Leaf Coppin

European Ecolabels for Biodegradable Hydraulic

Oils - A Challenge to Base Material Producers and
Formulators
F. Bongardt and A. Willing Cognis Deutschland GmbH & Co. KG,
Dusseldoe Germany

Abstract
‘Ecolabels’are a means to guide the user to more environmentallyfavourable
products. With regard to lubricants, the German Blue Angel UZ-79 and the
Swedish standard SS I55434 for biodegradable hydraulic fluids are perhaps
the most important. Whereas the Blue Angel is optional, the Swedish standard
SS 155434 is a legal requirement: hydraulicfluids notfilfilling the criteria of
SS I55434 are not permitted on the Swedish market, Version 4 of SS 15.5434,
which came into effect in July 2000, introduced new and more stringent eco-
logical requirements. In view of the growing importance of the Swedish
marketfor biodegradable hydraulic oils, the authors’ company launched a re-
search programme in early 2000 with the aim of offering SS-155434-
compliant oleochemical base oils by the end of the year.
First, the effects and the plausibility of the new assessment criteriafor the
ready biodegradability of raw materials were studied. A systematic com-
parison based on chemical oxygen demand (COD) and theoretical oxygen
demand (ThOD) evaluations confirmed that unqualified reliance on the COD
parameter can lead to false positive evaluations. The studies also showed,
however, that results based on COD determined by chemical analysis are
valid, provided a suitable oxidation method is used and the completeness of
the oxidation is carefully monitored.
Moreover, it was shown that the required use of the reference parameter
ThOD does not necessarily require complicated elementary analyses of the
test substance. Even in the case of oleochemical products with indefinable
structural formulas (C-chain fractions, alkoxylated compounds), structural
estimates enabled suficiently accurate ultimate oxidation values to be cal-
culated. The studies also showed that the restriction to only two degradation
test methods is scientifically unfounded. An extension of the approved test
methods to include the scientifically accepted CO, headspace test and two-
phase closed bottle test would enable existing data to be used without
detracting from the environmental standard.

J. Synthetic Lubrication 20-1, April 2003. (20) 53 ISSN 0265-6582 $10.00 + $10.00 (2375/0403)
54 Bongardt and Willing

On the basis of more recent degradation studies, it has been shown that
synthetic esters, especially various saturated and unsaturated TMP fatty acid
esters, satisfy the stringent criteria of the new SS 155434. Supplementary
studies of low-viscosity XXX-oils (hydrocrackates)and mixtures of XXX-oils
and synthetic esters indicated that this product class could be optimised to
make it satisfy the criteria of the Swedish ecolabel.

Keywords

etolabels, hydraulic fluids, biodegradability, standards compliance, synthetic esters

INTRODUCTION

Mineral oils are traditionally used as base fluids for water-immiscible hydrau-
lic oils. Mineral oils are economic and have performed satisfactorily over a
number of decades. In recent years, however, product suitability has increas-
ingly been judged in terms of environmental compatibility as well as
performance. This applies not only to consumer products (for example, deter-
gents) but also, and increasingly, to products for industrial applications.
Hydraulic fluids, especially for mobile hydraulics, are of particular signifi-
cance in this context in view of the quantities involved and their
environmental exposure. In Germany alone, the annual consumption of hy-
draulic oils is approximately 180,000 t (estimate for 2000), of which around
50% is used for mobile hydraulics. Mobile hydraulics are unavoidably asso-
ciated with the release of hydraulic fluids into the environment, be it due to
carelessness (spillage) or technical problems (leaks, torn tubes).
How effectively the environment can deal with this contamination de-
pends largely on the ecological properties of the hydraulic fluids involved.
The decisive factors are their biodegradability and ecotoxicity. The eco-
toxicity of hydraulic oils is mainly determined by the ecotoxicity of the
additives they contain,' whereas the overall biodegradability is primarily de-
termined by the biodegradability of the base fluids.* Therefore, the goal for the
raw material supplier is to provide a broad portfolio of well-characterised base
fluids and additives, whereas the optimum combination of these components
is the core competence of the formulator.
With regard to base oils, it can be generally stated that oleochemical prod-
ucts are usually readily biodegradable in both aerobic and anaerobic
environments, and that limited biodegradability is the problem of mineral

J. Synthetic Lubrication 20-1, April 2003. (20) 54 ISSN 0265-6582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 55
material producers and formulators

