ECS Transactions, 15 (1) 527-533 (2008)

10.1149/1.3046669 © The Electrochemical Society

Pb Detection in Soil Samples by Electroanalysis: Cyclic Voltammetry and

Osteryoung Square Wave Stripping Voltammetry

G. Beristain-Ortíz, E. G. Sumbarda-Ramos, M. García García, M. T. Oropeza-

Guzmán

Centro de Graduados e Investigación. Instituto Tecnológico de Tijuana, C.P.

22500, Tijuana, B. C., México

Carbon Paste Electrodes (CPE) and Chemical Modified Electrodes

(CMEs) are proposed as Pb sensors for soil samples treated with
ammonium acetate. The extracted fraction were analyzed by
electroanalytical techniques. The use of CPE and CMEs in
conjunction with electroanalytical techniques as Cyclic
Voltammetry (CV) and Anodic Stripping Voltammetry with
Osteryoung Square Wave (OSWSV) showed to be very suitable to
analyze the lead content in samples (under 10 ppm) of dangerous
residues collected from a historically polluted site in Tijuana B.C.,
Mexico.

Introduction

Heavy metal detections in solid and aqueous industrial wastes are traditionally a
domain of standard methods as atomic absorption spectrometry (AAS) and
inductively coupled plasma (ICP). Both methods are very accurate and allow
multidection; however, they require expensive instrumentation. Other alternative is
the UV-Vis spectrometry that is characterized by the consumption of exclusive
ligands to form stable metal complexes suitable to be detected. In addition, the
stability of formed metal complexes does not allow to get back the original sample
neither to recycle ligands. Attending these necessities (non expensive detection and
recyclable reagents), electroanalytical methods present an appropriate alternative.
Electroanalytical methods use small amounts of sample (µl) that even can be returned
to its original state and reuse the sensing electrode; however a right comprehension of
involved phenomena in the detection process are the key to have a successful
determination.

In this work amperometric electrodes are proposed as Pb sensors for soil and water
analysis in a practical, accurate and non expensive way. The use of non modified
carbon paste electrodes (CPE) and chemical modified electrodes (CMEs) in
conjunction with Cyclic Voltammetry (CV) and Anodic Stripping Voltammetry with
Osteryoung Square Wave (OSWSV) showed to be an appropriate option to analyze
Pb content in samples of dangerous residues collected from a historically polluted site
in Tijuana B.C., Mexico(1). The standard addition method was used to calculate lead
concentration in solution, thus in solid samples.

Carbon paste electrodes (CPE) have been widely used in numerous electroanalysis
due to the fact that their preparation and construction is quite easy and non expensive.
For example, CPE reproducibility leads to distinguish from mineral dissolution
mechanisms (2). Nava and coworkers reported the fabrication of CPEs with different
mineral materials prepared by dispersing several portions of graphite powder with
mineral powder (90:10, 80:20, 70:30). For their purpose they used the anodic

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 ECS Transactions, 15 (1) 527-533 (2008)

stripping voltammetry to determine the zinc content in each sample (3). CPEs also
have a great versatility as sensors for several mineral species.

Soo Beng and coworkers constructed carbon paste electrodes modified with different
insoluble mercury salts, in order to produce mercury microdrops on the surface when
applying a cathodic pulse. They show how mercury oxalate (HgC2O4) seems to be the
better option to fabricate these sensors, since a greater density of microdrops was
obtained after a cathodic potential pulse of 3 minutes in 0.1M HCl compared with
other salts. During the detection, heavy metals contained in aqueous samples form an
amalgam with mercury microdrops and by means of an anodic stripping voltammetry
metals are detected specifically, even in small concentrations. In that case, sensing
electrodes are not only modified in the surface, but also in all the electrode body,
allowing a quickly surface renewal (4).

Aminur Rahman and coworkers reported the fabrication of conductor polymers

synthesized on the electrode surface. Monomeric units were 3´,4´-diamino-2,2´;5´,2”-
tertiophene, with ethylendiaminethetracetate (EDTA) inserted in the polymer(5).

The EDTA insertion was done by three different ways: before, during and after the
polymerization. For the last case, EDTA seemed to improve the metal detection
exerting its complexing capacity to trap metals on the electrode surface. To avoid that
electrode active sites idle away, a nafion coating was used. Their electrodes
characterizations were done by Electrochemical Quartz Microbalance (EQCM),
Scanning Electron Microscopy (SEM) Electronic Spectroscopy for Chemical Analysis
(ESCA), Auger Electron Spectroscopy (AES) and Electrochemical Methods. For the
last mentioned experiments they tried to find an optimal group of parameters (EDTA
concentration, temperature, deposition time and pH) to achieve multidetections (Pb,
Hg and Cu) in the range of parts per billion (ppb). To prove the right performance of
electrodes, they used OSWSV.

