Corrosion Science 53 (2011) 18131824

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

Effects of ow, brass location, tube materials and temperature on corrosion of brass plumbing devices
Emily Sarver , Marc Edwards 1
Department of Civil and Environmental Engineering, 418 Durham Hall, Virginia Tech, Blacksburg, VA 24061, USA

a r t i c l e

i n f o

a b s t r a c t
Effects of plumbing-specic installation factors on brass corrosion were investigated in a series of pipeloop experiments. Increased ow velocity increased corrosion rates, but did not affect corrosion type. The presence of copper tubing in the plumbing system increased selectivity of brass corrosion for zinc, unless a galvanic connection was made between copper and brass, in which case corrosion became more uniform and was accelerated. Plastic tubing allowed oxidant (i.e., free chlorine) to persist in water, increasing brass exposure. Additionally, hot water signicantly increased lead leaching from brass. These ndings may inform future investigations into brass corrosion issues and plumbing designs. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 20 October 2010 Accepted 29 January 2011 Available online 4 February 2011 Keywords: A. Brass B. Weight loss B. SEM C. De-alloying C. Pitting corrosion

1. Introduction Brass is a copperzinc alloy, which contains small amounts of lead, iron, and other trace elements. In premise plumbing systems, brass devices (e.g., valves, couplings, faucets) are commonly used due to their relative durability, machinability, intricate functionality and low cost. Although brass corrosion does not present serious problems in most systems, certain types of non-uniform corrosion can signicantly impact performance in some cases. Most notably, dezincication is a type of de-alloying corrosion wherein zinc is selectively dissolved, either from small (i.e., plugs) or large areas (i.e., layers) that can penetrate deep into the brass surface. Dezincication can leave brass porous and subject to leaks, and can also lead to clogged water lines and burst failures when voluminous corrosion deposits called meringue build-up within affected devices. On top of economic consequences, water damage can result in harmful mould growth [1]. Brass pitting is another type of nonuniform corrosion, which may also result in leak failures [2]. Finally, waters that support dezincication or other brass corrosion may also cause lead leaching, which presents a potential health hazard if tap water is contaminated [37]. Red (i.e., low-zinc) and dezincication resistant (i.e., DZR or inhibited) brasses are made for use in plumbing [8], but these alloys are not always utilised due to their relatively high costs,
Corresponding author. Permanent address: Department of Mining and Minerals Engineering, 108 Holden Hall, Virginia Tech, Blacksburg, Va 24061, USA. Tel.: +1 540 231 8139; fax: +1 540 231 4070. E-mail addresses: esarver@vt.edu (E. Sarver), edwardsm@vt.edu (M. Edwards). 1 Tel.: +1 540 231 7236; fax: +1 540 231 7916.
0010-938X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2011.01.060

limited availability, or unfamiliarity. Recently, use of inexpensive, yellow (i.e., high-zinc) brasses has resulted in widespread dezincication failures in particular areas and product liability concerns (e.g., [9]). Lead free brasses are now required in many potable water applications [10], but these alloys may contain up to 8% lead (by weight) and may not be adequately reducing lead leaching [11,12]. There is also some evidence that DZR brasses may be more prone to lead leaching than un-inhibited brasses [7,13], and neither DZR nor lead-free brass specically offers protection against pitting. Thus, while problems are relatively rare, they do occur. In potable water systems, the type and extent of brass corrosion may often be controlled by alloying constituents and metallurgy, and water chemistry (e.g., pH, alkalinity, chloride, oxidant) [2,13 17]. However, corrosion may also be inuenced by physical or physiochemical factors associated with specic installations, including ow conditions, location of brass within a system, predominant tubing materials, galvanic connections, and water temperature. 1.1. Flow and brass location The effects of ow on brass corrosion are not straightforward. Although texts often state that dezincication is promoted by slowly moving or stagnant water at the affected surface (e.g., [18,19]), practical observations reveal that the corrosion may be accelerated by owing conditions (e.g., [20,21]). As explained by Kelly et al. [22], this discrepancy may be due to physical separation of anodic and cathodic sites on brass surfaces. If, for example, relatively small anode sites become occluded beneath meringue deposits, these sites would be shielded from bulk water ow

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E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824

conditions; whereas, larger cathode sites may be exposed to the bulk water conditions. In that case, increasing ow velocity would effectively increase the supply of oxidant (e.g., free chlorine or dissolved oxygen) to the cathodes2, aiding in development of a differential concentration cell and driving dezincication at the anode. Separation of anodes and cathodes may also occur on a much larger scale in plumbing systems if the location of brass within a system causes it to be subjected to differential ow. Such a scenario can exist when a brass T-connection branches one water line off of another, such that one section is subject to ow while another may not be, as is commonly the case in building plumbing systems. Furthermore, owing conditions could promote selective lead leaching from brass, which may be mechanistically analogous to dezincication (i.e., due to micro-galvanic currents between dissimilar alloy constituents). Additionally, increased ow could contribute to brass pitting similar to observations of some copper pitting phenomena (e.g., [24]).

1.2. Plumbing tube material Modern plumbing systems primarily utilise either copper or plastic (e.g., PEX) tubing [25], and the effects of the tube material on bulk water chemistry in a system may impact corrosion of brass devices. For example, while copper tubes can signicantly consume oxidants in potable waters, plastics tubes cannot. Thus, long lengths of copper tubing might dramatically reduce free chlorine residual3 of the water before it even reaches some brass components (e.g., a faucet), perhaps effectively reducing overall corrosion activity of those components. In contrast, plastic tubing can allow chlorine to persist in water for much longer periods of time, increasing the likelihood of high dose and duration of exposure. It is also possible that copper released from copper tubing may limit copper leaching from brass components through equilibrium and mass transport phenomena, thereby increasing selective zinc leaching from brass. In the case of copper tubing, brass corrosion can also be affected by galvanic connections between the two metals, which are commonplace in plumbing systems. Given the typically small wettedsurface-area ratios between brass and copper in these systems, and that copper is usually noble to brass, galvanic currents may signicantly accelerate brass corrosion. With respect to overall corrosion rate, a worst-case scenario may be represented by a copper-brass connection oriented such that the brass is additionally subject to differential ow conditions (Fig. 1).

