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Übersichtsbeiträge/Reviews

Oleochemical esters – environmentally compatible raw


materials for oils and lubricants from renewable resources*
Andreas Willing1

Due to the increasing market relevance of environmentally labelled Oleochemische Ester – umweltverträgliches Ausgangsmaterial
products, the ecological properties of oleochemical esters have been für Öle und Schmierstoffe aus nachwachsenden Rohstoffen.
intensively studied within the last couple of years. In general, their Die Öffentlichkeit ist heutzutage in Fragen des Umweltschutzes sehr
aquatic toxicity is very low or almost negligible, and they are readily sensibel, und die Verbraucher (insbesondere auch die industriellen
biodegradable in most cases. They have not to be labelled as “danger- Kunden) verlangen zunehmend Produkte mit entsprechend günstigen
ous for the environment” according to the EU Dangerous Substance Umweltkennzeichnungen. Vor diesem Hintergrund sind die ökolo-
Directive. Their origin from renewable resources results in lower net gischen Eigenschaften oleochemischer Ester (d. h. synthetische Ester,
CO2-emissions (”global warming”) compared to petrochemical prod- deren Säure- und/oder Alkoholkomponenten aus nachwachsenden
ucts. Not many lubricants have such rather positive ecological profiles. Rohstoffen wie tierischen oder pflanzlichen Ölen und Fetten stammen)
Thus, most of them are classified in the most favourable water hazard in den letzten Jahren eingehend untersucht worden. Dabei zeigte sich,
class, i.e. in WGK 0. In addition, they fulfill the requirements of daß oleochemische Ester für Wasserorganismen weitgehend untoxisch
several European environmental labels, e.g. “Blauer Engel”. These und unter Umweltbedingungen (sowohl im Boden als auch im Wasser)
favourable ecological properties together with their well established schnell und leicht biologisch abbaubar sind. Ihre gute biologische Ab-
technical performance recommend the oleochemical esters as suitable baubarkeit und die Tatsache, daß sie aus nachwachsenden Rohstoffen
base oils for the development of high performance “green” oil and stammen (Verminderung der CO2-Emission und des Beitrags zum
lubricant products. „Treibhauseffekt“), zeichnen die oleochemischen Ester dabei gegen-
über vergleichbaren Mineralölprodukten aus. Aufgrund ihrer guten
ökologischen Eigenschaften sind oleochemische Ester nicht als „um-
weltgefährlich“ (gemäß der 1994 in Kraft getretenen 4. Novelle der Ge-
fahrstoffverordnung) zu kennzeichnen. Hinsichtlich der in Deutschland
besonders wichtigen Einstufung in Wassergefährdungsklassen sind die
meisten oleochemischen Ester in die günstigste Wassergefährdungs-
klasse (d. h. WGK 0, im allgemeinen nicht wassergefährdend) einge-
stuft. Ferner erfüllen die oleochemischen Ester i.d.R. die Anforderun-
gen verschiedener Umweltzeichen für besonders umweltverträgliche
Schmierstoffprodukte, wie des in Deutschland gebräuchlichen „Blauen
Engels“. Ihre hervorragenden ökologischen und anwendungstechni-
schen Eigenschaften machen oleochemische Ester somit in idealer Wei-
se als Rohstoffe für die Entwicklung von Hochleistungsschmierstoffen
für die verschiedenen industriellen Anwendungsbereiche geeignet.

1 Introduction chemical esters originating from renewable resources gives


them an ecological advantage over comparable products
Today the general public is quite sensitive for environ- from petrochemical origin. With regard to the German Water
mental issues, and consumers (including industrial cus- Hazard Class (“Wassergefährdungsklasse”, WGK) most of
tomers) demand environmentally compatible oil and lubri- them are classified as WGK 0 (“in general not water pollut-
cant products with a good technical performance at a reason- ing”). According to the forthcoming WGK classification
able price. Whereas mineral oil based products can fulfill the scheme – the so-called “R-phrase”2 concept –, which cur-
last two criteria quite well, they are less favourable from an rently is under development by the German authorities, oleo-
ecological point of view. Oleochemical esters (i. e. synthetic chemical esters could even become non-classified due to
esters derived from renewable resources like natural fats and their non-water polluting properties. These favourable eco-
oils) could be a “green” alternative, exhibiting very good or logical properties, together with their well established tech-
even superior technical performance combined with very nical performance, make oleochemical esters ideally suited
favourable ecological properties. These properties have been as raw materials for the development of ecologically superi-
thoroughly studied over the last couple of years. The studies or high performance lubricants for many different industrial
show that oleochemical esters are easily biodegradable in and automotive applications, e.g. hydraulic oils, metal work-
soil and in the aquatic environment, and that they have a low ing fluids, and gear oils (Fig. 1). This article gives an over-
aquatic toxicity. The excellent biodegradability of the oleo- view about the physico-chemical and ecological properties

