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Critical Review on the Analytical Methods for the Determination of Sulfur and
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 Critical Reviews in Analytical Chemistry

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Critical Review on the Analytical Methods for the

Determination of Sulfur and Trace Elements in
Crude Oil

M. A. Gab-Allah, Emad. S. Goda, A. B. Shehata & Heba Gamal

To cite this article: M. A. Gab-Allah, Emad. S. Goda, A. B. Shehata & Heba Gamal (2020) Critical
Review on the Analytical Methods for the Determination of Sulfur and Trace Elements in Crude Oil,
Critical Reviews in Analytical Chemistry, 50:2, 161-178, DOI: 10.1080/10408347.2019.1599278

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CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
2020, VOL. 50, NO. 2, 161–178
https://doi.org/10.1080/10408347.2019.1599278

Critical Review on the Analytical Methods for the Determination of Sulfur and
Trace Elements in Crude Oil
M. A. Gab-Allaha , Emad. S. Godab, A. B. Shehataa, and Heba Gamalc
a
Reference Materials Lab, National Institute of Standards, Giza, Egypt; bFire Protection Laboratory, National Institute of Standards, Giza,
Egypt; cHome Economy Department, Faculty of Specific Education, Alexandria University, Alexandria, Egypt

ABSTRACT KEYWORDS
Determination of sulfur and deleterious trace elements in crude oil has long been an area of Crude oil; elemental
active investigation and still attracting interest due to their undesirable economic consequences determination;
and adverse environmental impacts. Therefore, analytical methods devoted to their sensitive, measurement techniques;
pretreatment procedures
rapid, and accurate determination are of paramount importance in various areas of oil refining
and petrochemical industry. In the present review, occurrence and implications of the main metal-
lic constituents in crude oil are summarized. Furthermore, currently available methodological
approaches including sample pretreatment procedures along with the most commonly used
measurement techniques employed for crude oil analysis are overviewed. A summary of the
applications and recent developments over the past years is discussed. The basic principle, pros
and cons of each analytical method are highlighted. The overview is based on 172 references.

Introduction origin, migration, oil–oil correlation, and geochemical charac-

terization of the oil,[9–15] (ii) their adverse effects on petrol-
In general, petroleum is considered the mainstay of modern
eum refinery and product’s quality,[16,17] and (iii) the need for
civilization. The primacy of petroleum as an essential source
incorporation and optimization of new technologies for the
of energy has provided a platform for social-economic devel-
desulfurization and demetalation procedures.
opments in the industrialized nations.[1] From a chemical Among the problems associated with trace elements
viewpoint, petroleum is a highly complex mixture composed in oils are catalyst poisoning in the refinery operation and
of saturated hydrocarbons, aromatics, and polycyclic corrosion of the refinery equipment. Atmospheric contamin-
compounds (resins and asphaltenes), where carbon and ation upon their release and health risks are also related
hydrogen represent 83–87% and 10–14% of the mass, subjects. For example, some elements (e.g., Cr, Fe, As, Cd,
respectively.[2–6] Sulfur is the third most abundant element Cu, Se, Hg, Pb, Sr, and Ba) can cause severe and irreversible
in crude oil ranging from 0.04 to 8% followed by oxygen catalysts poisoning, thereby reducing their efficiencies.[18–21]
and nitrogen.[4] Additionally, there are numerous trace In addition, these elements contribute to corrosion in
elements have been detected in crude oils. Of the many burners and boilers during oil refining and petrochemical
elements listed (Hg, As, Se, Ba, Ca, Cr, Cu, Fe, Pb, Na, processing, and are easily transported to petroleum products
Mg, Mn, Ni, Ag, Ti, V, Cd, Mo, Co, Sn, Sr, etc.), Ni and V such as gasoline and other fuels.[22,23] V compounds can
are the most abundant (up to 1000 and 200 mg kg
1, cause deterioration in refractory materials of furnaces, and
respectively).[7,8] These elements may be present either as sodium compounds have been found to cause superficial
organometallic compounds such as those of Ni and V fusion for fire brick.[6,16] Meanwhile, Ni interferes with
(as Ni2þ or VO2þ porphyrins) or in the form of inorganic crude oil refining process; it also deactivates the catalytic
salts, such as magnesium and sodium chlorides.[6] converters, leading to unfavorable side reactions and
The origin of trace elements in crude oil can be from decreasing gasoline yields.[6,24]
different sources: (i) naturally from rocks, soils, plants, and Special attention has been paid to Ni and V, and strict
marine sources, (ii) added as additives to improve some chem- regulations have been addressed in several countries due to
ical, physico–chemical characteristics of oils, and (iii) added as their mutagenic and carcinogenic effects.[25] Ca and Mg are
contaminants during extraction, refining, storage and trans- present in petroleum in the form of organometallic
portation via corrosion of tanks, towers, and pipelines.[9–11] compounds and inorganic contaminants such as chloride
Information on sulfur and trace element concentrations in and sulfate salts. Upon the hydrolysis of these salts, several
crude oil is of prime importance in petroleum technology in problems occur during crude oil refining including reduc-
several aspects: (i) the ratio of some elements (Ni, V, and rare tion in heat transfer efficiency and blockage of pipes by
earth elements) can provide important information about solid corrosion products resulted from the formation and

CONTACT M. A. Gab-Allah [email protected] National Institute of Standards, Tersa St, Haram, P. O. Box 136, Giza 12211, Egypt.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/batc.
ß 2019 Taylor & Francis Group, LLC
162 M. A. GAB-ALLAH ET AL.

Figure 1. Current strategies commonly employed for determination of elements in crude oil.

condensation of hydrochloric acid along the refining On the other hand, S has severe adverse effects on the
apparatus.[5,26,27] Besides, some volatile organometallic environment and human health such as acid rain formation,
compounds can lead to contamination of distillate fractions ozone-layer depletion, and respiratory diseases. In addition
causing reduction in their stability and malfunctions to sulfur, other elements such as Cr, Ni, V, Hg, Cd, Pb, Se,
of combustion engines. and As can also contribute to environmental pollution upon
Importantly, sulfur is present in crude oil in the form of their emission by the oil industry, either directly through
organic compounds (thiophenes, sulfides, benzothiophenes, industrial flue gases from refineries or indirectly through
and dibenzothiophene), as sulfuric acid and even in fuel combustion causing severe health problems.[8,32,33]
its elemental form. Whatever the form, S is considered A reliable control of deleterious elements in crude oil
a problematic in crude oil. It can easily affect acidic proper- relies directly on their unambiguous speciation and accurate
ties of the petroleum-derived products and has been found quantification. Therefore, the determination of sulfur and
to produce corrosive gases that damage engine parts.[28–31] trace elements level in crude oils is of paramount
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 163

