Microchemical Journal 109 (2013) 4145

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Determination of Hg in water associate to crude oil production by electrothermal

vaporization inductively coupled plasma mass spectrometry
Tatiana Dillenburg Saint'Pierre a,, Rafael Christian Chavez Rocha a, Christiane Batrice Duyck a, b
a
b

Departamento de Qumica, Pontifcia Universidade Catlica do Rio de Janeiro (PUC-Rio), Rua Marqus de So Vicente 225, Rio de Janeiro, RJ, CEP 22451900, Brazil
Departamento de Qumica, Universidade Federal Fluminense (UFF), Outeiro So Joo Batista s/n, Niteri, RJ, CEP 24020150, Brazil

a r t i c l e

i n f o

Article history:
Received 30 November 2011
Received in revised form 8 May 2012
Accepted 18 May 2012
Available online 23 May 2012
Keywords:
Mercury
ETV-ICP-MS
Crude oil production water

a b s t r a c t
Mercury is a toxic element that can be found in different chemical forms in the environment. It can be present
in crude oil and contaminate the water employed in the oil extraction and production. Sample treatment
required for most spectrometric techniques can lead to errors in the Hg determination, mainly by volatilization.
Vapor generation is the most recommended technique for sample introduction, but is too time consuming. In this
work, electrothermal vaporization was the chosen alternative for sample introduction in inductively coupled
plasma mass spectrometry to allow the accurate determination of Hg in production water. Samples were
analyzed by analyte addition in one sample with low Hg content. In order to avoid Hg loss, low temperatures
were employed in the ETV program, pyrolysis at 200 C and vaporization at 1000 C, and gold was used as modier. Limit of detection of 0.12 g L 1 and limit of quantication of 0.41 g L 1 were obtained. Accuracy was
checked using recovery test, by adding an urine certied sample to a production water sample and an average
recovery of 106% was obtained. Among the 10 samples analyzed, one presented Hg concentration over the
limit for efuents, established by Brazilian legislation. The proposed method presented better accuracy when
compared to the analysis by ICP-MS with direct introduction by means of a nebulizer specic for saline samples.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Mercury is a toxic element that can be found as contaminant in
many different chemical forms, which can be easily inter-converted
and transported through geochemical processes and pollute the environment. Important contamination by mercury is found in some aquatic
environments due to the extensive use of this metal in gold mining in
early years. In the environment, Hg absorbed by living organisms, like
shes, is converted into its most toxic forms, CH3Hg and C2H5Hg, increasing their concentration through the food chain. When consumed
by humans, these toxic forms accumulate in many parts of the body,
such as liver, muscles and brain [1,2]. In addition, this element has
specic characteristics that are largely employed for different industrial
purposes, such as in thermometers, batteries and lamps. Naturally, the
use of Hg by the industry should be strictly controlled to avoid contamination of the environment and living organisms and most countries
have specic legislation for limiting this element concentration in
efuents and environment. In Brazil, the maximum Hg concentration
in efuents, according to the environment agency CONAMA (Conselho
Nacional do Meio Ambiente), is 0.01 mg L 1 [3].
Mercury can be naturally present in crude oil and gas, mainly in the
volatile elemental form and inorganic forms, such as mercuric oxide,

Corresponding author. Tel.: + 55 21 35271328; fax: + 55 21 35271637.

E-mail address: tatispierre@puc-rio.br (T.D. Saint'Pierre).
0026-265X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2012.05.005