1 Henkel KGaA, Düsseldorf, Germany.

* Paper presented at the 52nd International Congress and Expo of the 2 R-phrase refers to the risk phrases of the EU Dangerous Substance
DGF, September 13–15, 1998, Magdeburg, Germany. Directive, e. g. R-22, harmful if swallowed.

192 Fett/Lipid 101 (1999), Nr. 6, S. 192–198 © WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0931-5985/99/0606-0192$17.50+.50/0
price compared to mineral oil based products. Although all
members of the above-mentioned groups have some physico-
chemical characteristics in common (low water solubility,
low vapour pressure), additional structural features have a
significant influence on their physico-chemical and technical
properties. Polyol esters are more heat stable than glycerol
esters due to the presence of a quarternary carbon atom. The
presence of double bonds, on the other hand, makes the
esters susceptible to oxidation and reduces their temperature
stability. Branched alkyl chains of the alcohol component
improve the low temperature properties and the hydrolytic
stability of the molecules, but reduce their viscosity index.
Thus, the different oleochemical esters have different techni-
Fig. 1. Field of technical application of oleochemical esters. cal properties, and some of the desirable properties do indeed
exclude each other. However, referring to the know-how of
of oleochemical esters, and focusses on the environmental research and development (R&D) and application experts,
compatibility and classification of the different groups of the for almost all applications a suited oleochemical ester can be
oleochemical esters. selected from the great variety of existing structures.

2 Structure and Physico-Chemical 3 Ecological Assessment of


Properties of Oleochemical Esters Oleochemical Esters – Basic Aspects
The structure of oleochemical esters is characterized by The intention of an ecological (risk)assessment is to
one or more carbon ester bonds in the molecule and by alkyl answer the question, if the use of the substance under con-
chains originating from oils and fats, i.e. the energy storage sideration is environmentally compatible or not. Therefore,
molecules of plants and animals. A typical animal fat is any ecological assessment has to cover the following two
tallow (less common fish oil). Plant oils are mainly produced aspects: the inherent ecotoxicological properties of a sub-
from coconuts, palm, and palm kernel, rapeseed, soy bean, stance (hazard) and the environmental fate of the substance
and sunflowers. Due to their biochemical synthesis the cor- (exposure scenario). A comprehensive discussion of the
responding fatty acids and their derivatives (e.g. the fatty systematics of an ecological safety assessment can be found
alcohols) have even numbered, linear alkyl chains, ranging in [2].
from 8 to 22 carbon atoms (C8–C22). The specific structure
of their alkyl chains determines to a great extent the physico- 3.1 Ecotoxicity
chemical as well as the ecological properties of the oleo- Ecotoxicity data describe the toxic effects of chemicals on
chemical esters, especially their biodegradability. From a organisms in the environment. Because it is not feasible to
chemist’s point of view, oleochemical esters can be divided investigate all the different wildlife species in the laboratory,
into four groups (Fig. 2). it has generally been agreed to evaluate the ecotoxicity of a
The physico-chemical properties of oleochemical esters substance by testing only certain standard species, represent-
can cover the complete spectrum of technical requirements ing the different levels of the natural food chain (Fig. 3). For
for the development of high-performance industrial oils and the aquatic compartment the fish, daphnia, algae, and bacte-
lubricants (e. g. excellent lubricating properties, good heat ria are the most relevant test organisms, and standardized test
stability, high viscosity index, low volatility, and superior methods, such as laid down for example in the OECD
shear stability). For a comprehensive review of their techni- “Green pages”, i.e. OECD methods 201-210 [3], have been
cal properties see [1]. A drawback, however, is their higher established for these end points (Tab. 1). The ecotoxicologi-
cal tests can be divided into two groups: acute tests investi-
gate the effects of high concentrations of chemicals during a
relatively short time of exposure (determination of lethality
= LC50-value or of other relevant effects = EC50-value),
whereas subchronic and chronic tests investigate long-term
effects at sublethal concentrations (determination of the No
Observed Effect Concentration = NOEC). The environmen-
tal classification of substances is usually based on data from
acute tests. If a substance is readily biodegradable and acute

Tab. 1. Standard ecotoxicity tests.

