Experience with evaluating biodegradability of lubricating base oils

Elz bieta Beran

Faculty of Chemistry, Wroc!aw University of Technology, Division of Fuels Chemistry and Technology, ul. Gdanska 7/9, 50-344 Wroc!aw, Poland
a r t i c l e i n f o
Article history:
Received 19 November 2007
Received in revised form
25 February 2008
Accepted 12 March 2008
Available online 1 May 2008
Keywords:
Lubricant
Base oils
Biodegradability
Standardised test methods
a b s t r a c t
Biodegradability analysis of lubricants by standardised tests provides valuable information for both
legislation purposes and assessment of how chemical structure inuences biodegradability. The choice
of an appropriate test for evaluating the ultimate biodegradability of oils raises serious problems as the
majority of lubricating base oils display a poor water solubility. The paper summarises the experience
gained and the results achieved from the evaluation of primary and ultimate biodegradability of
lubricating base oils differing in chemical structure, such as rapeseed oil, synthetic polyolester oils,
poly(a-olen) oils (PAO 4 and PAO 6) and the conventional mineral oil. Primary biodegradability was
evaluated using the CEC L-33-A-93 test. To evaluate the ultimate biodegradability of oils in an aerobic
aquatic environment, use was made of the testing methods OECD 301 B and OECD 310 for ready
biodegradability. Oils that fail to full the ready biodegradability criterion, e.g. pentaerythrite
tetra(sec-capronate) oil (polyolester with steric hindrance around the ester bonds), PAO 4, PAO 6, and
mineral oil, were evaluated for inherent biodegradability using the OECD 302 D (draft) test and the
OECD 302 B method where the test vessels were prepared via a modied procedure. The oils belonging
to this group differred in inherent biodegradability. Thus, PE tetra(sec-capronate) oil reached an extent
of biodegradation amounting to 65%, that of PAO 4 and mineral oil being equal to 48% and 38%,
respectively. Experiments have shown that ISO 14593 offers a convenient method for evaluating the
ready biodegradability of base oils according to OECD 310 and makes it possible to evaluate (with the
same apparatus and reagents) the inherent biodegradability of oils when the conditions and criteria
recommended by the OECD 302D (draft) CONCAWE test are satised.
& 2008 Elsevier Ltd. All rights reserved.
1. Introduction
Technological advance, on the one hand, and any actions as
regards environmental protection, on the other hand, have raised
public awareness of the importance of ecological information,
which makes it possible to assess the risks (and related effects)
involved with the penetration of chemical products into the
environment. Ecological information, particularly that pertaining
to the assessment of the biodegradability, ecotoxicity and bio-
accumulation of chemical substances or preparations in the
aquatic ecosystems, should be made available from paragraph
12 of the safety data sheet for chemical products. The manufac-
turer or supplier of the product has the responsibility to provide
such information in compliance with the relevant standard [1,2].
The results of biodegradability assessments are particularly
important when the chemical products enter the natural
environment during service, or due to inadequate use or
utilisation. The same holds true for lubricants [3,4]. The type,
quality and performance of lubricants depend on their main
componentsthe base oils, which account for 7580% in engine
oils and up to 99% in industrial lubricants. In sum, base oils are the
principal contributory factors in the biodegradability of lubricat-
ing materials [5,6].
What stimulates improvements in the quality and changes in
the type of the base oils being produced is not only technological
advance but also the ever increasing tendency to reduce the
environmental impact of the oils and to ensure an optimal use of
the available resources [7,8]. It is essential to note, however, that
these days approximately 75% of worlds annual base oil
production (estimated at 3738mtons) comprises conventional,
crude oil-derived mineral oils (Group I base oils according to API
classication) regarded as low-biodegradability products hazar-
dous to the environment [9]. About 15% of global base oil
production per annum includes Group II, Group II+ and Group III
oils. They all are derived from crude oil but, owing to the use of
advanced technologies, their composition and hydrocarbon
structure have been modied so they are classied as non-
conventional mineral oils. Some of these, specically low-
viscosity oils [5], display a high biodegradability potential. The
remaining 10% of worlds annual base oil production covers
poly(a-olen) oils (PAO) dened as Group IV base oils, as well as
the other synthetic base oils referred to as Group V base oils.