Fig. 1. Hypothesized effects of differential ow and galvanic connection (to copper) on brass corrosion. Water ows through the copper tube, but is relatively stagnant inside the brass. As zinc (or other alloy constituents) is oxidized, electrons are liberated at the brass surface and accepted at the copper surface where an oxidant (e.g., free chlorine as HOCl) is reduced. pH drops in the stagnant water due to Lewis acidity of metal cations (e.g., Zn2+), salt content increases as chloride (Cl) and other anions draw into satisfy electroneutrality, and corrosion deposits (e.g., meringue) may build-up on the brass surface. If ow velocity is increased, or oxidant concentration is increased in the owing water, brass corrosion is expected to accelerate.

when brass components are present (e.g., [30]), and it is highly desirable to understand if lead-bearing brass is a probable culprit. The objective of this work is to gain a broader understanding of the practical effects that the above factors of installation may have on the type(s) and extent of brass corrosion that may occur in potable water systems of specic buildings. 2. Materials and methods Three experiments were conducted (Table 1) in pipe-loop apparatuses (Fig. 2). The rst consisted of short-term proof of concept tests (i.e., tests AC) to study the hypothesized scenario in Fig. 1, while the second and third consisted of longer-term tests (i.e., tests DK) designed to isolate the effects of individual factors on corrosion of brass plumbing devices. 2.1. Pipe-loops Pipe-loops were constructed using new C36000 (i.e., high-zinc, un-inhibited) brass ttings, effectively smooth-walled brass tubing in the loops, and C12200 copper tubing (where specied). The brass ttings were either couplings or caps that would practically be utilised with PEX, or a combination of PEX and copper, plumbing tube systems (Fig. 3). The actual composition of the brass alloy (by weight) was determined by a handheld X-ray uorescence (XRF) instrument (Innov-X Systems, model Alpha 8000): 58.8% Cu, 37.2% Zn, 3.1% Pb, 0.3% Sn, 0.3% Fe and 0.1% Ni. Prior to assembling the pipe-loops, copper tubing was cut and de-burred, and all components were rinsed with de-ionised water, allowed to dry and weighed. All pipe-loops had continuously re-circulating ow of test water (chemistries and velocities in Table 1) from polypropylene plastic reservoirs (30L in exp. 1, 94 L in exp. 2 and 3), which were closed to limit atmospheric inuences on water quality (e.g., changes in pH, temperature). All brass and/or copper sections were physically separated using short lengths of clear vinyl tubing, but were electrically connected via external copper bridge wires (except in tests E and J as specied in Table 1). This allowed for collection of electrochemical data by temporarily replacing the wires with a multi-meter (as illustrated in Fig. 2). Magnet-drive centrifugal pumps (polypropylene construction) were used to re-circulate

1.3. Temperature Temperature might also play a role in the type(s) and extent of brass corrosion that occurs in potable water systems. While it is accepted that high temperatures can worsen dezincication-related failures [28] via precipitation and accumulation of meringue [23,29], or acceleration of zinc leaching [2,13], effects of temperature on other types of brass corrosion are not well understood under the chemical and physical conditions that may be encountered in real plumbing systems. For instance, some eld data suggests that lead levels can be higher in hot water tap samples than in cold
Dezincication of brass in potable water is often cathodically-limited [23]. Free chlorine is common disinfectant for potable water supplies. Relatively high concentrations may be dosed at a treatment facility for immediate disinfection, and residual concentrations provide subsequent protection against microorganisms throughout a water distribution system. In addition to disinfection and autodecomposition, chlorine may be decayed (i.e., to Cl-) via redox reactions associated with corrosion of plumbing materials (e.g., brass, copper, iron) due to its high oxidizing power. The concentration of free chlorine (e.g., as mg/L) at any point in the system is referred to as the free chlorine residual at that location; in the U.S., residuals may not exceed 4 mg/L in potable water systems [26], but even lower concentrations can contribute to signicant metals corrosion over time (e.g., [27]).
3 2

E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824 Table 1 Test conditions for three experiments. Test Duration days Pipe-loop Flow velocity (m/s) Water chemistry parameters Maintained Initial Target value (standard deviation) Variable Cl2a 4 mg/L Cl2a (0.8) pH 7.6 (0.3) 11 mg/L alkb (3) 38 mg/L Na+ (6) 50 mg/L Cl (5) 34 mg/L alkb (3) 16 mg/L Na+ (3) 20 mg/L Cl (3) 17 mg/L Ca2+ (2) 13 mg/L SO42 (3) 34 mg/L alkb (3) 29 mg/L Na+ (5) 40 mg/L Cl (5) 17 mg/L Ca2+ (2) 13 mg/L SO42 (3) Weekly Weekly

1815

Water change cycle

Experiment 1 A 14 B 14 C 21 Experiment 2 D 490 E 490 F 490

Loop 1 with variable free Cl2 Loop 1 Loop 1 with brass located in-ow (no T)

2.1 2.1 2.1

Loop 2 Loop 2 without galvanic connection to copper Loop 2 with PVC in-ow (instead of copper)

1.3 1.3 1.3

pH 9.2 (0.3) 4 mg/L Cl2a (0.5)

Every Every Every Every Every Every Every Every Every Every

other other other other other other other other other other

week week week week week week week week week week

Experiment 3 G 150 H 150 I 87 J 150 K 150

a b

Loop Loop Loop Loop Loop

3 3 3 3 3

at low velocity at 45 C without electrical connection with copper in-ow (instead of brass)

1.9 0.6 1.9 1.9 1.3

pH 8.3 (0.2) 4 mg/L Cl2a (0.5)

Free chlorine residual. Alkalinity as CaCO3.

