Archives of Environmental Protection PL ISSN 2083-4772

Vol. 47 no. 2 pp. 81–94 DOI 10.24425/aep.2021.137280

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Heavy metal content in used engine oils depending

on engine type and oil change interval
Joanna Szyszlak-Bargłowicz1, Grzegorz Zając1*, Artur Wolak2
1
 University of Life Sciences in Lublin
2
 Cracow University of Economics

* Corresponding author’s e-mail: [email protected]

Keywords: heavy metals, lubricating oil analysis, waste lubricant oil (WLO)

Abstract: The paper presents the results of the analysis of the content of selected heavy metals in used engine
oils collected in car service stations during oil change. The main purpose of the research was to determine the
difference in heavy metal content (Cr, Cu, Fe, Ni, Pb, Zn, Hg, Cd) depending on the engine type and oil change
interval. The analysis comprised 80 samples of used engine oils obtained from passenger cars. The content of heavy
metals was tested with use of the HDMaxine analyzer, operating on the basis of HDXRF (High-Definition X-Ray
Fluorescence). Upon analyzing the differences in the average content of the examined elements, depending on the
type of engine, it can be concluded that in oils coming from diesel engines the following elements showed a higher
concentration – Cr (three times), Fe (1/3 times ), Ni (two times), Pb (1/2 times), whereas in oils coming from
gasoline engines, only the average Cu content was higher (¾ times). Zinc had a comparable level of concentration.
The multi-factor analysis of variance showed that in diesel engines the levels of Fe, Cr, Pb and Ni are statistically
significantly different than in the reference group of gasoline engines. The study findings suggest that, depending
on the engine type, the content of selected heavy metal elements in used oils varies. Therefore, to ensure proper
handling of waste oils and reduce environmental risk, selective collection of used oils depending on the engine
type may definitely be considered.

Abbreviations:
AAS – Atomic Absorption Spectrometry
HDXRF – high definition X-Ray fluorescence
DE – diesel engines
GE – gasoline engines
PAO – polyalphaolefin
PAHs – polycyclic aromatic hydrocarbons
PCBs – polychlorinated biphenyls
ZDDP – zinc-dialkyl dithiophosphate
WLO – Waste Lubricating Oil
Cr, Cu, Fe, Ni, Pb, Zn, Hg, Cd – the analyzed elements
GI, GII, GIII, GIV, GV – five groups created according oil change intervals
GI – oil change interval <10k km
GII – oil change interval 10–12k km
GIII – oil change interval 12–14k km
GIV – oil change interval 14–16k km
GV – oil change interval >16k km

Introduction and they are generally used for gasoline- and diesel-powered
cars. Engine oils are composed of base oils and various
Lubricating oils primarily serve to reduce friction between refining additives, the content of which may reach up to 20%
moving parts of various machines and devices and to minimize (v/v). Base oils can be mineral (petroleum vacuum distillation
their wear, which consequently leads to the improvement of processing products) or synthetic (e.g., PAOs or synthetic
their overall efficiency, including energy and fuel savings. esters). During the use of an engine oil, several changes take
Among different lubricants, the most common are engine oils, place and various impurities occur, which gradually lead
82 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

to the decrease in oil quality and the loss of its predominant a universal utilization procedure for them (Nerı́n et al., 2000).
functions. As a result, the oil must be removed from the engine That is why, the proper disposal of used lubricating oils is
and replaced with a new one. Used oils may pose a serious a major challenge today, as inappropriate use of this hazardous
environmental problem, especially in terms of the logistics of waste can pose a direct threat to the environment and human
the waste disposal, mainly due to the fact that they are used in health. However, automotive lubricating oils are an excellent
small amounts by a large number of users located in different example of waste that can be recycled and turned into useful
places. The total amount of engine oils changed annually and valuable products. They can be processed and refined
in Europe is large and ranges from 1.7 to 3.5 million tons, and then used in the production of fuels or serve as a base for
according to various estimations. Such substantial quantities of lubricating oils (Pawlak et al., 2010; Pinheiro et al., 2020).
used engine oils have significant economic and environmental The recycling of used lubricating oils involves subjecting
consequences. Particularly because approximately 23% of the them to a series of processes that lead to the elimination of
reported amount of used oils (Kupareva et al., 2013) is in fact most impurities, including water, oxidation products, and
outside the waste collection system. It is either illegally burnt additives; thus, restoring the original properties of the base
or enters the natural environment directly (e.g., through car oil. To achieve this end, the most frequently used processes
leaks). The biggest concerns, however, have been raised over are vacuum distillation, solvent extraction, aluminum-acid
deliberate disposal of used engine oils into the eco-system by treatment and hydrotreatment (Hsu and Liu, 2011; Jafari and
the workers of service stations and local garages that deal with Hassanpour, 2015; Kamal and Khan, 2009; Osman et al., 2018;
engine repairs, during which used engine oils are generated, Salem et al., 2015). Yet, due to their level of contamination,
stored, and sometimes intentionally or accidentally dumped not all used lubricating oils can be re-refined (Nerı́n et al.,
into the soil or sewage system (Piecuch et al., 2015; Stout et 2000). It is estimated that only 60–65% of WLOs can be
al., 2018; Vazquez-Duhalt, 1989). The pollution with used recycled as they have to meet specific requirements regarding
engine oils creates environmental hazards due to its permanent the impurity level and viscosity index (Hsu and Liu, 2011;
nature and the tendency to spread into ground and surface Sanchez-Hernandez et al., 2020). By far the cheapest method
waters. These compounds are refractory to biodegradation, so of utilizing waste lubricating oils is burning them (Elnajjar et
their presence in waters is a serious problem (Bogacki and Al- al., 2019; Nukman et al., 2018). Because of high calorific value
Hazmi, 2017; Kryłów et al., 2018). of WLOs, they are readily used as on-site boiler fuel, which
The chemical composition of waste oils depends on many also eliminates the need for transporting these oils – a rather
factors, including the type of base oil, the additives used, costly undertaking for many individuals. However, due to
physical and chemical changes they were subject to during combustion processes, the metals accumulated in WLO pass
operation and the conditions in which the oil was operated into solid (Nerin et al., 1999) and gaseous (Pinheiro et al.,
(Magiera and Głuszek, 2009; Zając et al., 2015). They 2020) combustion products. According to data provided by the
usually contain polycyclic aromatic hydrocarbons (PAHs), US Department of Energy, the combustion of WLO releases
polychlorinated biphenyls (PCBs) and heavy metals (Delistraty more than 50% of its lead, cadmium, chromium, and zinc in the
and Stone, 2007; Hamawand et al., 2013). Heavy metals form of solid particles (US Department of Energy, 2006). In
found in engine oils cause many concerns, particularly due to other words, the combustion of WLO may result in the release
their adverse effects on the environment and human health, of 800 mg Zn and 30 mg Pb into the atmosphere, the amount
especially when their concentration is high. There are different which is 50–100 times higher than in the case of petroleum-
sources of metals in used oils. They can be native elements based heating oil (Boughton and Horvath, 2004; Pinheiro et al.,
of crude oil, residues from oil processing (most often residues 2020). Using WLOs for home heating purposes is especially
of catalytic processes), refining additives, as well as products dangerous if uncontrolled combustion processes take place in
of corrosion and wear of the metal surfaces which come into boilers that do not have built-in control systems and filtering
contact. The metals which are general constituents of crude devices.
oil are mainly nickel and vanadium. In turn, catalyst residues Pyrolysis is yet another method that can be applied for the
containing metals are introduced during various processes of management of used lubricating oils that cannot be refined.
catalytic hydrotreating of the oil base (Lynch, 2007); whereas, However, heavy metals are also found in the oil fractions
refining additives include, among others, detergents containing after the condensation of pyrolysis products from the waste
calcium or magnesium salt and zinc dialkyl dithiophosphate oil. Metals present in lubricating oils (e.g., Pb, Fe, Cu and Ni)
(ZDDP) (Stout et al., 2018). Waste engine oils also contain are transformed into volatile substances during the process of
metals which are products of wear of the metal surfaces that pyrolysis at a reaction temperature of 600°C and above (Nerı́n
contacting themselves, and which occur in the course of oil use et al., 2000).
(Fe, Cu, Al, Sn, Sb). The concentration of metals in used oils in Due to high costs associated with the disposal of waste
Europe reaches about 0.7% (w/w) (Magiera, 2006). lubricating oils, it is still a relatively common practice of
An appropriate waste management has become one irresponsible users to discard them illegally to sewers and soil;
of the most significant challenges facing the world today. especially, in the absence of clear regulations in this regard or
As lubricating oils are generally toxic and not readily non-compliance to the existing ones (Lam et al., 2016). The
biodegradable, extensive disposal of WLO into the introduction of WLO directly into the soil leads, for example,
environment may pose serious adverse effects to ecosystems, to the accumulation of the following chemical elements: K,
with a high risk of soil, water, and air contamination (Pinheiro Mg, Ca, Fe, Co, Ni, Cu, Zn, Al, Pb, Cd and their possible
et al., 2020). Due to the fact that the composition of waste translocation into plant tissue (Vwioko et al., 2006). In turn,
lubricating oils is not uniform, it is particularly difficult to find high concentrations of toxic heavy metals may inhibit the
 Heavy metal content in used engine oils depending on engine type and oil change interval 83

