Spectrochimica Acta Part B 98 (2014) 5459

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Spectrochimica Acta Part B

journal homepage: www.elsevier.com/locate/sab

Determination of trace Cd, Cu, Fe, Pb and Zn in diesel and gasoline by

inductively coupled plasma mass spectrometry after sample clean up
with hollow ber solid phase microextraction system
Philiswa N. Nomngongo, J. Catherine Ngila
Department of Applied Chemistry, Faculty of Science, University of Johannesburg, Doornfotein Campus, P.O. box 17011, Johannesburg 2028, South Africa

a r t i c l e

i n f o

Article history:
Received 4 November 2013
Accepted 6 June 2014
Available online 13 June 2014
Keywords:
Hollow ber-solid phase microextraction
Multivariate optimization
Trace metals
Diesel
Gasoline

a b s t r a c t
This study reports a simple and efcient method for the determination of trace Cd, Cu, Fe, Pb and Zn in diesel and
gasoline samples by inductively coupled plasma mass spectrometry after matrix removal and analyte preconcentration using hollow ber-solid phase microextraction (HFSPME). The optimization of HF-SPME
procedure was carried out using two-level full factorial and central composite designs. Four factors (variables),
that are, sample solution pH, acceptor phase amount, extraction time and eluent concentration were optimized.
Under the optimized experimental conditions, the precision was 3% (C = 10 g L1, n = 15), limits of detection
and quantication ranged from 0.1 to 0.3 g L1 and 0.30.9 g L1, respectively, and the maximum
preconcentration factor was 30. The HF-SPME method was applied for the determination of trace metals in
real gasoline and diesel samples.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The presence of metal ions in liquid fuels is undesirable, not only
because of the possibility of damaging vehicle parts, catalytic poisoning
and poor fuel performance, but also because of the pollution caused by
the release of toxic metals into the atmosphere during fuel combustion
[13]. In addition, considering the large number of vehicles circulating
in metropolitan areas, toxic metal ions such as Pb, has a potential of
presenting severe public health issues [35]. Taking into consideration
the aforementioned aspects, accurate determination and knowledge of
metal ions in liquid fuels is necessary to guarantee the quality of the
product [6].
The concentrations of metal ions in liquid fuel samples such as diesel
and gasoline are usually at trace levels which poses problems of detection limits. For this reason, sensitive, reliable and rapid techniques for
accurate determination of trace metals in liquid fuels are required [7].
A number of analytical methods based on spectrometric techniques
have been used for the quantication of metal ions in gasoline and
diesel samples [13,58]. Among others, electrothermal atomic absorption spectrometry (ETAAS) has been used for the quantication of metal
ions in gasoline. This is because it can tolerate samples with high organic
loading and can allow relatively good sensitivity and low detection
limits [3,9]. Due to the success of the technique, procedures based on
metal determination using ETAAS are frequently reported in the literature [10,11]. However, the technique is not employed for routine
Corresponding author. Tel.: +27 115596196; fax: +27 11559 6425.
E-mail address: jcngila@uj.ac.za (J.C. Ngila).

http://dx.doi.org/10.1016/j.sab.2014.06.001
0584-8547/ 2014 Elsevier B.V. All rights reserved.

analysis because of its low sample throughput when compared to

plasma-based methods [3]. As an alternative, inductively coupled
plasma based techniques have been used for routine analysis of trace
elements due their multielement capabilities and sensitivity. However,
with ICP-based techniques especially ICPMS, the analysis of liquid
fuels requires special attention to minimize the coke formation on the
cones (skimmer and sampler) and avoid the instability or even the complete extinction of the plasma due to organic vapor overloading [12,13].
Furthermore, polyatomic interferences caused by carbonargon species
could limit the quantication of Fe, Cu and Zn [13]. In order to address
this issue, electrothermal vaporization (ETV) coupled to ICPMS (that
is, ETVICPMS) has been reported in the literature [6,7,14,15]. The
advantages and disadvantages of using ETV as a sample introduction
system are reported by Saint'Pierre et al. [7] and Wang et al. [16],
respectively. In order to address this challenge with ETV, an accurate
and reliable analytical procedure based on simultaneous separation
and preconcentration of analytes prior to analysis in fuel samples, is
required. The advantage of using preconcentration procedures prior to
spectrometric techniques is that they provide matrix elimination,
reduce matrix effects and improve the detection limits of the analytical
techniques.
In view of the challenges associated with sample preparation when
using ETAAS and plasma based techniques, the current study strives to
address the problems of trace level determination, matrix interferences
and the limitations of direct analysis due to the physical properties
of the fuel sample. The properties include volatility, low viscosity,
corrosivity and immiscibility with water. Matrix elimination and
preconcentration procedures for the determination of trace elements

