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Survey of alkylphe-
nols and alkylphe-
nol ethoxylates
Part of the LOUS-review
Environmental project No. 1470, 2013
Survey of alkylphenols and alkylphenol ethoxylates 1

Title: Editing:
Survey of alkylphenols and alkylphenol Carsten Lassen 1

ethoxylates Allan Astrup Jensen 2
Jakob Maag 1
Frans Christensen 1
Jesper Kjølholt 1
Christian Nyander Jeppesen 1
Sonja Hagen Mikkelsen 1
Sally Innanen 1
1 COWI A/S, Denmark

2 NIPSECT, Denmark
Published by:
The Danish Environmental Protection Agency

Strandgade 29
1401 Copenhagen K, Denmark
www.mst.dk/english
Year:
ISBN no.
2013
978-87-92903-99-0
Disclaimer:
When the occasion arises, the Danish Environmental Protection Agency will publish reports and papers concerning re-
search and development projects within the environmental sector, financed by study grants provided by the Danish Envi-
ronmental Protection Agency. It should be noted that such publications do not necessarily reflect the position or opinion
of the Danish Environmental Protection Agency.
However, publication does indicate that, in the opinion of the Danish Environmental Protection Agency, the content
represents an important contribution to the debate surrounding Danish environmental policy.
Sources must be acknowledged.
2 Survey of alkylphenols and alkylphenol ethoxylates

Contents
Preface ...................................................................................................................... 5
Summary and conclusion .......................................................................................... 7
Sammenfatning og konklusion ................................................................................ 13
1. Introduction to the substance group ................................................................. 19

1.1 Definition of the substance groups ......................................................................................19
1.2 Substances within the substance groups ............................................................................ 22
1.3 Function of the substances for main application areas ...................................................... 32
2. Regulatory framework...................................................................................... 33
2.1 EU and Danish legislation ................................................................................................... 33
2.1.1 Existing legislation ................................................................................................ 33
2.1.2 Ongoing activities - pipeline ..................................................................................37
2.2 International agreements .................................................................................................... 39
2.3 Eco-labels ............................................................................................................................. 40
2.4 Summary on the regulatory framework .............................................................................. 42
3. Manufacture and uses ...................................................................................... 45

3.1 Global manufacture and use of AP/APEO .......................................................................... 45
3.2 Manufacture and use AP/APEO in the EU ......................................................................... 45
3.2.1 Nonylphenol and nonylphenolethoxylates .......................................................... 46
3.2.2 Octylphenol and octylphenolethoxylates ............................................................. 49
3.2.3 Dodecylphenol and dodecylphenol ethoxylate .................................................... 52
3.2.4 Butylphenols.......................................................................................................... 54
3.2.5 Dibutyl- and tributylphenols ................................................................................ 56
3.2.6 2,6-Di-tert-butyl-p-cresol ..................................................................................... 56
3.2.7 Other alkylphenols .................................................................................................57
3.2.8 Summary on the use of AP/APEO in the EU ........................................................57
3.3 Manufacture and use of AP/APEO in Denmark ................................................................. 58
3.3.1 Manufacture, import, export and consumption of AP/APEO on its own
and in mixtures ..................................................................................................... 58
3.3.2 Consumption of AP/APEO by main application areas ........................................ 63
3.4 Summary on the use of AP/APEO in Denmark and the EU .............................................. 69
4. Waste management .......................................................................................... 77

4.1 Waste from manufacture and industrial use of AP/APEO.................................................. 77
4.2 AP/APEO in waste and releases from disposal of solid waste ............................................ 77
4.3 Waste oil disposal ................................................................................................................ 78
4.4 AP/APEO in waste water and sewage sludge ..................................................................... 78
4.5 Summary for waste management........................................................................................ 83
5. Environmental effects and fate ......................................................................... 85

5.1.1 Nonylphenol and nonylphenol ethoxylates ......................................................... 85
5.1.2 Octylphenol and octylphenol ethoxylates ............................................................ 89
5.1.3 AP/APEO of a chain length of less that eight........................................................ 91
5.1.4 AP/APEO of a chain length of more than nine .................................................... 93

5.2 Summary of environmental effects ..................................................................................... 94
6. Human health effects ....................................................................................... 97

6.1 Introduction to human health effects of AP/APEO............................................................ 97
6.2 Nonylphenol and nonylphenol ethoxylates ........................................................................ 97
6.3 Octylphenol and octylphenol ethoxylates ......................................................................... 100
6.4 AP/APEO of a chain length of less than eight .................................................................. 104
6.4.1 4-tert-Butylphenol .............................................................................................. 104
6.5 AP/APEO of a chain length of more than nine ..................................................................105
6.6 Assessment across the groups ........................................................................................... 106
6.7 Summary on human health effects ................................................................................... 109
7. Monitoring data and exposure ......................................................................... 111

7.1 Monitoring of AP/APEO in the environment in Denmark and releases from point
sources ..................................................................................................................................111
7.1.1 AP/APEO in the environment ..............................................................................111
7.1.2 Groundwater ........................................................................................................ 112
7.1.3 AP/APEO in point sources................................................................................... 113
7.2 European Pollutant and Transfer Register (E-PRTR) ...................................................... 114
7.3 AP/APEO in the Baltic Sea and North Sea environments ................................................ 114
7.4 Human exposure and biomonitoring ................................................................................. 116
7.4.1 Intake of AP/APEO .............................................................................................. 116
7.4.2 Human biomonitoring data ................................................................................. 118
7.5 Summary regarding monitoring and exposure ................................................................. 119
8. Information on alternatives............................................................................. 121

8.1 Alternatives to alkylphenol ethoxylates ............................................................................. 121
8.2 Alternatives to 4-nonylphenol (NP), 4-tert-octylphenol and 4-tert-butylphenol .......... 130
8.2.1 Alternatives to other specific AP/APEO.............................................................. 131
8.3 Conclusion on alternatives ................................................................................................. 131
9. Overall conclusions ........................................................................................ 133
10. Abbreviations and acronyms ........................................................................... 141
11. References ..................................................................................................... 143
Annex 1: Uses and tonnage bands according to registrations ....................... 155
Annex 2: Self classification of AP/APEO ..................................................... 158
Annex 3: Background information to chapter 3 on legal framework ............ 172
Annex 4 AP/APEO in the Nordic environment ............................................ 177

Preface
Background and objectives

The Danish Environmental Protection Agency’s List of Undesirable Substances (LOUS) is intended
as a guide for enterprises. It indicates substances of concern whose use should be reduced or elimi-
nated completely. The first list was published in 1998 and updated versions have been published in
2000, 2004 and 2009. The latest version, LOUS 2009 (Danish EPA, 2011) includes 40 chemical
substances and groups of substances which have been documented as dangerous or which have
been identified as problematic using computer models. For inclusion in the list, substances must
fulfil several specific criteria. Besides the risk of leading to serious and long-term adverse effects on
health or the environment, only substances which are used in an industrial context in large quanti-
ties in Denmark, i.e. over 100 tonnes per year, are included in the list.
Over the period 2012-2015 all 40 substances and substance groups on LOUS will be surveyed. The
surveys include collection of available information on the use and occurrence of the substances,
internationally and in Denmark, information on environmental and health effects, on alternatives
to the substances, on existing regulation, on monitoring and exposure, and information regarding
ongoing activities under REACH, among others.
On the basis of the surveys, the Danish EPA will assess the need for any further information, regula-
tion, substitution/phase out, classification and labelling, improved waste management or increased
dissemination of information.
This survey concerns alkylphenols and alkylphenol ethoxylates (AP/APEO). These substances were
included in the first list in 1998 and have remained on the list since that time.
The entry in LOUS for these substances is “alkylphenols and alkylphenol ethoxylates” and it is indi-
cated that the group consists of many compounds, so no CAS numbers are given. Nonylphenols
(NP), octylphenols (OP) and nonylphenol ethoxylates (NPEO) are mentioned as examples of sub-
stances within the group. It is indicated that the substances are used as surfactants in paint and
varnish hardeners and adhesives, amongst other functions.
The main reason for the inclusion in LOUS is the classification of nonylphenols as toxic to repro-
duction, but also that NP, OP and NPEO are on the EU 'Priority list of substances for further evalua-
tion of their role in endocrine disruption'. Furthermore, some OP compounds have properties of
concern indicated in the companies’ ‘self-classification’ of the substances.
It is stated that the substances are only subject to partial restrictions on use; however, other uses
are also considered to be a cause for concern with regard to the environment.
The main objective of this study is, as mentioned, to provide background for the Danish EPA’s con-
sideration regarding the need for further risk management measures. The whole group of AP/APEO
has never been surveyed or reviewed in Denmark; therefore, one of the objectives is also to provide
a background for a more specific description of the substance group, along with a clear definition of
which substances are included in the group.

The process
The survey has been undertaken by COWI A/S in cooperation with NIPSECT from June to Novem-
ber 2012.The work has been followed by an advisory group consisting of:
• Sidsel Dyekjær, Danish EPA

• Ulla Hansen Telcs, Confederation of Danish Industry
• Cathrine Berliner Pedersen, Association of Danish Cosmetics, Toiletries, Soap and Detergent
Industries
• Allan Astrup Jensen, NIPSECT
• Carsten Lassen, COWI A/S
Data collection
The survey and review is based on the available literature on the substances, information from da-
tabases and direct inquiries to trade organisations and key market actors. During summer 2012
available literature, relevant legislation and regulatory activities in the pipeline, and statistics was
searched using search strings or CAS Numbers covering the different groups of alkylphenols and
alkylphenol ethoxylates. Data was mainly searched via the Internet on websites of relevant organi-
sations and databases. The data search included (but was not limited to) the following:
• Legislation in force from Retsinformation (Danish legal information database) and EUR-Lex
(EU legislation database);
• Ongoing regulatory activities under REACH and intentions listed on ECHA’s website (incl.
Registry of Intentions and Community Rolling Action Plan);
• Relevant documents regarding International agreements from HELCOM, OSPAR, the Stock-
holm Convention, the PIC Convention, and the Basel Convention.
• Data on harmonised classification (CLP) and self-classification from the C&L inventory data-
base on ECHAs website;
• Data on ecolabels from the Danish ecolabel secretariat (Nordic Swan and EU Flower) and the
German Angel.
• Pre-registered and registered substances from ECHA’s website;
• Production and external trade statistics from Eurostat’s databases (Prodcom and Comext);
• Export of dangerous substances from the Edexim database;
• Data on production, import and export of substances in mixtures from the Danish Product
Register (confidential data, not searched via the Internet);
• Date on production, import and export of substances from the Nordic Product Registers as
registered in the SPIN database;
• Information from Circa on risk management options (confidential, for internal use only);
• Monitoring data from the National Centre for Environment and Energy (DCE), the Geological
Survey for Denmark and Greenland (GEUS), the Danish Veterinary and Food Administration,
the European Food Safety Authority (EFSA) and the INIRIS database.
• Waste statistics from the Danish EPA;
• Chemical information from the ICIS database;
• Reports, memorandums, etc. from the Danish EPA and other authorities in Denmark;
• Reports published at the websites of: The Nordic Council of Ministers, ECHA, the EU Commis-
sion, OECD, IARC, IPCS, WHO, OSPAR, HELCOM, and the Basel Convention;
• US EPA, Agency for Toxic Substances and Disease Registry (USA) and Environment Canada.
• PubMed and Toxnet databases for identification of relevant scientific literature.
Besides, direct enquiries were sent to Danish and European trade organisations and a few key mar-
ket actors in Denmark.

Summary and conclusion
The Danish Environmental Protection Agency’s List of Undesirable Substances (LOUS) is intended
as a guide for enterprises. Over the period 2012-2015, all 40 substances and substance groups on
LOUS will be surveyed and reviewed, and, on the basis of the surveys, the Danish EPA will assess
the need for any further regulation, substitution/phase out, classification and labelling, improved
waste management or increased dissemination of information.
This survey concerns the substance group “alkylphenols and alkylphenol ethoxylates” (AP/APEO),
which has been on LOUS since the first version was published in 1998. It is indicated in LOUS that
the substance group consists of many compounds, but the group is not clearly defined. One of the
objectives of this survey is to provide a background for a more specific description of the LOUS
entry for these substances. The alkylphenols are phenol derivatives with one or more chains of car-
bons of varied length attached to the phenol group. The alkylphenol ethoxylates are chemicals de-
rived from the alkylphenols. Several hundred substances within the group of AP/APEO have been
pre-registered under REACH. Nonylphenols (NP, with a 9-carbon chain), octylphenols (OP, with an
8-carbon chain) and nonylphenol ethoxylates (NPEO, with a 9-carbon chain and a chain of ethox-
ylate groups) are mentioned in LOUS as examples of substances within the group.
An overview of the production and consumption for 29 substances or substances groups at EU level
and in Denmark is provided in Table 20 of section 3.4. Nonylphenols, octylphenols, dodecylphe-
nols, 4-tert-butylphenol and 2,6-di-tert-butyl-p-cresol (BHT) are the alkylphenols used in the larg-
est quantities, each with a production and consumption in the EU in the 10,000-100,000 t/y range.
Nonylphenol ethoxylates, with a consumption in the EU in the range of 2,000-20,000 t/y, are the
most used of the alkylphenol ethoxylates.
Nonylphenols and nonylphenol ethoxylates

Historically the AP/APEOs of main concern have been the nonylphenols (NP) and nonylphenol
ethoxylates (NPEO); these substances have been addressed by environmental release reduction
measures since the early 1990s in Denmark and internationally. An EU Risk Assessment for
NP/NPEO from 2002 identified the need for reducing the risk to the environment from the sub-
stances. A marketing and use restriction for applications which resulted in significant releases to the
environment went into force at EU level in 2004. The restriction addresses the use of these sub-
stances for nine purposes, including application in cleaning agents (with some exemptions), in
textiles and leather auxiliaries and as a coformulator in biocides/pesticides.
Nonylphenols are considered endocrine disruptors and classified as toxic to reproduction and toxic
to the environment. A REACH Annex XV dossier has recently been prepared for identification of 4-
nonylphenol (a group of linear or branched nonylphenols) as SVHC (Substance of Very High Con-
cern) on the basis of their endocrine disrupting properties. The endocrine potency of nonylphenols
in combination with its persistence and the high observed concentrations in the aquatic environ-
ment implies a risk of estrogen-like effects occurring as a result of organisms being exposed to the
substance. Monitoring data from recent years have demonstrated that the concentration of
nonylphenols in lake sediments in Denmark and in marine sediments from the Baltic Sea and the
Inner Danish Waters exceeded the so-called “predicted no-effect concentration”; i.e. actual effects
on organisms in the environment cannot be excluded.

