Sensors and Actuators B 155 (2011) 145153

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Sensors and Actuators B: Chemical
j our nal homepage: www. el sevi er . com/ l ocat e/ snb
A polymer lab chip sensor with microfabricated planar silver electrode for
continuous and on-site heavy metal measurement
Wooseok Jung
a
, Am Jang
b,
, Paul L. Bishop
b
, Chong H. Ahn
a
a
MicroSystems and BioMEMS Laboratory, Department of Electrical and Computer Engineering, University of Cincinnati, Cincinnati, OH 45221, USA
b
Department of Civil and Environment Engineering, University of Cincinnati, Cincinnati, OH 45221, USA
a r t i c l e i n f o
Article history:
Received 11 August 2010
Received in revised form
22 November 2010
Accepted 22 November 2010
Available online 26 November 2010
Keywords:
Lead (Pb(II))
On-site measurement
Reusable polymer lab chip sensor
Silver electrode
Square-wave anodic stripping voltammetry
(SWASV)
a b s t r a c t
This paper presents a reusablepolymer labchipsensor for continuous andon-siteheavymetal monitoring
in nature. In particular, detection of lead (Pb(II)), which is the most common heavy metal pollutant, has
been performed using the proposed lab chip sensor. The miniaturized lab chip sensor consists of a micro-
fabricated silver working electrode that replaces the conventional mercury and bismuth electrodes, an
integrated silver counter and quasi-reference electrode, and microuidic channels. The proposed sensor
targets on-site environmental monitoring in a continuous fashion without disturbing or contaminat-
ing the sensing environment when it is reused. The reusability of the miniaturized lab chip sensor was
characterized through forty-three consecutive measurements in non-deoxygenating standard solutions
inside the microchannels using square-wave anodic stripping voltammetry (SWASV). With only 13.5L
of sample volume the sensor chip showed a correlation coefcient of 0.998 for the Pb(II) concentration
range of 11000ppb with the limit of detection of 0.55ppb at 300s deposition time. The peak potentials
during the forty-three consecutive SWASV measurements showed a relative standard deviation of 1.0%,
with a standard deviation of 0.005V. The high repeatability and linearity of the sensor over the large,
three orders of magnitude, dynamic range of 11000ppb showed that the developed sensor chip can
be reused for a variety of on-site measurements such as for soil pore water or groundwater, using only
micro-volumes.
2010 Elsevier B.V. All rights reserved.
1. Introduction
With the increasing trend toward urbanization, the serious side
effects posed by heavy metals to human health and the environ-
ment have been a major concern [1]. In particular, as lead (Pb(II))
concentrations in public supply wells have reached unacceptable
levels in many parts of the world, it has become obvious that
more attention needs to be paid to linkages between the effects
of human activities on the surface and groundwater quality. It was
widely reported that the elevated levels of Pb(II) in drinking water
are primarily related to human health effects such as damage of
the brain and nervous system, behavioral and learning disabilities,
blood pressure increase, and kidney injury and anemia [2]. As a
consequence, the current stringent potable water standard (maxi-
mumcontaminant level, MCL) for Pb(II) has beenset by the U.S. EPA
at less than 0.015mg/L of Pb(II). The combination of high toxicity
and widespread occurrence has created a pressing need for effec-
tive monitoring and measurement of Pb(II) in surface waters and
groundwater. Since on-site measurement is essential toachieve the

Corresponding author. Tel.: +1 513 5561886; fax: +1 513 556 3930.

E-mail address: amjang68@gmail.com (A. Jang).
effective monitoring strategies, there is a clear need for reliable,
efcient and cost-effective monitoring technologies for Pb(II) that
adversely affects human health.