P.N. Nomngongo, J.C. Ngila / Spectrochimica Acta Part B 98 (2014) 5459

in fuel matrices, including diesel, biodiesel, diesel-like fuel, ethanol and

gasoline, are reported in the literature [1725]. Recently, sample pretreatment methods based on solid phase extraction (SPE) of Cd, Cu,
Fe, Mo, Pb, Sb, V and Zn in gasoline samples prior to inductively coupled
plasma optical emission spectrometric (ICPOES) determination, have
been successfully developed [26,27]. Despite the efforts to address
simultaneous separation and enrichment of trace elements in different
fuel matrices prior to their determination, there are still gaps in the
scientic literature [27].
The advent of hollow ber Solid-phase micro-extraction (HF-SPME)
technique has revolutionized trace metal preconcentration strategies
[2831]. This is because it integrates sampling, extraction and
preconcentration into a single step, and inherits the advantages of
both the solid phase microextraction (SPME) and membrane separation
[2932]. In addition, the advantages of HF-SPME include low cost,
simple operation, rapid, high selectivity, use of small sample/reagent
volumes, use of different sorbent/coating materials and it is easily automated [28]. Due to these advantages, HF-SPME has been widely used for
separation and enrichment of trace metal in different sample matrices
by either ofine or on-line extraction mode combined with different analytical detection techniques [2831]. The HF-SPME technique is based
on the establishment of an equilibrium between the analyte of interest
in the sample and ber coated stationary phase (which can be a liquid
polymer, a solid sorbent, or a combination of both) [28,32]. The stationary phase plays a signicant role in extraction and preconcentration of
target analytes [28]. For this reason, a number of extraction/coating materials have been developed. These include titania [29], alumina [30],
grapheme oxide-silica [28] and solgel combined with multi-walled
carbon nanotubes [31], among others.
This study explored the use of hollow ber solid phase microextraction (HF-SPME) technique using a hollow ber-supported sol
gel combined with Dowex 50W-x8 for extraction and preconcentration
of trace Cd, Cu, Fe, Pb and Zn in diesel and gasoline samples. The combination of solgel and cation exchange resin provides a versatile
preconcentration and matrix separation technique for the metal ion
analysis. The advantages of incorporating cation exchange inside the hollow ber membrane, include the possibility of ber regeneration and
high preconcentration factor. We carried out the HF-SPME system in a
batch (off-line) mode. However, the latter involves time-consuming
steps. To overcome this problem, multivariate techniques were used
for the optimization of factors inuencing preconcentration metal ions
prior to determination.

55

optimized daily and operated as recommended by the manufacturer.

The operating conditions are presented in Table 1. Argon of 99.996%
purity (Afrox, South Africa) was used. The Accurel S6/2 polypropylene
hollow ber membrane used here was obtained from Membrana
(Wuppertal, Germany). The wall thickness of the ber was 450 m,
the internal diameter was 1800 m, and the pore size was 0.2 m.
For comparative method, metal ions were determined using a
Spectro Arcos 165 ICPOES (SPECTRO Analytical Instruments, GmbH,
Germany) equipped with Cetac ASX-520 autosampler. The operating
conditions on the ICPOES spectrometer during the measurements
were adopted from our previous work [27]. The Microwave acid digestion procedure was carried out according to the procedure reported by
Kowalewska et al. [33]. The microwave digestions were carried out in an
Ethos Start D (Milestone, Sorisole, Italy) with maximum pressure
1450 psi and maximum temperature 300 C. The Start D microwave
system is equipped with advanced reaction sensors for temperature
and pressure control, vent-and-reseal vessels, high strength rotor
body that holds up to 10 digestion vessels. The high strength rotor guaranteed complete digestion of any sample matrix, namely, organic and
inorganic refractory materials.
2.2. Reagents, solutions and real samples

