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Spectrochimica Acta Part B 62 (2007) 939 – 951
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The determination of trace elements in crude oil and its heavy
fractions by atomic spectrometry ☆
Christiane Duyck, Norbert Miekeley, Carmem L. Porto da Silveira, Ricardo Q. Aucélio,
Reinaldo C. Campos ⁎, Patrícia Grinberg, Geisamanda P. Brandão
Departamento de Química da Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, 22451-900 Rio de Janeiro, Brazil
Received 5 February 2007; accepted 25 April 2007
Available online 3 May 2007
Abstract
A literature review on the determination of trace elements in crude oil and heavy molecular mass fractions (saturates, aromatics, resins and
asphaltenes) by ICP-MS, ICP OES and AAS is presented. Metal occurrences, forms and distributions are examined as well as their implications in
terms of reservoir geochemistry, oil refining and environment. The particular analytical challenges for the determination of metals in these
complex matrices by spectrochemical techniques are discussed. Sample preparation based on ashing, microwave-assisted digestion and
combustion decomposition procedures is noted as robust and long used. However, the introduction of non-aqueous solvents and micro-emulsions
into inductively coupled plasmas is cited as a new trend for achieving rapid and accurate analysis. Separation procedures for operationally defined
fractions in crude oil are more systematically applied for the observation of metal distributions and their implications. Chemical speciation is of
growing interest, achieved by the coupling of high efficiency separation techniques (e.g., HPLC and GC) to ICP-MS instrumentation, which
allows the simultaneous determination of multiple organometallic species of geochemical and environmental importance.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Trace elements in crude oil; ICP-MS; ICP OES; AAS; Fractionation; Speciation
Contents
1. Occurrences and importance of metals in crude oil and fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939

2. Elemental determinations by atomic spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
2.1. General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
2.2. Analysis after sample decomposition by ashing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
2.3. Direct sample introduction strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 944
2.4. Speciation of elements in crude oil and its fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947
3. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947
4. List of acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
☆
This paper was presented at the 9th Rio Symposium on Atomic 1. Occurrences and importance of metals in crude oil and
Spectrometry, held in Barquisimeto, Venezuela, 5–10 November 2006, and is fractions
published in the special issue of Spectrochimica Acta Part B, dedicated to that
conference.
⁎ Corresponding author. Crude oil is a complex matrix composed predominantly of
E-mail address: rccampos@rdc.puc-rio.br (R.C. Campos). saturated and aromatic hydrocarbons, but also containing
0584-8547/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2007.04.013
940 C. Duyck et al. / Spectrochimica Acta Part B 62 (2007) 939–951
heteronuclear compounds, emulsified water and minerals [1]. porphyrins are observed in intermediate polarity molecular
Consequently, metals occur in different organic and inorganic mass fractions of aromatic and N, S, O compounds [4,26]. Most
forms. The first organic forms identified, the porphyrins, were of the non-volatile elements and low volatility species are found
described in the beginning of the 20th century as tetrapyrrolic in the resin and asphaltene fractions, but mostly in the
complexes of vanadyl, iron (II) [2] and nickel(II) [3] with asphaltenes [31,33,34]. Molecular mass distribution studies
structures similar to chlorophyll and heme. These compounds using gel permeation chromatography revealed that metals
were easily identified by simple spectrographic methods concentrate predominantly in the asphaltene fraction of highest
because of their relatively high concentration, specifically in molecular mass and play a major role in asphaltene polarity
heavy crude oils (e.g., Venezuela Boscan oil) [4]. It was soon [35]. The number of trace elements recognized in the asphaltene
observed that the V/Ni ratio was constant in crude oils of fraction could be greatly expanded using ICP-MS detection and
common source rocks and dependent on the geological age of improved sample introduction methods. It could be shown that
the rocks (oils from Triassic or older age showing a value higher this fraction concentrates trace elements up to ten-fold higher
than unity) [5], and this ratio was used for tracing source effects than the corresponding crude oil, but still preserving its original
[6,7]. Presumably, the metalloporphyrins were derived from elemental fingerprint, allowing new applications in petroleum
chlorophyll-a, after the loss of Mg2+ at the sediment-water geochemistry and in environmental studies [18,30].
interface and the uptake of Ni2+ and VO2+ under the prevailing While advances in refinery processes enable the treatment of
Eh and pH conditions [8]. The high chelating constant resulted high sulfur crude oils, the increasing need for ultra-low sulfur
in high stability of these compounds, distributed between fuels requires the use of low sulfur crudes to reduce the costs of
kerogen and bitumen during oil formation [9]. Studies on the desulfurisation [36]. Metal accumulation in the heaviest polar
thermal evolution of the major vanadyl complex of deoxo- fractions of crude oils plays a significant role in establishing the
phylloerythroetioporphyrin (DPEP) to etioporphyrin indicated a refining procedure, since V, Fe, Ni and Mo have both negative
maturity dependence [10,11], thus suggesting the use of these and positive effects on product recoveries [37]. High metal
compounds as biomarkers [12]. In contrast to V and Ni, the content has a general negative effect due to catalyst deactivation
identification of organic forms of other metals in crude oils was by pore clogging, metal deposition, deformation and fissuration
achieved only later, with the advent of hyphenated techniques, of reactors [38]. However, Ni, Co and Mo have a catalytic effect
e.g., HPLC or GC coupled to AAS or ICP-MS for elemental on hydroprocesses and a careful adjustment of the demetalliza-
detection. Porphyrins of Co, Cr, Ti and Zn were identified in oil tion bed should be made [27]. Most of the metals are separated
shales [13] by HPLC–ICP-MS and volatile compounds of alkyl during deasphaltenation when processes include carbon remov-
and dialkylmercury were identified by GC–CV–AAS [14] and al. When hydrotreatment is used, the hydrodemetallization bed
GC–ICP-MS [15]. and catalyst pore diameter are optimized for a higher recovery
Total metal content in crude oils has an extended and reactor lifetime [39]. Crude oils with high metalloporphyrin
concentration range, and statistical analysis was the first tool content (e.g., Venezuela Boscan oil type) [4,26] are more
applied to investigate general elemental distribution patterns complicated to treat, since part of it is associated with fractions
[16–19]. of intermediate polarity. The process involves hydrogenation
The analysis of oils worldwide having different viscosities prior to demetallization [40], which raises the overall refining
and asphaltene concentrations showed that the more residual the costs. Metals and organometallic species are also incorporated
oil, the higher the metal content, being those metal species during petroleum refining. Nickel, Co, Mo and Ti are
possibly clustered by heavy molecular mass compounds constituents of catalysts [41,42]; vanadate and other metal
[18,19]. Alkaline and alkaline earth elements are predominantly oxides are used during fluid catalytic cracking and SO2
associated as carbonates and halides with the emulsified water oxidation/removal [43].
incorporated into the oil during migration and accumulation in Contamination of soils, water and sediments by crude oil and
the reservoir [20,21], but their presence can also be the result of its derivatives is conventionally evaluated by quantification of
contamination from injected water during secondary oil toxic hydrocarbons (BTX, poliaromatics). More recently, Ni, V
recovery [22]. In sulfate-rich waters, metals are associated and other metals (Cd, Cu, Pb and others) have been included in
with H2S production through bacterial and thermal reduction of the analysis of contaminated soils and organisms by crude oil
sulfates, which can alter their distributions in crude oils [23]. exudates and results show that they can be an important source
Crude oil complexity is simplified by separation steps into of contamination for these elements [44,45]. The final refinery
operationally defined solubility-class fractions. The IP 143 products seem to show a higher toxicity compared to crude oil,
method for asphaltene separation [24] and also a modified since metal speciation is altered and new metals are added to the
ASTM D 2007 method [25] (originally intended for heavy oils matrix. Experimental studies on enriched fuel combustion show
above 260 °C) for maltene fractionation into saturates, that Se and Hg tend to form volatile species, whereas other
aromatics and resin (SARA), were applied for the detection of elements are associated with the particulate matter (e.g., V, Ni,
metal partitioning and its implications in crude oil refining and Co, Zn, Cd, Pb) [46].
petroleum geochemistry [26–31]. Metals and organometallic Effects on human health are of growing concern [47].
compounds distribute roughly in accordance to their volatility. Tetraethyl lead, which was used as an automotive gasoline
The more volatile species (Hg0, MeHg, DMeHg) are found in additive, is a highly toxic compound now forbidden by
the more volatile saturated fraction [32] and vanadyl and nickel legislation [48,49]. Additionally, potentially toxic species like
C. Duyck et al. / Spectrochimica Acta Part B 62 (2007) 939–951 941
selenocyanate (SeCN) are present in wastewater from oil plants, essentially remains a monoelemental method, although the
requiring monitoring and water treatment to prevent pollution recent appearance of a continuum source FAAS instrument [64]
[50,51]. makes sequential analysis possible, similar to those performed
with sequential ICP OES instrumentation. Nevertheless,
2. Elemental determinations by atomic spectrometry detection limits for a series of elements is still poor for many
applications in crude oil analysis. In addition, although the great
2.1. General aspects thermal capacity of the flames used in FAAS with high enough
temperatures for the complete atomization of many elements,
As has been mentioned, crude oil is a complex matrix of different responses for different species for the same element
varying viscosity and mixed phases (organic, water and may be observed in the analysis of samples such as oil dissolved
particulate matter) and therefore not an ideal matrix for analysis. in organic solvents. Thus, a careful control of the atomization
Determination of metals in crude oils by atomic spectrometric (flame) conditions and of sample introduction parameters must
methods requires careful adjustment of experimental parameters be performed if oil dilution in organic solvents is the sample
[52] as well as sample manipulation before sample presentation pre-treatment of choice. Electrothermal atomization in a
to the instrument. Decomposition methodologies can suffer graphite furnace (ET AAS) and chemical vapor generation
from losses or contamination during sample solubilization (CVG) techniques overcomes the sensitivity limitations of
procedures [18,53,54], and if aerosol generation is needed, it FAAS. Nevertheless, while for CVG techniques samples must
may be affected by high amounts of salt that cause erosion of the be reduced in aqueous medium after mineralization or
nebulizer orifice and of the sampler and skimmer cones, in the extraction (with few exceptions) [65,66] ET AAS techniques
case of ICP-MS. Incomplete desolvation and high concentration have the potential to accept samples as they are, minimizing or
of acids result in low mass transport rates of the analyte(s) to the even dispensing with sample pre-treatment. However, carefully
plasma and reduced ion production [55]. Crude oil viscosity and optimized furnace operation conditions must be used for either
heavy molecular mass fractions are critical in sample introduc- atomization from platforms or directly from tube wall. The use
tion methodologies by solubilization in solvents [31] or by of improved atomizers, such as the transversally heated graphite
micro-emulsions [56], causing nebulizer clogging during atomizer (THGA), is recommended in order to improve
aerosol formation and differences in transport efficiencies pyrolysis and atomization efficiency, minimizing build-up of
between standards and samples. Degradation of the torch (ICP sample residues in the atomizer.
