HEALTH AND SAFETY

ASPECTS OF
NAPHTHENIC OIL

www.nynas.com/naphthenics

HEALTH AND SAFETY

ASPECTS OF
NAPHTHENIC OIL

CONTENTS

INTRODUCTION

1.1
1.2
1.3
1.4

Oils and their environmental impact

Natural resources and energy
Effects on human health and the environment
Waste

CLASSIFICATION AND ASSESSMENT

2.1
2.2

Chemical substances - product streams

Mixtures of substances

PRODUCT INFORMATION IN SDS

3.1
3.2
3.3
3.4
3.5
3.5.1
3.5.2
3.5.3
3.5.4
3.5.5
3.5.6
3.5.7
3.6
3.6.1
3.6.2
3.6.3
3.7

Identification of the substance/preparation

Composition
Dangerous properties
Physical and chemical properties
Toxicological information
Acute toxicity
Oils and toxicity
Local effects
Skin delipidising
Oils and local effects
Sensitisation
Oils and sensitisation
Chronic toxicity/long-term effects
Mutagenicity
Carcinogenicity
Teratogenicity
Oils and long-term effects

1
1
2
2
3
4
4
5
6
7
7
7
7
7
8
8
9
9
9
10
10
10
10
11
12
12

3.8
3.8.1
3.8.2
3.8.3
3.8.4

Ecological information
Mobility
Persistence/degradability
Bioaccumulation
Ecotoxicity

METHODS, TESTS AND

ORGANISATIONS

4.1
4.1.1
4.1.2
4.2
4.2.1
4.2.2
4.2.3
4.3
4.4
4.4.1
4.5
4.5.1
4.5.2

Skin irritation tests

Method
Results
Biodegradability
Marine discharges of crude oil
Oil escapes on shore
Refined oils
The Ames Test
Life-cycle analysis
ELU value of Nynas oil
Organisations and authorities
CONCAWE
Directorate General XI (DGXI)

APPENDIX

5.1
5.1.1
5.2
5.2.1
5.2.2
5.2.3
5.3
5.3.1
5.3.2
5.3.3
5.3.4
5.3.5

Chemistry
Chemical composition
Methods of PAC analysis
IP 346
HPLC
Gas chromatography
Refining technique
The various stages of refining
Distillation
Solvent refining
Hydrotreatment
Acid clay treatment

14
14
14
14
14

16
16
16
16
17
17
18
18
19
20
21
23
23
24
25
25
25
26
26
27
27
28
28
29
29
30
31

1 INTRODUCTION
Safety Data Sheets are by nature brief and leave many questions unanswered. We are often approached by customers who need more information than is supplied by the sheets: they might want to know what is
the difference between a preparation and a substance; or why one oil is
labelled and another with the same values is unlabelled; or what should
be done following skin contact with a particular oil. This handbook
aims to answer these questions, while providing a summary of current
(1997) knowhow concerning the labelling, toxicity and environmental
risks of oil products.
The environmental effects of industrial products are a topic of growing
concern. The Nynas Group is engaged in environmental work within
the oil industry organisation CONCAWE and the European Chemical
Industry Federation, CEFIC. As a result, the group companies are
working in compliance with the CEFICs Responsible Care programme and have comprehensive systems for labelling of products
according to EU requirements and ISO 11014.
With regard to Nynas Naphthenics product slate, labelling has led to
the decision to stop the production and marketing of toxic products. At
Nynas Naphthenics, it is our aim to maintain a high degree of environmental awareness and to act accordingly.
Mineral oils are complex materials, and both their environmental
impact and safety aspects demand careful consideration. This handbook
deals with aspects of European Union law and looks at some of our inhouse research findings which substantiate our labelling practice.
This handbook has been compiled as a complement to Nynas
Naphthenics Safety Data Sheets (SDS). Information specific to individual products is supplied in SDS which are obtainable from our sales
offices.

1.1 OILS AND THEIR

ENVIRONMENTAL IMPACT
In order to assess the environmental impact of a product, it is necessary
to perform a life-cycle analysis (see Life-cycle analysis, section 4.4).
This serves to identify all potential sources of environmental impact:
from sourcing and transport of the raw material, through production
and distribution, to use and final destruction.
A life-cycle analysis is not complete unless transport and refining
operations, which of course involve energy consumption, are included
in the analysis, although these factors are not specific to the production
of oils.

An important question regarding the environmental impact of oils concerns their degree of biodegradability (see Biodegradability, section 4.2)
and whether they are toxic - and if so, how toxic - to flora and fauna.
Decomposition products also have to be evaluated for toxicity.

1.2 NATURAL RESOURCES

AND ENERGY
All use of crude oil involves the exploitation of a finite natural resource.
Since total world use of oil is great in relation to existing reserves, the
magnitude of this consumption can be considered to cause serious environmental impact.
Here we might add that when a given quantity of oil is used as transformer oil, it has a working life that can be measured in decades. This
can be compared with the same amount of oil which when used as fuel,
would be transformed into exhaust fumes within a matter of hours if
used in a powerful speedboat. Furthermore, the inherent energy in the
transformer oil remains unused even at the end of its useful lifespan and
can either be combusted and converted into energy, or recycled.

3% Bitumen
1% Base
oil

Figure 1 describes the proportion of

oil used as base oils, in comparison
with fuel oil and bitumen. Seen in
these terms, transformer oils account
for only 0.01%, for example.

96% Fuel

1.3 EFFECTS ON HUMAN HEALTH

AND THE ENVIRONMENT
An oil can prove to be harmful to human health. The risk of health
hazards can range from high, to practically zero, depending on the oil
chosen and type of application. As for the oil itself, it is the degree of
refining which decides whether or not it can be harmful to the health
(see Refining technique, in the Appendix).
Oil spillage into the soil or water is another important issue. Though
spillage should, of course, never occur, the risk exists and the consequences have to be examined. Here again, the composition of the oil
makes a difference, although the damage depends mainly on the size of
the spill and the environment in which it occurs.

1.4 WASTE
Waste can be generated in the course of production, or it can constitute
the remains after the product has been used. (Internal waste is discussed
in section 4.4.1). The appropriate treatment of the used end product
varies from one application to another, depending on whether the oil
has been used, for example, as a plasticiser for rubber, a solvent for
printing ink or as an industrial lubricant. However it has been used, it
is very important that the used oil should be collected.
In the case of lubricating oils, it is commonly held that they can be
purified and reused, while others maintain that they should be burned.
The argument in favour of combustion is that, as long as feedstock for
base oils are still used in large quantities as heating oils, recycling of the
oil contained in used lubricants is not worth the trouble. Moreover,
additives and contaminants in the lubricant may be easier to deal with
by means of efficient combustion techniques and gas purification, than
in the concentrated form resulting from re-refining.
There are several methods for re-refining, and these have to be evaluated on a case-by-case basis (compare Life-cycle analysis, section 4.4).
Here we might note that purification on site, will probably always be
the preferred method from an ecological point of view.
Nynas always uses virgin oils, in order to avoid system contamination
with additives (for example PCB) and to ensure full control of the raw
materials from which our oils are manufactured.

2 CLASSIFICATION AND
ASSESSMENT
Classification and assessment cover only one aspect of the risk involved
in handling a chemical (n.b. an oil is considered a chemical by classification bodies). The other is exposure, i.e. if there is no exposure to a toxic
chemical, then use of that chemical does not entail any risk.
In all cases, however, it is recommended to minimise exposure to any
chemical. Special care is needed when handling used chemicals.
The classifications are based on pure chemicals (substances) and blends
of substances (preparations).

