Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: https://www.tandfonline.com/loi/lpet20

Determination of the content of metals in used

lubricating oils using AAS

Artur Wolak, Grzegorz Zając & Wojciech Gołębiowski

To cite this article: Artur Wolak, Grzegorz Zając & Wojciech Gołębiowski (2019): Determination of
the content of metals in used lubricating oils using AAS, Petroleum Science and Technology, DOI:
10.1080/10916466.2018.1511584

To link to this article: https://doi.org/10.1080/10916466.2018.1511584

Published online: 28 Jan 2019.

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PETROLEUM SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/10916466.2018.1511584

Determination of the content of metals in used lubricating oils

using AAS
Artur Wolaka , Grzegorz Zaja˛cb , and Wojciech GołeRbiowskib
a
Department of Industrial Commodity Science, Faculty of Commodity Science and Product Management,
Cracow University of Economics, Krak
ow, Poland; bDepartment of Power Engineering and Transportation,
Faculty of Production Engineering, University of Life Sciences in Lublin, Lublin, Poland

ABSTRACT KEYWORDS
This article focuses on the results of investigations of selected heavy atomic absorption
metals (Mg, Fe, Ni, Cu, Zn, Pb, Ca, Cr and Al) in engine oils of various man- spectrometry (AAS); heavy
ufacturers. The measurements were made using atomic absorption spec- metals; metallic elements;
oil condition monitoring;
trometry (AAS) THERMO-iCE 3000 Series. The aim of the study was to lubrication
determine the concentrations and the direction of changes of those heavy
metals and to determine the statistical relationship between the car mile-
age and the concentration levels of individual trace elements. Statistical
analysis of the test results showed significant changes in iron and copper
concentrations in engine oil, depending on the engine’s operating history.

1. Introduction
Proper lubrication is essential to maintain optimum engine performance. Lubricating oil fulfills
its role by protecting the engine against heat, corrosion, oxidation and various contaminants.
Moreover, it provides a barrier between moving parts of the engine, which reduces the friction
and wear of individual components, thereby limiting the concentration of wear elements in
engine oil (Al-Ghouti, Al-Degs, and Amer 2010).
Thorough analysis of the contents of heavy metals (Ag, Al, Cr, Cu, Fe, Ni, Zn, Mg, Mo, Pb, Ti
and Si) in oil can provide valuable information regarding the degree of wear of moving metal
parts of the engine. The concentration of heavy metals in fresh, used, recovered and waste oil has
been investigated by Abdul Zali M. et al. and Kim Y. et al. (Auc
elio et al. 2007; Kim et al. 2013;
Abdul et al. 2015). In their study, the content of metals was determined with the use of the ICP-
OES analysis (Inductively Coupled Plasma – Optical Emission Spectrometer). Carballo et al., on
the other hand, used the electro-thermal atomic absorption spectrometry (ETAAS) to determine
the concentration of metals in lubricating oils (Carballo et al. 2013). J. ZieR ba-Paulus focused his
scientific attention on Infrared Spectroscopy (ZieR ba-Palus, Ko
scielniak, and Ła˛cki 2001) whereas
Reardon et al. used gas chromatography in their research (Reardon et al. 2007). Aucellio et al., in
addition to the ICP-OES analysis, also propose the use of atomic absorption spectrometry and
inductively coupled plasma-mass spectrometry (Auc
elio et al. 2007). Among other available ana-
lytical techniques, X-ray fluorescence spectrometry is often applied in the studies of metal content
in oils (XRF, X-Ray Fluorescence). It has been widely used by researchers from all over the world
(Zaja˛c et al. 2015; Wieczorek 2012; Zararsiz, Kirmaz, and Arikan 1996; Pouzar 2001). In turn,

CONTACT Artur Wolak artur.wolak@uek.krakow.pl Department of Industrial Commodity Science, Faculty of Commodity
Science and Product Management, Cracow University of Economics, Sienkiewicza 4, Krak
ow 30-033, Poland.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
ß 2019 Taylor & Francis Group, LLC
2 A. WOLAK ET AL.