Fig. 3. New C36000 brass coupling (left) and cap (right). Left photographs show the ttings as installed in the pipe-loops; right show cross-sections to display smooth, interior shape.

Fig. 2. Pipe-loops for three experiments. Flow direction is indicated by arrows.

water, except in test H (exp. 3), which had a small submersible pump (polypropylene and stainless steel construction) that provided lower ow velocity. In experiment 1, the pipe-loops each had approximately 60 cm (total length) of Type M copper tubing (1.9 cm inner diameter) located in-ow, and one brass coupling (4.5 cm long, 1.75 cm inner

diameter). For tests A and B, the brass was located out-of-ow and plugged with a silicone stopper (i.e., as shown in Fig. 2, Loop 1) to create differential ow conditions; for test C, however, the brass was located in-ow, midway between two equal lengths of copper, such that water owed straight through all sections of tubing. In experiment 2, each pipe-loop had one brass coupling (dimensions above) which was located out-of-ow and plugged with a silicone stopper (as shown in Fig. 2, Loop 2). Located in-ow was approximately 91 cm (total length) of Type M copper (1.9 cm inner diameter) in tests D and E; in test F, instead of copper, the same length of equal-diameter of polyvinyl chloride (PVC) tubing was used. In experiment 3, each pipe-loop had one brass cap (1.3 cm long, 1.3 cm inner diameter) located out-of ow (i.e., no silicone plug was needed to create the dead-end), and one brass coupling (dimensions above) located in-ow (as shown in Fig. 2, Loop

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E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824

3). The only exception was test K, in which the brass coupling was replaced with a Type M copper tube of equal length (1.9 cm inner diameter). From this point forward, brass samples located in-ow in a pipe-loop are referred to as in-ow, and samples located out-of-ow are referred to as T due to their orientation at the dead-end of a T-connection. 2.2. Water chemistry In order to maintain relatively constant water chemistries in the pipe-loops, test waters were changed regularly (Table 1). Just prior to each water change, the test waters were synthesised using deionised water and reagent grade sodium and/or calcium salts. Free chlorine was added as sodium hypochlorite from a concentrated bleach stock (i.e., 6% NaOCl solution). Where applicable, pH was adjusted using NaOH and HNO3 stock solutions. pH was measured using a double-junction AgAgCl electrode, and free chlorine residual was measured with a Hach Chlorine Pocket Colorimeter II using a DPD (diethyl phenylene diamine) colorimetric test per Standard Method 4500-Cl G [31]. Except for in test I (exp. 3), water temperatures were governed by ambient room temperature and the heat generated by the pumps; temperatures ranged from 2433 C, which is within the cold water range for premise plumbing applications. In test I, temperature was maintained by an immersion heater at 45 C, which is considered hot water. In experiment 1, the synthesised potable water chemistry had a relatively high chloride to alkalinity ratio with a high dezincication propensity [13]. The water made using only sodium salts (i.e., it had no hardness), and had a relatively stable pH of 7.6, which was not purposefully maintained. Chlorine was not initially dosed to test A, but on day 3, free chlorine was dosed to the water to achieve a 4 mg/L residual concentration (as Cl2). This was manually maintained until day 6, at which time the chlorine was allowed to decay until the end of the test. In tests B and C, chlorine was manually maintained over the entire test duration. The synthesised potable water chemistry in experiment 2 had high pH, high free chlorine residual and low alkalinity a combination known to cause pitting of copper [24] and thus also expected to attack brass. A similar water chemistry was used in experiment 3, except that it had lower pH (i.e., 8.3 instead of 9.2) and higher chloride (i.e., 40 instead of 20 mg/L). These conditions were expected to produce severe meringue dezincication based on prior studies (e.g., [13,16]). In experiments 2 and 3, pH and chlorine targets were maintained via automatic feed systems in conjunction with manual adjustment (at least four times per week). 2.3. Data and analysis Corrosion currents (I) between metal sections were monitored for all tests having metals in electrical contact (i.e., all tests except E, F, and J). Measurements were taken at least once per water change cycle using a Fluke 189 True RMS multi-meter (internal resistance <100 X). In the convention utilised for this work, positive I values indicate anodic behaviour of a given metal section vs. all other metal in a system. Additionally, re-circulating bulk (i.e., from the pipe-loop reservoirs) and stagnant (i.e., from the dead-end T sections shown in Fig. 2) water samples were collected on a regular basis (i.e., weekly in exp. 1, every 6 weeks in exp. 2, and every 4 weeks in exp. 3), and metals concentrations (i.e., Zn, Cu, and Pb) were determined via inductively couple plasma mass spectrometry (ICP-MS). At the end of each test, brass samples were subject to forensic inspection. They were removed from pipe-loops and allowed to dry prior to removal of corrosion scales and cross-sectioning for visual and surface analyses. Copper enrichment (i.e., the relative increase in copper weight fraction of the brass surface after testing),

and zinc and lead depletion (i.e., the relative decrease in the zinc or lead weight fraction of the brass surface after testing) were determined by comparing elemental analyses (obtained via XRF) of un-exposed brass surface areas with (cleaned) areas which were obviously corroded during testing. The XRF instrument analysed an area of approximately 8 mm2, to a penetration depth of 1 lm or more. Enrichment and depletion were computed using Eq. (1) and (2):