Although from a technical point of view mineral oils can be easily re-
placed by appropriate biodegradable products in practically all hydraulic
applications, the significantly higher price of the ‘bioproducts’ has so far
proved a stumbling block to their rapid introduction into the market. While
Germany puts its faith in voluntary compliance with certain environmental
standards (‘Blue Angel’ ecolabel for readily biodegradable hydraulic oils4)
and thus relies on free-market forces, Sweden has elected for a more centrally
controlled approach by introducing an approval procedure for hydraulic oils.
In addition to defining the ecological requirements, both standards specify
minimum requirements for application-related properties in order to ensure
the suitability of the ecoproducts for long-term use.
Swedish standard SS 155434 regulates the technical (e.g., oxidation sta-
bility, corrosion protection), toxicological (no use of health-endangering or
allergenic substances), and ecological properties (degradability, aquatic tox-
icity) of hydraulic fluids and defines the measurement methods to be used.
Version 4, which came into force in July 2000, continues the trend towards
more stringent ecological criteria, whilst easing practice-related technical re-
quirement~.~ Changes in these latter, e.g., with regard to viscosity, air
separation, and water content, are accompanied by, in particular, changes re-
lating to the evaluation of biodegradability. The solubility properties of the
hydraulic fluids or components to be tested dictate which degradation method
will be used. If the water solubility is greater than 100 mg/l (20°C), the OECD
301 A or E methods6 are prescribed, while the biodegradability of chemical
substances with a solubility of less than 100 mg/l(20°C) must be determined
by monitoring the formation of carbon dioxide or by measuring the bio-
chemical oxygen demand (BOD). The C0,-based I S 0 9439 test7 should
preferably be used. Alternatively, the IS0 9408 test8 is acceptable, provided
theoretical oxygen demand (ThOD) is chosen as the reference value and the
test period does not exceed 28 days.
As a consequence of the restriction on the test methods that can be used
to evaluate hydraulic oils and the insistence on ThOD as the reference
parameter for BOD-based test systems, the degradation values used until now
to back up claims are no longer acceptable. This affects, for example, degra-
dation evaluations obtained with the help of the two-phase closed bottle test,’
which is especially suitable for evaluating poorly soluble test substances and
has, therefore, often been used to evaluate hydraulic fluids and their compon-
ents (e.g., in the context of their assignment to German water endangerment
categories). However, degradation evaluations carried out by means of the

J. Synthetic Lubrication 20-1, April 2003. (20)55 ISSN 0265-6582 $10.00 + $10.00
56 Bongardt and Willing

I S 0 9408 method (manometric respirometry test) specified in the Swedish

standard could also cause problems now the transition period has expired (31
December 2002), as they are usually based on ultimate oxidation values deter-
mined by chemical analysis (chemical oxygen demand; COD) rather than, as
now required, theoretical ultimate oxidation values (ThOD). In the authors’
opinion the newly defined requirements for minimum degradability cannot be
satisfied by the base oils of traditional mineral oils, and can probably only be
satisfied with difficulty by oleochemical products. In view of the technical re-
quirements, synthetic esters are practically the only candidates for use as base
oils. Anyone who wants to maintain a continued presence on the Swedish
market must face the prospect of developing new products based on such
esters. This will be a challenge to producers of raw materials and formulators.

OBJECTIVE OF THE RESEARCH

The restriction on the degradation methods and the introduction of the new
reference parameter ThOD necessitate a re-evaluation of the biodegradability
of the synthetic esters used until now in bio-hydraulic oils. In early 2000, the
authors’ company initiated a corresponding research project to find answers
to the following questions:
What consequences are to be expected from the more stringent require-
ments of the newly formulated SS 155434 standard?
Is the restriction to only two approved test methods sufficient to ensure an
objective evaluation of degradability?
Are there justifiable grounds for favouring the C0,-based IS0 9439 test?
How are past claims to be evaluated (validity of past evaluations)?
Which already available esters satisfy the requirements of the new
Swedish standard?
Are there new alternative base oils (newly developed synthetic esters,
hydrocrackates) available?
In addition, a review of the systematic study of the structure and viscosity of
key products (raw materials) was to be carried out. The aim of this study was
to find out how maximum flexibility can be achieved in terms of cost and per-
formance when products are optimised. Hydrocrackates were included in the
research project (low-viscosity XXX-oils) to allow an assessment of the
potential of this new development in admixtures with esters for the
forniulation of hydraulic oils that comply with SS 155434.