The main concern related to the nonylphenol ethoxylates (NPEO) is that they degrade to nonylphe-
nols in the environment and through the process of waste water treatment. Discharges of
nonylphenol ethoxylates from waste water treatment plants are considered the main source of
nonylphenols in the environment.
In the EU, nonylphenols are mainly used as raw material (co-monomer) in the manufacture of phe-
nolic and epoxy resins (polymeric material) and as intermediate in the production of NPEO and a
few other chemical substances. In 1999, consumption in the EU was close to 80,000 t/y, but today
it is likely to be in the 25,000-50,000 t/y range, mainly due to the restriction of the use of NPEO.
NPEO has historically been widely used as surfactant in cleaning agents, but the total consumption
in the EU has decreased from 118,000 t/y in 1999 to 2,000-20,000 t/y in 2011 as a consequence of
the restriction, which entered into force in 2004. In Denmark today, the main registered use of
nonylphenols is in paint, lacquers and varnishes, sealants, and filling agents. A significant quantity
of nonylphenol ethoxylates is still registered in the Danish Product Register as used in cleaning
agents and biocidal products. It is not clear if this is due to inadequate updating of the notifications
or if it represents non-restricted applications. About 12% of the registered quantity of nonylphenol
ethoxylates is used for paint, lacquers and varnishes which are not restricted.
NP/NPEO in textiles imported from countries outside the EU is likely the major source of
NP/NPEO to municipal waste water treatment plants and the main source of releases of the sub-
stances to the environment, as indicated in studies from several EU Member States. As a conse-
quence of this, Sweden is in the process of preparing a REACH restriction proposal on the manufac-
ture and import of textiles and leather containing NP/NPEO.
Human exposure to nonylphenols in food and consumer products is generally not considered to be
of concern. The few data available on dietary intake indicate that the level is well below the tolerable
daily intake (TDI) estimated by the former Danish Institute of Food Safety and Toxicology, but
newer data from Sweden indicate that the intake with food may be higher than previously reported.
A number of alternatives have substituted for nonylphenol ethoxylates for the restricted applica-
tions. The alternatives are mainly based on different groups of APEO-free surfactants although
octylphenol ethoxylates may have been used as alternatives to a limited extent. Assessments of the
environmental fate and effects of the APEO-free alternatives conclude that, in general, the alterna-
tives are of less environmental concern regarding persistence and aquatic toxicity of degradation
products. Alternatives to nonylphenol ethoxylates in paint and varnishes appear to be available, but
no recent assessment of their technical and economical feasibility has been carried out. Further-
more, no thorough assessment of alternatives to nonylphenols in paint and varnishes has been
identified.
Octylphenols and octylphenol ethoxylates

Octylphenols (OP) are used in quantities of approximately 20,000 t/y in the EU of which 98% is
used as raw material (co-monomer) for the manufacture of phenolic resins and tackifiers which are
mainly used in rubber for tyres. A small amount is used for production of octylphenol ethoxylates
(OPEO) which are used as surfactants for some of the same applications as nonylphenol ethox-
ylates, but in a lower quantity: about 1,000 t/y in the EU. The main non-confidential registered use
of OP/OPEO in Denmark is the use of octylphenol ethoxylates in paint, lacquers and varnishes but
in significantly lower quantities than the quantities of NP and NPEO used for this application area.
Octylphenol ethoxylates may be present in low concentrations as un-reacted substance in OP-based
plastics and rubbers.
Compared to the NP/NPEO, OP/OPEO are much less regulated, although the substance used in
highest quantity, 4-tert-octylphenol (also called p-tert-OP) has the same harmonised classification
for aquatic toxicity as NP. Octylphenol ethoxylates may be degraded into octylphenols in the envi-

ronment by the same mechanisms as the degradation of nonylphenol ethoxylates into nonyl-
phenols. The OP/OPEOs are, like NP/NPEO, included in the OSPAR list of priority substances and
the HELCOM Baltic Sea Action Plan. They are priority substances under the EU Water Framework
Directive and within the EU Community strategy for endocrine disrupters. 4-tert- Octylphenol is
not classified as toxic to reproduction.
The concentrations of the substances in municipal wastewater and in sewage sludge are significant-
ly lower than the concentrations of NP/NPEO. The concentrations in lake sediments in Den-mark
and in marine sediments in the Baltic region and the Inner Danish Waters are also significantly
lower than the concentration of NP/NPEO. However, HELCOM concludes in its most recent as-
sessment that about half of the surface sediment samples exceeded the threshold concentration for
octylphenols in sediments suggested in the context of the EU Water Framework Directive.
One of the main octylphenols, 4-tert-octylphenol, is included in the REACH candidate list with the
scope of environmental concern. A REACH Annex XV dossier has recently been prepared for identi-
fication of OPEO as SVHC (Substance of Very High Concern). The basis for the proposal is the deg-
radation of octylphenol ethoxylates to octylphenols, which has endocrine-disrupting properties in
the environment, and that short-chain octylphenol ethoxylates may cause endocrine-disrupting
adverse effects at similar or slightly higher concentrations compared to octylphenols.
Dodecylphenols and dodecylphenol ethoxylates

Dodecylphenols (DP, with a 12-carbon chain) are the only commercially important AP with a carbon
chain longer than 9. About 99% of the EU consumption (approximately 50,000 t/y) is used as an
intermediate in the production of lubricant additives. Dodecylphenols are present in the final addi-
tives at low levels. Less than 1% of the dodecylphenols is used for manufacturing of dodecylphenol
ethoxylates (DPEO) used as anti-rust agents in lubricants.
A harmonised classification and labelling proposal has been submitted for 4-(3,4,5-
trimethylheptyl)phenol (a branched dodecylphenol) suggesting classification as carcinogenic,
flammable, and eye damage/irritation. None of the dodecylphenols are listed in the EU list of endo-
crine disruptors. According to a PBT assessment of one of the dodecylphenols, the substance meets
the T criterion, and is likely to meet the P and vP criteria. It does not meet the B criterion and so is
not considered to be a PBT substance. The acute toxicity of dodecylphenols is at the same level as
the toxicity of octylphenols.
Dodecylphenols and dodecylphenol ethoxylates are not addressed by any EU regulation, are not
classified as priority substances under the Water Framework Directive and are not included in the
OSPAR list of priority substances or the HELCOM Baltic Sea action plan.
Very few monitoring data have been identified by the survey. In a screening of AP/APEO in the
Nordic environment, dodecylphenols were, alongside octylphenols, nonylphenols and nonylphenol
ethoxylates, the substances found in highest concentrations in all sewage water samples. A provi-
sional UK environmental risk assessment of dodecylphenols estimated that the main source of do-
decylphenols to the environment was releases of DP to waste water from lubricant use and disposal
(primary as spill and leakages). The environmental risk assessment indicated a potential risk to
some organisms in the aquatic environment for some scenarios, and a need for more reliable data
on environmental exposure.
Short chain alkylphenols (with <8-carbon chains)

The short chain alkylphenols are in general not used to produce alkylphenol ethoxylates, so the
issues of the ethoxylates being sources of the alkylphenols in the environment do not apply to the
short chain alkylphenols. The short chain alkylphenols are a highly diverse group of substances with

one, two or three short carbon chains attached to the phenol. The application areas of the short
chain alkylphenols are quite diversified.
The short chain alkylphenols are generally of less concern than nonylphenols and octylphenols in
the environment, because they are biodegradable and do not bioaccumulate to the same extent.
They are not included in the OSPAR list of priority substances, the HELCOM Baltic Sea action plan,
are not classified as priority substances under the EU Water Framework Directive, and are not
priority substances within the EU Community strategy for endocrine disrupters. The exceptions are
2,4,6-tri-tert-butylphenol, which is included in the OSPAR list of priority substances and indicated
as potentially toxic, persistent and bioaccumulative and 4-tert-butylphenol, which is a category 2
substance (evidence of potential to cause endocrine disruption) on the EU list of potential endo-
crine disruptors.
One the main reasons for concern about nonylphenols and octylphenols is the endocrine-disruptive
effects of the substances. The alkylphenols with alkyl groups having more than two carbons at-
tached at position 4 of the phenol showed profiles very similar to that of estrogen. The available
data indicate that both the position (para > meta >ortho) and branching (tertiary > secondary =
normal) of the alkyl group affect estrogenicity. Optimal estrogenic activity requires a single tertiary
branched alkyl group composed of between 6 and 9 carbons located at the 4-position on a phenol
ring without more alkyl groups. It should therefore be underlined that primary the para- (4-) mono-
substituted alkylphenols seem to be endocrine disruptors, and 4-nonyl phenol and 4-tert-octylpenol
are the most potent ones. 2,4-di-tert-Butylphenol, however is as mentioned in the following includ-
ed in the Community Rolling Action Plan (CoRAP) for substance evaluation because it is suspected
to be an endocrine disruptor.
The relatively few data available indicate that the concentrations of the short-chain alkylphenols in
municipal waste water and in sewage sludge is significantly lower (ten to hundred times lower) than
the concentrations of NP/NPEO. 4-tert-Butylphenol has been demonstrated to be present in sedi-
ments in the Baltic Sea in concentrations higher than octylphenols and comparable with nonylphe-
nols, while hardly any data for the other short-chain alkylphenols have been identified in this sur-
vey. The pathways of 4-tert-butylphenol to the environment have not been studied in detail.
Two of the substances are used in quantities of more than 20,000 t/y at EU level: 4-tert-
butylphenol (also named ptBP) and 2,6-di-tert-butyl-p cresol (BHT).
4-tert-Butylphenol is mainly used in a similar way as 4-nonylphenol and 4-tert-octylphenol as co-

monomer for production of phenolic resins and chain terminator in the production of polycar-
bonate. 4-tert-Butylphenol is the only one of the short chain alkylphenols for which an EU Risk
Assessment has been undertaken. According to the Risk Assessment, unreacted 4-tert-butylphenol
in 4-tert-butylphenol-based plastics and rubbers is considered the main source of consumer expo-
sure to the substance. The 4-tert-BP is prohibited for use in cosmetics but does not have a harmo-
nised classification. An proposal for a harmonised classification as irritating to skin, eye damaging,
toxic to reproduction and exerting specific target organ toxicity has recently been submitted.
2,6-di-tert-butyl-p cresol (BHT) is used as antioxidant in a wide group of products; among these,
food and feedstuff. The substance has been suggested for further environmental risk assessment by
the OECD.
2,4-di-tert-butylphenol, which is used as chemical intermediates for the production of plastic addi-
tives in quantities >1,000 t/y at EU level, is included in the Community Rolling Action Plan
(CoRAP) for substance evaluation due to its use and exposure pattern and that it is a suspected
endocrine disruptor.

2,4,6-tri-tert-butylphenol, is as mentioned included in the OSPAR list of priority substances. The
substance is mainly used as intermediate and the environmental releases from its use is estimated
to be small.
Thymol, used in cleaning agents and scented articles, has a harmonised classification as acute toxic,
skin corroding and aquatic chronic toxicity. According to the self classification notified to the Clas-
sification & Labelling (C&L) Inventory database at the website of the European Chemicals Agency
(ECHA), most of the related substances have quite similar classifications.
Overall conclusion concerning the grouping of the substances

NP and OP share some of the same environmental and health properties and the two substance
groups are together with their ethoxylates the AP/APEO of major concern. Dodecylphenols and
their ethoxylates are released to the environment in lower quantities, but of concern due to their
environmental and health properties. Among the short chain alkylphenols (<8 carbon atoms), 4-
tert-buylphenol is used for the same purposes as 4-nonylphenol and 4-tert-octylphenol, but the
release and exposure pattern is quite different. Most of the other short-chain mono-, di- and trial-
kylphenols are of less concern: the releases to the environment are in general significantly smaller
than for NP; they have a significantly lower potential for bioaccumulation than the long chain (C8-
C12) alkylphenols; they appear to be more biodegradable, and their estrogenic potency is lower.
Furthermore, they are used for different applications than NP and OP and their ethoxylates. How-
ever, some of the short-chain substances may be of some concern.
Based on the available data it appears not to be justified to target the short-chain alkylphenols and
the long-chain alkylphenols as one group, but rather to assess each of the short-chain alkylphenols
individually in order to identify any needs for measures to reduce the human and environmental
exposure.
Data gaps
The survey addresses a wide range of substances and for most of the substances limited data are
available on the life cycle releases of the substances, human health and environmental exposure and
concentrations in the environment. The most important data gabs identified, when considering
which substances are of major concern, are:
• Updated information on current uses and on the significance of the potential sources of releas-
es of NP/NPEO to the environment is missing.
• The registered quantities of NPEO used in cleaning and maintenance products in Denmark
calls for a clarification of actual uses.
• For several of the substances, the available information on the total manufacture and import to
the EU in the registrations is not in accordance with information obtained from the industry
and calls for a clarification.
• For substances used in lubricants and oils, data on the potential releases from spill and dispos-
al of waste oil are scarce or missing.
• Relatively high concentrations of 2,6-di-tert-butyl-p-cresol are found in waste water and the
OECD has concluded that more information on actual releases and environmental exposure to
this substance is needed.
• A review from HELCOM concluded that in general, there should be more measured data on
NP/NPEO and OP/OPEO in discharges in the Baltic Sea catchment area, in sea water, biota
and sediment of the Baltic Sea to examine if the substances cause harmful effects on the ma-
rine environment.
• The review HELCOM also concluded that there is a need for ecotoxicological data on sediment
dwelling organisms in order to better estimate the PNEC for nonylphenol and octylphenol for
the benthic community.

• More information on environmental levels and effects of dodecylphenol and 4-tert-
butylphenol would be of advantage for a further assessment of the need for reduction of releas-
es of these substances to the aquatic environment;
• Human toxicity data for long-chain alkylphenols other than nonylphenols are limited and data
on alkylphenol ethoxylates are nearly absent.
• For many of the short-chained alkylphenols no or insufficient data are available for the as-
sessment of the endocrine potency of the substances.
• Updated information on the technical and economic feasibility of substitution of remaining
uses of NP/NPEO and OP/OPEO is missing, this concerns in particular:
− Use in emulsion polymerization and for paints which represent the major registered uses
of the substances in Denmark.
− Alternatives to 4-tert-BP, 4-tert-OP and 4-NP for manufacture of different types if resins.

Sammenfatning og konklusion
Miljøstyrelsens Liste over Uønskede Stoffer (LOUS) er en signalliste og en vejledning til producen-
ter, produktudviklere, indkøbere og andre aktører om kemikalier, hvor brugen på længere sigt bør
begrænses eller helt stoppes. I perioden 2012-2015 vil alle 40 stoffer og stofgrupper på LOUS blive
kortlagt, og på grundlag af kortlægningerne vil Miljøstyrelsen vurdere behovet for yderligere regule-
ring, substitution/udfasning, klassificering og mærkning, forbedret affaldshåndtering eller en øget
informationsindsats.
Denne kortlægning vedrører stofgruppen "alkylphenoler og alkylphenolethoxylater" (AP/APEO),

som har været på LOUS siden den første udgave blev offentliggjort i 1998. Det er angivet i LOUS, at
stofgruppen består af mange forbindelser, men gruppen er ikke klart defineret. Et af formålene med
denne kortlægning er at give en baggrund for en mere præcis beskrivelse af listens indgang for disse
stoffer. Alkylphenolerne er phenolderivater med én eller flere kæder af kulstofatomer i varierende
længde fastgjort til phenolgruppen. Alkylphenolethoxylater er stoffer som er afledt af alkylphenoler.
Flere hundrede stoffer inden for gruppen af AP/APEO er blevet præregistreret under REACH.
Nonylphenol (NP, med en kulstofkæde med 9 kulstofatomer), octylphenol (OP, med 8 kulstofato-
mer) og nonylphenolethoxylater (NPEO, med en kulstofkæde på 9 kulstofatomer og en ethoxykæde)
nævnes i LOUS som eksempler på stoffer i gruppen.
En sammenfatning af produktion og forbrug af 29 stoffer eller stofgrupper på EU niveau og i Dan-

mark er vist i tabel 19 i afsnit 3.4. Nonylphenoler, octylphenoler, dodecylphenoler, 4-tert-
butylphenol og 2,6-di-tert-butyl-p-cresol (BHT) er de alkylphenoler som anvendes i de største
mængder med en produktion og et forbrug i EU i intervallet 10,000-100,000 t/år. Nonylphenol-
ethoxylater, med et forbrug i EU i intervallet 2,000-20,000 t/år, er de mest anvendte af alkylpheno-
lethoxylaterne.
Nonylphenol og nonylphenolethoxylater
Historisk set har nonylphenoler (NP) og nonylphenolethoxylater (NPEO) været de AP/APEO, der
har vakt den største bekymring, og siden begyndelsen af 1990'erne er der både i Danmark og inter-
nationalt blevet iværksat en række foranstaltninger til at reducere udledningerne af disse stoffer til
miljøet. En EU-risikovurdering for NP/NPEO fra 2002 pegede på behovet for at reducere risikoen
for stofferne i miljøet. En markedsførings- og anvendelsesbegrænsning for de anvendelser, der gav
anledning til de væsentligste udledninger til miljøet, trådte i kraft på EU-plan i 2004. Anvendelses-
begrænsningen omhandler brugen af NP/NPEO til ni formål, herunder anvendelse i rengørings-
midler (med visse undtagelser), tekstil- og læderforarbejdning og som hjælpestoffer i bioci-
der/pesticider.
Nonylphenol betragtes som et hormonforstyrrende stof og er klassificeret som reproduktionstoksisk

og giftigt for miljøet. Et REACH bilag XV-dossier er for nylig blevet udarbejdet med henblik på at
identificere 4-nonylphenol (en gruppe af lineære eller forgrenede nonylphenoler) som SVHC-stoffer
(stoffer som giver anledning til særlig bekymring) på grundlag af deres hormonforstyrrende egen-
skaber. Graden af hormonforstyrrende effekt i kombination med det forhold at nonylphenol er
tungtnedbrydelig og optræder i høje koncentrationer i vandmiljøet indebærer en risiko for østro-
gen-lignende effekter hos de organismer i miljøet, der udsættes for stoffet. Overvågningsdata fra de
seneste år har vist, at koncentrationen af nonylphenol i søsedimenter i Danmark og i marine sedi-
menter fra Østersøen og de indre danske farvande oversteg den såkaldte PNEC-værdi (den bereg-

nede nul-effekt koncentration), hvilket betyder at faktiske virkninger på organismer i miljøet ikke
kan udelukkes.
Den største bekymring i tilknytning til nonylphenolethoxylater er, at de nedbrydes til nonylpheno-
ler i miljøet og ved spildevandsrensning. Udledninger af nonylphenolethoxylater fra rensningsan-
læg anses for at være den vigtigste kilde til nonylphenoler i miljøet.
På EU-plan anvendes nonylphenoler hovedsageligt som råmateriale (co-monomer) til fremstilling