EM 100

MC MU MU

 DM 100

MU MC MU

 2

where EM and DM are enrichment or depletion, respectively, of a given element (e.g., Zn) during testing (expressed as%); MC is the weight percentage of that element on the corroded brass surface; and MU is the weight percentage of that element on the brass surface not exposed to test water. Selected samples from experiment 3 were also imaged and analysed using an FEI Quanta 600 FEG environmental scanning electron microscope (ESEM), equipped with a Bruker Quantax 400 energy dispersive X-ray spectroscope (EDX) (penetration depth of 1 lm). This allowed for precise geometric measurements and elemental analyses of specic regions of interest (e.g., pits, areas of plug dezincication). Eq. (1) and (2) also were used to calculate metal enrichment and depletion values for these regions from the ESEMEDX, which had surface areas of about 0.0050.05 mm2. Additionally, corrosion scales from experiments 2 and 3 were dissolved and analysed for metals contents via ICP-MS. 3. Results Dezincication was observed in all tests, though the severity of attack and particular manifestations (i.e., layer, plug and/or meringue) varied (Table 2). Brass pitting was also observed in some tests (i.e., G, H, and K in exp. 3), and selective lead leaching was evident from water, scale and brass surface analyses in another (i.e., I, exp. 3). The sections below provide detailed results from each of the three experiments. 3.1. Experiment 1: proof of concept Results from experiment 1 conrmed that the general hypothesis presented in Fig. 1 (i.e., acceleration of brass corrosion via a combination of differential ow and galvanic connection to copper) is valid. In test A, the galvanic corrosion current density (brass T vs. copper in-ow) was closely related to the free chlorine concentration in the bulk water (Fig. 4), demonstrating that corrosion on the anodic brass surface was affected by the supply of oxidant to the cathodic copper. When chlorine dosing began on day 3, the current jumped and then rose over about a two-day period, reaching a peak of nearly 14 lA/cm2; when chlorine dosing was stopped on day 7, the current fell slowly with chlorine residual and stabilised around 0.8 lA/cm2 on day 12. No meringue formed in this test (or other tests in exp. 1), but based on metal leaching (not shown), visual observations and XRF data (Table 2), the measured galvanic corrosion currents can be attributed to dezincication of the brass. In test B, where chlorine concentration was maintained throughout, comparison of the stagnant water localised inside the brass T to the bulk water proved that a large-scale differential concentration cell did indeed develop, as hypothesised. Water samples were taken on days 7 and 14, and on both occasions the water in the T had lower pH (i.e., by 0.4 pH units) and lower free chlorine concentration (i.e., by 1.11.3 mg/L) than the bulk water.

Table 2 Summary of selected results for all tests. Test Current densitya (T vs. In) Weight loss (%/year) T In. Observedb corrosion type(s) T LD (shallow) LD (shallow) NA NA NA NA MD, LD (shallow) MD, LD (shallow) MD, LD (shallow) BP, PD, LD (shallow) LD (shallow) MD, PD, LD (deep) PD, LD (deep) BP, LD (deep) In. NA NA LD (shallow) NA NA NA Surface Zn depletionc (%) T 18.1 ND ND 35.9 69.5 53.9 In. NA ND ND NA NA NA Surface Cu enrichmentc (%) T 10.6 ND ND 22.9 42.5 35.3 In. NA ND ND NA NA NA Surface Pb enrichmentc (%) T 41.5 ND ND 26.6 88.3 23.6 In. NA ND ND NA NA NA Scale Zn contentd (Weight%) T ND ND ND 47.6 57.1 56.8 In ND ND ND NA NA NA Scale Cu contentd (Weight%) T ND ND ND 4.7 0.6 0.1 In ND ND ND NA NA NA Scale Pb contentd (Weight%) T ND ND ND 2.9 2.3 2.6 In. E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824 ND ND ND NA NA NA

lA/cm2
Experiment 1 A NA B 5.9 C 3.2 Experiment 2 D 0.9 E F NA NA

95% CI

1.0 0.5 0.1

ND

1.2 1.0 0.9

Experiment 3 G 0.8 H I J K 0.2 0.5 NA 2.7

0.5 0.2 1.3

1.3 0.8 1.5 1.3

1.9 1.8 2.1 2.0 NA

LD (shallow) BP, LD (shallow) MD, LD (shallow) LD (shallow) NA

30.6 29.8 19.0 35.1 16.3

51.8 47.5 28.9 37.0 NA

20.1 18.4 13.9 21.0 8.4

30.9 31.0 21.4 23.3 NA

15.8 10.4 43.5 14.8 10.4

19.0 8.6 32.7 22.1 NA

48.8 49.3 64.6 58.9 44.8

46.9 52.1 47.9 40.0 NA

2.0 5.6 5.4 5.1 12.2

4.1 3.1 1.0 7.8 NA

1.0 1.4 4.4 1.3 1.4

2.6 2.2 3.1 2.7 NA

2.0

1.7

T Brass located out-of-ow, In. Brass/copper located in-ow, NA Not applicable, ND Not determined, LD Layer dezincication, MD Meringue dezincication, BP Brass pitting, PD Plug dezincication. a Average over duration (exp. 1, 2) or week 8 through end of test (exp. 3). b Based on visual inspection of cross-sectioned samples. c Computed from XRF data; negative enrichment values indicate depletion of element from brass surface. d Computed from ICP-MS data as the weight% of element contained in solid scale removed from brass sample following testing.

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E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824

A
Anodic Current Density (uA/cm )
2

C
6

Bulk Chlorine Concentration (mg/L)

15

Current Chlorine
10 4

12

12

12

16

20

Day
Fig. 4. Brass current density (vs. in-ow copper) and bulk chlorine residual over time for tests A, B and C.