OES and ICP-MS) and the sampler and skimmer cones (ICP- All of these facts make the analysis of crude oil and fractions
MS) is also observed when argon–oxygen plasmas are used to by AAS and ICP techniques a challenge. In the following
minimize carbon build-up [57–59]. These problems are avoided sections, different approaches to overcome these difficulties
or minimized in certain direct sample introduction methods, will be reviewed and critically discussed.
such as ETV–ICP-MS [60].
Together with a proper sample introduction technique, 2.2. Analysis after sample decomposition by ashing
multiple calibration curves are often employed in multielemental
techniques (ICP OES and ICP-MS) to cover the wide range of Matrix decomposition results in aqueous solutions that can
metal concentrations in crude oils, from below ng g− 1 to hun- be, in principle, analyzed by any spectrometric technique.
dreds of μg g− 1 [4,18,30]. Internal standardization is not only Ashing of the crude oil followed by dissolution of the ash in
used for instrumental drift correction, but also to account for mineral acids was the first decomposition method used, prior to
differences between blanks, calibration standards, and samples. the determination of metal content by FAAS or ICP OES [19].
For the most complex matrices, the analyte addition calibration About 5 to 10 g of crude oil is usually placed in a quartz beaker
is the only method that will yield reliable results [31]. or a platinum crucible and heated over a Bunsen gas burner to
Spectral interferences inherent to the analysis of highly achieve total ashing of the material. Although this procedure is
organic loaded samples by ICP techniques may occur, requiring still largely employed in industry, it is time-consuming (about a
the use of alternative wavelengths or isotopes of lower day-long), and dangerous due to the evolution of toxic vapors
abundance [57,61,62], e.g. 26Mg (11.01%) instead of 24Mg and the usually low flash point of petroleum. The simultaneous
(78.99%), the latter interfered by 12C2+ (see further below). use of mineral acids (e.g., H2SO4, HNO3, HCl) may be an
Spectral interferences of argon and carbon species are less advantageous alternative, but the main drawback of this method
critical in ICP OES since they can be minimized or avoided by is the loss of elements by volatilization (Hg, halides of As, Se, V
proper line selection and/or observation height [61]. Nonethe- and Pb), the contamination by the larger amount of reagents
less, they contribute to the overall background elevation. ICP used and the open environment, and the precipitation of sparely
OES is, however, limited by its reduced detection power (μg soluble salts during the final dissolution step (e.g., sulfates of
g− 1 range) for most elements, which restricts its applications in Pb, Ba and Sr) [18]. Since acid decomposition of the matrix in
geochemical and environmental studies [28,63]. open vessels avoids the safety risks characteristic of the dry
Due to its nature, good selectivity is associated with AAS ashing procedure and allows the simultaneous processing of a
methods. Flame AAS (FAAS) is a well established and high number of samples, it is still largely used [28]. Such a
accessible technique, less prone to spectral interferences in procedure is generally performed with larger volumes of
comparison to other spectrometric techniques. However, AAS oxidizing acids (e.g., 10 mL of acid per 0.5 g of sample) and
the time for complete decomposition is long (up to several and/or the application of desolvation systems for reducing the
days). solvent load [74]. Advances in ICP-MS instrumentation are
Contamination and losses are overcome by the use of acid likely to provide additional solutions to the problem of
decomposition in closed vessels, performed in conventional polyatomic interferences, with progress in dynamic reaction/
heating systems (such as the Parr reactor [67], or its improved collision cell technologies and high resolution spectrometers
version, the High Pressure Asher [68]) and microwave-assisted [76]. In the case of DRC–ICP-MS, the species are destroyed by
heating [69]. All of these procedures provide final light-colored collision with a reactive gas (CH4, NH3) and improvements on
and transparent solutions in contrast to the open vessel major interferences are achieved at a relatively low-cost [77].
procedures, indicating that carbon has been more efficiently HR-ICP-MS has, however, the advantage of resolving most
removed. Focused microwave-assisted heating decomposition spectral interferences [55], but instruments seem to be less
has been developed for on-line decomposition and low robust and are more expensive.
contamination of geological samples [70]. This is a promising Flame, electrothermal furnace as well as chemical vapor
technique for the decomposition of crude oil, and more generation AAS are well suited for trace-metal determinations
specifically its heavy fractions (asphaltenes and resin), in oil after ashing. Indeed, ashing of a sufficiently large sample
permitting automation of the processing; however, matrix mass may compensate for the comparatively lower FAAS
effects and spectral interferences due to residual carbon content sensitivity, although a longer analysis time is needed. However,
should be evaluated [71]. Additional oxidative reagents, such as losses of Ni and V, present as volatile compounds (metallopor-
H2O2 used after acid decomposition, are necessary for better phyrins), may occur if adequate care is not taken. For instance,
carbon removal [72]. All of these methods have a poorer Udoh et al. [78] and Platteau and Carrillo [79] suggest the use of
reproducibility of the results when compared to simple dilution linear alkylbenzene sulfonic acids for stabilizing these com-
in organic solvents or to micro-emulsion based methods. pounds. The former authors remember that the addition of sulfur
Unfortunately, only a very limited number of appropriate containing compounds has long been the strategy of choice for
certified reference materials (e.g., NIST 1634b and 1634c) are avoiding losses of Ni and V by volatilization during ashing.
available for the validation of decomposition methods for heavy According to Platteau and Carrillo [79], the simultaneous
crude oil and its fractions. A more recently available ignition of the oil–acid mixture, while it is still boiling, prevents
decomposition system, which uses pressurized quartz vessels, volatilization losses for Fe, Na and Ni, eliminates the coke
the High Pressure Asher (HPA), considerably reduces the residue and reduces the ashing time, thus allowing the
residual carbon content; however, the higher amounts of achievement of results similar to those obtained by standard
reagents used (e.g., 10 mL of HNO3) require an additional methods for the same samples. Ashing procedures based on the
vaporization step to get rid of excess HNO3, especially when use of sulfuric acid for the trace-metal determination in oil are
ICP-MS is employed for elemental detection [73]. also suggested in the literature and they were recently re-
External calibration procedures in atomic spectrometric approved as standard methods for the determination of Ni, V,
techniques for the analysis of crude oil after decomposition and Fe in crude oils and residual fuels [80]. Infrared heating
are similar to those employed for solutions of varying acidity (1 using a “mini-ash” device is also proposed [81]. An overview of
to 10%): they may use analytical solutions prepared in the same ashing procedures using sulfur compounds can be found in
medium as the blank solution (AAS) and/or by the corrections Sychra et al. [82]. Ashing followed by fusion, and post-
of an internal standard(s). The need for the “analyte addition determination by ICP OES and AAS is also proposed as
calibration” depends on several factors, including the carbon standard methodology for the determination of silicon and
content and viscosity of the matrix and, obviously, on the aluminum in fuel oils [83]. In general, hydrochloric acid is the
required accuracy and repeatability of the results. For a given acid of choice for the final dissolution of the mineral residue.
ICP instrument, detection limits are generally improved when In the case of mineral acid decomposition, the acid, salt and
desolvation devices are used, such as ultrasonic nebulizers and/ carbon content of the final solution to be presented to the
or membrane separators [74]. instrument is not as critical in AAS techniques as for ICP-MS.
In ICP-MS, spectral interferences may occur as crude oil This may lead to simpler sample dissolution procedures and
contains a high number of elements in the low concentrations lower dilution factors. EPA method 3031 [84] proposes the
range (ng g− 1). Doubly charged ions (Ba2+ at m/z 69, Ga) are use of an initial oxidization with an excess of KMnO4 in the
also potential interferents encountered during the analysis of presence of sulfuric acid, followed by heating and further
decomposed solutions of high salinity. Polyatomic interferences mineralization with HNO3 and an excess of HClO4. FAAS, ET
generally arise from the reaction products of argon with major AAS and ICP OES are indicated for the instrumental
matrix components (e.g., Na, Ca, Sr) or residual carbon [75]. determination of a number of trace elements. If ET AAS is
Ar-species of Na, Cl and Ca interfere respectively at m/z = 63 the technique of choice, the elimination of the excess HClO4 is
(Cu), m/z = 75 (As) and m/z = 78, 82 (Se); carbon species (C2, recommended. In the case of As, the crude oil samples were
ArC) interfere at m/z = 24 (Mg) and m/z = 52, 53 (Cr). In oils of digested with sulfuric acid and H2O2 under reflux, followed
high sulfur concentrations, additional interferences from S by measurement of As in the diluted digest by hydride
species may superpose (e.g., 32S32S and 34S32S species on Zn at generation AAS [85]. An acid digestion procedure with a
m/z 64 and 66). Frequently, polyatomic interferences are HNO3–H2SO4 mixture under reflux is proposed by Turunen
minimized or avoided by the choice of alternative isotopes et al. [86]. The whole procedure takes 2–3 h and special care
must be taken in the first digestion steps, due to risk of explosion. for oil digestion was critically investigated by Costa et al.
The determination of As, Cd, Cr, Cu, Mn, Ni, Pb and V was [71]. The authors conclude that a focused-microwave oven
performed by ET AAS, a technique that can deal well with designed with one magnetron and six reaction flasks led to
residual carbon if STPF conditions are followed, with the special different degrees of decomposition, depending on operating
attention to the background correction system. Acid digestion conditions, such as sample cavity position and applied power.
efficiency may be enhanced by microwave heating. In this way, The consequent variation in the residual carbon content could
EPA method 3051 [87] uses the digestion of oils and other affect the quantification of elements susceptible to carbon
samples with 10 mL of nitric acid; for 0.5 g-samples, only argide isobaric interferences when using ICP-MS.
