DOI 10.

1007/s10553-016-0691-4
Chemistry and Technology of Fuels and Oils, Vol. 52, No. 2, May, 2016 (Russian Original No.2, March– April, 2016)

DETERMINATION OF ELEMENTAL COMPOSITION OF PRECIPITATES

FORMED DURING USE OF PETROLEUM PRODUCTS BY FLAME
ATOMIC ABSORPTION SPECTROSCOPY

G. M. Balak, A. N. Privalenko, A. V. Oreshenkov, L. V. Krasnaya,

V. D. Zueva, and I. A. Smirnova

The results of studies on the development of the flame atomic absorption method for determining the
elemental composition of precipitates formed during use of petroleum products are reported. The
feasibility of applying this method to determine the elemental composition of pollutants removed
from the fuel and oil feed systems of the equipment and determination of the nature and causes of
formation of these pollutants is demonstrated.
Keywords: petroleum products, precipitates, elemental composition, atomic absorption spectroscopy,
resonance absorption, characteristic concentration.

Identification of the chemical, including elemental, composition of sediments and deposits, which
form in the bulk of fuels and lubricants and on the surface of parts and nodes of fuel equipment and oil feed
systems in the application of lubricants, as well as on the working surfaces of the process equipment and
technical means of storage, transportation, transfer, and dispensing of petroleum products is an integral part
of the work for the investigation of cases of failure of the corresponding technological systems. The formation
of precipitates in the oil bulk is responsible for their sub-standard quality in terms of the “Mass fraction of
mechanical impurities, %” indicator, leads to deterioration of anti-wear properties of fuels and lubricants and
fuel pumpability. Formation of deposits on the surface of parts and nodes is accompanied by a deterioration

____________________________________________________________________________________________________
25th State Research Institute of Chemmotology of the Ministry of Defence of the Russian Federation,
Moscoq, Russia E-mail: gmfth@yandex.ru. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2,
pp. 51 – 56, March – April, 2016.

0009-3092/16/5202–0203 2016 Springer Science+Business Media New York 203

of performance characteristics, including the reduction of permeability of fuel and oil filters leading to
clogging [1].
Formation of deposits / precipitates in the oil bulk and on surfaces of the technical devices and
technological equipment in contact with these products may be due to several factors. Thus, taking place in
conditions of the production and use of petroleum products and lubricants, and in the implementation of
technological process steps of oxidation of hydrocarbons and hetero-compounds followed by polymerization
/ polycondensation of oxidation products may cause low-ash tarry deposits to form. Oxidation processes are
catalyzed by metal compounds, particularly copper-based ones, which can be introduced into the fuels and
lubricants in the form of soluble in hydrocarbon media products of the early stages of corrosion / wear of
metal structural materials of parts and assemblies. As these processes intensify, the solubility of the products
of these processes decreases gradually until substantially insoluble particles form, which lead to formation of
ash precipitates in the oil bulk and on the surfaces of equipment including on the surfaces of the filter elements.
Components of atmospheric and soil origin, potentially brought into the oil in the process of their
application in technical devices and implementation of pre-production operations, and components of oil
refining catalysts can also participate in the formation of precipitates / deposits. These impurities are present
in the bulk of fuel and lubricants in the form of a second phase of mechanical impurities, which on the surface
of assemblies and technological parts and equipment can (also in combination with oxidation products) forms
deposits [2]. Formation on these surfaces of deposits containing products of wear / corrosion of metals and
components of atmospheric and soil origin can take place regardless of the contact of the respective surfaces
with the fuels and lubricants. Disruption of the phase stability of colloidal solutions of additives in the oil
base bulk, as well as chemical stability of the additives themselves, can also lead to the formation of metal
precipitates. Vanadium compounds are majority-metal-containing compounds in oils that concentrate during
pre-processing of raw oil in the heavy fractions and partially – in the middle distillates, and thus in residual
and a middle distillate fuels. Vanadium compounds are the precursors to the formation on the surfaces of gas
turbine blades of deposits of the respective oxides, causing high-temperature vanadium corrosion of structural
alloys.
The fact that the formation of precipitates and deposits is due to phenomena and processes occurring
in the production and use of petroleum products, as well as in the implementation of support technological
operations, makes it necessary to identify the composition of precipitates / deposits to study the causes of
their formation and development of preventive measures. Carrying out such work requires the development
of an integrated method of studying the composition of the sediments and deposits, and in particular – a
method of determining their elemental composition.
The list of elements included in the composition of substances introduced into the bulk of oil products
from different sources determines the source of the precipitates and deposits. Accordingly, within the
composition of metal-containing precipitates / deposits the following elements are to be determined:
Fe, Cu, Cr, Ni, Mn, Pb, Sn, Al, and Zn are the elements used to indicate wear / corrosion of the metal
structural materials, and introduction of the products into the composition of the precipitates, deposits, and
oil products;
Ca, Mg, Na, K, Si, and Fe and Al are the elements that indicate impurity of the precipitates and
deposits, and of oil products due to compounds of atmospheric and soil origin;
Ba, Mo, Li, Ca, Mg, and Zn are the elements that indicate the presence of lubricant impurities in oil
products forming sediments and deposits;

