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Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation

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DOI: 10.2516/ogst:2007006

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Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1, pp. 69-77
Copyright © 2007, Institut français du pétrole
DOI: 10.2516/ogst:2007006
Dossier
Recent Advances in the Analysis of Catalysts and Petroleum Products
Avancées récentes en analyse des catalyseurs et des produits pétroliers

Trace Metal Analysis in Petroleum Products:

Sample Introduction Evaluation in ICP-OES
and Comparison with an ICP-MS Approach
C.P. Lienemann1, S. Dreyfus1,2, C. Pecheyran2 and O.F.X. Donard2
1 Institut français du pétrole, IFP-Lyon, Direction Physique et Analyse, BP 3, F-69390 Vernaison - France
2 LCABIE, CNRS UMR 5034, Université de Pau et des Pays de l'Adour, 2, avenue P. Angot, F-64053 Pau Cedex 9 - France
e-mail: [email protected] - [email protected] - [email protected]

Résumé — Analyses de traces dans les produits pétroliers : évaluation de méthodes d'introduction
des échantillons en ICP-OES en comparaison avec une approche ICP-MS — Les besoins de l'industrie
pétrolière en analyse de métaux traces sont étroitement corrélés aux besoins de l'exploration géochimique,
mais aussi en raffinage et pétrochimie pour les problèmes de pollution.
L'ICP-OES et l'ICP-MS sont deux techniques pouvant répondre dans une large gamme de concentration
aux besoins exprimés en analyse de routine. La première est préférée pour l'analyse des éléments majeurs
et la seconde est particulièrement adaptée pour la détermination de métaux en ultra-traces.
L'introduction directe de produits pétroliers dans le plasma nécessite une approche méthodique pour
limiter les effets de matrice. Dans cet article, trois modes d'introduction ont été utilisés en fonction des
éléments d'intérêt et des matrices analysées. Un nébuliseur pneumatique classique et un nébuliseur ultra-
sonique ont été comparés pour l'ICP-OES. Ces deux modes d'introduction ont ensuite été comparés avec
un micro-nébuliseur concentrique associé à une chambre de nébulisation refroidie pour l'ICP-MS.
La nébulisation pneumatique couplée à l'ICP-OES permet d'atteindre des limites de quantification dans
les produits pétroliers de l'ordre du ppm. Elles sont cinq fois plus élevées dans les essences du fait du fac-
teur de dilution plus important. L'utilisation d'un nébuliseur ultrasonique réduit les limites de quantifica-
tion à environs 50 ppb dans les essences, mais des études plus approfondies sur les effets de matrice
engendrés par une telle nébulisation doivent être entreprises.
L'utilisation d'un PFA-100, associé avec une chambre de Scott refroidie sur un ICP-MS abaisse les limites
de quantification dans le produit pétrolier dans la gamme des 10 ppb pour la plupart des éléments.
L'important facteur de dilution initial en ICP-MS permet l'introduction de toutes les matrices, même les plus
légères, mais nécessite le recours aux ajouts dosés, méthode particulièrement longue à mettre en œuvre.
Ainsi, le choix d'une technique dans le laboratoire est directement dépendant des critères édictés par
celui-ci entre une productivité analytique importante et d'excellentes limites de quantification.

Abstract — Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in

ICP-OES and Comparison with an ICP-MS Approach — The needs of the petroleum industry in
studies dedicated to trace metals determination are highly related to exploration, but also to exploitation
activities for corrective actions during oil production and refining.
Two techniques provide a very large concentration range of metal compounds to be determined on a
routine basis, ICP-OES being preferred for major element analysis whereas ICP-MS is particularly
convenient for ultra trace metals analysis.
70 Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1

Direct introduction of petroleum product in the plasma require a methodical approach in order to
minimise matrix effect. Here, three different sample introduction modes have been investigated depend-
ing on the elements of interest and the matrix analysed. A classical pneumatic nebulizer and an ultra-
sonic nebulizer (USN) were compared for ICP-OES. These introduction modes were compared with a
microflow pneumatic concentric nebulizer associated with a chilled spray chamber used with ICP-MS.
Classical pneumatic nebulisation with ICP-OES leads to ppm range limit of quantification in the
petroleum product and five times higher with gasoline due to important dilution factor. The use of an
USN coupled with ICP-OES reduce limit of quantification in gasoline to the 50 ppb range, but further
study of matrix effects with such an introduction must be done.
The PFA-100 associated with a cooled Scott chamber used with ICP-MS reduce also limit of quantification
in the petroleum product to the 10 ppb range for most elements. The initial important dilution factor
allows the introduction of light matrices without further dilution, but require anyhow the use of a stan-
dard addition method, which is time-consuming.
Then, the choice of a technique is definitively dependant on the needs required by the laboratory between
high throughput analyses and very low limit of quantification.