2. Experimental

All reagents were of analytical grade unless otherwise stated and double distilled deionized water was used throughout the experiments. The
solgel precursor tetraethylorthosilicate (TEOS), absolute ethanol
(EtOH), 2-amino-2-hydroxynmethyl-propane-1,3-diol (TRIS), 1-octanol,
sodium hydroxide, hydrogen peroxide (H2O2), ultratrace nitric acid
(65%) and ammonium hydroxide (NH4OH) were obtained from Sigma
Aldrich (St. Loius, MO, USA). Dowex 50W-x8 cation exchange resins
(sodium form) with a mesh size of 200400, was obtained from Sigma
Aldrich. Conostan custom made multi-element oil standard used in the
experiment studies was obtained from SCP Science (Quebec, Canada).
Synthetic gasoline was prepared by mixing 91% isooctane and 9% nheptane (SigmaAldrich). Spectrascan stock solutions (1000 mg L1) of
Cd, Cu, Fe, Pb and Zn (Teknolab A/S, Drbak, Norway) were used to prepare the working solutions for HF-LPME at concentrations of 15 g L1
for each metal ion. A Spectrascan multi-element standard solution at a
concentration of 100 mg L1 was used to prepare working standard solutions for the calibration of ICPMS instrument. Gasoline (G1-93 unleaded
metal containing and G2-95 unleaded) and diesel (S and D1500 ppm S
and D250 ppm) samples from local lling stations (Westrand region,
Johannesburg, South Africa) were used for method development and
validation.

2.1. Instrumentation

2.3. Preparation of solgel and supported hollow ber membrane

A Perkin-Elmer Sciex ELAN 6000 (Perkin-Elmer SCIEX Instruments,

Concord, Canada) inductively coupled plasma mass spectrometer
(ICPMS) was used for all measurements. The ICPMS instrument was

The solgel solution was prepared by a method proposed by

Es'haghi et al. [31]. Describing the procedure briey, 640 L of TEOS,
130 L of TRIS aqueous solution (5%) as base catalyst and 500 L of

Table 1
Operational ICPMS parameters.
RF power

1100

Gas ow rates
Outer
Intermediate
Carrier
Resolution
Sweeps per reading
Dwell time
Readings per replicate
Replicates
Auto lens
Isotopes

15 L min1
1.2 L min1
0.95 L min1
0.7 a.m.u. (10% of the peak height)
1
25 ms
100
3
On
111
Cd, 63Cu, 56Fe, 208Pb, 66Zn 45Sc (ISa), 72Ge (IS), 115In (IS), 209Bi (IS)

IS = internal standard.

56

P.N. Nomngongo, J.C. Ngila / Spectrochimica Acta Part B 98 (2014) 5459

EtOH were added into a Teon beaker. The mixture stirred and heated
at 50 C for 23 h until turbidity appeared. Thereafter, 20 L of concentrated NH4OH was added into the mixture. The latter was then centrifuged at 1200 rpm for 5 min. The sol was removed and the gel was
washed twice, in succession, with double distilled deionized water
and once with ethanol to remove the un-reacted reactant and excess
catalyst. The resulting gel was transferred to a clean vial and dispersed
in 1 mL 1-octanol/ethanol (1:1 v/v) mixture and then used for metal extraction study.
The hollow ber was cut into segments approximately 4 cm long
with one end of the ber heat-sealed. The ber segments were cleaned
with acetone to remove impurities and directly dried in air, followed by
submerging it in 1-octanol solvent for a few seconds to ll the membrane pores of the hollow ber wall. Amounts (50150 mg) of Dowex
50W-x8 resin were added to the gel which was previously dispersed
in 1 mL 1-octanol/ethanol (1:1 v/v) mixture and stirred for 30 min. A
glass Pasteur pipette was used to introduce appropriate concentrations
of solgel/Dowex 50W-x8 (50150 mg mL 1) into the lumen of the
hollow ber via the remaining open end. The ber surface was washed
with water to remove excess organic solvent, dried with compressed air
and the other end of the ber heat-sealed. After this, the ber was then
ready for extraction and preconcentration of metal ions.
2.4. Extraction and preconcentration procedure
The procedure for the preparation of gasolineethanolwater
mixture was carried out according to Ozcan and Akman [34]. The
mixture was spiked with an appropriate volume of a 1.0 mg L 1
multi-element standard solution and made up to the mark with ethanol
to obtain 15 g L1 concentration of each metal ion. The mixture was
homogenized by shaking. The hollow bers were placed into the sample
solution present in plastic bottles containing 50 mL of the above mentioned model solutions. The bottles were covered and shaken at
500 rpm. During this procedure, the analytes from the sample solution
diffuse through the porous polypropylene membrane into the acceptor
phase (solgel/Dowex 50W-x8) [31]. At the end of the extraction, the
hollow ber was removed from the vial and rinsed with double distilled
deionized water then transferred into a polypropylene centrifuge vial
containing 5.0 mL of eluent solution. The analytes were eluted from
the ber with ultrasonic agitation for 5 min. The same procedure was
applied for the preparation of the blank solutions and real samples.
Between experiments, the hollow bers were washed with double
distilled deionized and stored in 1.0 M NaOH solution (this was done
in order to keep the resin in sodium form) for the next experiment.
2.5. Multivariate optimization of HF-SPME
Optimization of four variables, namely, sample pH, eluent concentration (EC), acceptor phase amount (APA) and extraction time (ET)
using multivariate analysis, was done for HF-SPME. In all experiments,
50 mL of model solution containing 15 g L 1 of each analyte were
used. Firstly, a screening of the inuential variables on the analytical response was tested by employing a two-level (24) full factorial design
with three central points (Table 2). The second step of the optimization
strategy involved the application of a response surface methodology
(RSM) based on a central composite design. The design of experiments
Table 2
Factors and levels used in 24 factorial design for the separation and preconcentration of
metal ions in fuel samples.
Variable

