Anal Bioanal Chem (2005) 381: 979–985
DOI 10.1007/s00216-004-2960-z
O R I GI N A L P A P E R
Andrew O. Simm Æ Craig E. Banks Æ Shelley J. Wilkins
Nikos G. Karousos Æ James Davis Æ Richard G. Compton
A comparison of different types of gold–carbon composite
electrode for detection of arsenic(III)
Received: 14 September 2004 / Revised: 2 November 2004 / Accepted: 4 November 2004 / Published online: 17 December 2004

Springer-Verlag 2004
Abstract A study has been conducted using abrasively
modified basal and edge-plane graphite, carbon-paste,
and carbon–epoxy electrodes to create gold–carbon
composite electrodes. Using either nano or micro-sized
gold particles their suitability for use in detecting ar-
senic(III) is assessed. It was found that gold arrays
prepared from micron-sized particles gave the best per-
formance for arsenic detection. In particular micron
arrays produced in carbon-paste electrodes with an
easily renewable surface work well for detection of ar-
senic, producing a detection limit of 5(±2)·10 9
mol L 1, with a high sensitivity of 10(±0.1) A mol 1 L.
Keywords Arsenic(III) Æ Carbon-paste electrodes Æ
Anodic stripping voltammetry Æ Gold microarrays Æ
Gold nanoarrays
Introduction
The claimed mass poisoning of millions of people by
arsenic in contaminated drinking water in the Far East
has been well reported over the last 20 years [1–6].
Bangladesh, in particular, has up to 50 million people at
risk in what the World Health Organisation (WHO) call
the worlds worst mass human poisoning disaster [7–9].
A. O. Simm Æ C. E. Banks Æ R. G. Compton (&)
Physical and Theoretical Chemistry Laboratory,
Oxford University, South Parks Road,
Oxford, OX13QZ UK
E-mail: Richard.Compton@chemistry.ox.ac.uk
Tel.: +44-1865-275413
Fax: +44-1865-275410
S. J. Wilkins
Department of Materials, Oxford University,
Parks Road, Oxford, OX13PH UK
N. G. Karousos Æ J. Davis
Chemistry Department, University of Surrey,
Guildford, Surrey, GU2 7XH UK
The increase in human consumption of contaminated
ground water in these areas over the last 20 years is
behind the mass poisoning outbreak. Hundreds of
thousands of wells were dug in remote villages as a
source of clean drinking water free from pathogens; it is
thought that in Bangladesh as many as 70% [10] of these
wells are contaminated with arsenic levels above the
WHO limit of 10 ppb (0.01 mg L 1) [11]. It is necessary
therefore that each of these wells is monitored for ar-
senic levels and closed if appropriate.
A variety of well known and accurate analytical
techniques are easily capable of measuring the arsenic
concentrations in these wells, for example chemilumi-
nescence [12], chromatography, spectroscopic methods
[13, 14], and various forms of ICP–MS [15, 16]. (For an
overview of these methods see [17, 18].) These methods
are expensive and laboratory-based requiring well
trained technicians to conduct the measurements. The
sheer number of contaminated wells that need to be
regularly monitored means that using these laboratory-
based methods would simply not be practical. Although
field based ‘‘kits’’ based on the colorimetric Gutzeit test
[19] are available for estimation of arsenic concentra-
tions in well samples, they are not reliable [20] at the low
concentrations required by the WHO and also require
the use of highly concentrated acids which produce the
extremely toxic gas arsine.
Electrochemical methods hold great promise for
portable use in the field. Anodic stripping voltammetry
(ASV) of arsenic(III) at gold [21], platinum [21] and
mercury [22–24] surfaces has been well documented for
many years. Optimisation of the accumulation period
and the use of staircase voltammetry during the strip-
ping step combined with either hydrodynamic methods
such as the dropping mercury electrode [22–26], the
rotating disc electrode [27, 28], the channel flow cell [29],
ultra- [30] and infra- [31] sonicated electrodes or
microelectrode arrays [32, 33] or nanoparticles [34] en-
able extremely low detection limits easily capable of
analysing samples down to the WHO required levels,
Table 1. However while some of these techniques could
980