INTRODUCTION Cu, Cd, Si, As and Pb are elements affecting catalyst’s

efficiency coming from different origins. They could be
The needs of the petroleum industry in studies dedicated to native in the petroleum crude or added in the refinery scheme
trace metals determination are highly related to exploration, by pollution or for a precise purpose. Their presence and
but also to exploitation activities for corrective actions during identification in feeds are highly needed in order to avoid fur-
oil production and refining. To date and for geochemical ther poisoning of the different catalysts present in a refinery.
identification, concentrations of Ni and V have been mostly Finally and from a geochemical point of view, Mn, Mo,
determined (Lopez and Mónaco, 2004) by inductively cou- Ba, V, Fe and Ni are potentially new bio-geochemical mark-
pled plasma atomic emission spectrometry (ICP-OES). ers to improve our knowledge in the formation and migration
However, this technique does not allow the detection of low of the oil.
concentrations (ppb level) and some other metals are sus- A list of elements is then identified to be of importance for
pected to be present at lower concentrations. For instance, the petroleum industry in general. However, the analytical
As, Pb, Si and Hg analyses in oil and on different location on tools used so far (ICP-OES, GFAAS) don’t allow the analy-
plant sites are required in order to follow pollution and poi- sis of the complete list, or in a reasonable analysis time that
soning of catalysts (Kellberg et al., 1993; Souza et al., 1999; fits with routine analysis requirements. A rapid, sensitive,
Didillon et al., 1997). Graphite furnace atomic absorption and multi-elemental method is then required to analyse trace
spectrometry (GFAAS) providing better limit of detection is elements occurring in crude oil or other petroleum products.
generally used as an alternative to ICP-OES when low Recently, ICP-MS was used to determine trace metals in
concentrations are investigated. This technique, however, petroleum samples, crude oils and their fractions (Dreyfus et
suffers from some limitations such as analysis time and al., 2005). In this study, an original method was developed
dynamic linear range. that allowed direct determination of very low level trace
Establishing an exhaustive list of the different metals or elements in the range of few ppb. Sample throughput and
non-metals, for which the petroleum industry would see an multi-elemental capabilities are some common benefits of
interest from an analytical point of view, is not an easy task. ICP-OES and ICP-MS compared to classical atomic absorp-
However, an alternative approach considering the different tion spectrometry or WDXRF. The inherent high sensitivity
origins of elements in a refining scheme, gives an accurate of ICP-MS detection together with isotopic ratio capabilities
idea of the main elements of interest in the petroleum opens new fields of applications in petrochemistry or
industry. geochemistry of petroleum products.
Ni, V and S originate from crude oils at quite high The combination of these two techniques thus provides a
concentrations and their analyses are usually performed by very wide concentration range of metal compounds to be
ICP-OES and Wavelength Dispersive X-Ray Fluorescence determined on a routine basis, ICP-OES being preferred for
(WDXRF). Al, Si, Mo, Sn, Ni, Co could be released by cata- major element analysis (Fe, Ni and V) whereas ICP-MS is
lysts, and Al, Mn, Cu, Cr, Fe, Ni, Zn could be released by particularly convenient for ultra trace metals analysis.
tubing and the different metallic parts that could corrode and However, these two techniques were not initially designed
be degraded during operation. Their presence could reveal for organic samples analysis and specific configuration of
operation problems that need repairing as soon as their sample introduction systems are required in order to mini-
detection has been shown. mize organic solvent load into the ICP plasma. The presence
 CP Lienemann et al. / Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in ICP-OES 71