Conventionally, levels of trace heavy metals in environmental
samples have been measured by atomic absorption spectrometry
(AAS) and inductively coupled plasma mass spectroscopy (ICP-MS)
under highly controlled laboratory conditions. Because of their
bulky size, high cost, and long analysis time, these methods are
not suitable for on-site environmental screening analysis [3]. Alter-
natively, stripping analysis has been widely studied for on-site
measurement of heavy metal ions [48]. In the stripping analy-
sis, heavy metal ions in the sample solution can be identied and
quantied by measuring the generated current at each reduction
potential that reduces specic metal ions as the potential sweeps
within the appropriate scan range after deposition of heavy metal
ions on sensors [911]. In particular, Mercury (Hg) working elec-
trodes have shown high sensitivity in measuring heavy metal ions
using anodic stripping voltammetry (ASV) [1214]. However, the
use of toxic Hg as a sensing material for environmental monitoring
is limited due to its toxicity to humans and animals. Additionally,
the necessity to stir the sample solution and to renew the Hg drop
for each measurement makes Hg undesirable for sensing applica-
tions [15]. As an alternative, Bismuth (Bi) has been suggested as the
0925-4005/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2010.11.039
146 W. Jung et al. / Sensors and Actuators B 155 (2011) 145153
working electrode material in ASV to detect various heavy metals
in different applications because of its low toxicity while showing
similar electrochemical performance to Hg [1621]. However, both
amalgam formation of Hg electrodes [22] and multi-component
formationof Bi [23] arenot desirableproperties for reusablesensors
as some of the heavy metals fused into these electrode materials
still remain after ASV leading to memory-effect.
Silver (Ag) solid electrodes can be an alternative sensing mate-
rial for reusable sensors because the electrodeposition of metals
proceeds via the formation of a monolayer of the target metal
(underpotential deposition, UPD) on these solid electrodes dur-
ing the adsorption process rather than amalgam formation. The
electrochemical mechanismof deposition and stripping reaction of
lead on the silver electrode surface may be simply represented by
equation, Pb
2+
+2e

Pb. As a result, the structure of the electrode

surface remains mainly unchanged during the electrodeposition
time, resulting in clear removal of deposited metals based on UPD
in conjunction with stripping voltammetry (UPD-SV), and thus
providing repeatable results [22]. The Ag electrode has exhib-
ited excellent characteristics for heavy metal detections in terms
of sensitivity and repeatability [2429]. However, most of this
research shows some limitations; for example, they cannot mea-
sure micro-volumes of sample andthey needadditional equipment
such as a rotator or a stirrer. However, with improved micro-
fabrication technologies, planar Ag electrodes can be produced
with well-dened patterns at the micro-scale. The ready-to-use Ag
working electrode (WE) along with the integrated Ag counter and
quasi-reference electrode (CE/QRE) can overcome the above lim-
itations. Furthermore, a desirable combination incorporating the
miniaturized on-chip electrochemical sensors with microuidic
components as a micro total analysis system (microTAS) or lab-
on-a-chip device is achievable, which provides a good platform for
chemical and biological analyses in a miniaturized format [30,31].
Polymer substrates, such as cyclic olen copolymer (COC), have
been used for lab-on-a-chip materials instead of the traditional
silicon and glass substrates because of their favorable properties
of biocompatibility, high optical transparency, and low cost [32].
Our laboratorydevelopedthe bismuth-baseddisposable sensors on
the COC with microfabrication technique for on-site and continu-
ous heavy metal ions measurement [3]. However, the automatic
sampling and analyzing device [33] was designed for only seven
measurements; the seven bismuth-based disposable sensors limit
its use for continuous monitoring.
For continuous and on-site heavy metal ions measurement,
therefore, a reusable heavy metal sensor with on-chip planar Ag
WE, integrated Ag CE/QRE, and microuidic channels has been
developed by standard microfabrication technology. It could be
expected that when the seven developed reusable sensors are
equipped on the developed automatic sampling and analyzing
device [33], at least three hundred and forty-three consecutive
measurements can be achieved without user intervention needed
to change sensor chips. This sensor is also suited for very low cost
and mass production, small analyte consumption and waste gen-
eration, and ease of use.