In this paper, authors would like to show how the use of simple CPEs and CMEs
respond correctly to the standard addition method to detect Pb extracted from a solid
residue by CV and OSWSV

Experimental

Materials

Lead standard solution (1000 ppm), was received from Spectrum, and diluted as
required (16 ppm). Graphite powder (APS 2-15) was delivered by Alfa Aesar, silicon
oil CAS 63148-62-9 from Alfa Aesar, potassium nitrate CAS #7757-79-1 was
delivered by Alfa Aesar, oxalic acid CAS144-62-7 was from Aldrich and Mercury (II)
Nitrate Monohydrate CAS77-83-34-8 was delivered by Sigma-Aldrich, disodic EDTA
salt CAS 6381-92-6 was received from Fermont, nafion solution® 117- CAS 31175-
20-9 was delivered by Fluka, deionized water and ammonium acetate solution 1M.

Electrodes preparation

Two types of electrode were prepared and used for Pb detection in ammonium
acetate solution.

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 ECS Transactions, 15 (1) 527-533 (2008)

EPC. After weighting 1g of graphite powder and mixed with 0,8 ml of silicon oil,
each electrode was packed in a 1 ml syringe and compacted using the piston, a silver
wire was inserted in the electrode as a current feeder.

CME- HgC2O4. The electrode was prepared with 0,25g of mercury oxalate
crushed in an Agatha mortar and mixed with 0,75g of graphite powder. We added
0,8ml of silicon oil and mix to get a homogeneous paste. Formed paste was packed in
a 1 ml syringe and compacted using the piston, a silver wire was inserted in the
electrode as current feeder.

CME-EDTA (C10H14N2Na2O8•2H2O) 90:10 with nafion. 0.10g of Na2H2EDTA

(C10H14N2Na2O8•2H2O) powder were crushed in an Agatha mortar and mixed with
0.90g of graphite, the paste were formed adding 0.8 ml of silicon oil and mixed to get
a homogeneous paste. Formed paste was packed in a 1 ml syringe and compacted
using the piston, a silver wire was inserted in the electrode as current feeder. A nafion
drop was placed in the top of the electrode surface. Drying time was 15 minutes to
allow a membrane formation. The electrode was placed in a three electrode cell giving
a hydration time of 15 minutes in the supporting electrolyte.

Electrodes Characterization

CV and OSWSV were performed using a three electrode cell (WE= CPE or CME,
CE= Pt wire and RE=Ag/AgCl) and a working electrochemical station BAS 100B.

Eight soil samples were taken from a real polluted site in Tijuana, B.C., and Mexico
(6) classified as:
A Left side 1 ft under level E Right side 1 ft under level
B Left side 2 ft under level F Right side superficial soil
C Medium 1 ft under level G Right side superficial pink residue
D Medium 2 ft under level H Right side superficial brown residue

Each soil sample has been classified by size under ASTM 2487 (43-61 µm) and
submitted to the Cationic Exchange Capacity (CEC) EPA-9081 protocol (7).
Fractions extracted from Ammonium Acetate washing were submitted to analysis. It
is important to remark that this lead fraction is bio-available.

Results

Even if the experimental work was done for eight different soil samples, in this
section only the analysis of the extractable lead fraction of soil sample H (obtained
after the ammonium acetate washing) are presented.

Figure 1i) shows the CV for a CPE in ammonium acetate solution resulting from the
last step of the soil CEC determination. In this case no signals corresponding to Pb
reduction or oxidation can be observed, apparently because the potential scan was
very fast (100 mV/s) and it did not detect the contained metallic species.

Figure 1ii) shows CVs made with a CME-HgC2O4 (75: 25), in the same ammonium
acetate solution. The observed signal corresponds to Hg contained in the electrode
surface, thus in ammonium acetate this metal is detected by dissolution. However, Pb
was still not visible and moreover, the sample addition as well as the standard
additions decreased the Hg dissolution current peak.