J. Synthetic Lubrication 20-1, April 2003. (20)56 ISSN 0265-6582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 57
material producers and formulators

ASSESSMENT OF ULTIMATE BIODEGRADABILITY

BOD-based test systems

Ultimate degradation tests based on the BOD parameter determine the miner-
alisation of the test substance by measuring the oxygen used during microbial
oxidation. Biodegradability is evaluated from either the ultimate oxidation
value (COD), which is determined by chemical analysis, or the theoretical
ultimate oxidation value (ThOD), calculated on the basis of the test
substance's structure. The usual test period is 28 days.

I S 0 9408: manometric respirometry test A defined volume of the

inoculated mineral medium and a known concentration of the test substance
(100 mg/l) are stirred in a closed flask at a constant temperature of 22kl"C in
the dark or in diffused light. The oxygen demand is determined by measuring
the (electrolytically generated) volume of oxygen that is needed to maintain a
constant volume of gas in the respirometer flask. The carbon dioxide formed
is absorbed by soda lime or another suitable absorbent. The test method thus
corresponds to OECD test 301 F, which is one of the five official OECD tests
for evaluating ready biodegradability.

I S 0 10708: two-phase closed bottle test' The two-phase closed bottle test
was developed on the basis of OECD 301 D (closed bottle test)." It is partic-
ularly suitable for evaluating the biodegradability of samples that are poorly
soluble in water and it enjoys wide acceptance. Evaluations based on the two-
phase closed bottle test are recognised under EU hazardous substances legis-
lation and by environmental labels such as the Blue Angel. In our own studies
we have been able to demonstrate the meaningfulness of this test and have also
shown, in a direct comparison with the especially stringent closed bottle test,
that false positive results are not to be expected."
Conical-shoulder bottles of known volume are partially filled with inocul-
ated mineral nutrient salt solution. After a one-week pre-incubation period
(I 8-22"C), the mineral nutrient medium is saturated with atmospheric oxygen
and the calculated amount of test substance (approx. 100 mg CODL) is
added. The closed bottles are agitated on a round agitator at 18-22°C and
biodegradation is determined by carrying out regular amperometric oxygen
measurements.

J. Synthetic Lubrication 2@1, April 2003. (20)57 ISSN 0265-6582$10.00 + $10.00

58 Bongardt and Willing

C02-based tests Ultimate degradation tests based on the CO, parameter de-
termine the mineralisation of the test substance by measuring the microbially
generated CO,. In order to evaluate the biodegradability of the test substance,
the amount ofCO, that would be produced if it were to be completely oxidised
is calculated from the substance’s structure. The usual test period is 28 days.
The following C0,-based tests were carried out.

I S 0 9439: CO, evolution test (Sturm test)’ This test method is similar to
OECD test 301 B, which is one of the five official OECD tests for evaluating
ready biodegradability.
The inoculated mineral nutrient salt solution, to which the test substance
(10-20 mg C L ) has been added, is incubated in a stirred aqueous test system
at 22+2”C. The CO, generated by microbial oxidation is forced into a collect-
ing vessel by a continuous stream of C0,-free air. The concentration of the
fixed CO, is determined with the help of suitable analytical detection systems
(e.g., carbon analysers).

I S 0 14593: CO, headspace test’2 The CO, headspace test, which involves
CO, evolution measurements, has been under discussion in official and indus-
trial circles across Europe as a ‘modern’ version of the official OECD 301 B
test (Sturm test). The test can be carried out more conveniently than the Sturm
test and, in the authors’ experience, is less subject to interference. The test is
gaining in popularity, is already accepted in some areas of environmental leg-
islation (EU hazardous substances legislation, Blue Angel), and has good
prospects of being included in the list of official OECD 301 tests.
The inoculated mineral nutrient salt solution, to which the test substance
(approx. 20 mg C L ) has been added, is incubated in a closed system (a 550
ml beaded-rim bottle sealed by a septum) at 22&2”C.The CO, formed by bio-
degradation is measured as carbonate in the aqueous phase. After sodium
hydroxide solution has been added and the test system has been stabilised, it
can be assumed that fixation of the CO, in the aqueous phase is complete.