Type Test organism Test method


Acute tests Algae OECD 201
Daphnia OECD 202/1
Fish OECD 203
Bacteria OECD 209
Chronic tests Daphnia OECD 202/2
Fish OECD 204
Fig. 2. Structure of the different types of oleochemical esters.

Fett/Lipid 101 (1999), Nr. 6, S. 192–198 193


Fig. 3. Scheme of the aquatic food chain indicating the
different trophic levels for ecotoxicity testing.

test data do not indicate an increased ecotoxicity, there is


generally no need to conduct the more costly chronic tests.
On the other hand, for high volume chemicals, that are
forseen to be quantitatively discharged into the waste water
(like e.g. detergent components), determination of chronic
data is necessary to conduct a reliable risk assessment.
3.2 Environmental fate
The most important aspect with regard to the environ-
mental fate of a substance is its biodegradability. Biodegrad-
ability means that a substance is susceptible to biochemical
breakdown by the action of microorganisms (Fig. 4). The
first breakdown step (i. e. the disappearance of the original
molecule) is called primary degradation. Determination of
primary degradability is of main relevance for surfactants Fig. 4. Primary and ultimate biodegradation of organic substances.
due to specific legal requirements (detergent law). Of con-
siderably more general importance is the determination of
the ultimate degradability (mineralization) of substances to ability (Tab. 2). They are laid down for example in the
CO2 and H2O (and, at the same time, the formation of bio- OECD “Yellow pages”, i. e. OECD methods 301 A-F [3], or
mass). A very special test is the so-called CEC test, original- ISO standard methods, e. g. ISO 10707 and 10708. Sub-
ly developed for two-stroke engine oils, because it does not stances surpassing the biodegradation limiting values for
clearly differentiate between primary and ultimate degrada- “ready biodegradability” in these tests (i. e. 60% of CO2-evo-
tion [4]. Nowadays the CEC test is of relevance only for the lution or oxygen consumption (BOD/COD) or 70% removal
German environmental label “Blauer Engel”, but will be re- of dissolved organic carbon (DOC), and fulfilling the 10-day
placed in the near future by tests for true ultimate biodegrad- time window criteria) are regarded as fast and ultimately
ability. Ultimate biodegradability guarantees the safe reinte- biodegradable in the environment. The evaluation if a sub-
gration of the organic material in the natural carbon cycle. stance is readily biodegradable or not is very important for
Simple but rather stringent standardized test methods have its environmental classification, and the determination of its
been established for the investigation of ultimate biodegrad- water hazard class. For some applications, e. g. drilling fluids
for off-shore oil production, also degradability under anaer-
obic conditions, as encountered on the seafloor, is highly
Tab. 2. Standard screening tests for ready biodegradability. desirable. In addition to biodegradability, bioaccumulation
behaviour (i.e. the potential of a chemical to concentrate in
Type Species Parameter* Method animal tissues) is also important with regard to the evalua-
“official” DDAT DOC OECD 301 A tion of a possible long-lasting adverse impact to biota3.
screening Sturm test CO2 OECD 301 B However, the ester linkage of the oleochemical esters is sus-
tests MITI test DOC OECD 301 C ceptible to enzymatic cleavage, and the liberated natural fat-
Closed Bottle test BOD/COD OECD 301 D ty acid and alcohol components can be metabolized. There-
MOST DOC OECD 301 E fore, oleochemical esters are not expected to bioaccumulate
Manometric BOD/COD OECD 301 F
Respirometry test in biota despite of their log Pow4 >> 3.

other screening BODIS test BOD/COD ISO 10708


tests CO2-Headspace test CO2 ISO 14593
* The limiting value for ready biodegradability is 60% (BOD/COD or 3 biota = all living organisms, i.e. animals, plants and microorganisms.
CO2) and 70% (DOC), respectively, within 10 days after the onset of 4 Pow = partition coefficient of a substance between an octanol and a
degradation. water phase.