af phenol- og epoxyharpikser (som er polymermaterialer – også kaldet resiner) og som mellempro-
dukt ved fremstilling af nonylphenolethoxylater og et par andre kemiske stoffer. I 1999 var forbru-
get i EU tæt på 80.000 t/år, men i dag er det sandsynligvis faldet til et niveau på 25.000-50.000
t/år, hovedsageligt på grund af begrænsningen af bruges af nonylphenolethoxylater. Nonylpheno-
lethoxylater har historisk set været meget anvendt som tensider (overfladeaktive stoffer) i rengø-
ringsmidler, men det samlede forbrug i EU af nonylphenolethoxylater er faldet fra 118.000 t/år i
1999 til 2,000-20,000 t/å i 2011 som følge af den begrænsning, der trådte i kraft i 2004. I Danmark,
er den vigtigste registrerede anvendelse af nonylphenoler i dag som bestanddel af maling, lak og
fernis, fugemasser og udfyldningsmidler. En væsentlig mængde af nonylphenolethoxylater er stadig
registreret i Produktregistret som anvendt i rengøringsmidler og biocidholdige produkter. Det er
ikke klart, om dette skyldes utilstrækkelig opdatering af virksomhedernes indberetninger, eller om
det er udtryk for faktiske anvendelser, der ikke er omfattet af anvendelsesbegrænsningen. Ca. 12%
af den registrerede mængde nonylphenolethoxylater anvendes til maling, lak og fernis, som ikke er
omfattet af begrænsningen.
NP/NPEO i tekstiler, som er importeret fra lande uden for EU, er sandsynligvis den største kilde til
NP/NPEO til kommunale rensningsanlæg og den vigtigste kilde til udslip af stofferne til miljøet.
Dette er påvist i undersøgelser fra flere EU-medlemslande. Som en konsekvens af dette er Sverige i
færd med at udarbejde et begrænsningsforslag under REACH, som vil have til formål at forbyde
produktion og import af tekstiler og læder, der indeholder NP/NPEO.
Human eksponering for NP/NPEO i fødevarer og forbrugerprodukter anses generelt ikke for at give
anledning til bekymring. De få tilgængelige data vedrørende indtag med fødevarer tyder på, at ni-
veauet er et godt stykke under det tolerable daglige indtag (TDI), som er estimeret af det tidligere
Institut for Fødevaresikkerhed og Toksikologi, men nyere data fra Sverige viser, at indtaget med
fødevarer kan være højere end tidligere rapporteret.
En række alternativer har erstattet brugen af nonylphenolethoxylater til de anvendelser, der i dag er
regulerede. Alternativerne er hovedsagelig baseret på forskellige grupper af APEO-frie overfladeak-
tive stoffer, selvom octylphenolethoxylater i et begrænset omfang kan have været anvendt som
alternativ. Vurderinger af de miljømæssige egenskaber og skæbnen i miljøet af de APEO-frie alter-
nativer konkluderer, at alternativerne generelt vækker mindre bekymring i forholdt til nedbrydelig-
hed og deres nedbrydningsprodukters giftighed for organismer i vandmiljøet. Alternativer til NPEO
i maling og lak ser ud til at være til rådighed, men der er ikke foretaget nogen nyere vurdering af
alternativernes tekniske og økonomiske fordele og begrænsninger. Desuden er der i denne kortlæg-
ning ikke fundet nogen grundig vurdering af alternativer til nonylphenol i maling og lak.
Octylphenoler og octylphenolethoxylater
Octylphenoler (OP) anvendes i mængder på omkring 20.000 t/år i EU hvoraf 98% anvendes som
råvare (co-monomer) til fremstilling af phenolharpikser og klæbemidler, der især anvendes i gummi
til dæk. En lille mængde anvendes til fremstilling af octylphenolethoxylater (OPEO), som anvendes
som overfladeaktive stoffer til nogle af de samme anvendelser som nonylphenolethoxylater, men i
en mindre mængde: omkring 1.000 t/år i EU. Den vigtigste registrerede anvendelse af OP/OPEO i
Danmark er brugen af octylphenol ethoxylater i maling, lak og fernis (der er andre anvendelser som
er fortrolige). Mængderne er dog betydeligt mindre end de mængder af NP og NPEO, som bruges til

dette anvendelsesområde. Octylphenoler kan være til stede i lave koncentrationer som uomsat stof i
gummi og plast, som er lavet på basis af octylphenoler.
Sammenlignet med NP/NPEO er OP/OPEO meget mindre reguleret, selv om det stof inden for
stofgruppen, der anvendes i størst mængde, 4-tert-octylphenol (også kaldet p-tert-OP) ligesom NP
er klassificeret som giftigt i vandmiljøet. Octylphenolethoxylater kan nedbrydes til octylphenoler i
miljøet ved de samme mekanismer som ved nedbrydningen af nonylphenolethoxylater til
nonylphenoler. OP/OPEO indgår lige som NP/NPEO, i OSPARs liste over prioriterede stoffer og
HELCOMs handlingsplan for Østersøen (Baltic Sea Action Plan). De er prioriterede stoffer under
Vandrammedirektivet og omfattet af EUs strategi for hormonforstyrrende stoffer. 4-tert-
Octylphenol er ikke klassificeret som et stof, der skader forplantningsevnen hos mennesker.
Koncentrationerne af OP/OPEO i kommunalt spildevand og spildevandsslam er betydeligt lavere

end koncentrationerne af NP/NPEO. Koncentrationerne i søsedimenter i Danmark og i marine
sedimenter i Østersøområdet og de indre danske farvande er også betydeligt lavere end koncentra-
tionen af NP/NPEO, men HELCOM konkluderer i sin seneste vurdering, at koncentrationen af
octylphenoler oversteg den tærskelværdi for octylphenoler i sedimenter, der er foreslået i forbindel-
se med EU’s vandrammedirektiv, i omkring halvdelen af prøverne af overfladesediment.
En af de vigtigste octylphenoler, 4-tert-OP, er inkluderet i kandidatlisten under REACH med be-

kymring for miljøet angivet som begrundelse. Et REACH bilag XV dossier er for nylig blevet udar-
bejdet med henblik på at identificere octylphenolethoxylater som SVHC-stoffer. Grundlaget for
forslaget er nedbrydningen af octylphenolethoxylater til octylphenoler, som har hormonforstyrren-
de egenskaber i miljøet, og at kortkædede octylphenolethoxylater kan forårsage hormonforstyrren-
de effekter ved lignende eller lidt højere koncentrationer sammenlignet med octylphenoler.
Dodecylphenoler og dodecylphenolethoxylater
Dodecylphenoler (DP, med 12 kulstofatomer i kæderne) er de eneste kommercielt vigtige al-
kylphenoler med en kulstofkæde længere end 9. Omkring 99% af forbruget i EU (50.000 t/år) an-
vendes som et mellemprodukt ved fremstilling af smøremiddeladditiver. Dodecylphenoler indgår i
de endelige additiver i små mængder. Mindre end 1% af dodecylphenolerne anvendes til fremstilling
af dodecylphenolethoxylater (DPEO), der anvendes som anti-rust midler i smøreolier.
Et forslag til harmoniseret klassificering og mærkning af 4-(3,4,5-trimethylheptyl)phenol (en for-

grenet dodecylphenol) foreslår, at stoffet klassificeres som kræftfremkaldende, brandfarlig, og som
givende øjenirritation/alvorlig øjenskade. Ingen dodecylphenoler er opført på EUs liste over
hormonforstyrrende stoffer. Ifølge en PBT vurdering af én af dodecylphenolerne, opfylder stoffet T-
kriteriet (giftigt for vandlevende organismer), og opfylder formentlig P-kriteriet (persistent) og vP-
kriteriet (meget persistent). Det opfylder ikke B-kriteriet (bioakkumulerbart) og kan derfor ikke
anses for at være et PBT-stof. Den akutte giftighed af dodecylphenoler ligger på samme niveau som
giftigheden af octylphenoler.
Dodecylphenoler og dodecylphenol ethoxylater er ikke omfattet af nogen EU-regulering, er ikke

prioriterede stoffer under Vandrammedirektivet og er ikke medtaget i OSPARs liste over prioritere-
de stoffer eller HELCOMs handlingsplan for Østersøen (Baltic Sea Action Plan).
Meget få overvågningsdata er blevet fundet ved kortlægningen. I en screening af AP/APEO i det

nordiske miljø, var dodecylphenoler sammen men octylphenoler, nonylphenoler og nonylphenol
ethoxylater, de stoffer, der blev fundet i de højeste koncentrationer i alle prøver af spildevand. En
foreløbig miljørisikovurdering af dodecylphenoler udført i Storbritannien anslog, at den vigtigste
kilde til dodecylphenoler i miljøet var udslip af dodecylphenoler til spildevand fra brug og bortskaf-
felse af smøremidler (primært som spild og lækager). Miljørisikovurderingen fandt, at der er en
potentiel risiko for organismer i vandmiljøet ved nogle scenarier, og at der er behov for mere pålide-
lige data om eksponering af organismer i miljøet.

Kortkædede alkylphenoler (med kæder med mindre end 8 kulstofatomer)
Kortkædede alkylphenoler anvendes generelt ikke til fremstilling af alkylphenolethoxylater, så pro-
blemstillingerne vedrørende ethoxylaterne som kilder til alkylphenoler i miljøet gælder ikke for de
kortkædede alkylphenoler. Den kortkædede alkylphenoler er en meget forskelligartet gruppe af
stoffer med én, to eller tre korte kulstofkæder bundet til en phenolgruppe. Anvendelsesområderne
for de kortkædede alkylphenoler er meget varierede.
De kortkædede alkylphenoler er generelt af mindre bekymring end nonylphenoler og octylphenoler

i relation til miljøet, fordi de generelt er biologisk nedbrydelige og ikke bioakkumuleres i samme
omfang. De er ikke omfattet af OSPARs liste over prioriterede stoffer, HELCOMs handlingsplan for
Østersøen (Baltic Sea Action Plan), er ikke klassificeret som prioriterede stoffer under Vandramme-
direktivet, og er ikke prioriterede stoffer inden for EUs strategi for hormonforstyrrende stoffer.
Undtagelserne er 2,4,6-tri-tert-butylphenol, som indgår i OSPARs liste over prioriterede stoffer og
som er angivet som potentielt giftige, persistente og bioakkumulerende og 4-tert-butylphenol, som
er et stof i kategori 2 (bevis for potentiale til at forårsage hormonforstyrrelser) på EUs liste over
hormonforstyrrende stoffer.
En de vigtigste årsager til bekymring vedrørende nonylphenoler og octylphenoler er de hormonfor-

styrrende effekter af stofferne. Alkylphenoler med alkylgrupper med mere end to kulstofatomer
fastgjort i position 4 på phenolen har vist at have virkninger meget lig østrogens. De tilgængelige
data tyder på, at både positionen (para> meta> ortho) og forgreningen (tertiær> sekundær = nor-
mal) af alkylgruppen påvirker østrogeneffekten. Optimal østrogenaktivitet kræver en enkelt tertiær
forgrenet alkylgruppe sammensat af mellem 6 og 9 kulstofatomer og placeret i position 4 på en
phenol. Det skal derfor understreges, at det primært er de 4-monosubstituerede alkylphenoler, der
synes at være hormonforstyrrende, og at 4-nonylphenol og 4-tert-octylphenol er de mest potente af
stofferne. 2,4-di-tert-Butylphenol er dog som nævnt i det følgende omfattet af den løbende hand-
lingsplan for Fællesskabets (CoRAP under REACH), fordi stoffet er mistænkt for at være hormon-
forstyrrende.
De relativt få tilgængelige data tyder på, at koncentrationerne af de kortkædede alkylphenoler i

kommunalt spildevand og spildevandsslam er markant lavere (10-100 gange lavere) end koncentra-
tionerne af NP/NPEO. 4-tert-Butylphenol er påvist i sedimenter i Østersøen i større koncentratio-
ner end octylphenoler og i koncentrationer, som er sammenlignelige med nonylphenoler, mens
næsten ingen data for de andre kortkædede alkylphenoler er blevet fundet ved denne kortlægning.
Hvorledes 4-tert-butylphenol spredes til miljøet er ikke undersøgt i detaljer.
To af stofferne anvendes i mængder på over 20.000 t/år i EU: 4-tert-butylphenol (også betegnet
ptBP) og 2,6-di-tert-butyl-p cresol (BHT).
4-tert-Butylphenol anvendes hovedsagelig på samme måde som 4-nonylphenol and 4-tert-

octylphenol som co-monomer til fremstilling af phenolharpikser og kædeterminator i produktionen
af polycarbonat. 4-tert-Butylphenol er den eneste af den kortkædede alkylphenoler, som der er
foretaget en EU-risikovurdering for. Ifølge risikovurderingen anses ureageret 4-tert-butylphenol i
plast og gumm for at være den vigtigste kilde til forbrugernes udsættelse for stoffet. 4-tert-
Butylphenol er forbudt til brug i kosmetik, men ikke har en harmoniseret klassificering. En forslag
til en harmoniseret klassificering som hudirriterende, skadeligt for øjnene, reproduktionstoksisk og
udvisende specifik målorgantoksicitet er for nylig blevet udarbejdet.
2,6-di-tert-butyl-p cresol (BHT) anvendes som antioxidant i en bred gruppe af produkter; blandt
disse fødevarer og foder. Stoffet er af OECD blevet foreslået til yderligere miljørisikovurdering.

2,4-di-tert-butylphenol, der anvendes som kemisk mellemprodukt til fremstilling af plasttilsæt-
ningsstoffer i mængder på over 1,000 t/år på EU plan, er omfattet af den løbende handlingsplan for
Fællesskabet (CoRAP) på grund af dets anvendelses- og eksponeringsmønster, og fordi stoffet er
mistænkt for at være hormonforstyrrende.
2,4,6-tri-tert-butylphenol, er som omtalt omfattet af OSPARs liste over prioriterede stoffer. Stoffet
anvendes primært som intermediat og udledningerne til miljøet fra brugen af stoffet er vurderet at
være små.
Thymol, der anvendes i rengøringsmidler og duftende artikler, har en harmoniseret klassificering

som akut giftigt, hudætsende og farligt for vandmiljøet. Ifølge selvklassificeringerne, som er med-
delt til C&L databasen (C&L Inventory) på Det Europæiske Kemikalieagenturs hjemmeside, har de
fleste af de beslægtede stoffer lignende klassifikationer.
Samlet konklusion vedrørende gruppering af stofferne

Nonylphenoler og octylphenoler deler nogle af de samme miljø- og sundhedsmæssige egenskaber,
og de to stofgrupper er sammen med deres ethoxylater, de AP/APEO som vækker størst bekymring.
Dodecylphenoler og deres ethoxylater anvendes til andre formål, og frigives til omgivelserne i min-
dre mængder, men er af bekymring på grund af deres miljø- og sundhedsmæssige egenskaber.
Blandt de kortkædede alkylphenoler (<8 kulstofatomer), anvendes 4-tert-butylphenol til samme

formål som 4-nonylphenol and 4-tert-octylphenol, men frigivelses- og eksponerings-mønsteret er
helt anderledes. De fleste af de andre kortkædede mono-, di- og trialkyl phenoler vækker mindre
bekymring fordi:
• udledninger til miljøet generelt er betydeligt mindre end udledninger af nonylphenoler og

nonylphenol-ethoxylater,
• de har et betydeligt lavere potentiale for bioakkumulering end de langkædede (C8-C12) al-
kylphenoler,
• de synes at være mere biologisk nedbrydelige, og
• deres østrogene potens er lavere.
De kortkædede alkylphenoler anvendes med få undtagelser til andre formål end nonylphenoler og
octylphenoler og deres ethoxylater. Dog kan nogle af de kortkædede stoffer være af en vis bekym-
ring.
Baseret på de tilgængelige data synes der ikke at være grundlag for at behandle de kortkædede al-
kylphenoler og de langkædede som én gruppe, men snarere at vurdere hvert af de kortkædede al-
kylphenoler enkeltvis for at identificere eventuelle behov for foranstaltninger til at reducere ekspo-
neringen af mennesker og miljø.
Datamangler
De vigtigste datamangler, når der tages hensyn til, hvilke stoffer der er af størst bekymring, er føl-
gende:
• Opdateret information om de aktuelle anvendelser af NP/NPEO og den relative betydning af

de potentielle kilder til udslip til miljøet mangler.
• De registrerede mængder af NPEO anvendt i rengørings- og vedligeholdelsesmidler i Danmark
kalder på en afklaring af de nuværende anvendelser.
• For flere af stofferne, er den tilgængelige information om den samlede produktion og import til
EU som registreret under REACH ikke i overensstemmelse med den information, som er ind-
hentet fra industrien, og dette kalder på en afklaring.

• For mange af stofferne, som anvendes i smøremidler og olie, mangler der data om de potenti-
elle udslip i forbindelse med spild og bortskaffelse af spildolie.
• Der er fundet relative høje koncentrationer af 2,6-di-tert-butyl-p-cresol i spildevand og OECD
har konkluderet at der er brug for mere information om de faktiske udledninger af dette stof og
om eksponering af organismer i miljøet.
• En oversigt fra HELCOM konkluderer at der generelt bør være flere målinger af NP/NPEO and
OP/OPEO i udledninger til Østersøens afstrømningsområde, samt i havvand, organismer og
sediment i Østersøen for at undersøge i hvilken grad stofferne har skadelige effekter i det ma-
rine miljø.
• Oversigten fra HELCOM konkluderer også, at der er brug for flere økotoksikologiske data om
sedimentlevende organismer for bedre at kunne estimere et nul-effekt niveau (PNEC) for or-
ganismerne i sedimentet.
• Mere viden om niveauer og miljøeffekter af dodecylphenol og 4-tert-butylphenol vil være gavn-
ligt for at kunne vurdere, om der er behov for en reduktion af udledningerne af disse stoffer til
vandmiljøet.
• Data vedrørende human toksicitet af andre af de lang-kædede alkylphenoler end nonylpheno-
ler er begrænsede, og data om alkylphenolethoxylater findes stort set ikke.
• For mange af de kort-kædede alkylphenoler er der ingen eller ufuldstændige data til at vurdere
i hvilken grad stofferne er hormonforstyrrende.
• Opdateret information om de tekniske og økonomiske fordele og ulemper ved at erstatte
NP/NPEO and OP/OPEO med alternativer til de tilbageværende anvendelser mangler. Dette
gælder især:
− Brug af stofferne til emulsion-polymerisering (se afsnit 3 for nærmere forklaring) og til
maling som udgør den største anvendelse af stofferne i Danmark.
− Alternativer til 4-tert-BP, 4-tert-OP and 4-NP til produktion af forskellige former for har-
pikser (resiner).