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 Co, W, and Mo point to the introduction of refining process catalyst components into the contents of
petroleum products;
V points to the introduction of heteroatomic components of oil feedstock into the contents of petroleum
products.
Among the methods for determining metal content, one of the most informative, timely, sensitive,
and free from spectral interference is the method of atomic absorption spectrometry (AAS). The method is
based on the measurement of resonant absorption analytical lines in the atomic spectra of elements and the
corresponding radiation sources – hollow cathode lamps for each of the determined elements – by atomic
vapor that forms during the atomization of solutions of the analyzed samples [3, 4]. Given the ease of
performing the analytical procedure and the prevalence of the equipment, in order to study the elemental
composition of sediments and deposits we developed an atomic absorption method for the determination of
metal content with flame atomization of the analyzed solutions.
One of the steps in the development of the method includes the study of the conditions for obtaining
the proper analytical form of the investigated objects suitable for analysis by AAS. In particular, we investigated
the possibility of extracting metal compounds in acidic and basic solutions and the maximum solubility of the
analytes upon their appropriate processing. For this, the sediment isolated from samples of fuels for jet engines,
and deposits isolated from the surface of fuel and oil filters for automotive and aviation devices were dissolved
in mineral acids and then subjected to alkali fusion. Residual fuel, oil, and their oxidation products were pre-
extracted in organic solvents from the bulk of the substance of the analyzed sediments and deposits, dried,
and subjected to ashing. The choice of organic solvents is determined by the specific objectives in the study
of sample composition, and if it is only necessary to determine the elemental composition the choice can be
limited to two or three solvents with different dissolving power / polarity, such as carbon tetrachloride and
heptane.
After extraction the residue was dried at 105 ± 5 °C to a constant weight. Ashing was carried out in
accordance with GOST 1461–75 at a temperature of 700 ± 50 °C for 2 hours, and at 500 ± 50 °C for 3 hours
for the determination of vanadium content. The lower ashing temperature in the determination of vanadium
was selected due to melting temperatures of its oxides, the lowest of which is 660 °C for V 3O 7 [5], and due to
the possibility of loss of analyte in vapor form at temperatures close to the specified value.
The obtained ash residues in porcelain or quartz crucibles used for ashing were treated sequentially
with dilute and concentrated HCl and HNO 3 solutions, with a 3.6:1 vol. mixture of the two acids, and mixtures
of HNO 3 with H 2 SO 4 (in a 2:1 vol. ratio), and of HNO 3, HCl, and H 2SO 4 (in 5:2:2 vol. ratio) while heating.
Upon complete dissolution of the ash the resulting solution was evaporated to moist salts, the salt was dissolved
in 0.1 N HNO 3 solution (solution 1), the resulting solution was quantitatively transferred to a 25 mL volumetric
flask and topped off with solution 1 to the nominal volume. In case of incomplete dissolution of ash and a
lack of need for determination of silicon and aluminum in the insoluble residue, the resulting slurry was
evaporated to a minimum volume, treated, and filtered through a paper filter “white ribbon.” The filtrate was
collected in a 25 mL volumetric flask. The residue on the filter paper was washed 2–3 times with 2–3 mL
aliquots of solution 1. The wash water was combined with the filtrate, and then the contents of the volumetric
flask were topped off to the 25 mL mark. The filter paper with the residue was dried at 105 ± 5 °C to a
constant weight. From the weight difference between the weights of the filter paper with and without the
residue we determined the mass fraction of the ash not soluble in the acids used, and therefore the mass of the
ash soluble therein.