RESULTS

Comparison of COD- and ThOD-based biodegradation values

When a BOD-based degradation test is carried out, it is the amount of oxygen

required to oxidise completely the test sample that needs to be known. Under

J. Synthetic Lubrication 20-1, April 2003. (20) 58 ISSN 0265-6582$10.00 + $10.00

European ecolabels for biodegradable hydraulic oils - a challenge to base 59
material producers and formulators

Table 1 Comparison of the theoretical oxygen demand (ThOD) with the

chemical oxygen demand (COD) for various chemicals
Test substance ThOD COD (KB) CODKhOD
fms 024) (mg 0247) factor
calculated from
elemental
analysis

Fatty acid ester A with trimethylolpropane 2513 2417 0.96

Fatty acid ester B with trimethylolpropane 2948 2779 0.94

Fatty acid ester C with trimethylolpropane 2967 2767* 0.93

Fatty acid ester D with trimethylolpropane 2960 2775* 0.94

Fatty acid ester E with trimethylolpropane 2635 2514* 0.95

Fatty acid ester F with trimethylolpropane 2929 2739* 0.94

Fatty acid ester G with trirnethylolpropane 2894 2242' 0.77

Fatty acid ester with pentaerythritol 2800 2243* 0.80

Fatty acid reaction products with 2765 2523* 0.91

ethanolamine, ethoxylated

Hydrocrackate XXX-A, modified mineral 3447 3264* 0.95

oil

HydrocrackateXXX-B, modified mineral 3450 3156* 0.92

oil

HydrocrackateXXX-Nester mixture I 3188 1800* 0.56

Hydrocrackate XXX-Nester mixture It 3180 1827* 0.57

HydrocrackateXXX-B/ester mixture 3443 1667* 0.48

Mineral oil derivative 3310 1997* 0.60

Hydrocrackedoil (lubricating oils, hydro- 3440 1658' 0.48

treated)

Fatty acid reaction product with 2757 1685* 0.61

aminoethyl-amino-ethanol

Oleyl-alcohol maleic-anhydridederivative 2788 222P 0.80

Fatty acids ethoxylated, reaction products 2085 2057 0.99

with epoxidised fatty acid
* After the reaction time had elapsed, signs of incomplete oxidation were observed (e.g., black flakes
in the reaction vessel).

J. Synthetic Lubrication 20-1, April 2003. (20) 59 ISSN 0265-6582$10.00 + $10.00

60 Bongardt and Willing

the current OECD guidelines this can be either the ultimate oxidation value
(COD) obtained by chemical analysis, or the ultimate oxidation value
calculated from the structure of the test substance (ThOD).
The COD can usually be determined faster and more easily, but is associ-
ated with a risk of false positive evaluations due to incomplete chemical
oxidation. In particular, samples that are poorly soluble in water or volatile
frequently yield ultimate oxidation values that are too low when their COD is
routinely determined in accordance with DIN 38409.13 More reliable COD
values can be obtained under more stringent oxidation conditions, such as
those of the Kelkenberg (KB) method.14The data shown in Table 1, however,
clearly demonstrate that complete oxidation of the test sample cannot always
be achieved even under Kelkenberg conditions. The requirement of the
Swedish standard SS 155434 that a BOD-based degradation test should only
be accepted if the ultimate oxidation value relates to the ThOD is thus
understandable.
Table 1 also shows that incomplete oxidation in the Kelkenberg method
is indicated by ‘recognisable signs’ (e.g., formation of black flakes in the re-
action vessel) and thus faulty interpretations based on too-low ultimate
oxidation values can be avoided. In all cases there would be visible signs of
incomplete oxidation at COD/ThOD ratios of less than 0.94, i.e., if no such
signs are observed after a COD determination it is safe to assume that the
COD and ThOD values correspond. This also means that the results of degra-
dation test evaluations based on ‘indication-free’ COD determinations can be
accepted without reservation.

Calculating the ThOD

When BOD tests were carried out and the COD determinations were obvious-
ly flawed, the theoretical oxygen demand was used instead. If the structure of
the test substance was known, the ThOD could be reliably estimated by carry-
ing out a calculation based on the structural formula. In the authors’
experience, the ThOD can also be reliably estimated, provided the reaction
equation is known, for products whose structural formula cannot be derived
with any certainty, e.g., oleochemical compounds with C-chain distribution
and/or ethoxylated compounds, for which only a statistical EO chain distribu-
tion is usually available. If the C-chain distribution is known, the calculation
is carried out using a structural formula with the average C-chain distribution
(e.g., C,, for palm oil with approx. 2% myristic acid, 42% palmitic acid, 5%

J. Synthetic Lubrication 20-1, April 2003. (20) 60 ISSN 0265-6582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 61
material producers and formulators