of organic vapours in the plasma generates plasma instability 1 MATERIALS AND METHODS
and high reflected power that could lead to plasma extinction.
In addition, emission lines broadening effects are usually
1.1 Instrumentation
observed with ICP-OES detection. In ICP-MS analysis, prob-
lems are even more severe since the incomplete carbon com- ICP-OES analysis were carried out with an Iris Advantage
bustion leads to high carbon deposition on the cones and the 200 (Thermo Jarrel Ash) operating at 27.12 MHz and
focus lenses that drastically limits ions extraction (and thus equipped with a cross flow “high solid” pneumatic nebulizer
the signal recorded) and requires an extensive cleaning of the fitted to a cylindric spray chamber equipped with baffle. For
ion optics after only a few seconds of nebulisation. This phe- gasoline introduction, an ultrasonic nebulizer U-5000 AT+
nomenon is especially pronounced when light organic prod- (CETAC, Omaha, USA) was used.
ucts (gasoline) are analysed. Moreover, severe matrix inter- ICP-MS analysis were done on a X7 Series CCT ICP-MS
ferences have already been observed during the analysis of (Thermo Electron Corporation, Winsford, UK) equipped
organic solutions in ICP-OES due to plasma interactions with a PFA-100 MicroFlow Nebulizer (Elemental Scientific
(Botto, 1987). In order to minimize these problems, five solu- Inc., Omaha, NE) fitted to a Scott-type double pass chilled
tions are globally described in the literature with organic spray chamber, and with Platinum Sampler and Micro
injection using micro-nebulisation system (Dreyfus et al., Skimmer cones (Thermo Electron Corporation, Winsford,
2005; Botto, 2002), desolvatation using ultrasonic nebulisa- UK). Oxygen was supplied continuously into the nebulizer
tion and membrane (Botto and Zhu, 1996; Duyck et al., gas flow for complete combustion of the sample and reduc-
2002), digestion of the sample (Wondimu et al., 2000; tion of carbon deposits on the cones. The instrument was also
Heilmann et al., 2004, Lopez and Monaco, 2004), micro- fitted with a modified demountable torch equipped with a
emulsion (Souza et al., 2004; Wang et al., 2003) for intro- reduced injector orifice, as described in Dreyfus et al. (2005).
duction of an aqueous phase in the plasma and finally elec- The ICP-MS, ICP-OES and USN-ICP-OES operating
trothermal vaporization (Resano et al., 2001; Saint’Pierre et conditions are listed in Table 1.
al., 2002). Micronebulization and ultrasonic nebulisation are
sometimes used in combination with oxygen addition into the
1.2 Reagents
plasma, which is particularly recommended with ICP-MS
detection. Xylene “Baker Analysed” ACS was purchased from J.T.
In our work, three different sample introduction modes Baker (Mallinckrodt Baker Inc., Phillipsburg, NJ).
have been investigated depending on the elements of interest Conostan® S-21 Blended Standards (100 ppm organic
and the matrix analysed. A classical pneumatic nebulizer was multi element standard in oil) and individual Conostan® stan-
used with ICP-OES in order to analyze various elements in dards (5000 ppm organic standard in oil) were used in this
different matrices such as asphaltene fraction, residue, crude work for the samples calibration (ConocoPhillips, Houston,
oil or diesel and gasoline. Depending on the type and volatil- TX). Working solutions were obtained after dilution of the
ity of the matrix, the sample must be diluted by a factor stock solutions in xylene.
ranging from 10 to 50 in xylene. The highest dilutions were Gasoline blanks, originating from different IFP pilot
typically performed when gasoline samples were analysed in plants, were obtained. These samples were also used in order
order to minimise the organic vapour load. However, this in to determine detection limits in gasoline using ultrasonic
turn degrades significantly the quantification limit of the nebulisation. Prior to measurements, each sample was diluted
elements in the gasoline. In order to reduce this effect, nebu- 1:5 and 1:50 in xylene, with the USN and the “high solid”
lisation with an ultrasonic nebulizer (USN) with a cooled nebulizer, respectively.
condenser was tested for gasoline, where lower dilution fac-
tor (typically 5) was found acceptable for the plasma due to
lower solvent load. Finally, a microflow pneumatic concen- 2 RESULTS AND DISCUSSION
tric nebulizer associated with a chilled spray chamber was
used for an optimal analysis of petroleum products by 2.1 Sample Introduction Parameters
ICP-MS. and Measurements
The work presented here gives an assessment of the limit
of quantification obtained with the three different approaches The effective introduction of organic aerosol into the plasma
used as regards to various trace elements occurring in differ- is a critical step that requires a sample introduction strategy
ent petroleum products. The aim of this article is also to char- taking into account the optimal aerosol penetration depth into
acterize the analytical limitation of such sample introduction the plasma, the solvent load, the soot deposition, and of
approaches according to the broad variety of matrices associ- course the signal to noise ratio. Beyond the fact that exces-
ated with the petroleum industry. sive amount of organic solvent may produce soot deposition
72 Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1

