is formed
on contact between Cu and water (Ives & Rawson,
1962b) because of the oxidation of Cu. The other half-cell
reaction occurs at the cuprite solution interface and con-
sists of the reduction of oxygen. The cuprite film remains
as the only contact with the metal (Callot et al, 1978).
In these experiments, cuprite was predicted to oxidize
to malachite or tenorite at pH values above 7 and with the
(4)
average Santiago water composition. No cupric ions are
liberated to solution with these electrochemical reactions.
At pH values under 6.0, cuprite may oxidize directly to
langite or brochantite. At very low pH values, oxidation
of these compounds to Cu2+ may occur. However, the
(5)
lowest pH measured in the Santiago survey was 6.4.
Therefore, oxidation of these compounds to cupric ion
was not expected to occur.
Simultaneously with these electrochemical reactions,
Cu compounds could have precipitated from solution,
(6) but this was considered unlikely because the distribution
system water contained negligible amounts of Cu. Nev-
ertheless, other solids (e.g., calcite) may precipitate from
the start. Dissolution of the electrochemically formed
scales starts immediately upon formation. This marks
(7)
the start of the aging process, because precipitation of
less-soluble compounds occurs simultaneously with dis-
solution when the solubility product of a solid has been
exceeded.
Figure 2 shows the dissolved Cu concentration versus
pH estimated with Eqs 37 (at 25oC and given the aver-
age Santiago water composition). At the average pH of
Santiago water (7.89), langite and cupric hydroxide give
way to the higher Cu concentration in solution, followed
by azurite, brochantite, and other compounds. Under
these conditions, cuprite is always the solid with lower sol-
ubilityalmost two orders of magnitude lower than the
other compounds. Therefore, if langite and cuprite were

100 NOVEMBER 2001 | JOURNAL AWWA | PEER-REVIEWED | LAGOS ET AL 2001 American Water Works Association
 present simultaneously in a pipe wall,
the dissolution of langite should be FIGURE 7 Plot of mean dissolved Cu concentration versus mean pipe age
almost three orders of magnitude
higher than that of cuprite.
Malachite Azurite
Generally, the dissolution of a high- Tenorite Brochantite
solubility compound can give rise to Cupric hydroxide Langite
0.5
the precipitation of a low-solubility
compound, provided all the appropri-
0.4
ate species are in solution. Thus, as

Mean Dissolved Cumg/L

shown in Figure 2, langite could give
rise to the precipitation of the remain- 0.3

ing Cu compounds (with the excep-

tion of cuprite, which requires Cu+ in 0.2
solution, and this species is not stable).
Under the conditions of Figure 2, it is 0.1
not expected that a low-solubility com-
pound should give rise after dissolu- 0.0
tion to the precipitation of a higher- 0 5 10 15 20 25
solubility compound. Therefore, aging Mean Pipe Age years
Cucopper
is a unidirectional process, provided
the water composition and the tem-
perature remain constant. FIGURE 8 Aging sequence for Santiago, Chile, water composition
Prediction of Cu compounds. Equi-
librium calculations using Software A
were carried out for each of the 217 Cupric
hydroxide
water composition samples in the n = 11
study, and a Cu compound was pre-
dicted to be in equilibrium with each
water composition. The solid selected Azurite
n = 11
n = 33 n = 33
was the one whose predicted Cu dis-
solved equilibrium concentration was
closest to the measured stagnant dis- Malachite Brochantite
solved Cu concentration. Estimations n = 53 n = 39
were made for the correlation coeffi-
cients between the predicted dissolved Langite
n=3
n = 11 n=3
Cu concentration and the measured n = 40 n=2
stagnant dissolved Cu concentration
(Table 5). Table 5 also shows pipe age,
measured stagnant dissolved Cu con- n = 36
n=8 Tenorite
centration, and number of homes in n = 70
which the solid would be present in
nnumber of samples
the inner pipe wall. The table indicates
that great variability was found in pipe
age and dissolved Cu concentration.
The correlation coefficients between pH and measured Eq 6 for langite, using the pH and SO4 values indicated,
dissolved stagnant Cu concentration, grouped by solids which corresponded to mean values for each solid.
shown in Table 5, ranged from 0.67 to 0.89. Figures 3 The correlation coefficients between the stagnant dis-
and 4 show plots of the measured dissolved stagnant Cu solved Cu concentration and SO4 were 0.52 for brochan-
concentration versus the HCO3 concentration for brochan- tite and 0.43 for langite. When data were grouped for
tite and langite, respectively, in equilibrium with water. narrower ranges of HCO3 concentrations, these values
The data points do not adjust to the linear relationships increased.
indicated by Eqs 5 and 6 because of the variability of pH For tenorite, malachite, and cupric hydroxide, it was
and SO4. The correlation coefficient between stagnant dis- important to make these plots at different pH values. For
solved Cu and HCO3 concentrations were 0.79 and 0.63, tenorite, the correlation coefficient between dissolved Cu
respectively, for all pH values. The dotted lines for Fig- concentration and HCO3 was 0.67 for pH between 7.5
ures 3 and 4 were calculated using Eq 5 for brochantite and and 7.8 and 0.21 for pH > 7.8. Figure 5 shows the plot

