Microchemical Journal 72 (2002) 1726

Flow injection spectrophotometric determination of copper in

petroleum refinery wastewaters
Ricardo J. Cassella1,*

Rio de JaneiroyRJ 20270-021,

Laboratorio
de Analise
Instrumental-CEFETEQyRJ, Rua Senador Furtado 121-125, Maracana,
Brazil
Received 8 August 2001; received in revised form 10 October 2001; accepted 21 October 2001

Abstract
This paper reports a new strategy for flow injection spectrophotometric Cu (II) determination in petroleum refinery
wastewaters, exploring its reaction with sodium diethyldithiocarbamate (DDTC), without solvent extraction step, thus
avoiding the use of harmful organic solvents. The influence of several chemical and flow variables was studied as
well as the possible interferences. Under optimized conditions, the flow system was able to process 63 samples per
hour, with a detection limit of 23 ng mly1 and a RSD of 2.1% at the 0.2 mg mly1 level. In order to attest the
accuracy of the methodology, seven samples of effluents were analyzed by the proposed method and the results were
compared with that obtained by FAAS. It was observed that the physical interferences verified in the FAAS procedure,
which only permits its use by the standard addition method, were not present in the FIA procedure. The results
obtained by FIA method were not statistically different from that obtained by FAAS-standard addition method. Also,
the analysis of three spiked samples provided recovery percentages between 93 and 103%. 2002 Elsevier Science
B.V. All rights reserved.
Keywords: Copper; Wastewaters; Petroleum refinery; Flow injection analysis

1. Introduction
Nowadays, the control and treatment of industrial effluents has become one of the most important steps of the productive process, since the
regulatory offices have been very rigorous about
this subject. This way, the development of analytical methodologies with suitable cost, velocity,
*Corresponding author. Tel.: q55-21-2569 1771, ext. 229;
fax: q55-21-2567 0283.
E-mail address: ricardoj@cefeteq.br (R.J. Cassella).
1
ricardo.cassella@uol.com.br

accuracy and precision has increased in last few

years.
Several heavy metals, as copper, may play a
double role in the environment, acting as essential
or toxic element, depending on their chemical
form and concentration w1x. Thus, various regulatory agencies, in different countries, have established rigid limits for the discharge of heavy metals
to the natural waters. In Brazil, the CONAMA
(Conselho Nacional de Meio Ambiente) limited
the concentration of copper in the final effluents
discharged in 1 mg mly1 Cu (II) w2x. In the United

0026-265X/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 6 - 2 6 5 X 0 1 . 0 0 1 5 4 - 0

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R.J. Cassella / Microchemical Journal 72 (2002) 1726

States, the EPA (Environmental Protection Agency) has also set 1 mg mly1 as the maximum
concentration of Cu (II) allowed in liquid effluents
from industries.
It is well known that sodium diethyldithiocarbamate (DDTC) and several metal ions react,
yielding sparingly water soluble metal complexes
which are easily extracted from an aqueous medium with a wide variety of non-polar organic
solvents. In the case of Cu (II), the addition of an
aqueous solution of DDTC to a slightly acidic or
alkaline solution of Cu (II) ion produces a brown
colloidal suspension of Cu(II)-DDTC which can
be extracted by chloroform or carbon tetrachloride.
This approach is classically employed in the spectrophotometric determination of copper w3x.
Some authors have avoided the extraction procedure by performing the analysis in a micellar
medium in which the complex can be adequately
solubilized, facilitating the measurement process
w46x. In this scenario San-Andres et al. developed
two methodologies w4,5x for the simultaneous spectrophotometric determination of Cu (II), Ni (II)
and Co (II) with DDTC, employing different
surfactant agents such as: hexadecyltrimethylammonium bromide (CTAB); chloride (CTAC) and
hydroxide (CTAOH) w4x; and sodium or ammonium dodecyl sulfates w5x. The same approach was
employed by Kompany-Zareh et al. w6x, which
simultaneously determined Cu (II) and Ni (II)
with DDTC in presence of sodium dodecyl sulfate.
However, in this case a partial least-square procedure was used to access data obtained from calibration solutions.
Recently, van Staden and Botha w7x developed
a procedure based on sequential injection analysis
(SIA) concepts to perform the spectrophotometric
determination of copper in plant food and water
samples with DDTC. Other research groups have
also successfully applied this reaction in aqueous
medium for copper determination in different kinds
of samples w8,9x. Also, the determination of copper
by the FIA-spectrophotometry approach is
described in the literature with different reagents
being employed w10,11x.
The goal of this work was to evaluate the
feasibility of the spectrophotometric copper determination in petroleum refinery wastewaters con-

