Fuel Processing Technology 91 (2010) 1702–1709

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Fuel Processing Technology

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Determination of trace metals in naphtha by graphite furnace atomic absorption

spectrometry: Comparison between direct injection and microemulsion
pretreatment procedures
Marcio V. Reboucas a,⁎, Daniela Domingos a,b, Aline S. O. Santos a, Leilacy Sampaio a
a
Braskem S. A., Unidade de Insumos Basicos Bahia, Rua Eteno 1561, Complexo Industrial de Camacari, Bahia, 42810-000, Brazil
b
Universidade Federal da Bahia, Instituto de Química, Campus Universitário de Ondina, Rua Barão de Geremoabo, Ondina, Salvador, Bahia, 40170-290, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Naphtha is a volatile petroleum fraction containing C4–C15 hydrocarbon compounds used as feedstock for
Received 26 December 2009 petrochemical processes which are seriously affected by trace metals. Simple methods for copper, iron, lead
Received in revised form 7 July 2010 and silicon determination in naphtha using graphite furnace atomic absorption spectrometry (GFAAS) have
Accepted 7 July 2010
been developed. Two different approaches are presented: direct injection of the sample and oil-in-water
microemulsion formation using a mixture of the sample, propan-1-ol and nitric acid aqueous solution. The
Keywords:
calibration curves showed linear response for each concentration range with correlation coefficients ranging
Metals
Naphtha
from 0.9728 to 0.9998. Precision figures of 1.7–20%, reported as the relative standard deviation, were
Petroleum products calculated from at least twenty consecutive measurements of solutions containing the metal in a
Microemulsion concentration level below 100 μg L−1. The characteristic masses varied from 8.5 to 44 pg and the limit of
GFAAS detection, defined as the metal concentration that gives a response equivalent to three times the standard
ETAAS deviation of the blank (n = 10), was found to be within the range 0.01–26 μg L−1. A critical analysis is
presented by the authors emphasizing the advantages and limitations of both approaches. The proposed
procedures have been used for copper, iron, lead and silicon determination in naphtha feeds processed in
Braskem S.A. (Camacari, Bahia, Brazil).
© 2010 Elsevier B.V. All rights reserved.

1. Introduction reported when those feedstocks are cracked or used as an energy

Determination of trace elements in crude oil and petroleum
products has received considerable attention because of its relevance
for petroleum cracking and refining processes. Even trace of these
metals can cause serious damages in refineries as they can lead to
equipment corrosion, catalytic poisoning or affect the quality of final
products. Among the petroleum products, naphtha is one of the main
feedstocks for the petrochemical industry, and it is by far the most
important raw material for aromatic production. Naphtha is a
petroleum fraction containing a complex mixture of C4–C15 hydro-
carbon compounds from which important basic petrochemicals such
as ethylene, propylene, toluene and p-xylene can be obtained [1].
Catalytic reactors are usually used to produce such basic petrochem-
icals aiming at removing specific contaminants, converting other
compounds into final products or improving the overall unit yield. The
presence of some metallic species may cause severe poisoning of the
process catalysts. Other problems related to equipment corrosion and
release of these metallic contaminants to the atmosphere have been
⁎ Corresponding author. Tel.: +55 71 3413 1637; fax: +55 71 3413 2480.
E-mail address: marcio.reboucas@braskem.com.br (M.V. Reboucas).
source. Copper, iron, lead, silicon, arsenic and mercury are the most
important metal contaminants monitored by petrochemical indus-
tries due to a high probability of occurrence in petroleum [1] and
catalyst poisoning effects.
Current literature for determination of metals in naphtha with
different approaches is summarized in Table 1 [2–12]. Although
copper and iron are two of the most relevant metals to be determined
in naphtha, to the best of the author's knowledge, no method for
determination of these metals in naphtha is available in literature.
Graphite furnace atomic absorption spectrometry (GFAAS) and
inductively coupled plasma mass spectrometry (ICP-MS) are the main
analytical techniques that have been used for metal determination in
naphtha samples. Other techniques such as inductively coupled plasma
atomic emission spectrometry (ICP OES) and flame atomic absorption
spectrometry (FAAS), widely used for elemental analysis in aqueous
samples, are not sensitive enough for direct metal determination down
to ppb level in a complex matrix such as naphtha. In such cases time-
consuming preconcentration steps would be required. The main
advantage of ICP-MS is its inherent feature of providing simultaneous
metal determination with high sensitivity. Comparing with ICP-MS, the
main advantages of GFAAS are the cost of acquisition and operation,
suitability to handle complex matrices (with application of Zeeman-

0378-3820/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.07.007
Table 1
Summary of literature references on metal analysis in naphtha [2–12].

Ref. Analyte Sample Sample preparation Technique Detection limit Details

[2] V, Ni, Zn, As, Cd, Ba, Hg, Pb Condensates and naphtha Dilution with xylene ICP-MS 0.004–0.02 μg kg−1
0.004 μg kg−1 (Pb)

[3] V, Co, Ni, As, Hg, Pb Naphtha Emulsion formation with Triton X-100 ICP-MS 0.05–0.7 μg L−1
0.09 μg L−1 (Pb)

[4] Si Naphtha None GFAAS 15 μg L−1 mo = 143 pg. No use of chemical modifier.