2. Experimental
2.1. Chemicals
All chemicals were of ACS grade and used without further
purication. De-ionized (DI) water was used throughout the exper-
iments. 70% HNO
3
(pharmco-AAPER, CT, USA) and 99.9995% KCl
(Fluka, MO, USA) were used for the preparation of the supporting
electrolyte containing 0.01M HNO
3
and 0.01M KCl. Lead stan-
dard for the calibration and characterization of the sensor was
prepared from 1000ppm stock atomic adoption standard solution
(SigmaAldrich Corp., MO, USA). Necessary dilutions were com-
pleted with the supporting electrolyte for daily preparation of the
standard solutions. Ready-to-use Cyless silver electroplating solu-
tion (Technic Inc., RI, USA) was used for Ag electroplating. 0.1mm
thick 99.998% Ag foil (Alfa Aesar, MA, USA) was used as an anode
to replenish the Ag in solution during Ag electroplating. 96% H
2
SO
4
(pharmco-AAPER, CT, USA) was usedtomake10%H
2
SO
4
for inhibit-
ing subsequent tarnishing after Ag electroplating.
2.2. Device fabrication
S1818 (MicroChem Corp., MA, USA) positive photoresist was
spin-coated and patterned on a COC substrate by the photolithog-
raphy technique. On top of the photoresist patterns, a titanium
layer of 10nm and a silver layer of 100nm were deposited on a
three inch blank COC substrate using an e-beam metal evaporator
(Temescal FC1800, BOC Edwards Temescal, CA, USA). The unde-
sired patterns of electrodes were lifted-off by acetone to obtain the
designed structures. Another silver (1.7m) layer was deposited
on the patterned electrodes using the electroplating method. After
plating and dragging out, the device was dipped into 10% H
2
SO
4
for 30s to inhibit subsequent tarnishing. It was then rinsed and
dried. There were not any mechanical pretreatment steps after the
electroplating.
Rapid prototyping methods [34] and plastic injection molding
were used for high throughput polymer uidic chip fabrication.
After drilling holes for uidic interconnection at the inlet and out-
let using a micro drill bit, the microuidic chip was bonded with
the sensor chip using the thermoplastic fusion bonding technique
using an embossing machine (MTP-10, Tetrahedron Associates Inc.,
CA, USA) to make the nal device. The standard microfabrication
processes used for making the miniaturized lead sensor are sum-
marized in Fig. 1.
Photographs of the fabricated device are shown in Fig. 2, which
illustrates the two-electrode conguration, electrical connections,
and microchannels. Inorder to maximize the area of the Ag CE/QRE,
the dimensions of the Ag CE/QRE are the same as the dimensions of
the uidic channel. Details of the Ag WE and Ag CE/QRE are illus-
trated in Fig. 2(a). The Ag WE has a length of 22.5mm, width of
100mand a spacing of 100mto the Ag CE/QRE. The Ag CE/QRE,
which has been used as a wire form in most prior literature, is
integrated into the sensor chip. In order to enable a two-electrode
conguration [24], the area of the Ag CE/QRE was set to around
50mm
2
, which is more than 20 times to the area of the Ag WE. The
fabricated sensor after PR lift-off is shown in Fig. 2(b) followed by
Ag electroplating resulting in a 1.7-m thick sensor as shown in
Fig. 2(c). The injection-molded uidic chip has 220m deep u-
idic channels as shown in Fig. 2(d). Fig. 2(e) shows the nal sensor
chip after the fusion bonding between the sensor chip and the u-
idic chip. The entire chip size is 3cm2cm, and the total sample
volume that the chip can accommodate is 13.5L. Thus, the pro-
posedfullyintegratedpolymer microuidic chipenables signicant
reduction of analyte consumption and waste generation. Addition-
ally, the sensor chip did not need to be stored in buffer solution to
avoid possible sensor deterioration since the sensor was covered
with the microuidic chip after bonding.