2.1 CHEMICAL SUBSTANCES

PRODUCT STREAMS
The basis for classification and assessment is to arrive at a clear definition of the substance in question.
The European Inventory of Existing Commercial Substances
(EINECS) is a register of chemical substances in the EU. The substances
listed are defined by their CAS (Chemical Abstracts Service) numbers,
an American descriptive reference system that includes a short description of the substance.
Since the composition of an oil distillate is highly complex and
refining can be varied - both in the choice of technique and the way in
which the different stages of refining are performed - the content of
finished oils is infinitely variable. It would therefore be out of the question to devise CAS numbers for all existing grades. Instead a number
of process streams have to be defined on the basis of different refining
processes, and these are then treated as if they were chemical substances.
Every process stream is identified by a CAS number and an
EINECS number. All oils can be referred to by one of these product
categories. The content of the individual oil has a composition within
the limit values that defines the process stream to which it belongs.
In describing the effects of an oil on health and the environment,
what we are really describing are the theoretically worst possible
properties of the different CAS categories. If a product stream is not
included in the CAS system, full testing of the substance is necessary.
However, this is so expensive that new products are difficult to introduce. Evaluation of existing process streams both can and should be
cross-referenced in the literature, to minimise animal testing of existing
products.
The European labelling of substances follows the Classification of
Dangerous Substances Directive, 67/548/EEC. This directive has been
revised several times, with seven amendments and 22 adaptations to

technical progress, the eighteenth of which prescribes procedures for

the self-classification of products not yet listed in the directive.
The main principle is that the best possible information should be
given for a process stream flow. The directive devotes a separate page
to each substance included, and for mineral oils, notas are used, e.g.
concerning carcinogenicity and aspiration hazards. There are some
substances to which these notas are inapplicable, and the directive has
therefore to be consulted for the CAS number of the product to be
evaluated; if the product is not listed in the directive, the self-classification procedure has to be employed.
Nynas Naphthenics manufactures a wide variety of products. These
can be divided into four main groups, with defined CAS numbers. Two
of these are especially prominent, i.e. hydrotreated light naphthenic distillate with a viscosity of less than 19 cSt, CAS number 64742-53-6, and
hydrotreated heavy naphthenic distillate, CAS number 64742-52-5. See
Chemistry, section 5.1.

2.2 MIXTURES OF SUBSTANCES

Some products are mixtures of two or more substances.
Products composed of two product streams, and thus defined as a
mixture of two substances, include the oil/bitumen blends used for
manufacturing printing ink and rubber. Here the product consists of an
oil with a certain CAS number and a bitumen grade with another CAS
number.
Assessment of these mixtures (preparations) is regulated by the
Preparation Directive 88/79/EEC. If, for example, a carcinogenic substance occurs in the mixture in concentrations exceeding 0.1 per cent,
the entire mixture has to be labelled. As yet there are no such conditions for mixture concentrations with regard to ecotoxicity, but these
will probably be included in coming adoptions to preparation directives.

3 PRODUCT INFORMATION
IN SAFETY DATA SHEETS
All customers purchasing oils from Nynas receive Safety Data Sheets
(SDS) indicating the properties and effects of the product concerning
safety, health and the environment.
The required information content of the sheet is based on the EEC
Directive on SDS (Commission Directive 91/155/EEC implementation
of Article 10 in Directive 88/379/EEC). There is also an international
standard for product information sheets (ISO 11014-1:1994), based on
the EEC standard. National standards may contain other conditions.
The product information sheet contains 16 obligatory main headings (categories of information). Neither the ISO standard nor the EEC
Directive specify the order in which the headings are to come. Some of
these main headings will be commented on below (e.g. Dangerous
Properties in section 3.3, Toxicological Information in 3.5 and
Ecotoxicological Information in 3.6) although the information supplied
under these headings is very clearly defined, it is hard to understand if
the definitions are not known.

Figure 2: Front page of a typical safety data

sheet.

The manufacturer
must be able to present
empirical data to support the information
supplied in the material safety data sheet. In
practice, this is administered by various
industrial organisations. Within the
European petroleum
industry, test results
are collected and disseminated by CONCAWE. Member companies contribute new
test results when they
are needed. These are
then made available to
all member companies.
Nynas, together with
all main member companies, have contributed to the common test
bank.

3.1 IDENTIFICATION OF
THE SUBSTANCE/PREPARATION
This heading in the SDS is followed by information concerning the designation of the product, its manufacturer and an emergency telephone
number. The organisation with this number has our SDS and can answer specific questions in an emergency. The CAS number can be stated
here, but this is not obligatory. The SDS may be valid for a range of
products with the same CAS number.

3.2 COMPOSITION
The substance or substances included in the product (see section 2.2,
Mixtures of substances) are stated here. The CAS number is obligatory,
and often the EEC number is given as well.
When several substances are used, their proportions are given, most
often expressed as an interval. This is not in any way to be regarded as
a recipe or specification. Instead a fairly wide interval is given, e.g. 4060 per cent. From this one may conclude that the properties stated in
all SDS apply to all products whose composition comes within this
interval. The percentage is important when deciding whether the mixture has to be labelled. The Preparations Directive bases labelling on
the quantity of the various substances.
Classification, if any, and danger labelling are also to be indicated
under this heading. No such particulars are given under this heading
for Nynas Naphthenic oils, because they are not classified as dangerous
to the health.

3.3 DANGEROUS PROPERTIES

The main properties considered dangerous to the environment, health
and safety are stated under this heading, together with relevant classifications.

3.4 PHYSICAL AND CHEMICAL

PROPERTIES
The properties stated here refer to the compositions shown under the
heading Composition. Thus the product in question may have a much
narrower specification than is indicated here, but it cannot have properties which fall outside these intervals. In other words, there is no single
specification for this product.

3.5 TOXICOLOGICAL INFORMATION

This section provides detailed information on all harmful effects to
health and the environment. Where some types of health hazards are
concerned, e.g. carncinogenic, information must always be given, even
if there are no risks involved. For other risks, e.g. defatting, information of this kind can be omitted.

This section falls into four parts:

Acute toxicity: This is always given, with the effects of ingestion
and dermal contact.
Local effects: These are always given, with the effects of inhalation,
ingestion, dermal contact and eye contact.
Sensitisation: This can be omitted.
Chronic toxicity or long-term effects: These can be omitted.

3.5.1 Acute toxicity

Acute toxicity means toxicity during brief, occasional exposure.
Acute toxicity is measured in LD50, which stands for Lethal Dose
50% and is given in mg/kg. In other words, the dose given in mg per kg
body weight is the dose which is lethal to 50 per cent of those receiving
it. LD50 is followed by an indication of the experimental animal used
(most often a rat or a rabbit) and whether the product was swallowed
by the animals, e.g. LD50/oral/rat, was applied to their skin, e.g.
LD50/dermal/rat or was inhaled by them, e.g. LD50/inhalation/rat.
Because the type of exposure is stated, e.g. dermal contact, this information is likely to be confused with the information presented under
the heading Local effects. Acute toxicity always refers to lethal doses,
whatever the type of exposure. The effect, in other words, is not local,
even if the exposure is. Exposure classification doses are appended.

3.5.2 Oils and toxicity

A typical LD50 value for a highly refined naphthenic oil is:
LD50/oral/rat <5,000 mg/kg. Assuming the oil has the same toxicity
for human beings, this figure means that the risk of death to a man who
weighs 80 kg and drinks more than 40 cl of the oil is 50 per cent.
Ingestion of mineral oil usually occurs by accident. If a large quantity of oil is ingested, this will result in signs of irritation in the digestive
tract, e.g. nausea and diarrhoea. Vomiting should be avoided, due to the
risk of oil (and especially oil of low viscosity) entering the respiratory
system and causing severe lung damage, i.e chemical pneumonitis.
There is little risk of oils being ingested or inhaled, and lung inflammations are therefore unlikely to occur.
A new risk phrase has been introduced in the twenty-second ATP
to the dangerous substance directive: Risk Phrase 65 Harmful may
cause lung damage if swallowed. This risk phrase should be used for
products with a viscosity lower than 7 cSt at 40C. Formally the risk
phrase does not need to apply if the surface tension is greater than
25mN/m at 40C. There is one Nynas product with a viscosity of less
than 7 cSt and a surface tension of approximately 40 mN/m, but this
product still carries this risk phrase.
TLV, Threshold Limit Values are the maximum allowable concentration
of a substance in air for human exposure in specified exposure conditions.