taining large amounts of unknown organic

compounds, exploring its well known reaction with
DDTC in a flow injection system. It is important
to notice that the application of the DDTC method
for Cu (II) determination in this kind of sample is
not related in the literature. Also, the special
features of the sample makes the copper analysis
by FAAS very difficult, due to strong matrix
intereferences (phenomena observed in this work).
Another purpose of this research was to perform
this classic determination without need of liquid
liquid extraction employed to separate andyor preconcentrate the analyte. Great emphasis must be
placed on the fact that, by using the procedure
proposed here, is possible to conduct an environmentally friendly analysis with high analytical
throughput, low generation of wastes and, especially, without handling of very harmful substances
such as the organic solvents commonly used in
the liquidliquid extraction step.
2. Experimental
2.1. Apparatus
The set-up consisted of a Unicam 5675 (Cambridge, UK) visible spectrophotometer equipped
with a Hellma (Jamaica, NY, USA) standard glass
flow cell of 80-ml internal volume and 10-mm
optical path. The instrument was set at 460 nm for
all absorbance measurements; coupled to an xy

recorder from Equipamentos Cientficos

do Brasil
Paulo, Brazil)
(Curitiba, Brazil). Micronal (Sao
and Milan (Curitiba, Brazil) peristaltic pumps,
furnished with flexible Tygon tubes, were used to
propel all solutions and a home-made proportional
commutator w12x was employed to inject the samples into the system. The manifold was built up
with polypropylene tubes with 0.8 mm bore and
laboratory-made glass connections.
Flame atomic absorption measurements were
carried out in a Perkin-Elmer (Norwalk, CT, USA)
Analyst 100 spectrometer equipped with a copper
hollow cathode lamp. The instrument was operated
at optimum conditions suggested by the
manufacturer.

R.J. Cassella / Microchemical Journal 72 (2002) 1726

2.2. Reagents and solutions

All solutions were prepared with analytical
grade reagents and high purity demineralized
water, obtained in a Milli-Q (Millipore, Saint
Quentin Yvelines, France) water purification
system.
Copper (II) solutions were prepared daily by
adequate dilution of a 1000 mg ly1 Cu (II) stock
standard solution obtained by dissolution of exactly 1 g metallic copper with 20 ml of 50% vyv
HNO3 and posterior dilution to 1000 ml in a
volumetric flask.
A 0.15% (wyv) DDTC (Merck, Darmstadt,
Germany) solution was prepared by dissolving
0.15 g of sodium diethyldithiocarbamate in approximately 80 ml of water heated to 60 8C. After this,
the solution was quantitatively transferred to a
volumetric flask and the volume was made up to
100 ml.
Borate buffer solution (0.5 mol ly1 H3BO3) was
prepared by adding 15.5 g of boric acid (Vetec,
Rio de Janeiro, Brazil) to a 400-ml of water with
posterior adjust to pH 9.0 with solid KOH. Afterwards, the volume was made up to 500 ml in a
volumetric flask.
The EDTA (Merck, Darmstadt, Germany) solutions (0.4 and 0.05 mol ly1) were prepared by
dissolving a suitable mass of di-sodium reagent in
exactly 500 ml of water and adjusting the pH to
5.5 with 2 mol ly1 KOH solution.
2.3. Flow diagram
In the developed flow system (depicted in Fig.
1), the sample (S, 3.52 ml miny1) and masking
solution (R3, 0.50 ml miny1) are mixed in a 250ml coil (MC1) before the injection into the carrier
stream. (C, 3.90 ml miny1). At the same time, the
reagent solution (R1, 0.41 ml miny1) is mixed
with the buffer solution (R2, 0.10 ml miny1) also
in a 250-ml coil (MC2), yielding a stream which
merges with the carrier one. The final stream flows
to the reactor coil (RC, 125 ml) and after this,
directly to the measuring cell, positioned in the
optical path of the spectrophotometer (D, 460 nm).
During the measurement cycle, the mixture of
sample with masking solution fills the sample loop