Table 1 A summary of different

methods developed for arsenic Authors Electrode Deposition time Limit of detection
detection material (mol L 1)
6
Tomčı́k Interdigitated n/a 7.0·10
et al. [33] platinum array
WHO safe human
consumption limit
1.3·10 7 mol L 1
8
Švancara et al. [40] Gold-coated 15 s 4.1·10
carbon paste
8
Prakash et al. [27] Rotating gold disc 60 s 2.7·10
8
Simm et al. [30] Ultrasound-assisted 60 s 1.2·10
gold disc
9
Huang et al. [29] Portable gold flow cell 180 s 7.0·10
9
Simm et al. [31] Gold disc integrated 120 s 3.7·10
into a portable sonotrode
9
Forsberg et al. [21] Gold disc 1200 s 2.7·10
9
Salimi et al. [35] Iridium oxide-modified n/a 2.0·10
boron-doped diamond
10
Feeney et al. [32] Micro fabricated gold 80 s 6.4·10
ultra microelectrode array
10
Dai et al. [34] Gold nanoparticle-modified 180 s 1.3·10
glassy carbon

be realistically turned into a portable arsenic detector,
the use of expensive gold or platinum surfaces would
likely make them prohibitively expensive. The cleaning
of the electrode surfaces to a suitable level prior to
analysis might also be troublesome in the field.
Although there has been some success in the elec-
trochemical detection of arsenic at other surfaces [35, 36]
it seems that gold electrodes in particular are key to the
detection. However although some gold-based methods
such as those based on micro and nano arrays enable
very low 10 10 mol L 1 detection limits it is difficult to
see how these could be cheaply turned into a practical
product. If an electrochemically based method could be
used to create a portable detection kit, the use of either
single-shot electrodes that might be mass produced
cheaply on a large scale and simply be thrown away after
the analysis has been completed, or electrodes with an
easily renewable surface would seem a sensible step in
making the product a practical and commercial reality.
In this paper we look at several different ways to
cheaply produce micro and nano-sized gold arrays on
different carbon surfaces, namely edge plane, basal plane
pyrolytic graphite (bppg), and graphite powder and
compare their ability to determine arsenic(III) to the
required trace levels.
Experimental
Reagents and chemicals
All chemicals used were of analytical grade and were
used as received without any further purification. These
were: sodium (meta) arsenite, (Fluka, +99.0%)—highly
toxic handle with care, synthetic graphite powder (Al-
drich, 1–2 lm), spherical gold powder 3.0–5.5 lm
diameter (Alfa Aesar.), gold colloid solution of 5 nm
diameter (Sigma, 0.01% as HAuCl4), mineral oil (Al-
drich, CAS 8042-47-5), epoxy resin (Durcisseur MA2),
nitric acid (Aldrich, 70%, double distilled PPB/Teflon
grade with trace metal impurities in parts per trillion
determined by ICP–MS).
All solutions were prepared with deionised water of
resistivity not less than 18.2 MW cm (Vivendi water
systems, UK) and degassed using N2 prior to measure-
ments.
Instrumentation
Voltammetric measurements were carried out using
a l-Autolab III (ECO-Chemie, Utrecht, The Nether-
lands) potentiostat. All measurements were conducted
using a three-electrode cell. The counter electrode was a
bright platinum wire, with a saturated calomel electrode
(Radiometer, Copenhagen, Denmark) as the reference.
Basel plane pyrolytic graphite and edge-plane electrodes
(4 mm diameter) sealed in Teflon housing were used as
working electrodes (Le Carbone, Sussex, UK). Dispos-
able plastic syringes (2 mL) (Gillette) with a 3 mm
diameter opening were used to contain carbon paste and
carbon epoxy electrodes, the syringe enabled simple re-
newal of the surface of carbon-paste electrodes. A digital
voltmeter was used to test the conductivity of manu-
factured electrodes, (Cirkit, TM 5315B). Pad-printed
electrodes were obtained using a PE-4C (Pad Printer
Eng., Supplied by Pad Print UK, Wellingborough, UK)
pad-printing machine from an etched stainless steel
plate/closed cup arrangement containing a silver-free
carbon ink (Creative Materials, Tyngsboro, USA). The
electrodes were typically comprised of five print layers
deposited on standard overhead projection film acetate