M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709

[5] Hg Naphtha Detergentless microemulsion formation GFAAS 0.78 μg L−1 Multiple injection technique for direct
preconcentration in the graphite tube.
Pd solution used as chemical modifier. mo = 990 pg.

[6] Hg Naphtha None GFAAS 32 μg kg−1 (GFAAS) Pd solution used as chemical modifier.
AFS-TD 3.3 μg kg−1 (AFS-TD) mo = 98 pg.

[7] Mn Diesel, gasoline and naphtha Detergentless microemulsion formation GFAAS 0.3 μg L−1 (naphtha) Sample throughput 7–10 h−1. mo = 3.4 pg.
0.5 μg L−1 (gasoline) No use of chemical modifier.
0.6 μg L−1 (diesel)

[8] Ni, V Fuel oils and naphtha Emulsion formation with Triton X-100 GFAAS 2–6 μg kg−1 (naphtha) W-Ir permanent chemical modifier.
100–500 μg kg−1 (oils) mo = 15-20 pg (Ni) and 80–150 pg (V)

[9] As, Sb Naphtha Emulsion formation with Triton X-100 GFAAS 2.7 μg L−1 (As) Ir permanent chemical modifier.
2.5 μg L−1 (Sb) mo = 48.9 pg (As) and 67.7 pg (Sb)

[10] As Naphtha None GFAAS 0.5 μg L−1 mo = 35 pg Pd solution used as chemical modifier.
−1
[11] As Petroleum condensates and naphtha None GFAAS 0.56–1.33 μg L mo = 63.5–69.3 pg. La solution used as chemical modifier.

[12] Pb Petroleum condensates and naphtha Dilution with xylene GFAAS 0.8 μg L−1 mo = 35 pg. Pd as permanent chemical modifier.

This work Cu, Fe, Pb Naphtha None GFAAS 0.64 μg L−1 (Cu) mo = 24.8 pg (Cu), 22.8 pg (Fe) and 24.8 pg (Pb).
0.01 μg L−1 (Fe) La solution used as chemical modifier for lead.
0.26 μg L−1 (Pb)

This work Cu, Fe, Pb, Si Naphtha Detergentless microemulsion formation GFAAS 1.58 μg L−1 (Cu) mo = 15.6 pg (Cu), 8.5 pg (Fe), 29.2 pg (Pb) and 44.0 pg (Si).
2.36 μg L−1 (Fe) La solution used as chemical modifier for lead and silicon.
2.90 μg L−1 (Pb)
25.6 μg L−1 (Si)

ICP-MS: inductively coupled plasma mass spectrometry, GFAAS: graphite furnace atomic absorption spectrometry, AFS-TD: atomic fluorescence spectroscopy with thermal desorption.

1703
1704 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709

effect background correction) and high sensitivity. Indeed, due to its
high cost, the ICP-MS equipment is rarely available in industry
laboratories. Besides, regarding the complex nature of the organic
naphtha sample, the analysis with ICP-MS requires special attention to
minimize the coke formation on the sampler and skimmer cones and
avoid the instability or even the complete extinction of the plasma due
to organic vapor overloading [13]. Interferences due to polyatomic
species, formed with carbon from the organic samples and with oxygen
from the auxiliary gas, should also be prevented. In fact, Olsen et al.
found the determination of low levels of Pb or Hg in naphtha by ICP-MS
very problematic [2].
Some of the proposed procedures employing GFAAS or ICP-MS have
suggested an emulsion formation as a first sample pretreatment step.
Previous studies showed the advantage of using sample emulsification
over acid digestion and sample dilution with an organic solvent as
sample preparation procedure for the determination of metals in
petroleum product samples [3,8,14]. Most of the published works have
proposed the use of a surfactant, e.g. Triton X-100, in the emulsification
process. The procedures employed by Kumar et al. [3], Meeravali et al.
[8], and Cassela et al. [9] established the use of a magnetic stirrer for
20 min in order to obtain a stable microemulsion between naphtha and
Triton X-100. Kumar et al. [3] and Cassela et al. [9] found the
microemulsion to be stable for more than 1 h, while Meeravali et al.
[8] reported 20 and 50 min as the maximum stability time for Ni and V
determination in naphtha, respectively. Santos et al. [5] and Brandão
et al. [7] used detergentless microemulsions, by mixing appropriate
amounts of propan-1-ol, nitric acid aqueous solution and sample for Hg