Limits are set locally for each country, in units of mg/m3.

The conditions normally refer to average exposure over a period of five
eight-hour working days. Measurements have to be taken in working
conditions and must include both particles and fumes.
For oil products, the value depends mainly on local conditions at
the workplace. Important conditions include ventilation efficiency, operating temperature versus boiling range of the product (choice of product) and how operating speed influences particle emission versus product viscosity.
The actual exposure of people working in an environment with a
certain substance concentration in the air is then influenced by the protective equipment used. In order to minimise fumes, oil with a higher
boiling range can be used.

3.5.3 Local effects

The local effects are stated for dermal contact, inhalation and eye
contact. Here, then, we are concerned, not with lethal doses but with
effects on the skin, the respiratory organs and the eyes. Usually it is
also stated here whether ingestion leads to nausea and vomiting.
A chemical substance can have different degrees of corrosive, irritant or delipidising effects on the tissues it comes into contact with.
Definitions of corrosive properties are based on tests on animal skin
or on the predictability of effects on animal skin. Effects on other
organs are presumed to be no less serious.

3.5.4 Skin-delipidising
A skin-delipidising substance does not really have any direct effect on
the skin, it only affects the fat which is secreted by normal skin, forming a protective layer. Substances which dissolve this fat, e.g. detergents, solvents and oils, leave the skin dry and unprotected, which can
cause skin disorders. These can be rectified by regularly applying a skin
lotion to the exposed area.
Over-frequent washing with detergents can also dry out the skin
and, the detergent as such can cause an allergic reaction. A mild type of
soap is recommended, and a neutral skin lotion should be placed close
to the basin. For exposure to oils in large quantities, oil-resistant gloves
or barrier lotions should be used.
The use of skin lotion is especially important in dry, cold weather.
Conditions of this kind tend to dry out the skin, causing it to crack.
Anyone handling oils should be on their guard against redness or skincracking.

3.5.5 Oils and local effects

Light oils, and especially light naphthenic oils, are widely supposed to
be more irritating to the skin than others. Nynas have therefore commissioned an independent institute to test different base oils naph-

thenic and paraffinic, light and heavier (see the chapter headed Skin
irritation tests, section 4.1), to establish their dermatological properties.
The results show that neither naphthenic nor paraffinic oils can be
classed as primarily skin irritant. The majority are classed as slightly
irritant, while some are classed as non-irritant. Naphthenic oils are
no more irritant than paraffinic.

3.5.6 Sensitisation
Sensitisation means that an individual repeatedly exposed to a certain
chemical substance becomes hypersensitive to it. The immune system
has learned to recognise the substance and in future will be mobilised
whenever the individual comes into contact with it.
This means that a substance which, for non-sensitised individuals, is
neither toxic nor irritant, produces severe inflammatory reactions in the
sensitised or allergic individual. This is what distinguishes allergenic or
sensitising substances from irritant ones. A substance classed as irritant
triggers reactions at the very first time of exposure, while a sensitising
substance only does so when the individual has become hypersensitive
to it.
Some natural products that are used, for example as solvents from
natural sources, have been shown to give allergic reactions.
Chemical substances can have sensitising effects in connection with
two types of exposure: inhalation and dermal contact.

3.5.7 Oils and sensitisation

There are no studies to suggest that oils can cause sensitisation.

3.6 CHRONIC
TOXICITY/LONG-TERM EFFECTS
The properties of chemical substances causing long-term effects in man
are divided into three types: mutagenic, carcinogenic and teratogenic.
All three types are concerned with damage to human genetic material. The differences between them concern the demonstrable effects of
such damage.

3.6.1 Mutagenicity
If a substance is mutagenic, this means that exposure to it can lead to
changes - mutations - in the genetic code. This is a very general definition; it does not say which organism can develop these mutations, nor
does it say anything about the consequences of the mutations for the
organism. What is tested, in other words, is the capacity to affect DNA
molecules. The fact that a substance is mutagenic does not mean that
the mutations it may cause can in turn lead to cancer, impaired reproductive capacity or any other risk.
Mutagenicity, as a criterion of the harmfulness of a substance, suffers from the obvious disadvantage that there is no absolute connection

10

between mutagenicity and, for example, carcinogenicity. The advantage

is that there is a simple, dependable method for testing a substance for
mutagenicity, namely the Ames test (see section 4.3). This test requires
only bacteria, not experimental animals, and it is both quick and relatively cheap.
Although the accepted way of testing a substance for mutagenicity
is to test it on bacteria, in the labelling context mutagenicity is designed
as the capacity of the chemical substance to cause hereditary genetic
injuries in human beings or increasing their incidence, the reason being
that this, and not what happens to bacteria, is the interesting question.
Hereditary genetic injuries can occur through mutations in gene
cells. A mutation occurring in a sperm or ovum can lead to defects in
the progeny. This, then, is a specific consequence of a substance's mutagenicity. But it is a very serious consequence. If there is evidence that a
chemical substance can cause this kind of injury, this means that the
substance is very dangerous.
For labelling purposes, mutagenicity is divided into three categories:
Category 1

Category 2

Category 3

There is enough evidence to establish a causal connection between exposure to the substance and hereditary
genetic injuries in man.
There are sufficiently strong reasons for presuming a
causal connection between exposure to the substance
and hereditary genetic injuries in man.
There is evidence from relevant mutagenicity studies,
but not sufficient to place the substance in category 2.

In order for a substance to be placed in category 1, there should be epidemiological studies showing, among persons exposed to the substance,
an increased number of hereditary genetic injuries compared with the
normal population. Placement in category 2 calls for animal studies
or other relevant information. Both these categories mean that the
substance is labelled with a skull and crossbones as toxic. Substances
in category 3 are regarded as harmful to health and labelled with the
cross of St. Andrew. These substances may, for example, have shown
mutagenicity in the Ames test but not in animal experiments.
If a substance is to be tested for mutagenicity and there are no previous data concerning its effect on genetic material, the Ames test
makes an appropriate beginning.

3.6.2 Carcinogenicity
Animal experiments or epidemiological studies are generally used in
order to establish whether a substance is carcinogenic. Epidemiological
studies are very expensive and can only provide firm information about
substances which many people have already been exposed to for a long
time, because often human beings do not develop cancer until several
decades after exposure to the carcinogenic substance.
Animal experiments too are expensive and time-consuming, but
they are performed quite often in order to investigate whether a substance is carcinogenic or not.

11

The most common way in which a chemical substance can provoke

cancer is by causing a mutation in a special part of the human genetic
material, known as an oncogene. An oncogenic mutation in a cell,
however, will not of itself lead to the formation of a tumour. Whether
or not this happens, will depend on a host of different factors, among
them the efficiency of the body's immune system. Some chemical
substances, although not themselves mutagenic, augment the risk of a
mutated oncogene leading to cancer. Substances like this are called
cancer promoters.
The mechanisms involved in the origins of cancer are complex and
not all factors are known, and so one cannot automatically infer that a
mutagenic substance is also carcinogenic or that only mutagenic substances can be carcinogenic. The two properties have to be separately
tested.

3.6.3 Teratogenicity
A chemical substance is defined as teratogenic if it impairs male or female
fertility or is capable of causing injury to the unborn child/progeny.
It is tempting to suppose that effects on human reproduction are
connected with damage to the genetic material. This is of course a possible cause, but there are others. For example, a substance may affect
the hormonal balance and affect fertility in this way. Gestation too can
be disrupted by various chemical substances, without any mutagenic
changes being involved.
Teratogenic substances are divided into three categories, each of
which has two different definitions: one for effects on human fertility,
and one for effects on the unborn child.