Low level (1)

Central point (0)

High level (+1)

pH
EC (mol L1)
APA (mg mL1)
ET (min)

4.0
1.0
50
10

6
2.5
100
25

8
4.0
150
40

was performed using Minitab 15 and Design Expert 8.0.7.1 Software

programs.
3. Results and discussion
3.1. Optimization procedure using two level full factorial design
The results of a 24 full factorial design (total of 19 experimental runs)
for HF-SPME preconcentration procedure for cadmium, copper, iron,
lead and zinc, respectively, are given in Table S1 in Appendix A. The effect of factors in the HF-SPME system was investigated by using analysis
of variance (ANOVA) considering the recovery as the analytical response. The information obtained from ANOVA presented in terms of
Pareto Charts (Fig. S1 in Appendix A)) indicated that APA, EC and ET
lead to a more pronounced improvement of the analytical response
and they required a nal optimization. Therefore, the sample pH was
xed at 7.0.
3.2. Final optimization of HF-SPME preconcentration system using a central
composite design
A central composite design matrix containing a total of 20 experiments and responses based on each of the experimental runs
(Table S2 in Appendix A), was used for nal optimization. The analysis
of variance (ANOVA) parameters of the predicted response surface quadratic model for the recoveries of Cd, Cu, Fe, Pb and Zn, were obtained.
The ANOVA data obtained were analyzed with quadratic equations
(not included) for the models to illustrate the dependence of the analytical response (% recovery) with respect to the evaluated variables.
The 3D response surface plots (Figs. S26 in Appendix A)) were used
to access the interactive relationship between independent variables
and analytical response [35]. For the interpretation of the 3D response
surface plot eluent concentration (less signicant) was kept constant
at 2.75 mol L1 while the other two variables were varied within the
experimental ranges. It was observed that for all the metal ions, the
maximum percentage recoveries of metal ions at APA 150 mg L1 and
ET 40 min, ranged from 96 to 101%. On the other hand, the minimum
recoveries were obtained at APA 50 mg mL 1 and ET 15 min. Based
on results obtained from both designs, the optimum conditions that
led to quantitative retention and elution of metal ions were as follows:
pH = 7.0, APA = 150 mg mL1, ET = 40 min and EC = 2.75 mol L1.
3.3. Regeneration studies
The regeneration of the column is one of the important parameters
in evaluating the stability of the HF-SPME supported solgel combined
with Dowex 50W-x8 resin. The recyclability of HF-SPME method was
achieved by performing adsorption and desorption repeatedly. The stability and regeneration of HF-SPME was evaluated by monitoring
changes in the recoveries of the target metal ions through retention
elution cycles. It was observed that the HF-SPME was stable up to 75
retention/elution cycles without obvious loss of its analytical performance. Therefore, the recycling of the proposed HF-SPME system is
possible.
3.4. Analytical features
Under the optimum conditions, calibration curves were constructed
for the preconcentration of target analytes according to the general procedure. In 50 mL sample, the linearity was obtained between 0.4 and
140, 0.1140, 0.5120, 0.8100 and 0.1-120 g L1 for Cd, Cu, Fe, Pb
and Zn, respectively. The sensitivity of the HF-SPME method dened
as the gradient (slope) of the calibration graph is shown in Table 3.
The highest sensitivity obtained was 106.8 cps L g1 for Zn while the
lowest was 34.0 cps L g1 for Pb. The possibility of enriching low concentrations of analytes from large volumes, the maximum applicable