and Mn determination in petroleum products, including naphtha. The
microemulsion was formed after manual shaking of the three
components without requiring any further agitation. Brandão et al. [7]
confirmed the Mn absorbance signal stability up to 18 days, which is
consistent with the 30 day-period observed by Campos et al. [15] in a
previous study for trace metal determination in gasoline.
In GFAAS methods, the use of chemical modifier may be required to
stabilize the more volatile species and prevent analyte losses during
drying and pyrolysis steps. The use of permanent chemical modification
of the graphite tube, through different coating procedures, have been
widely tested and proposed [16]. Although some improvement in
method sensitivity is commonly observed, such approach has limited
application in a routine quality control laboratory. The permanent
impregnation of the graphite tube implies this chemical modification is
suitable for all metals and matrices. If such assumption cannot be
confirmed, each application would require a different tube with specific
pretreatment, demanding extra technician handling and therefore
reducing productivity. Besides, a specific quality control routine must
be established on the modifier coating to ensure the maintenance of
sensitivity of the method within the acceptable range during the whole
tube lifetime. Finally, the employment of permanent modifiers usually
requires the use of higher atomization and cleaning temperatures,
leading to some deterioration in tube lifetime.
For further improvement of GFAAS methods, multiple injection
technique has also been applied to in situ preconcentration so that
lower limits of detection could be reached, dispensing any additional
sample pretreatment steps and speeding up the analysis [10].
From what has been mentioned, simple and accurate methods for
metal determination in complex naphtha samples are needed and can
be developed using the state of the art of some analytical
methodologies. Therefore, the present work proposes the use of a
widely available analytical technique (GFAAS) for development of the
methods based on direct sample analysis and detergentless micro-
emulsion formation. Simple and sensitive methods for trace metal
determination were obtained without the use of permanent modifiers
and low-stability detergent solutions. A critical comparative analysis
between the two approaches has also been presented, providing a
more practical rather than academic point of view.
2. Experimental
2.1. Instrumentation
A Varian SpectrAA 220Z (Australia) Zeeman atomic absorption
spectrophotometer equipped with a GTA 110 model graphite tube
atomizer, a PSD 100 model autosampler and Varian hollow cathode
lamps (Cu 327.4 nm, Fe 248.3 nm, Pb 283.3 nm, and Si 251.6 nm)
were used for all the measurements. The device was set up according
to the manufacturer's instructions and run in the single element
mode. Pyrolytic graphite-coated tubes with a center-fixed platform
(Varian, PN: 63-100026-00) were used. Argon 99.996% and Nitrogen
99.996% (White Martins, São Paulo, Brazil) were employed as a purge
and protective gas, as mentioned later on. Further details on
operational conditions are presented in Table 2.
2.2. Reagents and solutions
All reagents were of analytical grade quality and freshly distilled
and deionized water (electrical resistivity of 18.0 MΩ cm−1) was used
when necessary.
The working standard solutions of each metal were prepared by
appropriate stepwise dilution of a 1000 mg L−1 (Cu, Pb, Fe: Merck,
Darmstadt, Germany; Si: Conostan Oil Analysis Standards, Ponca City,
USA) stock standard solution to the required μg L−1 levels just before use.
A 99.99%m/m silicone (polydimethylsiloxane) fluid (PMX-200, Dow
Corning Corporation) was also used as standard in the recovery test.