3.7 OILS AND LONG-TERM EFFECTS

Because mineral oils contain a very large number of chemical substances,
assessments of different injury risks have to be based on tests of the
whole oil, not on each of the constituent chemical substances individually. In this way it can be established that a highly refined naphthenic
oil is neither mutagenic, carcinogenic nor teratogenic. This is because,
after extreme refining, very little remains of the substances which are
known to be mutagenic and also carcinogenic, namely the polyaromates.
There are several ways of analysing the polyaromatic content (PAC)
of an oil.
IP 346 (see section 5.2.1) is the method used for determining whether
an oil has to be labelled. This method supplies relevant information
about the oil, because good correlation has been found between PAC
as per IP 346 and mutagenicity and carcinogenicity. On the other hand,
IP 346 does not provide a good quantitative indication of PAC.
According to IP 346, labelling becomes obligatory at 3 per cent. If
this were the real PAC, an oil with a value just below the limit would
presumably be clearly carcinogenic. The problem is that IP 346 does
not measure PAC directly, but measures the proportion of the oil
ending up in the DMSO phase in an extraction. Analysing the DMSO

12

phase, one finds that, in addition to polyaromates, it also includes

monoaromates and naphthenes. The true PAC content at a IP 346 value
of 3 per cent is approximately 0.1 per cent.
% mice tumours
40
35
30
25
20
15
10
5
0
0

6
Paraffinic

8 IP 346
Naphtenic

Figure 3. Skin tumours versus IP 346.

The graph above illustrates the difference between different oils and
clearly shows that naphthenic oils at 3% IP 346 level are not carcinogenic. The data has been supplied by CONCAWE database and are
based on skin painting on mice. Four, five or more tumours on the
mice indicate that the oil is potentially carcinogenic. The percentage of
skin tumours is correlated to the IP 346. Other markers, such as
Benzo(a) pyren, have not shown this correlation with skin tumours,
hence the EU's decision to use IP 346 as a marker for labelling. It must
be pointed out that oils that are not included, such as re-refined oils,
used oils and blends of different substances can give misleading results.
Nynas oils have IP 346 values below 3%, and our oils have also
been tested by other methods, such as modified Ames tests, with good
results.
The above graph also shows that low-refined oils such as distillates
and aromatic extracts, which have a high PAC content according to IP
346, are carcinogenic to mice and therefore have to be labelled with a
skull and crossbones.

13

3.8 ECOLOGICAL INFORMATION

3.8.1 Mobility
The mobility of a substance is usually determined by its solubility in
water. This information is mainly of interest in relation to the toxicity
of the substance, but also in relation to its degradability.
A substance which is highly mobile in the environment can, for
example, enter the groundwater, which is serious if it is toxic. A substance which is slightly toxic but mobile and at the same time readily
degradable will quickly be diluted and therefore less dangerous.

3.8.2 Persistence/degradability
It is always beneficial for the environment if a substance is biodegradable
(see section 4.2). At the same time, this property is mainly interesting in
relation to toxicity.
A substance which does not degrade readily and, moreover, is toxic,
is much more harmful than one which is persistent but non-toxic. Polyaromates are both persistent and toxic, whereas naphthenes are much
more degradable and are also non-toxic.

3.8.3 Bioaccumulation
Bioaccumulation means that the concentration of a substance in living
beings may increase with the passing of time. DDT and PCB are familiar examples. A substance bioaccumulates because it dissolves much
more easily in fat than in water, with the result that it accumulates in
the fatty tissue of human beings and animals instead of being absorbed
by the blood and disposed of by the liver and kidneys.
Bioaccumulation is measured in log Pow (the logarithm of the distribution constant between octanol and water). A high value indicates a
risk of bioaccumulation.
Substances found in mineral oils have a relatively high log Pow
value of 3.9 to more than 6. Whether or not this matters depends on
whether or not the substances are toxic, i.e. basically the decision can
be made according to their PAC value.

3.8.4 Ecotoxicity
Ecotoxicity is measured and defined in essentially the same way as
other toxicity, but instead of being based on facts about acute toxicity
or long-term effects on man, it is concerned with effects on aquatic
organisms, soil organisms, flora and land animals.
Other effects on the environment can also come under the heading
of ecotoxicity, e.g. effects on the ozone layer, potential for forming
ground-level ozone, potential for contributing to the greenhouse effect
and effects on wastewater processing plants.

14

In the case of mineral oils, there is a clear relation between PAC and
ecotoxicity. Oils with high amounts of PAC such as aromatic extracts
should therefore be labelled with R53/R52.
The ecotoxicity which is measured is mainly related to effects on
aquatic life. Studies have shown that well-refined naphthenic oils do
not have any toxic properties capable of posing a long-term threat to
aquatic organisms. This is based on daphnia and fish studies. With reference to the above, the following text is included in our data sheets
(highly refined oils).
Aquatic toxicity data on base oils indicate an LC 50 value exceeding
1,000 mg/l. Substances may not meet the criteria for ready biodegradability and components have log Pow values ranging from 3.9 to greater
than 6. However, chronic toxicity studies show that they do not represent a long-term danger to the aquatic environment. No classification is
therefore needed.

15

4 METHODS, TESTS AND

ORGANISATIONS
In this chapter we describe tests conducted and the results obtained. We
also describe a number of organisations, such as CONCAWE and EU
DGXI.

4.1

SKIN IRRITATION TESTS

Nynas commissioned Hazleton Laboratories Ltd., an independent

institute in the UK, to test 17 base oils, partly to decide whether they
are skin irritants, but also to see whether there are differences between
naphthenic and paraffinic oils and between oils of differing viscosity.

4.1.1 Method
The test, which conformed to OECD Guidelines 404, was performed
on rabbits. Oil was applied to the shaved test area on the rabbits backs,
which was then kept under cover for four hours. When the oil had
been washed away, the skin was studied after 1, 24, 48 and 72 hours.
The occurrence of inflammation and swelling was noted and was rated
on a 4-point scale. The sum total of the scores from 24 and 72 hours
for all (12) animals were worked out and then divided by 6, to give an
irritation index ranging from 0 to 16.
This means, for example, that an average of 1 for the degree of irritation after both 24 and 72 hours gives an irritation index of 4. An irritation index below 2 means that grade 1 effect was noted in not more
than half the observations.
Irritation index
0
0-2
2-5
5

Classification
non-irritating
slightly irritating
moderately irritating
severely irritating

4.1.2 Results
Sample

Visc
cSt/40C

Irritation
index

Paraffinic oil

2.5
28
90

0
1.2
1.2

Low refined
naphthenic
oil

8
22
100

0.2
1.3
0.5

Sample

16

Visc
cSt/40C

Irritation
index

Solvent refined
naphtenic oil

2.5
8
22
100

0
0.3
1.0
0.2

Hydrotreated
naphthenic
oil

8
22
100

0.2
1.3
0.5

In order for a substance to be classified as a skin irritant, significant

irritation must occur and persist for at least 24 hours after an exposure
time of not more than four hours in tests on animal skin.
All the oils tested come outside this definition. There is no observable difference between naphthenic and paraffinic oils, nor can light oils
be termed more irritating to the skin than heavy ones. On the other
hand one finds that both lighter and heavier oils are less irritating than
those with a viscosity of about 20 cSt/40 C, the values for which are
slightly higher in the case of both naphthenic and paraffinic oils.