10 min of heating is, in principle, necessary. FAAS, ET AAS, Extraction appears to be an alternative to mineralization for
ICP OES and ICP-MS are indicated for the instrumental the determination of As in crude oil [92]. Extraction was
measurements. Alvarado et al. [88] optimized a method for the performed with boiling water or boiling aqueous nitric acid
microwave digestion of various crude oil samples, investigat- (concentration 0.25 to 2.5 M), followed by the mineralization of
ing various proportions of nitric and sulfuric acids. The the extracts with concentrated nitric/sulfuric acid, and reduction
solutions obtained were analyzed by ET AAS for Cr, Cu, Fe, of the arsenate to arsine in a hydride generator. Viscous
Mn, Ni and V and for Na and Zn using FAAS. Analyte hydrocarbons, such as fuel oil, must be dissolved in xylene for
addition had to be used for accurate results. As pointed out by the extraction to be successful. In the case of ICP-MS detection,
Bettinelli et al. [89] and Krachler et al. [90], the use of the direct determination of As in 1–10% HNO3 matrices was
microwave digestion in a high-pressure closed vessel reduces possible using 4% (v/v) ethanol to reduce the ArCl interference
sample decomposition time because higher temperatures can [93]. In hydride generation techniques, the separation of the
be achieved, leading to faster reaction times and the analyte from the matrix and its interference-free measurement is
decomposition of difficult samples, besides other advantages intrinsically associated with the method. However, attention
already pointed out in this review. In an attempt to determine must be paid to some potential interfering species, such as Ni2+,
As, Sb and Se in oily wastes by hydride generation AAS, in order to avoid their interference in the hydride generation
Campbell and Karnet [91] stated that any residual organic process in the liquid phase [94]. An extraction method is also
matter may cause difficulties, especially if the analytes are proposed for the determination of V in petroleum crudes, based
present as organometallic species. They overcame these on the synergistic extraction of the V(V)-5,′-methylene-
difficulties by complete oxidation of the organic matrix after disalicylohydroxamic acid (MEDSHA) complex with a 0.5 M
solvent extraction using microwave-assisted digestion in a tributyl phosphate (TBP) solution in isobutyl methyl ketone
closed system. The use of focused microwave-assisted heating (IBMK), followed by FAAS [95]. Table 1 summarizes matrices
Table 1
Elemental determination in crude oil and heavy fractions by ICP-MS and ICP OES
Matrix Element(s) determined Solubilization procedure Technique Reference
Crude oil V, Ni, Co, Cu, Mo, Fe, Mn, Zn, Ti Ashing decomposition ICP OES [19]
Crude oil S, Al, V, Ni, Co, Fe, Cu, Zn, Ba, Mo Micro-emulsion ICP OES [17]
Crude oil, saturates, aromatics, resin, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ga No ETV–ICP-MS [113]
asphaltenes
SRM residual fuel oil 1634c, crude oil, Ag, Al, Ba, Cd, Co, Cu, Fe, La, Mg, Mo, Microwave acid decomposition ICP-MS [18,30]
saturates, aromatics, resin, asphaltenes Mn, Na, Ni, Pb, Sn, Sr, Ti, Pb, U, V, Zn, Y, in closed vessels
La–Lu, Au, Pd, Pt, U, Th
Saturates, aromatics, resin, asphaltenes Co, Cr, Cu, Fe, Mo, Mn, Ni, Sr, V, Zn Acid decomposition in ICP OES [28]
open vessels
Crude oil Hg Combustion in Carius tubes ICP-MS [53]
SRM residual fuel oil 1634b Ag, Al, As, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, Microwave acid decomposition ICP-MS [72]
Mg, Mo, Na, Ni, Pb, Sb, Sn, Sr, Ti, Tl, U, V, Zn in closed vessels
SRM residual fuel oil 1634b Na, Mg, Al, Ti, Cr, Fe, Ni, Co, Cu, Ag, Pb No LA–ICP-TOF-MS [114]
Crude oil Li, Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sr, Mo, Micro-emulsion ICP-MS [56]
Ag, Cd, Sn, Sb, Ba, Pb
Crude oil Mo, Zn, Cd, Ti, Ni, V, Fe, Mn, Cr, Co Micro-emulsion ICP OES [112]
Crude oil cut (naphta) Na, P, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Dilution in xylene ICP-MS [98]
Y, Mo, Cd, Sn, Sb, Hg, Pb, Bi
Synthetic crude oil As, Cd, Hg, Ni, Pb, V Dilution in xylene DIHEN–ICP-MS [105]
SRM residual fuel oil 1634c, crude oil, Ag, Al, Ba, Cd, Co, Cu, Fe, La, Mg, Mo, Mn, Solubilization in toluene and ICP-MS [31]
saturates, aromatics, resin, asphaltenes Na, Ni, Pb, Sn, Sr, Ti, Pb, U, V, Zn, Y ultrasonic nebulization
Crude oil, gasoline, distillation cuts Cu Ashing, microwave-assisted and ICP-MS [54]
and residue combustion decompositions
Crude oil (oil spill) Cd, Cr, Cu, Pb, Mn, Ni, V, Zn Microwave-assisted acid ICP OES [63]
decomposition
analyzed by ICP OES and ICP-MS using different sample in solvents. The analysis of naphta was successfully achieved
preparation procedures. with a DIN [98] and a high efficiency DIN (DIHEN) [105]
using oxygen in the nebulizer gas flow, with solution uptake
2.3. Direct sample introduction strategies rates as low as 60 and 10 μL min − 1 , which reduced
considerably the carbon and oxygen levels in the plasma. The
Direct introduction of crude oil and derivatives into ICP DIN methodology [98] allowed the determination of volatile
instruments has been performed by two techniques. The first elements like As with limits of detection lower than 0.1 ng g− 1.
uses sample solubilization in an organic solvent (e.g., toluene, The solutions were weekly stable for As. The DIHEN was used
xylene, kerosene) and the second is an emulsification procedure for the determination of Hg and its organic species in hexane,
in aqueous solutions in the presence of emulsifiers. with similar detection limits and without significant memory
Solubilization of crude oil and derivatives in solvents is by effects [106]. SPL can also be lowered using micronebulizers
far the most studied and used direct introduction technique for from which the new Teflon ones showed improvements for the
ICP instruments and is widespread in the industry [58,96–98], liquid/gas interaction and are promising tools for solvent
essentially, because it is a fast and accurate technique. Its introduction [107,108].
advances follow closely the improvements in sample introduc- The availability of DRC- and CC–ICP-MS instruments and
tion systems and ICP instrumentation. Crude oil and derivatives the proper choice of reactive gases are also promising means for
dissolve in solvents like toluene, xylene chloroform and the removal of major spectral interferences caused by solvent
kerosene. In early studies, the Meinhard nebulizer was used in introduction into the plasma in the case of quadrupole mass
combination with a Scott spray chamber to introduce these spectrometers [77,108].
solvents into ICP OES instruments. The solvent plasma load Solubilization of crude oil by water-in-oil (w/o) or inverse (o/
(SPL) was identified as a critical problem, which causes w) emulsion formation has gained interest because it allows the
instability and sometimes extinction of the plasma and raises the determination of elements in the organic phase using inorganic
background level due to the strong C2 green and other emissions aqueous standards. The first study of o/w micro-emulsion used a
(e.g., CN, OH) [57,61]. Desolvation of the aerosol was achieved non-ionic surfactant to assist dispersion of oil as organic
through a − 10 °C refrigerated chamber, which was the micelles in water. Sample introduction into ICP-MS was
temperature calculated for a minimum SPL for low vapor performed with a Meinhard nebulizer/Scott spray chamber
pressure solvents like chloroform, and background level was system refrigerated at 8 °C [56]. The solutions were monthly
reduced by use of higher observation heights (15 mm) and stable, and carbon interferences on m/z 24 (Mg) and 56 (Fe)
higher plasma temperatures (1.5–2 kW of forward power) [57]. were considerably reduced, allowing the determination of these
When the technique is applied to ICP-MS, another critical effect elements even in the presence of the organic phase (1,2,3,4-
observed is the deposition of carbon on the sampler and tretrahydronaphtalene: Triton X-100). Good results were
skimmer cones, and a higher level of carbon interferences [99]. obtained for SRM NIST 1634c; however, limitations were
The problem was overcome by O2 addition to the argon [100] observed with heavy crude oil emulsions, which showed a
but new interferences appeared due to the presence of oxygen: signal drop of the internal standard of up to 50% [56]. Triton X-
e.g., ArO at m/z 56 (Fe), CO2 at m/z 48 (Ti). Chloroform could 100 emulsions were also successfully applied to the determi-
not be used due to Cl interferences (ClO and ArCl) at m/z 51 (V) nation of V, Co, Ni, As, Hg and Pb in naphta [109]. Another
and 75 (As), respectively. Determination of several elements in non-ionic emulsifier, polyoxyethylene nonylphenyl ether (Ige-
SRM NIST 1634b was performed with acceptable accuracy pal), was preferred for heavy crude oils because of his slightly
[62]. The use of a heated tube instead of refrigeration for aerosol higher hydrophile–lipophile balance number (Igepal CO-
desolvation was more efficient in reducing the SPL and pointed 720 = 14.2, instead of 13.5 for the Triton X-100), which enabled
to the limitation of the Meinhard/Scott refrigerated system higher solubility in water through hydrogen bonding [110]. In
[101]. order to reduce solution viscosity, the same authors added
The advent of ultrasonic nebulization devices, which xylene, without using a refrigerated spray chamber during
combined temperature and refrigeration along with a membrane sample introduction, which compromised the limits of detection
desolvator, finally retired the Meinhard nebulizer for this because of incomplete combustion of the organic matter [111].
purpose [58,96]. A universal calibration for solvents was Detergentless emulsions were reported for the determination of
proposed based on n-hexane with good recoveries [97]. elements in crude oils by ICP OES using acidified water for
Calibration was achieved using organometallic standards in element stabilization and propan-1-ol as a co-solvent, with
oil (Conostan, Conoco, USA). However, memory effects and addition of oxygen to the nebulizer gas flow [112].
higher dispersion of the droplet diameter were observed Direct introduction of crude oil and fractions in ICP-MS has
[102,103], as well as the loss of volatile species of Pb and Hg also been investigated using special introduction devices, such
during analysis of condensates and naphta [104]. For the as electrothermal vaporization (ETV) and laser ablation (LA).
analysis of crude oil and fractions, the USN device was used Ten elements in crude oils and fractions were determined by
without heating, and good accuracy was obtained for determi- ETV–ICP-MS for the study of oil migration [113], using 10–
nation of metals in fuel SRM by ICP-MS [31]. Direct injection 15 μL of sample and a vaporization temperature of 2550 °C.