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 In case of incomplete dissolution of the ash and the need to determine the silicon and aluminum
content in the insoluble residue, the obtained slurry was evaporated to a minimum volume and quantitatively
transferred into a platinum crucible using solution 1. After evaporating the entire volume of the slurry to
dryness the mass of the residue was determined form the difference of the mass of the clean crucible and the
crucible containing the residue, and then the residue was treated with concentrated HF or with a mixture
of HF with H 2SO 4 (in a 2:1 vol. ratio) while heating. In the presence of insoluble residue after acid treatment
of ash the mass fraction of the ash soluble in the acids used was determined. In the case of need to determine
silicon and aluminum content in the precipitate / deposits sample, alkaline fusion of the residue was carried
out. For this purpose, the undissolved residue was washed with solution 1 and transferred into a steel crucible,
and then the slurry was evaporated to dryness. From the difference in masses of the empty steel crucible and
the crucible containing the residue, the mass of the ash subject to fusion was determined.
In developing the methodology for studying the composition of the substance by AAS the basic
requirement for relative analytical methods based on the use of calibration curves was taken into
account – the need to ensure maximum agreement between the composition of samples and calibration solutions.
Failure to fulfill this requirement results in a difference in the mechanisms of atomization processes of the
respective solutions, which reduces the reliability of the analysis results [3]. Thus, the step of creating an
adequate calibration system was included in the circuit design of the method for determining the elemental
composition of sediments and deposits. Solutions of the reagents used for extraction of the analytes from ash
deposits and sediments were used as solvents for the preparation of the working solutions from the concentrated

Table 1
Working current of the Slit width (inlet / outlet),
Elements Wavelength, nm
hollow cathode lamp, mA nm
Fe 248.33 30 1.8 / 1.35
Cu 324.75 15 2.7 / 0.8
Cr 357.87 25 2.7 / 0.8
Ni 232.00 25 1.8 / 1.35
Mn 279.48 25 1.8 / 0.6
Pb 283.31 10 2.7 / 0.8
Sn 286.33 20 2.7 / 1.05
Al 309.27 25 2.7 / 0.8
Zn 213.90 15 2.7 / 1.8
Ca 422.67 15 2.7 / 0.6
Mg 285.21 15 2.7 / 1.05
Na 589.00 10 1.8 / 0.6
K 766.49 15 2.7 / 0.45
Si 251.61 40 1.8 / 1.35
Ba 553.55 25 1.8 / 0.6
Mo 313.26 30 2.7 / 0.8
Li 670.78 30 2.7 / 0.45
Co 240.73 30 1.8 / 1.35
V 318.40 40 2.7 / 0.8
W 255.14 40 1.08 / 0.6

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ones, and as reference solvents in atomic absorption analysis. These solutions were also used to prepare
analyte solutions.
Photometry of the resulting solutions was carried out using a double-beam atomic absorption
spectrometer from PerkinElmer, model AAnalyst 200 with a spectral range of 190-900 nm, a resolution of not
less than 0.3 nm, and photometry error of not more than 0.5%, equipped with a flame atomizer. Instrumental
parameters in atomic absorption determination of the concentration of metals in aqueous solutions of deposit
and sediment ash, optimized for maximizing optical density in photometric measurements of calibration
solutions, are shown in Table 1.
Identification of all the elements except Al, Si, Ba, Mo, V, and W was performed in an acetylene / air
flame, and determination of the mentioned elements – in an acetylene / nitrous oxide flame. To determine the
optimal order of measuring analytical signals we investigated the dependence of the optical density on the
concentration of the calibration solutions to yield calibration curves for each element subject to analysis.
In a preliminary study of the concentration dependence of the optical density of the calibration solutions
we found a deviation from linearity of the calibration curves for Al, Ba, and V during the atomization of the
solutions in the high temperature acetylene / nitrous oxide flame; a reduction of analytical signals relative to
the expected was observed for the solutions with a concentration above 2 mg/L. This is in agreement with the
described [3, 4] phenomenon of ionization of easily-ionized elements in high-temperature flames, which occurs
according to the pattern M 0  Mn+ + ne – and is accompanied by a decrease in the concentration of free
atoms, the absorption of which is to be measured, in the atomization zone.
Suppression of ionization interference, regarded as a shift of chemical equilibrium towards the starting
materials, may be achieved by introducing excess of an easily-ionized element different from those under
determination into the working calibration solutions, the solutions of analytes, and into the reference
solutions [6-8]. Aqueous potassium chloride was selected as the ionization buffer given its high solubility in
acidic / alkaline aqueous media and availability. Solution concentrations were optimized according to the
results of the study of the dependence of optical density of Al, Ba, and V solutions on potassium concentration
when co-present. The typical shape of such a plot is shown in Fig. 1 on the example of a 10 mg/L vanadium
solution.
Optical density