ARTICLE IN PRESS
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journal homepage: www.elsevier.com/locate/triboint
Tribology International
0301-679X/$ - see front matter & 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2008.03.003

Tel.: +4871320 6507; fax: +48713221580.

E-mail address: elzbieta.beran@pwr.wroc.pl
Tribology International 41 (2008) 12121218
According to the assessments reported by Murphy et al. [10],
approximately 80% of the synthetic base oil market has been
dominated by three groups of compounds: polyalphaolens (45%),
organic esters (25%) and polyalkyleneglycols (10%). It is expected,
however, that in near future there will be a rise in the
manufacture of synthetic ester base oils both in the form of
modied vegetable oils and in the form of synthetic ester oils
produced on the basis of plant and animal raw materials [7,11,12].
The increasing demand for biolubricants on the oil market is
attributable to the ecolable programme being implemented
for lubricating oils, as well as to the continuing actions under-
taken by the West-European countries with the aim to direct
public attention to the need of reducing the environmental impact
of lubricants.
It is worthnoting that every year 1315% of the oils produced
are made use of in open lubricating systems and that they will
unavoidably penetrate into the environment in the form of total
loss lubricants. That is why the application of biodegradable base
oils to the manufacture of such lubricants is taking on a sense of
importance to the control of environmental pollution. In 2004,
lubricants manufactured from synthetic ester oils (approx.
114,000tons) and vegetable oils (58,000tons) accounted for 3.6%
of the oil market in Western Europe [13]. Even if in the nearest
future the production of biolubricants increased twofold, this
would not cover the demand for total loss lubricants, whose
annual use in the European Union has been assessed at
approximately 600,000tons [14,15].
Taking into account the deciency of readily biodegradable
oils, it is necessary to make use of lubricating materials produced
from base oils that differ in their inherent biodegradability. Thus,
the general characteristics for each of the base oils produced
should specify their biodegradability (evaluated by standard tests)
in addition to their service properties. Ecological information is to
facilitate, on the one hand, the choice of optimal lubricating
materials for the applications desired, and, on the other hand, the
design of new lubricants, less hazardous to the environment as
compared to mineral oils.
The results presented further on (which have been obtained in
our research onto the biodegradability of oils classied as poorly
water-soluble organic compounds), as well as the authors own
observations, may be of support to the laboratory staff in coping
with the assessment of the ecological and service properties of
lubricants.
2. Materials and methods
2.1. Oils tested
The oils to be tested were chosen from a group of commercial
base oils and from a group of polyolester oils synthesised in
laboratories with the aim to demonstrate how the chemical
structure affects their biodegradability. According to API classi-
cation, the test oils chosen represent Group I, Group IV and Group
V base oils:
Mineral oil of viscosity grade ISO VG 32oil of SAE 10/95-type
obtained by a conventional method at the petroleum renery
Raneria Gdanska S.A.
Poly(a-olen) oils PAO 4 and PAO 6obtained in the form of
the following products: Nexbase 2004 (viscosity, 4mm
2
/s at
1001C) and Nexbase 2006 (viscosity, 6mm
2
/s at 1001C) from
Fortum Oil N.V.
Polyolester oil NYCOBASE 3118obtained in the form of
trimethylolpropane-trioleate, marketed under the brand name
TMP trioleate; a product of NYCO.
Polyolester oil PRIOLUBE 3999obtained by synthesis of
trimethylolpropane and modied fatty acids; a product of
UNIQEMA.
Rapeseed oillow-erucic rapeseed oil with oleic acid, linolic
acid, linolenic acid and other C
16
and C
18
acid structures
accounting for 63%, 19%, 7% and 11%, respectively; a product of
Z. T. Kruszwica S.A.
Polyolester oil PE tetracapronateobtained by esterication of
pentaerythrite and n-hexanoic acid [16].
Polyolester oil PE tetra(sec-capronate)obtained by esterica-
tion of pentaerythrite and 2-methyl-pentanoic acid [16].
Polyolester oils obtained via esterication of PE with carboxylic
acids (n-hexanoic or 2-methyl-pentanoic acid) of different
chemical structures are characterised by the same molecular
weight and elemental composition. There are, however, differ-
ences in the physicochemical properties of the oils, which are to
be attributed to the structure of the acids. Thus, the kinematic
viscosity at 401C amounts to 19.4mm
2
/s for PE tetracapronate
and 22.3mm
2
/s for PE tetra(sec-capronate). While planning
relevant tests, it was expected that they would show to what
degree the steric hindrance at the ester bonds might inuence the
extent of biodegradation in particular test.