Owrang et al. conducted their study with the use of nuclear magnetic resonance spectrometry
(Owrang et al. 2004).
Metals found in used oils come from different sources. They are mainly wear products of the
metal surfaces moving in contact with each other, but they may also be a result of corrosion or
may come from additives (Zaja˛c et al. 2015). Metals such as P, Ba, Ca, Mg, Zn, Sb, Ni, B, Cd,
Hg, Mo, Se, Sn and Cr are deliberately added to lubricating oils (additives containing metal
atoms, e.g. zinc – dialkyldithiophophate). Metallic elements that may be found in oil as a result
of the wear processes are mainly Al, Fe, Pb, Mn, Ni, whereas the concentration of K and Na is
mostly observed as an effect of the contamination of oil. The content of metals in European used
oils is roughly on the level of 0.7% (m/m) (Zaja˛c et al. 2015).
The aim of the study was to determine the concentrations and the direction of changes of
selected heavy metals (Mg, Fe, Ni, Cu, Zn, Pb, Ca, Cr and Al) found in engine oils produced by
different manufacturers. All of the oils were used in the same type of vehicles operated under
similar conditions. Another aim was to determine the statistical relationship between the car
mileage and the concentration levels of selected metallic elements.

2. Materials and methods

All of the tests were conducted on the samples of lubricating oils that fully met the specifications
of Mitsubishi – the producer of the engines used in the study. The research material comprised
of several oil samples coded as CE, MS, ME, PS and PE. The concentration of metallic elements
in lubricating oils operated in vehicles of the same type, under the same conditions and for the
same period of time was closely investigated. The cars used in the tests were uniform in terms of
brand, type and operating conditions and belonged to the Malopolska Driver Training and
Examination Center fleet. All of the cars were generally used for conducting driving license tests.
In total, the investigation included oil samples collected from 10 test vehicles fitted with petrol
engines (engine displacement of 1,332 dm3) and operating on fuel coming from the same produ-
cer. At the beginning of the investigation, a fresh oil sample was tested. Then, the samples were
collected and examined on a quarterly basis for a period of one year. It should be noted that the
tests as well as the sampling procedure were planned (and agreed with the fleet owners) in such a
way as to avoid topping up the oil between the test periods. Even a small portion of fresh oil
improves lubricant properties by bringing them closer to the starting value, and as a result the
obtained data on the physicochemical condition of the used oil immediately after such a refill
would be strongly distorted. Therefore, the assessment of changes in the amounts of metallic ele-
ments during the operating period was carried out through ongoing monitoring. The volume of
the monitored sample did not exceed 0.2 dm3 [AAS needs about 0.02 dm3, but 0.2 dm3 was
taken because all of the crucial parameters (kinematic viscosity, TAN, TBN etc.) were measured
as well – the results have been described in other publications, e.g. (Wolak and Zaja˛c 2017;
Wolak 2018) as the frequent sampling of engine oil and an increased sample volume might make
it necessary to refill the oil and thus distort the overall test results. The data presented in this
study provide insights into the changes occurring in used oil as a result of its degradation. The
actual operating conditions in urban traffic of medium intensity were taken into account when
analyzing the obtained data. The study was carried out in the period of 12 months, which was
consistent with the mileage (for each car) at the level of 12 198 km (d ¼ 2254 km). Such a time-
frame was considered essential to achieve an unambiguous, multi-dimensional measurable oil
degradation trend, all the while taking into account the manufacturer’s recommendations for oil
change intervals. The other reason why the period of 12 months was deemed most appropriate
for the purposes of this study resulted from the observations performed by car companies and
their research centers as to the car mileage at which an accelerated engine oil degradation gener-
ally appears (Wolak and Zaja˛c 2017; Besser et al. 2012; Onyekwere Nwosu et al. 2008).
 PETROLEUM SCIENCE AND TECHNOLOGY 3