Table 2
Operational conditions for direct injection and microemulsion methods.

Operational condition Direct injection methods Microemulsion methods

Copper Iron Lead Copper Iron Lead Silicon

Sample pretreatment None None None Microemulsion Microemulsion Microemulsion Microemulsion

Purge gas Argon Argon Argon Argon Argon Argon Nitrogen
Measurement mode Peak area Peak area Peak area Peak area Peak area Peak area Peak area
Wavelength (nm) 327.4 248.3 283.3 327.4 248.3 283.3 251.6
Slit Width (nm) 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Lamp current (mA) 10 10 10 10 10 10 10
Total volume (μL) 40 40 45 30 50 45 45
Sample volume (μL) 40 40 40 30 50 40 40
Modifier volume (μL) – – 5 – – 5 5
Modifier solution
(200 mg L− 1 La in 0.1% v/v HNO3) No No Yes No No Yes Yes
Number of multiple injections 2 1 2 1 1 1 1
Modifier mode – – Co-inject – – Co-inject Co-inject
Pre last dry step 5 – 5 – – – –
Injection rate 1 1 1 1 1 1 1
 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709 1705

Table 3 In the direct injection method, the pure sample was placed in the
Graphite furnace temperature programs for direct injection methods. autosampler vial right before the analysis, without any pretreatment. In
Cycle Copper Iron Lead Purge gas the microemulsion method, an aliquot of 3.0 mL of sample was placed in
flow 10 mL volumetric flasks and 1.0 mL of propan-1-ol and 600 μL of 0.1% v/
T (°C) Time (s) T (°C) Time (s) T (°C) Time (s)
(L min−1) v HNO3 were added. Then, the volumes were made up with propan-1-ol
Drying 50 2.0 50 2.0 50 2.0 3.0 and the mixtures were vigorously manually shaken. One-phase
90 5.0 90 5.0 90 5.0 3.0 transparent and stable microemulsion was obtained. Blank solutions
115 15.0 115 15.0 115 15.0 3.0
were prepared with a xylene mixture replacing the sample. All
122 25.0 122 25.0 122 25.0 3.0
40 6.0 180 15.0 40 6.0 3.0 analytical solutions used organometallic standards and were prepared
180 15.0 180 20.0 3.0 in the same way as described above in the microemulsion methods and
Pyrolysis 1000 5.0 850 5.0 500 5.0 3.0 by solubilization with the xylene solvent in the direct injection methods.
1000 40.0 850 20.0 500 20.0 3.0 In the case of direct injection method, the standard must be prepared
1000 2.0 850 2.0 500 2.0 0
and placed in the vial right before analysis, which must be performed
Atomization 2300 0.6 2500 0.9 2000 4.8 0
2300 2.0 2500 2.0 2000 2.0 0 within 40 min to avoid errors due to analyte decay, as it will be discussed
2300 1.3 2500 0.5 2000 1.8 3.0 later in this paper.
Cleaning / 2600 1.0 40 21.3 50 19.0 3.0 The naphtha or microemulsioned naphtha sample was injected
cooling 40 21.1 3.0
(30–50 μL) at a rate of ca. 2.3 μL s−1 into the graphite tube. When
Cycle time 3.23 2.93 2.13 multiple injections technique was applied, analyte preconcentration
(min) took place before pyrolysis and atomization steps. The sample aliquots
were introduced in the tube and the temperature was raised,
according to the appropriate temperature program presented in
Lanthanum oxide (La2O3) supplied by Merck (Darmstadt, Germany) Tables 3 and 4. Whenever the modifier was used, an aliquot of the
was used to prepare the 200 mg L−1 La modifier solution in 0.1% v/v solution was co-injected with the sample. After the temperature
HNO3. The HNO3 solution was of ultrapure grade, prepared by diluting program was completed the total amount of metal was determined
concentrated suprapure nitric acid, supplied by Merck (Darmstadt, from the integrated absorbance signal. It is worthy to point out that
Germany). the calculations using peak heights exhibited worse data precision, in
Propan-1-ol (Merck, Darmstadt, Germany) was used as co-solvent spite of a slightly better sensitivity.
and Braskem internal product known as mixed xylenes was used as the
organic blank sample. The typical mixed xylene composition is 50%m/m 3. Results and discussion
ethyl benzene, 25%m/m m-xylene, 13%m/m p-xylene, 8%m/m o-xylene
and 4%m/m other aromatic compounds. 99.9%m/m ethanol (Merck, 3.1. Methods development and optimization
Darmstadt, Germany) was used for apparatus cleaning.
The procedure of preparation of the microemulsion was optimized
2.3. Samples in a previous work of our group and therefore it was maintained in
this study [14]. The microemulsion was prepared by mixing 3.0 mL of
All naphtha samples were collected into clean bottles and stored in naphtha, 1.0 mL of propan-1-ol and 600 μL of 0.1% v/v HNO3 and the
a freezer at 4 °C prior to analysis. The sampling apparatus was cleaned volume completed with propan-1-ol in 10 mL volumetric flasks. Such
by nitric acid, deionised water and ethanol washings. The samples solution was found to be transparent, homogeneous and stable for a
were collected from the plant's raw material storage tank or directly period of at least 6 h, as discussed in the following paragraph. This
from carrier ship tanks. Typically, the collected samples presented time period is longer than the time required to complete the entire
distillation curves ranging from 30 to 200 °C and specific gravity analytical procedure.
values around 0.70. Studies on absorbance signal stability of the metal standards were
performed and are presented in Fig. 1. The metal standards were
2.4. General analytical procedure prepared in xylene solvent and as microemulsion solutions, except for
silicon which was only prepared as a microemulsion. The absorbance
The analysis was performed by both methods in a quite similar signal of the metal standard in xylene was followed until a drop of at
approach, although different sample preparation steps were applied. least 50% of the initial signal was observed. For comparison, the metal

Table 4
Graphite furnace temperature programs for microemulsions methods.

Cycle Copper Iron Lead Silicon Purge gas flow

(L.min−1)
T (°C) Time (s) T (°C) Time (s) T (°C) Time (s) T (°C) Time (s)

Drying 40 2.0 40 2.0 40 2.0 40 2.0 3.0

90 5.0 90 5.0 90 5.0 90 8.0 3.0
115 15.0 115 10.0 115 10.0 115 12.0 3.0
122 10.0 122 10.0 122 10.0 122 12.0 3.0
200 10.0 200 5.0 200 5.0 180 5.0 3.0
Pyrolysis 900 5.0 800 5.0 500 5.0 500 5.0 3.0
900 10.0 800 10.0 500 10.0 500 5.0 3.0
900 2.0 800 2.0 500 2.0 500 1.0 0
Atomization 2300 0.7 2400 0.9 2000 0.7 2850 1.0 0
2300 2.0 2400 2.0 2000 2.0 2850 2.5 0
2300 1.0 2400 1.0 2000 1.0 3.0
Cleaning /cooling 2600 3.0 2700 2.0 2400 2.0 2850 3.0 3.0