TABLE 1
ICP-MS and ICP-OES operating conditions for xylene introduction

ICP/AES IRIS 200 ICP/AES IRIS 200

ICP system ICP/MS X7 CCT THERMO® Electron
THERMO® Electron + USN CETAC AT 5000

RF power (W) 1550 1350 1550

Sampler (Platinum, 1.0);

Cones (orifice diameter, mm) none none
Skimmer (Platinum, 0.7)

cylindric spray chamber USN CETAC AT 5000+

Scott type double
Spray chamber equipped with baffle
pass at –7°C operated at 140°C and –3°C
at room temperature

Nebulizer PFA-100 MicroFlow “high solid” USN CETAC AT 5000+

Injector diameter (mm) 1.14 1.0 1.0

Ar plasma (L/min) 15.5 14 14

Ar outer (L/mn) 1.1 1.5 1.0

Ar nebulizer (L/mn) 0.5 0.45 0.4

O2 nebulizer (L/mn) 0.066 none none

Data acquisition parameters 7 [s] of integration

Resolution (amu) 0.8

Sweeps 100 ND
Dwell time (ms) 20

Replicates 5 3 3

Total acquisition time 10 sec/isotope 21 sec 33 sec

on the torch walls and/or the ICP-MS cones that prevents any where Qtotal is the amount of solvent introduced into the
analysis, experience shows that the minimization of solvent nebulisation device and Qdrain the amount of solvent col-
quantity introduced in the plasma is one of the most critical lected in the drain. These values were obtained after precise
parameters in term of signal stability and intensity. The weighting of the solutions.
reflected power generated by an excessive amount of solvent
may alter significantly the short term signal stability and even TABLE 2
lead to plasma extinction. Moreover, atomization and ioniza-
Efficiency of the different nebulisation system
tion processes taking place in the plasma are highly influ-
enced by the organic matrix which plays the role of a C+
Nebulizer Pump rate
reservoir (Larsen et al., 1994). Carbon (C+) content may then Efficiency
pressure (mL/min)
modify the elements ionisation yield in the plasma and con-
sequently generate sensitivity variation for ICP-MS detec- USN CETAC 5000+ 10% 1.24 Bar 1.8 mL/min
tion, and also biased ionic - elemental emission lines ratio in “high solid” nebulizer 7.5% 1.38 Bar 1.2 mL/min
ICP-OES detection (Botto, 1987). Extreme care must then be PFA-100 + Scott chamber 15.4% 1.5 Bar 0.5 mL/min
taken to minimise the amount of organic materials in the
plasma. Sample quantity was reduced by adjusting the differ-
ent parameters controlling the nebulisation and by using a 2.2 LOQ Assessment with Pneumatic Nebulisation
micronebulizer (100 μL/min) or a desolvatation unit (USN). ICP-OES and USN-ICP-OES
The efficiency of the different nebulisation system was mea-
sured after optimisation and is reported in Table 2. 2.2.1 Optimisation of the Pneumatic Nebulisation
The nebulisation efficiency was calculated as follows: ICP-OES

A 5 ppm multi-elemental (Al, Ba, Ca, Co, Cr, Cu, Fe, Hg,
Q − Qdrain
Efficiency = total ×100 (1) Mn, Mo, Ni, P, Pb, S, Si, Sn, V and Zn) solution in xylene
Qtotal was prepared from individual stock solutions at 5000 ppm.
 CP Lienemann et al. / Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in ICP-OES 73