Table 1. The number of kilometers traveled by each car

Mileage at Mileage after 1st Mileage after 2nd Mileage after 3rd Mileage after 4th
The sample code start (km) quarter (km) quarter (km) quarter (km) quarter (km)
CE 17977 6,033 2,973 5,640 8,796 9,975
CE 18716 9,477 3,080 6,360 10,009 12,169
ME 17764 15,484 3,752 8,593 11,620 14,501
ME 17973 8,015 2,811 5,513 7,579 9,029
MS 18011 13,486 2,205 5,199 7,265 9,005
MS 18128 14,571 1,808 5,218 8,773 10,803
PE 17939 12,370 4,180 8,806 11,990 13,066
PE 18689 13,290 3,944 8,749 13,974 15,531
PS 18149 13,556 4,269 8,317 12,412 14,384
PS 18799 14,154 4,083 8,035 11,792 13,523

The engine oils (grade SAE 5W-30) selected to the research: 4A90 (model code), DOHC
MIVEC (Type), MPI (Fuel supply). The manufacturer’s API and ACEA classification require-
ments are as follows:

CE: SH and A3/B3-10, C3-10;

ME: SM/SN and C2/C3-10;
MS: SM/SL and C3-10;
PE: API no classification and C2-10;
PS: SM and A3/B3-10.

Table 1 shows the details on the number of kilometers traveled after successive quarters of the
year by each car selected for testing. The sample code includes the oil code and the car code. All
of the cars in the study were generally used for examination purposes. When analyzing the
results, account should be taken of “harsh” operating conditions of the vehicles, i.e. frequent
changes of the speed, rapid acceleration and braking, low speed operation (and extended idling),
driving in street traffic, short distance driving causing under-heating of the engine, and frequent
startups at low engine temperatures.
With the use of atomic absorption spectrometry, the content of the following elements was
determined in selected engine oils (coded as CE, ME, MS, PE and PS): Mg, Fe, Ni, Cu, Zn, Pb,
Ca, Cr and Al. The measurements were made using THERMO-iCE 3000 Series. The limits of
determination for each element are as follows: Al – 0.29 mgkg1, Cr – 0.05 mgkg1, Ca –
0.0092 mgkg1, Pb – 0.073 mgkg1, Zn – 0.01 mgkg1, Cu – 00.033 mgkg1, Ni – 0.05 mgkg1,
Fe – 0.052 mgkg1, Mg – 0.0029 mgkg1.
The atomic absorption spectrometry method (AAS) was applied to determine the selected
chemical elements in the used engine oil. The source of the radiation is a halogen cathode lamp
(HCL). One lamp allows only one element to be examined. Flame atomization requires a liquid
analytical sample to be aerosolized. The aerosol is obtained in a pneumatic nebulizer. In the
nebulizer chamber, the analyzed solution is converted into a fine mist (aerosol), then the aerosol
is mixed with the flammable gas, and introduced uniformly into the burner using spray surfaces.
The suction gas is always an oxidizing gas. The flames of the burner must provide enough energy
to convert the solution into free atoms. The flame itself should only absorb a small fraction of
the radiation emitted by the source. An acetylene-air flame was used to determine the following
elements: Mg, Fe, Ni, Cu, Zn and Pb. It has a high temperature and only below 230 nm an
increasing self-absorption of the flame may be observed. For other elements (Ca, Cr and Al) that
form persistent oxides in the flame, it was necessary to use a reducing flame with nitrogen oxide
(I) oxide gas.
The graphs of concentration changes of the abovementioned elements in the oils tested were
prepared with the use of Statistica software version 12. The Pearson/Spearman correlation
4 A. WOLAK ET AL.

coefficient was used to examine the relationship between vehicle mileage and heavy metal content
in used engine oils. The results of the analyses are illustrated by scatter plots with regression lines.
Normal distribution was verified by the Shapiro-Wilk test. It should be noted that the direction
of changes in concentrations of determined elements in engine oils is to be interpreted against
the changes in the basic parameters of these oils in a given period of operation (Wolak and
Janocha 2015; Wolak and Hornik 2015; Wolak and Zaja˛c 2017; Wolak 2018; Wolak, Zaja˛c, and
Kumb
ar 2018). On such basis, the courses of lines may be interpreted more accurately and an
attempt may be made to correlate changes in the concentration of metallic elements in oils with
diagnostic inferences about the operating conditions and the wear of some of the components of
the monitored engines.