2.3. Apparatus
PalmSens (Palm Instruments BV, The Netherlands), a com-
mercial portable electrochemical analyzer, was used for the
electrochemical measurements. PSTrace (version 1.4.) software
provided by Palm Instruments BV was used for the characteriza-
tion of the microfabricated sensors. Because the fabricated sensor
employs a two-electrode conguration, the counter electrode clip
W. Jung et al. / Sensors and Actuators B 155 (2011) 145153 147
Fig. 1. The summary of the fabrication processes for the sensor chip (I) and the uidic chip (II), respectively.
andthe reference electrode clipof the PalmSens are shortedto each
other. For measurements, the working electrode clip is simply con-
nected to the Ag WE contact pad while the counter and reference
electrode clip is connected to the Ag CE/QRE contact pad as shown
in Fig. 2(f). The measured output was transferred to a personal
computer via Bluetooth and displayed from the PSTrace software
as shown in Fig. 2(g). All measurements were taken in unstirred
and non-deoxygenating solutions. Experiments were carried out
at room temperature to eliminate any temperature effect.
2.4. Procedure
The analysis was performed without removal of oxygen using
13.5L of solution containing 10mM HNO
3
and 10mM KCl. A
Fig. 2. (a) The schematic illustration of the reusable on-chip heavy metal sensor using microfabricated Ag electrodes, (b) the sensor electrode is composed of 10nm Ti and
100nm Ag after PR lift-off, (c) the sensor electrode after Ag electroplating gets 1.7m thick Ag, (d) the uidic chip after injection molding, (e) the entire chip including
the senor and the microuidic channel, (f) the potentiostat along with the chip for the measurement, and (g) the display of the measurement plot shown on the personal
computer with PSTrace software.
148 W. Jung et al. / Sensors and Actuators B 155 (2011) 145153
Fig. 3. The reproducibility of the background current on the base of SWASV curves
at anAg electrode innon-deaeratedsupporting electrolyte (0.01MHNO
3
and0.01M
KCl) recorded in successive electrochemical activation of the Ag electrode.
pipetter (Fisher Scientic, PA, USA) was used for sample loading
to the inlet port of the microuidic chip. Sample solutions were
then injected into the sensing chamber via the inlet channel. The
deposition step was E
dep
=0.75V for 300s vs. Ag QRE. There was
no stirring during the deposition time. Conditions for the square-
wave anodic stripping voltammetry (SWASV) are as follows: pulse
amplitude, 23mV; step amplitude, 3mV; step frequency, 23Hz;
E
begin
=0.75V; E
end
=0.2V vs. Ag QRE. After each measurement,
0.2V was applied for electrochemical cleaning of any remaining
Pb(II) after thestrippingstep. Then, a newtest solutionwas inserted
for another measurement.
3. Results and discussion
3.1. Inuence of electrochemical activation on background
current
Fig. 3 illustrates the changes of the background current in the Ag
WE during electrochemical activation. The voltammograms were
recorded in non-deaerated supporting electrolyte. The quality of
the Ag WE surface did not look stable for curves 13, which exhib-
ited high background current with rapid changes in the region of
Pb(II) peak current. Low and stable background level (curves 46)
was achieved with the consequent electrochemical activation of
the electrode. At this point, Ag WE indicated excellent activity for
the detection of Pb(II) with high sensitivity, stability and long-life.
3.2. Effect of SWASV parameters
Optimal parameters of the SWASVtechnique were chosenbased
on iterative trials. The best results with regard to precision, repro-
ducibility, andthe signal tobackgroundcurrent ratiowere obtained
with a pulse frequency of 23Hz, and this was the value chosen for
further work. The higher frequency did not give the distinguishable
left shoulder of the lead peak. Rather, the left shoulder of the peak
started from 0.75V, which is the E
begin
, and increased until the
peak of the current, resulting in inaccurate peak currents. As pulse
frequency was lowered, the starting point of the left shoulder of
the peak decreased from the E
begin
to ca. 0.6V. However, when
the pulse frequency was lower than 23Hz, the signal became very
coarse like the teeth of a saw, resulting in poor resolution as shown
in Fig. 4(a).