1. Introduction to the sub-
stance group
1.1 Definition of the substance groups

The following section introduces the two substance groups and some basic chemical nomenclature
of importance for the understanding of the naming of the substances.
An alkylphenol is a phenol derivative wherein one or more of the ring hydrogens have been replaced
by one or more alkyl groups. An alkyl group is a functional group or side-chain that consists solely
of single-bonded carbon and hydrogen atoms. A wide variety of alkylphenol structures are possible,
but many are not commercially important. Alkylphenols of the greatest commercial importance
have alkyl groups ranging in size from one (methyl) to twelve carbons (dodecyl) (Kirk Othmer,
2003). The alkylphenols are often named after their chain length e.g. nonylphenol (9 carbon atoms)
and dodecylphenol (12 carbon atoms).
It is common to consider the group synonymous with nonylphenol and nonylphenol ethoxylates
and other AP/APOE with similar application patterns without a more precise definition. As an ex-
ample the “alkylphenol and alkylphenol ethoxylates” are mentioned collectively in criteria docu-
ments for the Nordic Swan and the EU Flower ecolabels, but the substance group is not defined in
the documents and apparently not in any of the background documents.
The European Council for Alkylphenols and Derivatives, CEPAD, represents companies which
manufacture a variety of alkylphenols ranging from butylphenols with a chain length of 4 to the
dodecylphenol and derivatives with a chain length of 12.
Cresols and xylenols

The substances with the shortest chain length, i.e. with only one or two methyl groups, are most
often designated as cresols (o-, p- and m-isomers) and xylenols, respectively (a methyl group has
one carbon atom only and three hydrogen atoms). They differ significantly in their chemistry, tox-
icity and application pattern from the longer chained alkylphenols. The cresols and xylenols are not
considered as potential alternatives to the longer-chained alkylphenols, and the environmental and
health issues associated with these substances are different from the issues relevant for the longer
chained AP. Both cresol and xylenol have a harmonised classification as acute toxic.
It is common not to consider the methylphenols as part of the “alkylphenols” group. As an example,
Ullmann’s Encyclopedia of Industrial Chemistry lists 82 CAS numbers in the chapter on alkylphe-
nols, but has separate chapters on the methylphenols. Moreover, these substances do not have simi-
lar use patterns compared to the substances mentioned as examples in LOUS. Cresols are mainly
used as solvents and xylenols as pesticides. These substances have been considered beyond the
scope of this survey; they are included in the gross list of substances in the following section but are
otherwise not assessed in the report 1.
1 Cresols and xylenols have according to the CLP regulation (Regulation (EC) No 1272/2008) the hazard class and category
codes: Acute toxic 3, skin corr. 1B. Some of the xylenols further have the hazard class and category code Aquatic Chronic 2.

o-Cresol (2-methylphenol) 2,6-Xylenol (dimethyl phenol)
CAS No 95-48-7 CAS No 576-26-1
H3C
HO
HO
H3C
H3C
Mono-alkylphenols
The mono alkylphenols are phenol derivatives wherein only one of the benzene ring hydrogens has
been replaced by an alkyl group which as a group consists of a saturated chain of single bonded
carbon and hydrogen atoms. The mono-alkylphenols are commonly referred to by the number of C
atoms in the alkyl group. The most common are: butylphenols (C4), pentylphenols (C5), hexylphe-
nols (C6), octylphenols (C8), nonylphenols (C9), and dodecylphenols (C12). The alkyl group may be
linear or branched and the commercial products are often complex mixtures.
The prefixes sec- (from "secondary") and tert- (from "tertiary") refer to branched alkyl chains with
one, respectively two methyl groups attached to the first carbon in the alkyl group.
The substances are further named on the basis of additional side chains and the position of the first
carbon in the chain in relation to the OH groups.
The position of the alkyl group is designated either by the Latin designations o- (ortho), m- (meta),
and p- (para) or by the corresponding numbers based on a 1,2-, 1,3-, and 1,4-, relationship. The
common 4-tert-butylphenol (or p-tert-butylphenol) has the first carbon in the para position (oppo-
site the OH group) and a tertiary carbon to which three other carbons are attached. The substance is
often referred to as 4-tert-butylphenol or ptBP.
Three of the most common alkylphenols are shown below. They are all used as a co-monomer in the
production of phenolic resins and other types of resins which are polymeric materials (see descrip-
tion of resins in section 3.2.1). Among other applications, resins are used in the manufacture of
some thermosets such as two-component phenolic plastics and epoxy, and used in some types of
paints, lacquers, sealants, fillers and adhesives.
4-tert-Butylphenol 4-(1,1,3,3- 4-Nonylphenol, branched

CAS No 98-54-4 Tetramethylbutyl)phenol CAS No 84852-15-3
(4-tert-octylphenol)
CH3 HO
CAS No 140-66-9
HO CH3
CH3
CH3 CH3
CH3 i-Pr
HO
CH3
CH3 CH3
H3C
Dialkylphenols and trialkylphenols

The dialkylphenols and trialkylphenols are phenol derivatives wherein two or three of the benzene
ring hydrogens have been replaced by alkyl groups. The alkyl groups may be similar or different
alkylgroups may be attached to the ring.
Examples of some of the commonly used substances are shown below. If one of the derivatives is a
methyl group, the substance is often named cresol instead of phenol. These substances are in gen-
eral used for other purposes than the single chain butyl, octyl and nonylphenols; they have other
human health and environmental properties and may often not be considered part of the group

AP/APEO. Of the three substances shown below, 2,6-di-tert-butyl-p-cresol and thymol are used as
food additives, among other applications. They are, however, included in this survey in order to
elucidate whether they share some of the same characteristics as the long-chain alkylphenols.
2,6-Di-tert-butylphenol 2,6-Di-tert-butyl-p-cresol Thymol

CAS No 128-39-2 CAS No 128-37-0 CAS No 89-83-8
H3C H3C CH3

CH3 CH3
H3C H3C HO
HO HO CH3 H3C
H3C H3C CH3

H3C
CH3 CH3
H3C H3C
Alkylphenol ethoxylates
The second group of substances addressed in this survey are the alkylphenol ethoxylates (APEO)
which are produced from alkylphenols. Only ethoxylates of octylphenol, nonylphenol and do-
decylphenol have been identified as used in the EU. Two examples are shown below.
APEOs are manufactured by the addition of ethylene oxide (C2H4O) to the alkylphenol under pres-
sure. The length of the ethoxylate chain can be controlled by regulating the ratio of the alkylphenol
and the ethylene oxide and by the reaction time. Commercial APEOs are a mixture of ethoxylated
APs with differing ethoxy units. As an example, a commercial nonylphenol ethoxylate such as
Tergitol NP-9 from DOW contains a mixture of oligomers from about 3 ethoxylates to 14 ethox-
ylates with an average of 9 ethoxylates (Earls and Reydellet, 2006). The chemical and toxicological
properties are dependent on the ethoxy chain length (Earls and Reydellet, 2006). The APEOs may
be degraded in the environment to shorter chain APEOs and the parent AP.
In environmental monitoring. e.g. in Denmark, it is often the nonylphenol monoethoxylates and

nonylphenol diethoxylates that are measured. The notation is commonly NP1EO and NP2EO, re-
spectively.
Nonylphenol, branched, ethoxylated 20-[4-(1,1,3,3-Tetramethylbutyl)phenoxy]-

CAS No 127087-87-0 3,6,9,12,15,18-hexaoxaicosan-1-ol
(octylphenol ethoxylate)
H3C
CAS No 2497-59-
CH3
8
H3C H3C
CH3
H3C
O
H3C CH3
H O CH3
n
H3C
O O O O
HO O O O
Arylphenols
Some arylphenols, with two connected benzene rings, are sometimes considered together with the
AP/APOE, e.g. by CEPAD which mentions p-cumylphenol and o,p-dicumylphenol among the al-
kylphenols addressed by the organisation. The substances are used as intermediates in the produc-
tion of polycarbonates, epoxy resins and plastic additives. As the substances are not alkylphenols
(they do not meet the definition of an alkylphenol), they have been beyond the scope of this survey.
The cumylphenols do not have a harmonised classification.

2,4-Di(1-methyl-1-phenylethyl)phenol 4-(α,α-Dimethylbenzyl)phenol
(o,p-cumylphenol) (p-cumylphenol)
CAS No 2772-45-4 CAS No 599-64-4
CH3
H3C HO CH3
CH3
CH3
HO
CH3
1.2 Substances within the substance groups

The group of AP/APEO includes a large number of substances. UK Environment Agency (2005b)
lists in a prioritization of alkylphenols 50 CAS numbers of alkylphenols that appear to have been
produced commercially at some time and potentially on the market. Ullmann’s Encyclopedia of
Industrial Chemistry lists 82 CAS numbers in the section on alkylphenols (excluding cresols and
xylenols).
In total about 190 substances within the group of AP/APEO have been identified for this survey
from a number of data sources:
• Reports from national authorities;

• Annex XV reports and other assessment reports;
• Ullmann’s Encyclopedia of Industrial Chemistry and Kirk Othmer Encyclopedia of Chemical
Technology;
• The SPIN database of the Nordic Product Registries (SPIN, 2012) and REACH registrations
using the search strings “ylphenol”, yl)phenol”, “cresol” and “ethoxylate” and subsequent man-
ual selection;
• A search on the Internet for the less-used alkylphenols and their ethoxylates using the strings:
propyl-, pentyl-, hexyl-, heptyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, pentadecyl-,
hexadecyl-, heptadecyl-, octadecyl-, nonadecyl- and amylphenol and these strings combined
with “ethoxylate”, supplemented by a search on cresol and xylenol.
Of the identified substances, 177 are included in the list of pre-registered substances under REACH
and listed in Table 1. Some CAS numbers from the literature are not included in the list of pre-
registered substances, which indicates that they are used in low tonnage or not used at all, and these
CAS numbers are not considered relevant in an EU context and are consequently not included in
the table.
The table further indicates:
• Tonnage bands for substances which have been registered;

• Whether the substances are intended to be registered by 2013;
• Tonnage registered in the Danish Product Register with a total of import and production.
Substances registered with ECHA: The database on registered substances includes:
• substances manufactured or imported at 1000 tonnes or more per year,

• carcinogenic, mutagenic or toxic to reproduction substances above 1 tonne per year, and
• substances dangerous to aquatic organisms or the environment above 100 tonnes per year
(Deadline for registration was 30 November 2010).

Intentions 2013: The deadline for registration of substances manufactured or imported at 100-
1000 tonnes per year is 31 May 2013. The column indicates substances for which companies have
expressed their intentions for registration of the substances.
Substances registered in the Danish Product Register: Substances registered in the Danish
Product Register with an indication of the quantity (only substances with a registered quantity are
included in the table). The data are further described in section 3.3.
The substances in Table 1 are organised with the mono-alkylphenols and their ethoxylates listed
first, followed by the list of dialkylphenols and trialkylphenols. Please note that the chemical names
indicated are the names used by the pre-registration and the naming is not totally consistent.
One of the objectives of the table is to provide an initial indication of which substances are manu-
factured and used in the largest quantities. The consumption of the substances in the EU and Den-
mark is further described in chapter 0. Another objective is to serve as reference table listing the
substances which may be used within the different substance groups.
Cresols and xylenols (methylphenol and dimethylphenol), as well as the arylphenols, are included in
the table for reference, but are otherwise considered beyond the scope of the current survey.
Of the C3 – C7 APs, the butylphenols (C4) seems to be used in highest quantities in both the EU and
Denmark. However, the C8 (octyl) and C9 (nonyl) APs are manufactured and/or imported in signif-
icantly higher quantities than the C3 – C7 APs, both in the EU and in Denmark.
Of the substances with longer branches, the dodecylphenols (C12) are the substances with the high-
est tonnages both in the EU and Denmark.
Ethoxylates of octylphenol (OP), nonylphenol (NP) and dodecylphenol (DP) are registered in the
Danish Product Register, but of these, only nonylphenol ethoxylates have been registered under
REACH by 2010.

TABLE 1
IDENTIFIED SUBSTANCES WITHIN THE SUBSTANCE GROUP WITH INDICATION OF REGISTERED TONNAGE, REGIS-
TERING BY 2013 AND REGISTERED TONNAGE IN THE DANISH PRODUCT REGISTER JULY 2012
CAS No EC No Substance name *1 Carbon Registered, ton- Intention Danish

atoms nage band , t/y *2 2013 *4 Product
in alkyl Register, t/y
chains *3
Mono alkylphenols and ethoxylates
Methylphenol, cresols (out of scope of this report)
95-48-7 202-423-8 o-cresol 1 10,000 - 100,000

Total all 4:
106-44-5 203-398-6 p-cresol 1 10,000 - 100,000
6,343
108-39-4 203-577-9 m-cresol 1 10,000 - 100,000
1319-77-3 215-293-2 cresol 1 1,000 - 10,000
- 906-151-7 reaction mass of m-cresol 1 1,000 - 10,000 n.r.

and p-cresol
Ethylphenols
25429-37-2 607-726-2 *5 ethylphenol 2 n.r. confidential
90-00-6 201-958-4 2-ethylphenol 2 n.r. n.r.
Propylphenols
90480-88-9 291-826-2 phenol, isopropylated 3 intermediate use n.r.

only
88-69-7 201-852-8 2-isopropylphenol 3 n.r. n.r.
618-45-1 210-551-0 3- 3 n.r. n.r.

isopropylhydroxybenzene
Butylphenols
89-72-5 201-933-8 2-sec-butylphenol 4 1,000 - 10,000 n.r.
98-54-4 202-679-0 4-tert-butylphenol 4 intermediate use 8.3

only
88-18-6 201-814-0 2-tert-butylphenol 4 n.r. 0.2
99-71-8 202-781-5 4-sec-butylphenol 4 n.r. n.r.
585-34-2 209-553-4 3-tert-butylphenol 4 n.r. n.r.
1638-22-8 216-672-5 4-butylphenol 4 n.r. n.r.
4074-43-5 223-790-0 3-butylphenol 4 n.r. n.r.
27178-34-3 248-300-2 tert-butylphenol 4 n.r. n.r.
28805-86-9 249-246-2 butylphenol 4 n.r. 0.3
68610-06-0 271-847-3 phenol, isobutylenated 4 n.r. x
31195-95-6 250-509-9 isobutylphenol 4 n.r. n.r.

chains *3
Pentylphenols
80-46-6 201-280-9 p-(1,1- 5 n.r. n.r.

dimethylpropyl)phenol
(4-tert amylphenol]
136-81-2 205-261-6 o-pentylphenol 5 n.r. n.r.
87-26-3 201-736-7 2-(1-methylbutyl)phenol 5 n.r. n.r.
1518-84-9 216-179-5 2-cyclopentylphenol 5 n.r. n.r.
3279-27-4 221-916-9 2-(1,1- 5 n.r. n.r.

dimethylpropyl)phenol
(0-tert amylphenol]
14938-35-3 239-015-4 4-pentylphenol 5 n.r. n.r.
20056-66-0 243-487-7 m-pentylphenol 5 n.r.
Hexylphenols
119-42-6 204-322-4 2-cyclohexylphenol 6 n.r. 0.3
1131-60-8 214-465-4 4-cyclohexylphenol 6 n.r. 0.05
2446-69-7 219-501-2 4-hexylphenol 6 n.r. n.r.
26570-85-4 247-813-9 cyclohexylphenol 6 n.r. n.r.
Heptylphenols
1987-50-4 217-862-0 4-heptylphenol 7 n.r. x confidential
140-66-9 205-426-2 4-(1,1,3,3- 8 10,000 - 100,000 confidential

tetramethylbutyl)phenol
(4-tert-octylphenol)
949-13-3 213-437-9 o-octylphenol 8 n.r. n.r.
1806-26-4 217-302-5 4-octylphenol 8 n.r. n.r.
1818-08-2 217-332-9 4-(1-methylheptyl)phenol 8 n.r. n.r.
3307-00-4 221-989-7 4-(1-ethylhexyl)phenol 8 n.r. n.r.
3884-95-5 223-420-8 o-(1,1,3,3- 8 n.r. confidential

11081-15-5 234-304-1 isooctylphenol 8 n.r. n.r.
17404-44-3 241-426-9 o-(1-ethylhexyl)phenol 8 n.r. n.r.
18626-98-7 242-459-1 o-(1-methylheptyl)phenol 8 n.r. x n.r.
26401-75-2 247-663-4 o-sec-octylphenol 8 n.r. n.r.
27193-28-8 248-310-7 (1,1,3,3- 8 n.r. n.r.


chains *3
27214-47-7 248-330-6 4-sec-octylphenol 8 n.r. n.r.
27985-70-2 248-759-9 (1-methylheptyl)phenol 8 n.r. n.r.
67554-50-1 266-717-8 octylphenol 8 n.r. n.r.
93891-78-2 299-461-0 sec-octylphenol 8 n.r. n.r.
99561-03-2 308-979-9 Phenol, 4-octyl-, branched 8 n.r. n.r.
37631-10-0 253-574-1 o-(1-propylpentyl)phenol 8 n.r. n.r.
2497-59-8 219 -682-8 20-[4-(1,1,3,3- C8- n.r. n.r.

tetramethyl- ethox-
butyl)phenoxy]- ylate
3,6,9,12,15,18-
hexaoxaicosan-1-ol
9002-93-1 618-344-0 *5 poly(oxy-1,2-ethanediyl), C8- n.r.