chloride, sulde and selenide that can dissolve in the production

water employed in the petroleum extraction [4]. During oil rening
processes, Hg, as well as As and Se, can adsorb on the carbon produced
during oil combustion and exit the unit in the ue gas, contaminating
the wastewaters and efuents. Whatever the form, this element is a
problem in crude oil, not only due to the environmental problems,
but also because it can damage equipments and affect the catalysts
performance during the rening and, consequently, impair the quality
of the nal product [5].
The usual determination of total Hg is by vapor generation
coupled to a spectrometric technique, since it allows separating the
analyte from the sample solution, avoiding interferences and improving the sensitivity of the technique by analyte pre-concentration. The
mercury present in the sample is converted to the metallic form by
means of a reducing agent, mostly SnCl2 or NaBH4. For these reasons,
this sample introduction procedure requires the sample to be in a
water soluble form and not in a strongly oxidant medium, since the
Hg species have to be reduced to the volatile elemental form [6].
However, most procedures used in the analysis of petroleum and
derivatives employ oxidant acids, generally nitric acid, for oil decomposition and element stabilization in solution. As well, the efciency
of the analyte reduction can be affected by the presence of oxidant
species in the sample matrix that can compete with the analyte for
the reducing agent or by the occurrence of different species of the
analyte that react in different ways with the reducing agent. In addition, heating the sample or the solution during the sample dissolution

42

T.D. Saint'Pierre et al. / Microchemical Journal 109 (2013) 4145

can promote loss of this element by volatilization, leading to erroneous

results [7].
The direct Hg determination by ICP-MS has enough sensitivity for
most applications and is practically free from spectral interferences. The
problem concerns sample matrices presenting components that
can cause non-spectral interference, mainly environmental samples
[68]. For example, the high salinity present in seawater samples or
the high amount of dissolved solids present in geological samples can
promote signal suppression or even blocking in any part of the equipment, such as the nebulizer and cones. In order to circumvent these interferences, sample can be diluted, but the dilution factor is limited by
the capability of the technique to detect the analyte. This is especially
problematic for Hg, which is normally already in low concentrations
in environmental samples. Another option is to separate the analyte
from the sample matrix, but the procedures employed for that, such as
chromatography, although efcient in pre-concentrating the analyte,
can be time consuming and prone to contamination or analyte loss [2,9].
Electrothermal vaporization is an alternative technique for sample
introduction that minimizes the sample preparation procedures and
has been successfully applied in the Hg determination by inductively
coupled plasma mass spectrometry (ETV-ICP-MS) [914]. This approach
is especially adequate for samples difcult to dissolve or with high
salinity or dissolved solids, complex samples and when a low sample
volume is available. Few microliters of a sample solution (or a slurry)
are dispensed into a graphite furnace and submitted to a temperature
program to eliminate solvents, acids and most of the sample matrix before vaporizing and transporting the analytes into the plasma, to be quantied [15]. In addition, the ETV-ICP-MS allows the pre-concentration of
the analyte, resulting in better sensitivity for Hg and other toxic elements
in the environment [9,16]. Concerning the analysis of Hg by ETV-ICP-MS,
Vanhaecke et al. [12] have proposed the speciation of inorganic and
methyl mercury by changing the temperatures of the ETV program,
since these species have different volatilities. They reached a LOD of
6 ng g 1 for inorganic Hg and 2 ng g 1 of methyl Hg.
The challenge of this work was to propose an accurate method
for determination of the total concentration of Hg in production waters from the petroleum exploration. The samples supplier informed
that the samples presented high salinity and were preserved with
nitric acid. Naturally, production waters can also present high amounts
of sulfur and dispersed organic compounds, which could interfere in the
cold vapor generation and prevent the analysis by direct nebulization
ICP-MS. For that, the coupling of the ETV with ICP-MS was proposed
to allow introducing and analyzing production water samples for the
Hg content. The results were compared to the Hg determination by direct introduction in ICP-MS with a nebulizer specic for saline samples.
2. Experimental
2.1. Equipments and methods
The inductively plasma mass spectrometer, Elan 6000 (Perkin
Elmer Sciex, USA), was rstly optimized with sample introduction
by conventional nebulization to maximum sensitivity and minimum
formation of oxides and double charge ions (Daily Performance).
The general ICP-MS conditions are summarized in Table 1.
Then, the electrothermal vaporizer HGA 100 (Perkin Elmer) was
coupled to the ICP with a PTFE tubing. Volumes of 20 L of the sample
or of the analytical solution and 10 L of the modier solution were
dispensed into the graphite tube by the AS-60 autosampler (also
from Perkin Elmer). Different modiers were tested to improve the
Hg stabilization during the pyrolysis of the matrix and consequently
improve the element separation from the sample matrix. The ETV
temperature program was carefully optimized to avoid Hg loss in
any stage before its vaporization. The drying was carried out at two
temperatures (90 and 110 C) to avoid boiling the solution inside
the graphite tube. The optimizations were carried out with an

Table 1
ICP-MS operational conditions for sample introduction by electrothermal vaporization
(ETV-ICP-MS) or by pneumatic nebulization with a Vee-spray nebulizer (PN-ICP-MS).