Changes of the step potential (E
step
) caused increase of the peak
current by ca. 10%for Pb(II), from2to3mVanddecrease of the peak
current by ca. 7% for Pb(II), from 3 to 10mV as shown in Fig. 4(b).
Therefore, the step potential of 3mV was applied for the highest
peak current.
The best results were obtained for the pulse amplitude (E
ampl
)
of 20mV. At higher pulse amplitudes (>20mV), higher lead peak
current was achieved. However, higher pulse amplitudes caused
major growth of the background current. On the other hand, lower
pulse amplitudes (<20mV) caused a slightly wider width of the
peak at half-height height with some distortion in the peak point
as shown in Fig. 4(c).
As the deposition time and potential are also crucial parameters
to govern the SWASV measurement, the optimum deposition time
has to be properly chosen. The deposition time in this experiment
has been selected by looking at the slope between 1ppb and 10ppb
when the deposition time is 180, 240, and 300s, respectively. Addi-
tionally, the peak current in blank solution has to be detected by
the analyzer in order to nd out the limit of detection. As a result,
deposition time of 300s seemed optimal with higher slope while
the peak current in blank could be detected as shown in Fig. 5.
The deposition potential has been selected as 0.75V based on
the literatures [2429], which use the deposition potential from
0.8 to 0.65V and the overall shape of SWASV curve showing
that the left shoulder of the current peak starts from more positive
potential than the 0.75V. The chosen potential nally provided
the high linearity over the large dynamic range in the sensor.
3.3. Square wave anodic stripping voltammetry (SWASV) for
Pb(II) analysis
SWASV is one of the most frequently used methods in ASV as it
greatly reduces background noise coming from the charging cur-
rent duringthe potential scan[14]. As anexample, Pb(II) at different
concentrations was measured in the standard solutions with sup-
porting electrolyte using the proposed sensor.
Unlike for the bismuth electrode fabricated ex situ [3], the silver
electrode was not affected by natural oxidation and surface con-
tamination during storage. In addition, the natural oxidation and
surface contamination are further impeded by covering the sen-
sor with the bonded uidic chip. Thus, there was no need to have a
protection layer such as photoresist on top of the sensor after fabri-
cation in order to preserve the sensitivity and reproducibility of the
silver electrode. This makes the sensor preparation much simpler
because there are no additional steps to remove such a protection
layer before measurements.
Initially, buffer solution was injected into the sensing chamber
through the inlet by a pipetter for electrochemical activation of the
sensor. Another advantage of the silver electrode is that there was
no need to provide time for stabilizing the open circuit potential
between the working and reference electrodes, which indicates an
equilibrium time for the integrated Ag QRE is not necessary. Dis-
solved oxygen in the sample solution did not need to be removed
because SWASV is known to be insensitive to the oxygen level,
and Ag electrodes are also less susceptible to oxygen background
interferences [22].
The stable background signal was achieved after ve cycles of
SWASV in buffer solution, as shown in Fig. 3. After the activa-
tion step, the previously used buffer solution was removed from
the sensing chamber via the outlet and 13.5L of the appropri-
ate Pb(II) standard solution was injected into the sensing chamber.
First, 1ppb of Pb(II) standard solution was consecutively measured
seven times. After each measurement, 0.2V potential vs. Ag QRE
was applied for 20s to remove any remaining Pb(II) on the sur-
W. Jung et al. / Sensors and Actuators B 155 (2011) 145153 149
Fig. 4. (a) The SWASV plots when the frequency was 20, 23, 50Hz. (b) Plots when the step potential was 2, 3, 6, 10mV. (c) Plots when the pulse amplitude was 15, 20,
25mV. The SWASV plots were recorded in non-deaerated supporting electrolyte with 1ppb of Pb(II) performed under conditions: E
dep
=0.75V, t
dep
=120s, E
begin
=0.75V,
E
end
=0.2V.