2001 American Water Works Association LAGOS ET AL | PEER-REVIEWED | JOURNAL AWWA | NOVEMBER 2001 101
 to age to malachite and tenorite. It
FIGURE 9 Mean dissolved Cu concentration versus mean SO4 concentration was predicted that the dissolution of
langite resulted in the precipitation of
Malachite Azurite
Brochantite
atacamite and azurite when the water
Tenorite
Cupric hydroxide Langite had a pH of 7.2, 2 mg/L SO42, and
0.5
alkalinity of 10 mg/L as CaCO3. At
pH 7.8, 2 mg/L SO42, and alkalinity
of 10 mg/L as CaCO3, the dissolution
0.4
of langite was predicted to generate
Mean Dissolved Cumg/L

the precipitation of cupric hydroxide.

At pH 7.8, 300 mg/L SO42, and alka-
0.3
linity of 100 mg/L as CaCO3, the dis-
solution of langite was predicted to
0.2 produce the precipitation of cupric
hydroxide and azurite.
For particles < 1 m, the value of
0.1 solubility may increase considerably
(Stumm & Morgan, 1996), and thus,
stability should decrease. Therefore,
0.0 aging of small particles may involve
75 100 125 150 175 200
Mean SO4 Concentrationmg/L recrystallization into large ones. Pre-
Cucopper, SO4sulfate cipitation of tenorite is favored in cer-
tain water compositions > pH 7.5,
because its solubility is lower than
that of other Cu compounds (Figure
of the stagnant dissolved Cu concentration and pH for 2). When the precipitation of tenorite occurs with the
tenorite. For malachite, the coefficient value was 0.35 formation of fine particles, its solubility increases con-
for pH between 7.2 and 8 and 0.59 for pH > 8. For cupric siderably and can give way to chemical unstability and the
hydroxide, the value was 0.74 for pH between 7.5 and 7.9 formation of compounds such as cupric hydroxide, which
and 0.46 for pH > 7.9. For azurite, the value was 0.64. usually has higher solubility than tenorite (Schindler,
Low coefficient values may be attributable to differences 1967). When langite and cupric hydroxide are exposed
in pH, temperature, and pipe age. to air, they dehydrate to brochantite and tenorite, respec-
Figure 6 shows the plot of the stagnant dissolved Cu tively (Bockris et al, 1981). Malachite can dehydrate to
concentration versus pipe age. Figure 7 shows the plot of the azurite when exposed to air, but this process is slow.
mean stagnant dissolved Cu concentration for each calcu- The aging process was dependent on the SO4 content
lated compound versus the mean pipe age. No pattern was of the water, as shown in Figure 9. For high concentrations
found for Figure 6. However, when
the mean values were grouped with
respect to the dissolving solids (Figure REFERENCES Gubeli, A.O. et al, 1970. LAction de lAmmoniac
sur lOxyde Cuivrique et les Hydroxo-
7), it was observed that langite was Adeloju, S.B. & Hughes, H.C., 1988. Corrosion of
Complexes de Cuivre (II). Helvetica Chim-
the most soluble and youngest scale Copper Pipes in High ChlorideLow Car-
ica Acta, 53:186.
bonate Mains Water. Corrosion Sci., 26:851.
compound, followed in both solu-
Ives, D.J. & Rawson, A.E., 1962a. Copper Cor-
bility and age by cupric hydroxide, Bockris, J.O. et al, 1981. Comprehensive Trea-
rosion I. Thermodynamic Aspects. Jour.
tise of Electrochemistry. Plenum Press,
azurite, brochantite, malachite, and Elec. Soc., 109:6:447.
New York.
tenorite. Ives, D.J. & Rawson, A.E., 1962b. Copper Cor-
Callot, P.A. et al, 1978. Pitting Corrosion of Cop-
Prediction of aging. Figure 8 shows rosion III. Electrochemical Theory of Gen-
per Tubes and Carbon Deposits: ESCS
the aging sequence for these solids. Studies. Werkstoffe & Korr., 29:519. eral Corrosion. Jour. Elec. Soc., 109:6:458.
It was predicted that cupric hydrox- Lagos, G.E. et al, 1999. Model for the Popula-
Cruse, H.; Von Franque, O.; & Pomeroy, R.,
ide would be found in samples from 1988. Corrosion in Potable Water Sys- tion Exposure to Copper From Drinking
11 homes and that cupric hydroxide tems. Corrosion in Pipes. AWWA, Denver. Water. Sci. Total Envir., 239:13:49.
was aging to become either mala- Edwards, M.; Schock, M.R.; & Meyer, T.E., Mattson, E., 1988. Counteraction of Pitting in
chite or brochantite. The transitions 1996. Alkalinity, pH, and Cu: Corrosion By- Copper Water PipesCauses and Coun-
shown in Figure 8 are dependent on products Release. Jour. AWWA, 88:3:81. termeasures. Werkstoffe & Korro., 39:499.
the water composition. For exam- Edwards, M.; Ferguson, J.F.; & Reiber, S.H., Meyer, E., 1996. Determinants of Copper Intake
ple, for the 217 water compositions 1994. Pitting Corrosion of Copper. Jour. From Water. Proc. 1996 Natl. Insts. of
in the study, langite was predicted AWWA, 86:7:74. HealthUniv. of Chile Conf. on Genetic