Cycle time (min) 1.10 0.92 0.91 0.96

1706 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709
Fig. 1. Absorbance signals of 50 μg L−1 metal standards prepared in xylene solvent and
as a microemulsion (shown as the average of duplicates).
standard in microemulsion was then monitored in a similar period of
time as the respective standard prepared in xylene. The maximum
RSD defined by Horwitz (16.7%) for the 50 μg L−1 concentration level
used for all standards was established as a criterion for evaluation of
signal stability [17]. From Fig. 1, we can observe a fast and significative
drop in the analytical signal for all metal standards in xylene solvent.
A signal drop beyond the Horwitz limits was observed after
approximately 40, 50 and 60 min for iron, lead and copper,
respectively. After only 2 h the iron and lead signals were less than
50% of the original signal, while a similar drop for the copper standard
was observed after 5 h. On the other hand, a good signal stability
performance was observed for all metal standards prepared as
microemulsion solutions. Iron and lead showed the best performance.
Some signal variability was noticed on silicon, but probably more
related to the poorer precision of such determination. A slight
decrease on copper signal was also observed after 6 h, but it could
be related to the graphite tube deterioration since more than 250
firings were achieved at this point. Therefore, whenever the direct
injection method was used, immediate analysis after preparation of
the metal standard in xylene was performed. It is worth emphasizing
the signal drop observed for metal standards in xylene does not apply
to the samples, since the metals present in the samples are stabilized
as naturally-occurring organometallic species.
The GFAAS temperature programs were developed and optimized
from methods previously used in routine analyses and based on the large
experience of this research team in petroleum products analyses. Key
parameters such as pyrolysis and atomization temperatures were
optimized for each analyte, following the univariate and classical
approach. Firstly, the atomization temperature was kept high enough
to guarantee a significative absorbance signal, based on manufacturer's
manual and literature. The pyrolysis temperature was then randomly
and increasingly varied reaching temperatures until no significative
analyte signal was observed. The minimum pyrolysis temperature tested
was 300 °C to ensure a suitable sample ashing. The atomization
temperature was then randomly varied while setting the pyrolysis
temperature at the optimum condition, i.e. as high as possible to improve
sample matrix removal without analyte loss. The optimized pyrolysis
and atomization temperatures for each metal and method are shown in
Tables 3 and 4. Besides pyrolysis and atomization temperatures, the
drying step proved to be a quite critical step in the temperature program,
with noticeable influence on data repeatability. Naphtha composition is
quite complex and comprises a mixture of both light and heavy
compounds, which demands a very careful drying program optimization
to avoid both insufficient solvent evaporation and analyte losses. In
addition, whenever the multiple injection approach was used, a cool
down step (to 40 °C) was included to ensure the next aliquot would be
delivered to the tube in a lower temperature, improving precision and
atomization efficiency. Finally, for direct injection methods an additional
and long cleaning step was included to ensure complete removal of
sample and analyte residues and therefore minimize any memory effect.
In order to achieve the minimum acceptable limits of detection,
the technique of in situ preconcentration by multiple injections was
applied. In direct injection mode, two successive injections were used
for copper and lead. Single injections were used for all microemulsion
methods, as presented in Table 2.
The use of a chemical modifier was required for lead determination in
both operation modes, due to the highly volatile nature of the analyte.
Without a modifier, the lead determination would require to be
performed at a much lower pyrolysis temperature, not sufficient for
complete matrix removal. For silicon determination, the use of a chemical
modifier was also recommended as mentioned later in this section.
Lanthanum was chosen as the chemical modifier for this application since
it is already in use in our routine for arsenic determination [10,11], and
therefore, the same modifier solution could be applied for the other
metals leading to better laboratory working flow.
It is worthy to mention that the microemulsion method for
silicon was subjected to specific adjustments. Recent results from
interlaboratory studies conducted by and with some laboratories in
Brazil showed some degree of divergence on silicon results. Besides,
the possibility of naphtha contamination with some volatile silicon
species demanded special care. Therefore, further improvements in
silicon determination were required and implemented during the
development of the microemulsion method. Firstly, argon was
replaced by nitrogen as purge gas since it led to some signal
enhancement, according to the experience of Amaro et al. [4]. The
use of a chemical modifier was also introduced to reduce the risk of
analyte loss, if different and more volatile silicon species than that
used in the method development appeared in the sample. Finally, the
pyrolysis temperature was reduced from the optimum temperature
previously established down to 500 °C.
A direct injection method for silicon had also been developed and
validated together with the other metals. Due to the nature of the
species present in the samples at the time the work was performed,
the pyrolysis temperature was kept at 1200 °C and there was no need
of a chemical modifier. However, as more volatile silicon species
started occurring in naphtha samples, probably related to changes in
the crude oil extraction and refining processes, this method did not
prove to be robust enough to provide accurate results. Therefore, since
the method described by Amaro and Ferreira [4] did not include a
similar optimization as performed in the microemulsion method, it
may not be able to provide accurate determination when volatile
silicon species are present in naphtha samples.
3.2. Major figures of the proposed methods
The analytical performance of each proposed method was evaluated
following standard validation procedures. Results are shown in Tables 5,
6 and 7.
The lowest detectable concentration of copper, iron and lead was
between 1 and 3 μg L−1 in microemulsion mode while concentration
levels below 0.6 μg L−1 were found in direct injection mode. Due to
blank contamination and poorer detection the silicon detection limit for
microemulsion method was much higher (26 μg L−1). Low character-
istic concentrations were obtained in most cases, confirming the
method's high sensitivity. Therefore, the limits of detection are thought
to be mainly influenced by the precision in the measurement of the
blank signal.
The linearity over the typical concentration range of 0.5 to 100 μg L−1
was demonstrated. The analytical curves were obtained from at least five
 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709 1707

Table 5
Analytical figures of merit of the direct injection methods.

Figure of merit Copper Iron Lead

Characteristic concentration or sensitivitya (μg L−1) 0.31 0.57 0.31

Limit of detectionb (μg L−1) 0.64 0.01 0.26
Limit of quantificationc (μg L−1) 1.28 0.05 0.52
Characteristic mass (pg) 24.8 22.8 24.8
Working range (μg L−1) 1.5–80 0.6–100 0.5–80
Analytical curve equation Y = 0.0144 X − 0.0042 Y = 0.0077 X + 0.0031 Y = 0.014 X + 0.0025
Correlation coefficient (r) 0.9996 0.9728 0.9995
Concentration level for precision study (μg L− 1) 16.8 17.0 4.5
Relative standard deviation—RSD (%) 2.4 16.5 5.7
Maximum acceptable Horwitz RSD (%) 16.7 16.7 23.7
a
Calculated from the analytical curve as the minimum detectable concentration for an integrated absorbance of 0.0044.
b
3sblank criterion based on 10 replicates of a sample at concentration level near blank.
c
6sblank criterion based on 10 replicates of a sample at concentration level near blank.