19

(L, 600 ml). Afterwards, the commutator position

is changed and the carrier stream drifts the sample
plug to the point (x) where it merges with the
reagent stream. Then, the mixture formed flows to
the reaction coil, where the colorimetric reaction
takes place. After color development, the dispersed
sample zone reaches the flow cell and the absorbance is continuously measured at 460 nm, yielding
a transient signal (peak height was used as quantitative variable). This procedure was also applied
to standard solutions.
2.4. Sample collection and preservation
Samples were collected and stored in low density polyethylene flasks. In order to avoid the
adsorption of Cu (II) ions on flask walls, concentrated hydrochloric acid (analytical grade) was
added until pH 1.8. Just before the analysis, the
samples were filtered by using a PTFE filter unity
with a 0.45-mm pore. All material employed was
decontaminated by soaking in HNO3 10% vyv for
48 h.
3. Results and discussions
In order to attain a best performance for the
analytical flow system in terms of sensitivity and
selectivity, the influence of several chemical and
flow variables that could affect it were studied by
the univariate method except otherwise mentioned.
Also, a detailed study of possible interferences
was done.
3.1. Investigation of chemical variables
The first variable investigated was the best pH
in which the reaction takes place. This parameter
was tested in the range of 4.59.0 by employing
different buffer solutions (R2, always with 0.5 mol
ly1 total concentration), according to the desired
pH. To adjust the pH between 4.5 and 5.0, an
acetate buffer solution was employed, while a
phosphate buffer was used to maintain the pH
between 5.5 and 7.0. For the alkaline range (pH
between 8.0 and 9.0), a borate buffer solution was
used. As can be seen in Fig. 2, maximum absorbance signals were verified at pH higher than 6.0,

20

R.J. Cassella / Microchemical Journal 72 (2002) 1726

Fig. 1. Flow system manifold employed for spectrophotometric Cu (II) determination in petroleum refinery wastewaters. The flow
rate of the solutions is indicated in the figure just on the respective solution line, in ml miny1. (a) System manifold initially
mounted: Psperistaltic pump; Sssample; Cscarrier (water, 1.80 ml miny1 ); R1 sreagent solution (0.2% wyv DDTC); R2sbuffer
solution (0.5 mol ly1 H3BO3, pH 9.0); MCsmixing coil, 250 ml; RCsreaction coil (500 ml); Lssample loop (400 ml); (x)s
confluence point; Dsdetector, spectrophotometer, 460 nm; Wswaste. (b) Final system design: Psperistaltic pump; Sssample;
Cscarrier solution (EDTA 0.05 mol ly1, pH 5.5); R1sreagent solution (0.15% wyv DDTC); R2 sbuffer solution (0.5 mol ly1
H3BO3, pH 9.0); R3smasking solution (0.4 mol ly1 EDTA, pH 5.5); MC1smixing coil (250 ml); MC2smixing coil (250 ml);
RCsreaction coil (125 ml); Lssample loop (600 ml); (x)sconfluence point; Dsdetector, spectrophotometer, 460 nm; Wswaste.

confirming results already pointed out by the

literature w3x. This way, all further tests were
always performed employing a borate buffer solution (R2) to maintain the reaction pH in 9.0. This
value was selected in order to ensure that any pH
variation would not cause noticeable lost of
sensitivity.
The influence of the concentration of DDTC
solution (R1) on the analytical signal was examined, since this solution should provide a sufficient
amount of reagent to attain a quantitative colorimetric reaction, thus maximizing the absorbance

signals. Therefore, DDTC solutions in the concentration range of 0.0150.30% wyv were tested and
maximum absorbance signals were observed for
concentrations higher than 0.08% wyv, as shown
in Fig. 3. This way, in order to ensure an adequate
amount of DDTC even for samples with higher
Cu(II) concentrations, a 0.15% wyv DDTC solution was chosen for the methodology.
3.2. Study of FIA variables
The influences of carrier solution (C) flow rate
and reaction coil (RC) volume were examined

R.J. Cassella / Microchemical Journal 72 (2002) 1726

21

Fig. 2. Influence of the pH of buffer solution (s) and 0.4 mol l y1 EDTA masking solution (d) on the absorbance. In the EDTA
experiment, the buffer solution was 0.5 mol ly1 H3BO3 at pH 9.0. Cu (II)s2 mg mly1.