Fig. 5. The plots showing the peak currents and the slopes between 1ppb and 10ppb of Pb(II) when the deposition time is 180, 240, and 300s. When the deposition time
was 300s, the slope was 66nA/ppb while the slopes were 56nA/ppb and 39nA/ppb when the deposition time was 180s and 240s, respectively. The plots are recorded under
conditions dened in Section 2.4.
150 W. Jung et al. / Sensors and Actuators B 155 (2011) 145153
Fig. 6. (a) Calibration plot from 1ppb to 1000ppb for Pb(II). (b) Plots for Pb(II) at 1, 40, 100, 200, 500, 1000ppb. (c) Enlarged calibration plot from 1ppb to 40ppb for Pb(II).
(d) Plots for Pb(II) at 1, 5, 10, 20, 40ppb. The SWASV plots were recorded in non-deaerated supporting electrolyte performed under conditions: E
dep
=0.75V, t
dep
=300s,
E
begin
=0.75V, E
end
=0.2V, Estep =3mV, E
ampl
=20mV, Freq =23Hz.
face of the sensor. After the electrochemical cleaning step, new
solution was injected for each measurement. After the seventh
measurement with 1ppb of Pb(II) standard solution, 5ppb of Pb(II)
standardsolutionwas injectedfor the eighthconsecutive measure-
ment. The measurements with 5ppb of Pb(II) standard solutions
were conducted seven times in a row. Consecutively, peak currents
at 10, 20, 40, and 100ppb of Pb(II) standard solution were mea-
sured, ve times at each concentration. At 200, 500, and 1000ppb
of Pb(II) standard solution, three replicate measurements were
implemented at each concentration. The time for electrochemical
cleaning step was increased from20s to 60s to have more time for
removal of higher concentrations of Pb(II) on the surface at 200,
500, and 1000ppb of Pb(II) standard solutions. The total of forty-
three measurements were done consecutively over 8h. Without
baseline correctionsuchas backgroundsubtraction, SWASVs at dif-
ferent Pb(II) concentrations (11000ppb) are shown in Fig. 6(b)
and (d). Good peak shapes were obtained with the peak poten-
tial at 0.479V versus the integrated Ag QRE. The corresponding
calibration plot for Pb(II) was linear over the range of 11000ppb
(R
2
=0.999) with the limit of detection of 0.55ppb as shown in
Fig. 6(a). The sensitivity is 28.22nA/ppb at the deposition time of
300s.
3.4. Interferences
Silver electrode has been used in detecting not only Pb(II) but
also Cd(II) while showing the good selectivity between two ana-
lytes with good linearity [26,27,29]. This selectivity over Cd(II) in
detecting Pb(II) was investigated by examining the effect of co-
existing Cd(II) on the response for Pb(II) with 20ppb of Pb(II) and
40ppb of Cd(II). The results showed the clear separation between
the two current peaks of Pb(II) and Cd(II) as shown in Fig. 7. The
peak current of the 20ppb Pb(II) decreased 8.3% when there was
Fig. 7. Theplots showingthepeakcurrents of 20ppbPb(II), 40ppbCd(II), and20ppb
Pb(II) +40ppb Cd(II). The plots are recorded under conditions dened in Section 2.4
except the deposition time of 120s.
W. Jung et al. / Sensors and Actuators B 155 (2011) 145153 151
Fig. 8. Peak currents on the proposed sensor during forty-three consecutive measurements at each concentration from 1ppb to 1000ppb of Pb(II).
Fig. 9. Stable peak potentials onthe proposedsensor during forty-three consecutive
measurements.
40ppb Cd(II) on the solution while there was no change in the peak
potentials of Pb(II).
3.5. Reusability of the sensor
There are two mainobstacles preventing the bismuthelectrode-
based sensor chip from being reused. One is the memory-effect
on the electrode because of the formation of multi-component Bi
alloys with numerous heavy metals. Thus, even after the anodic
stripping and electrochemical cleaning steps, heavy metals still
remain inside the electrodes. This memory effect could be avoided
by utilizing the UPD-SV on silver electrodes. As a proof, forty-three
consecutivemeasurements, from1ppbto1000ppbPb(II), wererun
to characterize the reusability of the silver sensors fabricated on
polymer lab-on-a-chip for lead detection.