sheets. High-resolution scanning electron microscopy
(SEM) imaging was performed using a Jeol JSM 6500F
FEGSEM (Field effect gun). Conventional secondary-
electron imaging was employed for surface topology
together with backscattered electron detection to obtain
compositional contrast. Energy dispersive X-ray detec-
tion (EDX) was used to obtain information about the
composition of the sample. All samples were carbon-
coated prior to SEM analysis.
Results
Gold-modified carbon electrodes
In this section we compare micron and nano-sized gold
particles when immobilised on basal plane and edge
plane carbon electrodes in respect of their ASV response
to As(III). Immobilisation of the powder on an electrode
surface was chosen as an easy way of comparing the
performance of the different powders. Basal plane elec-
trodes have a higher resistance than edge-plane elec-
trodes, because of the alignment of the graphite sheets
with respect to the electrode surface; for this reason the
electron-transfer kinetics of edge-plane graphite are
faster than those of basal-plane graphite [37].
Colloidal gold-loaded carbon powder was prepared
by the method suggested by Ju et al. [38]. Colloidal gold
particles (4 nm) were immobilised on 1–2 lm diameter
graphite powder by adding a gold colloid solution
(0.01% as HAuCl4) to the graphite powder (2 lL:1 mg).
The solution was then thoroughly mixed with the
graphite powder and allowed to completely dry in air for
approximately 12 h. The dried powder was then used to
abrasively modify a basal plane pyrolytic graphite elec-
trode by rubbing a small amount of the powder into the
electrode surface on filter paper.
Anodic stripping voltammetry experiments using ar-
senic(III) in 0.1 mol L 1 nitric acid solution were then
carried out with the modified electrode, using a 60 s
deposition period at 0.5 V followed by a stripping step
at 50 mV s 1. No response was observed to arsenic in
0.1–10 lmol L 1 concentration. A small poorly defined
arsenic(III) stripping peak was observed at millimol
concentrations. The stripping peak appears at ca. 0.1 V
(vs. SCE) which corresponds well with literature values
[30, 31].
An amount of 20 lL 0.01% gold colloid solution was
then placed directly on the surface of a bppg electrode
and left to dry in air. ASV experiments using
1 lmol L 1 arsenic(III) additions were then conducted
using a deposition potential of 0.5 V for 60 s. A small
arsenic peak could be seen at ca. 0.1 V (vs. SCE).
However it did not become significantly large until
around 100 lmol L 1. This is a reasonable improvement
in sensitivity compared with abrasively modifying the
electrode surface with carbon powder modified with
adsorbed gold colloid.
981
Gold spheres, 3.0–5.5 lm, were first abrasively at-
tached to bppg and edge-plane electrodes by rubbing a
small amount on the gold powder into the electrode
surfaces on filter paper. Using a bppg-modified electrode
with a deposition potential of 0.5 V for 60 s no arsenic
signal was visible at the 0.1–100 lmol L 1 levels.
Repeating the same experiment, but this time using an
edge-plane electrode, resulted in no significant arsenic
signal being visible in the 0.1–10 lmol L 1 level. How-
ever a significant well defined arsenic stripping signal
was visible at 0.1 V (vs. SCE) at around 100 lmol L 1
concentration levels. This suggests that the lower back-
ground current of edge-plane graphite over basal-plane
graphite leads to increased sensitivity at the
100 lmol L 1 level over bppg for arsenic stripping at the
gold particles. However the extent is not significant en-
ough for the method to be analytically useful in the
context of groundwater evaluation.
Gold spheres, 3.0–5.5 lm, were then mixed with
1–2 lm carbon graphite powder, 1:1 by weight. The
mixture was then abrasively attached to edge-plane and
bppg electrodes by rubbing on filter paper. With the
bppg electrode again no significant ASV response to
arsenic after a 60 s deposition at 0.5 V was seen using
0.2–10 lmol L 1 concentrations. However a relatively
small stripping peak could be seen at 100 lmol L 1
levels. Using an abrasively modified edge-plane electrode
a very small arsenic signal was visible with 0.2–
10 lmol L 1 concentrations; however the signal did not
become significant until 100 lmol L 1 levels, where a
well defined stripping signal was seen, Fig. 1. The im-
proved sensitivity of gold particles mixed with graphite
powder would suggest that there is better adhesion of
the gold on the electrode surface probably because of the
Fig. 1 ASV response to 1 lmol L 1 arsenic(III) additions followed
by a large 100 lmol L 1 addition. From a micron gold–carbon
modified edge-plane graphite electrode. Potential held at 0.5 V
for 60 s followed by a stripping step using linear sweep voltamme-
try at 50 mV s 1
982