Fig. 3. Influence of the DDTC concentration on the analytical signal. (s) R3 swater and (d) R3 s0.4 mol ly1 EDTA, pH 5.5. Cu
(II)s1 mg mly1.

22

R.J. Cassella / Microchemical Journal 72 (2002) 1726

Fig. 4. Influence of the carrier flow rate and reaction volume on the analytical signal. Cu (II)s2 mg mly1 . Reaction coil volumes
are indicated in the legend.

together, since these parameters have a similar

effect on the sensitivity of the method, affecting
both the contact time between analyte and reagent
(R1) and the sample zone dispersion. This study
was performed by varying, simultaneously, the
carrier flow rate (from 1.4 to 4.5 ml miny1) and
the reaction coil volume (from 0 to 750 ml).
Obtained results (Fig. 4) evidence that the reaction
between Cu (II) ions and DDTC occurs quickly,
once that higher absorbance signals were verified,
when reaction coils with lower volumes were
employed, indicating that a short contact time
between sample and reagent is required to achieve
quantitative reaction. This way, a reaction coil of
125 ml was selected for the method in order to
ensure a better mixture between sample and reagent because when the system was operated without reaction coil a little disturbance of baseline
was observed due to occurrence of the Schilieren
effect.
The results also demonstrate that the analytical
signal is enhanced when the carrier flow rate is

increased only up to 3.90 ml miny1. Therefore,

the carrier flow rate was set at this value for the
method.
The effect of sample loop volume was examined
in the range of 100900 ml. In this experiment,
the absorbance increased continuously up to 600
ml and after this value the gain of sensitivity was
negligible. Also, the time required to complete an
analytical cycle increased from 55 s (with 600-ml
loop) to 65 s (900-ml loop), thus diminishing the
sampling frequency. So that, a loop volume of 600
ml was chosen in order to obtain a better compromise between sensitivity and analytical throughput.
3.3. Interference study and establishment of the
final system design
Generally, more than 40 elements other than
carbon, hydrogen, nitrogen and sulfur are present
in crude petroleum. Among these species, the most
important are V (up to 1000 ppm), nickel (up to
100 ppm) and iron (up to 30 ppm). However,

R.J. Cassella / Microchemical Journal 72 (2002) 1726

23

Table 1
Study of possible interferents in presence and absence of EDTA masking solution
Interferent

Concentration
added
(mg mly1)

Cu (II)
recovery (%) in
absence of EDTA

Cu (II)
recovery (%) in
presence of EDTA

Al (III)

2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50
2
20
50

100
104
116
118
352
464
125
367
540
108
245
648
99
102
109
102
100
105
189
450
897
105
105
100
175
657
875
134
468
766
150
443
750

100
100
98
100
100
105
102
112
118
100
100
103
100
100
103
100
99
100
98
100
101
102
104
101
101
110
114
102
99
101
101
101
101

Co (II)
Cd (II)
Fe (III)
Mn (II)
Mo (V)
Ni (II)
V (V)
Hg (II)
Pb (II)
Zn (II)

Cu (II)s1 mg mly1.

other metals such as Co, Cd, Hg, Cu, Cr, Pb, Mn

and Mo are also found (in the ppm range) with
their amount varying according to the geographic
origin of petroleum w13x. During the processing
step, a great part of these species is removed from
the crude oil, being accumulated in the liquid
waste of the process which is then submitted to a
suitable treatment, resulting in the final effluent of
the refinery. This final effluent is a complex
mixture of solvents (with water as a majority

component) containing residual amounts of several

metallic cations.
Following this information, the metallic cations
which react with DDTC and that can be present
in appreciable concentrations in petroleum refinery
wastewaters were tested as possible interferents for
the method. Their effect on the analytical signal
was investigated individually by preparing 1 mg
mly1 Cu (II) solutions with and without increased
concentrations of the possible interferent. The

