Environ. Sci. Technol.

2010, 44, 3895–3900

oxidative level which favors its existence such as in the

Reductive Dissolution of Lead presence of free chlorine (6, 7). However, under the right
Dioxide (PbO2) in Acidic Bromide conditions, it is subject to reductive dissolution which
results in the release of soluble Pb(II) into water (8-14).
Solution For example, alarmingly high and potentially toxic levels
of lead were recently observed in certain parts of the
drinking water distribution system in Washington, DC
Y I - P I N L I N * ,† A N D
(6, 15), which have resulted in elevated blood lead levels
RICHARD L VALENTINE‡
in children (16). These high levels of lead in drinking water
Division of Environmental Science and Engineering, Faculty were attributed to the likely dissolution of accumulated
of Engineering, National University of Singapore, PbO2(s) or increased rate of corrosion of elemental lead
Singapore 117576, and Department of Civil and
bearing materials caused by a change of disinfectant from
Environmental Engineering, University of Iowa,
free chlorine to monochloramine that produced a more
Iowa City, Iowa 52242-1527
reductive environment which inhibited the formation of
lead dioxide (6, 15, 17, 18). As a consequence of this
Received January 13, 2010. Revised manuscript received incident, there has been a renewed interest in better
March 15, 2010. Accepted April 6, 2010. understanding the processes that govern the stability of
PbO2 in drinking water distribution systems. In the past,
the reactions of PbO2(s) that have been studied are mostly
pertinent to the chemistry of electrochemical cells due to
Reductive dissolution of lead dioxide (PbO2(s)) has been its extensive use in lead acid batteries (19-24). The
attributed to a major route leading to elevated lead concentrations reactivity of PbO2(s) in aqueous solution has been much
in drinking water. However, surface processes involved in less studied.
this heterogeneous reaction have not been elucidated. In this PbO2(s) is subject to reductive dissolution involving a
study, the kinetics and mechanism of reductive dissolution number of species found in drinking water, but the whole
of PbO2(s) in acidic bromide solutions were investigated to reveal picture is not yet complete enough to allow estimation of the
the detailed surface reactions. The reduction of PbO2 by overall importance of these reactions. In this study, bromide,
bromide can be expressed as PbO2(s) + 2Br- + 4H+ f Pb2+ which is occurring in many drinking water sources, is used
+ Br2 + 2H2O. The reaction kinetics was found to be as a redox-active probe to investigate the reduction of PbO2(s)
in an acidic environment (pH 3.5-4.5). The use of acidic
proportional to the concentration of PbO2(s), and the reaction
solutions was based on our preliminary studies showing that
orders were 1.08 and 1.77 with respect to bromide and proton the reaction proceeds at a rate that allows its accurate
concentration, respectively. The observed kinetic data can quantification. The kinetics and mechanism of PbO2(s)
be explained by the following reaction mechanism: adsorption reduction by bromide were examined to explore the surface
of bromide on the PbO2(s) surface to form a precursor processes involved in this heterogeneous redox reaction. The
surface complex ≡PbIVBr, and two separate one-electron role of this reaction in increasing soluble lead levels in
transfers from adsorbed Br- to structural PbIV, followed by the drinking water is also evaluated.
release of Pb2+ and Br2 into water. The adsorption of bromide
ion on the PbO2 surface and the first one-electron transfer Materials and Methods
reaction were found to be important in regulating the overall Chemicals. Reagent grade chemicals were used in this study.
rate of the reaction. It is expected that a similar reaction scheme All solutions were prepared by deionized water obtained from
can be applied to other reductive ions. a Barnstead ULTRO pure water system (Barnstead-Ther-
molyne Corp.). Commercially available PbO2(s) was used
upon received without further purification (Fisher Scientific).
Introduction The specific surface area determined by the 7-point N2-BET
PbO2(s) is a strong oxidant possessing two different poly- method is 4.1 m2/g. Images acquired by the scanning electron
morphs including orthorhombic scrutinyite (R-PbO2(s)) and microscopy (SEM) indicated that the size of each individual
tetragonal plattnerite (β-PbO2(s)). Figure 1 shows the pe-pH particle ranges from 0.1 to 0.5 µm but they tend to agglomerate
diagram for lead (1). In neutral to acidic pH values (pH < 7.2), to form bigger aggregates as shown in Figure 2. X-ray
the oxidation potential of PbO2(s) is higher than that of the diffraction analysis (XRD) showed that this PbO2(s) is
H2O/O2 boundary suggesting that the reduction of PbO2(s) plattnerite (β-PbO2). Potassium bromide (Fisher Scientific)
by water is thermodynamically possible. was used for the source of bromide.
In nature, PbO2(s) is found in the oxidized zone of Kinetic Experiments. Kinetic experiments were con-
hydrothermal lead-bearing ores (2). Recently, PbO2(s) was ducted using 250 mL polypropylene bottles at 25 °C. The
identified in drinking water distribution systems. Its effects of PbO2(s) concentration (12-48 mg/L), bromide
presence has been attributed to the oxidation of lead- concentration (0-5 mM), and acidic solution pH (3.5-4.5)
containing plumbing material by free chlorine (3-5). Its on the rate of PbO2(s) reduction by bromide were determined.
stability in aqueous solution has drawn increasing interest All solutions were buffered by 10 mM acetate. The solution
because of its unique role in regulating lead concentration pH value was adjusted by 1 N NaOH and HCl. The solution
in drinking water. The solubility of PbO2(s) is extremely was mixed by a magnetic star bar at 400 rpm during the
low in water if the redox potential is maintained at a highly course of the experiment. The concentration of Pb2+ was
measured for up to 74 h. The initial rate of PbO2(s) reduction
was derived from the initial slope of the Pb2+ concentration
* Corresponding author phone: (65) 6516-4729; e-mail:
[email protected]. versus time curve. Duplicate experiments were conducted
†
National University of Singapore. in selected conditions. The data points shown in the duplicate
‡
University of Iowa. experiments are the average of the duplicates, and the error
10.1021/es100133n  2010 American Chemical Society VOL. 44, NO. 10, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3895
Published on Web 04/26/2010
FIGURE 1. pe-pH diagram of lead. The following conditions
are considered for the construction of the figure: total inorganic
carbon concentration ) 1 mM, total soluble Pb concentration
) 10-6 M, ionic strength ∼ 0, T ) 25 °C. Thermodynamic data
were obtained from Pankow (1).