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 ECS Transactions, 15 (1) 527-533 (2008)

In figure 1iii) CVs made with CME-EDTA (90:10) with nafion are presented.
Apparently a reversible redox process was observed between -41 and 0 mV/Ag/AgCl
attributed to proton transport through the nafion membrane (non faradaic current).
This hypothesis needs further analysis in order to be proved. After the sample
addition the first peak associated with lead reduction appeared at -450 mV/Ag/AgCl
and a second one at -731 mV/Ag/AgCl. These signals may correspond to the
reduction of Pb2+ and the second one to Pb-EDTA complex. After adding standards of
Pb2+, the second peaks increased uniformly, thus the oxidation peak even if this one
moved to the right. For the addition of 4.8x10-3 mg Pb (II) appeared a small peak in -
354 (mV/Ag/AgCl) which may indicate the presence of another species of Pb or
another metal that possibly is forming an alloy with Pb.

i) ii)

2 15

-1000 -500 0 500

8
I (µ A )

-4
E (mV/Ag/AgCl)
I (µ A ) 1
-10 -1000 -600 -200 200 600
-6
E (mV/Ag/AgCl)

-16 -13

iii)

90
15 ml ammonium acetate
+ 100 µl sample
30
+ 1.6x10-3 mg Pb
I (µ A )

+ 3.2x10-3 mg Pb
-30-1500 -1000 -500 0 500
+ 4.8x10-3 mg Pb
E (mV/Ag/AgCl)
-90

Figure1. Cyclic Voltammograms (CVs) for Pb extracted fraction from H sample using
three different electrodes: i) CPE, ii) CME-HgC2O4, iii) CME-EDTA. Three
additions of 100 µl Pb 16 ppm in a supporting electrolyte of CH3COONH4 1 M were
done.

As observed CV is not a suitable technique to quantify Pb in solotuion since faradaic

current are influenced by several parameters; however, it is the easy form to
distinguish the surface influence in reduction and oxidation processes. It is well
known that stripping voltammetry is a better quantification method. For this reason
the same experimental sequence was performed using OSWSV.

Figure 2 i) shows voltammograms of OSWSV made with a CPE. Comparing curve a

(supporting electrolyte) and b (sample addition), it can be observed the lead presence.
In the later additions (curves c, d and e) the uniform growth of Pb dissolution peak
allows to quantify Pb content in sample H. This technique is excellent for metal
quantification in low concentrations (ppb) since previous to the detection metal

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 ECS Transactions, 15 (1) 527-533 (2008)

electrodeposition is induced by a reduction pulse. Metallic species adheres to the

CPE surface and after that the pulsed potential sweep allows the Pb detection since
each current point is the difference between the oxidation and reduction current
obtained at different potential values.

In figure 2 ii) voltammograms of OSWSV made with CME-HgC2O4,75:25 are

presented, the signal in a corresponds to the supporting electrolyte and shows a large
capacitive current. The peak in signal b and the potential to which it is observed
exposes the presence of a metal mixture in the sample, competing by sites in the
surface of the electrode. In the later additions (signals c, d and e) the uniform growth
of peaks allows to quantify Pb in sample H. It is important to remark that previous to
the detection (pulsed stripping dissolution), the electrodeposition pulse not also
induces lead reduction but also Hg since it is contained in the electrode surface. For
this reason the voltammogram include Pb reduction over two different surfaces: Hg
microdrops and CPE, this effect can be detected comparing by b and c curves. Even
sensitivity is slightly lower than CPE electrodes.
i) ii)
2.0 1.1 e
e 0.9
1.5
d d
I (µ A )

0.7
I (µA)

1.0 c a
b 0.5 b c
0.5 a 0.3
0.0 0.1
-650 -600 -550 -500 -700 -650 -600 -550 -500 -450
E (mV/Ag/AgCl) E (mV/Ag/AgCl)

iii)
35 e
30 d
c 15 ml ammonium acetate
25 b + 100 µl sample
I (µ A )

20 + 1.6x10-3 mg Pb

15 a + 3.2x10-3 mg Pb
+ 4.8x10-3 mg Pb
10
-700 -600 -500 -400 -300
E (mV/Ag/AgCl)

Figure 2 i) CPE, ii) CME-HgC2O4, iii) CME-EDTA. OSWSV, three additions of 100
µl Pb 16 ppm in KNO3 0.1 M, support electrolyte of CH3COONH4 1 M: Right side
superficial brown residue (H).

Voltammograms in figure 2 iii), show the series of additions of Pb in solution using

CME-EDTA 90:10 with nafion. In the sample addition curve, a peak is observed at
potential of -532 (mV/Ag/AgCl) that clearly indicates the presence of Pb. As it can
be observed sensitivity is larger than CPE and CME-Hg electrodes. A second
dissolution peak at more positive potential indicates the presence of another
dissolution process perhaps coming from Pb alloy with another metal, since the soil
sample also contain Cu, Fe and Cd. In the signal corresponding to the first standard
addition of Pb an increase in current is observed. Nevertheless, in later additions, it is

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 ECS Transactions, 15 (1) 527-533 (2008)

observed an increase in the second dissolution peak as well. From other experimental
series with copper (not shown in this paper) it have been determined the presence of
Cu ions in H sample.