dezincication into the brass wall was too shallow to measure, at least on the two planes (i.e., wall thicknesses) revealed by crosssectioning the brass samples lengthwise. Signicant lead leaching was not observed in any of these short-term tests. 3.2. Experiment 2: plumbing tube materials In experiment 2, the inuences of plumbing tube materials on brass corrosion were tested. Meringue build-up was quite severe in all tests DF (Fig. 5), but was visually worst in the test (F) in which PVC tubes were installed in-ow instead of copper. While this test condition produced the least brass weight loss (Table 2), it maintained the highest pH levels in the stagnant T water (Table 3); so the increased build-up of meringue was likely due to reduced solubility despite the lower overall corrosion rate. In contrast, test D, where the brass T was galvanically connected to copper tubing inow, had the least meringue build-up, the greatest brass weight loss, the greatest pH drop in the stagnant water, and the greatest average zinc leaching (Fig. 6). In test E, where copper tubes were located inow but were not galvanically connected to the brass T, most results fell somewhere in between tests D and F. Beneath the meringue and other corrosion scales, the brass surfaces in all three tests exhibited shallow layer dezincication, which covered large non-uniform areas (Fig. 5). But, like in experiment 1, the depth of dezincication was too small to be quantied. Somewhat unexpectedly, brass pitting was not observed in this experiment even though the copper tubes in-ow (tests D and E) were severely pitted and began exhibiting pinhole leaks about 200 days into the testing. Brass pitting was, however, observed in experiment 3 (discussed below) where waters had lower pH and there was less meringue formation. As anticipated, chlorine consumption was impacted by the predominant tube material in the pipe-loops. The chlorine consumption rate with PVC tubes in-ow (test F) was at least 15 times lower than the rate with copper tubes in-ow (test D and E), and the chlorine residual in the stagnant T water (i.e., to which the brass was constantly exposed) also remained higher (Table 3). Since chlorine was expected to be aggressive with respect to corrosion, it was somewhat surprising that the brass in test F exhibited a lower weight loss than its counterpart in E (i.e., 0.9% vs. 1.0%, respectively); but the extreme difference in chloride concentrations in the T waters in these tests may have played a role as chloride is also known to be very aggressive towards brass dezincication [16]. Chloride built-up very quickly in test E due to the high chlorine consumption rate which necessitated a high chlorine feed rate to the pipe-loop in order to maintain the

Fig. 5. Brass Ts from tests in experiment 2. Meringue scale build-up is shown on the left; non-uniform layer dezincication (revealed after scale removal and crosssectioning) is on the right.

Table 3 T water chemistry and free chlorine consumption rates for tests in experiment 2. Test pH Average T water chemistry Cl2 (mg/L) D E F 8.6 8.7 8.9 1.4 2.0 2.5 54 44 9 280 210 208 417 580 2 1.3 0.5 1.2 Cl Zn Cu Pb Average Cl2 consumptiona (mg/h) 7.8 8.7 0.5

a Rate of chlorine addition required to maintain target concentration in bulk water.

Comparison of current densities from tests B and C (Fig. 4) additionally indicated that dezincication was more severe when the brass was located out-of-ow (as depicted in Fig. 1, Loop 1) than when it was located in-ow. The average current density was about 5.9 lA/cm2 in test B, but was only about 3.2 lA/cm2 in test C. Brass from tests A, B, and C all looked very similar upon removal of corrosion scales. The entire exposed surface was reddened indicating that layer dezincication occurred; however the depth of

E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824

1819

10

Zn

Cu

Pb

250

Average Zinc or Copper Accumulated (mg/week)

200

Average Lead Accumulated (ug/week)

150

100

50

0 D E F G H I J K Experiment 2 Experiment 3

Fig. 6. Average zinc, copper, and lead accumulated (either due to leaching or settling from bulk water) in stagnant T waters in experiments 2 and 3. The bulk water pH was 9.2 in experiment 2, and 8.3 in experiment 3. Data are normalized based on T water volume and sampling frequency; error bars show 95% condence intervals.

targeted 4 mg/L concentration and could have increased the overall corrosion rate of the brass in this test as compared to that in test F, where chloride build-up was minimal. In addition to accelerating the overall brass corrosion rate, as by evidenced by weight loss, the galvanic connection between copper tubes installed in-ow and the brass in test D also appears to have inuenced the selectivity of brass corrosion. The signicantly higher percentage of copper measured in the meringue from test D than that from E (i.e., about 4.7% vs. 0.7% by weight) suggests that the galvanically-inuenced brass may have leached much more copper than its uninuenced counterpart, effectively reducing the selectivity of brass corrosion for zinc (Table 2). Zinc depletion and copper enrichment data (as indicated by XRF) supported this nding, and also showed that, conversely, the brass corrosion in test E was highly selective for zinc indeed more so than in any other test presented here. This might be explained, at least partially, by the extremely high copper concentrations found in the T water from test E (Fig. 6), which were undoubtedly due to corrosion of the copper tubes installed in-ow in this test. While copper was also quite high in the T water in test D, again primarily due to corrosion of the inow copper tubing, it did not appear to inhibit copper leaching from the brass; perhaps this is because the galvanic voltage in this test was sufciently anodic to oxidize both zinc and copper from the brass. In test F, which was not inuenced by a galvanic connection or high background copper concentrations, corrosion was moderately selective for zinc (with respect to tests D and E), and nearly no copper was found in the T or bulk water, or in the meringue. From the perspective of lead leaching, all tests in experiment 2 behaved fairly similarly (e.g., Fig. 6). In addition to concentrations of lead measured in the T and bulk waters (i.e., about 0.52 mg/L and 0.11 lg/L on average, respectively), lead was also found in the meringue deposits in each condition. Lead ranged from about 2.32.9% by weight, which is relatively similar to the weight fraction of lead in the brass alloy itself. Interestingly, it was also observed that zinc and lead depletion were inversely related, such that as brass corrosion became more selective for zinc, it became less selective for lead, and vice versa (Fig. 7).

100 75 50

T brass in-flow brass

Pb Depletion on Exposed Surface (%)

25 0 -25 -50 -75 -100 0 25 50 75 100 Zn Depletion on Exposed Surface (%)

Fig. 7. Zinc vs. lead depletion on exposed brass surfaces from experiments 2 (unlled points) and 3 (lled points). Negative lead depletion values indicate lead enrichment.

served as a control (i.e., high velocity; electrical connection between brass T and brass in-ow to create differential ow conditions; cold water; no galvanic connection to copper). Before describing the results, several notes should be made regarding disruption to the experiment. First, the de-ionized water system utilised for these tests temporarily leached silica (i.e., 315 mg/L as Si) which briey affected all tests in experiment 3 between the rst and second water changes (i.e., days 1428)4. Second, a decision was made to interrupt chlorine dosing between the third and fourth water changes (i.e., days 2842), during which time it was conrmed

3.3. Experiment 3: other factors In experiment 3, effects of ow, temperature and galvanic connection to copper were studied in head-to-head tests (GK); test G
4 Silica has been previously observed to limit dezincication corrosion over short durations (e.g., [14]).