This xylene solution was taken as representative of the different Five parameters were retained as essential for organic
matrix conventionally introduced in ICP after 1 to 10 dilutions. introduction: sample introduction pump rate, nebulisation
The tuning of the instrument was done with the different wave- pressure, integration time of the signal, plasma power and
length illustrated on Table 3 for the elements of interest. The auxiliary gas. For each emission line, the effect of these para-
lines were classified according to their excitation energy meters on the signal intensity was evaluated by normalizing
compared to the energy of the plasma at 15.75 eV. the signal recorded to its maximum.
Sample introduction rate was controlled by adjusting the
TABLE 3
speed of a peristaltic pump between 60 and 105 rpm. Signal
Classification of the wavelength for the elements of interest
variations related to sample introduction within this speed
Classification
range are reported on Figure 1. Nebulisation pressure effects
Wavelength Excitation energy were also investigated and are presented on Figure 2. As
Element according
(nm) (eV) shown on Figure 1, the optimum sample rate value for a
to Botto (1987)
majority of elements studied is clearly defined at 105 rpm
SI 180.731 6.86 soft
which is equivalent to 1.6 ml/min. For Pb II (220.353 nm),
Mo II 202.030 13.24 hard
Si I 212.412 5.84 soft
P I (214.914 nm) and Ca II (393.366 nm), the maximum was
Zn I 213.856 5.80 soft obtained at 100 rpm, and S I (180.731 nm), Mn II (257.610 nm)
PI 214.914 5.77 soft and Mo II (202.030 nm) show a better response for 90 rpm,
Pb II 220.353 13.05 hard but for all elements the loss of intensity after their maximum
Ni II 221.647 13.22 hard was very small. However, considering the nebulisation pres-
Ba II 230.424 10.59 intermediate sure, distinct optima were observed according to the ele-
Mn II 257.610 12.24 intermediate ments and emission lines. For example, Cu I (324.754 nm),
Fe II 259.940 12.64 intermediate/hard
Ca II (393.366 nm), Al I (394.401 nm), and also, to a lesser
Cr II 283.563 11.14 intermediate
V II 310.230 10.74 intermediate
extend, V II (310.230 nm) present a singular pattern with an
Cu I 324.754 3.82 soft optimum signal shifted towards higher pressure. The
Ca II 393.366 9.26 intermediate selected value at 19 psi, equivalent to Ar flow rate of
Al I 394.401 3.14 soft 680 mL/min, is a compromise between the different lines.

202.030 nm - Mo II 394.401 nm - Al I 202.030 nm - Mo II 394.401 nm -Al I

212.412 nm - Si I Sum of 15 elements 212.412 nm -Si I Sum of 15 elements
259.940 nm - Fe II 259.940 nm -Fe II

100 100

80 80
Relative signal (%)
Relative signal (%)

60 60

40 40

20 20

0
60 70 80 90 95 100 105 16 17 18 19 20 21 22 23
Pump rate (rpm) Nebulizer pressure

Figure 1
Figure 2
Effect of sample introduction flow rate (pump speed) on the
signal response obtained by ICP-OES detection. For graph Effects of nebulizer pressure on the signal response obtained
legibility, only two "soft lines" and two "hard lines" covering by ICP-OES detection. For graph legibility, only two "soft
the spectra between 202 nm and 394 nm among all the wave- lines" and two "hard lines" covering the spectra between
lengths investigated, are presented. The mean curves were 202 nm and 394 nm among all the wavelengths investigated,
obtained by addition of the relative signals of the 15 wave- are presented. The mean curves were obtained by addition of
lengths studied. the relative signals of the 15 wavelengths studied.
74 Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1

2.2.2 Optimisation of the Ultrasonic Nebulisation Coupled 202.030 nm - Mo II 394.401 nm - Al I

to the ICP-OES 213.856 nm - Zn I Sum of 15 elements
259.940 nm - Fe II Mean RSD - right scale
Since ultrasonic nebulisation provides better signal
sensitivity than conventional nebulisation, a 500 ppb multi- 100
30
elemental (Al, Ba, Ca, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, P,
Pb, S, Si, Sn, V and Zn) solution in a mixture of gasoline 80
25
and xylene (1:5) was prepared from individual stock solu-

Relative intensity
tion at 5000 ppm. Gasoline was mixed with xylene in order 60 20
to match light organic matrices conventionally used with 15
USN-ICP-OES. This dilution was based on previous study 40
done in IFP showing that such proportions were sustainable 10
for the plasma. 20
5
The use of ultrasonic nebulisation introduces new
parameters which make the optimization of the USN- 0 0

65
70
80
85
90

0
0
0
0
0
0
0
0
0
10
11
12
13
14
15
16
17
20
ICP-OES coupling more delicate. A multivariate technique Pump rate speed (rpm)
was then applied in order to identify and optimize the
prevailing parameters to be adjusted. Sample pump rate,
heating and cooling of the primary aerosol in the USN, Figure 3
plasma power, auxiliary, and nebulisation gas flow rates Effect of pump speed on the signal response under USN-ICP-
were then selected. Table 4 lists the various parameters and OES conditions.
the experimental range.