As described above, seven measurements were done at each
concentration of 1, 1, and 5ppb of Pb(II) standard solutions. Five
measurements were consecutively done at each concentration
of 10, 20, 40, and 100ppb of Pb(II) standard solutions followed
by three measurements at each concentration of 200, 500, and
1000ppb of Pb(II) standard solutions. Peak currents fromthe forty-
three consecutive measurements are shown in Fig. 8(a) (140ppb)
and Fig. 8(b) (1001000ppb). At the concentrations of Pb(II) which
are higher than 20ppb, the relative standard deviations were less
than 3% indicating there was no remaining Pb(II) on the Ag WE, as
a result of the characteristics of UPD-SV.
A second reason preventing the bismuth electrode-based sen-
sor chip from being reused is the short life-time of the integrated
Ag/AgCl reference electrode. Because of the relatively thin Ag and
AgCl layers, which are both less than 100nm, the Ag/AgCl refer-
ence electrode quickly loses its functionality. This problem could
be resolved by increasing the thickness of the Ag QRE to ca. 1.7m
and enlarging the surface area of the Ag QRE. As a result of doing
this, the peak potentials in forty-three consecutive measurements,
plotted in Fig. 9, showed a standard deviation (STD) of 0.005V and
a relative standard deviation (RSTD) of 1.0%. When there were no
additional Ag electroplating steps, the initial 0.1m thick Ag QRE
after Ag e-beamevaporation was dissolved away in less than 5min.
The better performance of the silver electrode has been spec-
ulated to be due to continuous surface renewal on the working
electrode during the electrodeposition step, as silver ions dissolved
Fig. 10. (a) Pictures of sensors taken every 2h during 8-h long measurements. (b) Quantitative values of Ag WE and Ag CE/QRE in gray scale from0 to 255 analyzed in ImageJ
software.
152 W. Jung et al. / Sensors and Actuators B 155 (2011) 145153
at the counter silver electrode are uniformly redeposited. This
phenomenon is attributed to the large current during the elec-
trodeposition step, the close proximity between the counter and
the working electrodes, and the nite rate of the precipitation reac-
tion of Ag
+
+Cl

AgCl resulting in movement of part of the silver

ions toward the working electrode before precipitation [25]. This
phenomenon was clearly observed in the experiment; shortening
the distance between the counter and the working electrodes to
100m expedited the transport of the silver ions from Ag CE/QRE
to Ag WE. Photographs taken every 2h from the initial status of
the sensor to 8h showed that the surface quality of the working
electrode was maintained during the 8h of the experiment due to
the surface renewal phenomenon. For quantitative measurements,
the photographs of the Ag WE and the Ag CE/QRE were analyzed
by ImageJ software (National Institute of Health) to evaluate the
change of the brightness in the Ag WE and the Ag CE/QRE over
time. As shown in Fig. 10, it was experimentally veried that the
Ag WE maintained its brightness during the forty-three consecu-
tive experiments while the Ag CE/QRE decreased its brightness due
to the formation of silver chloride.
4. Conclusions
This paper characterized newAg electrodes used for continuous
heavy metal detections on polymer lab-on-a-chips. This solid-
state sensor provides reusability with effective detection of the
stable peak potentials for on-site SWASV measurement of heavy
metal ions in non-deaerated solutions without generating toxic
waste. Microfabrication technology has been utilized to realize a
new fully integrated sensor with planar Ag working electrode, Ag
counter/quasi-reference electrode and microuidic channel. The
stable peak potentials and the dynamic response over the three
orders of magnitude concentration range, from 1ppb to 1000ppb,
for forty-three consecutive measurements establish the sensors
reusability, thereby greatly minimizing the analysts labor needed
for sensor change, and for reduction in waste generation from the
sensors themselves, making them more environmental friendly.
Thus, the simple sensor structure and the detection scheme t best
for detecting trace metal from on-site environmental samples.