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E. Sarver, M. Edwards / Corrosion Science 53 (2011) 18131824

Si in DI system no Cl2 dosing

Current Chlorine

Bulk Chlorine Concentration (mg/L)

Anodic Current Density (uA/cm )

0 0 25 50 75 Day 100 125 150

Fig. 8. T brass current density (vs. in-ow copper) and bulk chlorine residual over time for test K. Periods of silica contamination and chlorine dosing interruption are indicated.

T brass weight loss In-flow brass weight loss Current density

6 Average Anodic Current Density (uA/cm2)

Weight Loss (%/year)

0 G H I J K

Fig. 9. T and in-ow brass weight loss rates, and average T brass current densities (vs. in-ow brass or copper) for tests in experiment 3. Current densities represent data from day 42 (i.e., after chlorine dosing resumed) through the end of tests; error bars show 95% condence intervals.

that electrochemical activity was signicantly depressed in all tests consistent with results from experiment 1. Fig. 8 shows the effects of the above events on the brass current density in test K (galvanic connection between brass T and copper in-ow). Additionally, test I (hot water) was only run for 87 days (vs. 150 days for other exp. 3 tests); and due to the high rate of chlorine auto-decomposition in this test, the average chlorine residual in the bulk water was only about 2.6 mg/L (vs. the maintained 4 mg/L target in all other conditions). Tests in experiment 3 produced various manifestations of brass corrosion (Table 2). Based on weight loss measurements, corrosion was most evident in the tests with hot water (I) or a galvanic connection between the brass T and copper in-ow (K), and was least aggressive in the low velocity test (H) (Fig. 9). The control (G) and the test where the T and in-ow brass samples were not electrically connected (J) produced similar weight losses, which were moderate with respect to the other tests. Overall, the tests with high weight losses also tended to have high current densities (measured between brass T vs. brass or

copper in-ow). However, the brass Ts lost less weight in every test condition than the in-ow brass despite the facts that the Ts were generally anodic to the in-ow samples, and that the stagnant T waters maintained consistently lower pH than the bulk waters (data not shown). The severity of dezincication (based on zinc depletion and copper enrichment as indicated by XRF data) was also determined to be lower on the T than on the in-ow brass in all tests. Thus, even though corrosion on the Ts was accelerated by their connection to in-ow metals, the overall corrosion rates of the Ts were still lower than those of the in-ow metals. It is considered likely that this was because the in-ow metals were exposed to relatively high, constant chlorine concentrations, whereas chlorine levels in the brass Ts were consistently much lower (i.e., about 2 mg/L on average) due to the differential concentration cells developed. All tests produced a relatively smooth, dark grey scale, which was covered by at least some meringue (Fig. 10). Test I produced meringue that covered a large portion of the T and in-ow brass surfaces, despite its shorter run time and lower chlorine residual,

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Fig. 10. T (top) and in-ow (bottom) brass from tests in experiment 3, prior to scale removal and cross-sectioning.

1100 m

600 m

Fig. 11. Photograph (lower left) and ESEM image (right) of pitting on in-ow brass from test H. Direction of sample cross-section is shown (upper left) and red box indicates location of imaging; white arrows indicate pit and dimensions are specied. This particular pit penetrated about 220 lm (i.e., roughly 15%) of the brass tube wall.

which is consistent with observations by other authors that hot water can increase meringue build-up [29]. In other tests, meringue deposits were round and isolated, and tended to be larger and fewer in number on the Ts than on the in-ow surfaces. After removing the corrosion scales and cross-sectioning the brass, varying degrees of layer dezincication were revealed on all samples. Some also exhibited plug dezincication and/or pitting. According to XRF analyses, corrosion was most selective for zinc in tests G, H and J, whereas corrosion was more uniform (i.e., lower zinc depletion and copper enrichment) in test K (Table 2), which is consistent with the ndings in experiment 2 (test D). Additionally, signicant lead leaching was observed in test I, which is discussed further below. All in-ow brass samples exhibited very shallow layer dezincication, characterized by copper enriched surfaces (Table 2), although the depth of dezincication could not be quantied. While no plug dezincication was observed on any of these samples, pitting was found on the in-ow brass from the low velocity test (H) (e.g., Fig. 11). ESEMEDX analyses indicated severe dezincication at the pit site shown in Fig. 11; zinc depletion associated with the pit was about 20% greater than that associated with the shallow layer dezincication observed on adjacent, un-pitted surfaces (Table 4). However, it is not possible to know whether the pitting observed here, or that observed in other tests (i.e., G and K), occurred via dissolution of all alloy constituents at the pit sites

or via a sequence of primarily zinc dissolution followed by fracture and detachment of the residual, porous material. The brass T samples from tests I, J, and K exhibited regions of deep layer dezincication (of varying size) that penetrated far enough into the surface to view at low magnication (e.g., Fig. 12). The deepest observed layers (i.e., on the surfaces revealed by cross-sectioning) were on the brass T from the hot water test (I), with a maximum depth of approximately 260 lm. However, the most uniform layer appeared to occur on the brass T in the galvanic test (K); upon cross-sectioning, nearly the entire surface that had been exposed to the test water was dezincied to a depth of roughly 100200 lm. Some pitting was also found on this sample, as well as the T from the control test (G). Signicant plug dezincication was additionally observed on the Ts from tests G, I, and J (e.g., Fig. 13). ESEMEDX analyses indicated that corrosion was more selective for zinc at sites of plug dezincication than at adjacent sites of layer dezincication (Table 4), as was generally the case for pitting sites. Metal concentrations in the bulk (data not shown) and T (Fig. 6) waters were quite variable over the test duration. On average, high levels of zinc were found in the T waters for tests H, I, and K. Considering the high brass weight loss rates in tests I and K, this result is not so surprising. For test H, this was unexpected, but might be explained by increased settling of metals into the T water due to the low ow velocity in the test. The high concentrations of copper