2.2. Methods used for the evaluation of oil biodegradability
2.2.1. CEC L-33-A-93: primary biodegradability test
Primary biodegradability was tested according to the CEC L-33-
A-93 [17] procedure, using triplicate asks containing the test oil,
triplicate asks containing DITA as the reference substance,
duplicate poisoned asks and duplicate neutral asks, all of them
being prepared for each duration of the test (0, 7, 14 and 21 days).
The inoculum made use of in the tests was a coarse-ltered
efuent from the mechanical stage of the Wroclaw Wastewater
Treatment Plant Jano wek, with bacterial levels of 10
7
CFU/ml. IR
spectroscopic grade carbon tetrachloride (Merck) was used both
as the solvent for the test oils and reference material (DITA) and as
the extraction solvent. The maximum absorption of CH
3
and
CH
2
bonds was measured at 2930cm
1
using the BRUKER FTIR
Vector 22 spectrophotometer.
2.2.2. Ready biodegradability tests
2.2.2.1. OECD 301 B: CO
2
evolution (modied Sturm test). The oils
were tested according to the OECD 301 B [18] method (which is
similar to the ISO 9439 procedure [19]), using Erlenmeyer asks of
a 1.5dm
3
volume, which permit magnetic stirring and aeration.
Duplicate asks were used for each of the test oils, duplicate asks
for the blank test and one ask for the test with aniline as the
reference substance. The test solutions (of a concentration varying
between 30 and 40mg C/l) were obtained by direct dosing of the
test oil into the mineral salts medium with a micropipette. The
solutions were treated with 10ml portions of the inoculum pre-
pared via the route applied in CEC L-33-A-93. The CO
2
evolved
was absorbed in a 0.0125M Ba(OH)
2
solution (three bottles in
series) and CO
2
evolution was assessed by titrating the Ba(OH)
2
(with 0.05M HCl) that remained in the absorption bottles.
2.2.2.2. OECD 310: CO
2
in sealed vessels (headspace test).
Biodegradability tests were performed according to the OECD 310
[20] and ISO 14593 [21] procedures, where sealed serum bottles
(600ml in volume) containing the test solutions (of a 400ml vo-
lume) were used as test vessels for incubation. In this way, a
headspace of an air-to-liquid volume ratio of 1:2 has been ob-
tained. The test solutions (of a concentration ranging between 20
and 25mg C/l) were prepared by adding watch glasses (f 18mm)
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E. Beran / Tribology International 41 (2008) 12121218 1213
with weighed quantities of the test oils into the vessels that con-
tained the mineral salts medium. Prior to the addition of the in-
oculum, the solutions were made subject to dispersion with
ultrasounds (25kHz, 201C). The inoculum was a 1ml dose of ac-
tivated sludge (10
8
CFU/ml) collected from the aeration tank at the
Wroclaw Wastewater Treatment Plant Jano wek. The test bottles
(two items for each duration, t
x
, of the test: 7, 14, 21 and 28 days)
were incubated in the dark at 22721C, using orbital bio-shakers.
The quantity of the total inorganic carbon (TIC) produced after time
t
x
of biodegradation was calculated in terms of the CO
2
con-
centration in the headspace gas that was taken for chromato-
graphic analysis after pH adjustment (with orthophosphoric acid)
in the medium to values lower than 3. The percentage of biode-
gradation was calculated from the quantity of the TIC evolved in
the oil-containing test asks (after having subtracted the quantity
of the IC evaluated in the blank test) in relation to the theoretical
amount of inorganic carbon (ThIC) based on the amount of the test
compound added initially. Aniline was used as the reference sub-
stance for the control of the biodegradation process.
2.2.3. Inherent biodegradability tests
2.2.3.1. OECD 302 D (draft) CONCAWE test. The inherent biode-
gradability of base oils was evaluated according to the test pro-
cedure described in the draft document OECD 302D [22], making
use of the same apparatus (e.g. serum bottles, orbital shaker, gas
chromatograph for analysis of CO
2
in the headspace gas) and the
same reagents as those used in the OECD 310 test.