importance in various areas of the petroleum industry. and graphite furnace atomic absorption spectrometry
Consequently, there is a need for accurate analytical meth- (GFAAS). Direct analysis is an effective alternative to other
ods for crude oil analysis. In this sense, a variety of norma- conventional methods of sample pretreatment in term
tive documents have been recommended, particularly, by of providing fast and reliable results. The main benefits
American Society for Testing and Materials (ASTM) and of this approach are being nondestructive and time-saving
International Organization for Standardization (ISO) for the in addition to having lower risk of cross-contamination and
analysis of diverse elements in crude oil.[34–46] In these analyte loss minimization. The main problem might be
methods, sample pretreatment is commonly carried out by considered is that the applied standards must be matrix
wet decomposition, dilution with organic solvent and ashing matched to samples because standards might have different
procedures. Analyses are mainly based on inductively behavior other than samples and this makes calibration
coupled plasma-optical emission spectrometry (ICP-OES), difficult.[32] Other drawback involves the interferences that
wavelength dispersive and energy dispersive X-ray can strongly affect the accuracy and precision of spectro-
fluorescence (XRF) spectrometry, flame atomic absorption scopic measurement techniques.[13] To overcome this limita-
spectrometry (FAAS), cold vapor atomic absorption tion, standard addition calibration and isotope dilution
spectrometry (CVAAS), electrometric, potentiometric, and techniques (ICP-IDMS) have been employed. The main
chemiluminescence analysis. The main goal of the present sample pretreatment procedures commonly performed for
review is to give an overview on the current status of analyt- crude oil analysis are described below.
ical methods devoted to performing elemental determination
in crude oil. For the sake of clarity, Figure 1 summarizes the
existing methodologies. Different sample pretreatment Wet digestion
strategies together with the most common measurement
Wet digestion (also referred to as acid mineralization)
techniques such as AAS, ICP-OES, inductively coupled
methods involve chemical decomposition of sample matrices
plasma-mass spectrometry (ICP-MS), XRF, neutron activa-
using the oxidizing and dehydrating power of concentrated
tion analyzer (NAA), chromatography, and other techniques
mineral acids into aqueous solutions, which is ideal to be
are overviewed. The basic principle, advantages, and draw-
introduced into the analytical instruments.[48,49] Sample
backs of each analytical method are indicated as well.
digestion can be carried out in open or closed vessels using
conventional heating or microwave radiation. Digestion in
Sample pretreatment procedures for crude oil open vessels is commonly performed in elemental analysis.
Different combination between nitric, hydrochloric, sulfuric,
Sample pretreatment is recognized as the key element in all
perchloric acids, and hydrogen peroxide can be used for
analytical procedures. The search for new sample pretreat-
sample decomposition.[22,50–55] Open vessel digestion is sim-
ment methodologies is still a challenge in analytical labora-
ple, inexpensive and requires high sample mass; therefore
tories, since the largest portion of time employed for the
being ideal for inhomogeneous samples. However, it is cur-
analysis process is dedicated to this task. With regard to
rently more liable to systematic errors due to contamination
crude oil, the complexity and high organic load of the
risk and loss of volatile species.[12,56] Safety, long decompos-
matrix, which provide high stability for oil, make the ana-
lysis very laborious. Thus, it becomes difficult to bring oil ition time, high acids consumption and inevitable sample
into solution.[14] As a consequence, it is essential to select dilution are also related limitations.[32,48] Additionally,
convenient sample pretreatment methods which ensure digestion efficiency is reduced in ambient pressure and
unbiased measurement results with minimum interfering low-temperature conditions. Thus, combination of different
substances. In fact, the most desirable characteristics of sam- acids can be achieved to raise the digestion temperature.
ple pretreatment procedures are rapid processing with no However, possible interferences with spectrometric techniques
contamination, improved accuracy and precision, little waste can occur especially when H2SO4 is used.[57,58]
generation (i.e., compatible with green chemistry concepts) Akinlua et al.[22] and Ajayi et al.[53] proposed wet
and the possibility to use aqueous standard solutions for digestion methods for the determination of metals in Niger
calibration purpose. Another factor could be considered is Delta oil. They used a combination of concentrated sulfuric
the traceability of the measurement results to the acid and hydrogen peroxide, and were able to calibrate AAS
International System of Units (SI) to ensure credibility and using aqueous standard solutions. Mastoi et al.[51] presented
comparability of the measurement results (i.e., development a method for determination of Cu in crude oil by spectro-
of higher order reference methods).[32] Ideal selection of the photometer based on wet digestion by classical heating on
method is strongly related to several parameters such as a hot plate. They used a large amount of samples (20–100 g)
measurement technique, chemical, and physical properties of and digestion was performed using sulfuric, nitric and
the matrix, sample mass, number of samples, concentration perchloric acids into clear aqueous solution. Kowalewska
ranges of the analyte and desired accuracy and precision.[47] et al.[54] studied several approaches for sample digestion for
Direct sample introduction with minimum or no sample the determination of Cu in crude oil and heavy petroleum
pretreatment is most compatible with NAA, XRF, laser- fractions using FAAS, GFAAS, and ICP-MS. They found that
induced breakdown spectroscopy (LIBS), laser ablation the best pretreatment procedure for analysis of copper in
inductively coupled plasma-mass spectrometry (LA-ICP-MS) crude oil and heavy petroleum products was mineralization
164 M. A. GAB-ALLAH ET AL.

Figure 2. MIC technique characteristics related to MW-AD and combustion techniques (performed in closed vessels).

in open vessels using a mixture of sulfuric acid and Cavalcante et al.[6] and Munoz et al.[55] used a combin-
n-butanol. ation of HNO3, H2O2, and H2O for oil digestion. The later
In contrast to open system, closed system is used to studied a comparison between focused-microwave (FM)
increase the digestion efficiency and reduce its time. It has digestion and closed-vessel microwave (CVM) digestion and
the advantages of retaining potentially volatile elements such found out that CVM was suitable for retaining volatile
as Hg, P, and Se in addition to reducing contamination elements like Hg while the recovery values showed Hg loss
risk.[13,47–49,59] Closed system digestion can be performed in via volatilization during the FM digestion. Pereira et al.[14]
Carius tube, calorimetric bomb, SchOniger € combustion proposed high-efficient method that combines microwave-
flasks, combustion bombs (Parr bomb), oxygen flask, poly- assisted digestion and ultraviolet radiation. In this proposed
tetrafluoroethylene (PTFE) or platinum vessels.[60–66] Closed method, UV radiation is generated using electrodeless Cd
vessels have also the benefit of increasing boiling points of discharge lamps positioned inside quartz digestion vessels.
the acids due to high pressures inside vessels. Therefore, Residual carbon content (RCC) was lower than 13 mg
higher digestion temperatures can be achieved which C/100 mg of sample, and it was possible to use dilute acid
improve digestion efficiencies of the acids. Despite that, solutions and relatively large sample quantities (500 mg).
these applications were not found to be frequently used MIC combines some advantages of MW-AD and com-
because most of these systems usually require long time to bustion techniques in a single system (Figure 2).[56]
accomplish the digestion. Moreover, it avoids the use of concentrated acids, thereby
Microwave-assisted-acid digestion (MW-AD) and micro- reducing the hazardous wastes. In this system, sample com-
wave-induced combustion (MIC) have been considered to bustion is performed inside quartz vessels under oxygen
be state of art nowadays and capable of solving the long- pressure (15–25 atm). The ignition step is performed using
time limitations in traditional digestion.[13] These systems microwave radiation and the gaseous products can be
utilize the use of microwave heating under the effect of absorbed into a suitable solution.[13] Pereira et al.[72] pro-
pressure, thereby being rapid and more efficient in addition posed a method for MIC of light and heavy crude oil. They
to the possibility of reducing the organic load of oil.[26,66] used ammonium nitrate as aid for ignition and dilute nitric
In addition, they yield highly repeatable and reproducible acid as absorbing solution. They also performed a compari-
results and being compatible with green chemistry recom- son with MW-AD and the efficiency of MIC and MW-AD
mendations, especially considering volume of reagents procedures was evaluated by determination of RCC in
employed and wastes generated.[8,67] Sample contamination samples. RCC was about 15% and <1% for MW-AD and
and analyte loss are minimized during the digestion. The MIC, respectively. Quiet similar methods were proposed by
literature survey revealed that microwave digestion has been Pereira et al.[11] and Pereira et al.[74] for determination Cl, S
extensively used for crude oil analysis.[5,6,9,11,14,25,26,55,68–77] and rare earth elements in crude oil by ICP-OES and ultra-
MW-AD method is recommended by United States sonic nebulization (USN) ICP-MS. It was also possible
Environmental Protection Agency (U.S. EPA) according to to use relatively high sample mass (0.5 g) without exceeding
US EPA 3051 A for the determination of several elements in the maximum pressure operated. Moreover, interferences by
sediments, sludge and oils using nitric and hydrochloric AAS, ICP-OES, and ICP-MS in the determination step were
acids.[78] The method provides a rapid multielement acid minimized due to low acid content of the digests.
extraction or dissolution prior to analysis. However, the Additional reflux step was performed after combustion to
addition of HCl may limit the quantitation methods, or improve the analyte recovery (better than 96%). The time of
increase the difficulties of quantitation with some techni- digestion was 25 minutes (including the cooling step) and
ques. Nitric acid has been used by Savonina et al.[70] for up to eight sample vessels could be employed, hence being
microwave decomposition of oil samples for the determin- appropriated for routine analysis and allows a convenient
ation of a wide spectrum of trace elements. Dreyfus et al.[77] sample throughput.
presented microwave-assisted acid digestion method to
measure lead isotope ratios in crude oil. These authors used
Ashing
a mixture of HNO3 and H2O2 and selected progressive
ramp of temperature to avoid leaks generated by a sudden Ashing procedure involves the ignition of organic substances
over pressure. Heilmann et al.[71] presented a quiet similar in air for complete removal of organic mass fraction, leaving
digestion method for multielement determination in crude behind inorganic ash. It is performed at elevated tempera-
oil by using isotope dilution LA-ICP-MS. ture, with subsequent dissolution of inorganic ash in mineral
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 165