RF power, W
Ar nebulizer ow rate, L min 1
Ar carrier ow rate, L min 1
Dwell time, ms
Sweeps per reading
Reading per replicate
Number of replicates

ETV-ICP-MS

PN-ICP-MS

1100
0.90
0.3
50
1
100
1

1200
0.94
N/A
60
5
1
5

acidied 10 g L 1 Hg solution and with a sample spiked with Hg to

a nal concentration of 10 g L 1 to monitor differences between
the behaviors of the analyte in the two media. The optimized conditions are listed in Table 2.
For comparison and to check for the accuracy of the method, the
analysis of the samples was also carried out by direct introduction
in the ICP-MS by means of a Vee-spray (Glass expansion, MA, USA)
suitable for saline samples and analyte addition calibration. The
isotopes 199Hg, 200Hg, 201Hg and 202Hg were monitored to check for
interferences and the most abundant 202Hg was chosen for the
quantication.

2.2. Reagents and samples

A 1000 mg L 1 Hg solution in 5% HNO3 (Perkin Elmer, Shelton, USA)
was employed for method development and optimization and for
the analytical curve construction. Au or Ir was added as modiers, as
10 mg L 1 solutions prepared from the original 1000 mg L 1 ones
(Aldrich, Milwaukee, USA (Au) and Sigma, St. Louis, USA (Ir)). In addition, thioacetamide at a 0.3% concentration was tested as another modier for Hg, since these waters may content sulfur forms (mercaptans)
and Liu et al. [14] tested this solution for the same purpose. A monoelementar Hg organic standard (Hg in oil, Conostan, Conoco, Ponca
City, OK, USA) dissolved at a nal concentration of 10 g L 1 in heptane
was tested for simulating Hg in organic form.
Since no certied sample with a matrix similar to the production
water is available, the accuracy of the proposed method was also
checked through a recovery test. For that, a sample with Hg concentration below the limit of detection (LOD) was spiked with a certied urine
sample (Lyphochek urine metals control Level 1, BioRad, USA) with Hg
concentration of 50 10 ng mL 1. This sample was employed for this
purpose due to its high salinity, in order to not dilute the salinity of
the production water and, consequently, not changing signicantly its
physical chemical properties.
The 10 samples received to be analyzed were production water
acidied with HNO3 (1:1 v/v) and were kept under refrigeration at
4 C until before the analysis, when they were let to reach the room
temperature. Some samples had some reddish brown color, probably
due to some component from the oil, but no precipitate was observed.

Table 2
Temperature program for electrothermal vaporization of Hg.
T (C)

Ramp (s)

Hold (s)

Ar carrier (L min 1)

2500
20
90
110
200
20
1000
20

5
5
5
30
15
1
1
5

5
5
5
0
15
5
8
5

0.3
0.3
0.3
0.3
0.3
0.3
0
0

T.D. Saint'Pierre et al. / Microchemical Journal 109 (2013) 4145

Fig. 1. Transient signals generated without modier and without pyrolysis temperature.

Fig. 2. Transient signals generated with thioacetamide and Ir as modier and without
pyrolysis temperature.