102 NOVEMBER 2001 | JOURNAL AWWA | PEER-REVIEWED | LAGOS ET AL 2001 American Water Works Association
 of SO4, cupric hydroxide is more soluble than langite;
therefore, cupric hydroxide could age to langite. In this
study, langite was predicted for high SO4 concentration
water (Figure 9).
CONCLUSIONS
Precipitation and dissolution were predicted to be
main causes of aging for Cu scales present on the inner
walls of copper pipes. When data were grouped by the
solid that controls solubility, the average stagnant (8-h)
Cu concentration in drinking water decreased linearly
with average pipe age. For these average values, langite
was the most soluble and youngest film, followed in both
solubility and age by cupric hydroxide, azurite, brochan-
tite, malachite, and tenorite. This hierarchy of solubility
and age may change for given water compositions. The
more stable solidsmalachite and tenoritewere 8 and
16 times less soluble, respectively, than the most soluble
solid, langite.
More than one solid was usually present or predicted
in scales. Several electrochemical reactions led to the for-
mation of compounds on the inner walls of copper pipes.
Also, in some water compositions, it can be expected that
several compounds will precipitate simultaneously.
Changes in temperature and variability of the water com-
position led to precipitation of different compounds. Dur-
ing precipitation, parts of a young scale surface area may
be covered and blocked for further reaction by a precipi-
tate. During long stagnation periods, changes in pH, oxy-
gen, and carbon dioxide concentration and precipitation
of calcium solids may induce a different Cu compound
precipitate. Generally, a prediction of the primary com-
pound present in the inner scale can be made, based on a
knowledge of the water composition (i.e., pH, HCO3,
Cl, SO42, Ca2+) and provided dissolved organic carbon,
chlorine, sulfide, and phosphate concentrations are low.
ACKNOWLEDGMENT
This project was part of the Program Risk Assessment
of Copper in the Environment (MP-01) sponsored by the
Government Research Development Fund of the Corpo-
racin de Fomento de la Produccin and was funded by
grants from the Chilean copper industry and the Inter-
national Copper Association (New York). The authors
thank the many organizations that participated in the
project, particularly the Center for Metallurgical and
Mining Research (Santiago, Chile), which provided some
of the chemical analysis and other project support. The
authors also thank Herbert Allen of the University of
Delaware (Newark, Del.) and Marc Edwards of Virginia
Polytechnic Institute (Blacksburg) for their enthusiasm
and advice.
ABOUT THE AUTHORS:
Gustavo E. Lagos is a professor at the Catholic Univer-
sity of Chile, Av. Vicuna Mackenna 4860, Santiago,
Chile, <glagos@ing.puc.cl>. He holds an MS degree in
mining engineering from the University of Chile in San-
tiago and a PhD and postgraduate
diploma in mineral processing from
the University of Leeds (Great
Britain). He has 25 years of experi-
ence in electrochemistry and has
studied dissolution of copper pipes
in drinking water for seven years.
Claudia A. Cuadrado is an MS can-
didate and M. Victoria Letelier is a PhD candidate at
the Catholic University of Chile.
If you have a comment about this article, please contact
us at <journal@awwa.org>.

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2001 American Water Works Association LAGOS ET AL | PEER-REVIEWED | JOURNAL AWWA | NOVEMBER 2001 103