nebulizers (DIN) and micronebulizers appear as the next path Recovery values for the crude oil fractions were not satisfactory
for multielemental analysis of crude oil and derivatives diluted for six elements, which raise serious doubts about the overall
methodology. However, ETV–ICP-MS is an interesting due to the leveling effect of the matrix on some of the physical–
technique for heavy crude oils and fractions like resin and chemical properties involved in the atomization process. The
asphaltenes, because of the total removal of the matrix, but authors recommended the accuracy being checked with the
possible interferences from the volatilized carbon of the furnace dilution method for each set of samples by comparing the results
should be further investigated. with those achieved using a wet-ashing procedure. Neverthe-
Laser ablation was also investigated for the direct introduc- less, Bettinelli and Tittarelli [120] validated a procedure for the
tion of SRM NIST 1634b into ICP-TOF-MS [114]. The laser determination of Ni and V in fuel oil based on the 1 + 9 dilution
was a nanosecond Nd-YAG working at 266 nm wavelength. with xylene and calibration with Conostan organometallic
The ablation cell was modified for higher efficiency of analyte standards, using base oil for matching the viscosity or fuel oil
transport to the plasma and narrower transient signal profile. with known metal content. Nickel was determined in air–
Calibration was achieved in wet plasma conditions introducing acetylene flame and a nitrous oxide–acetylene flame was used
simultaneously the aqueous calibration solutions through a for V. The procedure was compared with a series of independent
Meinhard nebulizer/Wu–Hieftje vertical-rotary spray chamber methods in the analysis of six samples with different metal
system, or in dry plasma conditions using organometallic contents. Results very close to the consensus values were
standards. The technique showed high sensitivity for multiel- observed. The authors state that the better repeatability and
ement determination and good accuracy, however, chemical reproducibility observed in comparison to other similar methods
fractionation was not investigated. came from the more detailed specification of experimental
Oil dilution in an appropriate solvent followed by direct parameters, such as checking the instrumental performance,
analysis by FAAS appears as a natural and simpler alternative to alignment of the burner head and radiation beam, and selection
sample mineralization and has been long applied. The solvent of the aspiration rate. A limited aspiration rate of the organic
must offer a stable and non-luminous flame, low toxicity and, of solution (b 2ml min− 1) was recommended.
course, be able to completely dissolve the sample. The final The association of sample dilution with ET AAS would, in
solution must be homogeneous and stable in time. For instance, principle, overcome problems encountered with determinations
use of FAAS after dilution of the oil with an organic solvent is by FAAS. Its higher sensitivity would permit the determination
proposed in an ASTM standard test method for the determina- of less concentrated elements and the high temperatures during
tion of Ni, V, Fe, and Na in crude oils and residual fuels [80]. the pyrolysis step would eliminate most of the matrix and bring
Dilution in xylene was used in the comparative determination of the analyte to the same chemical form, avoiding differences in
Ni and V in crudes and heavy crude fractions by ICP OES and sensitivity due to different compounds. Moreover, the larger
FAAS [115]. Solubilization with MIBK was used in the analysis dilution factor permitted due to the higher sensitivity would
of crudes and its burning residues for the determination of V reduce the chances of matrix interferences. In this way, Bruhn
[116] as well as Cd, Pb and Ni [117], also by FAAS. The authors and Cabalin [121] proposed the determination of Ni in gas oil
note, however, that analyte addition calibration with organo- after dilution with xylene. However, analyte addition had to be
metallic standards is necessary for accurate results. A toluene– used and analyte solutions prepared from different Ni organo-
acetic acid mixture was used as solvent for the dilution of compounds led to different sensitivities. The choice of the
petroleum crudes and further determination of Ni, Cu, Zn, Na, adequate Ni compound for calibration had to be decided after
Pb, Cd, and Fe by FAAS. Calibration was performed with comparison with the reference wet-ashing results obtained with
inorganic salts and by analyte addition. Systematic errors the FAAS methodology. The author also pointed out problems
between the proposed procedure and a comparative one related to analyte solution stability at the μg L− 1 range. A
consisting of sample dilution in xylene and organometallic discussion on possible losses of volatile Ni species during
calibration ranged from 2 to 25% [118]. As early as 1981, pyrolysis is also presented, as well as the promising use of
Sychra et al. [82] presented a detailed discussion on the flame chemical modifiers to overcome such losses. Taking all findings
analysis of crude oils, heavy petroleum oils and residues using into consideration, good concordance between proposed and
dilution methods. The authors reviewed the application of this reference methods was obtained. The problems reported by
procedure up to that date, and pointed out problems that must be Bruhn and Cabalin [121] summarize all factors that must be
addressed: Hardly a single solvent or a solvent mixture is able to considered in solvent dilution–ET AAS approaches and agree
completely dissolve all the different kinds of oil samples. Thus, with the critical observations, presented by Sychra et al. [82], on
dissolution efficiency varies for each class of oil sample, with early ET AAS work. Vanadium, Ni, Fe and Pb were determined
highly paraffinic oils presenting the major difficulties. Also, in crude and fuel oil following dilution with xylene and MIBK
different organic compounds of the same element present [122]. The authors report good agreement with certified values
different responses in the flame, no matter if an air or a nitrous for the analysis of SRMs and analyte addition calibration curves
oxide acetylene flame is used. This leads to calibration showed the same slope as those obtained with organic analytical
difficulties as well as different responses depending on the solutions. No modifier was used, even for the determination of a
organometallic composition of the sample [119]. Matching the volatile element such as Pb. Bermejo-Barrera et al. [123]
analytical solutions' and sample's physical properties is also a observed that xylene dissolution and dry calcination were
challenge. In short, the authors state that external calibration equivalent for the determination of V in petroleum samples by
should only be used for a rapid and rough estimation of the ET AAS. The authors propose that the crude oil must be so
metal content; analyte addition calibration being more accurate strongly diluted that matrix interference is eliminated. The
behavior of a series of chemical modifiers for the determination emulsified by stirring with 3% Triton X-100 in water.
of V in a water and oil matrix was studied by Thomainidis and Calibration was performed with organometallic standards
Piperaki [124]. Since a longitudinally heated furnace was prepared in the same way. The emulsions were stable from 20
employed, no platform was used, but all other STPF conditions to 50 min. Different permanent modifiers were studied under
were followed. In the determination of V in a multielement STPF conditions. The W–Ir permanent modifier proved its
standard diluted with MIBK, Pt as modifier enhanced the utility for the determination of Ni, while for V the untreated tube
pyrolysis temperature from 1000 °C to 1400 °C, with appeared to be more suitable. Excellent agreement between
improvements in sensitivity. No difficulties on mixing the found and certified results was observed in the analysis of two
aqueous modifier with the organic sample is reported, as well as SRM. Burguera and co-workers [128] determined Cr in heavy
no application to real samples. The determination of Cd, Cr and crude oil and in a bitumen-in-water emulsion by ET AAS after
Cu in crude oils was also performed by Stigter et al. [85]. sample emulsification. The optimum sample emulsion compo-
Atomization from a platform, Zeeman-effect background sition was 7:3 v/v (w/o) + 0.2% w/w of a non-ionic surfactant,
correction as well as oxygen ashing during the pyrolysis step which was 1 + 8 diluted with a 0.2% w/w solution of the
was used. For Cd, the authors diluted the samples with carbon surfactant. STPF conditions permitted the calibration with
tetrachloride. Due to the toxicity of this solvent, xylene was aqueous analytical solutions, and good concordance with a
used for the other metals. The authors pointed out the instability comparative procedure was obtained. Emulsification was used
of samples and organometallic standards in these media, and in a detailed study on the optimization of the Ni determination
finally changed to a 4:1 v/v mixture of toluene and acetic acid as in petroleum using both line source and high resolution
solvent. Cadmium, Cu, and Cr were determined by ET AAS and continuum source ET AAS [129]. After verifying that samples
Zn by FAAS. The authors noted that the analytical solutions and analytical solutions diluted with xylene and MIBK were not
(Conostan standards diluted in the solvent mixture) as well as useful due to their poor stability, the authors stabilized samples
the diluted sample should be freshly prepared, due to potential and analyte solutions as an o/w emulsion consisting of xylene,
lack of stability after 48 h. The efficiency of the sample Triton X-100 and water. An ultrasonic bath was used in the
homogeneity procedure was also addressed and relative emulsification process and the mixture was further homoge-
standard deviations (n = 10) up to 26% for Cd and 7% for Cr nized just before the measurement by manually flushing them
were observed. Validation was performed by comparison with with a micropipette. The authors observed that significant Ni
wet-ashing methods, and in contrast to the agreement observed losses occur at pyrolysis temperatures as low as 500 °C, most
for other elements, significantly lower results for Cd were probably due to the presence of volatile Ni species. Thus, good
presented. It is worth noting that no modifier was used. A concordance between found and expected results could be
tungsten-coated graphite furnace was used for the determination achieved only if a pyrolysis temperature of 400 °C was used.