metabolism and growth of most plant species and this may have to the wear of various engine parts, such as camshafts and
a detrimental effect on the food chain (Morkunas et al., 2018). crankshaft, pistons, gears, rings and oil pump. A high content
Heavy metals can also strongly inhibit coal mineralization, of this element in oil indicates advanced processes of wear of
nitrogen transformation, as well as sulfur and phosphorus engine parts (Hamawand et al., 2013).
mineralization (Pinheiro et al., 2020; Srivastava et al., 2017). Nickel has immunotoxic and carcinogenic effects, it is
Considering the above, it is both purposeful and necessary also a very strong allergen (Śpiewak and Piętowska, 2006).
to determine the level of heavy metal contamination of used Despite the fact that this element introduced into water
lubricating oils, since the data available in the literature relate reservoirs is largely absorbed by bottom sediments, it is also
to either a relatively small number of samples (Zając et al., bioaccumulated, especially in phytoplankton, which results
2015), waste oils that were collected from special recycling in its rapid incorporation into the food chain (Kabata-Pendias
containers (Kashif et al., 2018) or the data are outdated and & Pendias, 1999). What is more, soluble nickel salts easily
inadequate to the current compositions of lubricating oils and dissociate in an aqueous environment, which allows metal ions
their operating conditions (Stout et al., 2018). to penetrate cell membranes (ATSDR, 2005). The assessment
Hence, due to insufficient data available in the literature, by (Tóth et al., 2016) indicates that soils throughout Europe are
this paper contributes to filling the research gap by presenting to some extent affected by nickel pollution.
the concentrations of selected heavy metals (Cr, Cu, Fe, Ni, Pb, Lead, next to cadmium and mercury, belongs to the group
Zn, Hg, Cd) in used lubricating oils coming from passenger of the most toxic elements for living organisms. Anthropogenic
cars of different mileage, and by determining the differences accumulation of lead is observed in most soils as a result
in heavy metal content depending on engine type and oil life. of global pollution with this element. In almost all soils,
The results of the study not only expand the literature the lead balance is positive and indicates a steady increase
database with information on the content of selected heavy in concentration. From the point of view of ecotoxicity or
metals in used engine oils, but they may also facilitate the phytotoxicity, even the permissible content or slightly elevated
decision-making process regarding the management of waste level of lead in soil may pose a threat to humans, and above
oils. all to children (Kabata-Pendias and Pendias, 1999). Even
a relatively low lead exposure can cause toxic effects. The
The environmental impact of the heavy widespread occurrence of Pb content in agricultural land
metals tested above the permissible threshold indicates the need for strict
control of lead in the environment and ultimately in the food
On a global scale, there is little risk of contamination of the chain (Tóth et al., 2016). The Pb content in engine oil is mainly
natural environment with chromium. Nevertheless, if locally associated with the wear of plain bearings (Hamawand et al.,
introduced into the atmosphere, waters and soils, it may 2013; Nwosu et al., 2008; Palkendo et al., 2013).
contribute to its inclusion in the bio-geochemical circulation in Zinc, just like copper, is more easily extracted from
excessive amounts, which poses a potential risk to human and anthropogenic sources than from its natural occurrence in
animal health (Kabata-Pendias and Pendias, 1999). According soil (Kabata-Pendias and Pendias, 1999). Due to the high
to Tóth et al., around 2 million ha of Europe’s agricultural land solubility, zinc easily penetrates into groundwater. Excess zinc
is ecologically endangered because of high concentration of found in soil can reduce nitrification processes and adversely
chromium in the soil (Tóth et al., 2016). The content of Cr in affect many microbiological processes. Furthermore, zinc is
engine oil is usually associated with the wear of piston rings. an essential element for both plants and people, but its excess
A high content of this element may be caused by impurities is toxic (Swartjes, 2011). That is why it is very important to
coming from the air supplying the engine or it may be the result control its proper amount in agricultural soils. Large amounts
of wear of chromium parts, for instance rings and bushings of zinc probably also inhibit copper absorption, which causes
(Hamawand et al., 2013; Nwosu et al., 2008; Palkendo et al., symptoms of copper deficiency. The main source of zinc in
2013). fresh oil is a package of antioxidant additives, corrosion
Copper is another element heavily introduced into the inhibitors, anti-wear additives, detergents and additives that
environment as a result of human activity, which represents increase resistance to extremely high pressure (Hamawand et
a significant risk of local biological contamination due to the al., 2013; Nwosu et al., 2008; Palkendo et al., 2013).
relatively high bioaccumulation factor (Kabata-Pendias and
Pendias, 1999). In many cases, uncontrolled precipitation or Methods of research
discharge of copper into the soil may severely undermine its
chemical balance, thus leading to soil degradation (Tóth et The study material consisted of 80 samples of used engine oils
al., 2016). Toth et al. indicate that the accumulation of copper collected from passenger cars of different manufacturers. The
in soil is mainly of anthropogenic origin, such as mining or oils were collected at car service stations during oil change. In
industrial activities, although the agricultural use of copper- the course of sampling, the following information regarding
containing products, especially in pesticides, is also common. each sample was also gathered: car mileage, oil change
It is not specified how much iron contributes to interval, and engine type.
environmental pollution, as it does not pose a threat to The content of heavy metals was tested with the use of
the environment. However, as the most commonly used the HDMaxine analyzer. It is a multi-element device used
metal, it may provide information on the impact of some for the determination of trace elements in liquid samples on
anthropotechnical elements on the natural environment (Zając a hydrocarbon matrix, and operating on the basis of high-
et al., 2015). Fe is introduced into the engine oil mainly due -definition fluorescence (X-ray Fluorescence – HDXRF).
84 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