Finally an important observation is the dissolution potential values that change

depending on the electrode surface. This result was expected since each electrode has
a different work function as showed in the CV series.

The results obtained in the determination of Pb (ppm and mg/Kg) contained in the real
samples are different for each electrode (Table I). Nevertheless, the electrodes
displayed good answer in each case. Even if the Pb content seems to be similar it is
important to analyze each of the electrode phenomena and decide which one is closer
to the real value. After analyzing the electrodes response for three different metals
and a multidetection procedure it was found that CME-EDTA 90:10 enables the
multidetection task with good results but CPE is more accurate for only one species.
TABLE I. Pb (II) in ammonium acetate solution, obtained by OSWSV with three different electrodes.
CME-EDTA 90:10
CPE CME-Hg2C2O4 75:25
(with covering of nafion)
Concentration Soil Concentration Soil Concentration Soil concentration
Sample [ppm] concentration [ppm] concentration [ppm] [mg/Kg]soil
[mg/Kg]soil [mg/Kg]soil
A 17.7 442.6 11.73 293.2 ND ND
B 31.5 788.6 17.58 440 24 600
C 35.6 889 33.24 830 ND ND
D 56 1,407 33.86 846.5 12 300
E 1,020 25,502 173.2 4,330 ND ND
F 1,671 41,781.5 4,782.74 119,562.5 4,656 116,400
G 838 20,947 1.611.57 40,289.2 871.8 21,795
H 1,100 27,500 1,769.29 44,232.5 6243.5 156,087.5
ND= Non detected

Sensitivity and limit of detection of the CPEs and CMEs

Concerning the sensitivity and the limit of detection in the CPEs and CMEs, it
varies depending on the sample, support electrolyte, metal or metal mixture that is
analyzed. In the case of Pb and Cu content in real samples, detection limit
corresponds to the added standard of 100 ppb (8). On the other hand, sensitivity is
related to the slope between current dissolution peak and lead concentration (see
Table II).
TABLE II. Sensitivities of the electrodes in the determination of Pb (II)
Type of electrode Sample Sensitivity (µA/mgL-1)
F Right side superficial soil 13.26
CPE H Right side superficial brown residue 34.10
G Right side superficial pink residue 14.95
F Right side superficial soil 1.35
CME-HgC2O4 75:25 H Right side superficial brown residue 1.65
G Right side superficial pink residue 1.21
F Right side superficial soil 12.89
CME-EDTA 90:10 with covering of H Right side superficial brown residue 28.87
nafion G Right side superficial pink residue 47.14

Conclusions

CPEs and OSWSV showed to be suitable for Pb(II) detection is samples with
concentrations >100 ppb. In some samples where the concentration is <100 ppb no
signals were detected.

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 ECS Transactions, 15 (1) 527-533 (2008)

Using CMEs-HgC2O4 75:25, Pb(II) current signals were detected in all the samples.
In some cases smaller content values are observed than those obtained for CPEs,
because those samples contain other metals in equal concentration as Pb(II). This fact
creates a competition between metals for Hg sites.

In this study CMEs-HgC2O4 75:25 showed a greater sensitivity, reason why the
results obtained is nearer the reality, this as long as single a metallic species is
determined.

In the obtained results CMEs-EDTA 90:10 with nafion, there were samples that did
not show any signal because the metals are in very low concentrations. If the sample
contains several metals, with different oxidation states, or they form complexes in
solution, there were observed peaks for each case, reason why the qualitative and
quantitative analysis of studied samples can be obtained.

In the characterization of the CMEs-EDTA 90:10 with nafion, a favorable detection

was obtained with metal mixtures, reason why these electrodes turn out favorable to
make multidetections.

Sensitivity as well as detection limit of the CPEs and CMEs varies depending on the
supporting electrolyte and analyzed metal. That is to say, that lead detection depends
on chemical speciation of the electrode surface and solution.

To improve CMEs-HgC2O4 performance it is recommended to use an independent

cell to form Hg microdrops to avoid interference of electroplating processes during
the reduction pulse of the OSWSV.

Acknowledgments

CONACyT, Sociedad Mexicana de Electroquímica and Electrochemical Society and

DGEST through the project: “Utilización de técnicas electroquímica para el estudio de
sistemas redox de interés analítico y catalítico”

References

1. Comisión Nacional del Agua, Cibercita, in Comisión Nacional del Agua

(CoNaGua). Página virtual. Normas Oficiales Mexicanas,
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(2002)
2. C. Felix-Robles. Recuperación de Pb(II) en medio libre de EDTA y en
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Universidad Autónoma de Baja California, Tijuana, B.C. (2007)
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