surface roughening. It is also possible that the graphite
powder prevents the aggregation of the gold particles as
they are abrasively attached to the surface.
Gold-loaded carbon electrodes
Now we turn to the construction of solid electrodes in
the form of carbon paste and carbon epoxy electrodes
created from the gold–carbon mixtures investigated in
the previous section.
Carbon epoxy electrodes
form a solid polishable electrode surface have been de-
scribed by Lawrence et al. [39] as a way of preparing an
alternative renewable carbon surface to that of classical
carbon-paste-based electrodes. Electrodes were prepared
in the manner described using the suggested 3:1 by
weight ratio of electrode material (gold and carbon
mixture) to epoxy resin. Once prepared however, al-
though the electrodes were found to be conductive using
a digital voltmeter, no response to arsenic addition, even
at the millimol level, was seen for either gold colloid or
gold micron particle-based carbon epoxy electrodes,
suggesting the resin probably coated the gold particles
leaving little or no gold exposed at the electrode surface.

Carbon epoxy electrodes where the modified carbon carbon-paste electrodes

powder is effectively ‘‘glued’’ in place by the epoxy to
Fig. 2 SEM image of the micron-sized gold carbon-paste electrode
surface at 600· magnification
Gold-plated carbon-paste electrodes have been de-
scribed by Švancara et al. [40] for the detection of ar-
senic(III), for which they achieved a detection limit of
4·10 8 mol L 1. However in the present report we
investigate their use with carbon–gold mixtures rather
than coating the carbon paste to form a gold macro
surface. The gold colloid-modified graphite powder was
prepared as described in Sect. 3.1. When the mixture had
dried completely in air, mineral oil was added to the
mixture (2 graphite:1 mineral oil by weight), forming a
paste. This paste was then transferred to a 2-mL plastic
syringe and the surface of the paste in the nozzle used
directly as the working electrode enabled easy renewal of
the electrode surface. Before use a small amount of paste
was squeezed out and then rubbed down on sand paper.
ASV experiments were unable to detect any response to
arsenic even at the millimol level suggesting the oil may
have completely covered the gold colloid.
The experiment was then repeated using the micron
sized gold particles prepared in the same way (2:2:1
gold:graphite:mineral oil, by weight). SEM images,

Fig. 3 Square-wave ASV

response to successive 20 nmol
L 1 arsenic(III) additions.
From a micron sized gold–
carbon paste composite
electrode. Potential held at
0.5 V for 120 s followed by a
stripping step using square-
wave voltammetry with the
conditions: amplitude 250 mV,
frequency 50 Hz, step potential
5 mV