For the sake of compliance with the procedure of the
CONCAWE test [22,23], the following modications had to be
made in the mode of inherent biodegradability evaluation as
compared to the OECD 310 and ISO 14593 tests:
the inoculum was prepared in the form of a mixed population
of microorganisms (from soil and activated sludge collected at
the Wroclaw Wastewater Treatment Plant Jano wek), which
was pre-exposed to the test oils according to OECD 302D
(draft);
the mineral salt medium contained higher concentrations of
ammonium chloride (2.0g/l stock solution) in order to provide
a sufcient quantity of nitrogen in the medium;
the number of adequately prepared test bottles had to be
increased in order to ensure an incubation period of 56 days,
n-hexadecane and low erucic rapeseed oil were used as
reference substances for test control.
Using the ISO 14593 procedure modied in the way shown
above, inherent biodegradability evaluation was performed for the
base oils that failed to meet the ready biodegradability criterion in
the OECD 310 test.
2.2.3.2. OECD 302 B ZahnWellens/EMPA test. The method de-
scribed in OECD 302 B [24] complies with that of ISO 9888 [25]
and enables the inherent biodegradability of water-soluble or-
ganic compounds to be evaluated by analysing dissolved organic
carbon (DOC) reduction or measuring chemical oxygen demand
(COD) variations in the test solutions. Because this test was de-
signed for soluble substances, the test for poorly water-soluble
oils required the application of our own, appropriately modied
method for the preparation of the test vessels. The primary ob-
jective of the modication was to reduce the errors resulting from
the insufcient size of the samples being collected, which failed to
represent the mean concentrations of the test oils in the aqueous
dispersion.
The tests were conducted in 250ml Erlenmeyer asks, which
had been prepared for the periods (t
x
) of 3.5h (at the beginning of
the test), 7, 14, 21 and 28 days. For each period, there were
duplicate asks which contained the oil tested, one ask with
ethylene glycol as the reference substance and one blank ask.
Each ask contained 150ml of the dispersion tested (with an oil
concentration of 200mg/l), which was obtained by adding watch
glasses with weighed quantities of the test oils into the asks that
contained the mineral medium. Prior to inoculation with 10ml of
activated sludge (the same as in the OECD 310 test), the solution
was made subject to ultrasonic dispersion (25kHz, 201C) in
compliance with ISO 10634 [26]. During the test, the asks were
incubated in the dark at 20711C in a mechanical bio-shaker.
After a dened incubation time, the aqueous medium in the
ask (prepared for the test duration t
x
) underwent ultrasonic
dispersion and two samples of 50ml volume were collected for
COD determination according to the ISO 6060 method [27]. The
extent of biodegradation was calculated in terms of the mean COD
values obtained from the analysis of two simultaneously incu-
bated test asks.
3. Results and discussion
Although the biodegradability of organic substances can be
evaluated using a wide variety of testing procedures, the greatest
signicance is put to the standard tests specied in the OECD
Guidelines for the testing of chemicals and in the ISO standardised
methods [28]. The biodegradation process can be analysed under
aerobic or anaerobic conditions, in fresh water or seawater, or in
soil. In the majority of instances, biodegradability is evaluated by
analysing the aerobic biodegradability of a substance in an
aqueous medium. The principles that underlie the biodegrad-
ability evaluations in standard screening tests are depicted in
Fig. 1. The choice of an appropriate test is an essential prerequisite
for the determination of the biodegradability of lubricants [15].
The CEC L-33-A-93 test [17], for example, enables the evaluation
of primary biodegradability while the OECD test permits the
ultimate biodegradability to be assessed [29]. The OECD tests for
ready biodegradability (OECD 301 series and OECD 310) play an
important role in the environmental classication of chemicals. A
substance is considered as readily biodegradable if it has reached
a sufcient level of degradation in one of these tests, 70% in the
case of DOC removal or 60% for CO
2
or BOD. The pass-levels have
to be reached within the 28-day test period by the end of a 10-day
window, which begins when biodegradation reaches 10%. When
the substance fails to meet the ready biodegradable criterion, it
can be made subject to inherent biodegradability tests, which
are used to assess whether a substance has any potential for
biodegradation. Biodegradation rates above 20% (measured as
ThCO
2
, ThOD, DOC or COD) may be regarded as evidence of
inherent, primary biodegradability, whereas biodegradation rates
above 60% ThCO
2
, ThOD or 70% DOC or COD may be regarded as
evidence of inherent, ultimate biodegradability.