of V in heavy fuel oils [125]. Sulfur interference was studied in The BG-correction ability of the continuum source AAS was
detail. These studies showed that the solution presented to the able to deal with the high BG values observed with such a low
instrument should contain less than 1% sulfur. Good concor- pyrolysis temperature. Similar stabilization difficulties were
dance between the results obtained from the proposed (sample experienced by Aucélio and co-workers [130] in the determi-
dilution with tetrahydrofurane + light oil, 1 + 1) and comparative nation of V in the asphaltene petroleum fraction. A solution of
procedures was reported. asphaltene in dichlorethane was obtained as the result of the
The use of emulsions for the dilution of organic liquid fractionation procedure, and this solution showed clear loss of V
samples is an alternative to the dilution with organic solvents, as a function of the sample solution storage time (formation of
with some potential advantages. In the case of FAAS, less insoluble V species or/and their adsorption of on the wall of the
organic solvent is presented to the flame, while for ET AAS the storage vial) as well as during ET AAS analysis due to the
use of modifiers is facilitated and the sample and analytical formation of volatile compounds. The solution was stabilized
solutions are more stable at the μg L− 1 level. Emulsification by simply mixing with propan-1-ol and 6 mol L− 1 HNO3,
retains the simplicity of the dilution process and permits the use forming a detergentless micro-emulsion. The micro-emulsion is
of inorganic standards for calibration. The determination of Ni spontaneously and immediately formed, and its stability was
in fuel oil by FAAS using 4% v/v oil-in-water emulsion is confirmed up to 80 h. Calibration was performed by spiking
described [126]. The oil sample is diluted in water in white spirit inorganic V in the same micro-emulsion medium. The analysis
emulsion. An Ni aqueous working solution dispersed in the of the asphaltenic fraction of a fuel oil SRM showed a coherent
same medium is used for calibration. For matching the viscosity result taking into consideration the certified value for V in the
between samples and analytical emulsions, water and lubricat- whole fuel oil. Damin and co-workers [131] investigated the use
ing oil are respectively added to these dispersions. Comparison of Pd as a chemical modifier for the stabilization of the volatile
of the slopes of analyte addition curves and analytical curves Ni and V compounds in oil samples, since the BG ability of line
prepared in the same way as the sample confirmed the source ET AAS was not able to correct the high BG values
possibility of external calibration. The comparison with a imposed by the necessary low pyrolysis temperatures if no
reference method led to concordant results. Nickel and V were modifier was used. The oil sample was stabilized as an o/
determined in naphtha and fuel oils after emulsion formation by w emulsion, whose composition was optimized by a multivar-
ET AAS using W–Ir as permanent modifier [127]. The oil iate method. The use of Pd (20 μg) as chemical modifier
samples were diluted in toluene, and this solution was permitted pyrolysis temperatures high enough to lead to low BG
without any analyte loss. Good agreement was observed occur, and also by a loss of sensitivity due to the reduced
between found and expected values, using analytical solutions electroosmotic flow (nL min− 1), inherent to this separation
prepared in the same way as the samples spiked with inorganic technique. If HPLC is the method of choice for high boiling
standard solution. point organometallic compounds, GC is the one for volatile
Another approach is direct sample introduction for ET AAS, species. Mercury species were successfully determined by GC–
in which the sample is used without any further treatment other CV–AAS [14] and GC–ICP-MS [15] in natural gas conden-
than homogenization [132]. This technique can also be used for sates and require a cryogenic trap for retention of MeHg and
highly viscous liquids, and has applied to the determination of DMeHg prior to GC separation.
Ni [133], Ni and V [134] as well as Cu, Fe and V [135] in oil
samples. This approach brings the advantage of no chemical 3. Conclusions
sample pre-treatment, eliminating contamination and losses
related to this step. The adequate use of modifiers avoids From a general point of view, there is not a unique meth-
analyte losses during the pyrolysis step. The addition of Triton odology for determination of elements of interest in crude oil
X-100 to the modifier solution improved its efficiency, probably and its derivatives. The choice of the methodology should be
due to a more effective interaction between the aqueous based on the matrix, on the element (or series of elements) to be
modifier solution and the oily sample. Calibration curves with determined, and on the objectives of the analysis. Decompo-
aqueous analytical solutions were used, and the results for oil sition methodologies are time-consuming; however, they are
samples and SRM were concordant with those derived from generally more robust and accurate than direct sample intro-
conventional procedures. duction after sample dilution in organic solvents. This results in
more complex matrices. Decomposition by wet-ashing is the
2.4. Speciation of elements in crude oil and its fractions most frequently applied technique, even in standard methods.
Losses may be avoided by adding a sulfur containing com-
The hyphenation of HPLC and GC with elemental detectors, pound, but strict control of the ashing temperature must be
such as ICP-MS, ICP OES, AAS and AFS, permits the observed, otherwise volatile species may be lost. Naturally, care
determination of elements in their organometallic form. The is necessary to avoid contamination. The use of microwave-
chromatographic techniques are used to separate and also assisted heating is the better way to perform acid mineralization.
identify the different forms, while the atomic spectrometric Sample dilution is evidently very attractive, due to its simplicity.
detectors are used for quantification, using adequate standards. However, this simplicity must not lead the analyst to forget that
In a few early studies [136,137], HPLC was interfaced with ET oil is a very complex mixture, and its composition changes
AAS in order to investigate the presence of different Ni and V according to its origin. Complete solubilization may be difficult,
compounds in heavy crudes and asphaltenes as a possible fin- due to the presence of water clusters that may contain inorganic
gerprint of the oil. However, ET AAS is not well suited as a salts. Furthermore, not all organic compounds are soluble in
specific detector in hyphenated techniques, due to its stepwise the more common organic solvents that are appropriate to
characteristic. FAAS [138] was used in the comparison of three the subsequent atomic spectrometric measurement. In some
analytical methods to isolate and characterize V and Ni cases, an appropriate solvent mixture, with solvents of different
porphyrins from heavy crude oil. However, the use of FAAS polarities, may be the best choice. In the case of ICP techniques,
as a detector in hyphenated speciation analysis fails, in general, more frequent replacement of spectrometer consumables
due to its low sensitivity. Recently, Lepri et al. [139] proposed a (sampler, skimmer, torches, injectors) due to the higher
speciation (fractionation) analysis between volatile and non- corrosion caused by an oxygen–argon plasma is necessary.
volatile Ni and V compounds in crude oil based on their ICP-MS requires periodic lens cleaning due to carbon build-up.
different characteristics during the ET AAS pyrolysis step. The direct solvent introduction technique is limited by the
Partial information on the nature of these compounds could be availability of organometallic standards and calibration pro-
obtained. However, speciation analysis with a much higher blems as well as the stability of the sample (after dilution)
level of information can be performed by hyphenating HPLC to and analytical solutions at the μg L− 1 level, which must be
an ICP-MS, since it does not require a heated interface and addressed. However, it is a fast methodology, less prone to
delivers sample in a liquid state at flow rates of around 1 mL contamination and losses, and gives better precision than
min− 1, compatible with most nebulizers. The identification and decomposition procedures. In fact, for comparative results, the
quantification of metalloporphyrins was performed by HPLC– instrumental conditions must be strictly known, for ICP as well
ICP-MS using a reversed phase C 18 column [13,140]. as for flame techniques. In the case of ET AAS, the presence of
Introduction of the mobile phase into the ICP does not volatile compounds that are lost during the pyrolysis step is well
necessarily need the presence of oxygen in the nebulizer gas, demonstrated. Their stabilization must be considered, and the
depending on: (i) if an oxygenated solvent like methanol is use of an appropriate modifier, even for elements known as non-
used, instead of aromatic or chlorinated solvents, and (ii) the volatile, is necessary. Proper emulsion formation techniques
percentage of solvent in the mobile phase. Capillary electro- produce systems stable enough for a practical atomic spectro-
phoresis has also been employed for the separation step [141]; metric determination and are promising for elements difficult to
however, the technique is limited to ionizable metalloporphyrin stabilize and to determine by decomposition or solvent dilution
(with a COOH function), otherwise the separation does not procedures. However, they are more time-consuming and less
reproducible than solvent solubilization procedures. Results SRM Standard reference material
derived from emulsion methods correspond to total element STPF Stabilized temperature platform furnace
content, whereas those based on the solubilization by aro- THGF Transversely heated graphite furnace
matic or aliphatic solvents allow the determination of elements w/o water-in-oil emulsion
associated only with the organic phase. The applicability of
direct “solid” sampling of oil samples has been demonstrated
for few elements using ET AAS. In this case, as well as in the Acknowledgements
previous ones, STPF conditions must be closely followed,
together with the use of an efficient background correction The authors thank CNPq (Brazil) for scholarships and
system. In this sense, CS–ET AAS will certainly open new Petrobras for research funding.
possibilities. Direct sampling procedures may also be easily
adapted to ETV–ICP-MS. Polyatomic interferences in quadru- References
pole ICP-MS must also be considered. For instance, the ma-
[1] B.P. Tissot, D.H. Welte, Petroleum Formation and Occurrence, 1st ed.
trix interference on Cr does not seem to be resolved by any
Springer-Verlag, Berlin, 1984.
methodology, since residual carbon is always present, and [2] A. Treibs, Chlorophyll-und Häminderivate in bituminösen Gesteinen,
only the use of DRC/CC- or HR-ICP-MS can overcome this Erdölen, Erdwachsen und Asphalten, Liebigs Ann. Chem. 510 (1934) 42–62.
problem. These limitations lead, once again, to the necessity of [3] E.A. Glebovskaya, M.V. Volkenshtein, Spektry porfirinov V neftyakh i
improvements in sample preparation steps. The early method of bitumakh, Zh. Obshch. Khim. (USSR) 18 (1948) 1440–1451.
[4] T.F. Yen, The Role of Trace Metals in Petroleum, Ann Harbor Science
extraction of water-soluble salts from the crude oils, often
Publishers Inc., Michigan, 1975.
neglected in the past, is recommended for generating reliable [5] J.S. Ball, W.J. Wenger, H.J. Hyden, C.A. Horr, A.T. Myers, Metal content
results on trace element concentrations in the organic phase. of twenty-four petroleums, J. Chem. Eng. Data 5 (1960) 553–557.
The determination of trace elements in operationally defined [6] H. Al-Shahristani, M.J. Al-Atyia, Vertical migration of oil in Iraqi oil
fractions of crude oil is another step forward for its better fields: Evidence based on vanadium and nickel concentrations, Geochim.
Cosmochim. Acta 36 (1972) 929–938.
characterization, allowing new geochemical applications.
[7] M. El-Gayar, M.S. Mostafa, A.E. Abdelfattah, A.O. Barakat, Application
Following the general trend in analytical chemistry, metal of geochemical parameters for classification of crude oils from Egypt into
speciation will also have its important place in oil analysis, source-related types, Fuel Process. Technol. 79 (2002) 13–28.
specifically for less explored fractions, such as resin and [8] M.D. Lewan, J.B. Maynard, Factors controlling enrichment of vanadium
asphaltenes. and nickel in the bitumen of organic sedimentary rocks, Geochim.
Cosmochim. Acta 46 (1982) 2547–2560.
[9] M.D. Lewan, Factors controlling the proportionality of vanadium to
4. List of acronyms nickel in crude oils, Geochim. Cosmochim. Acta 48 (1984) 2231–2238.
[10] B.M. Didyk, Y.I.A. Alturki, C.T. Pillinger, G. Eglington, Petroporphyrins
AFS Atomic fluorescence spectrometry as indicators of geothermal maturation, Nature 256 (1975) 563–565.
ASTM American Society for Testing Materials [11] A.J.G. Barwise, Mechanisms involved in altering deoxophylloerythroe-
tioporphyrin–etioporphyrin ratios in sediments and oils, J. Am. Chem.
BTX Benzene, toluene and xylene
Soc. Spec. Pub. 344 (1987) 100–109.
CC Collision cell [12] K.E. Peters, C.C. Walters, J.M. Moldowan, 2nd ed., The Biomarker
CV Cold vapor Guide, Volume 2: Biomarkers and Isotopes in the Petroleum Exploration
CVG Chemical vapor generator and Earth History, Cambridge University Press, New York, 2004.