P.N. Nomngongo, J.C. Ngila / Spectrochimica Acta Part B 98 (2014) 5459

57

Table 3
Analytical performance of the HF-SPME system for preconcentration of metal ions obtained under optimum conditions: standard solution composition was synthetic gasolineethanol
water.
Analyte

Cd
Cu
Fe
Pb
Zn

Linearity (g L1)

Sensitivity (cps L g1)

0.4140
0.1140
0.5120
0.8100
0.1120

Correlation coefcient

79.8
103.6
75.5
34.0
103.8

0.9965
0.9997
0.9988
0.9967
0.9989

LOD (g L1)

0.1
0.1
0.2
0.3
0.1

LOQ (g L1)

0.4
0.3
0.5
0.9
0.3

EFc (%)c

%RSD
R1a

R2b

0.4
0.7
2.8
2.5
0.6

5.3
4.8
4.5
5.9
4.8

97.8
99.3
99.8
98.3
98.6

5.2
4.8
4.5
5.8
4.7

P1 = repeatability, n = 15.
P1 = reproducibility, n = 5.
c
EC = extraction efciency (%) =
concentration.
b

CF


Ci

 100, where CF is the nal analyte concentration in the acceptor and can be obtained from experimental measurements; Ci is the initial

sample volume should be investigated [26]. It was observed that quantitative recoveries for all target metal ions were stable ( 95%) when
sample volume was 150 mL. Therefore, the highest preconcentration
factor for the proposed method was 30 with 150 mL used for further
investigations.
The limits of detection (LOD) and limits of quantication
 (LOQ) were
calculated according to IUPAC denition; that is, LOD 3Sd m and LOQ

10Sd
, respectively, where m and Sd are the slope of the respective anm
alytical curve and the standard deviation of 20 consecutive measurements of the blank signal, respectively. It should be noted that model
(synthetic) gasoline samples were used as blank solutions. The LOD
and LOQ results are presented in Table 3. It can be seen from the results
in Table 3 that the LODs obtained were relatively lower than or equal to
the typical ICPMS LODs (0.1, 0.1, 1, 0.03 and 0.2 g L1 for Cd, Cu, Fe, Pb
and Zn, respectively) for water analysis, except for Cd and Pb. It should
be noted that LOD and LOQ reported in this table are for the initial sample of the gasoline and diesel.
The precision (repeatability) of the HF-SPME method, calculated as
the relative standard deviation (RSD, n = 15), ranged from 0.4 to 2.8%
for concentration of 10 g L1 of each metal ion. The RSD ranged between 4.5% and 5.9% (n = 5) for reproducibility between ve working
days and the extraction efciencies ranged from 97.8%99.8%. It should
be noted that the supported hollow bers were newly prepared for each
day. The results obtained indicated that the proposed method has good
precision for the analysis of trace elements in the fuel samples. The time
required for preconcentration of 150 mL of sample (40 min extraction
and 5 min elution) was about 45 min. It should be noted the thermostat
shaker can handle up to 32 samples at the same time. Therefore, the
throughput sample was approximately 32 samples h1.

Table 4
Comparison of LOQ (g L1) for Cd, Cu, Fe, Pb and Zn obtained by HF-SPME with other
methods reported in the literature.
Methods

Sample

Cd

Cu

Fe

Pb

Zn

Ref.