24

R.J. Cassella / Microchemical Journal 72 (2002) 1726

results are shown in Table 1 and they are expressed

as percentage of Cu (II) recovery in each test. As
can be seen in Table 1, very strong interferences
are observed when various cations are present in
the sample solution together with Cu (II) ions.
In order to eliminate these interferences, an online addition of EDTA (as masking agent) to the
sample was carried out by an extra line connected
to the system, which allowed the mixture between
sample and EDTA solutions just before filling the
sampling loop. Once that Cu (II) reacts in a large
degree with EDTA (as well as the interferent
species), the influence of the EDTA on the Cu
(II) signal was evaluated before proceeding to a
new study of interferents in the presence of EDTA.
The establishment of the suitable concentration,
pH and flow rate of EDTA solution was required
to avoid an excessive lost of sensitivity due to Cu
(II) complexation by EDTA.
In this study, both the flow rate and concentration of EDTA solution were fixed in 0.51 ml
miny1 (in order to avoid excessive dilution of
sample) and 0.4 mol ly1, respectively. Only the
pH was tested between 5.5 and 9.5 in order to
control the EDTA availability. A continuous
decrease of Cu (II) absorbance was observed with
the increase of the pH of EDTA solution (also
shown in Fig. 2) which enhanced the Cu (II)
complexation by EDTA (more available EDTA),
thus affecting the reaction between Cu (II) and
DDTC. Then, a masking solution containing 0.4
mol ly1 EDTA with pH 5.5 was selected for the
method.
Afterwards, all possible interferences were
investigated in the presence of EDTA. As can be
seen in Table 1, by using 0.4 mol ly1 EDTA (pH
5.5) as a masking solution, merging with the
sample before injection, is possible to overcome
almost all interfences. Operating the system at this
condition, only Cd (II) and Hg (II) at concentrations 20-fold higher than that Cu (II), can cause a
noticeable interference in the method.
In order to achieve a suitable design for the
flow system, the influence of DDTC concentration
and the composition of the carrier solution was
investigated one more time, in presence of EDTA
masking solution. The results presented in Fig. 3
show that the influence of DDTC concentration

Table 2
Amount of waste generated by FIA system per hour of
operation
Substance

Amount wasted
per hour

EDTA (as di-sodium salt)

DDTC
Boric acid

8.82 g
37 mg
186 mg

on absorbance was the same verified in the previous investigation. Only a decrease of approximately 10% was observed for the overall range tested.
This fact, as previously observed, can be attributed
to the presence of EDTA. Therefore, a DDTC
solution previously selected (0.15% wyv) was
maintained for the method.
Taking into consideration that the sample injected contained approximately 0.05 mol ly1 EDTA
(calculated by using the ratio between masking
solution and sample flow rates), the carrier stream
(water) was replaced by a 0.05 mol ly1 EDTA
solution. This action avoided the appearance of
any baseline noise due to the Schilieren effect.
4. Method evaluation
4.1. Analytical features of the proposed system
The proposed FIA system was critically evaluated with regard to accuracy, precision, detection
limit, quantification limit, linear range and sampling frequency.
Operating the system under optimized conditions a linear fit was derived between 0.2 and 2
mg mly1, with a typical equation As
0.132wCumg mly1.xq0.001 with a correlation
coefficient rs0.9992, where A is the absorbance
signal measured as peak height.
The detection limit, estimated as three times the
standard deviation of 10 measurements of blank
solution w14x, was 23 ng mly1. In the same way,
the quantification limit, derived from 10 times the

R.J. Cassella / Microchemical Journal 72 (2002) 1726

Table 3
Results obtained in the determination of Cu (II) in petroleum
refinery wastewaters by the proposed methodology (FIA) and
by flame atomic absorption spectrometry (FAAS)
Sample

FIA
(mg mly1)

FAASa
(mg mly1)

FAASb
(mg mly1)

A
B
C
D
E
F
G

0.63q0.02
0.78"0.02
0.41"0.03
0.54"0.03
0.78"0.03
0.76"0.03
0.44"0.02

0.81"0.02
1.02"0.03
0.51"0.03
0.74"0.02
0.98"0.04
0.98"0.02
0.57"0.01

0.64"0.02
0.80"0.01
0.43"0.03
0.52"0.01
0.81"0.04
0.73"0.02
0.42"0.02

a
b

Flame atomic absorption by external calibration method.