Table 2 Comparison of ultimate oxidation results from various methods

Test substance ThOD from ThOD from COD (KB)
structural elemental (mg 0247)
estimates analysis
(mg 0.M (mi7 0247)
Fatly acid ester with 2470 ~c,,H,,,o,J 2513 2417
trimethylolpropane
Fatty acid ester with 2747 2800 2243*
pentaerythritol F,,H,,o,I
* After the reaction time had elapsed, signs of incomplete oxidation were observed (e.g., black flakes
in the reaction vessel).

stearic acid, 41% oleic acid, and 10%linoleic acid) and the average degree of
ethoxylation. The reliability of COD values calculated from estimated struc-
tures can be demonstrated by using the fatty acid polyols listed in Table 2 as
an example. Although, strictly speaking, it is impossible to arrive at a definite
structure in terms of the number and amounts of reaction products, the ThOD
estimated on the basis of the initial compounds (fatty acid and alcohol) corre-
lates very well with the ThOD calculated on the basis of an elementary
analysis of the reaction product. The deviations, of less than 2%, are within
the range of analytical error.
It is therefore only necessary to carry out elementary analysis for the
purpose of calculating the ThOD if it is not possible to estimate the structure
of the reaction product or products. Structure-based ThOD estimates cost less,
especially when molecules containing hetero-atoms (e.g., N, S) are present as
well as C, H, and 0, so that the analyses have to go beyond simply
determining the C, H, and 0.

Degradation results of C0,-based vs. BOD-based tests

The Swedish standard SS 155434 recommends that the degradation of chem-

ical substances with a solubility of less than 100 mgA (20°C) should be
determined by means of the C0,-based Sturm test. As a result, BOD-based
tests tend to be regarded as less suitable, and C0,-based tests are carried out
in preference. A direct comparison of BOD- and C0,-based test systems has
shown that the latter do not necessarily yield more reliable degradation values.
Table 3 (overleaf) shows a comparison of degradation results obtained
with the BOD-based I S 0 9408 test (manometric respirometry test) and C0,-
based methods. As the number of available Sturm test results was too small to

.
ISynthetic
. Lubrication 20-1, April 2003. (20) 61 ISSN 0265-6582 $10.00 + $10.00
62 Bongardt and Willing

Table 3 Comparison of degradation results from the manometric respirometry

test and C0,-based test systems
Test substance % BOD/ThOD % CO, formation
(IS0 9408)
(28d) (28d) Test

Fatty acid complex ester with 70 59 IS0 9439

TMP

Modified mineral oil XXX-A 47 52 IS0 9439

Modified mineral oil XXX-B 57 54 I S 0 9439

Fatty acid ester with TMP 71 83 IS0 9439

C,, guerbet alcohol 36-63 79 IS0 14593

Alkyl epoxides with 10 EO 54 62 I S 0 14593

Fatty alcohol + 2 PO + 2 EO 68 60 I S 0 14593

Fatty alcohol + 3,7 EO + 7 PO 66 67-7 1 I S 0 9493

Fatty alcohol + 4,l PO + 2,3 EO 64 67 I S 0 14593

Fatty alcohol + 5 EO + 2 PO 77 68 I S 0 14593

Fatty alcohol + 5 EO + 4 PO 75 76 I S 0 14593

Fatty alcohol + 4 EO + 5 PO 63 86/89 I S 0 14593

Fatty alcohol + 3 EO + 6 PO 76 72 IS0 14593

Alkylmethyl glucarnide 63 (CSB) 85 I S 0 14593

Alkyl polyglucoside 58 (CSB) 78 IS0 9439

allow a representative evaluation, results obtained with the CO, headspace test
are also included.
The results shown in Table 3 clearly demonstrate that, with few excep-
tions, both evaluation parameters yield degradation values of the same order
of magnitude. Some unfavourable results stand out, however, especially those
obtained with the IS0 9408 test for C,, guerbet alcohol and for alkylmethyl
glucamide and alkyl polyglucoside. Other test systems have reliably demon-
strated that these compounds are readily and completely biodegradable.”
A significantly better correlation between the oxygen demand rates ob-
tained with C0,- and BOD-based test systems is observed when the
degradation values obtained in the two-phase closed bottle test are taken into
consideration (Table 4).