SPE/FAAS
SPE-FAAS
SPE/XRF
SPEFAAS
SPE/EDXRF
SPE/FSaFAAS
SPE/ICPOES
ETAAS
ETAAS
ETVICPMS
ETVICPMS
HF-SPME/ICPMS

Gasoline
Ethanol fuel
Automotive gasoline
Ethanol fuel
Ethanol fuel
Gasoline
Gasoline
Gasoline
Naphta
Gasoline
Fuel alcohol
Gasoline and diesel

0.8

0.3
0.1
0.1

0.8
1.7
15
2.3
13
3.1
0.4
0.4
0.1
2.0
0.2
0.1

10
5.0
15
2.2
0.6
3.0
1.0
5.0
0.7
0.2

2.3
1.0
1.8
0.9
0.4
0.02
0.3

0.1
0.3

0.1
12
2.3
0.5

[21]
[20]
[8]
[17]
[19]
[18]
[27]
[36]
[37]
[1]
[14]
This work

0.1

SPE = solid phase extraction, FAAS = ame atomic absorption spectrometry;

ETAAS = electrothermal atomic absorption spectrometry; ICP-OES = inductively couple
plasma optical emission spectrometry; ETVICPMS = electrothermal vaporization
inductively mass spectrometry, HF-SPME = hollow ber solid phase microextraction.
a
FS = fast sequence.

3.5. Comparison with other reported methods

The LOD results using HF-SPME method compared to literature
values, are presented in Table 4. It can be seen from this Table that,
the present method showed better LOD for the studied analytes than
those reported in the literature [1,8,18121,27,36,37]. On the other
hand, LODs obtained indicated that the proposed preconcentration
method has relatively low or similar LODs when compared with reported by Ref. [14].
3.6. Effect of other metal ions on the HF-SPME procedure
Liquid fuel samples normally contain a number of metal ions that
exist naturally on the Earth's crust. Under optimum conditions, the effect of interfering ions was investigated in order to assess the applicability of the proposed HF-SPME procedure. The tolerance limit was set as
the concentration of the ion required to cause 5% error. If the presence
of an interfering ion caused a variation more than 5% in the recoveries of
metal ions, it was then considered as an interferent. All studied ions
were found not to affect the retention and recoveries of the target
analytes (Table S8 in Appendix A)). In addition, higher concentrations
of group I and II metals can be tolerated. These results suggest that
HF-SPME method can be applied for determination of trace Cd, Cu, Fe,
Pb and Zn in liquid fuel samples that contains higher concentrations of
secondary cations.
3.7. Validation and application of the HF-SPME method
Due to the lack of CRMs for liquid fuel, the accuracy of the proposed
method was veried through spike recovery experiments, by adding
20 g L1 of each metal ion to diesel and gasoline samples. In addition,
one of the main problems associated with the preconcentration and determination of trace elements in liquid fuels is the lack of knowledge
about the form of the analyte in the sample [18,38]. Therefore, the standard addition method was carried out using metalorganic and aqueous
standards. It should be noted that nitric acid was added as a part of
aqueous component in the gasolineethanolwater mixture. This was
done in order to convert different analyte organometallic species
found in real samples, into simple inorganic species [39]. This implies
that, only one metal species was involved in all analysis stages including
the pre-concentration step. The results of recoveries (Table 5) obtained
(n = 3 replicates) using either inorganic or organic standards were
greater than or equal to 95%. This means that the Cd, Cu, Fe, Pb and Zn
present in liquid fuel samples can be determined through the calibration technique using either inorganic or organic standards. Moreover,
as it can be seen in Table 5, the method has relatively good accuracy
and the recoveries were between 95% and 103%.
The HF-SPME method was applied for extraction and
preconcentration of metal ions in commercial diesel and gasoline samples collected from different lling stations in Johannesburg (Westrand
region, South Africa). For comparison (reference method), the samples

58

P.N. Nomngongo, J.C. Ngila / Spectrochimica Acta Part B 98 (2014) 5459

Table 5
Analytical results obtained in the analysis of spiked diesel sample. The concentration and recovery values are expressed as the mean standard deviation of the three replicates.
Sample

Added (g L1)

Analytes

D1

Cd

0
20
0
20
0
20
0
20
0
20
0
20
0
20
0
20
0
20
0
20

Cu
Fe
Pb
Zn
G1

Cd
Cu
Fe
Pb
Zn

Inorganic standard

Metallo-organic standard

Found (g L1)

Recovery (%)

Found (g L1)

Recovery (%)

3.1 0.5
22.9 0.8
361. 4
381 4
468 5
488 3
153 4
173 2
175 4
195 3
5.2 0.6
24.9 0.3
272 4
291 4
428 4
444 4
bLODa
19.5 0.5
157 2
176 2

99.0 1.7

99.4 2.3

98.4 2.1

98.7 3.4

101 3

98.7 1.3

98.3 2.3

99.1 3.0

97.5 1.1

97.8 2.6

3.1 0.5
22.4 1.2
361 4
379 2
468 5
488 4
153 4
172 2
175 4
195 2
5.2 0.6
24.3 1.3
272 4
292 3
424 4
443 2
bLOD
19.3 1.0
157 2
177 2

96.5 2.1

97.5 1.5

99.5 2.4

95.5 0.9

98.5 1.3

95.5 1.8

101 3

95.5 1.3

96.5 0.8

102 3

LOD = 0.3 g L1.