standards covering this range. The limits of detection and working ranges
were suitable to the process requirements all metals, as demonstrated by
sample typical results and process requirements presented in Table 8.
Precision was evaluated from 20–25 replicates of a spiked naphtha
sample for copper, lead and silicon since the naphtha samples available
at the time of the precision study were quite near or below the limit of
detection. For iron precision study a naphtha sample was used instead.
The observed Cochran coefficient and the ANOVA F-test values were
both below the critical values at the 95% confidence level. The data sets
were then assumed to be homogeneous, and the overall relative
standard deviation (RSD) was calculated. The obtained results were
found to be below the maximum acceptable RSD defined by the Horwitz
criterion at each concentration level [17].
Accuracy was assessed from spiked naphtha samples. As shown in
Table 7, good analyte recovery (86–114%) was obtained. Sample
spiking was used for accuracy assessment since a standard reference
material is not available in a suitable matrix such as naphtha, xylene,
toluene or light oil at the working concentration range. Additionally,
there is no standard method (e.g. ASTM) available for comparison for
copper, iron, lead and silicon determination in naphtha at this
concentration level. The silicon recovery tests (at 30 and 60 μg L−1)
were performed with a silicone standard, since it is the most probable

Table 6
Analytical figures of merit of the microemulsion methods.

Figure of merit Copper Iron Lead Silicon

Characteristic concentration or sensitivitya (μg L− 1) 0.52 0.17 0.73 1.10

Limit of detectionb,c (μg L− 1) 1.58 2.36 2.90 25.6
Limit of quantificationd,c (μg L− 1) 3.15 4.72 5.80 51.2
Characteristic mass (pg) 15.6 8.5 29.2 44.0
Working range (μg L− 1) 1.6–100 2.4–40 2.9–150 26–200
Analytical curve equation Y = 0.0085 X − 0.0108 Y = 0.0265 X + 0.0192 Y = 0.0060 X − 0.0025 Y = 0.0042 X + 0.0589
Correlation coefficient (r) 0.9988 0.9970 0.9998 0.9949
Concentration level for precision study (μg L− 1) 22.2 8.6 12.7 86.0
Relative standard deviation (%) 1.7 20.4 3.0 14.7
Maximum acceptable Horwitz RSD (%) 16.7 21.3 16.7 15.1
a
calculated from the analytical curve as the minimum detectable concentration for an integrated absorbance of 0.0044.
b
3sblank criterion based on 10 replicates of a sample at concentration level near blank.
c
calculated considering the dilution factor (3.33).
d
6sblank criterion based on 10 replicates of a sample at concentration level near blank.

Table 7
Metals concentration obtained in spiked naphtha samples.

Metal Sample Direct injection method Microemulsion method

Added (μg L− 1) Founda (μg L− 1) Recovery (%) Added (μg L− 1) Founda (μg L− 1) Recovery (%)

Copper Naphtha 1 10 10.23 ± 0.46 102 10 10.12 ± 0.25 101

Naphtha 2 15 15.01 ± 0.37 100 20 21.17 ± 0.61 106
Naphtha 3 – – – 30 31.9 ± 1.1 107
Iron Naphtha 1 10 11.4 ± 1.7 114 10 9.4 ± 2.6 94
Naphtha 2 15 14.55 ± 2.1 97 16 15.3 ± 1.1 96
Naphtha 3 – – – 20 17.3 ± 1.5 86
Lead Naphtha 1 10 11.21 ± 0.93 112 10 10.21 ± 0.64 102
Naphtha 2 20 17.6 ± 1.4 88 20 20.2 ± 1.1 101
Naphtha 3 – – – 30 29.13 ± 0.91 97
Silicon Naphtha 1 – – – 28b 27.0 ± 4.2 96
Naphtha 2 – – – 30c 33.4 ± 2.8 111
Naphtha 3 – – – 60c 64.9 ± 3.7 108
a
Confidence interval estimated from one standard deviation of three replicates.
b
Conostan standard.
c
Silicone standard.
1708 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709

Table 8
Metal determination in naphtha samples.

Sample or item Copper (μg L− 1)a Iron (μg L− 1)a Lead (μg L− 1)a Silicon (μg L− 1)a

Direct injection Microemulsion Direct injection Microemulsion Direct injection Microemulsion Microemulsion

Naphtha 1 bLOD b LOD 12.3 ± 3.7 15.4 ± 4.6 1.32 ± 0.25 b LOD ND
Naphtha 2 11.4 ± 1.2 9.71 ± 0.72 10.5 ± 4.1 8.1 ± 2.0 3.50 ± 0.18 4.11 ± 0.37c ND
Naphtha 3 29.71 ± 0.95 31.5 ± 2.3 bLOD b LOD 8.45 ± 0.57 7.71 ± 0.48 ND
Naphtha 4 5.77 ± 0.45 6.45 ± 0.31 47.3 ± 1.2 40.7 ± 2.3 5.31 ± 0.43 5.97 ± 0.38 ND
Naphtha 5 11.73 ± 0.88 15.73 ± 0.72 21.91 ± 0.99 18.8 ± 1.2 3.10 ± 0.51 2.45 ± 0.27 ND
Naphtha 6 ND ND ND ND ND ND b LOD
Naphtha 7 ND ND ND ND ND ND 267 ± 31
Naphtha 8 ND ND ND ND ND ND 116 ± 11
Naphtha 9 ND ND ND ND ND ND 2290 ± 91
Naphtha 10 ND ND ND ND ND ND 93.4 ± 9.2