It has been widely acknowledged that the testing of lubricants
for biodegradability raises problems and trouble. The majority of
lubricating base oils are poorly water-soluble. The water-solubility
of synthetic ester oils, for instance, is lower than 1mg/l [7], and
the concentrations recommended for the substance examined in
the test solution are higher than the limit water-solubility values
for oils. What is more, lubricants generally constitute a mixture of
compounds differing in their chemical structure. That is why a
careful choice of the test for evaluating their biodegradability, as
well as the application of an additional procedure for the
preparation of the test solutions that contain the oils to be
examined, has become an issue of particular signicance [15,26].
It is essential to underline, however, that the choice of the
biodegradability test has a number of limitations. Thus, OECD
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E. Beran / Tribology International 41 (2008) 12121218 1214
301A and E, and OECD 302 A and B (Fig. 1) are based on the
analysis of reduction in DOC in the test solution; OECD 301 C and
302 C are applicable in Japan (MITI I and II). Therefore, the tests
that are of choice include four screening tests for ready
biodegradability evaluation (OECD 301 D and F, based on the
analysis of BOD/ThOD variations, as well as OECD 301 B and OECD
310, based on the analysis of CO
2
/ThCO
2
variations) and only one
screening test for the determination of inherent biodegradability,
namely the OECD 302 D draft test [22], also known as the
CONCAWE Test [23].
To evaluate the ultimate biodegradability of the set of various
oils, we made use of the OECD 301 B and OECD 310 tests alongside
with the CEC L-33-A-93 test for assessing primary biodegrad-
ability. It has been found that, compared to OECD 310, the OECD
301B procedure is a labour-consuming one (both at the stage of
preparation and the stage of test control), the laboratory setup
demands a large space, and the results suggest that the CO
2
values
are underrated (Fig. 2).
The plots in Fig. 2 illustrate the course of primary biodegrada-
tion (CEC L-33-A-93) and that of ultimate aerobic biodegradation
(OECD 301B and OECD 310). Their analysis makes it clear that of
the two polyolester oils (having the same molecular mass and
elemental composition but differing in chemical structure) only
the one characterised by the pentaerythrite tetracapronate
structure (Fig. 2, oil a) belongs to the class of readily biodegrad-
able. When use was made of the OECD 301B and OECD 310 tests,
the extent of biodegradation obtained for this oil exceeded 60% (as
determined from the CO
2
evolved during 28 days in either of the
two tests). What is more, the biodegradation plot obtained in the
OECD 310 test indicates that the oil has reached the sufcient
ARTICLE IN PRESS
Biochemical oxygen demand related to
theoretical oxygen demand for total
mineralisation (BOD/ThOD)
*OECD 301D: Closed Bottle Test
*OECD 301F: Manometric
Respirometry Test
OECD 301C: Modified MITI Test (I)
intermediate
products
A B C D
organic
substance
new
biomass
mineralisation products
CO
2
+ H
2
O
inorganic salts
Primary biodegradation: microorganisms-induced alteration
in the chemical structure of the substance resulting in the
loss of a specific property. CEC L-33-A-93 test for lubricants
microorganisms
(N, P)
H
2
O, O
2 H
2
O, O
2
microorganisms
Reduction
in dissolved organic carbon (DOC)
OECD 301A: DOC Die-Away-Test
OECD 301E: Modified OECD
Screening Test
Measured quantity of CO
2
evolved
related to theoretical quantity of CO
2
evolved for total mineralisation
(CO
2
/ThCO
2
)
*OECD 301B: CO
2
Evolution Test
*OECD 310: CO
2
in Sealed Vessels
(Headspace Test)
OECD 302A : Modified SCAS Test
OECD 302B: Zahn-Wellens/EMPA Test
OECD 302C: Modified MITI Test (II)
*OECD 302D (draft):
CONCAWE Test
TEST METHODS FOR EVALUATION OF ULTIMATE BIODEGRADABILITY
Ready biodegradability tests
Inherent biodegradability tests
in aerobic aquatic environment
Fig. 1. Principles of evaluating the biodegradability of organic substances in aerobic aquatic media by means of screening tests [29].
*
Tests recommended for evaluating the
biodegradability of poorly water-soluble substances (including lubricating oils).