TABLE 4
Parameters used for the determination of optimal conditions
dropped slightly at higher pump speed. The overall signal
with USN injection device stability (mean RSD) showed an opposite trend, increasing
with the pump speed from 5% at 65 rpm to 30% at
Part of the 200 rpm. At 80 rpm, an acceptable RSD value (6%) was
Parameters Minimum Maximum
apparatus measured considering the fact that organic solvents were
Sample pump 135 200 directly introduced into the plasma. This pump speed provid-
rate speed (rpm) ing the best signal intensity was finally chosen. These condi-
USN tions corresponded also to the best signal to noise ratio for
Heater (°C) 120 150
most of the emission lines. It is worthwhile to note that
Cooling system (°C) –5 10 different signal intensity optima, shifted towards higher
Plasma power (W) 1350 1750 pump speed, were observed for Cu I (324.754 nm), Ca II
(393.366 nm), Al I (394.401 nm) and P I (214.914 nm).
ICP-OES Auxiliary gas (L/min) 0.5 1.5
However these maxima corresponded also for Al I and P I to
Nebulizer gas (psi) 16 22 the maximum RSD which consequently didn’t improve the
signal to noise ratio.
Eight experiments were then performed, and results The three different plasma power values proposed on the
showed that the more important parameters affecting signal IRIS were studied. Ten percent increase in signal intensity
intensity are sample pump rate and plasma power. In view of was observed from 1350 to 1750 W, while improving RSD.
these results, special attention has been paid to these two A value of 1550 W was retained for further experiments.
parameters and a few tests have been performed on the other Auxiliary Ar was studied between 0.5, 1 and 1.5 mL/min
parameters in order to confirm their minor influence, and also and an optimum was found at 1 ml/min. Nebulisation pres-
to determine their optimal conditions. sure and integration time were optimized between 16 and
The sample flow rate introduced into the nebulizer was 22 psi and from 5 to 13 seconds respectively. The best signal
controlled by adjusting the speed of a peristaltic pump response was found at 18 psi and 11 seconds. The optimal
between 65 and 200 rpm corresponding to 1.2 mL/min and working temperatures of the USN coil were studied between
3 mL/min respectively. The effects of this parameter on sig- 140 and 158°C for the heating module and from –5 to 10°C
nal intensity and signal stability are reported on Figure 3. for the cooling module. The best signal intensity response
The signal intensity resulting from the sum of the various was obtained for 140°C and –3°C respectively for the heating
emission lines was found to be optimal for 80 rpm and and cooling module.
 CP Lienemann et al. / Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in ICP-OES 75