3. Results and discussion

3.1. Method development
The ETV program and the use of a modier were studied. Initially,
since Hg is highly volatile, the direct vaporization of Hg from the sample,
without applying a pyrolysis temperature and without modier, was
tested. In this case, the temperature program consisted basically of a
drying stage in two steps (90 and 110 C) and a vaporization stage at
1000 C. However, this strategy did not succeed. The resulting signals
for the blank, for the analytical solution and for a sample added of
10 g L 1 Hg, presented in Fig. 1, were noisy and very similar for all
solutions. The similar shapes obtained for the blank, standard and spiked
sample indicate that the Hg could not be totally released from the sample,
being still bonded to the sample matrix. In this case, the use of a modier

43

would be mandatory to increase the Hg thermal stability and allow that a

pyrolysis temperature could be applied to remove part of the sample
matrix before the Hg vaporization.
Next step was to test modiers suggested in the literature.
Then, according to the strategy proposed by Liu et al. [14], a 10 L of
a solution containing 0.3% (w/v) thioacetamide in 4% HCl (w/v) and
10 L of a 10 mg L 1 Ir were pipetted into the graphite tube before
pipetting 20 L of the sample solution. Again, no pyrolysis step was
applied and the best signal was obtained at 1200 C vaporization.
However, this strategy was not efcient for these samples, since a
memory effect was observed, as shown in Fig. 2 where an increase
in peak tailing is observed between the replicates. It seems that
employing these conditions, Hg remains in the carbon tube and is
released during several cycles, even with a cleaning temperature of
2500 C. It can be that some component of the sample is affecting
the modier effect, since this was not observed in the original paper
from Liu et al. [14].
Pozebon et al. [13] have employed Ir as a modier for Ag, Cd, Hg,
Pb and Tl in biological samples by ETV-ICP-MS. Different concentrations were tested and a reproducible signal was obtained for a 0.18%
(w/v) Ir solution containing 1% HNO3 and HCl. Then, 10 L of the Ir solution was pipetted with 20 L of the 10 g L 1 Hg solution. In this
case, a fast optimization of the pyrolysis and vaporization temperatures was carried out and employed 200 and 1000 C, respectively,
in the program. Fig. 3 shows the behaviors of the blank and analytical
solutions analyzed by this proposed method. A memory effect is
clearly observed between the rst and second replicates of the analytical solution. As well, the blank intensity increased after the measurement of the analytical solution (detail on Fig. 3). Again, this behavior
is attributed to some components of the production water samples,
since it was not observed by those authors.
Then, Au was tested as modier, by pipetting 10 L of a 10 mg L 1
solution together to the sample [11]. This condition offered better stability for Hg, but only for low pyrolysis temperatures. The temperature
program was optimized and the temperatures were adjusted at 200 C
for pyrolysis and 1000 C for vaporization. During the vaporization
step, the Ar ow rate was stopped and the plasma gas (0.9 L min 1)
transported the Hg to the plasma for quantication. Fig. 4 shows the
transient signals obtained for the blank, the 10 g L 1 Hg analytical solution and for a sample added of 10 g L 1 Hg, all in triplicate, conrming that no memory effect occurred.
The 10 g L 1 Hg solution in heptane was analyzed with the technique (Fig. 5) in order to investigate Hg as an organic form. Although
this is only a preliminary result, it can be seen that the transient signal
generated is quantiable, indicating that volatile Hg was not lost during
the pyrolysis step.
These conditions were employed for the analysis of the samples.

Fig. 3. Transient signals for the Hg analytical solution and for the blank, in the detail, generated with Ir as modier and pyrolysis temperature at 200 C.

44

T.D. Saint'Pierre et al. / Microchemical Journal 109 (2013) 4145

3.3. Samples analysis

Fig. 4. Transient signals generated with Au as modier and pyrolysis temperature at 200 C.

Hg199

Intensity (counts)

140000

Hg200

120000

Hg201

100000

Hg202

80000
60000
40000
20000
0

10

Acquisition time (s)

Fig. 5. Transient signals of Hg isotopes obtained with a 10 g L 1 Hg organic solution
with Au as modier.