The device has the capability to simultaneously determine The obtained data show that the content of particular
the content of Cr, Cu, Fe, Ni, Pb, Zn, Hg, Cd in the ranges metals varied quite considerably depending on the type of
corresponding to the concentrations of these elements found engine and the oil mileage, which was confirmed by means of
in engine oils. The limits of detection of the analyzed elements statistical analysis.
are summarized in Table 1. The average Cr content in DE oil samples was three times
Due to the fact that the analyzer does not require any higher than in GE oil samples, and so was the median (two times
additional sample preparation, the oil samples were poured higher). A clearly wider range of outlying concentrations was
directly into measuring cups. The analyses were performed in observed for DE oils – 0.4–4.2 mg·kg-1 (max value 8.1 mg·kg-1),
triplicate for each sample. The quality of the analytical results which may suggest that it could be more difficult to predict the
was tested with the use of the metal-organic standard. Cr content in this type of engine. This was also confirmed by
In order to determine the differences in heavy metal a twice higher coefficient of variation for DE oils (90%). For
content depending on the type of engine and the oil change GE oils, the range of outlying results was 0.3–1.2 mg·kg-1 (max
interval, the oil samples tested were divided, according to the value 1.9 mg·kg-1). Kashif et al. (Kashif et al., 2018) tested used
type of car engine they were collected from, into two groups engine oils collected from gasoline-powered passenger cars
designated as GE (Gasoline Engine) and DE (Diesel Engine). (GE) by applying the AAS method. They found significantly
In terms of oil change interval, the samples were divided higher Cr concentration in the range of 16–27 mg·kg-1. In turn,
into 5 groups marked as follows: GI oil change interval <10k Wolak et al., using the AAS method to test engine oils from
km, GII – oil change interval 10–12k km, GIII – oil change passenger cars powered by gasoline engines (GE), determined
interval 12–14k km, GIV oil change interval 14–16k km, and the chromium content in the range similar to the one obtained in
GV >16k km. this study – 1.47–3.14 mg·kg-1 (Wolak et al., 2019). Moreover,
To determine the impact of several factors (independent Zając et al. assessed used oils collected from agricultural tractors
variables – engine type, oil consumption) on the dependent powered by diesel engines (DE) by means of the XRF method
variable (metal content in engine oils), a multifactor analysis and obtained the average of 1.4 mg·kg-1 for chromium (Zając
of variance was performed. This analytical tool was used to et al., 2015), however, with a wider range (min-max) of the
seek answers to the following questions: a) is heavy metal results 0.4–10.7 mg·kg-1. A higher content of chromium was also
content influenced by the type of engine, depending on the reported by Stout et al. (Stout et al., 2018).
degree of oil consumption, b) does the car mileage (degree Considering the concentrations of elements in groups
of oil consumption) affect the concentration of a given heavy established according to oil change intervals (Table 2, Fig. 1),
metal regardless of the type of engine, and c) do the car engine it can be seen that in all of them (GI-GV) the average content
type and car mileage affect the heavy metal content? of chromium was lower in oil samples collected from GE
In addition to the two-way analysis of variance (Two- engines, and also the coefficient of variation for oil samples
-way ANOVA), the Tukey HSD test was also performed. The taken from these engines was lower compared to DE oils. These
significance level of 0.05 was adopted in the analysis. All findings are consistent with those drawn at an earlier stage of
p values below 0.05 were interpreted as indicating significant the study, where the comparison focused only on different
relationships. The analysis was performed with the use of the types of engine. Therefore, as a result of oil use (different car
R software, version 3.6.1. (R Core Team, 2019) mileages), the average, the coefficient of variation and the
The obtained results were then statistically analyzed with non-outlier range are higher for DE oils, also when broken
STATISTICA software. Data mining methods were also used. down into separate stages of oil use (oil change intervals). The
In each of the analyzed groups (depending on the type of engine median value in oil samples collected from GE engines was
and oil change interval) the results were presented with the use close to their average value.
of box-and-whisker plot, taking into account the following Having analyzed the lengths of the whiskers for the results
data: median of measured values, outliers and extreme values, obtained for the samples taken from DE engines, it should be
interquartile range (quartiles – 25 and 75 percentile) and stated that the distribution of the variable is characterized by
whiskers denoting the minimum and maximum non-outlier clear right-hand asymmetry (GI-GIV). The highest content of
values. Statistical significance was measured with Student’s chromium was found in the samples collected from DE engines
t-test for independent samples. (groups GI and GII) – 8.1 and 7.8 mg·kg-1, respectively.
The maximum content of Cr for GE engine oil samples was
Results and discussion observed in GII group – 1.9 mg·kg-1.
Cu is introduced into engine oils due to wear of bearings
The concentrations of heavy metals in used engine oils, divided and valve guides. The average Cu content in GE oils was
into groups according to engine types and oil change intervals, 75% higher than in DE oils (25.8, 14.8, respectively), while
are presented in Table 2. The information regarding average the median was 40% higher (18.6, 13.3, respectively).
values and standard deviations is provided in Tables 3 and 4, Moreover, there was a clearly wider range of non-outlying
while the information on medians is provided in Figures 1–6. values in GE oils – 3.1–80.9 mg·kg-1 (the range from the first

Table 1. The limits of detection of the analyzed elements

Metal Cr Cu Fe Ni Pb Zn Hg Cd
Limit of detection [mg kg ]
-1
0.4 0.14 0.7 0.1 0.08 0.14 0.08 0.06
 Heavy metal content in used engine oils depending on engine type and oil change interval 85
to the third percentile was also wider – 13.3–49.9 mg·kg-1). to those reported by (Zając et al., 2015), with an average
Furthermore, the maximum value was recorded for GE oils as content of 18 mg·kg-1; however, the maximum content of Cu
well – 82.0 mg·kg-1 (GII, GIV). A much higher coefficient of was 76 mg·kg-1. In turn, Stout et al. (Stout et al., 2018) reported
variation for GE oils (75%) compared to DE oils (41%) may a higher average value (33 mg·kg-1) compared to that obtained
indicate a more difficult prediction of Cu concentration in in the study (21 mg·kg-1). Considering the distribution of the
GE oils. For DE oils, the range of non-outlying values was Cu content in individual groups of oil change interval (Table 2,
10.2–16.9 mg·kg-1. The Cu content in GE oils obtained in this Fig. 2), it can be seen that the greater differentiation in copper
study was higher than that reported by (Kashif et al., 2018) concentration applies to the results obtained for GE oils; in all
4.7–8.5 mg·kg-1 and (Wolak et al., 2019) 1.8–25 mg·kg-1. groups the coefficient of variation was higher for oils coming
However, in DE oils the average values obtained were similar from these engines. Additionally, the average and median

Table 2. Selected positional measures of variability of the heavy metal contents in the oils tested, divided into groups according
to engine types and oil change intervals

GI GII GIII GIV GV

Metal

value

[45]

[35]
unit

GE

DE

GE [7] DE [9] GE [6] DE [9] GE [7] DE [4] GE [13] DE[7] GE [12] DE [6]
x̅ [mg kg-1] 0.7 2.1 0.6 2.3 1.1 2.4 0.7 1.2 0.7 1.4 0.7 2.9
Cr M [mg kg ] 0.7
-1
1.5 0.5 1.5 1.1 2.0 0.6 1.0 0.7 1.0 0.6 3.7
V % 44.18 89.7 60.3 106.5 50.5 96.4 31.9 82.6 24.4 71.0 36.3 54.6
x̅ [mg kg ] 25.8
-1
14.8 21.2 13.0 28.3 13.6 21.2 12.8 25.3 18.6 30.6 16.5
Cu M [mg kg-1] 18.6 13.3 18.7 13.1 16.9 13.2 15.4 12.7 21.7 14.1 15.3 14.2
V % 75 41.0 36.6 10.0 94.8 17.0 54.0 4.9 71.5 66.1 82.6 30.1
x̅ [mg kg ] 49.9
-1
64.2 27.3 56.1 79.9 73.9 49.6 48.2 60.3 59.0 36.8 78.7
Fe M [mg kg ] 43.7
-1
52.6 24.7 47.8 60.1 58.4 51.1 30.6 53.2 49.4 25.6 60.6
V % 71.1 75.0 58.2 84.4 62.0 72.9 34.7 95.1 67.6 87.9 70.2 60.8
x̅ [mg kg ] 0.5
-1
1.0 0.4 1.0 0.8 1.1 0.5 0.7 0.5 0.7 0.5 1.3
Ni M [mg kg ] 0.5
-1
0.8 0.3 0.6 0.8 0.9 0.5 0.8 0.4 0.7 0.5 0.9
V % 58.2 82.9 67.3 104.7 49.6 84.7 53.4 38.7 66.3 55.2 48.0 68.3
x̅ [mg kg-1] 0.6 0.9 0.4 0.9 1.1 1.4 0.5 0.4 0.6 0.9 0.5 0.6
Pb M [mg kg ] 0.4
-1
0.3 0.4 0.5 0.9 0.7 0.4 0.4 0.5 0.3 0.4 0.3
V % 64.0 124.2 21.5 131.0 60.0 95.3 49.1 13.9 45.3 164 61.3 116.9
x̅ [mg kg ] 872.9
-1
906.6 820.8 894.5 907.6 1027.5 789.2 869.2 962.2 842.9 837.9 842.8
Zn M [mg kg-1] 868.3 820 834 823.7 909.3 902.7 828.7 826.8 921.3 786.3 841.0 812.2
V % 15.8 31.1 11.6 30.3 12.4 43.6 12.4 15.1 15.8 15.1 15.9 22.5
x̅ – arithmetic average, M – median, V – coefficient of variation

200

180

160

140

120
Fe[mg/kg]

100

80

60

40

20

0
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]