J. Synthetic Lubrication 20-1, April 2003. (20)62 ISSN 0265-6582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 63
material producers and formulators

Table 4 Comparison of degradationresults obtained in different BOD-based test

systems with results from C0,-based test systems
Test substance % BODflhOD % CO, formation

(28d) Test (28d) Test

Fatty acid complex ester 70 I S 0 9408 59 IS0 9439

+ trimethylolpropane 69 IS0 10708
Modified mineral oil 47 I S 0 9408 52 IS0 9439
Modified mineral oil 57 IS0 9408 54 IS0 9439
Fatty acid ester 71 IS0 9408 83 IS0 9439
+ trimethylolpropane 76 IS0 10708
C,, guerbet alcohol 36-63 IS0 9408
88 IS0 10708 79 IS0 14593
C, guerbet alcohol 64-65 IS0 10708 64 IS0 14593
Fatty acid reaction product 47 IS0 9408
+ aminoethyl-amino-ethanol 60* IS0 10708 58/63 I S 0 14593
C
,, epoxides + 10 EO 54 IS0 9408
56 IS0 10708 62 I S 0 14593
Fatty alcohol + 2 PO + 2 EO 68 IS0 9408 60 I S 0 14593
Fatty alcohol + 3,7 EO + 7 PO 66 IS0 9408 67-71 I S 0 9439
70 I S 0 10708 82-88 IS0 14593
Fatty alcohol + 4,l PO + 2,3 64 IS0 9408 67 IS0 14593
EO
0x0 alcohol + 6,3 EO + 4,9 PO 72 IS0 10708 79 I S 0 14593
Fatty alcohol + 5,5 PO + 2 EO 66 IS0 10708 63 I S 0 14593
Fatty alcohol + 5 EO + 2 PO 77 I S 0 9408
73 IS0 10708 68 I S 0 14593
Fatty alcohol + 5 EO + 4 PO 75 IS0 9408 76 I S 0 14593
Fatty alcohol + 4 EO + 5 PO 63 IS0 9408
72 IS0 10708 86/89 I S 0 14593
Fatty alcohol + 3 EO + 6 PO 76 IS0 9408
62 IS0 10708 72 I S 0 14593
Alkylmethyl glucamide 63 (CSB) IS0 9408
83 (CSB) IS0 10708 85 I S 0 14593
Alkyl polyglucoside 58 (CSB) IS0 9408 78 I S 0 9439
89 (CSB) IS0 10708 84 I S 0 14593

J. Synthetic Lubrication 20-1, April 2003. (20)63 ISSN 0265-6582$10.00 + $10.00

64 Bongardt and Willing

Table 4 clearly shows that in all those cases where the Sapromat test (IS0
9408) gave ultimate degradation rates that were too low, the two-phase closed
bottle test confirmed the results obtained using the C0,-based test systems,
and the ultimate degradation rates were not observed to be significantly higher
than the rate of formation of CO,. The inclusion of the results of the two-phase
closed bottle test reinforces the conclusion that CO, and BOD are equivalent
evaluation parameters and that the decision to accept only I S 0 9408 as a
BOD-based test system can result in under-evaluations of biodegradability.
From a scientific point of view, it would seem reasonable to augment the
approved analysis methods defined in the Swedish standard SS 155434 with
the two-phase closed bottle test in order to remove the possible need for
companies to test such substances again.

Limitations consequent upon stringent choice of approved test methods

The newly formulated requirements of the Swedish standard allow only two
test methods to be used to evaluate chemical substances with a solubility of
less than 100 mg/l (20°C). Alongside the recommended Sturm test (IS0
9493), which evaluates biodegradability on the basis of CO, evolution, only
the BOD-based manometric respirometry test (IS0 9408) is approved. Our
own studies show that in some cases this test gives ultimate degradation val-
ues that are much too low (see results for alkylmethyl glucamide, alkyl
polyglucoside, and C,, guerbet alcohol). The discrepancy relative to the C0,-
based degradation test, for which no theoretical explanation has been found,
did not occur when the two-phase closed bottle test, a degradation test that is
also based on the BOD parameter (IS0 10708),was used. In all cases in which
the manometric respirometry test gave ultimate degradation rates that were
too low, the two-phase closed bottle test gave ultimate values corresponding
to those obtained with the C0,-based test systems. A reconsideration of the
stringent restriction to only two test methods, and the approval of another
BOD test (BODIS test, I S 0 10708), would therefore seem to be called for. As
the standard CO, test ( I S 0 9439) is relatively complicated to carry out and is
also susceptible to interference (incomplete removal of CO, in the incoming
air), the approval of an additional C0,-based test system is also desirable. A
suitable test system is available in the form of the CO, headspace test (IS0
14593), which can be regarded as a simplified ‘modem’ variant of the Sturm
test.