FIGURE 3. Effects of PbO2(s) concentration on the reduction of

PbO2(s) by bromide. (a) Pb2+ concentration as a function of time
at different PbO2(s) concentration. (b) Initial Pb2+ formation rate
as a function of PbO2(s) concentration. pH ) 4.0, Br- ) 2.5 mM,
acetate buffer ) 10 mM, and T )25 °C.

background absorbance considering our experimental con-

ditions. Thus, only Br3- was used qualitatively as an indicator
for the bromide oxidation
Analytical Methods. A Nano-Band Explorer II anodic
stripping voltammetry instrument (TraceDetect, Seattle)
was used for measuring Pb2+ concentration resulting from
the reduction of PbO2(s) by bromide. The presence of
PbO2(s) particles does not cause interference in this
method. For each measurement, 0.1 M acetate was added
to serve as the background electrolyte and a standard
addition approach was employed. The UV-vis absorbance
spectrum was acquired by a UV-vis spectrometer (UV-
1601, Shimadzu). SEM images were acquired by the Hitachi
S-4000 SEM. A MiniFlex II desktop X-ray diffractometer
(Rigaku Americas) was used to determine the XRD pattern
of the PbO2(s) employed. The solution pH value was
measured by a pH meter (A15, Fisher Scientific) coupled
with a calomel combination pH electrode pre-equilibrated
by pH 4 and 7 standard buffers.
FIGURE 2. SEM images of the PbO2(s) employed in this study. Results and Discussion
The size of each individual particle ranges from 0.1 to 0.5 µm.
Influence of PbO2(s) Concentration, Bromide Concentra-
The specific surface area is 4.1 m2/g.
tion, and pH Value on Reaction Kinetics. The influence of
PbO2(s) concentration, bromide concentration, and pH on
the rate of PbO2(s) reduction by bromide is shown in Figures
bar represents the range of the measurements. Selected
3-5, respectively. The reduction of PbO2(s) by bromide can
samples were collected for the UV-vis absorbance measure-
be expressed by the following reaction:
ment to qualitatively show the oxidation of bromide. There
are two oxidation products of bromide: Br2 and Br3- which
possess molar absorptivity of 173 M-1 cm-1 at 390 nm and PbO2(s) + 2Br- + 4H+ f Pb2+ + Br2 + 2H2O (1)
35 000 M-1 cm-1 at 266 nm, respectively (25). Although Br2
was found to be the dominant species, its small molar A small fraction of Br2 can react with excess Br- to form
absorptivity resulted in insignificant absorbance above Br3- based on the following equilibrium reaction (25)