2.3 Determination of LOQ for ICP-OES between samples of different origins, a dilution in xylene is
and USN-ICP-OES usually required and a ratio of 1 to 10 with ICP-OES or 1 to
50 in the case of light matrices is retained. Due to the reduc-
For each emission line of interest, the limit of quantification tion of the carbon load with the USN, the dilution factor for
was calculated according to Equation 2 and results are gasoline using this injection device can be decreased to 1:5.
presented on Figure 4: However, improvements in sensitivity and limits of quan-
c tification are far from being sufficient to define the analytical
C LOQ = 10σ
SNet (2) quality of a technique. Robustness and reliability in complex
matrices should also be taken into account. The important
with: dead volume of the nebulizer (around 200 mL) together with
c element concentration various heating and cooling stages is prone to condensation
σ standard deviation of the blank (n = 10) of organic metal species or complexes either on the glass-
SNet net signal intensity the emission line (SNet = raw count- ware, or in the drain solutions. Underestimation of the true
Background), on a basis of a 5 ppm solution for metal content is then likely to occur (Botto and Zhu, 1996).
ICP-OES detection and a 500 ppb solution for USN- In addition, heavy fractions such as asphaltenes or oil
ICP-OES detection residues can also partially deposit residue on the glass tube in
Due to the lack of certified materials at these low levels of the heated (and cooled) part of the USN suggesting memory
concentrations, validations of the LOQ were done by spiking effects (Botto and Zhu, 1994). In these conditions, the use of
a blank of xylene, or gasoline in the case of USN-ICP-OES, ultrasonic nebulisation is critical and should be limited to
in order to obtain solutions containing element concentra- light fractions like gasoline. Although providing higher limits
tions at the LOQ level. These prepared solutions were then of quantification and limited memory effects, conventional
analysed and the result obtained compared to the true value pneumatic nebulisation should then be preferred in case of
(Fig. 5). Twenty percent difference with the true value was complex matrices. USN is only applicable on light fractions
considered as acceptable, but a higher value for Sn, Fe and of petroleum products, mainly gasoline. Despite the fact that
Ca does not allow us to validate these limits and will require this nebulizer allows better detection limits, important losses
further work on these elements. of metal species and petroleum fractions have been observed
Depending on the emission line, the limits of quantification during the desolvation (Botto, 1993). As a result, the use of
were improved by a factor 5 to 8 with the use of USN. This the USN is restricted to gasoline analysis.
gain is even enhanced by the dilution factor of gasoline in
the final product injected in the plasma. The desolvatation 2.4 Determination of LOQ for ICP-MS
process of the USN permits a reduction in the carbon load
into the plasma, and therefore minimizes the risks of plasma The instrument optimization for the direct analysis of
extinction. In order to reduce instability of the plasma petroleum samples have been previously described by

ICP-AES USN-ICP-OES ICP-MS True value

Result obtained with this work
1000
50

100
40
Concentration (ppb)
LOQ (ppb)

10
30

1
20

0.1
10

0.01
Al Ba Ca Co Cr Cu Sn Fe Mn Hg Mo Ni Pb Si V Zn 0
Al Ba Ca Co Cr Cu Sn Fe Mn Mo Ni Pb Si V Zn

Figure 4 Figure 5
LOQ obtained with the different techniques with pure xylene. Validation of the LOQ with USN-ICP-OES (ng/g).
76 Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1