3. Results and discussion

The changes in concentrations of the following elements: Cu, Fe, Ca, Mg and Zn in the engine
oils tested are shown in Figure 1. The data presented of graphs come from an averaged value
after triple repetitions of the measurement. The obtained data show that the content of different
metals varied depending on the type of oil and mileage.
Copper found in used oils is mainly the effect of the wear of bearing, valve rings and guides,
although (in much smaller quantities) it may also be introduced into the oil in the form of addi-
tives (Onyekwere Nwosu et al. 2008). When looking at the graph (Figure 1), it may be noticed
that for most of the oil samples tested the trends are regular with no sudden peaks – only in the
case of the oil sample PE 018689, a significant decline in concentration after the third quarter
and a sharp increase in the fourth are clearly noticeable. The copper content of the samples tested
ranged from 1.77 up to 24.93 mgkg1 (on average: 12.22 mgkg1) with the standard deviation at
5.59 mgkg1. The concentration of Cu in fresh oils was on comparable levels in all five oil
groups (average: 2.25 mgkg1). Changes in Cu content for all analyzed oil groups showed
approximately linear character, which may additionally confirm wear as a principal source of cop-
per presence. The greatest change in copper concentration was observed for PE 018689 (more
than 13-fold increase from 1.91 up to 24.93 mgkg1).
Iron is the most common engine wear product present in engine oil. Its concentration in used
oil depends mainly on the lubrication conditions inside the engine. Upon analyzing the graph
presenting the concentration changes of Iron (Figure 1), a clear – fairly regular – trend is visible
of approximately linear character. The highest Fe content was measured for the ME 017764 oil
sample (73.87 mgkg1). The average content of this element for all tested samples after
12 months of oil use stood at 60.23 mgkg1. Among the used oils, the lowest increase in Fe con-
centration at the end of the test was found in the following oils: CE 017977 (31.22 mgkg1) and
PS 018799 (47.23 mgkg1).
The presence of Fe in base oils is not particularly desirable and it is usually removed from
such oil. It is, therefore, worth noting that the concentrations of this element varied across fresh
oil samples. For ME, MS and PE oils, the content levels were around 3.75 mgkg1, whereas for
the other two groups they were almost three times higher. Monitoring concentration changes of
Fe and Cu in lubricating oils may provide useful information about the wear processes occurring
in the engine. Consistent changes of Fe and Cu levels in the studied oils indicate that the wear
processes in all tested vehicles were similar. Moreover, the lack of clear differences between indi-
vidual oils tested indicates good wear protection performance.
When analyzing the Ca concentration graphs (Figure 1), an irregular form of the lines charac-
terized by sudden increases and decreases in concentration levels clearly stands out. This is par-
ticularly noticeable for MS, ME and PE oils, whereas CE and PS oils are more regular. The
highest content of Ca was found in MS oils (above 2000 mgkg1). Calcium may be present in
engine oils as an impurity or an additive (Besser et al. 2012). When comparing Ca levels in used
 PETROLEUM SCIENCE AND TECHNOLOGY 5

Figure 1. Ca, Zn, Fe, Cu, Mg concentration changes.