194 Fett/Lipid 101 (1999), Nr. 6, S. 192–198


oleochemical esters) is not trivial. However, the problems
associated have been overlooked for a long time. Testing of
poorly watersoluble substances requires special knowledge
and experimental skills. The first difficulty is to get the
necessary information about the water solubility of a test
substance. Usually water solubilities are not determined very
precisely (e.g. in mg/l). Instead, verbal descriptions are
given in the Safety Data Sheet like “insoluble” or “of low
solubility”. Whereas the statement “insoluble” could still
mean a solubility of 0.1% (i. e. of 1,000 mg/l), determination
of the real water solubility of substances described as “of
low solubility” could yield values in the range of < 20 µg/l.
Thus, if there is any uncertainty about the water solubility of
a test substance it is advisable to determine this parameter
experimentally or, in the case of degradation tests, determine
Fig. 5. Elements of an ecological risk assessment. at least the TOC/DOC ratio (total organic carbon/dissolved
organic carbon). Whereas it is rather trivial that degradation
tests, which are analytically based on the DOC-parameter,
3.3 Ecological risk assessment are not suitable for the investigation of insoluble substances,
Ecotoxicity as well as biodegradability tests determine the the proper choice between the other available test systems is
environmentally relevant substance-inherent properties of not easy. The situation is even more complicated with re-
chemicals and do not include the aspect “exposure”. Thus, spect to ecotoxicity testing. Especially the determination of
the fact that a substance is toxic to aquatic organisms or that EC50-values for algae and daphnia can be biased by insolu-
it is poorly biodegradable does not per se mean that this sub- ble portions of the test substance floating on the surface of
stance actually exerts adverse effects to the environment. To the test media. If these small test organisms get to the sur-
address this question a risk assessment has to be conducted. face, they can be physically trapped in the organic layer. This
A schematic view of the elements of an ecological risk phenomenon is in fact hardly distinguishable from immobi-
assessment is shown in Fig. 5. Very generally speaking, an lization caused by systemic toxicity of the test substance.
ecological risk assessment simply compares the predicted Thus, an overestimation of the toxicity may be the result.
environmental concentration (PEC) of the chemical under To avoid such misleading results industry and the German
consideration with the predicted ecotoxicological limit con- Environmental Protection Agency (UBA) have agreed on a
centration (PNEC) that is expected to be tolerated even by special test protocol for water insoluble substances (Fig. 6).
the most sensitive aquatic organisms without adverse effects. It is based on testing of Water Accommodated Fractions
If the quotient PEC/PNEC is lower than 1, the use of such a (WAF). WAFs are prepared by stirring the test substance for
substance is considered to be environmentally compatible. at least 24 h in water, and subsequently removing the insolu-
ble portions by an appropriate method, e.g. by filtration. If it
has been shown that WAFs up to a loading of 100 mg/l are
4 Testing of Water-Insoluble Substances not toxic, an EC50 > 100 mg/l can be used for environmental
classification. However, with regard to WGK 0 it has to be
The experimental investigation and the assessment of the shown that even up to a loading of 10,000 mg/l the resulting
ecological properties of water-insoluble substances (like WAF is not toxic.

Fig. 6. Scheme for testing and evaluating


water-insoluble substances.