Gasoline || Diesel || Outliers || Extreme values

 
Fig. 1. The content of Cr in the tested engine oils divided into groups according to engine type
and engine oil mileage
86 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

values in individual oil change interval groups were higher for min 50 mg·kg-1; while, on the other hand, it should be borne
GE oils than for DE oils (Fig. 2). The highest Cu contents of in mind that during operation drivers use refills that effectively
approx. 80 mg·kg-1 (GII, GIV, GV) were found for GE oils, refresh the oil and reduce Fe concentration (e.g., the average
whereas the highest concentration of this element for DE oils and median for GE-GV) and then the min Fe concentration
was lower by almost half – 46 mg·kg-1 (GIV). may decrease to about 20 mg·kg-1.
The average content and median content of Fe in DE oils When analyzing the results obtained in individual oil
were higher than in GE oils (29% higher average and 17% change interval groups (Table 2 Fig. 3), it can be seen that in
higher median, respectively). A narrower range of non-outlying the GII group, the average and the median Fe content in GE and
values was observed in GE oils – 13.2–104 mg·kg-1 (DE oils DE oils were similar, in the GIII and GIV group – the average
12.9–176.0 mg·kg-1), but the maximum values were similar (GE and the median were higher for GE oils, while in the lowest
oils – 180 mg·kg-1, DE oils – 176 mg·kg-1). The content ranges and highest mileage groups (GI and GV), the average and the
(min-max) of Fe indicated by (Kashif et al., 2018) were much median content for GE oils were lower by half as compared to
narrower 98.5–138 mg·kg-1 than those obtained in the study. DE oils. In turn, when analyzing the lengths of the obtained
Also, the average value (60.2 mg·kg-1) reported by (Wolak et whiskers for DE oils coming from the GII, GIII, GV groups
al., 2019) falls within the ranges obtained in presented study. and for GE oils from the GIV group, it should be stated that the
Moreover, average values indicated for DE oils were similar distribution of the variable is clearly characterized by a right-
to those obtained by (Zając et al., 2015) with an average -sided asymmetry. The maximum content of Fe for both GE
content of 53.5 mg·kg-1. However, (Stout et al., 2018) report and DE engines was found in group GII (180 and 176 mg·kg-1,
an average Fe content of 256 mg·kg-1, which is much higher respectively). In addition, 3 values close to the maxima (above
than the maximums obtained in this study. It therefore follows 160 mg·kg-1) were identified for 3 other DE samples.
that on the one hand, it is possible to estimate the increase of The main source of nickel in used engine oils are piston
Fe after only one period of oil use (10–15k km) at the level of rings and shaft (Palkendo et al., 2013). The average Ni

90

80

70

60

50
Cu [mg/kg]

40

30

20

10

-10
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]
Gasoline || Diesel || Outliers || Extreme values

Fig. 2. The content of Cu in the tested engine oils divided into groups according to engine types
and engine oil mileage

200

180

160

140

120
Fe[mg/kg]

100

80

60

40

20

0
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]

Gasoline || Diesel || Outliers || Extreme values

Fig. 3. The content of Fe in the tested engine oils divided into groups according to engine type
and engine oil mileage
 Heavy metal content in used engine oils depending on engine type and oil change interval 87

content in GE oils (0.5 mg·kg-1) was half that of DE oils obtained in the study. Conversely, (Stout et al., 2018) pointed to
(1 mg·kg-1). Also, for DE oils a clearly wider range of non- the average Pb content of 2777 mg·kg-1. Yet, it should be noted
outlying values was noted – 0.15–2.5 mg·kg-1 with a maximum that in this case such a high Pb value may be due to the fact
value of 3.4 mg·kg-1. For both types of oils, the results were that Stout reports on oils that cover the period when gasoline
characterized by strong variability (58% – GE, 83% – DE); containing lead was widely used. Analyzing the lead contents
hence, the prediction of Ni concentration in oils may be rather in individual oil change interval groups (Table 2, Fig. 5), it can
difficult. The Ni contents in GE oils obtained in the tests were be observed that the median values in GI, GIII and GV are
lower than those reported by (Kashif et al., 2018), where Ni similar, while in GII and GIV they are clearly higher for GE
was determined in the range of 6–11.75 mg·kg-1. However, oils. However, the coefficient of variation is much higher for
in the paper by (Wolak et al., 2019), the content indicated is DE oils (except for group GIII).
similar (average – 0.8 mg·kg-1) to the average content obtained The average Zn content in the tested oils, for both types of
in this study. engines, was similar (GE – 873 mg·kg-1, DE – 907 mg·kg-1), with
The average Ni concentration in DE oils reported by a higher median for GE oils (868 compared to 820 mg·kg-1). The
(Zając et al., 2015) is lower and amounts to 0.4 mg·kg-1 with range of non-outlying values for GE oils was 729–1064 mg·kg-1;
a minimum of 0.14 mg·kg-1 and a maximum of 0.75 mg·kg-1. however, the range of recorded values (min-max) was wider and
In turn, a higher average content of this element is reported by amounted to 653–1431 mg·kg-1. Yet, the variability of results for
Stout et al. – 2.1 mg·kg-1 (Stout et al., 2018). Considering the these oils was low (16%). For DE oils, a higher range of non-
Ni concentration in individual groups of oil change interval -outlying values 576–1383 mg·kg-1 was found at a maximum
(Table 2, Fig. 4), it can be observed that the average and value of 1790 mg·kg-1 (GII), with an average variation of
median values in GE oils were lower than in DE oils, only in 31%. On the other hand, in the study by (Wolak et al., 2019),
the GII group the values were at a similar level. For DE oils Zn content in the range of 840–1112 mg·kg-1 was obtained. In
in groups GI, GIV and GV, the distribution of the variable is contrast, in DE oils, the average content reported by (Zając et al.,
characterized by a clear right-hand asymmetry. Likewise, for 2015) was 1106 mg·kg-1. The average value reported by (Stout et
DE engines, the highest content of this element was found to al., 2018) was 873 mg·kg-1.
be 3.4 mg·kg-1, while for GE engines this value was 60% lower Analyzing the results of lead content in individual groups
(1.3 mg·kg-1) – GII and GIV. of oil change interval (Table 2, Fig. 5), it can be seen that the
The average Pb content in DE oils (0.9 mg·kg-1) was average and median values in the groups GI, GII, GIII and GV
higher than in GE oils (0.6 mg·kg-1), with the median higher for both engine types are similar; the differences are visible in
for GE oils (0.3 mg·kg-1) compared to the median for DE oils GIV – the average and median for GE oils are clearly higher
(0.4 mg·kg-1). The range of non-outlying values was the same than for DE oils.
(0.3–1.1 mg·kg-1) for both types of oils; however, for GE oils Particular attention is currently paid to pollution of the
the max. content was 2.2 mg·kg-1, while for DE oils it was environment with mercury and cadmium compounds due to the
almost twice as high – 4.0 mg·kg-1. This was confirmed by anthropogenic distribution of these elements in the environment
the coefficient of variation, which for DE oils showed a very and high toxicity. It should be noted that these toxic elements
strong variability of results (124%), and for GE oils – a strong were not detected in the engine oils tested. The obtained Cd
variability (64%). The Pb contents reported by (Kashif et al., and Hg content was below the level of quantification (Table 1).
2018) 8.5–12.75 mg·kg-1 were higher than those obtained in the This, however, does not mean that the risk related to the toxic
study, whereas Wolak et al. indicated a very similar range to effects of cadmium should be excluded. It is introduced to
the one obtained in this study 0.27–4.57 mg·kg-1 (Wolak et al., engine oil as an impurity during use (Hamawand et al., 2013).
2019). Likewise, for DE oils, the average Pb contents reported From the literature it follows that the Cd content in used engine
by (Zając et al., 2015) – 3.6 mg·kg-1 were higher than those oils is from 0.27 to 1 mg · kg-1 (Cassap, 2008; Hamawand et

4,0

3,5

3,0

2,5
Ni[mg/kg]

2,0

1,5

1,0

0,5

0,0
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]

Gasoline || Diesel || Outliers

Fig. 4. The content of Ni in the tested engine oils divided according to groups of engines
and engine oil mileage
88 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

4,5

4,0

3,5

3,0

2,5

Pb[mg/kg] 2,0

1,5

1,0

0,5

0,0
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]

Gasoline || Diesel || Outliers || Extreme values

Fig. 5. The content of Pb in the tested engine oils divided into groups according to engine type
and engine oil mileage

2000

1800

1600

1400
Zn [mg/kg]

1200

1000

800

600

400
<10k 10‐12k 12‐14k 14‐16k >16k
Mileage [km]