acids. The system consists of an open inert vessel (pure analyte loss by volatilization. Platteau and Carrillo[84] devel-
quartz beaker or platinum crucible) containing the sample oped an ashing method for analysis of V, Fe, Ni, Mg, and Na
that undergoes thermal decomposition over a Bunsen gas in crude oil–water emulsions. They used ethyl alcohol to
burner or inside a muffle furnace.[13] Typical ashing temper- facilitate sample dehydration and linear alkylbenzene sulfonic
atures are 450–600  C. acid (LASA) as an ashing auxiliary which avoided loss of
Dry ashing is one of the cheapest decomposition methods volatile porphyrinic compounds through transformation to a
used and the first one applied for crude oil, prior to the deter- more stable form. The sample (3 g) was heated using a hot
mination by spectrometric techniques.[79,80] The main attrib- plate and a Fisher burner flame until charring, and then
utes of this procedure are easy operation, ability to use high ignited in a muffle furnace. Sample ash was digested using
sample mass (1–20 g), and the possibility of reconstitution of HNO3 and HCl on a hot plate prior to analysis by FAAS.
the obtained ash residue in small volume of dilute mineral Udoh et al.[85] proposed a method in which p-xylenesul-
acid for analyte enrichment.[79] However, the time required phonic acid was applied as ashing reagent to the determin-
for complete ashing is one of its drawbacks. Other concerns ation of Ni, Cu, Fe, Ca Mg, Na, and Zn in crude oil. In
are contamination risk, loss of volatile species and generation this method, sample (20 g) was mixed with p-xylenesulphonic
of toxic vapors upon heating.[47,59,81,82] Solutions have been acid (1 g per gram of oil). The mixture was boiled, charred,
proposed to control possible loss of certain elements through and then muffled in a muffle furnace at 500  C. The resulting
addition of elemental sulfur or sulfur-containing compounds ash was digested in dilute HCl on a steam bath. p-
before sample ignition.[17,34,38,66,83–89] Sulfated (wet) ashing Xylenesulphonic acid offers some benefits over other reagents
is an alternative mean that involves treatment of the sample as it is convenient with more complex matrices, not very
with a moderate amount of sulfuric acid, as ashing aid, before hygroscopic, and can be prepared easily. Additionally, it
charring. In such cases, the losses by volatilization are avoided decreases ashing time to about 5 h avoiding additional filtra-
because metal sulfates are relatively nonvolatile and retain tion step due to complete removal of carbon, and had the
in the sulfated ash (SA) at furnace temperatures.[48] ability to strengthen the release of all elements in this study.
Ashing method is recommended by ASTM according to
ASTM D5863 for the determination of Ni, V, Fe, and Na in
Dilution in organic solvent
crude oils and residual fuels by FAAS.[34] The method
proposes ashing of 1–20 g oil sample using sulfuric acid Direct oil dilution in an appropriate solvent has been used
as an ashing agent (0.5 mL of acid per each gram of oil). as natural and simpler alternative to sample decomposition
Gentle sample heating is performed by an infrared lamp and has been extensively employed. This procedure is rapid,
from the top for the steady evolution of fumes. The residual effortless, and does not affect the qualitative composition of
carbon is burned off by heating at 525  C in a muffle the oil.[49,90] The most frequently used solvents are xylene,
furnace and the inorganic residue is digested in dilute nitric toluene, kerosene and methyl isobutyl ketone (MIBK).
acid. A quiet similar method is also recommended according Dimethylbenzene, octane, propan-2-ol, n-pentane, and
to ASTM D5708 for the determination of Ni, V, and Fe in heptane have been also used. Solvent selection is of critical
crude oils and residual fuels by ICP-OES.[38] In the method importance. Proper solvent must totally dissolve the sample,
proposed by Shehata et al.[17] for determination of iron in has low volatility and toxicity, offers a non-luminous in add-
crude oil, 5 g of oil sample was used. These authors studied ition to stable flame and reduces non-spectral interferences
the effect of varying ratio of sulfuric acid to oil and found in plasma-based techniques.[59,79] The main limitations of
that 3 mL of sulfuric acid per gram of oil was the minimum this method are that oil solutions contain high organic load
volume required to avoid volatilization of Fe and increase and large solid particles (>10 mm) which affect sensitivity of
its recovery. The sample was coked with concentrated FAAS and ICP-based techniques due to matrix effects and
H2SO4 on a hot plate at 300  C until drying, and then polyatomic interferences.[13,91] Additionally, carbon depos-
burned off inside a muffle furnace at 550  C until complete ition on the sampling cone contaminates the instrument and
ashing. The ashing step lasted for 4.5 h. The inorganic resi- leads to clogging the cone orifice, and hence reduces sensi-
due was then reconstituted in dilute nitric acid. Barbooti[83] tivity. This can be minimized by feeding oxygen into the
also used sulfuric acid as an ashing agent. Oil was heated on plasma for carbon removal as CO2 in addition to optimizing
a hot plate for 4–5 h with subsequent charring at 180 C. the position of the torch. Thus, ICP-based techniques
Samples were then burned off in a muffle furnace at 550 C usually require specially designed nebulizers, desolvation
for 6 h. The ash residue was reconstituted in HCl and V, Ni, systems, and proper argon flow adjustment.[14,19,68,77,92–99]
Cu, and Fe were determined by FAAS. Other concern is the inevitable use of low stability and
A recent approach was presented by Sugiyama et al.[8] in high-cost oil-based standards for calibration.
which 5 g of oil sample was combusted in PyrexTM culture Variation in viscosities among samples which leads to
tube capped with quartz wool. The combustion procedure different uptake rates as well as rapid solvent evaporation
was followed by chemical oxidation and acid digestion using can produce analytical errors in measurement results.
HNO3, H2O2, and HCl. Concentrations of Ni and V were However, this procedure is widely accepted and nominated
then determined by ICP-MS. This ashing-digestion technique by international standards for elemental determination in
is a cost-effective and overcomes the drawbacks of conven- petroleum and its fractions. For example, it is recommended
tional ashing procedure including cross-contamination and by ASTM according to ASTM D5863[34] and ASTM
166 M. A. GAB-ALLAH ET AL.