E. Beran / Tribology International 41 (2008) 12121218 1215
level of biodegradation within the time of the so-called 10-day
window. The fact that the oil failed to meet this criterion in the
OECD 301B test suggests an underestimation of the CO
2
evolved.
This is because CO
2
is trapped and determined outside of the
system. Seemingly, the large volume of the asks in the OECD 301
B test, an insufcient stirring of the solution and the sophistica-
tion of the testing system have contributed to the persistence of
some CO
2
portions in the test vessels and solutions [30]. It is
worthy to note that this does not occur when use is made of the
OECD 310 test, which seems to be better suited for determining
the ultimate aerobic biodegradation of poorly water-soluble
substances.
Polyolester oil of a pentaerythrite tetra(sec-capronate) struc-
ture cannot be classied as readily biodegradable since none of
the tests performed provided the desired extent of biodegradation
(exceeding 60%) during 28 days (Fig. 2, oil b). This oil exhibits
steric hindrance around the ester bonds, which is attributable to
the use of the branched 2-methyl-pentanoic (i.e. sec-caproic) acid
for its synthesis. The comparison of the biodegradation curves
presented in Fig. 2 clearly shows that the steric hindrance around
the ester bonds exerts an inhibiting effect on the initial stage of
ester oil biodegradation, which involves enzymatic hydrolysis of
the ester bonds and then is followed by the stage of b-oxidation of
carboxylic acids leading to their ultimate biodegradation. Litera-
ture data have shown that the extent of primary biodegradation of
synthetic ester uids is higher than the extent of ultimate
biodegradation and that the differences can result from the
chemical structure of esters [6,9].
In the case of PE tetra(sec-capronate) (Fig. 2, oil b), ultimate
biodegradability was unexpectedly found to be higher than
primary biodegradability. Primary biodegradability was expressed
in % as the difference in residual oil content between the poisoned
ask and respective test asks (according to the CEC test). An
abiotic degradation (which reached 20%) was observed in the
poisoned asks. Thus, chemical hydrolysis can support the process
of biological degradation of PE tetra(sec-capronate) oil and can be
responsible for the higher extent of ultimate than of primary
biodegradation. And so we see that, contrary to the common belief
that ester oils are readily biodegradable, it has to be agreed that
their biodegradability may noticeably vary from one ester oil to
another according to their chemical structure.
The oils that failed to meet the ready biodegradability criterion
were subjected to the CONCAWE test [22] in order to assess their
inherent biodegradability. For the purpose of comparison, some of
the oils were tested using OECD 302 B [24] alongside a procedure
modied at our laboratory. The fact that aqueous dispersions of
lubricating oil were used instead of real water solutions has been
taken into account.
The method was standardised using model aqueous systems of
water-soluble substances (ethylene glycol, pentaerythritol and
caproic acid) and aqueous systems applied as dispersions of
poorly water-soluble substances (pentaerythrite tetracapronate,
di-isotridecyl adipate, TMP trioleate, PAO 4 oil and mineral base
oil). Thus, the solutions were homogenised by ultrasonic disper-
sion in order to minimise the effect of the hydrophobic oil
properties manifesting in the adsorption of oil droplets on the
vessel walls and in the formation of agglomerates on the surfaces
of the aqueous dispersions.
In order to verify the dosing concentrations of base oils
(200mg/l) in the aqueous systems (of 150ml volume), the study
was conducted with the most popular analytical techniques for
COD measurement, namely the miniaturised instrumental Hach
Dichromate COD Method 8000, approved by US EPA [31], and the
ISO 6060 method [27] using conventional COD determination by
titration. The results obtained are summarised in Table 1. The
comparison of the mean COD values (obtained for the substance
tested) with the ThOD value (calculated in terms of the molecular
formula and reaction stoichiometry) shows the efciency
ARTICLE IN PRESS
0
10
20
30
40
50
60
70
80
90
100
0
Time [days]
B
i
o
d
e
g
r
a
d
a
t
i
o
n

[
%
]
OECD 301B test
OECD 310 test
CEC L-33-A-93 test
oil (a)
oil (b)
28 21 14 7
Fig. 2. Extent of biodegradation related to time, obtained with different tests for
two polyolester oils: PE tetracapronate oil (a) and PE tetra(sec-capronate) oil (b).