Fett/Lipid 101 (1999), Nr. 6, S. 192–198 195


5 Ecological Properties of classified as WGK 0 by the Commission for the Evaluation
Oleochemical Esters of Water Polluting Substances (KBwS).
5.3 Polyol esters
5.1 Fatty acid esters
Polyol esters consist of multifunctional synthetic alcohols
The common fatty acid esters for lubricants consist of esterified with long-chain linear fatty acids of 8 to 18 carbon
long-chain linear fatty acids of 8 to 18 carbon atoms (from atoms (of plant or animal origin). In contrast to glycerol,
plant or animal feedstock), that are esterified with short to which is devoid of a quarternary carbon atom, the synthetic
medium-chain length synthetic (mainly branched) alcohols polyol esters contain at least one quarternary carbon atom,
of 4 to 13 carbon atoms. Against fish and bacteria these which improves the chemical stability of the molecule.
mono esters are only scarcely or not toxic (LC50-values in This increased stability is reflected by the slightly reduced
the range of 1,000–10,000 mg/l), certainly due to their very degradation rates compared to the glycerol esters (Tab. 4).
low water solubility (Tab. 3). In the 301 A–F OECD tests for However, polyol esters are still readily biodegradable, and
ready biodegradability, or comparable stringent ISO tests reach sufficiently high degradation rates even in degradation
(e.g. the BODIS-test, Biological Oxygen Demand of Insol- tests with reduced bacterial inoculum (i.e. surface-water
uble Substances, ISO 10708), they exhibit high degradation conditions, as required for a WGK 0 classification). Like
rates, generally exceeding the level for ready biodegradabil- glycerol esters, polyol esters are almost not toxic for aquatic
ity (Tab. 4). This result might be a surprise for those expect- organisms (Tab. 3). Because of their great economic im-
ing poor biodegradability of insoluble substances. Although portance due to their excellent technical performance, the
degradation of water insoluble substances is, compared to ecological properties of these substances have been exten-
homogeneously distributed soluble substances, certainly sively investigated (i. e. data for additional aquatic species
rendered more difficult due to the limited bioavailability of like algae and/or chronic toxicity studies are available,
the test substance, these results show that biodegradability is too). On the basis of these data the polyol esters certainly
mainly determined by chemical structure and less by water qualify for WGK 0, even with regard to the aggravated
solubility. Mineral oils are degraded under these conditions requirements of the latest amendment of the corresponding
to only 20–50% BOD/COD, i.e. they cannot be regarded as administrative regulation (VwVwS) of April 18, 1996 (see
readily biodegradable. Fatty acid esters are classified in below) [6].
WGK 0, whereas mineral oil, due to its limited biodegrad-
ability, is generally classified in WGK 1. In addition, fatty 5.4 Complex esters
acid esters are biodegradable under anaerobic conditions, Like polyol esters, complex esters consist of a multifunc-
too, whereas mineral oils are not [5]. tional synthetic alcohol and long-chain linear fatty acids of
preferably 18 carbon atoms (of plant or animal origin). They
5.2 Glycerol esters differ from the normal polyol esters by the fact that esterifi-
Glycerol esters consist of the natural, tri-functional alco- cation is done in presence of suitable dicarboxylic acids like
hol glycerol esterified with one to three moles of linear fatty adipic acid acting as a cross-linker. Depending on the type
acids. Both components usually originate from renewable and the molar ratio of the educts, medium- to high-viscosity
resources. Their identity with natural lipid structures results products with special technical properties are obtained via
in the very favourable ecological properties of the glycerol this synthetic pathway. The toxicity of the complex esters
esters (Tab. 3 and 4). They are not toxic for fish and bacteria, towards fish, daphnia, and bacteria is comparable to the
and they are almost quantitatively biodegraded within 28 normal polyol esters, i.e. it is rather low (Tab. 3). Biodegrad-
days, even under the stringent OECD screening test condi- ability, however, is significantly influenced by the degree of
tions. In addition, they are easily biodegradable under anaer- cross-linking in the molecule (Fig. 7). Whereas the 68 cSt-
obic conditions, too. Therefore, glycerol esters are officially and 140 cSt viscosities are readily biodegradable even under

Tab. 3. Ecotoxicological properties of representative oleochemical esters.

Ester type Substance (example) Fish toxicity (LC50) Daphnia toxicity (EC50) Bacteria toxicity (EC0)
Fatty acid ester 2-Ethylhexylcocoate 10,000 mg/l >> water solubility* 10,000 mg/l
Glycerol esters Glycerol-tri-oleate 10,000 mg/l >> water solubility* 10,000 mg/l
Polyol esters Trimethylolpropane-tri-oleate 5,500 mg/l > 1,000 mg/l 10,000 mg/l
Complex esters TMP mixed esters with adipinic- 5,500 mg/l >> water solubility* 10,000 mg/l
and oleic acid
* water accommodated fraction (WAF) tested after removal of insoluble organic material.

Tab. 4. Anaerobic and aerobic biodegradability of representative oleochemical esters.