D5708[38] for metal determination in crude oil and residual with 200 ng g
1 standard solution prepared in a given solv-
fuel using FAAS and ICP-OES, respectively. Mixed xylenes, ent. THF was selected for sample dilution due to its high
o-xylene, tetralin, and mixed paraffin-aromatic solvents are polarity and intense interaction with silica gel TLC plates so
proposed as dilution solvents.[34,38] that elemental adsorption on silica gel could be higher.[97]
Shehata et al.[17] described a comparative dilution method Kahen et al.[98] proposed a method in which they used dir-
for the determination of iron in crude oil samples. The ect injection high-efficiency nebulizer (DIHEN) ICP-MS for
method involved warming up the oil samples at 40  C and multielement analysis in oil samples diluted in xylene. The
subsequent shaking for homogenization then dilution ten- flow rate of the solution was optimized (10 ml min
1) to
fold in xylene prior to analysis by FAAS[17]. In the method reduce the solvent effect and provide stable plasma condi-
proposed by Stigter et al.[52], carbon tetrachloride and xylene tions for organic matrices. As a result, the formation of car-
were used for dissolution of oil sample for determination of bon-based products on the nebulizer tip, plasma region and
Cu, Cd, Zn, and Cr by AAS. The pre-diluted solutions were sampling cone of the mass spectrometer interface was suc-
aspirated as a 1:4 solution in the toluene-glacial acetic acid cessfully eliminated. Giusti et al.[92] developed an interface
solvent to reduce signal suppression and memory effects. based on a total consumption micronebulizer (DS-5) which
Guidroz et al.[100] applied MIBK as dilution solvent proceeded at a higher flow rate (30 ml min
1) for the intro-
for determination of V by nitrous oxide–acetylene FAAS duction of xylene solutions into ICP-MS. At these condi-
in burned and unburned Venezuelan crude oil. De tions, the problems due to clogging, pressure instability and
Albuquerque et al.[101] proposed a method for determination memory effects were minimized. The developed method
of As and Se in crude oil by ICP-MS. In this case, oil allowed the simultaneous determination of Mo, Ni, and V
samples were diluted 20-folds (m/m) in xylene and analyzed with high sensitivity at the sub-ng mL
1 levels in petrol-
after standard addition calibration. A dynamic reaction cell eum samples.
(DRC) filled up with methane was used and succeeded in
minimizing the interference by 40Ar2þ on 80Se.[101] Duyck
Emulsification
et al.[68] developed a method for trace determination of V,
Ni, Co, Y, Mo, Cd, Ba, La, Al, Ti, Fe, Zn, Sr, Ag, Sn, and Pb As was previously mentioned, introduction of organic sam-
in crude oil samples by ICP-MS. They used toluene for ples into spectrometric techniques (e.g., FAAS, ICP-OES,
sample dissolution and USN for sample introduction. and ICP-MS) generally causes serious problems including
Desolvation system of the USN, along with oxygen/argon instability in the flame/plasma and carbon deposition on
ratio optimization, was effective in minimizing carbon built- nebulizer tip, plasma region and sampling cone.[97,98,103] An
up at the interface and ion lenses. Standard addition calibra- efficient alternative to minimize these limitations is to pre-
tion combined with internal standardization (115In) was pare oil samples as three component solution. An emulsion
applied. In this way, it was possible to properly correct for is generally obtained by dispersing oil sample in an aqueous
signal suppression, especially observed in a sample of high medium as microdroplets stabilized by vesicles or micelles
concentrations of asphaltenes. that are generated by the addition of suitable surfac-
In the method proposed by Ellis et al.[102], Ni and V tant.[47,103–105] After dispersion under controlled experimen-
metalloporphryins were determined in crude oil and crude tal conditions, a cloudy (emulsion) or a transparent mixture
oil fractions by gas chromatography (GC) coupled to ICP- (microemulsion) can be obtained. Microemulsion is thermo-
MS (GC-ICP-MS). Samples were diluted ten-fold in carbon dynamically stable in which the droplets are much finer
disulfide. The method required uniform heating of a transfer (from 5 to 100 nm). However, it is sensitive to temperature
line and ICP injector. Rapid transfer of separated species changes and requires much amount of surfactant.[104]
from the GC to the ICP-MS was achieved in a heated argon In comparison with other methods (ashing, wet digestion,
gas. Bettmer et al.[19] described an attractive alternative for and dilution in organic solvents), emulsion and microemul-
accurate and precise analysis of heavy metals in crude oil sion provide advantages of being time-saving sample
samples. Toluene was used for oil dissolution. The approach pretreatment procedures, do not require a large volume of
involved a combination of l-flow direct injection and iso- organic solvents and feasibility of using aqueous inorganic
tope dilution ICP-MS (ICP-IDMS). The proposed combin- standards instead of expensive oil-based standards for
ation provided a matrix-independent quantification without calibration purpose.[32,49,106–108] Furthermore, the surfactant
any sample pretreatment except sample dilution and mixing provides a stable and homogeneous system for a relatively
with the internal standard solutions. long time.[13,109] Acid may be used to enhance the analyte
Vorapalawut et al.[97] described the application of laser stabilization. Quadros et al.[110] proposed an oil-in-water
ablation inductively coupled plasma mass spectrometry (LA- emulsion method for pretreating crude oil samples for the
ICP-MS) for multielement analysis in crude oil. The use of a analysis of Ni and V as their total and nonvolatile fraction
double- focusing sector-field mass analyzer allowed the elim- by high-resolution continuum-source GFAAS (HR-CS
ination of carbon-related polyatomic interferences, matrix GFAAS). Oil was warmed up and subject to ultrasonic agita-
interferences and carbon deposition on the sampler and tion for homogenization then dissolved in xylene. 5% (m/v)
skimmer cones. They compared the use of xylene, cyclohex- solution of Triton X-100 was added to enhance miscibility
ane and tetrahydrofuran (THF) as dilution solvents after between oil and water. Concentrated HNO3 was added to
impregnation of a thin-layer chromatography (TLC) plate the emulsion solution to increase stabilization of Ni and V
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 167