α-[4-(1,1,3,3- ethox
tetramethylbutyl)phenyl]-
ω-hydroxy *5
12
9036-19-5 618-541-1 *5 poly(oxy-1,2-ethanediyl), C8- n.r.
α-[(1,1,3,3- ethox
tetramethylbutyl)phenyl]-
ω-hydroxy
68987-90-6 614-869-4*5 poly(oxy-1,2-ethanediyl), C8- n.r. n.r.

α-(octylphenyl)-ω- ethox
hydroxy-, branched
Nonylphenol and nonylphenol ethoxylates
284-325-5 phenol, 4-nonyl-, 9 10,000 - 100,000 1.4

84852-15-3
branched
104-40-5 203-199-4 4-nonylphenol 9 n.r.
440-740-5 4-(4-trans- 9 intermediate use n.r.

-
propylcylohexyl)phenol only
136-83-4 205-263-7 o-nonylphenol 9 n.r. n.r.
139-84-4 205-376-1 m-nonylphenol 9 n.r. n.r.
11066-49-2 234-284-4 isononylphenol 9 n.r. n.r.
17404-66-9 241-427-4 4-(1-methyloctyl)phenol 9 n.r n.r.
25154-52-3 246-672-0 nonylphenol 9 n.r. 33
26543-97-5 247-770-6 4-isononylphenol 9 n.r. n.r.
27938-31-4 248-741-0 o-isononylphenol 9 n.r. n.r.
4-(1,1- 9 n.r. n.r.

30784-30-6 250-339-5
dimethylheptyl)phenol

chains *3
4-(1-ethyl-1- 9 n.r. n.r.

52427-13-1 257-907-1
methylhexyl)phenol
90481-04-2 291-844-0 phenol, nonyl-, branched 9 n.r. n.r.
9016-45-9 500-024-6 nonylphenol, ethoxylated C9- n.r. 120

ethox
20427-84-3 243-816-4 2-[2-(4- C9- n.r. n.r.

nonylphe- ethox
noxy)ethoxy]ethanol
26027-38-3 500-045-0 4-nonylphenol, ethoxylat- C9- n.r. 0.01

ed ethox
37205-87-1 609-346-2 *5 poly(oxy-1,2-ethanediyl), C9- n.r. 5.0

α-(isononylphenyl)-ω- ethox
hydroxy-
68412-54-4 500-209-1 2-{2-[4-(2,4,5- C9- 1,000 - 10,000 44.0

trimethylhexan-3- ethox- 1,000 - 10,000
yl)phenoxy]polyethoxy}et ylate
hanol
127087-87-0 500-315-8 4-nonylphenol, branched, C9- n.r. 0.5

ethoxylated ethox
Decylphenol
27157-66-0 248-271-6 decylphenol 10 n.r. n.r.
93891-77-1 299-460-5 sec-decylphenol 10 n.r. n.r.
Dodecylphenol and docecylphenol ethoxylates
104-43-8 203-202-9 4-dodecylphenol 12 n.r. 0.05
121158-58-5 310-154-3 phenol, dodecyl-, 12 10,000 - 100,000 4.4

branched intermediate use
only
11067-80-4 234-287-0 isododecylphenol 12 n.r. n.r.
27193-86-8 248-312-8 dodecylphenol 12 n.r. 0.04
9014-92-0 9014-92-0 dodecylphenol, ethoxylat- C12- n.r.

ed ethox 2.4
74499-35-7 616-100-8 phenol, (tetrapropenyl) C12- n.r.

derivs. ethox
Pentadecylphenols
501-24-6 207-921-9 3-pentadecylphenol 15 n.r. n.r.
Hexadecylphenols
2589-78-8 219-980-8 4-hexadecylphenol 16 n.r. n.r.
Di- and trialkylphenols

chains *3
Dimethylphenols (xylenols) (out of scope of this report)
576-26-1 209-400-1 2,6-xylenol 1+1 10,000 - 100,000 n.r.
1300-71-6 215-089-3 xylenol 1+1 n.r. 3,719
108-68-9 203-606-5 3,5-xylenol 1+1 intermediate use n.r.

only
- 905-287-4 reaction mass of 2,4- 1+1 1,000 - 10,000 n.r.

xylenol and 2,5-xylenol
95-65-8 202-439-5 3,4-xylenol 1+1 n.r. n.r.
95-87-4 202-461-5 2,5-xylenol 1+1 n.r. n.r.
105-67-9 203-321-6 2,4-xylenol 1+1 n.r. n.r.
526-75-0 208-395-3 2,3-xylenol 1+1 n.r. n.r.
Trimethylphenols
2416-94-6 219-330-3 2,3,6-trimethylphenol 1+1+1 1,000 - 10,000 n.r.
496-78-6 207-832-5 2,4,5-trimethylphenol 1+1+1 n.r. n.r.
Tetramethylphenols
488-70-0 207-684-1 2,3,4,5-tetramethylphenol 1+1+1 n.r. n.r.

+1

+1

+1
Pentamethyl phenols
2819-86-5 220-580-0 pentamethylphenol 1+1+1 n.r. n.r.

+1+1
Ethyl methyl phenols, diethyl phenols
3855-26-3 223-361-8 2-ethyl-4-cresol 2+1 n.r. n.r.
1123-73-5 214-377-6 3-ethyl-o-cresol 2+1 n.r. n.r.
1123-94-0 214-382-3 4-ethyl-m-cresol 2+1 n.r. n.r.

chains *3
2219-73-0 218-733-1 4-ethyl-o-cresol 2+1 n.r. n.r.
6161-67-7 228-189-7 3-ethyl-4-cresol 2+1 n.r. n.r.
936-89-0 213-318-1 2,4-diethylphenol 2+2 n.r. n.r.
Propyl methyl phenols
89-83-8 201-944-8 thymol 3+1 1,000 - 10,000 0.002
499-75-2 207-889-6 carvacrol 3+1 n.r. n.r.
3228-01-1 221-760-1 2-isopropyl-m-cresol 3+1 n.r. n.r.
4427-56-9 224-611-9 2-isopropyl-4-cresol 3+1 n.r. n.r.
Di- and tri-propylphenols
2078-54-8 218-206-6 disoprofol 3+3 n.r. n.r.
2934-05-6 220-906-1 2,4-diisopropylphenol 3+3 n.r. n.r.
26886-05-5 248-086-0 3,5-diisopropylphenol 3+3 n.r. n.r.
2934-07-8 220-907-7 2,4,6-triisopropylphenol 3+3+3 n.r. n.r.
Butyl methyl phenols, butyl ethyl phenol, butyl dimethyl phenols, butyl tetramethyl phenol
88-60-8 201-842-3 6-tert-butyl-m-cresol 4+1 intermediate use n.r.

only
98-27-1 202-651-8 4-tert-butyl-o-cresol 4+1 n.r. n.r.
2219-72-9 218-732-6 4-tert-butyl-m-cresol 4+1 n.r. n.r.
2219-82-1 218-734-7 6-tert-butyl-o-cresol 4+1 n.r. n.r.
2409-55-4 219-314-6 2-tert-butyl-p-cresol 4+1 intermediate use 0.001

only
4892-31-3 225-514-4 5-tert-butyl-m-cresol 4+1 n.r. n.r.
25567-40-2 247-108-6 tert-butyl-p-cresol 4+1 n.r. n.r.
96-70-8 202-526-8 2-tert-butyl-4-ethylphenol 4+2 n.r. n.r.
1879-09-0 217-533-1 6-tert-butyl-2,4-xylenol 4+1+1 n.r. 0.02
879-97-0 212-910-7 4-tert-butyl-2,6-xylenol 4+1+1 n.r. n.r.

chains *3
3884-95-5 223-420-8 o-(1,1,3,3- 4+1+1 n.r. n.r.

tetramethylbutyl)phenol +1+1
Dibutylphenols, dibutyl methyl phenols, tributylphenols
96-76-4 202-532-0 2,4-di-tert-butylphenol 4+4 100 - 1,000 0.3

100 - 1,000
100 - 1,000 19.6

100 - 1,000
128-39-2 204-884-0 2,6-di-tert-butylphenol 4+4
Intermediate use
only
1138-52-9 214-513-4 3,5-di-tert-butylphenol 4+4 n.r. n.r.
5510-99-6 226-854-6 di-sec-butylphenol, mixed 4+4 intermediate use n.r.

isomers mixed only
26967-68-0 248-146-6 dibutylphenol 4+4 n.r. n.r.
31291-60-8 250-550-2 di-sec-butylphenol 4+4 intermediate use n.r.

only
1,000 - 10,000 138

1,000 - 10,000
128-37-0 204-881-4 2,6-di-tert-butyl-p-cresol 4+4+1
10,000 - 100,000
497-39-2 207-847-7 4,6-di-tert-butyl-m-cresol 4+4+1 n.r. confidential
616-55-7 210-485-2 4,6-di-tert-butyl-o-cresol 4+4+1 n.r. n.r.
732-26-3 211-989-5 2,4,6-tri-tert-butylphenol 4 +4 +4 intermediate use 0.7

only
5892-47-7 227-572-6 2,4,6-tri-sec-butylphenol 4 +4 +4 n.r. x n.r.
17540-75-9 241-533-0 4-sec-butyl-2,6-di-tert- 4 +4 +4 n.r. confidential

butylphenol
Dinonylphenols
137-99-5 205-310-1 2,4-dinonylphenol 9+9 n.r. n.r.
1323-65-5 215-356-4 dinonylphenol 9+9 n.r. confidential
Other alkylphenols
1596-09-4 216-478-0 2-cyclohexyl-p-cresol 6+1 n.r. n.r.
16152-65-1 240-303-7 2-(1-methylcyclohexyl)-p- 7+1 n.r. n.r.

cresol
6-(1-methylcyclohexyl)- 7+1+1 n.r. n.r.

77-61-2 201-042-4
2,4-xylenol

chains *3
120-95-6 204-439-0 2,4-di-tert-pentylphenol 5+5 n.r. n.r.

[2,4-di-tert-amylphenol]
51437-89-9 257-203-4 2-(p-octylphenoxy)ethanol 8+2 n.r. n.r.
4130-42-1 223-945-2 2,6-di-tert-butyl-4- 4+4+2 n.r. n.r.

ethylphenol
4306-88-1 224-320-7 2,6-di-tert-butyl-4- 9+4+4 n.r. 0.2

nonylphenol
68025-37-6 268-192-0 bis(tert- 20 n.r 1.6

butyl)dodecylphenol
29988-16-7 249-991-3 dioctylphenol 8+8 n.r. n.r.
- 931-468-2 C14-16-18 alkylphenol mixed, intermediate use n.r.

14,16,18 only
- 906-550-6 reaction mass of 2,3- 1 +1 1,000 - 10,000 n.r.

xylenol and 3,5-xylenol mixed
and 3-ethylphenol and 4- with 2
ethylphenol
- 905-278-5 reaction mass of 3,4- mixed n.r. n.r.

xylenol and 3,5-xylenol
and 3-ethylphenol and 4-
ethylphenol
Arylphenols (out of scope of this report)
599-64-4 209-968-0 4-(α,α- Intermediate only not included

dimethylbenzyl)phenol in search
[4-cumylphenol]
2772-45-4 220-466-0 2,4-bis(1-methyl-1- n.r. not included

phenylethyl)phenol in search
[2,4-di-cumylphenol]
84962-08-3 284-702-4 dinonylphenol, branched n.r. not included

in search
88-24-4 201-814-0 6,6'-di-tert-butyl-4,4'- n.r. not included

diethyl-2,2'- in search
methylenediphenol
*1 For registered substances the registered name is indicated; for other substances included in ESIS (with EC
number), the substance name in ESIS is indicated (http://esis.jrc.ec.europa.eu/). However, for all substanc-
es the p- has been replaced by 4- for consistency in the remaining part of this report.
*2 As indicated in the lists of pre-registered and registered substances at ECHA’s website. For each separate
registration (which may cover more than one manufacturer) the registered tonnage is indicated. For sub-
stances indicated as “Intermediate use only” no tonnage band is reported.
*3 Tonnage indicates the registered import + manufacturing in the Danish Product Register July 2012. n.r. =
not registered.
*4 Included in list of substances that companies have indicated to ECHA they intend to register by the 2013
REACH registration deadline. Based on responses to a survey ECHA has conducted. 31 May 2013 is the

deadline for industry to register all phase-in substances manufactured or imported in the EU at or above
100 tonnes a year.
*5 The substance has no EC number, but has been given a list number in the EC format through the preregis-
tration. Chemical name from preregistration is indicated.
1.3 Function of the substances for main application areas

The uses and consumption of the substances are further described in Chapter 3 whereas this section
describes the function of the substances.
The main application of 4-tert-bytylphenol, 4-tert-octylphenol and 4-nonylphenols, as described in

Chapter 0, is as raw material in the production of phenolic resins and other resins. The function of
the alkylphenols is to react with other raw materials leading to the formation of polymers. As an
example, 4-tert-octylphenol is used in the production of phenol–formaldehyde (Bakelite) resins
which are some of the oldest-known thermosetting and thermoplastic synthetic polymers (Envi-
ronment Agency, 2005a). The initial stage of production is the base-induced reaction of the phenol
and formaldehyde to give a hydroxybenzyl alcohol. With 4-tert-octylphenol the addition takes place
at the ortho-position. The next step in the condensation is the formation of a dihydroxydiphenylme-
thane derivative with elimination of water. Continuation of these reactions leads to a two-
dimensional polymer for 4-tert-octylphenol. The phenol–formaldehyde resins may be made with 4-
tert-octylphenol alone or in a mixture with other phenols depending on the properties desired for
the final resin. The different alkylphenols are used for production of slightly different resins, but
there is some degree of interchangeability between the alkylphenols as they have the same function.
(Environment Agency, 2005a).
Besides this application, the octylphenols, nonylphenols and dodecylphenols mainly function as
intermediates in the production of ethoxylates.
Other mono-alkylphenols, dibutylphenols and tributylphenols mainly function as intermediates in

the production of various substances, e.g. herbicides, plastic additives, and constituents for the
fragrance industry.
A number of the substances have their main application area as constituents of lubricants and fuel
additives or as intermediates in the production of such additives: dodecylphenol, 2,6-di-tert-
butylphenol, 2,6-di-tert-butyl-4-nonyl-phenol, 2,4,6-tri-tert-butylphenol and bis(tert-
butyl)dodecylphenol. In the applications where the APs are used directly as additives (i.e. not func-
tion as an intermediate), the substances have various functions, which have not been described in
detail in the reviewed literature
2,6-di-tert-butyl-p-cresol function as an antioxidant for a variety of applications; among these,

antioxidants in food. The substance primarily acts as a terminating agent that suppresses auto oxi-
dation, a process whereby unsaturated organic compounds are attacked by atmospheric oxygen.
Nonylphenol ethoxylates (NPEO) are nonionic (no charge) surfactants that are used in many appli-
cations. NPEO surfactants function as emulsifiers, wetting agents, dispersants, foam control agents
and surface tension agents. The surfactants provide increased surface activity and reduce the sur-
face tension of water, allowing easier spreading, wetting, and better mixing of liquids. The oc-
tylphenol ethoxylates (OPEO) have similar overall applications as the NPEO, though the OPEOs
have slightly different properties.