Ester type Substance Ultimate (aerobic) biodegradability* Anaerobic biodegradability#


Fatty acid ester 2-Ethylhexylcocoate 95% 77%
Glycerol esters Glycerol-tri-oleate 100% 86%
Polyol esters Trimethylolpropane-tri-oleate 86% 75%
Complex esters TMP mixed esters with adipinic- and oleic acid depending on viscosity depending on viscosity
* BOD/COD: the limiting value for ready biodegradability is 60% BOD/COD in OECD 301 tests.
# CH +CO evolution.
4 2

196 Fett/Lipid 101 (1999), Nr. 6, S. 192–198


Fig. 7. Biodegradability of complex esters: viscosity-dependent decrease Fig. 8. German water hazard classification scheme for chemicals.
of degradability.

low inoculum conditions, the higher viscosity types (320 cSt their components (mixing rule, “Mischungsregel”). Only in
and 1,000 cSt) do not surpass the OECD limiting values for cases where calculation would obviously result in a mislead-
ready biodegradability. Thus, only the medium viscosity ing classification, a direct experimental determination of the
products up to 140 cSt qualify for WGK 0. relevant ecotoxicological properties of the formulation is
permitted. In such cases the classification has to be approved
by the KBwS.
6 Environmental Classification and However, the current VwVwS has several drawbacks. It is
Labelling of Oleochemical Esters a rather complex regulation still giving some room for un-
certainties (e. g. when to give a Bonus/Malus) and, most im-
6.1 Water hazard class portantly, it is considered as a trade barrier by other coun-
In 1986, as a result of a great fire in a Sandoz storage tries. Therefore, the German Ministry of the Environment
facility, large amounts of chemicals were flushed into the (BMU) is currently developing a new classification scheme
river Rhine by the fire fighting measures and caused a that is based on the risk phrases (“R-Sätze”) laid down in
tremendous dying of fish. To avoid such environmental dis- the EU Dangerous Substance Directive. Although recently a
asters in the future it is required in Germany that all chemi- “final” draft version of the new concept had been issued [7]
cal products (raw materials and formulations) produced or and had passed the first legislative hurdle in Federal Assem-
marketed are to be classified in one out of four water hazard bly, it was rejected by the Federal Council. Thus, at the
classes (WGK) depending on their water endangering prop- moment the possible consequences for the WGK-classifica-
erties (Fig. 8). This classification has to be stated in Chapter tion of oleochemical esters and comparable mineral oil based
15 of the EU Safety Data Sheet, indicating the possible en- products are still unclear.
vironmental impact that may result in case of a spill or an ac-
cident. Depending on the WGK-classification, more or less 6.2 Environmentally dangerous
severe (costly) precaution measures are required for hand- Whereas the EU Dangerous Preparation Directive has
ling and storage facilities. The WGK-classification is based required an indication of dangerous toxicological (e. g. Xi,
on the acute oral toxicity, the fish toxicity, and the bacterial irritating) and physico-chemical (e.g. F, flammable) proper-
toxicity of the substance. In addition, other positive (readily ties of substances on the package for many years, a corre-
biodegradable = Bonus) and/or negative (carcinogenic = sponding environmental labelling was not required until
Malus) properties have to be considered. For WGK 0 addi- 1994. However, since May 1994 chemical substances (raw
tional data are required (toxicity data for a second aquatic materials, but not formulations) have to be environmentally
species, e.g. algae or daphnia, and even more stringent classified in Germany on the basis of their aquatic toxicity
degradability requirements). These requirements are laid (fish, daphnia, and algae), their biodegradability, and their
down in a special administrative regulation (“Verwal- bioaccumulation potential (Tab. 5). Substances classified as
tungsvorschrift wassergefährdender Stoffe”, VwVwS). Until dangerous for the environment have to be labelled with N,
1996, besides official classifications by the German Com- and the pictogram “Dead fish, dead tree” (Fig. 9). However,
mission for Water Endangering Substances (KBwS), self- oleochemical esters are not environmentally dangerous due
classification by industry was accepted by the authorities, to their low aquatic toxicity (LC/EC50-values >> 100 mg/l),
provided that it was done according to the acknowledged their ready biodegradability, and their low bioaccumulation
guidelines (the VCI-scheme, as developed by the German potential. With regard to the EU Dangerous Substance Di-
Chemical Industry Association (VCI)). After the revised rective no classification and labelling is required.
WGK-directive has come into force (VwVwS of April 18,
1996) [6], only official classifications issued by the KBwS 6.3 Eco-labels
and “preliminary safe” classifications are accepted. To be Whereas the EU environmental classification scheme has
regarded as “preliminary safe”, the classification has to be the intention to indicate dangerous properties, eco-labels
offically documented, i.e. the corresponding test data includ- work just the opposite way. They indicate that a certain prod-
ing the calculation of the WGK must be submitted to the uct is, from an ecological point of view, better than others.
KBwS. Substances that are not considered as “preliminary Ideally thinking, as a consequence of an increased consumer
safe” have to be considered as WGK 3-substances. For for- demand for these “greener” products, the whole market will
mulations, the WGK has to be calculated from the WKGs of shift to more environmentally compatible products. In the