4.2 BIODEGRADABILITY
One of the most important environmental properties of a chemical substance is whether it is biologically or chemically degradable or stable.
A toxic substance which breaks down rapidly in the environment generally causes less environmental problems than a less harmful substance
which accumulates in the environment. DDT, PCB and CFC are typical examples of substances whose greatest fault is their stability.
Most, but not all, organic substances can be broken down by
various microorganisms. Even substances which are toxic to humans
can serve as food for bacteria and fungi, for example. Some bacteria can
adjust to using the most varied substances as carbon and energy sources.
Stability, of course, is also a positive property in a substance. It
would not exactly be an advantage if oil were to turn rancid in storage,
perhaps necessitating the addition of preservatives in order for it to
retain the properties conferred by refining. The preservatives could
then cause more harm than the oil itself. The use of oils in some emulsions has in fact proved conducive to health problems, as a result of
bacterial growth in the emulsions.
It is a fact that large quantities of oil are, for various reasons, released
into the environment. The harm the oil can do there depends on:

the amount of oil per unit of area

the type of environment contaminated

the composition of the oil.

4.2.1 Marine discharges of crude oil

Most often when oil is mentioned as an environmental problem, the
reference is to heavy discharges or escapes of oil at sea. In such cases,
the acute damage is great, even though most of the oil can eventually be
degraded. Degradability is still worth studying, in order to find out
whether the oil released will persist in the environment for a long time
to come. Also, there are various ways of accelerating biodegradation
when the mechanisms are known.
Some environments are more sensitive than others to the acute
effects of oil discharges. Biodegradability also varies from one environment to another. These differences depend mainly on the needs of the
so-called oil-eating bacteria.

17

First and foremost, the bacteria need to be able to get at the oil.
Because the bacteria need water, they can only get at the surface layer
of the oil if it is sufficiently large. This is why emulsifiers are sometimes
spread after an oil escape, so as to divide up the oil into small droplets
which will have a large interface with the water. The problem with this
method is that the emulsifier may be ecotoxic.
Once the bacteria have reached the oil, they need oxygen and other
nutrients. At sea, oxygenation is usually so good that oxygen supply is
not a limiting factor. Sheltered bays with stagnant water are an exception to this rule. On the other hand, there may be a shortage of nitrogen and sulphur, for example. In connection with the tanker disaster off
the coast of Alaska in 1989, the expedient was tried for the first time of
spreading various fertilisers to boost the growth of the oil eaters.
It can take time for a strain of bacteria to develop which is adapted
to living on the escaped oil, and so sometimes an attempt is made to
spread bacteria which are already adapted in this way. Grafting oil
eaters can be difficult, because the bacteria have to come from outside
and compete in an alien ecosystem, albeit an ecosystem containing the
very food they are adapted to. Grafting of this kind produces good
results in laboratory experiments, but is usually less successful in natural conditions. In environments which are constantly being subjected to
small escapes of oil, the bacteria population consists to a very great
extent of oil eaters, in which case biodegradation will be faster and
more efficient than in environments where escapes have not occurred
previously.

4.2.2 Oil escapes on shore

When oil gets into the ground, the oxygen supply can vary a great deal,
depending on the type of soil and moisture conditions. After an escape
of oil on land, the soil can be ventilated in various ways to improve the
supply of oxygen, e.g. by sucking in air with a vacuum pump dug into
the ground. A simpler way is to plough the soil. Oxygen can also be
added indirectly, e.g. by spreading hydrogen peroxide. This is an
expensive method and requires careful dosages. Excessive dosage harms
bacteria and under-dosage has little effect. Spreading nitrates which are
denitrified in the soil can also be an effective method, but it may cause
problems if the nitrates leach into the groundwater.
There may also be a shortage of various nutrients in the soil, and the
spreading of fertilisers may hasten the degradation process.

4.2.3 Refined oils

Although the big tanker accidents are responsible for the most spectacular escapes of oil into the seas, they do not by any means account for
the greater part of escapes. Used industrial oils and motor oils account
for 63 per cent of discharges into the seas, whereas tanker accidents
account for only 2 per cent. There are no figures showing the quantities
of these types of oil which end up in the soil.

18

Generally speaking, the simpler the molecules, the faster the biodegradation. Molecules with double bonding, aromatic rings and heteroatoms degrade more slowly. The more complex the molecule, the harder
it is to break down.
Alkanes, i.e. paraffins and naphthenes, are the hydrocarbons which
are most easily degraded by bacteria. Paraffins degrade somewhat more
easily than naphthenes, straight paraffins more easily than branched
ones, and naphthenes with few rings more easily than naphthenes with
many rings.
Aromates are more difficult for bacteria to break down. The smaller
the number of aromatic rings, the faster the biodegradation. Benzene is
the most readily degradable of the aromates, while polyaromates can be
very persistent.
Bitumens, i.e. asphaltenes and resins consisting of molecules with
more than eight aromatic rings, degrade very slowly. Extrapolation of
results from experiments indicates between 25 and 75 per cent biodegradation in 1,000 years. The molecules in bitumen form lumps of tar
and stable emulsions which are not toxic but will remain present in the
seas for a very long time. These substances are present in crude oil but
seldom in refined products.
The polyaromates occupy a special position in the above list. These
substances are both the most persistent and the most toxic. Asphaltenes
and resins are the only substances which degrade even more slowly, but
they are not toxic. There is reason, therefore, to be extra vigilant with
oils containing large quantities of polyaromates. From an environmental
viewpoint, it makes no difference whether the oil used is paraffinic or
naphthenic, because neither paraffins nor naphthenes are toxic, and
both paraffins and naphthenes are readily degradable. Environmentally,
it is PAC that matters most.

4.3 THE AMES TEST

The Ames test has been accepted by some companies and organisations
as a marker for predicting carcinogenicity. Some scepticism persists
concerning this method, but it is cheap and relatively fast. It has the
advantage of being a routine test and commercially available. Skin testing remains the ultimate method accepted as final evaluation, but tests
of this kind are expensive and take about two years to perform. A
general effort is, however, being made to substitute short-term tests for
painful tests on animals. The method is based on the fact that mutated,
histidine-dependent salmonella bacteria mutate back to histidine-independent when exposed to a mutagenic substance and the colonies start
to grow.
Ames testing was adapted to petroleum products by Mobil, who
have found a correlation to skin painting on mice. Most sample preparations for Ames tests are diluted with cyclohexane and extracted with
DMSO to obtain an aromatic fraction from the oil. Liver homogenate
from hamster and salmonella bacteria, commonly strain T98, are used
for measuring frame test mutation. They are added to agar plates and

19

the colonies counted after 48h. The number of colonies is proportional

to mutagenicity.
A mutagenicity index is calculated from these results, and an MI of
more than one is considered mutagenic.
125

TA98 Revertants per Plate

TA98 Revertants per Plate

300
275

100

250
225
200

75

175
150
50

125
100
75

25

50
25
0

10

20
30
40
l of Extract per Plate

50

60

10

20
30
40
l of Extract per Plate

50

60

Figure 4. The figure above shows two curves: one for a non-mutagenic
product and one for a positive control oil mutagenic.

4.4 LIFE-CYCLE ANALYSIS

A life-cycle (LCA) analysis is an analysis of a system's environmental
impact throughout its life-cycle. Note that the reference here is to a
system, not to a product. In order to mean anything, a LCA must refer
to a system performing a certain function. For example, one studies,
not a litre of process oil for rubber production but the amount of
oil needed to achieve a certain plasticising effect in a certain amount of
rubber.
A LCA, in order to be meaningful, should involve some kind of
comparison, perhaps a comparison between two different systems or
between different parts of one and the same system. For purposes of
comparison, one would like to be able to convert the different parts of
a complete LCA into figures which could then be added up. This
would give two numerical values, one of which would be incontestably
higher than the other, thus showing one product or system to have a
more negative environmental impact than the other.
To arrive at numerical values of this kind, we have to evaluate different
types of environmental impact, which in turn calls for a valuation system. There ought preferably to be just one, universally accepted valuation system. Eventually there will presumably be a standard which is
universally valid, but at present we have a host of different valuation
systems.
Nynas have not decided in favour of any particular valuation method,
but one of our products on the other hand has been analysed and evaluated by ABB Transformers, using the Swedish EPS system, in which
environmental impact is calculated in terms of ELUs (Environmental

20

Load Units). If a customer wishes to work out the score for a Nynas
product under some other valuation system, Nynas will supply all the
data required.
Valuation in the Swedish EPS (Environmental Priority Strategies in
product design) system is based on how much people in the OECD
countries are prepared to pay in order to preserve a number of qualities
of the environment, such as biodiversity, human health, the productive
capacity of ecosystems, and so on. Willingness to pay may sound like a
subjective starting point, but it is in the nature of things that, as soon as
we depart from straight collection of data and begin to evaluate the
importance of the data, a certain subjective element creeps in.