Potassium concentration, mg/L

Fig. 1. Dependence of the optical density of a vanadium solution on the concentration
of potassium therein.

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 The lowest concentration of potassium at which stabilization of the analytical signal of the determined
element is achieved – 1000 mg/L in terms of potassium – was chosen as optimal.
In carrying out the above preliminary operations the actual values of the characteristic concentrations
of the elements (Table 2) were achieved – concentrations of the element Cx in solution, mg/L, at which
photometric absorption reaches 1% (99% transmittance, optical density of 0.0044 units). A comparison of the
obtained values of these variables with the reference values is proposed for evaluation of accuracy in performing
the analytical procedure for determining the elemental composition of the analyzed objects.
The results of these experiments allowed us to develop the concept of the method of atomic absorption
determination of the elemental composition of sediments and deposits.
Solution-extracts of the obtained acidic / alkaline solutions of ash residue of the investigated
residue / deposit sample are sprayed into the flame, and optical density is recorded. Before and after spraying
the solution into the flame the reference solution is sprayed therein and optical density values are recorded.
The corrected optical density values (D corr ) are calculated by the formula

b  b 
Dcorr  Dexp   1 2 
 2 

w h e r e D exp i s t h e e x p e r i m e n t a l l y d e t e r m i n e d o p t i c a l d e n s i t y v a l u e o f t h e c a l i b r a t i o n s t a n d a r d
solution; b 1 and b 2 are the optical density values recorded when the reference solution is sprayed before and
after the calibration solution.

Table 2
Elements Characteristic concentration, mg/L Minimum detectable concentration, wt. %
Fe 0.05 0.0002
Cu 0.02 0.0001
Cr 0.55 0.003
Ni 0.04 0.0002
Mn 0.02 0.0001
Pb 0.11 0.0005
Sn 1.3 0.005
Al 0.54 0.003
Zn 0.005 0.00002
Ca 0.15 0.0006
Mg 0.002 0.00001
Na 0.004 0.00002
K 0.004 0.00002
Si 1.7 0.007
Ba 1.3 0.005
Mo 0.73 0.005
Li 0.04 0.0003
Co 0.05 0.0002
V 1.9 0.01
W 7.4 0.05

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 Linearity of the dependence of optical density on concentration of elements in solutions is checked,
and calibration curves are constructed for the corrected optical density values as a function of concentration
of each element in the calibration solutions. If the corrected optical density values obtained in the determination
of each element lie outside the range of optical density values for the working calibration solutions for the
corresponding element, the dilution factor for samples is selected so that the optical density values of the
diluted samples are in the range of optical density values of the working calibration solutions.
Concentrations of elements in the sample solution are determined from the calibration curves. Content of
elements Cel. i , wt. %, in the ash, in the fraction soluble in the acids used, and in the fraction transferred into
solution after alkaline fusion, is calculated by the formula