prior to analysis.[110] Damin et al.[111] presented a similar thermally stable fraction in Brazilian crude oil using HR-CS
method for the determination of Ni, V, and volatile analyte GFAAS. Oil samples were prepared as oil-in-water emul-
fractions in crude oil by HR-CS GFAAS using Triton X-100 sions with composition of crude oil/xylene/Triton X-100/
as surfactant and Pb modifier for avoiding any losses of V water. Ethanol was introduced into the graphite tube with
and Ni up to pyrolysis temperatures of 1200  C and 1450  C, the samples to prevent foam formation and palladium solu-
respectively. In this case, small volume of ethanol was intro- tion was used as a modifier.[116] A rapid methodology for
duced with the emulsion into the graphite tube to prevent the determination of S, Ni, and V in heavy crude oil by
foam formation. The same research group[112] performed a ICP-OES was presented by Murillo and Chirinos.[117].
comparison between direct solid sampling and oil emulsion Emulsions were prepared with ethoxy nonilphenol and
formation using a filter furnace (FF) for Pb analysis in crude aqueous standards were employed. This nonionic emulsifier
oil by GFAAS. Pd and Mg nitrates together with Triton of high hydrophilic–lipophilic balance (HLB) was efficient
X-100 were used as chemical modifier and calibration for heavy crude oil and allowed the formation of sta-
against inorganic standard solutions was performed. ble emulsions.
Emulsion analysis using FFAAS provided better sensitivity
and relative standard deviation (RSD) than direct sampling
Extraction
GFAAS (DS-GFAAS). Whereas, DS-GFAAS allowed the
use of higher sample mass and provided the fastest results Extraction (also referred to as leaching) is the process of
without sample preparation. moving the retained analytes from their active sites in the
Determination of S in crude oils was performed after sample matrix and subsequent solubilization into physically
microemulsion formation by high-resolution continuum- separate location (extractant medium), where further treat-
source graphite furnace molecular absorption spectrometry ment and analysis occur.[13] Extraction of elements from the
(HR-CS-GF MAS) as SnS molecules[31]. Pd was used as oil seems to be an interesting way of sample pretreatment
permanent modifier and it was possible to use aqueous that combines the possibility of their determination and also
standards for the calibration purpose. Luz et al.[113] pro- speciation which is essential to study the origin of oils and
posed a fast emulsion-based method in which an oil/hexane environmental monitoring.[12]
mixture was mixed with Triton X-100 in ultrasonic bath The important benefits of this methodology are simpli-
and diluted in deionized water to simultaneously determine city, selectivity, rapidity and being environmental friendly
Co, Cu, Pb, and Se by GFAAS. Determination of ten trace where it is possible to use dilute solutions of mineral acids,
elements (Mo, Zn, Cd, Ti, Ni, V, Fe, Mn, Cr, and Co) in alkalis, oxides and complexing reagents. However, the
crude oil by ICP-OES was proposed by de Souza et al.[25] suitability of the methodology for a wide range of elements
In this case, samples were prepared as detergentless micro- may be limited due to the complexity of sample matrix
emulsion with composition of crude oil/propan-1-ol/water/ which hampers the extraction mechanism.[4,13]
concentrated nitric acid. Addition of HNO3 acid to micro- Souza et al.[26] proposed a method for chloride determin-
emulsions allowed the use of aqueous inorganic standards ation in crude oil by ICP-OES through the determination of
for calibration. Higher amounts of crude oil were used chloride counterions (Na, Ca, Mg, Sr and Fe) in the aqueous
and allowed to reduce the dilution factor when compared extract. The method was based on liquid–liquid extraction
to other sample preparation procedures. The possibility (modified ASTM D6470-99) in an extractor flask using acet-
of cross-contamination was reduced due to minimizing one, isopropyl alcohol and hot deionized water. The aqueous
sample handling and reagent addition. extract was then collected and diluted with 0.2% HNO3
Lord[114] applied the use of microemulsion pretreatment (v/v), for reducing the salinity, prior to determination by
of crude oil for the determination of trace metals by ICP- ICP-OES.[26] A novel strategy for elemental determination
MS with excellent accuracy and precision. The microemul- in crude and diesel oil by ICP-MS was proposed by
sion system composed of crude oil/tetralin/Triton X-100/ Maryutina and Soin.[62] In this case, they developed an
deionized water. Tetralin was effective in minimizing extraction system in which the oil sample was continuously
polyatomic ion background interferences due to its low pumped through a rotating coil column containing nitric
vapor pressure (16 times less than xylene). This technique acid as stationary phase. The method was rapid, reliable and
offered considerable savings in time and manpower required accurate where it utilized the combination of preconcentra-
for sample preparation. The problems related to the tion by counter current chromatography (CCC) and the
high organic load, analyte loss, contamination were high the sensitivity of ICP-MS. A quiet similar method was
minimized.[114] presented by Soin et al.[118] for the determination of rare
Oil-in-water emulsion-based method for heavy crude oil earth elements (REE) in crude oil.
and bitumen-in-water emulsion was optimized by Burguera Some extraction procedures require a previous digestion
et al.[115] The method enabled Cr determination by transver- step using concentrated or dilute mineral acids. A rapid,
sally heated GFAAS (TH-GFAAS). In this case, the samples simultaneous method was presented by Amoli et al.[87] for
were emulsified by Intan-100 as a nonionic surfactant. The the determination of V, Ni, Fe and Cu in crude oil by
optimized methodology was easy to operate and did not reversed-phase high-performance liquid chromatography.
require a long time sample pretreatment. Lepri et al.[116] The method was based on wet ashing using sulfuric acid in
proposed a method for determination of total V and addition to subsequent solvent extraction of metal ions using
168 M. A. GAB-ALLAH ET AL.

Table 1. Selected publications on trace element determination in crude oil by AAS.

Solubilization procedure Sample mass (mg) Technique of determination Analyte Limit of detection Reference
Direct analysis 0.5–4.7 DS-GFAAS Mg, Ca – [5]
Wet digestion 100 GFAAS Ni 0.003 mg g
1 [6]
V 0.002 mg g
1
Direct analysis 1–10 DS-GFAAS As 5.1 mg kg
1 [18]
Cd 0.2 mg kg
1
Direct analysis 0.1–4.0 HR-CS GFAAS Cr 1.0 mg kg
1 [20]
Fe 0.6 mg kg
1
Wet digestion – GFAAS Cr, Co, Cu, Fe, Mn, Ni, Pb, V – [22]
Emulsification 0.1–1.0 FAAS Ca 0.54 mg g
1 [23]
Mg 0.09 mg g
1
Sr 0.10 mg g
1
GFAAS Ba 0.04 mg g
1
Direct analysis 0.1–0.6 DS-GFAAS Ni 0.23 ng [24]
Dry ashing Sample dilution 1000–3000 FAAS V, Ni, Cu, Fe – [83]
Dry ashing 3000 FAAS V, Ni, Fe, Mg, Na – [84]
Sample dilution 5000 FAAS V – [100]
Emulsification 25–300 HR-CS GFAAS Ni 3.0 mg g
1 [110]
V 1.0 mg g
1
Emulsification 50–2000 GFAAS Ni 0.02 mg g
1 [111]
V 0.06 mg g
1
Direct analysis 0.5–3.0 DS-GFAAS and FF AAS Pb 0.004 mg g
1 [112]
Emulsification 500
Emulsification 100–1000 GFAAS Co 0.02 mg g
1 [113]
Cu 0.03 mg g
1
Pb 0.04 mg g
1
Se 0.11 mg g
1
Emulsification – TH-GFAAS Cr 0.52 mg L
1 [115]
Emulsification 50–2000 HR-CS GFAAS V 0.04 mg g
1 [116]
EIEB 20 mL CVAAS Hg 0.6 mg L
1 [132]
Direct analysis 0.6–8.0 HR-CS GFAAS Co 8 mg g
1 [137]
V 1.2 mg g
1
Direct analysis 5 DS-GFAAS Na 30 mg kg
1 [138]
Wet digestion 750 K 3.2 mg kg
1
Sample dilution 100–5000 GFAAS V – [139]
Sample dilution Emulsification 1000–2000 HR-CS GFAAS Ni 0.07 mg g
1 [140]
Direct analysis 0.1–3 DS-GFAAS Cu 10 pg [141]
Fe 200 pg
V 800 pg
Direct analysis 0.1–10 DS-GFAAS Ni 0.017 mg g
1 [142]
V 0.018 mg g
1
Direct analysis 0.1–2 DS-GFAAS Ni 0.09 mg g
1 [143]
V 0.10 mg g
1