Typical rangeb 2–20 5–60 b 2–10 5–300

Specification or maximum recommended 10 300 20 100
concentration
a
Confidence interval estimated from the one standard deviation of three replicates.
b
Obtained from a 5-month period and ca. 50 samples.
c
Concentration between limit of detection and quantification.

source of silicon contamination of naphtha (once silicone is used as an
anti-foaming additive in petroleum exploration).
3.3. Methods comparison
Both approaches, using direct injection and microemulsion forma-
tion, proved to be valid and fit for the analytical purpose. However,
singular differences and features have been observed.
The procedures based on direct injection are less prone to
contamination since no reagent is added, except the blank solvent
used for standards preparation and the chemical modifier solution used
for lead analysis. Besides, lower limits of detection could be achieved
since no sample dilution is required.
On the other hand, the main advantages of using microemulsion
procedures rely on the higher sample throughput and sample/standards
stability. Since a much lower organic load is used, the microemulsion
GFAAS program is at least 58% faster than the respective direct injection
program. As a result of using shorter furnace programs we can also
observe an improvement in the graphite tube lifetime, leading to
reduction of the overall analysis cost. As already pointed out by Campos
et al. [15], the analyte stabilization by microemulsion formation is
remarkable. Consequently, both standards and samples can be prepared
and simultaneously placed in the autosampler and left for analysis. Such
procedure cannot be applied in the direct injection mode because of the
evaporative losses of the samples and the instability of metal standards
in xylene. If the volatile naphtha sample is placed in the autosampler
from the very beginning of the analysis run, a significative amount of the
sample is evaporated from the vial, as already pointed out elsewhere
[8,9]. The evaporative losses can be minimized by dilution with xylene,
but this approach leads to deterioration of the limits of detection and
quantification. Besides, as already discussed from the results shown in
Fig. 1, accurate results from direct injection methods can only be
obtained if the standard is analyzed immediately after preparation, due
to a significant drop in the absorbance signal after 40–60 min. In
microemulsion methods, the same standard solution can be used for at
least 6 h without any significative impact in sensitivity and accuracy.
As one would expect, since no dilution step is required in the direct
injection approach, lower limits of detection and quantification were
obtained compared to the microemulsion methods. On the other hand,
lower characteristic masses, i.e. higher sensitivity, for copper and iron
were achieved. Such apparent contradiction may be better understood
through the evaluation of other parameters such as characteristic
concentration and sample volume. Although the characteristic concen-
trations were in the same order of magnitude in both modes, the total
sample volumes used in direct injection mode were much higher, except
for iron, leading to higher characteristic masses. The application of simpler
and faster temperature programs in microemulsion methods, due to less
organic sample content and total sample volume (no multiple injections),
may also lead to less analyte losses and therefore better characteristic
masses figures.
The application of multiple injection technique was required to
achieve low limits of detection but was also applied to ensure suitable
measurement repeatability. In some cases, single injection would lead
to lower absorbance signals and poorer precision, since the direct
injection of pure naphtha samples would require a more elaborated
and long temperature program even when a single aliquot was
delivered into the graphite tube. The use of multiple injections was
not introduced in the microemulsion mode so that the advantages of
using faster methods were retained. However, it is known this is a
straightforward approach that can be applied to improve the
sensitivity and achieve lower limits of detection, if required.
Finally, further improvements in the limits of detection of the
microemulsion methods can be achieved using lower dilution factors,
i.e. using higher sample volumes in the microemulsion formation.
The slopes of the silicon standard addition curves were not significantly
different when sample volumes of 3 mL (analytical curve equation:
Y=0.0048x+0.291) or 5 mL (analytical curve equation: Y=0.0045x+
0.113) were used. Similar behavior was observed for copper, iron and lead.
3.4. Analytical application
Ten naphtha samples taken from different lots were analyzed for
copper, iron, lead and silicon under the recommended analytical settings
described in Tables 2–4. The results are shown in Table 8. The samples
results were above the limits of detection, except for one determination
of each metal. One could suggest the direct injection method would be
more suitable for lead determination, since quite low levels of this
contaminant are usually observed in naphtha samples. However, the
limit of detection of the microemulsion method for lead is almost ten
times below the required process specification, ensuring its fitness for
this analytical purpose. Finally, the concentration level of silicon in some
samples was quite high and therefore a proper dilution with blank xylene
solution was used for these samples before microemulsion formation.