4. Conclusion

were digested using microwave-assisted digestion (MAD) method and

the concentrations of the analytes were determined using ICPOES.
The results obtained (Table 6) using the proposed method show low
concentration of Cd ( 10 g L1) for all the samples. Copper concentrations were high for almost all the samples except for G2 sample. The
possible sources that lead to high Cu concentration might be the car
feeding systems originating from metallic parts containing copper in
their alloy which might leach into gasoline and diesel [40]. Iron and
Zn concentrations on the other hand were higher in D1 and G1 samples.
The highest concentration of lead was observed in the D1 sample. The
results obtained indicated that Cd, Cu, Fe Pb and Zn in liquid fuels
could be quantitatively extracted and preconcentrated using HF-SPME
method before their ICPMS determination.
Using the paired student t-test to evaluate the accuracy of the method (Table 6) in the analysis of target analytes in diesel and gasoline samples using the reference method, it showed no signicant difference at
95% condence level. In addition, these the results proved that HFSPME/ICPMS analytical response (metal ion concentration) was not affect by the different species that might be present in the real samples.
Although the results from the two methods (our method against the reference method) were not signicantly different, the advantage of our
method is that it minimizes the risks of incomplete mineralization of
the organic matrix and cross-contamination. In addition, it avoids the
use of concentrated acids and signicantly reduces the laboratory
waste and analysis time (sample throughput 32 samples h 1),
which is an important aspect for routine analysis. Furthermore, ICP
MS after HF-SPME offered lower detection limits and matrix elimination
as compared to ICPOES after samples mineralization.

We have developed an ofine HF-SPME system based on bersupported solgel combined with cation exchange resin for preconcentration of trace metal ions in liquid fuel samples prior to their ICP
MS determination. The experimental conditions were optimized by
two-level factorial and central composite designs. The accuracy of the
proposed method was assessed by analysis of the spiked diesel and gasoline samples. The metal concentrations obtained were in good agreement at 95% condence level, with concentrations of in the spiked
samples. The repeatability (n = 3) and reproducibility, expressed as
relative standard deviation, were less than or equal to 3% and 6%,
respectively. The optimized method was applied for simultaneous
preconcentration of the target analytes in commercial diesel and gasoline samples.
Acknowledgments
The authors wish to thank Sasol (Grant number IF 021/11-3) and
NRF (Grant number SFH20110713000020772) for nancial assistance.
University of Johannesburg (Spectrau and Chemistry) is acknowledged
for providing ICPOES/MS and other laboratory facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.sab.2014.06.001.

Table 6
Determination of Cd, Cu, Fe, Pb and Zn (g L1) in commercial diesel (D1500 ppm S) and D250 ppm S) and gasoline (G1-93 unleaded and G2-95 unleaded) samples by proposed (HFSPME/ICPMS) and comparative method (MAD/ICPOES); n = 3, at 95% condence level.
Analytes

Cd
Cu
Fe
Pb
Zn
a

D1

D2

HF-SPME

MAD

3.0
361
468
153
175

2.9
357
470
152
175

0.5
4
5
4
1

0.9
4
6
4
1

G1

HF-SPME

MAD

7.0
486
131
60.0
50.5

7.1
485
130
60.2
51.2

bLOD = 0.3 and 0.96 g L1 for HF-SPME and MAD; ICPOES.

0.4
4
2
2.5
1.1

0.3
5
3
3.0
1.4

G2

HF-SPME

MAD

HF-SPME

MAD

5.2 0.6
273 4
424 4
bLODa
157 2

4.8 1.2
269 4
425 5
bLOD
156 2

8.1
89.4
113
61.9
59.9

7.9
90.2
113
62.1
59.3

0.3
2.7
1
1.7
1.8

0.5
2.6
2
2.0
1.5

P.N. Nomngongo, J.C. Ngila / Spectrochimica Acta Part B 98 (2014) 5459

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