8-hydroxiquinoline solution as a ligand. The effect of pH Cassella et al. for the analysis of trace metals in diesel
on extraction efficacy was studied and it was found that pH oil samples.[120,121] Since then, several various kinds of
(3-4) gave the best results. Recently, a sequential extraction matrices[122–132] including crude oil have been successfully
method for the determination of Ni and V species was analyzed using this approach which shows to be a promising
developed by Cavalcante et al.[6] The separation was based methodology for crude oil analysis. EIEB is based on the
on column chromatography using silica gel as the stationary formation of oil-in-water emulsion using surfactant in add-
phase and organic solvents (hexane, toluene, dichlorome- ition to acid followed by emulsion breaking by heating and/
thane (DCM) þ methanol and methanol) as the mobile or centrifugation. The analytes are then transferred to the
phase. The extracts obtained in each fraction were analyzed aqueous phase which is separated from both oil and surfac-
by gas chromatography–mass spectrometry (GC–MS), infra- tant, making possible their analysis by several spectrometric
red (IR) and GFAAS measurements for both identification techniques. The main advantages of this new strategy are
of organic compounds and determination of the concentra- the possibility of the preconcentration of the analytes before
tion of Ni and V.[6] analysis, calibration using aqueous standards and elimin-
Ultrasonic waves could be applied to increase the extrac- ation of matrix interferences. Trevelin et al.[108] proposed an
tion rate and improve its efficiency.[76,119] de Souza et al.[76] extraction method based on emulsion breaking for crude oil
proposed a method for determination of nine trace elements samples. The method allowed the analysis of Ba, Ca, Mg
(Cr, Mo, Ti, V, Cd, Fe, Mn, Ni, and Zn) in crude oil by and Na by ICP-OES after total extraction in the aqueous
ICP-OES. The method was based on ultrasound-assisted phase. Emulsion composition was crude oil/xylene/Triton
acid extraction of the trace elements into the hot X-100/water. Emulsion breaking was achieved by heating
concentrated nitric acid solution. Inorganic standards were and centrifugation. The method was cheap, sensitive and
employed in the calibration process. accurate with minimum ICP-OES interferences.
Recently, a novel extraction strategy named extraction Recently, Wuyke et al.[130] presented a quiet similar
induced by emulsion breaking (EIEB) was first proposed by method for the analysis of six trace elements (As, Co, Cr,
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 169

Mn, Mo, and Pb) in crude oil by ICP-MS. It was possible to Plasma-based techniques
eliminate the increment of interferences and carbon build-
Plasma-based techniques namely, ICP-OES and ICP-MS
up on the sampler and skimmer cones as only aqueous solu-
have been widely employed for elemental analysis in crude
tions were introduced into the instrument. Determination of
oil. In these techniques, plasma of a very high temperature
Cl by ion chromatography in Brazilian crude oils after EIEB
was performed by Robaina et al.[131] Triton X-114 was used (6000–10,000 K) is used for atomization, excitation, and ion-
as an emulsifier and provided higher extraction efficiency ization of elements.[144] In ICP-OES, sample solution is con-
than Triton X-100. The obtained emulsion was broken by ducted into a spray chamber and then the aerosol is lead to
centrifugation and the results were not statistically different the central channel argon plasma. Excited atoms and ions
from those obtained by the ASTM D6470 method at a 95% produce their own characteristic emission spectra. The main
confidence level. advantages of ICP-OES are multielement analysis capability
for over 70 elements per run, wide linear dynamic range
(several orders of magnitudes) and low limit of detec-
Analytical techniques tion (LOD).[12,79,144]
In ICP-MS technique, plasma is used to produce ions
A variety of analytical techniques have been employed for
which are removed from the plasma into the MS part
the determination of sulfur and trace elements in crude oil
(Magnetic sector, quadrupole and time of flight (TOF))
depending upon the measured element, measurement range,
which isolates different ions based on their mass-to-charge
pretreatment method used, the studied oils, sample mass
(m/z).[49,145] This technique is of a prime importance as it
and number of samples. The most commonly used analytical
techniques are AAS, ICP-OES, ICP-MS, XRF, NAA, and allows multielemental determination down to the sub-parts-
chromatographic techniques. per-trillion level and isotopic-ratio measurement. Isotope
dilution technique (ICP-IDMS) can be employed for the
development of higher order reference methods for SI-trace-
Atomic absorption spectrometry (AAS) able value-assignment of elements in oils.[19,65,71] Moreover,
the application of laser ablation technique to ICP-MS
AAS is one of the most frequently used spectroanalytical
(LA-ICP-MS) provides an efficient tool for direct analysis of
techniques for trace elemental analysis.[133] AAS is so sensi-
oil samples without sample pretreatment.[15,71,97] Despite
tive as it can measure up to parts per billion of a gram (lg
these advantages and applications of ICP-based techniques,
dm
3) in a sample and can be applied for the determination
the analysis of organic samples is more challenging. As was
of over 70 various elements.[134] In this technique,[49] the
stated above, the operator should consider problems associ-
samples are aspirated or directly injected into an atomiza-
ated with plasma instability, matrix interferences, polyatomic
tion system that provides a necessary energy for conversion
interferences together with carbon deposition on sampler
of the analyte into an appropriate chemical form to absorb
radiation (gas phase atom). The resulting atoms are radiated and skimmer cone during the analysis of high carbon
by electromagnetic energy of a characteristic wavelength of content samples. Adequate sample preparation and special
the element of interest (ultraviolet or visible light) emitted ICP accessories have to be applied to overcome most of
by a hollow cathode lamp (HCL). The amount of light these limitations.[14,19,92–94,98,99,146] More recently, a highly
absorbed is directly proportional to the amount of analyte advanced technique named triple quadrupole ICP-MS
atoms in the sample. (QQQ-ICP-MS) was employed to solve problems related to
AAS technique involves three variants: FAAS, GFAAS, polyatomic and isobaric interferences.[147] A number of
and CVAAS. Additionally, hydride generation AAS selected publications about ICP-based techniques employed
(HGAAS) is used to determine certain elements. The main for the analysis of crude oil samples are summarized in
difference among these techniques is the atomization Table 2.[8,11,14,19,25,26,50,71,76,92,101,129,130,148–152]
method.[135] In general, AAS is economically affordable,
user-friendly and of easy operation. Additionally, as was pre- X-ray fluorescence (XRF) spectrometry
viously mentioned, GFAAS can provide solid sampling strat-
egy for direct analysis (DS-GFAAS) with minimum or no XRF spectrometry is a nondestructive method of qualitative
sample pretreatment. Despite all of these benefits and appli- and quantitative analysis of chemical elements. XRF is based
cations, conventional AAS is not a multielement technique on the emission of characteristic secondary X-ray photons
and, in most cases, requires increasing sample pretreatment. from a material that has been excited by bombarding with
High-resolution continuum-source atomic absorption primary high-energy X-rays (0.01–10 nm). Every element
spectrometry (HR-CS AAS) was commercially introduced in produces a unique emission line whose intensity is directly
2003 to overcome this limitation. This approach utilizes the proportional to the concentration of the element in the sam-
use of xenon short-arc lamp as high-intensity continuum ple.[49,153] There is a clear advantage for the use of XRF
radiation source (190–900 nm) to determine numerous technique in providing direct analysis of samples thereby,
elements in a fast sequential mode.[136] Several methods for avoiding the tedious and laborious sample pretreatment
trace element determination in crude oil samples have been steps. In addition, it provides fast and multielemental ana-
developed for quantification by AAS, some of which are pre- lysis with a very wide field of practical applications. The
sented in Table 1.[5,18,20,23,24,83,84,100,110–113,115,116,132,137–143]. main limitations of the technique are limited sensitivity,
170 M. A. GAB-ALLAH ET AL.