4.4.1 ELU value of Nynas oil

At the time when ABB Transformers performed their life-cycle analysis
of a transformer oil from Nynas, not all data from crude oil production
in Venezuela were available, and so use has been made of the value
which North Sea oil would have yielded, namely 0.458 ELU/kg.
Transport to the Nynshamn refinery contributes 0.0024 ELU/kg.
Transport of the finished product naturally makes contributions of
various sizes, depending on where the customer is, but seldom contributes more than the crude oil transport.
Refining involves the use of electrical energy, roughly half of which
in Sweden comes from nuclear power and half from hydro power. In
addition, fuel oil is used for heating. Energy consumption contributes a
total of 0.0305 ELU/kg.
All Nynas speciality oils undergo hydrotreatment. This requires
hydrogen, which is produced from naphtha and water. Hydrogen production makes the biggest single contribution to the ELU/kg of the oil
in refining, partly because naphtha and energy are consumed and carbon
dioxide is formed. Naphtha consumption in itself contributes 0.0358
ELU/kg. This, however, is not to say that hydrotreatment is environmentally a bad method. On the contrary. The alternative would be solvent refining, which would reduce the naphtha requirement, but would
instead mean a lower yield and as a by-product would generate exotoxic
waste. To remove sulphur in the process would increase the ELU index,
but on the other hand, using the oil after use as a source for energy would
lower the amount of SO2 emission compared to traditional heavy fuel
oils. In addition to the product itself, hydrotreatment yields by-products:
naphtha and sulphur. The naphtha can be used for hydrogen production.
Altogether, refining leads to emissions of carbon dioxide, carbon monoxide, sulphur oxides, nitrogen oxides, hydrocarbons and dust. All
these emissions taken together, however, make a contribution of 0.0660
ELU/kg.

21

Crude oil
Shipping
Refinery

3%
Bitumen

96%
Fuel

1% Base oil

Refining

Energy, raw material

Emission
Waste

Application

Losses during
application

Rerefinings

Collection used oil

Energy, raw material
Emission

Figure 5. The figure above shows the life cycle of a base oil/transformer
oil. It shows that, after use, the oil can be used as an energy source.
Nynas produces Bitumen and Naphthenic oils only and has only a small
output of fuel.
ELU/kg oil
Raw materials (mostly oil and naphtha)
Electricity
Non-electrical energy
Atmospheric emission
Effluent
Waste
Total

0.50267
0.00065
0.02985
0.06599
0.00000025
0.0124
0.60039

The total, then, comes to 0.6 ELU/kg oil, a figure which only becomes
interesting when viewed in relation to the value for other products,
i.e. alternative products for the same function and products with other
functions relating to the end product.
A transformer manufacturer may find it interesting, for example,
that the oil has a very low ELU value compared with other materials.
The value for copper, for example, is 28.7 ELU/kg.
The quantity of crude oil used is estimated to account for nearly 80
per cent of the total ELU value. This is because the Nynas refinery has
small emissions and also because the use of crude oil is rated highly
under the EPS system. This means that measures to improve the refining yield, do a great deal to give transformer oil a low ELU value.
Hydrotreatment refining gives a yield of about 0.8, whereas solvent
refining gives about 0.5.
Using a life-cycle analysis for marketing is hazardous. It presupposes
that the result of the analysis can be generalised so as to apply to all

22

functions which a product can perform. One interesting application,

however, may be that of comparisons between subcontractors' environmental impacts. Perhaps one's own environmental impact can be reduced
by changing suppliers.
The strategy is in its infancy and methods are gradually being refined.

4.5 ORGANISATIONS AND

AUTHORITIES
Below we present some of the bodies that exercise an important influence on the formulation of Nynas policy.

4.5.1 CONCAWE
CONCAWE is the European organisation of the petroleum companies
for the environment, health and safety. The emphasis of its work is on
technical and economic studies of the refining, distribution and marketing of oil in Europe. CONCAWE was formed in 1963 and its secretariat has been located in Brussels, Belgium since 1990.
Work within CONCAWE is divided between eight Management
Groups:
Air Quality
Automotive Emissions
Health
Oil Pipelines
Petroleum Products
Safety
Water Quality
Refining Planning
The compilation of reports of different kinds is an important part
of CONCAWE's work. These reports contain the results of scientific
studies performed by experts in various working groups. The reports
are distinguished by their dependability, and they supply technical and
economic information to companies and authorities concerned with the
environment, health and safety. A very large part of the data used by
member companies in their safety data sheets has been compiled by
CONCAWE working groups.
There are various types of reports with various types of content,
indicated by the cover design. Yellow reports deal with matters of general interest, blue reports are product dossiers, reports in A5 format
are known as field guides and the white reports deal with matters of
special interest to different groups.
CONCAWE also arranges seminars, often resulting in reports, on
important subjects.
Because the content of CONCAWE's reports is becoming increasingly
complex and is of a high scientific standard, the organisation has also
begun disseminating its results in more readable form by publishing the
CONCAWE Review. For more information see:
http://www.concawe.be

23

4.5.2 Directorate General XI (DGXI)

DGXI is the European Union Directorate for Environment, Nuclear
Safety and Civil Protection. Its tasks are as follows:
Determining and managing standards and criteria for environmental
quality and environmental space
Addressing target groups with tasks and visions for solutions
Developing and managing legal, economic, financial and social
instruments
Promoting the application of policy instruments, environmental
infrastructure and appropriate implementation conditions
Enforcement, monitoring and evaluation of the implementation of
EU policies and regulations.
DGXI is divided into five Directorates, of which Directorate E is especially interesting to industry. Directorate E is responsible for the promotion and integration of environmental protection requirements into
industrial, internal market and consumer policies; the co-ordination of
policies and activities in the field of environmental control of industrial
installations and their emissions, industrial products and biotechnology,
and waste management.
Directorate E covers the following areas:
Industrial installations and emissions
Industrial hazards, environmental management and eco-audit
Chemical substances and biotechnology
Waste management
Industry, internal market, products and voluntary approaches.
The work of DGXI has been governed since 1993 by the Fifth
Environmental Action Programme, the title of which, Towards
Sustainability, underlines a concern with more long-term goals
than previously, as well as a global perspective.
The following instruments are used in pursuit of the programme
objectives:
Legislation to set environmental standards
Economic instruments to encourage the production and use of
environmentally-friendly products and processes
Horizontal support measures (information, educations, research)
Financial support measures (funds).
For more information see:
http://www.europa.eu.int/en/comm/dg11 /dg11home.html

24

5. APPENDIX
5.1 CHEMISTRY
Labelling for each product group, e.g. CAS, is decided by the chemical
composition of each group. Under this section, different ways of characterising oil products will be discussed.

5.1.1 Chemical composition

The naphthenic distillates used for Nynas' various product flows, all
come from the same kind of crude oil. This crude oil is distinguished
by high naphthene and aromate content, low paraffin content and a
large proportion of heavy molecules.
During distillation, the heavy molecules end up in the bitumen fraction. The lighter fractions are used for production of naphthenic base
oils, process oils and insulating oils.
The molecules in these fractions can be divided into three main
groups:
paraffins
naphthenes
aromates.