25  Cel .,sol  n
Cel .i , sol  100
mash  106

where C el. i, sol is the concentration of the element in the analyzed solution, mg/L; 25 is the volume of the
analyzed solutions, mL; n is the dilution factor for the analyzed solution; m ash is the mass of ash or its fraction
soluble in the acids / fraction transferred into the solution after alkaline fusion, g; 10 6 is the dilution
factor, g·L/mg·mL.
Conversion of the obtained results to reflect the content of the elements in the original
sediment / deposit sample is done by multiplying them by the coefficient m ash / m sed, where m sed. is the mass of
the original sediment / deposit samples.
Preliminary assessment of the reliability of the results was carried out in accordance with
the GOST requirements [9]. Elemental composition was determined of artificial mixtures prepared from
preparations of iron oxide (III), copper, nickel, manganese, lead, tin, aluminum, zinc, silicon, molybdenum,
cobalt, vanadium and tungsten, potassium dichromate, and calcium carbonate, magnesium, sodium, potassium,
lithium, and barium. These data confirm the adequacy of the experimentally determined concentrations of
these elements in the mixtures.
An example of applying the method to determine the elemental composition of deposits from an
intake filter in an oil system in automotive technology (MT-16p oil) with lower relative standard permeability
is described below. The deposits themselves had the visual appearance of an oily mass of black color with
inclusions of yellow particles with a metallic sheen. After processing the deposits with heptane and methylene
chloride and ashing, actual ash content of 64.09% was determined; the remaining 35.91% apparently
corresponds to anions, resin, and sooty deposits. In the course of treating of the ash with
dilute HCl and HNO 3 solutions almost complete dissolution was achieved, which is typical for ashes of deposits

Table 3

Element Concentration, wt. % Element Concentration, wt. %

Fe 0.84 Al 0.96
Cr 0.10 Ca 0.67
Ni 0.04 Mg 3.09
Mn 0.02 Na 2.47
Cu 38.7 K 0.18
Zn 2.46 Al 0.96

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mostly containing wear / corrosion products of metal structural materials easily soluble in mineral acids with
low concentrations of impurities of atmospheric and soil origin, usually poorly soluble in these acids. The
concentrations of elements (wt. %) in the composition of deposits calculated from the AAS data for these
solutions are given in Table 3.
These results indicate a predominance of copper compounds in the composition of the deposits. The
concentrations of zinc and lead are very high, especially compared with the concentrations of other elements
in the group of elements that indicate processes / corrosion of metal structural materials. The values and
concentration ratio of copper, zinc, and lead in the composition of deposits, as well as the results of visual
inspection of the sediment material, washed from residue of oil and its decomposition products, suggest the
presence in the composition of deposits of wear products of friction components made of copper- and zinc-
containing brass alloys with different dopants, including lead. A minor concentration in the composition of
deposits of calcium together with data on the elemental and phase composition of oil samples virtually eliminate
the possibility of introduction of a calcium-containing component from the bouquet of additives in oil. A
similar statement can be extended to the zinc-containing component of additives. Increased magnesium content
in the deposits may be due to the presence of this element in the structural alloys of friction nodes, and by
introduction into the oil filter of components of atmospheric and soil origin also containing aluminum, iron,
calcium, sodium, and potassium compounds.
Thus, the developed method allows for the determination of the elemental composition of sediments
in the oil bulk and deposits on the surface of parts and components of technical objects. The method can be
used to identify the origin of sediments and deposits, and to determine the causes of equipment failure, predict
the preconditions of such failures, and to develop measures to prevent them.

REFERENCES
1. V. M. Kapustin, Petroleum and Alternative Fuels with Additives [in Russian], Koloss, Moscow (2008)
232 p.
2. G. F. Bolshakov, Physico-Chemical Basis of the Formation of Precipitation in Jet Fuels [in Russian],
Khimiya, Leningrad, (1972) 231 p.
3. A. A. Pupyshev, Atomic Absorption Spectral Analysis [in Russian], Tekhnosfera, Moscow (2009)
784 p.
4. A. S. Alemasova, A. N. Rokun, and I. A. Shevchuk, Analytical Atomic Absorption Spectroscopy.
Tutorial [in Russian], Donetsk (2003) 327 p.
5. Chemical Encyclopedia: in 5 vol. [in Russian], Vol. 1, Sov. Encyc., Moscow (1988) 623 p.
6. A. N. Privalenko, G. M. Balak, E. K. Bagramova, et al., Mezhdunarodnyi Nauchny Zhurnal,
No. 5, 95-103 (2013).
7. A. N. Privalenko, G. M. Balak, E. K. Bagramova, et al., Mezhdunarodnyi Tekhniko-Ekonomicheski
Zhurnal, No. 5, 97-108 (2013).
8. A. V. Oreshenkov, A. N. Privalenko, G. M. Balak, et al., Tekhnologii Nefti i Gaza, No. 5, 38-43
(2014).
9. GOST R ISO 5725-6-2002 “Accuracy (accuracy and precision) of measurement methods and results.
Part 6: Use of accuracy values in practice” [in Russian].

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