Fig. 4 SEM image of the pad-printed electrode surface at 850·
magnification
(Fig. 2) clearly show gold spheres on the electrode sur-
face; a surface density of one gold sphere per 131 lm2
was calculated from the images. A well defined arsenic
signal was seen to respond with significant sensitivity to
additions of 1 lmol L 1 arsenic(III), the stripping signal
could be seen at approximately 0.1 V (vs. SCE), despite
a large background current from the carbon paste visible
in the 0.2–0.5 V (vs. SCE) region. Square-wave vol-
tammetry was then conducted to further enhance the
stripping signal and obtain a limit of detection for the
detection of arsenic(III). Using a 5 lmol L 1 concen-
tration of arsenic and a 120 s deposition period at
0.5 V (vs. SCE) a stripping signal was obtained at
0.1 V. The square-wave measurements were optimised
by first varying the square-wave amplitude from 10 to
Fig. 5 EDAX image-analysis plots showing the composition of the
electrode surface. In the left hand plot the beam is centred on one of
the gold particles whereas in the right hand plot the beam is centred
away from the particles on the bare carbon surface
983
250 mV while keeping the frequency constant at 50 Hz.
Increasing the amplitude was found to slightly broaden
the stripping peak but also significantly increase the
signal while shifting the stripping peak away from the
carbon paste background signal, therefore an amplitude
of 250 mV was used. Using this value the frequency was
then varied from 50 to 200 Hz. While increasing the
frequency was found to increase the signal peak height
there was an associated increase in signal noise therefore
the original value of 50 Hz was used, because no noise
was present using this value. Using optimised square-
wave voltammetry the limit of detection (based on 3r)
from the arsenic peak height using additions of 20 nmol
L 1 was found to be 5(±2)·10 9 mol L 1, with a sen-
sitivity of 10(±0.1) A mol 1 L, ( 1.9·10 7 A
(±2.4·10 8) R=0.9995), the response was found to be
linear in the range 20–220 nmol L 1, Fig. 3. The sen-
sitivity was monitored over several weeks and was not
found to decrease significantly during that time.
Pad-printed carbon/Au electrodes
‘‘Pad-printed’’ electrodes are a relatively cheap way of
mass producing ‘‘single-shot’’ electrodes for use as
sensing devices [41]. A conductive carbon-based ink is
used to pad print a pattern containing ca. 30 electrodes
with a surface area of 18 mm2 on to acetate sheets. By
mixing gold particles with the ink it is possible to print
large numbers of carbon–gold array electrodes.
The 3–5.5 lm gold particles were mixed to a com-
position of 10% by weight with the conductive carbon
ink. The ink was then used to ‘‘pad print’’ single-shot
electrodes on to an acetate sheet. Figure 4 shows an
SEM image of the pad-printed electrode, micron size
spheres are clearly visible as being well spread out on the
electrode surface with little aggregation. EDAX analysis
confirms the spheres to be gold, Fig. 5, clearly having a
different composition to the carbon ink. It is estimated
984
Fig. 6 SEM images of a carbon
pad-printed electrode with no
gold present (left, 20,000·
magnification) and a gold–
carbon pad-printed electrode
(right, 13,000· magnification)
from the SEM analysis that there is one gold sphere per
370 lm2 on the electrode surface.
The response to arsenic(III) was tested in 0.1 mol L 1
nitric acid solution. Using a 60 s deposition time at
0.5 V a small peak was visible at ca. 0.1 V with
1 lmol L 1 additions. Using square-wave voltammetry
to enhance the sensitivity a limit of detection (based on
3r) from peak area was found to be 9 (±3)·10 7
mol L 1, (2.1·10 8 A (±2.6·10 9) R=0.9887, the lin-
ear range was found to be from 1 to 5 lmol L 1. Several
pad-printing runs were tested and all were found to
achieve detection limits at this level.
The much higher detection limit achieved with the
pad-printed electrodes compared with the performance
of the carbon-paste electrodes might be explained by the
SEM images in Fig. 6. The left hand image shows a bare
pad-printed surface from an electrode composed of only
the carbon ink and no gold particles, ink globules ca.
0.1 lm in diameter can clearly be seen covering the
electrode surface. The right hand image shows a gold–
carbon pad-printed electrode, two gold spheres are
clearly visible on the electrode surface however the same
globular ink deposits appear to have completely covered
the gold surface.
Conclusion
Carbon composite gold electrodes have been shown to
be a valid alternative to solid gold surfaces for arsenic
detection, and several different electrode types have been
explored. Although most show a response to arsenic,
only the carbon-paste-based electrodes were able to
achieve a detection limit sufficiently low to be of ana-
lytical value.
The attempt to produce gold–carbon electrodes on
a large scale via pad printing, although not able to
reproduce the sensitivity found in the carbon-paste
electrodes, did provide a limit of detection close to the
magnitude required by the WHO [11] for groundwater
analysis (10 ppb). With further optimisation they
might provide an inexpensive basis for the production
of single-shot arsenic detectors in the future.
Acknowledgements AOS thanks the EPRSC and Abington Partners
Sensing for support via an Industrial CASE studentship. CEB
thanks the EPRSC for support via a project studentship (Grant
GR/R14392/01).
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