Paraffin

Isoparaffin

Naphthenes

Aromatic

Polyaromatic

Figure 6. Schematic molecule structures.

The paraffins are straight hydrocarbon chains with varying numbers

of carbon atoms.
The naphthenes are hydrocarbons containing one or more rings
with 5-6 carbon atoms each. There are no double bondings between the
carbon atoms in the rings. Paraffinic chains and aromate rings may be
bonded to a naphthenic ring.
The aromates consist of one or more aromatic rings, i.e. hydrocarbon rings with six carbon atoms and three double bondings between
them (the numbers of single and double bondings vary, and so the

25

molecule is usually drawn as a hexagon with a ring in the middle). The

aromates are divided into monoaromates (1 ring), diaromates (2 rings)
and polyaromates (3 rings). In addition to aromatic rings, aromatic
molecules can also contain naphthenic rings, paraffinic chains and heteroatoms. Hetero-atoms like sulphur and nitrogen are nearly 100 per cent
bonded to aromatic structures.
Complex structures with high molecular weight form part of the
bitumen fraction.

5.2 METHODS OF PAC ANALYSIS

When discussing polyaromate content, one is very liable to find oneself
in a chalk-and-cheese situation. Measurements performed using methods
like IP 346, HPLC and GC give a very wide variety of results, because
they measure completely different things, and so comparisons between
results are meaningless.
It is important to have a clear understanding about what the different methods measure and what it is one wishes to know.

5.2.1 IP 346
IP 346 is the method used for deciding which oils have to be labelled
under EU regulations. The limit for labelling is three per cent by
weight.
IP 346 measures the content of substances which are soluble in
dimethyl sulphate oxide (DMSO). DMSO is a polar organic solvent,
and substances which are soluble in it have to be fairly polar. The
occurrence of aromatic rings, naphthenic rings and so-called heteroatoms (such as sulphur, nitrogen and oxygen) make organic molecules
polar. The more rings and/or hetero-atoms, the more polar the molecules become.
DMSO dissolves all polyaromates. Quite a number of single aromates and naphthenes are also dissolved, especially if they contain heteroatoms. As a result, IP 346 values are a good deal higher than true PAC,
especially where naphthenic oils are concerned, naphthenes being a
good deal more polar than paraffins.
Nynas' R&D department has studied the composition of the molecules extracted with DMSO from severe hydrotreated naphthenic oil
and from an aromatic extract. With IP 346, severe hydrotreated naphthenic oil scored 1.7 per cent and the aromatic extracts 30 per cent. The
analysis was performed using HPLC (High Performance Liquid Chromatography). The DMSO-soluble severe hydrotreated naphthenic oil
fraction had a PAC of 5-10 per cent. The PAC of the DMSO-soluble
fraction from the aromatic extract proved to be between 20 and 50 per
cent. This means that a severely hydrotreated naphthenic oil had a PAC
of 0.1-0.2 per cent and the aromatic extract 6-15 per cent.
From these results one might jump to the conclusion that IP 346 is
a bad method. First, though, we should discuss what it is we really
want to know.
The main reason for wanting to measure PAC is that we want to

26

know whether the product may be carcinogenic. Results from IP 346

analyses show good correlation with the occurrence of skin cancer in
mice. The method, then, is relevant, even if it yields a percentage well
over the true PAC.
IP 346, in fact, does not purport to measure PAC, only to measure
the content of substances which are soluble in DMSO.

5.2.2 HPLC
HPLC is one of the methods which Nynas uses in-house for measuring PAC. It is faster than IP 346 and does not involve handling DMSO,
which is a very unpleasant chemical.
The Nynas HPLC method measures the quantity of substances
which are more polar than a given marker. The marker used is generally
either naphthalene or anthracene.
With naphthalene which has two aromatic rings as a marker,
severe hydrotreated naphthenic oil scores 1.7 per cent. An aromatic
extract scores 30 per cent with the same marker. This measurement
includes molecules with at least two aromatic rings, the majority of
polar diaromates and some monoaromates with hetero-atoms.
If instead we use anthracene (a three ring aromatic) as a marker, the
majority of aromates with at least three rings and a number of monoand di-aromates with hetero-atoms will be included. This time severe
hydrotreated naphthenic oil scores 0.17 per cent.

5.2.3 Gas chromatography

Gas chromotography mass spectrophotometer (GC-MS) measures the
concentrations of individual substances. If, for example, we wish to
measure the content of individual polyaromatic hydrocarbons (PAH)
or to know the PAH profile of an oil, GC-MS is the best method.
Sometimes, however, one comes across studies in which a number
of polyaromatic hydrocarbons have been selected and their concentrations measured and added together. The sum total is then claimed to
equal the total PAC. Often, only about 10 or so PAH has been measured, whereas the oil analysed may actually contain several thousand
polycyclic aromates.
A Swedish firm of environmental consultants has performed a GCMS analysis, using an ordinary standard method. Two Nynas oils and
an aromatic extract were measured for their content of 15 PAH (see
figure 7). The test showed that the total content of the individual polyaromates measured in severe hydrotreated naphthenic oil is less than 10
ppm, while mildly hydrotreated naphthenic oil contains upwards of
100 ppm and an aromatic extract about 850 ppm. In percentages this
comes to 0.001, 0.01 and 0.085 respectively.
There is a big difference between the severe hydrotreated naphthenic oil scores of 0.001 per cent by GC-MS and 1.7 by IP 346, and also
between the extract's 0.085 per cent by GC and 30 per cent by IP 346.
If the total content of polyaromatic hydrocarbons is to be obtained
by adding the individual concentrations, then of course one has to add

27

the concentrations of all polyaromates in the sample. For severe hydrotreated naphthenic oil, more than 345 individual polyaromates have
been identified. All one then sees is PAH. All substances with heteroatoms have been removed by extraction prior to GC-MS analysis.
Once again, therefore, one has to ask: What is it we wish to know?
If we want to know which oils may be carcinogenic, IP 346 will supply
the answer. If we wish to know the total PAC, there is no really exact
method, but a good answer can be obtained using HPLC or a CG
method which includes all polyaromates.

Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)fluorene
Benzo(a)anthracene
Chrysene-Triphenylene
Benzo(j)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno(1,2,3,cd)-Pyrene
Benzo(g,h,i)-Perylene
Anthatrene
Dibenzo(a,c) anthracene
IP 346

Severely
hydrotreated

Mildly
hydrotreated

Aromatic
extracts

<0.9
<0.9
<0.5
<0.3
<0.5
<0.5
<0.5
<0.6
<0.6
<0.6
<0.6
<0.9
<0.9
<0.9
<1
1.7%

8.5
1.6
<2
7.9
15
8.3
<4
15
27
6
<2
<1
<1
<1
<1
>3%

58
1.6
19
41
100
29
290
89
110
2
68
<0.5
<0.5
<0.5
7.6
30%

Figure 7. PAC ppm measured by GC-MS.

5.3 REFINING TECHNIQUE

There are several choices to be made when naphthenic crude is refined
to different grades. The technique chosen depends on a number of preconditions. Various environmental problems arise, some of them more
easy or difficult than others to deal with, depending on the technique
adopted.

5.3.1 The various stages of refining

The first stage in refining is vacuum distillation, in which the oil is

divided into different fractions, depending on molecular boiling
points.
After distillation the oil can pass through an extraction process to
remove aromatic molecules.
Whether it has gone through extraction or not, the oil can be gently
or severely hydrotreated.

28

5.3.2 Distillation
The first step in the refinery train is always distillation. In this process
the crude is separated into different boiling ranges by fractionation. For
light crudes this is done under normal pressure. For heavy crudes or
residues the fractionation is performed under vacuum conditions.
Different viscosities are obtained for different oils with a given boiling range depending on their chemistry. The higher the boiling ranges,
the more complex the structure that will be obtained. Gasoline, for
example, might contain benzene, which will not be found in heavier
products such as lube oils. On the other hand, the complex PAC molecules will show up more isomers with increasing boiling ranges.