J. Synthetic Lubrication 2@I, April 2003. (20) 64 ISSN 0265-6582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 65
material producers and formulators

Table 5 Biodegradability of different base fluids in different test systems

Test substance Chemical characterisation Biodegradability (%%)

IS0 9439 IS0 10708 IS0 9408

Edenor TMP 0 5 Fatty acid ester with TMP - 86 86

Edenor TMP 05/68 Fatty acid ester with TMP - 83 85

Edenor TMP 0 9 1 4 0 Fatty acid ester with TMP 59 69 70

Edenor TMTC Fatty acid ester with TMP 64 64 78

Edenor VP 3358 Fatty acid ester with TMP 63 73 84

Edenor VP 3345 S Fatty acid ester with TMP 83 76 71

Edenor VP 3345 Fatty acid ester with TMP - 80 61

XXX-A Hydrocracked oils 52 - 47

XXX-B/l Hydrocracked oils 60 - 57

XXX-BIZ Hydrocracked oils 61 - -

Re-evaluationof base oils

The re-evaluation of the biodegradability of base oils used in the hydraulic

sector in accordance with the more stringent requirements of the Swedish en-
vironmental standard SS 155434 confirmed the good biodegradability of the
tested synthetic esters. Complex esters are also available, for which the vis-
cosity of the products can be selectively adjusted to the relevant requirements.
The evaluation of the newly developed low-viscosity XXX-oils (hydro-
cracked oils) also yielded very promising results, although some product
optimisation is still necessary. The threshold value of 60%required to justify
a product claim was not always reliably exceeded (Table 5)
The BODIS (IS0 10708) results are listed in Table 5 for purposes of com-
parison. They confirm the good correlation between the degradation
evaluations and the results of the methods specified in the Swedish standard.
This is a further indication of the validity of the degradation evaluations
previously performed on the basis of the BODIS test.
In addition to exhibiting the required biodegradability, synthetic esters
should have a relatively high viscosity in order to facilitate maximum flexibil-
ity in product formulation. The degradation data for saturated and unsaturated
TMP fatty acid esters of different viscosities illustrate that degradability

J. Synthetic Lubrication 20-1, April 2003. (20)65 ISSN 0265-6582$10.00 + $10.00

66 Bongardt and Willing

Table 6 Dependence of the biodegradability of polyolesters on viscosity

Test substance Viscosityat Biodegradability (“’7)

40°C (mn?/s)
IS0 9439 IS0 10708 IS0 9408

Edenor VP 3345 S (saturated) 100 83 76 71

Edenor VP 3345 (saturated) 100-1 20 - 80 61

Edenor TMP 05/68 64-78 - 83 85

(unsaturated)

Edenor TMP 05/140 130-1 45 59 69 70

(unsaturated)

Edenor TMP 05/320 300-352 - 42 -

(unsaturated)

Edenor TMP 05/1000 980-1 080 - 37 -

(unsaturated)

decreases as the viscosity of the esters increases (Table 6). By selecting a suit-
able degree of viscosity, it is possible to develop an optimal product in terms
of both of the above requirements.

CONCLUSIONS

The amendments in version 4 of the Swedish standard SS 155434 represent an

intensification of the previous degradation requirements. With respect to the
requirement for BOD-based test results to be related to the theoretical ultimate
oxidation value (ThOD), these amendments are justified and will serve to
avoid false positive evaluations. The use of the DIN COD as the ultimate ox-
idation value can, however, lead to false positive degradation evaluations. In
some cases this is due to inadequate oxidation conditions and can be largely
avoided by using the Kelkenberg COD method. Whilst this method does not
always lead to the complete oxidation of the test sample that is desired, in-
complete oxidation can be optically recognised and false positive evaluations
can be avoided. In the course of our past studies of degradation, we resorted
to the ThOD in such cases. Irrespective of future acceptance, it can therefore
be assumed that earlier COD-based evaluations are reliable.
The very stringent delimitation of the approved test methods is scientific-
ally unjustifiable. A comparison of the degradation evaluation obtained with
the approved BOD- and C0,-based test methods shows that the evaluations