2. Regulatory framework
This chapter gives an overview of how alkylphenols and alkylphenoletoxylates are addressed in
existing and upcoming EU and Danish legislation, international agreements and also by eco-label
criteria.
In Annex 3 a brief overview of legal instruments in the EU and DK and how they are related may be
found. The appendix also gives a brief introduction to the chemicals legislation, explains the lists
referred to in Section 2.1.2, and provides a brief introduction to international agreements and se-
lected eco-label schemes.
2.1 EU and Danish legislation

This section will first list existing legislation addressing AP/APEO and then give an overview of on-
going activities, focusing on which substances are in the pipeline in relation to various REACH
provisions.
2.1.1 Existing legislation

Table 2 gives an overview of existing legislation addressing AP and APEO. For each area of legisla-
tion, the table first lists the EU legislation (if applicable) and then possible transposition of this into
Danish law and/or other national rules. The latter will only be elaborated upon in case of Danish
rules differing from EU rules.
The first international measure for reducing the emission of nonylphenol and nonylphenolethox-
ylates (NP/NPE) was the PARCOM Recommendation 92/8 on nonylphenol-ethoxylates which re-
quired the phasing out of the use of NPEs as cleaning agents for domestic uses (1995) and industrial
uses (2000) in the OSPAR counties. An EU Risk Assessment for nonylphenol and nonylphenoleth-
oxylates (NP/NPEO) from 2002 (ECB, 2002 ) identified the need for reducing the risk to the envi-
ronment from the substances and marketing and use restrictions for applications which caused
significant discharges, emissions or losses to the environment was introduced at EU level in 2003
and went into force 27 October 2004 (Directive 2003/53/EC amending Council Directive
76/769/EEC). The requirements are currently included in Annex XVII to the REACH Regulation.
The table illustrates that nonylphenol and nonylphenolethoxylates are widely regulated, whereas
octylphenol and octylphenolethoxylates are covered by fewer regulatory provisions. Only one other
alkylphenol (4-tert-butylphenol) is regulated: prohibited in the cosmetic industry.

TABLE 2
EU AND DANISH LEGISLATION ADDRESSING AP/APEO
Legal instrument *1 Substances Requirements
Regulation No 1907/2006 Included in Annex XVII: Shall not be placed on the market, or used, as substances or in
concerning the Registra- a) Nonylphenol mixtures in concentrations equal to or greater than 0,1 % by
tion, Evaluation, Authorisa- C6H4(OH)C9H19 weight for the following purposes:
tion and Restriction of CAS 25154-52-3 (1) industrial and institutional cleaning except: — controlled
Chemicals (REACH) (b) Nonylphenol ethox- closed dry cleaning systems where the washing liquid is recycled
ylates or incinerated, — cleaning systems with special treatment where
(C2H4O)nC15H24O the washing liquid is recycled or incinerated.
(2) domestic cleaning;
(3) textiles and leather processing except:
— processing with no release into waste water,
— systems with special treatment where the process water is pre-
treated to remove the organic fraction completely prior to biolog-
ical waste water treatment (degreasing of sheepskin);
(4) emulsifier in agricultural teat dips;
(5) metal working except: uses in controlled closed systems
where the washing liquid is recycled or incinerated;
(6) manufacturing of pulp and paper;
(7) cosmetic products;
(8) other personal care products except: spermicides;
(9) co-formulants in pesticides and biocides. However, national
authorisations for pesticides or biocidal products containing
nonylphenol ethoxylates as co-formulant, granted before 17 July
2003, shall not be affected by this restriction until their date of
expiry.
Regulation 649/2012 con- Nonylphenols Subject to export notification procedure

cerning the export and C6H4(OH)C9H19
import of hazardous chemi- Nonylphenol ethoxylates
cals (PIC) (C2H4O) n C15H24O
Regulation (EC) No 4-tert-Butylphenol (98- Included in list of substances prohibited in cosmetic products
1223/2009 on cosmetic 54-4)
products Nonylphenol
(25154-52-3)
4-Nonylphenol,
branched
Bekendtgørelse om (84852-15-3)
kosmetiske produkter
[Statutory Order on cos- Same Same
metic products]
BEK no 422 of 04/05/2006

Regulation (EC) No The operator of a facility that undertakes one or more of

166/2006 concerning the the activities specified in the Regulation above the applicable
establishment of a Europe- capacity thresholds shall report the amounts annually to its
an Pollutant Release and competent authority if the releases are above the following
Transfer Register (PRTR threshold for releases:
Regulation)
Nonylphenol and To water: 1 kg/year
nonylphenol ethoxylates To land: 1 kg/year
(NP/NPEOs)
Octylphenols and oc- To water: 1 kg/year

tylphenol ethoxylates
Bekendtgørelse om visse Same Same

virksomheders afgivelse af
miljøoplysninger [Statuto-
ry Order on certain com-
panies’ delivery of en-
vironmental information ]
BEK no 210 of 03/03/2010
Directive 2000/60/EC es- Nonylphenols, 4- Framework for e.g. setting Environmental Quality Standards for
tablishing a framework for nonylphenol, octylphe- 33 ‘priority’ and ‘hazardous priority’ substances presenting a
the Community action in nols, 4-tert-octylphenol significant risk to the aquatic environment and water used for
the field of water policy the production of drink water.
(Water Framework Di-
rective) The APs were included in the first list priority substances.
Directive 2008/105/EC on Sets the Environmental Quality Standards as annual average and
environmental quality maximum allowable concentration.
standards in the field of
water policy Requires Member States to take measures aimed at ensuring that
the concentrations do not exceed the standards and do not sig-
nificantly increase in sediment and/or relevant biota.
Bekendtgørelse om
miljøkvalitetskrav for van- Same Transposes the Water Framework Directive
dområder og krav til
udledning af forurenende
stoffer til vandløb, søer
eller havet [Statutory Or-
der on environmental qual-
ity standards for water
bodies and requirements to
the discharge of pollutants
into rivers, lakes or the sea]
BEK no 1022 of 25/08/2010

Council Directive Does not include limit

86/278/EEC on the protec- values for any AP/APEO
tion of the environment,
and in particular of the soil,
when sewage sludge is used
in agriculture ( The Sewage
Sludge Directive)
Bekendtgørelse om anven- Nonylphenol and Limit value in sludge: 10 mg/kg dw

delse af affald til jordbrugs- nonylphenol ethoxylates
formål (Slambekendtgørel- with 1-2 ethoxy groups
sen) [Statutory Order on
the use of waste for agricul-
tural purposes ]
BEK no 1650 of 13/12/2006
Bekendtgørelse om Sum of octylphenol and

vandkvalitet og tilsyn med nonylphenol
vandforsyningsanlæg
Requirement of water quality:
[Statutory Order on water
Concentration by exit from waterworks: 20 µg/L
quality and supervision of
Concentration by entrance of consumer’s property: 20 µg/L
water supply systems] Other phenols, each
Concentration by consumer’s tap: 20 µg/L
BEK no 1024 of 31/10/2011 compound
Requirement of water quality:

Concentration by exit from waterworks: 0.5 µg/L
Concentration by entrance of consumer’s property: 0.5 µg/L
Concentration by consumer’s tap: 0.5 µg/L
Bekendtgørelse om kvali- Nonylphenol and Sets requirement to the quality of environmental analyses
tetskrav til miljømålinger nonylphenol ethoxylates
[Statutory Order on quality with 1-2 ethoxy groups
requirements for environ-
mental measurements]
BEK no 900 of 17/08/2011
*1 Unofficial translation of name of Danish legal instruments.
Classification and labelling

Table 3 lists alkylphenols for which a harmonised CLP classification and labelling has been agreed
upon. It shows that nonylophenol and octylphenol are both classified for severe acute and chronic
aquatic toxicity. Thymol is classified f0r less severe aquatic toxicity.
Industry classifications for substances without a harmonised classification and labelling agreement
are summarised in Annex 2 and will be taken into account in Chapters 5 and 6 on environment and
human health assessments.

TABLE 3
HARMONISED CLASSIFICATION ACCORDING TO ANNEX VI OF REGULATION (EC) NO 1272/2008 (CLP REGULATION)
Index No International CAS No Classification

Chemical
Hazard Class and Hazard state-
Identification
Category Code(s) ment Code(s)
601-053-00-8 nonylphenol; [1] 25154-52-3 [1] Repr. 2 H361fd

4-nonylphenol, Acute Tox. 4 * H302
branched [2] 84852-15-3 [2] Skin Corr. 1B H314
Aquatic Acute 1 H400
Aquatic Chronic 1 H410
604-075-00-6 4-(1,1,3,3- 140-66-9 Irrit. 2 H315

tetramethylbutyl)phenol; Eye Dam. 1 H318
4-tert-octylphenol Aquatic Acute 1 H400
604-032-00-1 thymol 89-83-8 Acute Tox. 4 * H302

Skin Corr. 1B H314
Authorisation List / REACH Annex XIV

As of November 2012, none of the AP/APEOs are included in REACH annex XIV which is a list
substances that require authorisation for continued use in the EU.
2.1.2 Ongoing activities - pipeline

Table 4 shows that REACH substance evaluations that may lead to a restriction or authorisation, for
example, are planned/ongoing for '2,4-di-tert-butylphenol', '4-nonyl phenol, branched' and 'p-
cresol'.
TABLE 4
SUBSTANCES IN THE COMMUNITY ROLLING ACTION PLAN (ECHA, 2012A)
CAS No EC No Substance Year Member State Initial grounds for concern

Name
96-76-4 202-532-0 2,4-di-tert- 2014 Belgium Suspected Endocrine Disruptor;

butylphenol Human health/potential STOT-
RE classification; Exposure/Wide
dispersive use, consumer use,
high aggregated tonnage
84852-15-3 284-325-5 phenol, 4-nonyl-, 2014 United Suspected Endocrine Disruptor;

branched Kingdom Exposure/Wide dispersive use,
high tonnage; Risk characterisa-
tion ratios close to 1 (human
health)
Registry of Intentions
Table 5 shows Registry of Intentions by ECHA and Member States’ authorities for restriction pro-
posals, proposals for harmonised classifications and labelling and proposals for identifying
AP/APEOs as Substances of Very High Concern (SVHC). It also shows the intentions for introduc-
ing further restrictions on the import, use and marketing of NP and NPEO, that harmonised classi-
fication and labelling proposals have been submitted for dodecyl- and butylphenol, and that there
are intentions for proposing nonylphenols and octylphenolethoxylates as SVHCs.

TABLE 5
AP/APEO IN REGISTRY OF INTENTIONS (AS OF 3 AUGUST 2012)
Registry of: CAS No Substances Scope (reproduced as indi- Dossier Expected

cated in the Registry of intended date of
intentions) by: submission:
Restriction 25154-52-3 nonylphenol NP and NPEO in textiles have Sweden 03/08/2012

proposal been identified as a significant
intentions source of NP in the environ-
ment. A restriction on the plac-
ing of the market of textile and
leather articles containing NP or
NPEO
84852-15-3 phenol, 4-nonyl-, - “- Sweden 03/08/2012

branched
no CAS or EC nonylphenol ethoxylates - “- Sweden 03/08/2012

number specified
Submitted 121158-58-5 phenol, dodecyl-, Proposed classification accord- Germany Submitted:

Harmonised branched [Tetrap- ing to CLP: 12/04/2012
Classification ropenylphenol (TPP)] Skin Irrit.2
and Labelling Eye Irrit.2
intentions Repr. 2
Aquatic Acute 1,
Aquatic Chronic 1
98-54-4 4-tert-butylphenol Proposed classification accord- Norway Submitted:

ing to CLP: 11/06/2010
STOT SE 3, H335
Skin irrit. 2, H315
Eye dam. 1; H318
Repr 2, H361f
Not classified for the environ-
ment
Submitted 335-67-1 Phenol, 4-nonyl-, Equivalent level of concern Germany Submitted:

SVHC inten- branched and linear (EQC), because they are sub- 06/08/2012
tions covering all individual stances with endocrine disrupt- Public consul-
isomers with an alkyl ing properties for which there is tation 3 Sep
chain of carbon number 9 scientific evidence of probable 2012
and UVCB substances serious effects to the environ-
which include linear and ment.
branched alkyl chains
with a carbon number of
9
no CAS or EC 4-(1,1,3,3- Equivalent level of concern Germany 06/08/2012

number specified tetramethylbutyl)phenol, (EQC) Public consul-
ethoxylated (4-tert- tation 3 Sep
octylphenol ethoxylates) 2012

Candidate list
As of November 2012, one substance, 4-(1,1,3,3-tetramethylbutyl)phenol (CAS N0 140-66-9) has
been included in the candidate list with the scope of equivalent level of concern (EQC); having
probable serious effects to the environment (REACH article 57 f).
Annex XIV recommendations

The latest lists of Annex XIV recommendations (2 August 2012) do not include any AP/APEO.
2.2 International agreements
Table 6 gives an overview of how AP/APEOs are addressed by various international agreements. It
shows that NP and NPEO are subject to phasing out and strict restrictions in the OSPAR and HEL-
COM conventions, whereas OP/OPEO under these conventions are priority substances and subject
to further assessment, which may lead to restrictions. One tri-butyl-phenol is a priority substance
under the OSPAR convention.
TABLE 6
INTERNATIONAL AGREEMENTS ADDRESSING AP/APEO
Agreement Substances How the AP/APEO are addressed
OSPAR Conven- Nonylphenol ethoxylates PARCOM Recommendation 92/8 on Nonylphenol

tion ethoxylates : Phasing out of the use of NPEOs as clean-
ing agents for domestic uses (1995) and industrial uses
(2000)
2,4,6-tri-tert-butylphenol, Included in OSPAR list of priority substances, as Part A

octylphenol, nonylphenol, substances.
nonylphenol ethoxylates
and related substances
HELCOM (Hel- HELCOM Baltic Sea Action Plan adopted on 15 Novem-

sinki Convention) ber 2007 by the HELCOM Extraordinary Ministerial
Meeting:
Nonylphenol By 2008 to work for strict restrictions on the use in the
/nonylphenolethoxylates whole Baltic Sea catchment area of the Contracting
(NP/NPEOs) States
By 2009, if relevant assessments show the need, to
Octylphenol initiate adequate measures such as the introduction of
/Octylphenolethoxylates use restrictions and substitutions in the most important
(NP/NPEOs) sectors identified by the Contracting Parties
Rotterdam Con- No AP/APEOs are included in Annex III which lists

vention (PIC Con- substances that have been banned or severely restricted
vention) for health or environmental reasons by two or more
Parties and which the Conference of the Parties has
decided to be subject to the PIC procedure.
Basel Convention No specific AP/APEO Waste AP/APEOs is included in the hazardous waste
mentioned class A3070 of Annex VIII “Waste phenols, phenol
compounds including chlorophenol in the form of liq-
uids or sludges”. The substances may be included in
other wastes as well, but are not specifically mentioned
in the description of the wastes.

2.3 Eco-labels
Table 7 gives an overview of how AP/APEOs are addressed by the EU, Nordic and German eco-
labelling schemes. The German ecolabel is included because Germany takes up the major part of the
North European market for articles. It shows that the schemes do not distinguish between sub-
stances or sub-groups of substances, but broadly address the presence/absence of AP/APEO, as well
as "alkylphenol derivates". The criteria documents generally do not define the group alkylphenol
and alkylphenoletoxylates.
TABLE 7
ECO-LABELS TARGETING AP/APEO
Eco-label Substances Mixtures and articles + criteria Document title
Nordic Swan Alkylphenol derivatives Dishwasher detergent Nordic Eco-labelling of

dishwasher detergent
Alkylphenol derivatives Paper envelopes: Nordic Eco-labelling of

Adhesives must not contain the substanc- Paper envelopes – Supplementary
es Module
Alkylphenol derivatives Printing companies: Nordic Eco-labelling of

Must not be added to chemicals Printing companies
Alkylphenol ethoxylate Must not be deliberately added to cleaning Nordic Eco-labelling of

Alkylphenol derivatives agents or dispersants. Paper Products - Chemical Module
Alkylphenol Furniture and fitments: Nordic Eco-labelling of

Alkylphenol ethoxylate must not be present in/added to the Furniture and fittings
Alkylphenol derivatives chemical product or material
Alkylphenol Outdoor furniture and playground Nordic Ecolabelling of

Alkylphenol ethoxylate equipment: must not be present in/added Outdoor furniture and playground
Alkylphenol derivatives to the chemical product or material equipment
EU Flower Alkylphenol ethoxylate Footwear production: COMMISSION DECISION of 9

shall not be used in the product up until July 2009 on establishing the
purchase. ecological criteria for the award of
the Community eco-label for
footwear
Alkylphenol ethoxylate Indoor and outdoor paints and varnishes: COMMISSION DECISION
shall not be used in the product before or Of 13 August 2008 establishing
during tinting (if applicable). ecological criteria for the award of
the Community eco-label to indoor
paints and varnishes
(2009/544/EC)
Same for outdoor paint: Commis-
sion Decision (2009/543/EC)
Alkylphenol ethoxylate Bed mattresses: COMMISSION DECISION

shall not be used and shall not be part of of 9 July 2009
any preparations or formulations used. establishing the ecological criteria
for the award of the Community
Eco-label for bed mattresses

Alkylphenol ethoxylate Tissue-paper products: COMMISSION DECISION
Alkylphenol derivatives shall not be added to cleaning chemicals, establishing the ecological criteria
de-inking chemicals, foam inhibitors, for the award of the Community
dispersants or coatings. Eco-label to tissue-paper products
Alkylphenol ethoxylate Textile floor coverings: COMMISSION DECISION

shall not be used and shall not be part of of 30 November 2009
any preparations or formulations used. on establishing the ecological
criteria for the award of the Com-
munity Ecolabel for textile floor
coverings
Alkylphenol ethoxylate Printed paper products: COMMISSION DECISION
Alkylphenol derivatives shall not be added to cleaning chemicals, establishing the ecological criteria
de-inking chemicals, foam inhibitors, for the award of the Community
dispersants or coatings. Ecolabel to printed paper products
Alkylphenol ethoxylate Textile products: COMMISSION DECISION

shall not be used and shall not be part of of 9 July 2009
any preparations or formulations used. establishing the ecological criteria
for the award of the Community
Ecolabel for textile products
German Alkylphenol ethoxylate Fabric Towel Rolls Supplied in Towel Basic Criteria for Award of the
Blue Angel Dispensers : Environmental Label:
Washing and cleaning agents as defined in Fabric Towel Rolls Supplied in
Section 2, para.1, Wasch- und Reinigung- Towel Dispensers
smittelgesetz - WRMG (Act on Washing RAL-UZ 77
and Cleaning Agents), may be used for the
washing of the fabric towel rolls at laun-
dries only if they are free from the sub-
stance.
Alkylphenol ethoxylate Low-Solvent Bitumen Coatings and Adhe- Basic Criteria for Award of the
sives : Environmental Label:
Products containing the substances shall Low-Solvent Bitumen Coatings
not be added to the bitumen coatings or and Adhesives
adhesives. RAL-UZ 115
Alkylphenol ethoxylate Low-Pollutant Fire Extinguishers: Basic criteria for the award of the
The anionic and non-ionic surfactants environmental Label:
contained in the fire-extinguishing foams Low-Pollutant Fire Extinguishers
must be biodegradable by at least 90 per RAL-UZ 66
cent. Their total degradability must be
70%. In addition, they shall not contain
any APEO surfactants.
Alkylphenol ethoxylate Textile Floor Coverings: Basic Criteria for Award of the
Polymer dispersions, resins or similar Environmental Label:
components (binders) containing al- Low-Emission Textile Floor Cover-
kylphenol ethoxylates shall not be added ings
to binders and coatings used in the manu- RAL-UZ 128
facture of textile floor coverings.