4. Conclusions
Two sets of methods for trace metal determination in naphtha
samples with and without sample microemulsion formation were
developed using graphite furnace atomic absorption spectrometry.
Successful techniques of in situ preconcentration with multiple
 M.V. Reboucas et al. / Fuel Processing Technology 91 (2010) 1702–1709
injections and chemical modification by solution co-injection were used
whenever necessary. Both modes are simple and do not require the
sample to be subjected to any drastic or time-consuming pretreatment,
such as concentrated acids heating or microwave digestion. The
detergentless microemulsion methods showed singular advantages
over the direct injection methods and therefore have been used for
routine analyses in Bahia Basic Petrochemicals Unit Braskem Laboratory
(Camacari, Bahia, Brazil). The direct injection methods were kept as
backup methods, when lower detection limits were required or in case of
suspect of reagents contamination.
The analytical methods were developed using the more widely
available GFAAS analytical technique, instead of ICP-MS. In addition, the
chemical modifier was applied as a solution, instead of the commonly
used and routine-troublesome permanent modifier approach. Finally, the
use of detergentless microemulsion provided the long-stability standard
solution required for accurate and routine-friendly methodology.
Acknowledgements
The authors are grateful to the Brazilian research funding agency
CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico),
Braskem S. A. for supplying technical resources required for this work
and Ann Marie Moreira for the final manuscript revision.
References
[1] S.C. Pandey, D.K. Ralli, A.K. Saxena, W.K. Alamkhan, Physicochemical character-
ization and applications of naphtha, J. Sci. Ind. Res. India 63 (2004) 276–282.
[2] S.D. Olsen, S. Westerlund, R.G. Visser, Analysis of metals in condensates and
naphtha by inductively coupled plasma mass spectrometry, Analyst 122 (1997)
1229–1234.
[3] S.J. Kumar, S. Gangdharran, Determination of trace elements in naphtha by inductively
coupled plasma mass spectrometry using water-in-oil emulsions, J. Anal. At. Spectrom.
14 (1999) 967–971.
[4] J.A.A. Amaro, S.L.C. Ferreira, Application of factorial design and Doehlert matrix in the
optimisation of instrumental parameters for direct determination of silicon in
naphtha using graphite furnace atomic absorption spectrometry, J. Anal. At. Spectrom.
19 (2004) 1–5.
1709
[5] W.N.L. Santos, F.S. Dias, M.S. Fernandes, M.V. Reboucas, M.G. Pereira, V.A. Lemos, L.S.G.
Teixeira, Mercury determination in petroleum products by eletrocthermal atomic
absorption spectrometry after in situ preconcentration using multiple injections,
J. Anal. At. Spectrom. 21 (2006) 1327–1330.
[6] C. Ceccarelli, A.R. Picón, M. Paolini, E.D. Greaves, Total mercury determination in
naphthas by either atomic fluorescence or absorption spectroscopy, Petrol. Sci.
Technol. 18 (2000) 1055–1075.
[7] G.P. Brandão, R.C. Campos, E.V.R. Castro, Determination of manganese in diesel,
gasoline and naphtha by graphite furnace atomic absorption spectrometry using
microemulsion medium for sample stabilization, Spectrochim. Acta Part B 63
(2008) 880–884.
[8] N.N. Meeravali, S.J. Kumar, The utility of a W-Ir permanent chemical modifier for
the determination of Ni and V in emulsified fuel oils and naphtha by transverse
heated electrocthermal atomic absorption spectrometer, J. Anal. At. Spectrom. 16
(2001) 527–532.
[9] R.J. Cassela, B.A.R.S. Barbosa, R.E. Santelli, A.T. Rangel, Direct determination of
arsenic and antimony in naphtha by electrothermal atomic absorption spectrom-
etry with microemulsion sample introduction and iridium permanent modifier,
Anal. Bioanal. Chem. 379 (2004) 66–71.
[10] M.V. Reboucas, S.L.C. Ferreira, B. Barros Neto, Arsenic determination in naphtha by
electrothermal atomic absorption spectrometry after preconcentration using
multiple injections, J. Anal. At. Spectrom. 18 (2003) 1267–1273.
[11] M.V. Reboucas, S.L.C. Ferreira, B. Barros Neto, Behaviour of chemical modifiers in
the determination of arsenic by electrothermal atomic absorption spectrometry in
petroleum products, Talanta 67 (2005) 195–204.
[12] F.S. Dias, W.N.L. Santos, A.C.S. Costa, B. Welz, M.G.R. Vale, S.L.C. Ferreira,
Application of multivariate techniques for optimization of direct method for
determination of lead in naphtha and petroleum condensate by electrothermal
atomic absorption spectrometry, Microchim Acta 158 (2007) 321–326.
[13] E. Bjorn, W. Frech, Introduction of high carbon content solvents into inductively
coupled plasma mass spectrometry by a direct injection high efficiency nebuliser,
Anal. Bioanal. Chem. 376 (2003) 274–278.
[14] W.N.L. Santos, F.S. Dias, M.S. Fernandes, M.V. Reboucas, M.G.R. Vale, B. Welz, S.L.C.
Ferreira, Application of multivariate technique in method development for the
direct determination of copper in petroleum condensate using graphite furnace
atomic absorption spectrometry, J. Anal. At. Spectrom. 20 (2005) 127–129.
[15] R.C. Campos, H.R. Santos, P. Grinberg, Determination of copper, iron, lead and
nickel in gasoline by electrothermal atomic absorption spectrometry using three-
component solutions, Spectrochim. Acta Part B 57 (2002) 15–28.
[16] A.B. Volynsky, Comparative efficacy of platinum group metal modifiers in electrother-
mal atomic absorption spectrometry, Spectrochim. Acta Part B 59 (2004) 1799–1821.
[17] W. Horwitz, Evaluation of analytical methods used for regulation of foods and
drugs, Anal. Chem. 54 (1982) 67A–76A.