Table 1
Comparison of ThOD with COD determined for model aqueous systems of water-soluble and poorly water-soluble substances by two analytical methods
Test substance and molecular formula ThOD
a
(g O
2
/g) COD
c
determined according to Hachs method COD
d
determined according to ISO 6060
Mean value (7s. d.)
b
(gO
2
/g) COD/ThOD (%) Mean value (7s. d.)
b
(gO
2
/g) COD/ThOD (%)
Ethylene glycol C
2
H
6
O
2
1.290 1.277 (70.014) 99 1.280 (70.012) 99
Pentaerythritol (PE) C
5
H
12
O
4
1.412 1.403 (70.012) 99 1.398 (70.016) 99
Caproic acid C
6
H
12
O
2
2.207 2.170 (70.092) 98 2.162 (70.083) 98
Pentaerythrite tetracapronate C
29
H
52
O
8
2.303 1.313 (70.362) 57 2.285 (70.193) 99
DITA, di-isotridecyl adipate C
32
H
62
O
4
2.855 1.613 (70.311) 56 2.626 (70.279) 92
TMP trioleate C
60
H
110
O
6
2.920 1.606 (70.436) 55 2.745 (70.080) 94
PAO 4 C
29,2
H
59,6
3.442 1.893 (70.268) 55 3.166 (70.206) 92
Mineral oil C
28
H
52
3.381 1.961 (70.339) 58 3.077 (70.170) 91
a
ThOD calculated from molecular formula.
b
7s. d.: standard deviation (n 6).
c
COD measured by analysing small-sized samples of test solution (1.33% v/v).
d
COD measured by analysing large-sized samples of test solution (33% v/v).
E. Beran / Tribology International 41 (2008) 12121218 1216
(expressed as COD/ThOD (%)) with which the content of the test
substance in the aqueous system was evaluated.
The data in Table 1 make it clear that in the case of water-
soluble substances the two analytical techniques produce com-
parable COD values and low standard deviations. The comparison
of the COD/ThOD ratios shows that the efciency of assessing the
content of the test substances in water solutions with both the
methods is very high (9899%).
The application of Hachs method to oil samples displaying
hydrophobic properties has produced COD/ThOD ratios below
60%. The COD values determined (too low as compared to those of
ThOD), as well as the high standard deviations, disclose consider-
able errors in the assessment of dispersed model solutions. What
should be blamed for those errors is the fact that the samples
collected for the analysis of COD in model aqueous systems
containing poorly water-soluble substances were very small in
size (1.33% v/v), so they fail to represent the real concentrations of
the substance tested, the most likely cause being the hetero-
geneity of dispersion.
More representative were the samples of lubricating oil
dispersion collected for the evaluation of COD by the ISO 6060
method, where the size of the model solution sample for analysis
approached 33%v/v. The agreement between the COD values
established via this route and the ThOD values exceeded 90%.
These results have prompted us to evaluate the inherent
biodegradability of lubricating oils by making use of the OECD
302 B Zahn-Wellens/EMPA Test, where the test vessels were
prepared via a modied procedure based on our own concept.
Fig. 3 shows the biodegradation curves obtained for PE
tetra(sec-capronate) oil, PAO 4 oil and conventional mineral oil.
Subjected to the ready biodegradability test, the oils have not
achieved the required extent of biodegradation (460% ThCO
2
). In
this context, they had to be assessed (in compliance with the
OECD guidelines) for inherent biodegradability using the OECD
302 test. As can be inferred from the test results (Fig. 3), the PE
tetra(sec-capronate) oil may be regarded as having an inherent
ability to undergo ultimate biodegradation under aerobic condi-
tions (the criterion of a biodegradability higher than 60% has been
fullled) although it cannot be classied as readily biodegradable.
The other oils are to be classied as having an inherent ability to
undergo primary biodegradation (the criterion of biodegradability
exceeding 20% has been satised). As for the PAO 4 oil, no plateau
phase was achieved after 56 days, which suggests that the extent
of ultimate biodegradation will be substantially higher if the
duration of the test is extended. A similar rise in the extent of
primary biodegradation determined for PAO 4 and PAO 8 during
the time-extended CEC L-33-T-82 test has been reported by
Carpenter [32].
Comparing the results of the OECD 302D (draft) test with those
of the OECD 302B test we can assume that the OECD 302D (draft)
test has produced more reliable results since it has been designed
for poorly water-soluble substances, such as lubricating base oils.