Alkylphenol ethoxylate Floor Covering Adhesives and other In- Basic Criteria for Award of the
stallation Materials : Environmental Label :
Products containing alkyl phenol ethox- Low-Emission Floor Covering
ylates shall not be added to the installa- Adhesives and other Installation
tion materials. Materials
RAL-UZ 113
Alkylphenol ethoxylate Thermal Insulation Material and Basic Criteria for Award of the
Suspended Ceilings: Environmental Label:
Products containing alkylphenol ethox- Low-Emission Thermal Insulation
ylates shall not be used. Material and
Suspended Ceilings for Use in
Buildings
RAL-UZ 132
Alkylphenol ethoxylate Wall paints: Basic Criteria for Award of the

From January 1st , 2004 products contain- Environmental Label:
ing alkyl phenol ethoxylates shall no Low-Emission Wall Paints
longer be added to wall paints or binders. RAL-UZ 102
2.4 Summary on the regulatory framework
Nonylphenol and nonylphenolethoxylates

Currently the main legal focus is on emission to the environment of nonylphenol and nonylpheno-
lethoxylates due to their significant aquatic toxicity properties, most notably via existing restrictions
on marketing and use of these substances for nine purposes, including applications in cleaning
agents, in textiles and as a coformulator in biocides/pesticides. Furthermore, the presence in tex-
tiles may be in the restrictions pipeline (Registry of intension) and the specific substance '4-nonyl
phenol, branched' is on the community rolling action plan for substance evaluation, which may lead
to further restrictions. The substances are further regulated by EU legislations addressing ex-
port/import, cosmetics, pollutant release and transfer register and the Water Framework Directive,
as well as a number of Danish statutory orders dealing with sludge, water quality/drinking water
and quality criteria in various environmental compartments. Nonylphenols are also in the Registry
of intentions for identification as SVHC because they are substances with endocrine disrupting
properties for which there is scientific evidence of probable serious effects to the environment. The
substances are addressed for phase out and strict restrictions in the OSPAR and HELCOM conven-
tions.
Octylphenol and octylphenol-ethoxylates

Octylphenol and octylphenol-ethoxylates are often considered alternatives to nonylphenol and
nonylphenolethoxylates. These substances are much less regulated, however, although octylphenol
has the same harmonised classification for aquatic toxicity as nonylphenol. These substances are
addressed under the pollutant release and transfer register and the Danish statutory order dealing
with water quality/drinking water (only octylphenol). They are also on addressed by the OSPAR and
Helsinki conventions; indicated as priority and subject to further assessment for possible re-
strictions. Finally, 4-tert-octylphenol is on the candidate list due to probable serious effects to the
environment (equivalent concern) and the registry of intentions includes a proposal for identifica-
tion of 4-(1,1,3,3-tetramethylbutyl) phenol, ethoxylated as SVHC because is may be degraded to
substances with endocrine disrupting properties.

Dodecylphenol
A harmonised classification and labelling proposal has been submitted for 4-(3,4,5-
trimethylheptyl)phenol (a branched dodecylphenol), suggesting classification as flammable, eye
damaging/irritating and carcinogenic.
Butylphenols
4-tert-butylphenol (4-tert-butylphenol) is prohibited for use in cosmetics, which seems logical
given the submitted registry of intention for a harmonised classification as irritating to skin, eye
damaging, toxic to reproduction and exerting specific target organ toxicity.
2,4-di-tert-butylphenol, being a suspected endocrine disrupter and potential specific target organ
toxicity substance in wide dispersal (including consumer use) and with high aggregated tonnage, is
on the community rolling action plan for substance evaluation.
2,4,6-tri-tert-butylphenol is a priority substance under the OSPAR Commission.
Thymol
Thymol has harmonised classifications.
Eco-labelling criteria generally refer to alkylphenols and alkylphenol ethoxylates

All three reviewed Eco-labelling schemes do not distinguish between substances or sub-groups of
substances, but broadly address the presence/absence of AP/APEO, as well as "alkylphenol deri-
vates". The substances are addressed in criteria for various product groups, including paper, print-
ing, furniture/mattresses, textiles/footwear and paints/adhesives/coatings.

3. Manufacture and uses
3.1 Global manufacture and use of AP/APEO
Publicly available overviews of the total global consumption of the AP and APEO have not been
found.
Campbell (2002) reports that the global consumption of APEO in 2000 was 700,000 t/y, corre-
sponding to about 7% of the total global consumption of surfactants of 10,400,000 t/y (excluding
soap). The total surfactant consumption in Western Europe was 898,000 tonnes, of which APEO
accounted for 86,000 t/y.
OECD Screening Information DataSets (SIDS) for high production volume chemicals have been
prepared for six of the substances: (OECD 1995a,b; 2000; 2002a,b,c). Only one of the SIDS, howev-
er, provides information on global production. In 2000, the world production capacity of 2,6-di-
tert-butyl-p-cresol (BHT, CAS No 128-37-0) amounted to about 62,000 t/y, manufactured by more
than 20 producers (OECD, 2002a).
3.2 Manufacture and use AP/APEO in the EU
Registered uses of AP/APEO and tonnage bands of registered AP/APEO are summarised in Annex
1. The information from the registrations (ECHA, 2012e) is further discussed in the following chap-
ter on manufacture and uses in the EU.
Some of the main manufacturers of AP/APEO in the EU are organised in the European Council of
Alkylphenols and Derivatives, CEPAD, which is a sector group under the European Chemical Indus-
try Council (CEFIC). The following companies are members of CEPAD: Chemtura Corporation,
Dow Europe GmbH, Rhodia, Sasol Olefins & Surfactants GmbH, SI Group, Inc., Sumitomo Bakelite
Europe NV. Associated members are Akzo Nobel Surface Chemistry and BASF SE.
The Council has been contacted in order to obtain an updated overview of the consumption of AP
and APEO in the EU. CEPAD has summarised the information on manufacture and use of the sub-
stances in the EU in a presentation, which is further discussed for each substance or substance
group below.
Statistics on manufacture and import/export of AP/APEO on its own

EU external trade in tonnes of butylphenol, octylphenol and nonylphenol and salts thereof on their
own is shown in the table below. The remaining AP/APEOs are included in aggregated commodity
groups which also include other phenols.

TABLE 8
EU27 EXTERNAL IMPORT AND EXPORT OF BUTYL- OCTYL- AND NONYLPHENOL AND SALTS THEREOF (EUROSTAT,
2012A)
CN code Text Import, t/y Export, t/y
Average 2011 Average 2011

2006-2010 2006-2010
2907 1300 Octylphenol, nonylphe- 4,523 4,020 1,268 1,413

nol and their isomers;
salts thereof
2907 1910 n-Butylphenol 3,902 *1 3,256 2,070 3,498
*1 Average 2007-2010, as no data for 2006 are available.
3.2.1 Nonylphenol and nonylphenolethoxylates

The nonyl group is a chain of 9 carbon atoms, which may be branched or linear. The list of pre-
registered substances includes 13 CAS numbers of nonylphenols. Of these two substances are regis-
tered. Branched 4-nonylphenol is registered with a manufacture and import in the 10,000-100,000
t/y range. 4-(4-Trans-propylcylohexyl) phenol is registered for intermediate use only.
The most comprehensive description of the use of NP and NPEO is presented in the EU Risk As-
sessment from 2002 presenting 1997 data (ECB, 2002).
According to the EU Risk Assessment, the EU production of NP in 1997 was 73,500 tonnes. With an
overall net import, around 78,500 tonnes of NP were used in Europe in 1997. The NP was used for
production of nonylphenol ethoxylates (60% of total), production of resins, plastics, stabilisers etc.
(37%) and production of phenolic oximes (3%). Phenolic oximes are used as a reagent for the ex-
traction and purification of copper from ore and all of the produced volume was exported to coun-
tries outside the EU. The 29,000 tonnes used in the polymer industry was split between the differ-
ent application areas as follows: phenolic resin production (22,500 tonnes), 4-nonylphenyl phos-
phite (TNPP) production (4,000 tonnes), catalyst in epoxy resin production (1,500 tonnes) and use
in other plastic stabilisers (1,000 tonnes).
The EU-production of NPEOs in 1997 was estimated at 118,000 tonnes, produced from 47,000
tonnes of nonylphenol. At that time, the most important sector was the industrial and institutional
cleaning sector, including domestic cleaning, which consumed 30% of the total. Other uses included
emulsion polymerisation (12%), textile auxiliaries (10%), chemical industry, for example synthesis
of nonylphenol ether sulphates and nonylphenol ether phosphates (9%), leather auxiliaries (8%),
agriculture (5%), paints (4%), metal industry (2%) and pulp and paper (1%). Other applications, of
which the majority was not specifically indicated, accounted for the remaining 16%.
EU-wide marketing and use restrictions of NP and NPEO were introduced in 2004 and the con-
sumption of NP and NPEO has decreased markedly since then.
For nonylphenol, the restriction primarily means that the consumption for manufacturing of NPEO
has decreased due to the restriction on the used of NPEO, whereas the other major application
areas have not been restricted.
CEPAD has provided the following overview of the flow of NP and NPEO in the EU (+Switzerland
and Norway) in 2010.

Use in Western
Europe
Phenolic resins
>1.000 t
TNPP
Export
Phenolic oximes
Production
> 1,000 t Epoxy resins
NP
Import Exports
Plastic stabilisers
> 1.000 t
NP for Ethoxylates > 1,000 t

>1,000 t
NPEO
Import Use in WE
> 1.000 t NPEO
FIGURE 1
FLOW OF NONYLPHENOL AND NONYLPHENOLETHOXYLATES IN WESTERN EUROPE (EU +SWITZERLAND AND
NORWAY) IN 2010 (CEPAD, 2012)
The flowchart confirms that NP is still used for the main application areas described in the EU Risk
Assessment, but provides very limited information on quantities. According to the registration of
branched 4-nonylphenol (CAS nr. 84852-15-3), the total import and production of NP is in the
10,000-100,000 t/y range (ECHA, 2012e).
Considering that 40% of the consumption of 78,500 tonnes in 1999 was for unrestricted uses and
that a small part is still used for production of NPEO, the total consumption in 2011 was likely in the
range of 30,000-50,000 tonnes. With a total import of NP and OP of approximately 4,000 tonnes,
the data indicated that around 90% of the NP used is also manufactured in the EU.
The registration of NPEO (CAS No 8412-54-4) indicates that the manufactured volume of NPEO is
in the 2,000-20,000 t/y range (ECHA, 2012e) and consequently, roughly estimated, some 800-
8,000 t/y NP are used for the production of NPEO assuming the same NP/NPEO ratio as used in
the Risk Assessment (ECB, 2002). More exact figures are available for ECHA and Member States’
authorities from the confidential parts of the registrations and this information is summarised in a
confidential annex to the Annex XV dossier for 4-nonylphenol, branched and linear and nonylphe-
nol ethoxylates (ECHA, 2012b).
Use of nonylphenol
NP is used almost exclusively as an intermediate in the production of various NP derivatives and
resins. Releases of NP from these production processes are estimated to be very low (OSPAR,
2009). As a result, small quantities of NP enter into the environment directly. The primary source
of NP in the environment is rather considered to be NPEOs, which can break down into NP after
being released into the environment during their production, their formulation into various other
products, and the use of such products (OSPAR, 2009).
4-NP is together with 4-t-OP and 4-tert-BP used in the production of different phenolic resins and a
common description of the resins is provided here.
“Resins” are polymeric materials and the basis for plastics, coating, adhesives, etc. Phenol formal-
dehyde resins (PF) are synthetic polymers obtained by the reaction of phenol or substituted phenol
with formaldehyde. They are generally transparent, hard materials. The term “resin” is also used for

the thick liquids used as the polymer component of two-component systems where they are mixed
with a hardener to initiate a polymerization.
The APs are used in phenol/formaldehyde resins, either alone or mixed with other phenols depend-
ing on the properties desired for the final resin. Phenolic resins are of two main types:
• Novolacs, which are thermoplastic, are among others used in rubber compounding (tyre
manufacture) and are ethoxylated for use in oil recovery.
• Resoles, which are heat reactive, are used as intermediates in contact and pressure sensitive
adhesives, coatings, printing inks and electrical varnishes.
Phenol–formaldehyde resin manufacture is based almost exclusively on discontinuous batch pro-

cesses using a traditional reactor, the resins being formed by a stepgrowth polymerisation reaction
in which the AP is used as a monomer. Most of the AP in the resins is chemically bound and cannot
be released even on subsequent chemical or biological degradation, but the resins may also contain
a small proportion (~3-4%) of unreacted AP (Environmental Agency, 2005a).
Since the resins are further processed to finished products, the concentration of free residual mon-
omers in the final products is much lower (ECB, 2008).
Besides the direct use of NP in end products, the substance may be present in phenol-
formaldehyde-resins made from NP (ECHA, 2012b). This may be the case in a wide range of prod-
ucts made of phenolformaldehyde-resins such as rubber products, printing inks, paints, adhesives
and others. Consumer products may consequently contain very low levels of residual, unreacted
nonylphenol; in certain products, the derivative compound may break down to release small
amounts of nonylphenol (ECB, 2002).
NP is used for a few non-industrial applications which will be mentioned below together with the
applications of NPEO.
Use of nonylphenol ethoxylates

At least six NPEOs are pre-registered; of these, one is registered with a tonnage band of 2,000-
20,000 t/y.
The total use of NPEOs is consequently assumed to be in the 2,000-20,000 t/y range; less than
20% of the consumption in 1997. No breakdown of the total consumption by application areas today
has been pinpointed in the research.
For the major use areas of NPEO in 1997, the substances are currently restricted: cleaning agents
(except for controlled closed dry-cleaning systems and cleaning systems with certain special treat-
ment), leather and textile auxiliaries (except processing with no release into waste water, and sys-
tems with certain special treatment), agriculture, metal industry (except uses in controlled closed
systems where the washing liquid is recycled or incinerated) and pulp and paper.
An Annex XV SVHC dossier for nonylphenol and its ethoxylates from 2012 (ECHA, 2012b) lists a
number of applications for which NP and NPEO are still used. Some of the main applications will
briefly be mentioned here and further discussed in the Danish context in section 3.3.
In paints and printing inks, nonylphenol ethoxylates are typically used in concentrations of 0.6 to
3%. Nonylphenols or their ethoxylates are mainly used in paints used on wet-room floors, water-
based paints and varnishes for indoor use, printer’s ink, concrete floor paint, metal coating and
anticorrosive paints. (ECHA, 2012b) In 1997, 4,000 t/y were used for paint and varnishes.