Table 2. Selected publications on elemental determination in crude oil using ICP-based techniques.
Solubilization Technique of
procedure Sample mass (mg) determination Analyte Limit of detection Reference
Dry ashing 5000 ICP-MS Ni 0.11 mg kg
1 [8]
V 0.61 mg kg
1
Wet digestion 100–500 ICP-OES Cl 12 mg g
1 [11]
S 5 mg g
1
Wet digestion 350–500 ICP-MS La, Ce, Pr, Nd, Sm, Eu, Gd, – [14]
Tb, Dy, Ho, Er, Tm, Yb, Lu, Y
Sample dilution – ICP-IDMS Ni 0.8 mg kg
1 [19]
Mo 0.25 mg kg
1
Sn 0.35 mg kg
1
Pb 0.09 mg kg
1
Emulsification 600 ICP-OES Mo 4.1 mg kg
1 [25]
Zn 1.1 mg kg
1
Cd 7.1 mg kg
1
Ti 2.8 mg kg
1
Ni 1.0 mg kg
1
V 2.4 mg kg
1
Fe 0.4 mg kg
1
Mn 0.5 mg kg
1
Cr 12.7 mg kg
1
Co 13.0 mg kg
1
Extraction 40,000 ICP-OES Na 0.99 mg L
1 [26]
Ca 0.025 mg L
1
Mg 0.33 mg L
1
Sr 0.06 ng L
1
Fe 0.26 mg L
1
Wet digestion 2000 ICP-MS 139
La, 140Ce, 141Pr, 146Nd, 152Sm, – [50]
153
Eu, 158Gd, 163Dy,166Er, 174Yb

1
Wet digestion 250–500 ICP-MS Hg 10 pg g [65]
Direct analysis and 100–500 LA-ICP-IDMS Cr 0.012 mg g
1 [71]
wet digestion Fe 0.21 mg g
1
Cu 0.016 mg g
1
Zn 0.08 mg g
1
Cd 0.04 mg g
1
Sn 0.05 mg g
1
Pb 0.08 mg g
1
Ni 0.14 mg g
1
V 0.02 mg g
1
Wet digestion 100 ICP-OES Cr 0.005 mg g
1 [76]
Extraction 200 Mo 0.06 mg g
1
Ti 0.01 mg g
1
V 0.003 mg g
1
Cd 0.03 mg g
1
Fe 0.01 mg g
1
Mn 0.002 mg g
1
Ni 0.09 mg g
1
Zn 0.19 mg g
1
Sample dilution – ICP-MS 51
V 0.9 ng mL
1 [92]
60
Ni 0.6 ng mL
1
98
Mo 0.1 ng mL
1
Sample dilution – ICP-MS 78
AS 0.04 mg kg
1 [101]
Wet digestion 700 80
Se 0.1 mg kg
1
EIEB 200 ICP-OES Ba 0.12 lg L
1 [129]
Ca 1.2 lg L
1
Mg 0.14 lg L
1
Na 5.8 lg L
1
EIEB 500 ICP-MS As 0.17 mg kg
1 [130]
Co 0.15 mg kg
1
Cr 0.31 mg kg
1
Mn 0.20 mg kg
1
Mo 0.22 mg kg
1
Pb 0.27 mg kg
1
Wet digestion 100 ICP-OES Ni 0.24 mg g
1 [148]
V 0.06 mg g
1
Wet digestion 1000 ICP-OES Co 0.1 mg kg
1 [149]
Cr 1 mg kg
1
Cu 1 mg kg
1
Fe 1 mg kg
1
Mn 0.3 mg kg
1
Ni 4 mg kg
1
V 4 mg kg
1
Wet digestion 500 ICP-OES Cd, Cr, Cu, Pb, Mn, Ni, V, Zn 0.05–0.10 mg g
1 [150]
Wet digestion 100–500 ICP-MS 51
V, 60Ni, 55Mn, 59Co, 75As, 95Mo, – [151]
138
Ba, 208Pb
(continued)
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 171

Table 2. Continued.
Solubilization Technique of
procedure Sample mass (mg) determination Analyte Limit of detection Reference
Sample dilution 1000 ICP-OES Ca 20 mg kg
1 [152]
Fe 20 mg kg
1
Ni 20 mg kg
1
V 20 mg kg
1
Sample dilution 1000 ICP-MS 40
Ca 6.87 mg kg
1 [152]
56
Fe 5.17 mg kg
1
62
Ni 0.70 mg kg
1
51
V 0.84 mg kg
1