3896 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 10, 2010
 KBr
Br2 + Br- 798 Br-3
3
(2)

where KBr3 ) 16.6 M-1 (25). Considering the bromide

concentration (25) employed in this study, the ratio of [Br3-]/
[Br2] ranges from 0.017 to 0.083.
The rate of PbO2(s) reduction to form Pb2+ is proportional
to the PbO2(s) concentration (Figure 3) from which a surface
area normalized reaction rate can be determined. The rate
of PbO2(s) reduction increases with increasing bromide
concentration and decreasing solution pH. The apparent
reaction orders with respect to bromide and proton con-
centration are 1.08 (Figure 4) and 1.77 (Figure 5), respectively.
It should be noted that in control experiments without
bromide, a small amount of Pb2+ was still formed (Figure 4a,
Pb2+ ) 0.75 µM at the end of the experiment). This observation
is consistent with the pe-pH diagram (Figure 1) and a
previous study showing that water can serve as a reductant
for PbO2(s) (9). However, the rate of this water-induced
PbO2(s) reduction is insignificant compared to that resulting
from bromide and does not contribute significantly to the
overall rate of PbO2(s) reduction.
Br3- possesses a peak UV absorbance at 266 nm with
a molar absorbance of 35 000 cm-1 M-1 (25). The formation
of Br3- is indicated by the increase of UV absorbance at
266 nm as a function of time for a selected experimental
condition shown in Figure 6 (PbO2 ) 12 mg/L, Br- ) 2.5
mM, pH ) 4). Br3- can be slowly lost due to the evaporation
of Br2 in to the air. Because of the long period (up to 74 h)
and continuous stirring employed in our experiments that
may enhance Br3- loss, its formation is only used for FIGURE 5. Effects of pH on the reduction of PbO2(s) by bromide.
qualitative purpose to verify the oxidation of bromide by (a) Pb2+ concentration as a function of time at different pH
PbO2(s). values. The dashed line represents the maximum possible Pb2+
from added PbO2 concentration. (b) Pb2+ formation rate as a
function of [H+]. Br- ) 2.5 mM, PbO2(s) ) 12 mg/L, acetate
buffer ) 10 mM, T ) 25 °C.

FIGURE 6. Formation of Br3- indicated by the increase of UV

266 nm as a function of time. Br- ) 2.5 mM, pH ) 3.5, PbO2(s)
) 12 mg/L, acetate buffer ) 10 mM, T ) 25 °C.

We initially assumed that the overall rate could be

expressed as a single term

R ) kobs(SA)[Br-]a[H+]b (3)

where R is the rate of PbO2(s) reduction (M/h), kobs is the

FIGURE 4. Effects of bromide concentration on the reduction of observed rate constant, SA is the available surface area of
PbO2(s) by bromide. (a) Pb2+ concentration as a function of time PbO2(s) (m2), and a and b are apparent reaction orders with
at different Br- concentration. (b) Pb2+ formation rate as a respect to bromide and proton concentrations, respectively.
function of Br- concentration. pH ) 4.0, PbO2 ) 12 mg/L, Using the experimental data from Figures 3-5, the following
acetate buffer ) 10 mM, and T ) 25 °C. least-squares regression can be obtained:

VOL. 44, NO. 10, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3897
 R ) [3.93 × 106](SA)[Br-]1.08[H+]1.77 (4) k8
≡PbIIOH 98 ≡ PbIVOH + Pb2+ (12)
-1 -2 -1.85
The unit of the rate constant is h m M . The
noninteger power to which hydrogen ion is raised indicates On the basis of the proposed reaction scheme and with
a potentially complex overall mechanism. the assumption that a steady state is achieved for each of the
Reaction Mechanism. Reductive dissolution of higher surface species, the following rate expression for the rate of
oxidation state metal oxides, such as manganese and iron PbO2(s) reduction or Pb2+ formation can be obtained
oxide/hydroxide, have been shown to involve several
reaction steps, including adsorption of the reductive ion k1k2
on the oxide surface, electron transfer between the R) {≡PbIVOH}[Br-][H+] (13)
adsorbed ion and the structural metal, release of the k2 + k-1
reduced metal ion and the oxidized foreign ion from the
surface, and possibly the formation of highly reactive where the braces denote surface concentration.
intermediate resulting from the electron transfer (26-31). The rate expression indicates that the adsorption of
Inaone-electrontransferreaction,theLangmuir-Hinshelwood bromide ion on the PbO2(s) surface and the first one-electron
kinetic law has been successfully used to explain the redox transfer reaction are both important in regulating the overall
kinetics if it is assumed that the adsorption of the reductive rate of the reaction. It should be noted that {≡PbIVOH} is
ion and the electron transfer are rate determining steps, pH-dependent and can be expressed in terms of the total
the rate of back electron transfer is negligible, and the surface PbIV concentration according to the following
surface coverage of reductive ions on the oxide surface acid-base reaction:
achieves a steady state (30). It is anticipated that the
oxidation of PbO2(s) by bromide would follow a broad Ksurf
≡PbIVOH 798 ≡ PbIVO- + H+ (14)
surface reaction scheme because of the involvement of
PbO2(s) solid phase although two electrons are involved
in the overall reaction.
It is postulated that the two-electron transfer occurs {≡PbIV}tot[H+]
through two separate one-electron transfer reactions because {≡PbIVOH} ) (15)
Ksurf + [H+]
a one-step two-electron transfer reaction is not likely to
happen. The following reaction steps considering Pb2+ and
Br3- as the final products are proposed to describe the By substituting eq 15 into eq 13, the rate equation can be
reduction of PbO2(s) by bromide: (1) Adsorption of bromide expressed as
on the PbO2(s) surface forms a precursor surface complex (≡
denotes surface species): k1k2
R) {≡Pb(IV)}tot[Br-][H+]2
(k2 + k-1)(Ksurf + [H+])
k1
≡PbIVOH + Br- + H+ a ≡ PbIVBr + H2O (5) (16)
k-1

Assuming that k2 is much greater than k-1 due to the fast

(2) Two one-electron transfer reactions occur subse- electron transfer and slow desorption, eq 16 can be simplified
quently, each of which is followed by the release of the as
bromine radical (Br · ) into the solution:
k1
k2 R) {≡Pb(IV)}tot[Br-][H+]2 (17)
≡PbIVBr 98 ≡ PbIIIBr (6) (Ksurf + [H+])

k3
This overall rate expression suggests that the reaction
≡PbIIIBr + H2O 98 ≡ PbIIIOH + Br·+H+ (7) orders with respect to Br- and PbO2(s) concentration (or
surface area) are both 1 which are consistent with the
observed apparent reaction orders (eq 4). Equation 17 also
k4 indicates that the reaction order with respect to [H+] can
≡PbIIIOH + Br- + H+ 98 ≡ PbIIIBr + H2O (8) range from 1 if Ksurf , [H+] to 2 if Ksurf . [H+]. When neither
of these assumptions is true, the “apparent” order with
respect to proton concentration will appear to be a noninteger
k5
≡PbIIIBr 98 ≡ PbIIBr (9) between these two limits. The apparent reaction order with
respect to proton concentration determined in our experi-
ments is 1.77 which is in the suggested range. The oxidation
k6 of nitrite by monochloramine was empirically described by
≡PbIIBr + H2O 98 ≡ PbIIOH + Br·+H+ (10) a similar single term rate expression with a noninteger
dependence on proton concentration (32), which was later
found to be consistent with a much more complicated
(3) Br · radicals dimerize to form Br2 mechanism over the relatively limited range in reaction
conditions used in its derivation (33). It should be pointed
k7
2Br· 98 Br2 (11) out that, in our case, the apparent order of 1.77 with respect
to proton concentration would likely change if a much larger
pH range had been studied.
and Br2 can further react with aqueous Br- to form Br3- By employing the nonlinear regression of our experimental
according to eq 2. data to eq 17 and using PbO2(s) surface area to represent
(4) Release of Pb2+ ion into the solution and exposure of PbO2(s) concentration, the values of k1 and Ksurf determined
the underneath structural Pb(IV) forms a new surface site from the least-squares fitting were 9.61 × 103 h-1m-2 M-1
(below the surface structural Pb(IV) in the reactant side is and 3.63 × 10-4 M, respectively. Equation 17 can subsequently
not shown): be revised as

3898 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 10, 2010
 9.61 × 103 drinking water distribution systems which is governed by
R) (SA)[Br-][H+]2 (18) the net effect of formation and dissolution reactions.
(3.63 × 10-4 + [H+])
where (SA) is the total surface area of PbO2(s) particles. Figure Acknowledgments
7 shows the relationship between the experimentally de- The authors would like to acknowledge financial support
termined initial rates and those calculated using eq 18. The from National University of Singapore (R-288-000-054-133)
close correspondence indicates that the proposed mechanism and American Water Works Association Research Foundation
provides a good explanation for the experimental observa- (Now Water Research Foundation, Project No. 3172).
tions. It should be noted that, in our previous study on the
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