DIN Direct injection nebulizers [13] E. Les Ebdon, H. Evans, W.G. Pretorius, S.J. Rowland, Analysis of
geoporphyrins by high-temperature gas chromatography inductively
DIHEN Direct injection high efficiency nebulizer
coupled plasma mass spectrometry and high-performance liquid
DRC Dynamic reaction cell chromatography inductively coupled plasma mass spectrometry, J.
ET AAS Electrothermal atomic absorption spectrometry Anal. At. Spectrom. 9 (1994) 939–943.
ETV Electrothermal vaporization [14] C. Schickling, J. Broeckaert, Determination of mercury species in gas-
FAAS Flame atomic spectrometry condensates by online coupled high-performance liquid-chromatography
and cold-vapor atomic absorption spectrometry, Appl. Organomet. Chem.
GC Gas chromatography
9 (1985) 29–36.
HG AAS Hydride generation atomic absorption spectrometry [15] H. Tao, T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in
HPLC High performance liquid chromatography natural gas condensate by gas chromatography-inductively coupled
HR-ICP-MS High resolution inductively coupled plasma mass plasma mass spectrometry, J. Anal. At. Spectrom. 13 (1998) 1085–1093.
spectrometry [16] J. Ellrich, A. Hirner, H. Stärk, Distribution of trace elements in crude oils
from southern Germany, Chem. Geol. 48 (1985) 313–323.
ICP-MS Inductively coupled plasma mass spectrometry
[17] M. Alberdi-Grenolet, R. Tocco, Trace metals and organic geochemistry of
ICP OES Inductively coupled plasma optical emission the Machiques Member (Aptian–Albian) and La Luna Formation
spectrometry (Cenomanian–Campanian), Venezuela, Chem. Geol. 160 (1999) 19–38.
ICP-TOF-MS Inductively coupled plasma time-of-flight mass [18] T.C.O. Fonseca, PhD Thesis, Chemistry Department, PUC-RJ, Brazil,
spectrometry (2000), 135 pp.
[19] J.A. Curiale, Distribution and occurrence of metals in heavy crude oils
NdYAG Neodymium-doped yttrium aluminum garnet
and betumens, AAPG Stud. Geol. 25 (1987) 207–219.
o/w oil-in-water emulsion [20] S.D. Olsen, R.H. Filby, T. Brekket, G.H. Isaksen, Analysis of metals in
SARA Saturated, aromatic, resin and asphaltene fractions condensates and naphta by inductively coupled plasma mass spectrom-
SPL Solvent plasma load etry, Analyst 120 (1995) 1379–1390.
[21] B. Hitchon, E.H. Perkins, W.D. Gunter, Recovery of trace metals in [45] L.C. Osuji, S.O. Adesiyan, Extractable hydrocarbons, nickel and
formation waters using acid gases from natural gas, Appl. Geochem. 16 vanadium contents of Ogbodo–Isiokpo oil spill polluted soils in Niger
(2001) 1481–1497. Delta, Nigeria, Environ. Monit. Assess. 110 (2005) 129–139.
[22] R.H. Filby, Origin and nature of trace element species in crude oil, [46] M.P. Pavageau, A. Mirin, F. Seby, C. Guimon, E. Krupp, C. Pécheyran,
bitumens and kerogens: implications for correlation and other geochem- J. Poulleau, O.F.X. Donard, Partitioning of metal species during an
ical studies, Geol. Soc. Spec. Pub. 78 (1994) 203–219. enriched fuel combustion experiment. Speciation in the gaseous and
[23] H.G. Machel, Bacterial and thermochemical sulfate reduction in diagenetic particulate phases, Environ. Sci. Technol. 38 (2004) 2252–2263.
settings — old and new insights, Sediment. Geol. 140 (2001) 143–175. [47] H.Y.N. Holeman, R. Goth-Goldenstein, D. Aston, M. Yun, J. Kengsoontra,
[24] IP 143: Determination of asphaltenes (heptane insolubles) in crude Evaluation of gastrointestinal solubilization of petroleum hydrocarbon
petroleum and petroleum products, Energy institute (former Institute of residues in soil using an in vitro physiologically based model, Environ. Sci.
Petroleum), 2004, ref: 978 0 85293. Technol. 36 (2002) 1281–1286.
[25] ASTM D, Standard Test Method for Characteristic Groups in Rubber [48] M.F. Soto-Jimenez, S.A. Hibdon, C.W. Rankin, J. Aggarawl, A.C. Ruiz-
Extender and Processing Oils and Other Petroleum-Derived Oils by the Fernandez, F. Paez-Osuna, A.R. Flegal, Chronicling a century of lead
Clay–Gel Absorption Chromatographic Method, 2007, pp. 1–8. pollution in Mexico: stable lead isotopic composition analyses of dated
[26] J.G. Speight, in: John Wiley (Ed.), Handbook of Petroleum Product sediment cores, Environ. Sci. Technol. 40 (2006) 764–770.
Analysis (Chemical Analysis: A Series of Monographs on Analytical [49] W. Kovarik, Ethyl-leaded gasoline: how a classic occupational disease
Chemistry and Its Applications), Wiley-Interscience, 2001, pp. 245–259. became an international public health disaster, Int. J. Occup. Environ.
[27] J.G. Speight, New approaches to hydroprocessing, Catal. Today 98 Health 11 (2005) 384–397.
(2004) 55–60. [50] X.G. Meng, S. Bang, G.P. Korfiatis, Removal of selenocyanate from
[28] L. Lopez, S. Ló Monaco, Geochemical implications of trace elements and water using elemental iron, Water Res. 36 (2002) 3867–3873.
sulfur in the saturate, aromatic and resin fractions of crude oil from the [51] N. Miekeley, R.C. Pereira, E.A. Casartelli, A.C. Almeida, M.F.B.
Mara and Mara Oeste fields, Venezuela, Fuel 83 (2004) 365–374. Carvalho, Inorganic speciation analysis of selenium by ion chromatog-
[29] S. Ló Monaco, L. Lopez, G. Garban, A. Lira, A. Rojas, Determinación de raphy-inductively coupled plasma-mass spectrometry and its application
elementos traza en kerogeno, bitumen y fracciones del petróleo, to effluents from a petroleum refinery, Spectrochim. Acta 60B (2005)
utilizando espectrometría de plasma (ICP), Rev. Lat.-Am. Geoquim. 633–641.
Org. 3 (1997) 43–54. [52] C.P. Lienemann, Analyse de métaux traces dans les produits pétroliers,
[30] C. Duyck, PhD Thesis, Chemistry Department, PUC-RJ, Brazil, (2001), état de l'art, Oil Gas Sci. Technol.- Rev. IFP 60 (6) (2005) 951–965.
203p. [53] R.W. Kelly, S.E. Long, J.L. Mann, Determination of mercury in SRM
[31] C. Duyck, N. Miekeley, C.L.P. Silveira, P. Szatmari, Trace element crude oils and refined products by isotope dilution cold vapor ICP-MS
determination in crude oil and its fractions by inductively coupled plasma using closed-system combustion, Anal. Bioanal. Chem. 376 (2003)
mass spectrometry using ultrasonic nebulization of toluene solutions, 753–758.
Spectrochim. Acta 57B (2002) 1979–1990. [54] Z. Kowalewska, A. Ruszczynska, E. Bulska, Cu determination in crude
[32] S.M. Wilhelms, L. Liang, D. Kirchgessner, Identification and properties oil distillation products by atomic absorption and inductively coupled
of mercury species in crude oil, Energy Fuels 20 (2006) 180–186. plasma mass spectrometry after analyte transfer to aqueous solution,
[33] T.F. Yen, G.V. Chiligarian (Eds.), Asphaltenes and Asphalts, 1st. ed., Spectrochim. Acta 60B (2005) 351–359.
Developments in Petroleum Science, vol. 1, Elsevier, New York, 2000. [55] A. Montaser (Ed.), Inductively Coupled Plasma Mass Spectrometry, 1st.ed.,
[34] M. El-Gayar, Aromatic steroids in Mideastern crude oils: identifica- Wiley-VCH, New York, 1998.
tion and geochemical application, Pet. Sci. Technol. 21 (2003) [56] C.J. Lord, Determination of trace metals in crude oil by inductively
719–726. coupled plasma mass spectrometry with micro-emulsion sample
[35] T.J. Kaminski, H.S. Fogler, N. Wolf, P. Wattana, A. Mairal, Classification introduction, Anal. Chem. 63 (1991) 1594–1599.
of asphaltenes via fractionation and the effect of heteroatom content on [57] A.W. Boorn, R.F. Browner, Effects of organic solvents in inductively
dissolution kinetics, Energy Fuels 14 (2000) 25–30. coupled plasma atomic emission spectrometry, Anal. Chem. 54 (1992)
[36] J.G. Gary, G.E. Handwerk, Chemical Processing and Engineering, 1402–1410.
4th. ed.Marcel Dekker Inc., New York, 2001. [58] R.I. Botto, J. Zhu, Use of an ultrasonic nebulizer with membrane
[37] N. Panariti, A. Del Bianco, G. Del Piero, M. Marchionna, Petroleum desolvation for analysis of volatile solvents by inductively coupled plasma
residue upgrading with dispersed catalysts. Part 1. Catalysts activity and atomic emission spectrometry, J. Anal. At. Spectrom. 9 (1994) 905–912.
selectivity, Appl. Catal. 204A (2000) 203–213. [59] I.B. Brenner, A. Zander, M. Plantz, J. Zhu, Characterization of an
[38] K.H. Altgelt, M.M. Boduszynski, Composition and Analysis of Heavy ultrasonic nebulizer-membrane separation interface with inductively
Petroleum Fractions (Chemical Industries), 1st. ed.Marcel Dekker Inc., coupled plasma mass spectrometry for the determination of trace elements
New York, 1994. by solvent extraction, J. Anal. At. Spectrom. 12 (1997) 273–279.
[39] J.G. Speight, Petroleum asphaltenes — Part 1 — asphaltenes, resins and [60] T.D. Saint'Pierre, L.F. Dias, D. Pozebon, R.Q. Aucélio, A.J. Curtius, B.
the structure of petroleum, Oil Gas Sci. Technol.-Rev. IFP 59 (2004) Welz, Determination of Cu, Mn, Ni and Sn in gasoline by ETV–ICP-MS
467–477. and emulsion sample introduction, Spectrochim. Acta 57B (2002)
[40] J.G. Reynolds, Nickel in petroleum refining, Pet. Sci. Technol. 19 (2001) 1991–2001.