Dreyfus et al. (2005). LOQs (LOQ-10σ) were calculated from CONCLUSION

the sensitivity (slope) of the analyte addition curve and the
standard deviation of a xylene blank as shown in Equation 2. Quantification limits are dependant on the detector used, but
When injecting organic solution in the ICP-MS, carbon- also on the sample introduction device. In the case of ICP-
argon-oxides species generate polyatomic interferences which OES used with conventional cross-flow nebulizer and Scott
prevent the accurate and precise quantification of some low chamber, limits of quantification are in the 10 to few hundred
M/Z elements such as Mg (12C2+), Cr (40Ar12C+), and ppb range. The dilution factor used for most samples is
Fe (40Ar16O+). These interferences are difficult to overcome 10 times in xylene, degrading the initial limits of quantifica-
with a quadrupole ICP-MS. In this study, the isotopes of inter- tion by the same factor. As a consequence, limits of quantifi-
est were selected depending on the degree of their interfer- cation in pure naphta, middle distillate and residue range
ences. Three elements were identified as highly interfered in between 0.1 and 3 mg/kg depending on the element mea-
the studied matrix composed of petroleum products: sured. For gasoline, the dilution factor used is approximately
Fe (40Ar16O+), Cr (40Ar12C+) and Si (12C16O+). In order to 50 in order to maintain the plasma stability. This important
obtain the most reliable results, only minor or non interfered dilution factor leads to limits of quantification above 0.5 μg/g
analytes were retained in this study for the determination of for the most sensitive elements tested (Ba and Mn), and
between 2 and 15 μg/g for most elements. Silicon, which is
the quantification limits. The list of the selected isotopes is the
an element of interest in gasoline can not be measured below
following: 51V, 55Mn, 58Ni, 63Cu, 98Mo, 120Sn, 138Ba, 208Pb.
5 mg/kg. An effective sample introduction device must then
LOQs obtained for the trace elements are presented in Figure 4
be used in order to reduce the dilution factor for volatile
and range from 0.02 ng.g-1 for Pb to 1.2 ng.g-1 for Mn.
matrices. USN allows the introduction of gasoline diluted
Depending on the elements, ICP-MS provides LOQs 10 to 5 times in xylene. Moreover, the limits of quantification
a 1000 times better than those obtained with USN-ICP-OES obtained with such an apparatus are significantly improved
that is only applicable to gasoline. For all other petroleum for most elements and range between 1 and 30 ng/g. The
matrices, comparison must be done with classical ICP-OES, resulting quantification limits in pure gasoline are then in the
and in this case, measured LOQs with ICP-MS are 10 to 10 to 150 ng/g range. This nebulizer is however used for light
15 000 times lower. matrices only, which is a limiting aspect for laboratories hav-
On the other hand, the ICP-MS instrument is less robust ing different kinds of petroleum products to be measured at
than the ICP-OES. The presence of organic vapours in the the same time. Discrimination effect due to the warming of
plasma from the solvent causes carbon deposit on the cones the aerosol obtained after ultrasonic nebulisation has to be
and on the extraction lenses. Such deposits may later affect checked and concordance of the response of different species
the transport efficiency of the ions, clog the cones and even of metals has also to be verified.
cause plasma extinction. For complete combustion of the The last method tested in this work is based on the ICP-
sample and reduction of carbon deposits on the interface MS technology. In that case, quantification limits obtained
cones, oxygen was continuously supplied to the nebulizer gas with petroleum product are very low, within the 20 pg/g to
flow as described by Dreyfus et al. (2005). Furthermore, 1 ng/g range. Due to the numerous matrix effects observed
combustion processes occurring in the plasma are not similar with the injection of organic product in ICP-MS, the use of
when pure xylene or mixed petroleum products are injected. standard addition methods together with a high dilution fac-
Matrix effects have already been mentioned during the analy- tor are recommended. In our case, a dilution factor of 50 to
sis of different dilution of petroleum products (Botto, 1987). 100 times was found to be sufficient and lead to quantifica-
Organic matrices are known to change the ionization effi- tion limits in the pure sample ranging between 1 and
ciency of elements in the plasma resulting, under some con- 100 ng/g. At this dilution factor, any kind of petroleum matri-
ditions, in enhanced sensitivity for elements incompletely ces, including gasoline, can be injected in the ICP-MS with-
ionized in argon plasma (Munoz-Olivas et al., 1995). out any fluctuation of the plasma. Although discrimination
External calibration procedures do not integrate possible cor- and matrix effects are also reduced by the use of the standard
rections needed for matrix interferences. To overcome this addition method, this method is prejudicial to the sample
problem, the use of standard addition methods must be per- throughput and is only applicable to a small number of sam-
formed for the analysis of petroleum products. Another way ples requiring very low limits of quantification.
to reduce matrix effects is to use high dilution factor. In conclusion, direct injection of petroleum product is
Moreover, concentrations of metals in petroleum products possible with ICP-OES and ICP-MS. The choice between the
must be compatible with ICP-MS potential (linearity span) to two techniques must be based on the required quantification
obtain consistent results. Under organic conditions, experi- limit but also on the number of samples to be analysed per
ence shows that concentrations detected by the mass spec- day. USN injection has to be restricted to gasoline analyses
trometer should be ideally in the range of 1 to 100 ng/g. only, but will require a clear knowledge of the possible
Therefore, according to these two considerations, petroleum discrimination obtained with the treatment of the aerosol
products need to be diluted 1:50 to 1:100. before its introduction in the plasma.
 CP Lienemann et al. / Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in ICP-OES 77

ACKNOWLEDGEMENTS Kellberg L., Zeuthen P. and Jakobsen H.J. (1993) Deactivation of

HDT catalyst by formation of silica gels from silicone oil.
Characterization of spent HDT of coker naphta using 29Si and 13C
Thermo Electron is acknowledged for the loan of ICP-MS. CP/MAS NMR. J. Catal., 143, 45-51.
Stephane Romba is acknowledged for work on USN-ICP- Larsen, E.H. and Stürup, S.(1994) Carbon enhanced inductively
OES, Catherine Bayle, Isabelle Muller and Alban Saunier are coupled plasma mass spectrometric detection of arsenic and sele-
acknowledged for work on ICP-OES. nium and its application to arsenic speciation. J. Anal. Atom.
Spectrom., 9, 1099-1105.
Lopez, L. and Mónaco, S.L. (2004) Geochemical implications of
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