J. Synthetic Lubrication 20-1, April 2003. (20)66 ISSN 02656582 $10.00 + $10.00
European ecolabels for biodegradable hydraulic oils - a challenge to base 67
material producers and formulators

obtained with the only approved BOD test (IS0 9408) are sometimes too low.
To avoid false negative degradation evaluations, it would seem necessary to
approve another, more broadly applicable, BOD-based test system alongside
the manometric respirometry test (IS0 9408). The proposed two-phase closed
bottle test gives degradation evaluations that correlate well with the I S 0 9439
test favoured in the Swedish standard and is also eminently suitable for eval-
uating test samples that are poorly soluble in water. Although no such
evaluation problems have been observed when the C0,-based method (IS0
9439) approved by the Swedish standard is used, in this case as well the
approval of another test system would seem appropriate. The complex pro-
cedure and interference sensitivity of the IS0 9439 test system has led to the
development of a ‘modem’ variant (CO, headspace test/ISO 14593), which is
a suitable alternative and is already widely accepted in the context of
environmental legislation.
The re-evaluation of the biodegradability of various base oil components
in accordance with the more stringent requirements of the Swedish environ-
mental standard SS 155434 confirmed the good biodegradability of certain
ester-based oils. Alongside the traditional polyol esters, complex esters pro-
vide an interesting alternative. By varying the type and quantity of the
reactants, base oils with optimised properties can be created, which satisfy,
either on their own or in combination with the newly developed hydro-
crackates, the more stringent requirements of the Swedish standard for
biodegradable hydraulic oils.

References

1. FeSenbecker, A., RoRbrucker, T., and Korff, J., Mineraldtechnik, 44 (2000) 1-19.
2. Steber, J., Proc. 8th lnt. Coll. Trib.,ed. W.J. Bartz, Technische Akademie Esslingen, 1992,
V O ~1,.pp. 12.6.1-12.6.12.
3. Steber, J., Herold, C.-P., and Limia, J.M., Chernosphere, 31,4 (1995) 3105-18.
4. RAL Deutsches Institut fur Gutesicherungund Kennzeichnunge.V., UmweltzeichenRAL
UZ-79, January 1998.
5. Swedish standard ‘Hydraulic fluids -requirements and test methods’, SS 15 54 34.
6. Organisation for Economic Cooperation and Development (OECD), ‘Guidelines for test-
ing of chemicals, section 3: degradation and accumulation, 301 ready biodegradability’
(OECD-301 A = DOC die-away test, OECD 301 E = modified OECD screening test).
7. IS0 9439: ‘Water quality - evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium by analysis of released carbon dioxide’ (corresponds to
OECD guidelines for testing of chemicals: 301 ready biodegradability; 301 B CO,
evolution test).
8. IS0 9408: ‘Water quality - evaluation of ultimate aerobic biodegradability of organic
compounds in aqueous medium by determination of oxygen demand in a closed

J. Synthetic Lubrication 2&1, April 2003. (20)67 ISSN 0265-6582 $10.00 + $10.00
68 Bongardt and Willing

respirometer’ (corresponds to OECD guidelines for testing of chemicals: 30 1 ready biode-

gradability; 301 F manometric respirometry test).
9. IS0 10708: ‘Water quality evaluation in an aqueous medium of the ultimate aerobic bio-
degradability of organic compounds: method by determining the biochemical oxygen
demand in a two-phase closed bottle test’ (BODIS test).
10. OECD guidelines for testing of chemicals: 301 ready biodegradability; 301 D closed bottle
test.
11. Richterich, K., Berger, H., and Steber, J., ‘Two-phase closed bottle test - a suitable method
for the determination of “ready biodegradability” of poorly soluble compounds’, Chemo-
sphere, 37,2 (1998) 319-26. (OECD Ringtest BODIS (BOD test for insoluble substances)
(1988 OECD Ringtest of methods for determining ready biodegradability).)
12. I S 0 14593: ‘Water quality - evaluation in an aqueous medium of the “ultimate” aerobic
biodegradability of organic compounds - method by analysis of produced inorganic car-
bon in sealed vessels’ (CO, headspace test).
13. DIN 38409 Part 41-1, ‘Determination of the chemical oxygen demand’ (COD).
14. Variant of the IS0 method 6060 (closed system with a pressure equaliserKelkenberg
method, 2. fur Wasser und Abwasserforschung, 1975, p. 146.
15. Steber, J., et al., Tenside Suif Det., 32, 6 (1995) 515-21.

This paper was first presented at the 13th International Colloquium on Tribology, Technische
Akademie Esslingen, Germany.

.
ISynthetic
. Lubrication 20-1, April 2003. (20) 68 ISSN 0265-6582$10.00 + $10.00