979–1007. [61] F.J.M.J. Maessen, P.J.H. Seeverens, G. Kreuning, Analytical aspects of
[41] E. Furimsky, Selection of catalysts and reactors for hydroprocessing, organic solvent load reduction in normal-power ICPs by aerosol
Appl. Catal. 171A (1998) 177–206. thermostating at low temperatures, Spectrochim. Acta 39B (1984)
[42] M.S. Rana, M.S. Ancheyta, J. Maity, S.K., P. Rayo, Comparative study 1171–1180.
for heavy oil hydroprocessing catalysts at micro-flow and bench-scale [62] D. Hausler, Trace element analysis of organic solutions using inductively
reactors, Catal. Today 109 (2005) 61–68. coupled plasma-mass spectrometry, Spectrochim. Acta 42B (1987) 63–73.
[43] J.P. Dunn, H.G. Stenger, I.E. Wachs, Molecular structure-reactivity [63] J. Sneddon, C. Hardaway, K.K. Bobbadi, J.N. Beck, A study of a crude
relationships for the oxidation of sulfur dioxide over supported metal oil spill site for selected metal concentrations remediated by a controlled
oxide catalysts, Catal. Today 53 (1999) 543–556. burning in Southwest Louisiana, Microchem. J. 82 (2006) 8–16.
[44] A. Samecka-Cymerman, K. Kolon, A.J. Kempers, Differences in [64] B. Welz, H. Becker-Ross, S. Florek, U. Heitman, High-resolution
concentration of heavy metals between native and transplanted Continuum Source AAS: The Better Way to do Atomic Absorption
Plagiothecium denticulatum: a case study of soils contaminated by oil Spectrometry, 1st. ed.Wiley-VCH, Weinheim, 2005.
well exudates in South East Poland, Arch. Environ. Contam. Toxicol. [65] R.C. Campos, M.C.R. Resende, A.J. Curtius, Application of the cold
49 (2005) 317–321. vapor technique to the speciation of mercury in fish samples after solvent
extraction and methylmercury reduction directly in the organic medium, [88] J. Alvarado, A.R. Picon, C.M. de Vecchi, Microwave wet acid digestion
J. Anal. At. Spectrom. 8 (1993) 247–251. in the preparation of crude oil samples for AAS determination of their
[66] R.C. Campos, G.P. Brandão, A.S. Luna, Determination of mercury in chromium, copper, iron, manganese, sodium, nickel, vanadium and zinc
gasoline by cold vapor atomic absorption spectrometry with direct reduction content, Acta Chim. Ven. 41 (1990) 306–319.
in micro-emulsion media, Spectrochim. Acta 60B (2005) 625–631. [89] M. Bettinelli, S. Spezia, U. Baroni, G. Bizzarri, Determination of trace
[67] M. Murillo, N. Carrión, J. Chirinos, Determination of sulphur in crude elements in fuel oils by inductively coupled plasma mass spectrometry
oils and related materials with a Parr bomb digestion method and after acid mineralization of sample in microwave oven, J. Anal. At.
inductively coupled plasma atomic emission spectrometry, J. Anal. At. Spectrom. 10 (1995) 555–560.
Spectrom. 8 (1993) 493–495. [90] M. Krachler, H. Radner, K.J. Irgolic, Microwave digestion methods for
[68] A.L.M. Bastos, M.Sc. Thesis, Chemistry Department, PUC-RJ, Brazil, the determination of trace elements in brain and liver samples by
(2005). inductively coupled plasma mass spectrometry, Fresenius' J. Anal. Chem.
[69] F.E. Smith, E.A. Arsenault, Microwave-assisted sample preparation in 355 (1996) 120–128.
analytical chemistry, Talanta 43 (1996) 1207–1268. [91] M.B. Campbell, G.A. Kanert, High-pressure microwave digestion for the
[70] V.F. Taylor, A. Toms, H.P. Longerich, Acid digestion of geological and determination of arsenic, antimony, selenium and mercury in oily wastes,
environmental samples using open-vessel focused microwave digestion, Analyst 117 (1992) 121–124.
Anal. Bioanal. Chem. 372 (2002) 360–365. [92] B.K. Puri, K.J. Irgolic, Determination of arsenic in crude petroleum and
[71] L.M. Costa, F.V. Silva, S.T. Gouveia, A.R.A. Nogueira, J.A. Nóbrega, liquid hydrocarbons, Environ. Geochem. Health 11 (1989) 95–99.
Focused microwave-assisted acid digestion of oils: an evaluation of the [93] Z.C. Hu, S. Gao, S.H. Hu, H.L. Yuan, X.M. Liua, Y.S. Liu, Suppression
residual carbon content, Spectrochim. Acta 56B (2001) 1981–1985. of interferences for direct determination of arsenic in geological samples
[72] T. Wondimu, W. Goessler, K.J. Irgolic, Microwave digestion of residual by inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom.
fuel oil for the determination of trace elements by inductively coupled 20 (2005) 1263–1269.
plasma mass spectrometry, Fresenius' J. Anal. Chem. 367 (2000) 35–42. [94] B. Welz, M. Melcher, Mechanisms of transition metal interferences in
[73] T. Wondimu, W. Goessler, Comparison of closed-pressurized and open- hydride generation atomic absorption spectrometry. Part 3. Releasing
refluxed vessel digestion systems for trace elements in the residual fuel oil effect of iron(III) on nickel interference on arsenic and selenium, Analyst
reference material (SRM 1634c), Bull. Chem. Soc. Ethiop. 14 (2000) 109 (1984) 577–579.
99–113. [95] G. Bagur, D. Gazquez, M. Sanches, A.M. Martin, Synergistic extraction
[74] N. Jakubowski, J. Feldmann, D. Stuewer, Analytical improvement of atomic spectrophotometric determination of vanadium in foods and
pneumatic nebulization in ICP-MS by desolvation, Spectrochim. Acta petroleum crudes with 5,5′-methylenedisalicylohydroxamic acid (med-
47B (1992) 107–118. sha), Anal. Lett. 26 (1993) 125–140.
[75] S.H. Tan, G. Horlick, Background spectral features in inductively [96] R.I. Botto, Applications of ultrasonic nebulization in the analysis of
coupled plasma/mass spectrometry, Appl. Spectrosc. 40 (1986) 445–460. petroleum and petrochemicals by inductively coupled plasma atomic
[76] V.N. Epov, D. Lariviere, E.N. Epova, R.D. Evans, Polyatomic emission spectrometry, J. Anal. At. Spectrom. 8 (1993) 51–57.
interferences produced by macro elements during direct multi-elemental [97] R.I. Botto, J. Zhu, Universal calibration for analysis of organic solutions
ICP-MS hydrochemical analysis, Geostand. Geoanal. Res. 28 (2004) by inductively coupled plasma atomic emission spectrometry, J. Anal. At.
213–224. Spectrom. 11 (1996) 675–681.
[77] D.W. Koppenaal, G.C. Eiden, C.J. Barinaga, Collision and reaction [98] R.I. Botto, Trace element analysis of petroleum naphtas and tars using
cells in atomic mass spectrometry: development, status, and applications, direct injection ICP-MS, Can. J. Anal. Sci. Spectrosc. 47 (2002) 1–13.
J. Anal. At. Spectrom. 19 (2004) 561–570. [99] R.C. Hutton, Application of inductively coupled plasma source mass
[78] A.P. Udoh, S.A. Thomas, E.J. Ekanem, Application of p-xylenesulphonic spectrometry (ICP-MS) to the determination of trace metals in organics,
acid as ashing reagent in the determination of trace metals in crude oil, J. Anal. At. Spectrom. 1 (1986) 259–263.
Talanta 39 (1992) 1591–1595. [100] B. Magyar, P. Lienemann, H. Vonmont, Some effects of aerosol
[79] O. Platteau, M. Carrillo, Determination of metallic elements in crude oil– drying and oxygen feeding on the analytical performance of an
water emulsions by flame AAS, Fuel 74 (1995) 74–76. inductively coupled nitrogen–argon plasma, Spectrochim. Acta 41B
[80] Standard test methods for determination of nickel, vanadium, iron, and (1986) 27–38.
sodium in crude oils and residual fuels by flame atomic absorption [101] G.R. Peters, D. Beauchemin, Characterization of an interface allowing
spectrometry ASTM D5863-00a (2005). either nebulization or gas chromatography as the sample introduction
[81] S.H. Kagler, R. Kotzel, Die Bestimmung von Cd im Bereich b10 μg/kg in system in ICP-MS, Anal. Chem. 65 (1993) 97–103.
Mineralölprodukten mittels Graphitrohrofen, Fortschritte in der atomspek- [102] L.C. Alves, M.G. Minnich, D.R. Wiederin, R.S. Houk, Removal of
trometrischen Spurenanalytik, Band, vol. 1, Verlag Chemie, Berlin, 1984. organic solvents by cryogenic desolvation in inductively coupled plasma
[82] V. Sychra, I. Lang, G. Sebor, Analysis of petroleum and petroleum mass spectrometry, J. Anal. At. Spectrom. 9 (1994) 399–403.
products by atomic absorption spectroscopy and related techniques: [103] I.B. Brenner, J. Zhu, A. Zander, Evaluation of an ultrasonic nebulizer-
Crude oils. Heavy petroleum oils and residues, Prog. Anal. At. Spectrom. membrane separation interface (USN-MEMSEP) with ICP-AES for the
4 (1981) 349–372. determination of trace elements by solvent, Fresenius' J. Anal. Chem. 335
[83] Standard test methods for determination of aluminum and silicon in fuel (1996) 774–777.
oils by ashing, fusion, inductively coupled plasma atomic emission [104] S.D. Olsen, S. Westerlund, R.G. Visser, Analysis of metals and
spectrometry, and atomic absorption spectrometry, ASTM D5184-01 condensates in naphta by inductively coupled plasma mass spectrometry,
(2006). Analyst 122 (1997) 1229–1234.