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Table 4 Maximum depth of corrosion and metal enrichment/depletion (vs. un-exposed surfaces) on brass surfaces at specic corrosion sites as computed from ESEMEDX data. Test Sample Corrosion type Maximum deptha (lm) Zinc depletionb % G H I J K T T In. In. T T T T T T BP PD BP LD (shallow) LD (deep) PD LD (deep) PD BP LD (deep) 150 240 220 ND 260 170 160 340 100 160 ND 79.3 59.6 ND 67.4 ND 85.0 ND 45.1 0.7 14.6 14.5 3.2 21.1 28.7 18.3 29.2 32.2 18.0 2.6 7.0 6.5 6.1 11.4 318.1 98.1 142.1 220.1 94.5 7.4 33.3 56.2 119.1 0.0 95% CI Copper enrichmentb % 95% CI Lead enrichmentb % 95% CI

ND Not determined, T Brass located out-of-ow, In. Brass located in-ow, BP Brass pitting, LD Layer dezincication, PD Plug dezincication. a Observed on surfaces exposed upon cross-sectioning; site of maximum depth not necessarily site of ESEMEDX analysis. b Computed from ESEMEDX data; negative enrichment values indicate depletion of element from brass.

90 m

Fig. 12. Photograph (lower left) and ESEM image (right) of deep layer dezincication on T brass from test K. Direction of sample cross-section is shown (upper left) and red box indicates location of imaging; white arrows indicate dezincication layer and depth at imaged point is specied.(For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

560 m 280 m

190 m

Fig. 13. Photograph (lower left) and ESEM image (right) of plug dezincication on T brass from test J. Direction of sample cross-section is shown (upper left) and red box indicates location of imaging; white arrows indicate plug and dimensions are specied. Only a portion of the plug in the photograph is shown in the SEM image.(For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

accumulated in the T water in test K were largely due to corrosion of the copper tubing located in-ow in this test, similar to tests D and E in exp. 2. A very high weight fraction of copper (i.e., more than 12%) was also found in the corrosion scale on the T brass, reminiscent of the result from test D too. Extremely high concentrations of lead were observed in the T water from the hot water test (I), which was somewhat surprising,

but nevertheless consistent with other data. Lead was signicantly depleted from the exposed brass surfaces from this test; as indicated by XRF data, the lead weight fraction on the T and in-ow surfaces decreased by approximately 44% and 33%, respectively. These values are even higher than corresponding zinc depletion values (19% and 29%, respectively) for this test. Brass samples in tests G and H were also depleted in lead following testing, but to

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a much lesser extent. Additionally, there was signicant lead uptake to the corrosion scales. The T and in-ow scales contained 4.4% and 3.1% lead by weight, respectively, which were the highest lead contents measured for any test (Table 2). Moreover, these results do not appear to be merely an artefact of increased metal solubility with temperature. As evidence, the lead-to-zinc weight ratios of the T water and solid corrosion scales from the hot water test (I) were about 34 times higher than those from the control (G). While ESEMEDX analyses showed that brass corrosion was highly selective for zinc at specic plug or layer dezincication sites in test I (as well as in other tests), signicant lead leaching was not indicated at these sites (Table 4). Thus, while the most severe zinc leaching seems to have been localised, lead leaching appears to have been more generalised. Additionally, like in experiment 2, zinc and lead depletion on the exposed brass surfaces in experiment 3 were generally inversely related (Fig. 7). This is consistent with Zhangs [13] recent observations from both his own original tests and his review of metal leaching data from previous works (by other authors, e.g., [4]) on brass corrosion. The inverse relationship suggests that the tendency for lead release from brass may not be mechanistically coupled with severe dezincication although both can certainly occur on the same brass component.

(T and in-ow brass not connected) in experiment 3 suggested that electrical connection between in-ow (cathode) and T (anode) brass did not inuence the overall corrosion rate of either sample (i.e., weight losses were similar in both tests). However, the mode of corrosion did appear to be affected. Specically, the selectivity of corrosion for zinc was greater in test G than in J. For example, zinc depletion on the in-ow brass surface was about 15% greater in test G than on its counterpart in J, and the weight ratio of zinc to copper in the corrosion scales were also much higher in test G than in J. 4.2. Copper vs. plastic plumbing systems In comparing plastic to copper plumbing tube materials, experimental observations generally conrmed initial hypotheses. Plastic (i.e., relatively inert) tubing tended to keep free chlorine levels high, and therefore allowed brass to be exposed to higher free chlorine than was the case in systems with copper tubes. Although this did not result in higher corrosion rates here, in more realistic systems where chlorine residuals in bulk water are not maintained constantly and chloride does not build-up, relatively high corrosion rates and meringue build-up (as was demonstrated in test F) would be expected. This might partly explain why some PEX plumbing systems have been associated with high rates of brass failures (e.g., [9,32]), which are prompting responses from the perspective of both alloy certication (i.e., [33] and regulation (e.g., [34]). While copper tubing, on the other hand, quickly consumed free chlorine, it also released copper ions to the water signicantly limiting copper dissolution from brass surfaces which were not galvanically connected to copper tubing. Although background levels of dissolved copper could be somewhat lower in real systems than in the pipe-loop tests presented here (i.e., depending on water chemistry and exposed copper surface areas), the presence of copper tubing in a plumbing system may promote more selective zinc leaching from brass. Galvanic connections between copper tubing and brass were found to be highly inuential on both the rate and type of corrosion that occurred on brass in this work. Weight loss rates of the brass Ts (connected to copper tubing in-ow) in tests D and K were 20% and 31% higher, respectively, than their counterparts in tests E and G (no galvanic connection). Moreover, the galvanic connection in tests D and K resulted in brass corrosion being less selective for zinc. This was somewhat unexpected, as it was originally thought that the galvanic current may worsen dezincication; but it is logical given the overall highly anodic behaviour of brass when connected to copper. The unique, very uniform layer of dezincication in test K which was relatively less selective for zinc than other layer or plug dezincication or pitting observed in other tests was likely the result of the consistently high corrosion currents measured on brass in this test (e.g., Fig. 8). In contrast, the brass pitting that occurred in this test was likely induced by water chemistry, given that pitting was also found in tests G and H, which did not have galvanic connections to copper. Pit depths were relatively shallow in test K as compared to G and H (Table 4), which is consistent with the observations that brass corrosion was more uniform when the brass was connected to copper. 4.3. Hot vs. cold water systems The most signicant effects of hot water on brass corrosion were observed in the meringue formation and lead release in test I (exp. 3). The increased meringue build-up seen in this test is consistent with prior observations that meringue dezincication problems are often worse in hot water plumbing lines than in cold (e.g., [23,29]). Additionally, weight losses of the brass samples in test I