6 A. WOLAK ET AL.

Figure 2. Scatter plots with regression lines, correlation coefficients, significance level (p), regression equation and 95% confi-
dence interval (normal distribution).

engine oils with those measured in fresh oil, it should be noted that in most cases the source of
calcium lies in oil additives, as evidenced by the decrease in its content in the course of oil’s use-
ful life. Only the MS 018128 sample measured after the second quarter of use showed a signifi-
cant increase in Ca concentration – 2679 mgkg1 which might indicate that in this particular
case the source were oil impurities. The average calcium content in CE, ME, PE and PS oils was
1507 mgkg1 with standard deviation on the level of 144 mgkg1. The greatest concentration of
calcium was found in the CE3 sample (2056 mgkg1). In the group of PE and PS oils, a slight
upward trend was noticeable.
 PETROLEUM SCIENCE AND TECHNOLOGY 7

Magnesium is present in the additive as a detergent, but may also be used as a wear product
(used in aluminum alloys). Hence, a very large discrepancy between the measurement results in
different samples (even for the subsequent samples of the same oil). For CE, ME, and MS oils,
the concentration lines show a downward trend, which indicates a gradual decrease of additives
in the oil (Figure 1). On the other hand, for PE and PS oils the concentration lines first show a
downward and then an upward trend (except for the PE 017939 oil). All lines exhibit more or
less distinct peaks of concentration changes. It is noteworthy that for CE, ME and MS oil sam-
ples, all of the measurements conducted on used oils show values below the levels determined for
fresh samples. In the case of the other two oil groups, practically all of the results are above the
levels found in fresh oil. Moreover, for CE, ME and MS oils the levels of Mg in fresh oil were
higher than in the other two oils.
The studies carried out by ZieR ba-Palus et al. showed that engine oils generally differ from each
other in terms of magnesium content, although these differences are relatively small (ZieR ba-Palus
and Ko
scielniak 2000).
Zinc is a basic element of high-temperature antioxidant additives. It is also found in the com-
position of anti-wear additives or corrosion inhibitors added to engine oils (Onyekwere Nwosu
et al. 2008). The results of conducted tests revealed high variability of Zn concentration with no
clear overall trend except for the PS oil group. Here, an upward tendency was observed for both
magnesium and zinc. The lowest concentration of Zn was also noted for this group (x ¼
736 mgkg1). For three sample measurements from the ME group and two from the MS group,
the limit value of 1100 mgkg1 was exceeded. For these samples, the increase in zinc content
compared to fresh oil may have resulted from the presence of wear products. When analyzing the
concentration changes of the metallic elements tested, the upward trends are markedly visible for
typical wear elements (Fe and Cu). The other elements showed considerable variability and irreg-
ularities in the trend. Furthermore, in some of the oils tested, rapid changes in the concentration
of wear metals have been observed. They may have their cause in the conditions of vehicle use.
Varying operating conditions and engine load could have affected such rapid changes in concen-
tration levels. It is also worth noting that although the oils had similar quality grades and were
approved by the engine manufacturer, the varying levels of metallic element contents (Zn, Mg,
Ca) found in fresh oils indicated their non-uniform quality. This may affect engine performance
and the speed of wear.
However, full interpretation of this problem requires additional analyses of the physicochemi-
cal parameters of the oil and goes beyond the scope of this paper.
Upon analyzing wear metal concentration changes for the CE 018716 oil, an anomaly was
detected for the sample taken after the 4th quarter (4K). That sample was characterized by a notice-
able change in the trend at the last measurement point. A possible interpretation here is that the
oil was unfortunately “topped” with a portion of fresh oil. Although in the methodology of the
research it was assumed that no fresh oil would be added to lubricating systems before the end of
the sampling procedures (i.e. during a period of 12 months), it cannot possibly be ruled out, with
respect to this particular vehicle, that the oil was not topped during a car service without it being
brought to the knowledge of the researchers. The nature of the changes in the analyzed elements
strongly points to this having been the case. This confirms the need for further studies whose aim
would be to determine the effect of oil "topping" during the operation of the vehicle on the metal
concentration changes, as well as possible changes in other physicochemical parameters.
For the remaining four analyzed elements – Al, Cr, Ni, Pb – it was impossible to determine
the trends of concentration changes, because for most samples the values obtained were beyond
the detection range of the device. Aluminum and nickel were detected only in individual cases.
Aluminum was found in only one sample (ME 4K017764 – 1.77 mgkg1). It was the same sam-
ple for which the maximum concentration of Fe was detected (73.87 mgkg1). Nickel was meas-
ured in the PE4K 017939 sample (0.8 mgkg1). Chromium was determined in eight samples
8 A. WOLAK ET AL.