Fett/Lipid 101 (1999), Nr. 6, S. 192–198 197


Tab. 5. European environmental classification and labelling scheme for chemicals.

Aquatic toxicity Long-term presence Environmental labelling R-phrases*


(LC/EC50 fish, daphnia, algae) in the environment expected?
(biodegradability, bioaccumulation)
≤ 1 mg/l yes N R-50/53
no N R-50
1–10 mg/l yes N R-51/53
no – –
> 10 mg/l no# – –
* R-50 = very toxic for aquatic organisms, R-52 = harmful for aquatic organisms,
R-51 = toxic for aquatic organisms, R-53 = long-term adverse effects possible.
# refers to “inherent” biodegradability.

application field of hydraulic oils and lubricants there are bricants. Secondly, there is the Swedish “Clean Lubricants”
two eco-labels being of general importance. The first to men- label, also for hydraulic oils. Both labels require a ready
tion is the German “Blauer Engel”, which is issued for biodegradation, and that the products, i.e. base oils plus ad-
biodegradable hydraulic fluids, biodegradable loss lubri- ditives, are not harmful for aquatic organisms. In addition,
cants, and slab oils and biodegradable power saw chain lu- for products to be classified in the best category, the “Clean
Lubricants” label requires an origin of the products – at least
partly – from renewable resources (Fig. 10). Oleochemical
esters fulfill the requirements (except for some less degrad-
able complex esters) of these eco-labels. However, the addi-
tives necessary to achieve the required technical perfor-
mance are often the limiting components.

Abbreviations
BOD = Biological Oxygen Demand
BODIS = Biological Oxygen Demand (test) for Insoluble
Substances
COD = Chemical Oxygen Demand
DDAT = DOC Die Away Test
DOC = Dissolved Organic Carbon
MITI = (Japanese) Ministery of International Trade and
Industry
MOST = Modified OECD Screening Test
OECD = Organization for Economic Cooperation and
Development.

References
[1] F. Bongardt: Synthetic Esters as Multipurpose Basestocks for
Lubricants, in: Jahrbuch für Praktiker, Verlag für chemische
Industrie H. Ziolkowsky GmbH (1996), 348–361.
[2] J. Steber, Systematik der ökologischen Absicherung chemischer
Produkte, SÖFW-Journal 121 (1995), 1063–1080.
Fig. 9. Label for chemicals “environmentally dangerous”. [3] Organisation for Economic Cooperation and Development, OECD
Guidelines for Testing of Chemicals (1995).
[4] N. S. Battersby, P. A. Fieldwick, T. Ablitt, S. A. Lee, and G. R. Moys,
The Interpretation of L-33-T-82 Biodegradability Test Data,
Chemosphere 28 (1994), 787–800.
[5] J. Steber, C.-H. Herold, and J. M. Limia, Comparative Evaluation
of Anaerobic Biodegradability of Hydrocarbons and Fatty Deriva-
tives Currently Used as Drilling Fluids, Chemosphere 31 (1995),
3105–3118.
[6] Verwaltungsvorschrift wassergefährdender Stoffe (VwVwS),
April 18, 1996.
[7] “R-Satz Konzept”, Verwaltungsvorschrift wassergefährdender
Stoffe (VwVwS), Draft from 17.9.98.

Address of the author: Dr. Andreas Willing, Henkel KGaA, 40191


Düsseldorf, Germany.
Fig. 10. Eco-labels for environmentally compatible oils and lubricants. [Received: January 28, 1999; accepted: March 17, 1999].

198 Fett/Lipid 101 (1999), Nr. 6, S. 192–198

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