It should, however, be stressed that although the OECD 302D
(draft) test [22] for inherent biodegradability and the OECD 310
test [20] for ready biodegradability involve the same procedure of
the ISO 14593 test [21], they obviously differ in the conditions of
incubation and in the principle that underlies the interpretation of
the results obtained.
Finally, the whole set of the oils tested was examined. The
results obtained from assessing the primary and ultimate
biodegradability of these oils are depicted in Fig. 4. As shown by
the bars, rapeseed oil, polyolester oils NYCOBASE 3118 and
PRIOLUBE 3999, and PE tetracapronate can be classied as readily
biodegradable substances whereas the other oils differ in their
inherent biodegradability and can be ordered as follows: PE
tetra(sec-capronate)4PAO 44PAO 6 and mineral oil ISO VG 32.
The results visualised in Fig. 4 make it clear that the CEC test fails
to reveal the relationship between chemical structure and
biodegradability in the case of readily biodegradable ester oils.
The OECD 310 (ISO 14593) test discloses the effect of chemical
structure on the biodegradability of the oil, as can be inferred
from the lowest ultimate biodegradability value for PRIOLUBE
3999, which is attributable to the branching in the structure of the
acid residue in the polyolester molecule.
As for the oils that are not classied as readily biodegradable
(e.g. oils 58 in Fig. 4), the determination of their inherent
biodegradability provides the data needed for the assessment of
the potential environmental impact, as well as for the optimal
choice of the base oils for the manufacture of lubricants that are to
be used in devices operated in protected areas.
4. Conclusions
Evaluation of the biodegradability of lubricating oils by
standard screening tests provides information that is useful to
legislators but primarily to the staff of research laboratories
helping them to acquire a better knowledge of how the chemical
structure inuences the biodegradability of lubricants.
The choice of an appropriate standard test for the evaluation of
ultimate biodegradability is troublesome since the majority of
lubricating base oils do not dissolve in water. The ISO 14593 test is
ARTICLE IN PRESS
0
10
20
30
40
50
60
70
80
90
100
0
Time [days]
B
i
o
d
e
g
r
a
d
a
t
i
o
n

[
%
]
oil( b) OECD 302B test oil (b) OECD 302D draft test
oil (c) OECD 302B test oil (c) OECD 302D draft test
oil (d) OECD 302B test oil (d) OECD 302D draft test
28 days with OECD 302B test
56 49 42 35 28 21 14 7
56 days with OECD 302D draft test
Fig. 3. Extent of biodegradation related to time, obtained with two inherent
biodegradability tests (OECD 302B and OECD 302D draft) for three base oils: PE
tetra(sec-capronate) oil (b), conventional mineral oil (c) and PAO 4 oil (d).
0
10
20
30
40
50
60
70
80
90
100
1
B
i
o
d
e
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a
d
a
b
i
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i
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y

[
%
]
CEC L-33-A-93 test
OECD 310 test
OECD 302D (draft) test
readily biodegradable oils
oils differing in potential
inherent biodegradability
8 7 6 5 4 3 2
Fig. 4. Biodegradability of lubricating base oils differing in chemical structure:
rapeseed oil (1), NYCOBASE 3118 oil (2), PRIOLUBE 3999 oil (3), PE tetracapronate
oil (4), PE tetra(sec-capronate) oil (5), PAO 4 oil (6), PAO 6 oil (7) and conventional
mineral oil ISO VG 32 (8). The tests in the left-hand panel were repeated three
times; the tests in the right-hand panel were repeated three times (CEC and OECD
302D) or twice (OECD 310).
E. Beran / Tribology International 41 (2008) 12121218 1217
a useful tool of practical signicance to the staff of research
laboratories where lubricants are extensively tested for their
ecological and service properties. The procedure of the ISO 14593
test, combined with the consideration of the conditions and
criteria made use of in the OECD 310 testing method, permits the
ready biodegradability of the oils to be evaluated. Using the same
apparatus and reagents, and taking into account the conditions
and criteria of the OECD 302D (draft) testing method, it is possible
to assess the inherent biodegradability of the oils.
As more than 95% of the base oils applied to the manufacture of
lubricants fail to meet the ready biodegradability criterion, the
determination of their inherent biodegradability may be of great
practical importance to the designers of new lubricating materials.
Acknowledgement
This work was supported by the Polish Ministry of Science and
Higher Education under Grant N205 072 32/4249.
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