Gasoline || Diesel || Outliers || Extreme values

Fig. 6. The content of Zn in the tested engine oils divided into groups according to engine type
and engine oil mileage

al., 2013). However, there is no information about the content between the mean values (for respective oil groups GI-GV)
of Hg in used and new engine oils, despite the fact that mercury concerned the concentration of Cr and Zn. In the case of this
was found in crude oil (Klojzy-Karczmarczyk, 2013). Mercury element, five comparisons showed statistically significant
was not detected in the tested samples, so it can be concluded differences. The smallest differences in concentrations of
that the threat posed by this metal is rather insignificant. these elements were observed for Cu. Only in two sets (GI vs
Tables 3 and 4 present the mean values, standard deviations GIV and GI vs GV), the differences in mean values of these
and p* values for selected elements (Cr, Cu, Fe, Ni, Pb, Zn). elements were statistically significant.
Table 3 presents the results for 5 groups, different in terms of Analyzing the results presented in Table 4, it was observed
oil mileage (GI – <10k km, GII – 10–12k km, GIII – 12–14k that the differences in mean concentrations of elements in
km, GIV – 14–16k km, GV – > 16k km). Table 4 presents the various engines (diesel, gasoline) in nearly every case (except
results for two groups differentiated in terms of the type of Zn) were highly statistically significant (p lower than 0.01).
engine to which the engine oil was applied (GE – gasoline, The largest variation in mean values in the case of different
DE – diesel). The threshold for statistical significance was set engine types was obtained for Cr. In each case, this difference
to 0.05. Any result below the value was considered statistically was two-fold. In the case of the Cr, the average concentration
significant (the values were indicated in bold). P values for oils from diesel engine was 3 times higher than the average
(P-value resulting from the application of Student’s t test for for gasoline engine oils.
independent samples) below 0.01 were considered highly In the next step, a multivariate analysis of variance was
statistically significant (the values were indicated in bold and performed. It provides much more information than a Student’s
underlined). t-test. The interaction effect (introduction of another factor)
The analysis of the results presented in Table 3 suggests can change the view of a given phenomenon. The Student’s
that the largest number of statistically significant differences t-test only compares two groups with each other. The results
 Heavy metal content in used engine oils depending on engine type and oil change interval 89

of the statistical analysis presented in Table 4 show that the group of gasoline engines. With the indication that this only
type of engine affects the content of the heavy metals tested, applies to the basic oil change interval, i.e., the GI group.
but the effect of oil consumption needs to be investigated. In Table 5 also presents the results for both the car mileage
order to be able to draw more comprehensive conclusions, it is and the type of engine analysis. The significance of statistical
necessary to take into account the impact of the type of engine differences was obtained for GII:DE (Fe) and for GIV:DE
in the context of the degree of oil consumption (oil change (Cr, Zn), which showed lower concentrations of the analyzed
interval). Table 5 shows the parameters of ANOVA two-factor elements than in the base GI:GE combination (-35 for Fe, -1
analysis. for Cr and -193 for Zn, respectively).
In the GII group, half of the analyzed elements (Fe, Ni, Pb) In the next step, various combinations of car mileage
showed a statistically significant difference in concentration groups and engine types were compared using post hoc
in relation to the reference group (GI). It should be indicated, analysis. The results are shown in Table 6.
however, that it only applies to the basic type of engine For the correct interpretation of the results in Table 6, it is
(gasoline). The iron concentration in this group is on average necessary to use the data from Table 5. This makes it possible
higher by 53 compared with the reference group GI. In the GIV to compare the sets of variables, taking into account both
group, statistical significance was demonstrated by Fe and Zn. different engine types (gasoline, diesel) as well as different car
The concentrations of these elements are higher by 33 and 141, mileages/oil change intervals (GI-GV).
respectively, when compared with the reference group. By type The first important observation is that with respect to
of engine, it was shown that in diesel engines the level of Fe, gasoline engines, when comparing extreme mileages (GV:GE
Cr, Pb and Ni is significantly different than in the reference vs GI:GE), none of the analyzed elements showed statistical

Table 3. Mean values, standard deviations and p* values for groups of oils divided based on oil mileage

GI GI GI GI GII GII GII GIII GIII GIV

[In
GI GII GIII GIV GV vs vs vs vs vs vs vs vs vs vs
total]
GII GIII GIV GV GIII GIV GV GIV GV GV
x̅ (s)
p
Metal N=80 N=16 N=15 N=11 N=20 N=18
1.3 1.5 1.9 0.9 1.0 1.4
Cr 0.391 0.056 0.038 0.712 0.003 0.001 0.165 0.438 0.040 0.037
(1.4) (2.0) (1.9) (0.6) (0.7) (1.4)
21.0 16.6 19.5 18.1 22.9 25.9
Cu 0.279 0.384 0.011 0.004 0.682 0.297 0.109 0.118 0.051 0.400
(15.9) (6.5) (17.8) (9.8) (16.3) (21.6)
56.1 43.5 76.3 49.1 59.8 50.8
Fe 0.001 0.475 0.042 0.344 0.005 0.071 0.005 0.198 0.825 0.244
(41.8) (38.9) (50.4) (28.4) (43.5) (38.9)
0.7 0.8 1.0 0.6 0.6 0.8
Ni 0.127 0.279 0.162 0.850 0.004 <0,001 0.106 0.954 0.100 0.041
(0.6) (0.9) (0.8) (0.3) (0.4) (0.6)
0.7 0.7 1.3 0.4 0.7 0.6
Pb 0.004 0.093 0.903 0.365 <0,001 0.001 <0,001 0.099 0.118 0.414
(0.8) (0.9) (1.1) (0.2) (0.8) (0.5)
887.6 862.3 979.6 818.3 920.4 839.5
Zn 0.047 0.266 0.094 0.520 0.011 0.236 0.008 0.001 0.476 0.005
(212.7) (210.1) (350.5) (111.8) (152.0) (148.3)
GI – < 10k km, GII – 10–12k km, GIII – 12–14k km, GIV – 14–16k km, GV – >16k km; N – the number of samples tested,
x̅ – arithmetic average, s – standard deviation, p – p-value

Table 4. Mean values, standard deviations and p* values for groups of oils divided based on engine type

[In total] GE DE GE vs DE
x̅ (s)
p
Metal N=80 N=45 N=35
Cr 1.3 (1.4) 0.7 (0.3) 2.1 (1.9) <0.001
Cu 21.0 (15.9) 25.8 (19.3) 14.8 (6.1) <0.001
Fe 56.1 (41.8) 49.9 (35.4) 64.2 (48.2) 0.008
Ni 0.7 (0.6) 0.5 (0.3) 1.0 (0.8) <0.001
Pb 0.7 (0.8) 0.6 (0.4) 0.9 (1.1) 0.003
Zn 887.6 (212.6) 872.9 (138.2) 906.6 (282.3) 0.223

GE – gasoline, DE – diesel; N – the number of samples tested, x̅ – arithmetic average, s – standard deviation, p – p-value
90 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

significance. Similar results were obtained for DE engines. In no indication because it is the base level), for GII:GE the total
the GIII:GE vs GI:GE and GIV:GE vs GI:GE combinations, amounts to 52.535].
statistical significance was found for Fe in two adjacent When comparing the last period of car use (GV), taking
periods only (GI and GII – GE). Statistically significantly more into account engine types (GE, DE), the highest number of
iron is found in GII for GE [the calculations were done in the statistically significant differences was found (4 elements
following way: the ANOVA parameters from Table 5 are added – Cr, Cu, Fe, Ni). This means that used oils (after GV) contain
for each component, i.e., for GI:GE the total is 0 (for GI – there statistically more Cr, Fe and Ni when the oils come from DE
is no indication because it is the base level, for GE – there is engines, whereas they contain statistically more Cu when the
no indication because it is the base level, for GI:GE – there is oils come from GE engines. Hence, the content of respective

Table 5. Two-factor analysis of variance (ANOVA)