difficulties in the determination of lighter elements, and the authors, the results obtained by NAA pointed out that the
relatively high cost.[49] concentration ranges of the elements showed some variability
Special designs have been proposed such as total reflection and the crude oils have low detrimental impact on the
XRF (TXRF) to minimize matrix interferences and improve environment. NAA was used later as a direct method for
LODs. Ojeda et al.[154] used TXRF in the analysis of S, V, Fe, the determination of metals, metalloids and REE for compar-
and Ni in crude oil samples. The samples were homogenized ing results with those obtained by ICP-MS after MIC of
and placed on a quartz sample holder then irradiated without crude oil.[72,74]
any treatment. Reproducibility of the measurement results
was 2–6% and the accuracy was within 4%. LODs for S, V,
Chromatographic techniques
Fe, and Ni were 20, 0.6, 0.1, and 0.4 ppm, respectively.
ED-XRF analysis of sulfur in petroleum and petroleum As was previously discussed, speciation analysis of crude oils is
products is also recommended by ASTM according to of great importance in determining their origin and for classifi-
ASTM D4294.[45] Doyle et al.[27] proposed ED-XRF method cation into families. Additionally, it can be utilized for the
for the direct determination of Cl in crude oil. Sample optimization of different technologies (hydrodesulfurization
homogenization was crucial to get accurate results. Simple and hydrodemetallation) that are necessary for the removal of
calibration strategy using inorganic standards was achieved certain elementary species such as S, Ni and V compounds.[13]
and the LOD was 8.6 mg g
1. Recently, the same research One of the most common methods for achieving speciation
group[28] performed ED-XRF method for the direct deter- analysis in crude oil is the use of hyphenated techniques,
mination of S, Ca, Fe, Ni, and V in crude oil. Oil samples combining the chromatographic resolution (e.g., HPLC and
were homogenized and diluted with toluene (1:1 v/v). The GC) with element specific detection.[102,165]
mixture was deposited on a substrate and inserted between Chromatographic techniques are employed for separating
two polypropylene films then introduced to the instrument a mixture of chemical substances into their individual
cell for analysis.[28] The determination of S and heavy components, so that the individual components can be
metals in crude oil and petroleum products by ED-XRF thoroughly analyzed. GC-ICP-MS was employed by Ellis
spectrometry was also described.[155] et al.[102] for the determination of volatile Ni and V species
in crude oil. Caumette et al.[165] applied the coupling of size
exclusion chromatography (SEC) and normal phase HPLC-
Neutron activation analyzer (NAA)
ICP-MS for fractionation and speciation of nickel and
NAA is used to determine the concentration of trace and vanadium in crude oils. SEC allowed fractionation of the
major elements in a variety of matrices. The material is irra- metal species using three columns in series for covering
diated with a neutron beam, which results in the capture of the molecular mass range between 300 and 2  106 Da.
neutrons by various nuclei of the elements in the sample, Meanwhile, normal phase HPLC-ICP-MS allowed the
yielding many radioactive isotopes. Upon their decay, they advanced separation of the porphyrin-type fraction and the
emit gamma rays whose energies are characteristic for each remaining species into three distinct fractions according to
nuclide.[156] NAA enables nondestructive, multielement ana- their polarities. According to these authors, the effective
lysis with no or minimal sample pretreatment. Moreover, it coupling had the potential to fingerprint oils according to
provides good accuracy, precision, and high selectivity. In their origins, and to monitor fractionation and oil refining
contrast, this technique is expensive, generates hazardous in terms of metal speciation.[165] Metal analysis in crude oil
radioactive wastes and requires a nuclear reactor, which is has also been performed using chromatographic techniques
commonly not available in most laboratories.[13,74] According after solvent extraction and metal complexation.[6,87,131,166–170]
to literature, employing this technique for the analysis of
crude oil was relatively high in the past.[157–164] Shah
Other measurement techniques
et al.[157] used NAA for simultaneous determination of
thirteen trace elements (Sc, Cr, Fe, Co, Ni, Zn, As, Se, Sb, Eu, Ultraviolet–visible (UV–Vis) spectrophotometry has been
Au, Hg, and U) in crude oil. The method was sensitive, successfully employed for trace metal analysis in crude oils.
precise without sample pretreatment. Analysis of Al, Au, As, More recently, Shehata et al.[17] proposed a simple method
Br, Cl, Ga, K, Mn, Mo, Na, V, and Zn in Nigerian crude oils for Fe determination by UV–Vis spectrophotometer. In this
was performed by Adeyemo et al.[164] According to these case, they used 1,10-phenanthroline as chelating agent and
172 M. A. GAB-ALLAH ET AL.

the absorbance maximum of the solution was measured at DRC dynamic reaction cell
510 nm (k max). Percentage recovery value was 97% and DS-GFAAS direct sampling graphite furnace atomic
absorption spectrometry
percentage RSD was less than 1%. LOD and limit of quanti- EIEB extraction induced by emulsion breaking
fication (LOQ) obtained were 0.017 and 0.051 lg mL
1, FAAS flame atomic absorption spectrometry
respectively.[17] Mastoi et al.[51] determined V spectrophoto- FFAAS filter furnace atomic absorption spectrometry
metrically in crude oil after derivatization with 2-pyrroleal- FM focused-microwave
dehyde phenylsemicarbazone (PPS) and the absorbance was GC gas chromatography
GC-ICP-MS gas chromatography inductively coupled plasma-
measured at 510 nm. mass spectrometry
LIBS technique was used by Martınez et al.[171] for quantita- GC–MS gas chromatography–mass spectrometry
tive analysis of Ni and V in crude oil samples. Samples were GFAAS graphite furnace atomic absorption spectrometry
encapsulated in Zr xerogels to form homogeneous and durable HCL hollow cathode lamp
HGAAS hydride generation atomic absorption
pellets that avoided sample spattering during ablation. Y was
spectrometry
used as internal standard that efficiently minimized matrix HLB hydrophilic–lipophilic balance
interference effect. LODs for V and Ni were 7 and 4 lg g
1, HPLC high-performance liquid chromatography
respectively. El-Hussein et al.[172] employed LIBS technique for HPLC-ICP-MS high-performance liquid chromatography
discriminating crude oil grades through the direct analysis of inductively coupled plasma-mass spectrometry
HR-CS AAS high-resolution continuum-source atomic
atomic, ionic and molecular species in oil samples. A pulsed absorption spectrometry
Nd-YAG was used as the laser source. The obtained results dis- HR-CS GFAAS high-resolution continuum-source graphite
played a correlation between the American Petroleum Institute furnace atomic absorption spectrometry
(API) gravity values of the different oil samples and the relative HR-CS-GF MAS high-resolution continuum-source graphite
abundance of the elements and molecular radical species. Based furnace molecular absorption spectrometry
ICP-IDMS inductively coupled plasma isotope dilution mass
on this correlation, identifying the API gravity values of spectrometry
unknown oils was also possible.[172] ICP-MS inductively coupled plasma-mass spectrometry
ICP-OES inductively coupled plasma-optical emission
spectrometry
Conclusion ISO International Organization for Standardization
LA-ICP-MS Laser ablation inductively coupled plasma-mass
The primary interest in elemental determination in crude spectrometry
oils stems from the fact that S and trace elements have LASA linear alkylbenzene sulfonic acid
significant detrimental impacts on their conversion into use- LIBS Laser induced breakdown spectroscopy
LOD limit of detection
ful petroleum fractions and on the environment in addition
LOQ limit of quantification
to serving as indicators for tracing maturation, origin, and MIBK methyl isobutyl ketone
geochemical characterization of oils. This article provides MIC microwave-induced combustion
a review on the current status of analytical methods for MW-AD microwave-assisted-acid digestion
determination of S and trace elements in crude oils. NAA neutron activation analyzer
PPS pyrrolealdehyde phenylsemicarbazone
Different pretreatment procedures of oil samples and all PTFE polytetrafluoroethylene
common measurement techniques are indicated. A summary QQQ-ICP-MS triple quadrupole ICP-MS
of the applications and developments over the past years is RCC residual carbon content
described. Depth analysis data evidenced that decomposition REE rare earth elements
RSD relative standard deviation
by wet digestion is the most widely used technique.
SA sulfated ash
However, it was noticed that researchers are migrating SEC size exclusion chromatography
toward direct analysis protocols, being nondestructive in THF tetrahydrofuran
addition to providing fast and reliable results. On the other TH-GFAAS transversally heated graphite furnace atomic
hand, methods based on plasma-based techniques have absorption spectrometry
TLC thin-layer chromatography
enormously evolved due to their multielement analysis TOF time of flight
capability, wide linear dynamic range and very low detection TXRF total reflection X-ray fluorescence
limit. The development of new advanced strategies for crude U.S. EPA United States Environmental Protection Agency
oil analysis is also required taking into account compatibility USN ultrasonic nebulization
with green chemistry concepts. UV–Vis ultraviolet–visible
XRF X-ray fluorescence

Abbreviations Disclosure statement

ASTM American Society for Testing and Materials No potential conflict of interest was reported by the authors.
CCC counter current chromatography
CVAAS cold vapor atomic absorption spectrometry
CVM closed-vessel microwave ORCID
DCM dichloromethane
DIHEN direct injection high-efficiency nebulizer M. A. Gab-Allah http://orcid.org/0000-0002-0993-5991
 CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 173

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