(CE4K 018716 – 1.72 mgkg1; ME4K 017764 – 2.21 mgkg1; MS4K 018011 – 2.96 mgkg1;
PE4K 017939 – 2.24 mgkg1; CE4K 017977 – 1.47 mgkg1; ME4K 017973 – 1.98 mgkg1;
MS4K 018128 – 3.41 mgkg1; PE4K 018689 – 2.99 mgkg1), whereas lead was detected in only
five (MS4K 018011 – 2.67 mgkg1; CE4K 017977 – 1.21 mgkg1; ME4K 017973 – 0.27 mgkg1;
MS4K 018128 – 2.63 mgkg1; PE4K 018689 – 4.57 mgkg1). All of these oil samples were col-
lected in the fourth measurement period. None of the abovementioned elements were detected in
the PS oils.
Lead is generally removed from the base oils, hence its presence in used oils is mainly related
to the wear of the bearings, but for petrol-fueled engines, it may also be connected with the fuel
itself (Onyekwere Nwosu et al. 2008; Zaja˛c et al. 2015). The average lead content for the five sam-
ples tested was on the level of 2.27 mgkg1 with the highest value obtained for the PE4K 018689
sample (4.57 mgkg1). The same sample was also characterized by relatively high contents of Cu
(24.9 mgkg1) and Fe (68.38 mgkg1).
The presence of chromium in lubricating oil is usually related to engine wear (chrome parts
such as rings and sleeves) (Zaja˛c et al. 2015). Detection of this element in the samples collected
in the last quarter of the research indicates that there was a gradual increase in its concentration
in the oil. The chromium content in the samples tested ranged from 1.47 in the case of the CE4K
017977 sample, up to 3.41 mgkg1 for the MS4K 018128 sample. The average concentration was
on the level of 2.37 mgkg1. This is almost twice as much as the average concentration levels
measured by Zaja˛c et al. (1.43 mgkg1) (Zaja˛c et al. 2015). In order to further verify whether
there are statistical relationships between car mileage and Mg and Cu levels, the Pearson correl-
ation coefficient was applied. The results of the analysis are presented below in the form of scat-
ter plots with regression lines (Figure 2). The results for Zn, Ca and Fe have no normal
distribution, so the correlation was calculated using the Spearman’s rank correlation coefficient.
When analyzing the obtained significance levels (0.7796; 0.5644; 0.7494 and 0.000), it was
found that for Cu and Fe concentrations the p value was below the limit value (0.05). Therefore,
it may be concluded that there are statistically significant relationships between the car mileage
and the concentration levels of Cu and Fe. The obtained correlation coefficients (0.7828 for Cu
and 0.8453 for Fe) confirm a strong positive correlation, thus suggesting that the actual growth in
the concentration levels of the investigated metals is related to the process of wear progressing
during engine operation.
The observed metal concentration changes and statistical analyses show that for vehicles oper-
ated under similar conditions the concentrations of metals in engine oils exhibit linear trends
only in the case of typical wear metals (i.e. Cu and Fe). The other elements analyzed showed a
high degree of irregular variability (sudden growths intertwined with falls). Although all of the
oils tested met the specifications set forth by the manufacturer, the range of concentration
changes indicates that oils strongly differ in terms of their ability to deal with “harsh” operating
conditions. This demonstrates the necessity of proper oil selection which would be in line with
the character of operating conditions.