Linear model (two-way ANOVA) parameters

Engine
Metal Mileage (ref. level: GI2) Interactions
(ref.level: GE3)
GII GIII GIV GV DE GII:DE GIII:DE GIV:DE GV:DE
Cr 0.484 0.05 0.136 0.044 1.646 * -0.343 -1.099 -1.004 * 0.626
Cu 7.187 0.019 4.123 9.424 * -8.138 -6.604 -0.259 1.42 -5.957
Fe 52.535 * 22.233 32.958 * 9.516 28.75 * -34.705 * -30.112 -30.074 13.062
Ni 0.393 * 0.102 0.107 0.116 0.6 * -0.263 -0.407 -0.426 0.148
Pb 0.66 * 0.027 0.13 0.096 0.44 * -0.161 -0.542 -0.162 -0.354
Zn 86.802 -31.571 141.37 * 17.052 73.709 46.198 6.22 -192.984 * -68.737
* statistically significant (p<0.05)
2
Five groups of samples were analyzed. In ANOVA, one of them must serve as a reference group – the GI group was selected; yet, indicating that
this does not affect the entire analysis
3
Two types of engine were analyzed. In ANOVA, one of them must serve as a reference type – the GE engine was selected; yet, indicating that this
does not affect the entire analysis

Table 6. Tukey HSD post-hoc

Tukey HSD post-hoc p-value

Mileage:Engine
Cr Cu Fe Ni Pb Zn
GII:GE vs GI:GE 0.971 0.886 0.002 * 0.524 0.169 0.947
GIII:GE vs GI:GE 1 1 0.718 1 1 1
GIV:GE vs GI:GE 1 0.99 0.068 1 1 0.244
GV:GE vs GI:GE 1 0.381 0.997 0.999 1 1

GI:DE vs GI:GE <0.001 * 0.676 0.272 0.017 * 0.597 0.965

GII:DE vs GII:GE 0.025 * 0.04 * 1 0.666 0.969 0.648

GIII:DE vs GIII:GE 0.97 0.862 1 0.996 1 0.986

GIV:DE vs GIV:GE 0.668 0.807 1 0.984 0.937 0.488

GV:DE vs GV:GE <0.001 * 0.037 * 0.011 * 0.001 * 1 1

GII:DE vs GI:DE 1 1 0.816 0.998 0.311 0.334

GIII:DE vs GI:DE 0.318 1 1 0.886 0.619 1
GIV:DE vs GI:DE 0.338 0.956 1 0.679 1 0.997
GV:DE vs GI:DE 0.757 0.999 0.682 0.894 0.982 0.998
* statistically significant (p<0.05)
 Heavy metal content in used engine oils depending on engine type and oil change interval 91

heavy metals in used engine oils varies depending on the a comparable level of concentration. The multi-factor analysis
engine type and oil mileage. of variance, taking into account the mileages from the GI
group, showed that in diesel engines, the level of Fe, Cr, Pb and
Conclusions Ni is statistically significantly different than in the reference
group of gasoline engines. The differences in the content of
Waste engine oils contain metals that may pose a threat to heavy metals in used lubricating oils, depending on the engine
human health and/or to the environment after entering soil type, suggest that their separate collection may definitely be
and water. That is why it is important to handle used oils in considered, which will facilitate the proper handling of these
an adequate way. Directive 2014/955/EU explicitly states that oils and reduce the risk to the environment.
WLO (waste lubricant oil) should be classified as hazardous In turn, the post hoc analysis, taking into account both
waste and appropriate methods of disposal should be ensured. different mileage as well as the type of engine, showed that in
By ordering the elements in terms of their decreasing oil, which was operated for above 16k km in the DE engine, the
average content in the examined oils, it can be stated that the concentrations of Cr, Fe and Ni are statistically higher, whereas
dominant element was Zn – the average content of this element in oil operated in the GE engine – there is statistically more Cu.
in both types of oils was at a similar level – 900 mg·kg-1, Mercury and cadmium were not measured in any of the engine
followed by Fe and Cu, the content of which, however, was oil samples tested. However, based on the literature data, it
one order of magnitude lower. In GE oils, the next elements should be borne in mind that cadmium may appear in the form of
marked in descending order were Cr, Pb and Ni, and their impurities during the use of engine oils. Further research should
content was below 1 mg·kg-1, while in DE oils it was Cr, Ni be expanded to include the heavy metal content analysis of used
and Pb. Analyzing the differences in the average content of the engine oils with significant oil change intervals (over 20k km
examined elements, depending on the type of engine, it can of mileage). This is due to the possible intensification of the
be stated that in oils coming from DE engines the following concentrations of wear elements and pollutants after such a time
elements showed a higher concentration – Cr (three times of use, and their potential leakage into the environment. As the
higher concentration), Fe (1/3 times higher concentration), authors’ own research suggests, car users oftentimes change the
Ni (two times higher concentration), Pb (1/2 times higher oil themselves, especially when its mileage is significant, which
concentration). In oils coming from GE engines, only the raises concerns about non-compliance with the rules for the
average Cu content was higher (¾). In both cases, zinc had management of waste oils.

Supplementary data

Oil
Car Cr Cu Fe Ni Pb Zn
change
Code mileage Engine type
interval
(km) mg·kg-1
(km)
G_01 53,173 18,440 Gasoline 0.59 56.91 15.86 0.27 0.31 833
G_02 59,988 19,764 Gasoline 0.43 14.73 18.79 0.46 0.58 868
G_03 59,200 8,349 Gasoline 1.36 13.41 27.41 1.02 0.37 944
G_04 20,000 14,000 Gasoline 0.72 15.43 51.08 0.50 0.44 835
G_05 22,301 7,718 Gasoline 0.49 30.78 13.21 0.24 0.37 834
G_06 55,650 14,230 Gasoline 0.76 14.94 63.96 0.57 0.38 894
G_07 7,125 7,125 Gasoline 0.77 18.73 60.65 0.49 0.56 731
G_08 34,537 19,387 Gasoline 1.18 32.84 104.00 1.00 0.87 1035
G_09 117,000 13,000 Gasoline 1.01 12.32 72.88 1.07 0.37 669
G_10 15,150 15,150 Gasoline 0.77 82.04 32.08 0.33 1.12 853
G_11 24,500 14,623 Gasoline 0.53 23.08 20.60 0.42 0.63 907
G_12 72,000 15,200 Gasoline 1.04 19.44 144.00 1.30 0.39 869
G_13 63,212 13,503 Gasoline 0.84 41.07 30.30 0.35 0.31 829
G_14 231,293 18,272 Gasoline 0.93 12.59 23.61 0.26 0.31 1064
G_15 31,182 16,617 Gasoline 0.54 65.69 17.49 0.28 0.38 833
G_16 60,666 19,101 Gasoline 0.66 14.81 27.57 0.34 0.52 853
G_17 30,802 15,000 Gasoline 1.02 21.49 94.25 0.59 0.35 940
G_18 52,916 14,660 Gasoline 0.69 27.48 19.75 0.24 0.33 846
92 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