[84] Acid digestion of oils for metals analysis by atomic absorption or ICP [105] K. Kahen, A. Strubinger, J.R. Chirinos, A. Montaser, Direct injection
spectrometry, US-EPA Method 3031 (1996). high efficiency nebulizer-inductively coupled plasma mass spectrometry
[85] H.P.M. Stigter, R. de Haan, C.P.A. Guicherit, M.L. Dekkers, Determi- for analysis of petroleum samples, Spectrochim. Acta 58B (2003)
nation of cadmium, zinc, copper, chromium and arsenic I crude oil 397–413.
cargoes, Environ. Pollut. 107 (2000) 451–464. [106] E. Björn, W. Frech, Introduction of high carbon content solvents into
[86] M. Turunen, S. Peraniemi, M. Ahlgrén, H. Westerholm, Determination of inductively coupled plasma mass spectrometry by a direct injection high
trace elements in heavy oil samples by graphite furnace and cold vapor efficiency nebuliser, Anal. Bioanal. Chem. 376 (2003) 274–278.
atomic absorption spectrometry after acid digestion, Anal. Chim. Acta [107] S.E. Maestre, J.L. Todoli, J.M. Mermet, Evaluation of several pneumatic
311 (1995) 85–91. micronebulizers with different designs for use in ICP-AES and ICP-MS.
[87] Microwave assisted acid digestion of sediments, sludges, soils and oils, Future directions for further improvement, Anal. Bioanal. Chem. 379
US-EPA 3051 (1994). (2004) 888–899.
[108] S. Dreyfus, C. Pécheyran, C. Magnier, A. Prinzhofer, C.P. Lienemann, O. [126] M. de la Guardia, M.J. Lizondo, Direct determination of nickel in fuel oil
F.X. Donard, Direct trace and ultra-trace metals determination in crude oil by atomic absorption spectrometry using emulsions, At. Spectr. 6 (1993)
and fractions by inductively coupled plasma mass spectrometry, ASTM J. 208–211.
2 (2005) 1–8. [127] N.N. Meeravali, S.J. Kumar, The utility of a W–Ir permanent chemical
[109] S.J. Kumat, S. Gangadharan, Determination of trace elements in naphta modifier for the determination of Ni and V in emulsified fuel oils and
by inductively coupled plasma mass spectrometry using water-in-oil naphtha by transverse heated electrothermal atomic absorption spectrom-
emulsions, J. Anal. At. Spectrom. 14 (1999) 967–971. eter, J. Anal. At. Spectrom. 16 (2001) 527–532.
[110] M. Murillo, J. Chirinos, Use of emulsion systems for the determination of [128] J.L. Burguera, R.M. Avila-Gomez, M. Burguera, R.A. de Salaguer, J.L.
sulfur, nickel and vanadium in heavy crude oil samples by inductively Salaguer, C.L. Bracho, M. Burguera-Pascu, C. Burguera-Pascu, R. Brunetto,
coupled plasma atomic emission spectrometry, J. Anal. At. Spectrom. M. Gallignani, Y.P. de Pena, Optimum phase-behavior formulation of
9 (1994) 237–240. surfactant/oil/water systems for the determination of chromium in heavy
[111] M. Murillo, J. Chirinos, Study of the effect of organic emulsified samples crude oil and in bitumen-in-water emulsion, Talanta 61 (2003) 353–361.
in inductively coupled plasma atomic emission spectrometry, J. Anal. At. [129] M.G.R. Vale, I.C.F. Damin, A. Klassen, M.M. Silva, B. Welz, A.F. Silva,
Spectrom. 11 (1996) 253–257. F.G. Lepri, D.L.G. Borges, U. Heitmann, Method development for the
[112] R.M. Souza, A.L.S., C.L.P. da Silveira, R.Q., Determination of Mo, Zn, determination of nickel in petroleum using line-source and high-
Cd, Ti, Ni, V Fe, Mn, Cr and Co in crude oil using inductively coupled resolution continuum-source graphite furnace atomic absorption spec-
plasma optical emission spectrometry and sample introduction as trometry, Microchem. J. 77 (2004) 131–140.
detergentless micro-emulsions, Microchem. J. 82 (2006) 137–141. [130] R.Q. Aucelio, A. Doyle, B.S. Pizzorno, M.L.B. Tristão, R.C. Campos,
[113] T. Greibrokk, E. Lundanes, H.R. Norli, K. Dyrstad, S.D. Olsen, Electrothermal atomic absorption apectrometric method for the determi-
Experimental simulation of oil migration–distribution effects on organic nation of vanadium in diesel and asphaltene prepared as detergentless
compound groups and on metal/metal ratios, Chem. Geol. 116 (1994) microemulsions, Microchem. J. 78 (2004) 21–26.
281–299. [131] I.C.F. Damin, M.G.R. Vale, M.M. Silva, B. Welz, F.G. Lepri, W.N.L.
[114] N.H. Bings, Direct determination of metals in lubricating oils by laser Santos, S.L.C. Ferreira, Palladium as chemical modifier for the
ablation coupled to inductively coupled plasma time-of-flight mass stabilization of volatile nickel and vanadium compounds in crude oil
spectrometry, J. Anal. At. Spectrom. 17 (2002) 759–767. using graphite furnace atomic absorption spectrometry, J. Anal. At.
[115] J.L. Fabec, M.L. Ruschak, Determination of nickel, vanadium, and sulfur Spectrom. 20 (2005) 1332–1336.
in crudes and heavy crude fractions by inductively coupled argon plasma/ [132] M.N.M. Reyes, R.C. Campos, Determination of copper and nickel in
atomic emission spectrometry and flame atomic absorption spectrometry, vegetable oils by direct sampling graphite furnace atomic absorption
Anal. Chem. 57 (1985) 1853–1863. spectrometry, Talanta 70 (2006) 929–932.
[116] J.M. Guidr, J. Sneddon, Fate of vanadium determined by nitrous oxide– [133] G.P. Brandão, R.C. Campos, E.V.R. de Castro, H.C. de Jesus, Direct
acetylene flame atomic absorption spectrometry in unburned and burned determination of nickel in petroleum by solid sampling-graphite furnace
Venezuelan crude oil, Microchem. J. 73 (2002) 363–366. atomic absorption spectrometry, Anal. Bioanal. Chem. 386 (2006)
[117] J.L. Hammond, Y. Lee, C.O. Noble, J.N. Beck, C.E. Proffitt, J. Sneddon, 2249–2253.
Determination of cadmium, lead, and nickel by simultaneous multiele- [134] M.M. Silva, I.C.F. Damin, M.G.R. Vale, B. Welz, Feasibility of using
ment flame atomic absorption spectrometry in burned and unburned solid sampling graphite furnace atomic absorption spectrometry for
Venezuelan crude oil, Talanta 47 (1998) 261–266. speciation analysis of volatile and non-volatile compounds of nickel and
[118] O. Osibanjo, S.E. Kakulu, S.O. Ajayi, Analytical application of inorganic vanadium in crude oil, Talanta 71 (2007) 349–359.
salt standards and mixed-solvent systems to trace-metal determination in [135] G.P. Brandão, R.C. de Campos, E.V.R. de Castro, H.C. de Jesus, Direct
petroleum crudes by atomic absorption spectrophotometry, Analyst 109 determination of copper, iron and vanadium in petroleum by solid sampling-
(1984) 109–127. graphite furnace atomic absorption spectrometry, Spectrochim. Acta Part B
[119] Sebor, G.I. Lang, D. Kolihova, O. Wasser, Effect of the type of 62 (2007) 962–969 (this issue)8 doi:10.1016/j.sab.2007.05.001.
organometallic iron and copper compounds on the determination of both [136] R.H. Fish, J.J. Komlenic, Molecular characterization and profile
metals in petroleum samples by flame atomic-absorption spectroscopy, identifications of vanadyl compounds in heavy crude petroleums by
Analyst 107 (1982) 1350–1355. liquid chromatography/graphite furnace atomic absorption spectrometry,
[120] M. Bettinelli, P. Tittarelli, Evaluation and validation of instrumental Anal. Chem. 56 (1984) 510–517.
procedures for the determination of nickel and vanadium in fuel oils, [137] R.H. Fish, J.J. Komlenic, B.K. Wines, Characterization and comparison of
J. Anal. At. Spectrom. 9 (1994) 805–812. vanadyl and nickel compounds in heavy crude petroleums and asphaltenes
[121] C.F. Bruhn, V.G. Cabalín, Direct determination of nickel in gas oil by by reverse-phase and size-exclusion liquid chromatography/graphite furnace
atomic absorption spectrometry with electrothermal atomization, Anal. atomic absorption spectrometry, Anal. Chem. 56 (1984) 2452–2460.
Chim. Acta 143 (1983) 193–203. [138] N. Marqueza, F. Ysambertta, C. De La Cruz, Three analytical methods to
[122] M.C. González, A.R. Rodriguez, V. González, Determination of isolate and characterize vanadium and nickel porphyrins from heavy
vanadium, nickel, iron, copper, and lead in petroleum fractions by crude oil, Anal. Chim. Acta 395 (1999) 343–349.
atomic absorption spectrophotometry with a graphite furnace, Micro- [139] F.G. Lepri, B. Welz, D.L.G. Borges, A.F. Silva, M.G.R. Vale, U. Heitmann,
chem. J. 57 (1987) 94–106. Speciation analysis of volatile and non-volatile vanadium compounds in
[123] P. Bermejo-Barrera, C. Pita-Calvo, F. Bermejo-Marinez, Simple prepa- Brazilian crude oils using high-resolution continuum source graphite
ration procedures for vanadium determination in petroleum by atomic- furnace atomic absorption spectrometry, Anal. Chim. Acta 558 (2006)
absorption spectrometry with electrothermal atomization, Anal. Lett. 195–200.
24 (1991) 447–458. [140] U. Kumar, J.G. Dorsey, J.A. Caruso, Metalloporphyrin speciation by
[124] N.S. Thomaidis, E.A. Piperaki, Comparison of chemical modifiers for the liquid chromatography and inductively coupled plasma mass spectrom-
determination of vanadium in water and oil samples by electrothermal etry, J. Chromatogr. Sci. 32 (1994) 282–285.
atomization atomic absorption spectrometry, Analyst 121 (1996) 111–117. [141] K.L. Ackley, J.A. Day, J.A. Caruso, Separation of metalloporphyrins by
[125] Y. Nakamoto, T. Ishimaru, N. Endo, K. Matsusaki, Determination of capillary electrophoresis with UV detection and inductively coupled
vanadium in heavy oils by atomic absorption spectrometry using graphite plasma mass spectrometric detection, J. Chromatogr., A 888 (2005)
furnace coated with tungsten, Anal. Sci. 20 (2004) 739–741. 293–298.

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Spectrochimica Acta Part B 62 (2007) 939 – 951

1. Occurrences and importance of metals in crude oil and fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939

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