Flame atomic absorption by standard addition method.

standard deviation of the blank w15x, was 75 ng

mly1. The RSD observed was 2.1% at the 0.2 mg
mly1 level. An analytical throughput of 63 hy1
was derived with a system operating at optimum
conditions, where the space of time passed
between two injections is considered a complete
analytical cycle.
Another important feature of all methodologies
that must be emphasized is the amount of waste
generated at the end of their application. In the
present case, the system generates approximately
500 ml of effluent per hour of operation. Table 2
expresses the composition of this effluent in terms
of the amount of each substance wasted.
4.2. Applications of the proposed methodology
The applicability of the developed methodology
was studied by analyzing several samples of industrial effluents and comparing the obtained results
with those determined by flame atomic absorption
spectrometry. The accuracy of the methodology
was also tested carrying out the analysis of spiked
samples. All results are summarized in Tables 3
and 4.
As can be seen in Table 3, the results obtained
by the FIA method did not agree well with those
obtained by FAAS employing an external calibration procedure. However, comparing the results of
FIA and FAAS (standard addition procedure) it is
possible to observe that there is no statistical
(applying the t-test with a confidence level of

25

95%) difference between the results. This fact

indicates that the FIA methodology is not subject
to the same interferences observed in FAAS determinations, in this kind of sample. These interferences occurred due to the physical differences
observed between the samples and aqueous standard solutions, generated by the presence of large
amounts of organic substances in the industrial
effluents analyzed, which modified the sample
viscosity. Taking this fact into account it is possible
to affirm that the developed procedure is an excellent alternative to FAAS, providing a simplest
analytical procedure with suitable analytical
throughput that is free of matrix interferences.
The accuracy of the methodology can be also
confirmed by observing the results obtained in the
analysis of spiked samples, which yielded recovery
percentages between 93 and 103% when Cu (II)
was added in the range of 0.150.40 mg mly1, as
shown in Table 4.
5. Conclusions
The proposed methodology developed here
proved to be successful for the analysis of Cu (II)
in industrial effluents containing organic substances. The system presented adequate sensitivity,
allowing the determination of copper at levels
under those established by regulatory offices. Also,
the high productivity of the system (63 hy1) makes
it very suitable for routine analysis in environmental and quality control laboratories.
Comparison between the developed FIA system
and FAAS revealed that the proposed methodology
Table 4
Results obtained in the analysis of spiked samples by FIA
methodology
Sample

Cu (II) added
(mg mly1)

Cu (II) found
(mg mly1)

0
0.15
0.30
0
0.20
0.40
0
0.20
0.40

0.63"0.02
0.77"0.03
0.94"0.02
0.41"0.03
0.61"0.02
0.80"0.02
0.78"0.03
0.99"0.02
1.17"0.05

Recovery

93%
103%
100%
98%
101%
98%

R.J. Cassella / Microchemical Journal 72 (2002) 1726

26

is not subjected to the same type of physical

interferences observed in the analysis of complex
samples by FAAS, avoiding the direct determination of Cu (II) in none of the treated samples.
Also, time is saved once that analysis by standard
addition method is avoided.
The methodology has remarkable advantage
over classical spectrophotometric determination of
Cu (II) using DDTC as colorimetric reagent which
is the possibility to carry out the analytical process
without use of a solvent extraction step before
absorbance measurement. This fact yields an analytical methodology with fewer risks to the analyst
and to the environment, since the handling of toxic
organic solvents is not needed.
Acknowledgments
The author is grateful to CNPq (Conselho

Nacional de Desenvolvimento Cientfico

e Tecnol
ogico,
process no. 300906y00-5) for the fellowship
and to SEMTECyMEC and CEFETEQyRJ for the
financial and logistic support.
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