G_19 60,278 19,858 Gasoline 0.66 15.78 19.09 0.49 0.38 849
G_20 103,250 12,500 Gasoline 0.60 13.45 24.71 0.29 0.33 867
G_21 28,218 9,961 Gasoline 0.47 32.94 24.09 0.32 0.37 859
G_22 27,521 8,766 Gasoline 0.59 13.81 27.71 0.32 0.46 832
G_23 39,500 21,754 Gasoline 0.63 80.94 61.57 0.83 0.54 943
G_24 138,000 18,000 Gasoline 0.51 3.08 22.72 0.52 0.33 739
G_25 19,602 19,602 Gasoline 0.92 43.03 54.53 0.94 1.46 744
G_26 300,000 12,000 Gasoline 1.40 14.48 67.95 1.09 1.00 892
G_27 130,000 15,000 Gasoline 0.42 12.47 22.72 0.41 0.38 917
G_28 230,000 12,000 Gasoline 1.87 16.00 59.62 1.29 2.23 1081
G_29 11,000 11,000 Gasoline 1.44 82.00 180.33 1.13 1.51 873
G_30 90,000 15,000 Gasoline 0.94 21.69 122.33 1.18 0.45 1061
G_31 16,000 10,000 Gasoline 0.33 18.56 13.49 0.27 0.38 660
G_32 135,000 17,600 Gasoline 0.39 14.04 38.87 0.55 0.38 653
G_33 25,593 13,000 Gasoline 0.44 14.60 47.12 0.56 0.44 729
G_34 32,600 18,200 Gasoline 0.44 12.55 38.04 0.44 0.42 640
G_35 27,600 14,000 Gasoline 0.58 17.51 60.30 0.59 0.42 677
G_36 25,300 10,800 Gasoline 0.46 17.80 51.34 0.50 0.43 733
G_37 14,200 14,200 Gasoline 0.57 31.23 71.36 0.30 0.96 921
G_38 13,000 13,000 Gasoline 0.44 33.87 60.54 0.27 0.98 919
G_39 12,000 12,000 Gasoline 0.69 11.70 59.23 0.50 0.68 927
G_40 15,000 15,000 Gasoline 0.66 24.29 43.71 0.35 0.63 980
G_41 16,000 16,000 Gasoline 0.74 25.20 53.25 0.30 0.79 925
G_42 12,000 12,000 Gasoline 0.71 28.10 60.71 0.36 0.76 940
G_43 15,000 15,000 Gasoline 0.84 11.90 77.11 0.67 0.69 964
G_44 92,000 9,000 Gasoline 0.27 19.88 24.74 0.25 0.58 886
G_45 125,000 15,000 Gasoline 0.72 13.41 18.60 0.17 0.32 1431
D_01 60,849 19,700 Diesel 0.87 14.38 29.40 0.50 0.37 722
D_02 62,000 12,000 Diesel 2.11 14.00 101.00 3.36 0.71 723
D_03 184,748 16,000 Diesel 0.96 15.12 58.50 0.36 0.36 745
D_04 68,527 18,000 Diesel 4.18 14.09 107.36 2.32 0.30 831
D_05 215,872 19,579 Diesel 3.91 16.90 161.33 2.46 2.11 586
D_06 149,172 14,725 Diesel 1.42 46.21 165.67 0.76 0.35 786
D_07 120,151 17,123 Diesel 0.90 26.30 52.62 0.59 0.31 793
D_08 225,450 13,673 Diesel 1.45 12.88 114.67 0.92 0.36 833
D_09 50,000 10,000 Diesel 3.18 13.14 58.55 0.71 0.46 985
D_10 150,500 14,500 Diesel 2.64 16.55 76.19 1.05 4.01 987
D_11 152,000 16,000 Diesel 0.75 14.06 23.34 1.32 0.31 798
D_12 150,000 14,000 Diesel 0.38 13.59 18.55 0.96 0.44 820
D_13 148,000 12,000 Diesel 0.63 12.84 14.29 0.82 0.28 779
D_14 146,000 10,000 Diesel 0.36 12.55 12.94 0.48 0.28 824
D_15 180,000 10,000 Diesel 0.37 13.75 31.81 0.60 0.43 886
D_16 136,000 16,000 Diesel 0.55 12.66 19.87 0.33 0.35 747
D_17 133,000 15,000 Diesel 0.53 12.45 19.80 0.35 0.27 776
D_18 134,000 14,000 Diesel 0.49 12.14 16.96 0.38 0.35 763
D_19 260,000 12,000 Diesel 3.49 11.16 100.67 1.45 1.47 1791
 Heavy metal content in used engine oils depending on engine type and oil change interval 93

D_20 400,000 11,000 Diesel 2.02 18.64 120.00 0.88 3.35 917
D_21 180,000 11,000 Diesel 8.06 15.54 176.00 1.58 2.33 1774
D_22 320,000 10,000 Diesel 2.75 14.97 66.90 1.10 3.88 1384
D_23 89,000 10,000 Diesel 7.76 10.21 171.00 2.23 1.10 1247
D_24 10,000 10,000 Diesel 3.35 13.14 66.27 3.31 0.69 806
D_25 64,000 19,000 Diesel 3.53 13.73 63.72 0.95 0.32 1064
D_26 62,000 17,000 Diesel 4.18 13.52 57.51 0.87 0.33 1060
D_27 60,010 15,000 Diesel 2.88 12.90 49.38 0.73 0.31 1061
D_28 58,000 13,000 Diesel 2.52 12.51 42.62 0.60 0.32 1060
D_29 56,015 11,000 Diesel 2.16 12.40 36.26 0.52 0.33 1056
D_30 130,000 10,000 Diesel 1.47 13.90 47.83 0.25 0.54 576
D_31 139,000 10,000 Diesel 0.59 12.95 26.11 0.23 0.26 662
D_32 140,000 11,000 Diesel 0.75 13.21 30.18 0.15 0.30 670
D_33 141,000 12,000 Diesel 0.71 13.27 28.39 0.26 0.30 636
D_34 138,000 8,000 Diesel 0.50 12.58 23.30 0.25 0.28 681
D_35 162,000 11,500 Diesel 1.66 11.36 58.38 1.30 3.37 903

Acknowledgements Kabata-Pendias, A. & Pendias, H. (1999). Biochemistry of Trace

Elements. PWN – Polish Scientific Publishers, Warszawa. (in
Funded from the 'Excellent science' program of the Ministry Polish)
of Science and Higher Education as a part of the contract Kamal, A. & Khan, F. (2009). Effect of extraction and adsorption
no. DNK/SP/465641/2020 “The role of the agricultural on re-refining of used lubricating oil. Oil & Gas Science and
engineering and environmental engineering in the sustainable Technology-Revue de l’IFP, 64(2), pp. 191–197.
Kashif, S.-R., Zaheer, A., Arooj, F. & Farooq, Z. (2018). Comparison
agriculture development”.
of heavy metals in fresh and used engine oil. Petroleum
Science and Technology, 36(18), pp. 1478–1481, DOI:
References 10.1080/10916466.2018.1496105
Klojzy-Karczmarczyk, B. (2013). Analysis of long-term research on
Bogacki, J.P. & Al-Hazmi, H. (2017). Automotive fleet repair facility mercury content in the soils in the immediate surroundings of the
wastewater treatment using air/ZVI and air/ZVI/H2O2 processes. southern ring road of Krakow. Rocznik Ochrona Srodowiska, 15,
Archives of Environmental Protection, 43(3), pp. 24–31, DOI: pp. 1053–1069.
10.1515/aep-2017-0024 Kryłów, M., Kwaśny, J.A. & Balcerzak, W. (2018). Oily wastewater
Boughton, B. & Horvath, A. (2004). Environmental Assessment of treatment using a zirconia ceramic membrane – a literature
Used Oil Man-agement Methods. Environmental Science & review. Archives of Environmental Protection, 44(3), pp. 3–10,
Technology, 38(2), pp. 353–358, DOI: 10.1021/es034236p DOI: 10.24425/aep.2018.122293
Cassap, M. (2008). The analysis of used lubrication oils by inductively Kupareva, A., Mäki-Arvela, P. & Murzin, D. Yu. (2013). Technology
coupled plas-ma spectrometry for predictive maintenance. for rerefining used lube oils applied in Europe: a review. Journal
Spectroscopy Europe, 20(1), pp. 17–20, of Chemical Technology & Biotechnology, 88(10), pp. 1780–1793,
Delistraty, D. & Stone, A. (2007). Dioxins, metals, and fish toxicity DOI: 10.1002/jctb.4137
in ash residue from space heaters burning used motor oil. Lam, S.S., Liew, R.K., Jusoh, A., Chong, C.T., Ani, F.N. & Chase, H.A.
Chemosphere, 68(5), pp. 907–914, (2016). Progress in waste oil to sustainable energy, with emphasis
Elnajjar, E., Al Omari, S.A.B., Hamdan, M.O., Ghannam, M. & Selim, on pyrolysis techniques. Renewa-ble and Sustainable Energy
M.Y.E. (2019). Characteristics of external furnace combustion of Reviews, 53, pp. 741–753, DOI: 10.1016/j.rser.2015.09.005
used lube oil with different percentages of diethyl ether additives Lynch, T.R. (2007). Process chemistry of lubricant base stocks. CRC
burned with liquefied petroleum gas. Biofuels. Scopus. DOI: Press.
10.1080/17597269.2019.1608035 Magiera, J. (2006). Re-refining used oil. WN-T, Warszawa. (in Polish)
Hamawand, I., Yusaf, T. & Rafat, S. (2013). Recycling of Waste Magiera, J. & Głuszek, A. (2009). Used-oils – the rules of collection
Engine Oils Using a New Washing Agent. Energies, 6(2), and ecological utilization. Polish Journal of Environmental
pp. 1023–1049. DOI: 10.3390/en6021023 Studies, 18(3A), pp. 230–235.
Hsu, Y.-L. & Liu, C.-C. (2011). Evaluation and selection of Morkunas, I., Woźniak, A., Mai, V. C., Rucińska-Sobkowiak,
regeneration of waste lu-bricating oil technology. Environmental R. & Jeandet, P. (2018). The Role of Heavy Metals in Plant
Monitoring and Assessment, 176(1), pp. 197–212, DOI: 10.1007/ Response to Biotic Stress. Molecules, 23(9), DOI: 10.3390/
s10661-010-1576-3 molecules23092320
Jafari, A.J. & Hassanpour, M. (2015). Analysis and comparison Nerin, C., Domeño, C., Ignacio Garcia, J. & del Alamo, A. (1999).
of used lubricants, regenerative technologies in the world. Distribution of Pb, V, Cr, Ni, Cd, Cu and Fe in particles formed
Resources, Conservation and Recycling, 103, pp. 179–191, DOI: from the combustion of waste oils. Chemosphere, 38(7),
10.1016/j.resconrec.2015.07.026 pp. 1533–1540, DOI: 10.1016/S0045-6535(98)00373-7
94 J. Szyszlak-Bargłowicz, G. Zając, A. Wolak