4. Discussion 4.1. Effects of ow velocity and differential ow conditions The enhanced delivery of oxidant (i.e., free chlorine) to a cathode surface under ow did inuence corrosion on a remote (i.e., removed from ow) brass anode. Kelly et al. [22] rst demonstrated this effect (in an analogous but smaller-scale version of the control test apparatus in exp. 3) by varying ow velocity of oxygenated water past one brass sample and noting the effects on the corrosion current of a second brass sample, which was in electrical contact with the rst but removed from ow. In that work, increasing ow velocity (i.e., increasing oxidant delivery rate) tended to increase corrosion current. In the present work, oxidant delivery rate was varied by varying bulk oxidant concentration (i.e., test A, exp. 1), as well as ow velocity (i.e., tests G and H, exp. 3); and, in both cases, it was conrmed that increasing oxidant delivery rate to the cathodic metal surface can result in increased corrosion of anodic brass located out-of-ow. In experiment 3, not only did average corrosion current on the remote T brass increase with ow velocity, but so did the rate of weight loss. The T weight loss in test G (high velocity) was nearly 40% higher than in H (low velocity). Inuences of ow velocity on mode of corrosion were subtle. Apart from the fact that plug dezincication was observed in test G but not in H, brass samples from the two tests appeared very similar. Additionally, computed zinc depletion and copper enrichment values were nearly identical between tests G and H. This suggests that only the corrosion rate changed with velocity, not the corrosion mechanism(s). By comparing results (e.g., metal depletion/enrichment) of the T and in-ow brass samples from test J (which were not electrically connected), it appears that the corrosion mechanisms were even similar between stagnant and owing conditions. Again, the predominant inuence was on corrosion rate, which was higher for the in-ow brass than for the T. With respect to differential ow, results from tests B (differential ow) and C (uniform ow) in experiment 1 indicated that, when connected to a noble cathode (e.g., copper) being supplied with oxidant, brass corrosion may be accelerated if the brass is located out-of-ow (vs. in-ow). When brass is not connected to a more noble metal, the effects of differential ow conditions may not be as signicant. Results from tests G (differential ow) and J

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were higher than their counterparts in test G (cold water), which is also consistent with ndings of other researchers (e.g., [2]). Lead release was considerably higher at higher temperature, and this could not simply be attributed to increased total metal leaching or increased solubility. Instead, lead appeared to be more selectively leached by hot water. This result was not anticipated, especially considering that the average chlorine residual in test I was relatively low as compared to that of other tests. The literature surrounding effects of water temperature on brass lead leaching is scarce, and while some eld reports indicate that hot water may increase lead concentrations (e.g., [30]), other laboratory tests show that increased temperature may have no effect or may even decrease lead release [35]. Given the limitations of the current work (e.g., testing of a single brass alloy, lack of replication) and heterogeneities (e.g., pooling) associated with lead distribution in brass devices, further research on this topic is certainly warranted. 5. Conclusions Some factors associated with specic plumbing installations can affect the type and extent of corrosion that occurs on brass devices. For high-zinc, un-inhibited brass alloys exposed to aggressive water chemistries, the current ndings may inform investigations into existing corrosion issues, as well as design of future plumbing systems: (1) Increased ow velocity of chlorinated water tends to accelerate brass dezincication and/or uniform corrosion rates via increased delivery of oxidant to cathodic surfaces; however, at the velocities tested, the type of brass corrosion is not signicantly affected. (2) Differential ow conditions could accelerate corrosion of brass surfaces that are removed from ow but are in electrical contact with brass or a more noble metal (e.g., copper) located in-ow. (3) Galvanic connections between copper and brass tend to increase overall brass corrosion rates, while making corrosion less selective for zinc. In these tests, the galvanic connection was found to increase brass corrosion rate, reduce meringue build-up, and render brass corrosion less selective for zinc. (4) Plastic plumbing tubes do not signicantly consume chlorine, and therefore allow brass devices to be exposed to higher chlorine residuals than do copper tubes. (5) Aside from potential galvanic effects, copper plumbing tubes may also inhibit copper leaching from brass devices, thereby making brass corrosion more selective for zinc. (6) Increased water temperature might signicantly increase lead leaching from brass, while reducing selectivity of corrosion for zinc and promoting meringue build-up. (7) In addition to other brass corrosion types, pitting may occur in waters with high chlorine residuals.

References
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Acknowledgments The authors thank the Water Research Foundation (WaterRF) for funding experimental work under project #4289, as well as The National Science Foundation (NSF), which supported advanced analyses and writing of the manuscript under grant CBET-0933246. The views, conclusions and/or recommendations expressed herein are those of the authors, and do not necessarily represent those of WaterRF or NSF. Additionally, special thanks are extended to Paolo Scardina, Jaquelyn Dalrymple and Caitlin Grotke for their assistance with experimental work and analyses.