Acknowledgements
This work was supported by the National Institute of Environ-
mental Health Sciences (NIEHS, R01 ES015446) in the National
Institute of Health (NIH). The authors thank Mr. Ron Flenniken in
theInstitutefor NanoscaleScienceandTechnologyat theUniversity
of Cincinnati for his technical support regarding Ag evaporation,
andalsothankMr. Kees vanVelzenfor his technical support regard-
ing the PalmSens and PSTrace operation.
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Biographies
Wooseok Jung received his BS degree in biomedical engineering from Yonsei
University, Korea, in 2006. He is currently working toward the Ph.D. degree in elec-
W. Jung et al. / Sensors and Actuators B 155 (2011) 145153 153
trical engineering at the University of Cincinnati, Cincinnati, OH, USA. Mr. Jungs
research interests focus on BioMEMS, micro total analysis system (microTAS) and
lab-on-a-chip, microuidics, miniaturized electrochemical sensors, and a closed
micro-volume blood sampling device.
Am Jang is currently research assistant professor at the University of Cincinnati,
Cincinnati, OH, USA. He joined the Department of Civil and Environmental Engi-
neering, University of Cincinnati in 2003 as a post-doctoral fellow. He received
his PhD from the Gwangju Institute Science and Technology (GIST), South Korea
in 2002. His current research interests are to monitor soil biolms contaminated
with heavy metals and to develop portable heavy metal sensors using lab-on-a-chip
technologies.
Paul L. Bishop is currently the Environmental Engineering Program Director at the
National Science Foundation. He is alsothe Associate Vice President for Researchand
Professor of Environmental Engineering at the University of Cincinnati, Cincinnati,
OH, USA. He received his PhD in 1972 from Purdue University, USA. His current
research interests are measuring the impacts of in situ environmental conditions on
biodegradation of toxic chemicals in biolm treatment processes and polyaromatic
hydrocarbons (PAHs) in soils at Superfund sites.
Chong H. Ahn received the PhD degree in electrical and computer engineering
from Georgia Institute of Technology, Atlanta, in 1993. From 1993 to 1994, he
was a Postdoctoral Associate with the Georgia Institute of Technology and then
with the IBM T.J. Watson Research Center. In 1994, he joined the Department of
Electrical and Computer Engineering and Computer Science, University of Cincin-
nati, Cincinnati, OH, as an Assistant Professor and is currently a Professor with the
Microsystems and BioMEMS Laboratory, Department of Electrical and Computer
Engineering, and the Department of Biomedical Engineering. He is also the Director
of the Center for BioMEMS andNanobiosystems. He is currentlya member of the Edi-
torial Board of the Journal of Micromechanics and Microengineering, Microuidics
and Nanouidics, and Small. He has published approximately 300 journal and peer
reviewed conference proceedings papers related to microelectromechanical sys-
tems, bioMEMS, microuidics, and lab-on-a-chip areas. He is the holder of four U.S.
patents. His research interests include the design, fabrication, and characterization
of nanostructures and nanobiosensors, magnetic sensors, magnetic MEMS/NEMS
devices, magnetic nano bead-based immunoassays, microuidic devices and sys-
tems, BioMEMS/NEMS devices, plastic based disposable biochips, point-of-care
blood analyzers, portable biochemical detection systems, protein chips, lab on a
chip, and biophotonic devices. Dr. Ahn is a Co-chair and Organizer of several inter-
national conferences on MEMS/NEMS and BioMEMS/NEMS. In addition, he served
on the programcommittee of numerous international conferences on microsensors,
BioMEMS, and MEMS, including the IEEE International Conference on Microelec-
tromechanical Systems (MEMS) and the International Conference on Solid-State
Sensors and Actuators (TRANSDUCERS). He has presented numerous invited talks in
several international conferences. From2003 to 2004, he was an Associate Editor for
the IEEE Sensors Journal. He is currently a Subject Editor of the IEEE/ASME Journal
of Microelectromechanical Systems (JMEMS).