Nerı́n, C., Domeño, C., Moliner, R., Lázaro, M. J., Suelves, I. & water. The Journal of Supercritical Fluids, 164, pp. 104912,
Valderrama, J. (2000). Behaviour of different industrial waste DOI: 10.1016/j.supflu.2020.104912
oils in a pyrolysis process: metals distribution and valuable Śpiewak, R. & Piętowska, J. (2006). Nickel-allergen unique. From
products. Journal of Analytical and Applied Pyrolysis, 55(2), the structure of the atom to legal regulations. Alergol. Immunol,
pp. 171–183, DOI: 10.1016/S0165-2370(99)00097-2 3, pp. 3–4,
Nukman, Sipahutar, R., Taufikurrahman, Asmadi & Surya, I. (2018). Srivastava, V., Sarkar, A., Singh, S., Singh, P., de Araujo, A.S.F. &
Used lubricating oil as a fuel for smelting waste aluminum. Singh, R.P. (2017). Agroecological Responses of Heavy Metal
ARPN Journal of Engineering and Applied Sciences, 13(10), Pollution with Special Emphasis on Soil Health and Plant
pp. 3412–3417. Scopus, Performances. Frontiers in Environmental Science, 5, pp. 64,
Nwosu, F.O., Olu-Owolabi, B.I., Adebowale, K.O. & Leke, L. DOI: 10.3389/fenvs.2017.00064
(2008). Comparative Investigation of Wear Metals in Virgin and Stout, S.A., Litman, E. & Blue, D. (2018). Metal concentrations
Used Lubricant Oils. Terrestrial and Aquatic Environmental in used engine oils: Relevance to site assessments of soils.
Toxicology, 2(1), pp. 38–43, Environmental Forensics, 19(3), pp. 191–205,
Osman, D.I., Attia, S.K. & Taman, A.R. (2018). Recycling of used Swartjes, F.A. (2011). Introduction to Contaminated Site Management.
engine oil by different solvent. Egyptian Journal of Petroleum, [In] F.A. Swartjes (Ed.), Dealing with Contaminated Sites: From
27(2), pp. 221–225, DOI: 10.1016/j.ejpe.2017.05.010 Theory towards Practical Application (pp. 3–89). Springer
Palkendo, J.A., Kovach, J. & Betts, T.A. (2013). Determination of Netherlands, DOI: 10.1007/978-90-481-9757-6_1
Wear Metals in Used Motor Oil by Flame Atomic Absorption Tóth, G., Hermann, T., Da Silva, M. & Montanarella, L. (2016).
Spectroscopy. Journal of Chemical Education, 91, pp. 579–582, Heavy metals in ag-ricultural soils of the European Union with
DOI: 10.1021/ed4004832 implications for food safety. Environment International, 88,
Pawlak, Z., Urbaniak, W., Kaldonski, T. & Styp-Rekowski, M. pp. 299–309.
(2010). Energy con-servation through recycling of used oil. US Department of Energy. (2006). Used oil re-refining study to
Ecological Engineering, 36(12), pp. 1761–1764, DOI: 10.1016/j. address energy policy act of 2005, section 1838, Office of Fossil
ecoleng.2010.08.007 Energy, https://fossil.energy.gov/epact/used_oil_report.pdf
Piecuch, T., Andriyevska, L., Dąbrowski, J., Dąbrowski, T., Juraszka, Vazquez-Duhalt, R. (1989). Environmental impact of used motor oil.
B. & Kowalczyk, A. (2015). Treatment of Wastewater from Car Science of the Total Environment, 79(1), pp. 1–23.
Service Station. Rocznik Ochrona Środowiska, 17, pp. 814–832, Vwioko, D.E., Anoliefo, G.O. & Fashemi, S.D. (2006). Metal
Pinheiro, C.T., Quina, M.J. & Gando-Ferreira, L.M. (2020). concentration in plant tissues of Ricinus communis L. (Castor oil)
Management of waste lubricant oil in Europe: A circular economy grown in soil contaminated with spent lubricating oil. Journal
approach. Critical Reviews in Environmental Science and of Applied Sciences and Environmental Management, 10(3),
Technology, pp. 1–36, DOI: 10.1080/10643389.2020.1771887 pp. 127–134, DOI: 10.4314/jasem.v10i3.17331
Salem, S., Salem, A. & Babaei, A.A. (2015). Application of Iranian Wolak, A., Zając, G. & Gołębiowski, W. (2019). Determination
nano-porous Ca-bentonite for recovery of waste lubricant oil of the content of metals in used lubricating oils using AAS.
by distillation and adsorption techniques. Journal of Industrial Petroleum Science and Technology, 37(1), pp. 93–102, DOI:
and Engineering Chemistry, 23, pp. 154–162, DOI: 10.1016/j. 10.1080/10916466.2018.1511584
jiec.2014.08.009 Zając, G., Szyszlak-Bargłowicz, J., Słowik, T., Kuranc, A. & Kamińska,
Sanchez-Hernandez, A.M., Martin-Sanchez, N., Sanchez-Montero, A. (2015). Designation of Chosen Heavy Metals in Used Engine
M.J., Izquierdo, C. & Salvador, F. (2020). Different options to Oils Using the XRF Method. Polish Journal of Environmental
upgrade engine oils by gasification with steam and supercritical Studies, 24(5), pp. 2277–2283, DOI: 10.15244/pjoes/58781

Zawartość metali ciężkich w przepracowanych olejach silnikowych

w zależności od rodzaju silnika i przebiegu oleju

Streszczenie: W pracy przedstawiono wyniki analizy zawartości wybranych metali ciężkich w przepracowanych
olejach silnikowych zebranych w  warsztatach samochodowych podczas wymiany oleju. Głównym celem
przeprowadzonych badań było określenie różnicy zawartości metali ciężkich (Cr, Cu, Fe, Ni, Pb, Zn, Hg, Cd)
w zależności od typu silnika i czasu eksploatacji oleju. Analizę przeprowadzono na 80 próbkach przepracowanych
olejów silnikowych z  samochodów osobowych różnych producentów. Zawartość metali ciężkich badano
za pomocą analizatora HDMaxine, działającego w  oparciu o  fluorescencję wysokiej rozdzielczości (X-ray
Fluorescence – HDXRF). Analizując zróżnicowanie średnich zawartości badanych pierwiastków w zależności od
rodzaju silnika można stwierdzić, że w olejach pochodzących z silników o zapłonie samoczynnym następujące
pierwiastki wykazały wyższe stężenie – Cr (trzykrotnie wyższe stężenie), Fe (o  1/3 wyższe stężenie), Ni
(dwukrotnie wyższe stężenie), Pb (o ½ wyższe stężenie). Jedynie średnia zawartość Cu była wyższa (¾) w olejach
pochodzących z silników o zapłonie iskrowym. Cynk w obu przypadkach charakteryzował się porównywalnym
poziomem stężeń. Wieloczynnikowa analiza wariancji, wykazała, że w  silnikach dieslach, poziom Fe, Cr, Pb
oraz Ni jest istotnie statystycznie różny niż w referencyjnej grupie silników benzynowych. W żadnej z badanych
próbek oleju silnikowego nie oznaczono rtęci i kadmu. Uzyskane wnioski uprawniają do stwierdzenia, że istnieją
różnice w  zawartości metali ciężkich w  przepracowanych olejach w  zależności od typu silnika. Można zatem
rozważyć selektywną zbiórkę przepracowanych olejów w zależności od typu silnika co może zapewnić właściwe
postępowanie z tymi olejami i zmniejszy zagrożenie dla środowiska.