4. Conclusions
Lubricating oil is an integral part of the engine system, contributing significantly to its efficient
and reliable operation. Yet, it will only perform its role as long as its quality parameters are fully
maintained; hence, the need to monitor its condition changes by (for example) controlling the
content of metallic elements in oil. Thorough analysis of metal concentration changes in lubricat-
ing oil as well as in-depth examination of the character of those changes (favorable or unfavor-
able) make it possible to determine the actual condition of both the oil and the engine.
Based on the conducted research and the interpretation of the trends of changes in the con-
centration of metallic elements in engine oils, the following conclusions have been made:
 PETROLEUM SCIENCE AND TECHNOLOGY 9

1. Cu and Fe concentration changes occurring in the course of the research in all oil groups
showed approximately linear character. These findings are consistent with the results obtained
by ZieR ba-Palus (1998). As the number of kilometers traveled (car mileage) went up, the iron
and copper content in the oil samples tested increased likewise [y ¼ 5.67 þ 0.0038x (Fe) and
y ¼ 4.30 þ 0.001x (Cu)]. The greatest concentration of Fe was found in the ME 017764 oil sam-
ple (73.87 mgkg1). An average concentration of this element for all tested samples after 12
months was 60.23 mgkg1. The concentration of copper ranged from 1.77 up to
24.93 mgkg1, on average: 12.22 mgkg1 with standard deviation on the level of 5.59 mgkg1.
2. Significant differences in the concentrations of Ca and Fe were observed in fresh oil samples
of each oil group. The content of Fe in the fresh oils CE and PS stood at 10.81 and
13.90 mgkg1, respectively. An average Fe concentration level observed in the other three
groups was 3.76 mgkg1. The content of Ca in the fresh MS oil was as high as 2110 mgkg1,
whereas in all other groups it was on the level of 1473 mgkg1 (on average).
3. Of the following four analyzed elements: Al, Cr, Ni, Pb, the most commonly detected was
chromium. It was found in as many as eight samples (average concentration level:
2.37 mgkg1). Chromium as well as Al, Ni, and Pb were always found in used oil samples
from the fourth measurement period. It is also worth mentioning that lead was detected in
five sample (average concentration level: 2.27 mgkg1), whereas nickel and aluminum were
found in single samples only.
4. Statistical analysis of the test results showed significant changes in iron and copper concen-
trations in engine oil, depending on the engine’s operating history. In the case of all other
metallic elements tested, no statistically significant correlation was found between their con-
centrations in used engine oils and engine mileage.
5. The study confirms that it is not always easy to interpret and evaluate the data obtained
from concentration measurements of metallic elements in used engine oils. This is due to the
fact that the same elements can come from different sources – processes of consumption and
wear, additives or other external pollutants. This can be seen on the example of Ca and Mg
concentration changes. It may be helpful to interpret these results together with other physi-
cochemical parameters of the oil.

This paper only partly confirms the usefulness and practicability of the AAS technique in
determining changes (and observing their character) in the concentration of metallic elements in
engine oils as well as, indirectly, in assessing the technical condition of the combustion engine
and the character of its operation. The analysis of the study results suggests that further research
in this field is needed, the scope of which should be broadened by the application of X-ray fluor-
escence (XRF) and analytical ferrography methods. It would facilitate making fuller and more
accurate diagnostic inferences based on the analysis of changes in the properties of used engine
oils and in the concentrations of metallic elements and wear particles.

Funding
The publication was funded by appropriations of the Faculty of Commodity Science, Cracow University of
Economics and Faculty of Production Engineering University of Life Sciences in Lublin within the framework of
grants to maintain the research potential.

ORCID
Artur Wolak http://orcid.org/0000-0003-4145-8862
Grzegorz Zaja˛c http://orcid.org/0000-0002-9025-4551
Wojciech GołeR biowski http://orcid.org/0000-0002-4170-1351
10 A. WOLAK ET AL.

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