3.2. Figures of merit

The calibration curve for samples with low Hg content and for the
limit of detection (LOD) calculation was prepared by addition of Hg in
a sample with concentration below the limit of detection, in a range of
0.53.0 g L 1. The calibration curve used for samples with a higher
Hg concentration was ranging from 540 g L 1. The LOD was calculated as 3 times the standard deviation of 10 measurements of the blank
divided by the slope of the calibration curve. In this case, the blank
was the own sample employed for constructing the calibration curve,
so that the LOD was realistic to the sample and was 0.12 g L 1,
corresponding to a limit of quantication (LOQ) of 0.41 g L 1.
Since there is no available certied sample with the same matrix of the production water samples, the accuracy was checked by
analyzing a highly saline sample with certied Hg concentration.
For that, a reference urine sample (Lyphochek urine metals control
Level 1, BioRad) with Hg concentration of 50 10 g L 1 was added
to a sample with Hg concentration below the LOD, for a nal concentration of 1 g L 1 in the analytical solution. The obtained Hg concentration was 53 2 ng mL 1 of the urine sample, which corresponds
to an average recovery of 106% of the certied value. Table 3 summarizes the results obtained with the proposed methodology.

Considering that the 10 production water samples have similar

matrix, all of them were analyzed against the same calibration
curve, prepared by analyte addition with one sample containing
Hg concentration below the LOD. Most of them presented Hg concentration also below the LOD, except for two samples. One had Hg
concentration higher than the LOD, but in the same order of the
LOQ, i.e. 0.4 0.1 g L 1, and another sample presented a high Hg
concentration, 20.3 0.7 g L 1, even higher than the limit established
by CONAMA [3] for efuents, which is 10 g L 1.
In order to conrm the high value obtained for one sample, it was
also proposed the analysis of the samples by direct introduction in the
ICP-MS by means of a Vee-spray nebulizer, specic for saline solutions.
In this case, samples were 5-times diluted with water to allow the direct
introduction, since the acid content was very high, due to the preservation with nitric acid carried out already in the sampling and an analyte
addition calibration curve was prepared for each sample. The plasma
conditions were optimized again through the daily performance procedure and were 1200 W of RF power and 0.94 L min 1 of Ar nebulizer
ow rate. A 30 g L 1 Rh solution introduced on line with the sample
was used as internal standard.
Applying this methodology, the LOD was 0.54 g L 1, corresponding
to a LOQ of 1.80 g L 1 of Hg in the sample. The concentration values
obtained for the reference urine sample and for the production water
sample that presented Hg concentration over the LOQ were lower than
those obtained by ETV-ICP-MS, as shown in Table 3. These lower values
obtained with the direct introduction indicate that signal suppression
probably occurred, due to the high salinity and high acid content in the
samples, which did not interfere in the ETV methodology because they
could be eliminated by the temperature program. The salt concentration
estimated by the sum of Na, Mg and Ca concentrations in the samples
determined by ICP OES was as high as 5.4%. The high salinity is especially
problematic for seawater and can require analyte separation from the
sample matrix prior its determination by ICP-MS [2,8]. It can be that an
additional sample dilution could allow the accurate determination of
Hg in production water by direct nebulization ICP-MS, but this would
imply in sensitivity loss.
4. Conclusion
The use of the ETV-ICP-MS allowed eliminating solvents and interferences from the sample matrix before the vaporization, making possible
an accurate determination of Hg in crude oil production water, which
are highly saline and acidied water samples. The direct introduction
of samples into the plasma by means of a nebulizer specic for saline
samples did not reach accurate results, even by analyte addition calibration. The analysis of a reference urine sample leads to a 106% recovery
of the certied value. Most production water samples presented Hg
concentration below the LOD of the method (0.12 g L 1), except for
two samples, being one with Hg concentration in the same order of magnitude of the LOQ and another with Hg concentration higher than
the limit established for efuents by the Brazilian legislation, which is
10 g L 1.
References

Table 3
Results obtained with the proposed method and with a comparative methodology.

LOD (g L )
LOQ (g L 1)
Certied urine (50 10 ng mL 1)
Recovery of the certied value (%)
Production water (g L 1)

ETV-ICP-MS

ICP-MS

0.12
0.41
53 2
106
20.3 0.7

0.54
1.80
44 4
88
18.4 0.8

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