Temperature

Temperature
The 5% point correlates
with the flashpoint
Crude
The 50% point correlates
with the viscosity

50

100

Dist.curve

50

100

Bitumen

Figure 8. Distillation process.

5.3.3 Solvent refining

In solvent refining, the distillate is extracted with a polar solvent in
order to remove aromatic and polyaromatic compounds. Extraction
results in two phases, one with low aromatic content and one consisting almost entirely of aromatic compounds plus the extraction agent,
normally furfural. The normal aromatic content obtained with solvent
extraction is between 5 and 11%. It is hard to achieve more or less than
this, due to equilibrium between the phases. If higher aromatic content
is aimed for, the content of individual PAC will also increase.
The extract coming out of this process is of less value today, due to its
high PAC content and because it is labelled with a skull and crossbones
both for carcinogenicity and for ecotoxicity. Furthermore, the sulphur
content is also high, which makes it of small worth for heating oils (SO2
emissions).

29

Solvent
Solvent
Raffinate

D = Distillate
R = Raffinate
E = Extract

Dist

D
Mixing
R

Extract

Oil

CA%
20-25
5-12
>40

Dist
E

Figure 9. In the figure above, the extract emerging from the process
possesses low commercial value due to the high content of sulphur and
PAC.

5.3.4 Hydrotreatment
Hydrotreatment of the distillate involves adding hydrogen in the presence of a catalyst at high temperature and high pressure. The hydrogen
then reacts with aromatic rings, causing the double bondings to break
and hydrogen atoms to take over the free bonding spaces. The bondings between hetero-atoms and hydrocarbons are also broken, with the
result that the hetero-atoms are replaced by hydrogen atoms. Hydroxyl
groups also disappear, which leads to the disappearance of naphthenic
acids, for example.
As a result, aromatic rings are converted into naphthenic rings and
hetero-atoms are removed. The proportion of aromates and heteroatoms reacting with the hydrogen depend on the process conditions.
Higher pressures and temperatures together with more efficient catalysts will mean a larger proportion of the aromates reacting with the
hydrogen.

CA %
20-25

H2

X
H

H.

H.

H.

CATALYST

MEDIUM SEVERITY

CA 25%
feed

CA %
2-17

H2

X
.
. .
H.
H. H H H
H. H.
H

H.
H. H. H.
H.
H
HIGH SEVERITY

CATALYST

Light products, H2S, NH3, H2O

Figure 10. Simplified hydrogenation process (where x=sulphur, nitrogen and oxygen).

In theory, hydrotreatment can be taken to any lengths, but in practice,

of course, there are limits. Besides, excessively severe treatment would
cause the naphthenic rings to disintegrate and paraffins to form, which
is undesirable if one plans to utilise the special properties of naphthenes,
such as good solubility and good low temperature properties. If refin-

30

ing is to be taken to extreme lengths, as for example in the production

of white oils, it may be preferred to extract first and hydrotreat the
oil afterwards.

5.3.5 Acid clay treatment

Sulphuric acid is the most versatile refining agent known. It acts as an
extraction medium and as a reactive agent, depending on temperature
and concentration. Oleum is still used in some countries for production
of petroleum sulphonate, but is being successively replaced by hydrotreatment. Acid clay is an obsolete process today, due to labelling and
the ecotoxic waste which the process generates.

31

Responsible Care
Nynas is a signatoriy to the international Responsible Care programme of the
CEFIC (European Chemical Industry Federation).
The programme is the chemical industrys commitment to continuous
improvement in all aspects of health, safety and environmental protection.
Responsible Care is a voluntary initiative, fundamental to the industrys
present and future performance and a key to regaining public confidence and
maintaining acceptability.
The signatories pledge that their companies will make health, safety and
environmental performance an integral part of overall business policy on all
levels within their organizations.

SALES OFFICES
Australia & New Zealand
Nynas (Australia) Pty Ltd. One Park Road, Milton, QLD 4064, Brisbane, Australia
Tel: +61 7 387 66 944. Fax: +61 7 387 66 480
Belgium
Nynas N.V., Haven 281, Beliweg 22, BE-2030 Antwerp
Tel: +32 3 545 68 11. Fax: +32 3 541 36 01
Brazil
Nynas Do Brasil LTDA, Rua Jesuino Arruda 676, 9th Floor cj. 91, Itaim Bibi, So Paulo, SP
Tel: +55 11 3083-1399. Fax: +55 11 3082-2537
Canada
Nynas Canada Inc., Suite 610, 201 City Centre Drive, Mississauga, Ontario, Canada L5B 2T4
Tel.: +1 905 804-8540. Fax: +1 905 804-8543
China
Nynas (Hong Kong) Ltd. Beijing, Room 703C, Huapu International Plaza
No. 19 Chaoyangmenwai Street, Beijing, 100020
Tel: +86-10-6599 26 95. Fax: +86-10-6599 26 94
France
Nynas S.A., Le Windows, 19 Rue dEstienne dOrves, F-93500 Pantin
Tel: +33 1 48 91 69 38. Fax: +33 1 48 91 66 93
Germany
Nynas GmbH, Berliner Allee 26, D-40212 Dsseldorf
Tel: +49 211 828 999 0. Fax: +49 211 828 999 99
Great Britain
Nynas Naphthenics Ltd, Wallis House, 76 North Street, Guildford, Surrey, GU1 4AW
Tel: +44 1483 50 69 53. Fax: +44 1483 50 69 54
Hong Kong
Nynas (Hong Kong) Ltd, 1301 Chinachem Johnston Plaza, 178-186 Johnston Road, Wanchai
Tel: +852 2591 99 86. Fax: +852 2591 49 19.
Italy
Nynas S.r.l., Via Teglio 9, I-20158 Milan
Tel: +39 02 607 01 87. Fax: +39 02 688 48 20
Malaysia
Nynas HK Ltd, Representative office, Suite No 7, 22nd Floor, MNI Twins Tower 2
11 Jalan Pinang, 50 450 Kuala Lumpur
Tel: +603 21 69 65 08. Fax: +603 21 69 64 09
Poland
Nyns Sp. z.o.o., ul. Toszecka 101, 44-100 Gliwice
Tel: +48 32 232 74 10. Fax: +48 32 279 28 50
South Africa
Nynas South Africa (PTY) Ltd, Gatesview House A3, Constantia Park
Cnr 14th Avenue and Hendrik Potgieter Street Weltevreden Park
Tel: +27 11 675 1774. Fax: + 27 11 675 1778
Spain
Nynas Petrleo S.A., C/Serrano 45 - 7Dcha, E-28001 Madrid
Tel: +349 1 431 53 08. Fax: +349 1 575 49 12

Turkey
Nynas Naphthenics Yaglari Tic. Ltd. Sti. Kantaciriza Sokak 15/3, 81070 Erenky, Istanbul
Tel: +90 216 368 38 42. Fax: +90 216 368 37 48
Central- and Eastern Europe / Middle East / Latin America
Nynas Naphthenics AB
Box 10701, S-121 29 Stockholm, Sweden. Tel + 46 8 602 12 00. Fax: + 46 8 508 665 10
RESEARCH & DEVELOPMENT
Nyns Naphthenics AB, S-149 82 Nynshamn, Sweden
Tel: +46 8 520 65 000. Fax: +46 8 520 20 743
Internet: www.nynas.com/naphthenics

adept/RiksbyTryck, Solna, Sweden 98.011

Sweden
Nyns Naphthenics AB Norden, P.O. Box 10701, S-121 29 Stockholm
Tel: +46 8 602 12 00. Fax: +46 8 81 20 12