NPEOs are added to acrylic esters used for specialist coatings, adhesives and fibre bonding. This
application is the application indicated as “emulsion polymerisation” in the EU Risk Assessment;
this use accounted for 12% of the total use in 1997 (13,000 t/y). The NPEOs act as dispersants and
increase the stability of the formulation.
NPEOs are still used in metal working fluids under certain conditions and in lubricating oils.
Nonylphenols and their ethoxylates may be used as antioxidants and plasticizers in plastic products.
Besides the direct uses of the NPEOs, the substances may also be present in imported articles. 4-
Nonylphenol and its ethoxylates are still used in textile production outside the EU as detergent and
auxiliaries, such as dispersing agents for dyeing, emulsifiers and spinning lubricants (ECHA,
2012b). Imported textiles may therefore contain nonylphenol ethoxylates as contamination. This is
further discussed in the Danish context in section 3.3.
3.2.2 Octylphenol and octylphenolethoxylates

The octyl group is a chain of 8 carbon atoms, which may be branched or linear. Seventeen different
CAS numbers of octylphenols are pre-registered. Only one of the substances is registered: 4-tert-
octylphenol (4-t-OP) (CAS No 140-66-9). 4-t-OP is manufactured in the EU in the 10,000-100,000
t/y range according to the current registrations (ECHA, 2012e).
One other octylphenol, o-(1-methylheptyl)phenol (CAS No ) 18626-98-7 is included in the list of

2013 registration intentions, indicating the manufactured and imported tonnage may be in the 100-
1,000 tonnes range (ECHA, 2012e).
Use of 4-tert-octylphenol
The most comprehensive description of the use of 4-t-OP in the EU is from a UK environmental risk
evaluation report for 4-t-OP (Environment Agency, 2005a). The data concerns 2001. For the cur-
rent study, CEPAD has indicated these data as the most updated information on the use of OP in the
EU. The same data are used for an Annex XV SVHC report for 4-t-OP published in 2012 (ECHA,
2012c).
The use of 4-t-OP is not restricted and it is expected that the consumption patterns today are more
or less the same as in 2001.

OP for phenolic
Captive use
Resins/tackifiers
20,060 t
Eksport 20,060 t
150 t OP for phenolic resins
2,398
Production OP for ethoxylates
22,633 t
22.858 t 400 t
Import
Octylphenol
375 t
ethoxylates
Octylphenol 1,000 t
ethoxylates
1,000 t OP-ethoxylates for Octylphenol
ethersulphates ethersulphates
200 t 250 t
FIGURE 2
FLOW OF 4-t-OP IN WESTERN EUROPE (EU + SWITZERLAND + NORWAY) IN 2001 (ENVIRONMENT AGENCY ,
2005A)
As shown in Figure 2, 4-t-OP is mainly used as an intermediate in the production of phenolic resins
(about 98 percent of the whole amount of 4-t-OP) and an intermediate in the production of oc-
tylphenol ethoxylates (about 2%).
Based on information from registration dossiers (ECHA, 2012e), the uses of OP are:
• As a monomer for polymer preparations ;

• As an intermediate for manufacture of ethoxylates which to some extent will be a component
of products (e.g. paints) used by industry, professional users and consumers;
• As a component in phenolic resins used in the formulation of adhesives which are used by
industry, professional users and consumers;
• As a component in coatings, printing inks and some types of paints, which are used by indus-
try, professional users and consumers;
• As tackifiers in the production of rubber products.
Basic information on the phenolic resins is provided in the section on NP.
Rubber compounding for tyres is the main use of 4-t-OP -based resins. The function of the resins is
to increase the tackiness of the rubber and improve adhesion of the different layers during vulcani-
sation (Environment Agency, 2005a). The resins are added to rubber in amounts up to 1.5% of the
rubber formulation, though the maximum figure for the percentage of resin in rubber used for tyres
is 10% (Nwaogu et al., 2006).
According to Environment Agency (2005a) citing CEPAD (2002), this results in a maximum con-
centration of free 4-t-OP in tyres of 0.3%. In response to the Annex XV report for 4-t-OP (ECHA,
2012c), the European Tyre & Rubber Manufacturers' Association (ETRMA, 2011) indicates that the
resins used for tyres generally contain free 4-t-OP monomer impurity of between 1 and 5%. Specifi-
cally, 4-t-OP-based resins are sometimes used in tyre compounds, typically in the carcass plies or
steel belts, in order to ensure adequate adhesion. According to company data on annual use of 4-t-
OP-based resins and tyre production, and assuming an average content of 3% free impurity 4-t-OP
in the resins, it has been calculated that an average EU tyre contains between 0,007 % and 0,012 %

of 4-t-OP (ETRMA, 2011); i.e. significantly below the 0.3% indicated by Environment Agency
(2005a).
The 4-t-OP -based resins are also used in printing inks and in marine paints (Nwaogu et al., 2006)
which is indicated in the flow chart as 4-t-OP for phenolic resin. The total EU consumption in 2001
for the two applications was 1,000 tonnes and 800 tonnes, respectively.
Use of octylphenol ethoxylates

At least 4 OPEOs are pre-registered but none of these are registered yet or included in the list of
2013 intentions.
According to an Annex XV report for a group entry of 4-tert-octylphenol ethoxylates (ECHA,

2012d), the registration dossiers for 4-tert-octylphenol provide some information on the production
of 4-tert-octylphenol ethoxylates without pointing out specific characteristics (ECHA, 2012e). The
overall amount produced or imported per year may be in the range of 200 to 2000 tons. According
to CEPAD, there were only four to five manufacturers of octylphenol ethoxylates within the EU
(ECHA, 2012d).
The Annex XV report quotes the COHIBA Summary report for Germany (COHIBA 2011c) that
about 2,100 tonnes of 4-tert-octylphenol were produced in Germany in the year 2000. About 70%
of this volume was used to produce 4-tert-octylphenol ethoxylates, which would mean that close to
5,800 tonnes of 4-tert-octylphenol ethoxylates were produced in Germany in 2000 considering a 36
percent weight contribution of 4-tert-octylphenol. This tonnage is much higher than the tonnage
described in the UK risk evaluation report (Environment Agency, 2005a) and is not supported by
any registration dossier (ECHA, 2012e). The original source of the information on the German pro-
duction (Hillenbrand et al., 2007) makes also reference to the UK risk evaluation figures as being
the best estimate of the total EU use. As the estimate from the UK risk evaluation is well in concord-
ance with the data on the registered volumes, this estimate (shown in Figure 2) is here considered
the best estimate.
CEPAD (2012) has indicated the flow chart from the Environment Agency (2005a) report as the
best indication of the flow of octylphenol ethoxylates in the EU for the current study.
In 2001, the total manufacture of OPEOs was 1,000 tonnes, corresponding to approximately 400
tonnes OP used for the manufacture of OPEO (Environment Agency, 2005a). Octylphenol ethox-
ylates were at that time mainly used in emulsion polymerisation, textile processing, water-based
paints, pesticide and veterinary medicine formulations and for ethersulphates, as shown in Figure
3. Two hundred t of OPEO was used to produce 250 t of octylphenol ethersulphates, which were
thereafter used for agriculture and paints.
A significant part of the OPEO used for textile and leather auxiliaries, paints and agriculture, as well
as the octylphenol ethersulphates used for agriculture and paint may end up in the environment.

Export 0 t Emulsion
polymerisation 550 t
Production 1,050 t Textile auxiliaries 150 t

1,000 t
Agriculture 100 t
Import 50 t
Leather auxiliaries 50 t
Paints 50 t
200 t
Agriculture 50 t
Octylphenol
ethersulphates 250 t
Paints 200 t
FIGURE 3
FLOW OF OCTYLPHENOL ETHOXYLATE IN WESTERN EUROPE (EU + SWITZERLAND + NORWAY) IN 2001 (ENVI-
RONMENT AGENCY, 2005A)
The major application in 2001 was emulsion polymerisation. Emulsion polymerisation is basically a
type of polymerisation (e.g. to make styrene–butadiene polymers or PTFE polymers) which takes
place in an emulsion typically incorporating water, monomer and surfactant (Nwaogu et al., 2006).
The end applications for the polymer dispersions include paints, paper, inks, adhesives and carpet
backings.
OPEOs are used in textile and leather auxiliaries (e.g. hot melts, textile printing, leather finishing).
They generally act as emulsifiers in finishing agents, which are mainly styrene-butadiene copoly-
mers. Finishing agents cover leather and textiles with a thin polymer film to make the material
more resistant to water, dust and light. They also give leather a shiny appearance. The OPEO is
physically bound in the polymer matrix, which adheres to the substrate. Releases of OPEO from this
insoluble polymer structure are indicated to be unlikely (Environmental Agency, 2005).
In water-based paints, OPEOs act as emulsifiers and dispersants, although the emulsifying proper-
ties are more dominant (Environmental Agency, 2005).
OPEOs can be used to produce octylphenol ether sulphates (OPEO-Ss). These are mainly used as
emulsifiers in water-based paints.
A risk reduction strategy for octylphenol and an analysis of advantages and drawbacks at EU level
have been prepared by DEFRA in 2008 (Nwaogu et al., 2006), which form the basis for the descrip-
tion of substitution options in Chapter 8.
3.2.3 Dodecylphenol and dodecylphenol ethoxylate

The dodecyl group is a chain of 12 carbon atoms, which may be branched or linear. Four CAS No of
dodecylphenol are included in the list of pre-registered substances.
Of these, branched dodecylphenol (CAS No 121158-58-5) is registered with a manufactured and

imported tonnage in the 10,000-100,000 t/y range. The indicated uses are as chemical intermedi-
ate and monomer for synthesis of polymers. The CAS No in fact represents a large number of highly

branched isomeric alkyl groups ranging from C10 to C15, in different positions (Brooke et al.,
2007).
The overall flow of dodecylphenol in Western Europe in 2010 as provided by CEPAD is shown in
Figure 4.
DP for oil and lubri-

Captive use
cant additives
> 1.000 t
Export > 1,000 t
DP for oil and
Lubricants additives
Production > 1.000 t
> 1,000 t > 1.000 t DP for phenolic
resins/lacquers
Import
DP for
ethoxylates
Dodecylphenol
ethoxylates
< 1,000 t
FIGURE 4
OVERALL FLOW OF DODECYLPHENOL IN WESTERN EUROPE (EU + SWITZERLAND + NORWAY) IN 2010 (CEPAD
2011). CAPTIVE USE IS THE USE OF THE SUBSTANCE IN THE CHEMICAL INDUSTRY FOR SYNTHESIS OF OTHER
CHEMICALS.
For an assessment of para-C12-alkylphenols (dodecylphenol and tetrapropenylphenol) prepared by

the Brooke et al. (2007), members of CEPAD and RATG (Risk Assessment Task Group of the Amer-
ican Chemistry Council’s Petroleum Additives Panel) have provided European production and im-
port quantities for the period 1998–2002. The individual tonnages and capacities were confidential,
but the total European consumption of the two substances was indicated to be approximately
50,000 t/y in 2004. It is indicated that the consumption was mostly as tetrapropenylphenol.
“Tetrapropenylphenol” refers to the common name for the substance tetrapropenylphenol deriva-
tives (CAS No 74499-35-7), which is also a dodecylphenol. This substance is not included in the
database of registered substances or the list of 2013 intentions, whereas branched dodecylphenol
(CAS No 121158-58-5) is registered with a manufactured and imported tonnage in the 10,000-
100,000 t/y range. Consequently, it does not seem that the tetrapropenylphenol derivative would
take up the majority of the manufactured or imported totals today.
At EU level, around 99% of the consumption volume of the two substances was used in the produc-
tion of oil and lubricant additives (primarily calcium alkylphenate sulphides). Lubricant additives
are complex mixtures of synthetic chemicals. They are combined with highly refined lubricant base
oils to blend lubricants or are added to petroleum fuels to achieve a particular end use or level of
performance (e.g. two-cycle oils).
The dodecylphenol is present in the final lubricants at low levels. In Norway the average content of
dodecylphenol in those lubricants indicated by the MSDS as containing dodecylphenol was 0.15%
(Lambert, 2010). Import of dodecylphenol in oils was estimated to represent the major flow of do-
decylphenols in Norway; consequently, improper disposal of used oil has been identified as the
main source of environmental emission of dodecylphenols.
A relatively small amount was used to produce phenol/formaldehyde resins for printing inks and
rubber tyre manufacturing (Brooke et al., 2007)

A very small proportion (<1%) of the overall tonnage of tetrapropenylphenol was used to make
ethoxylates. These are used as anti-rust agents in finished lubricants at levels of 0.05-0.30% w/w.
Tetrapropenylphenol can be used to make 2,4-di-tert-butyldodecylphenol (CAS no.68025-37-6).

This substance is also used to make lubricant additives. No specific information on the production
or use of this substance has been obtained.
Dodecylphenol ethoxylates
At least two dodecylphenol ethoxylates are pre-registered but none are included in the database of
registered substances or the list of 2013 intentions.
A very small proportion (<1% i.e. < 500 t/y) of the overall tonnage of tetrapropenylphenol was used
to make dodecylphenol ethoxylates in 2004. These are used as anti-rust agents in finished lubri-
cants at levels of 0.05-0.30% w/w. The number of ethoxy units is 10-15. Since the tetrap-
ropenylphenol molecule has high oil solubility, its ethoxylate derivatives are never used in water-
based applications. The volume of these materials used in lubricants has been dropping since the
late 1980s, a continuing trend. The industry believes they will eventually be totally phased out. The
residual content of free dodecylphenol in the ethoxylates is unknown but most likely <1%. (brooke
et al., 2007).
3.2.4 Butylphenols
The butyl group is a chain of 4 carbon atoms, which may be branched or linear. At least 11 CAS
numbers of butyphenols are included in the list of pre-registered substances. Two of these are regis-
tered in ECHA’s database of registered substances: 4-tert-butylphenol (4-tert-BP) (CAS No 98-54-
4) and 2-sec-butylphenol (CAS No 89-72-5).
The 4-tert-butylphenol is registered for use as intermediate only, without an indication of tonnage
band.
The 2-sec-butylphenol is registered with an imported and manufactured tonnage in the 1,000-
10,000 tonnes range.
Furthermore, phenol isobutylenated (CAS No 68610-06-0) is included in the list of 2013 registra-
tion intentions, indicating the manufactured and imported tonnage may be in the 100-1,000 tonnes
range (ECHA, 2012e).
4-tert-butylphenol (4-tert-BP)
The manufacture and use of 4-tert-BP in the EU is described in the EU Risk Assessment report for
4-tert-butylphenol from 2008 (ECB, 2008) presenting production and consumption figures for
2001 (see Figure 5). CEPAD has indicated these data as the best indication of the flow of 4-tert-BP
in the EU for the current study.
The report does not provide a detailed breakdown of the consumption by application area but indi-
cates that the consumption is >1,000 tonnes for three application areas: production of phenolic
resins, production of polycarbonates and production of alcohols through hydrogenation.
4-tert-BP is mainly used as a co-monomer in the polymer industry in the same way as 4-
nonylphenyl, which means 4-tert-BP is polymerized with other ingredients such as phenol and
formic aldehyde (see description under NP). In the polymers, 4-tert-BP is chemically bound in the
matrix (covalent binding). (ECB, 2008) The phenolic resins and epoxy resins are used for a range of
applications. With respect to consumer exposure the use of 4-tert-BP in epoxy for canned food is
considered to potentially be the major source (ECB, 2008) as further discussed in section 7.4.

Use in WE
For the production of:
Phenolic resins
> 1,000 t
Eksport
Polycarbonates
734 t
> 1,000 t
Alcohols through
Production 26,617 t
hydrogenation
Butylphenol > 1,000 t
Import Epoxy resins
> 1,000 t
Oil field additives
> 1,000 t
Agro chemicals
> 1,000 t
FIGURE 5
FLOW OF 4-TERT-BP IN WESTERN EUROPE (EU + SWITZERLAND + NORWAY) IN 2001 (ECB , 2008)
It is common for commercial 4-tert-BP/formaldehyde resins to contain up to 3% free 4-tert-BP.

However, in all of the processes the resin is mixed with other resins/components and, with the
exception of tyre tackifiers, further reaction takes place. This reaction will also occur with any free
4-tert-BP in the resin, and this dilution and reaction will reduce the free monomer to very low lev-
els. Residual 4-tert-BP concentrations far below 0.1% have been measured in butylphe-
nol/formaldehyde resins used to improve the tack of compounded rubber for tyres.
4-tert-BP is used as a chain terminator in the synthesis of polycarbonate polymers. Polycarbonate

resins produced with 4-tert-butylphenol contain 1-3 % (w/w) of 4-tert-BP, reacted and bound into
the polymer chain. Since the polymers are further processed to finished products, the concentration
of free residual monomers in the final products is much lower. The residual concentrations of non-
reacted 4-tert-BP in polycarbonate is found to be non detectable, at a limit of detection of 5 ppm
(ECB, 2008). The main uses of polycarbonate are the following: Compact discs, DVD, and CD Rom
manufacture, solid and multi-wall sheet in glazing applications and films, as polycarbonate blends
for diverse injection moulded functional parts used mainly in the electrical and electronics industry
and the automotive industry, containers for storage of food and beverages, and tableware (ECB,
2008). Exposure to 4-tert-BP from polycarbonate used for food contact applications is estimated to
be the second major source of consumer exposure to 4-tert-BP (ECB, 2008).
Butylphenol/formaldehyde resins are ethoxylated to produce specialised surfactants for the separa-
tion of crude oil in aqueous refinery effluent from off-shore oil. Release of ptBP is restricted to the
production process of the ethoxylated resins products and no additional environmental releases of
ptBP therefore are expected during the production of oilfield chemicals (ECB, 2008).
4-tert-BP is also hydrogenated to form the corresponding alcohol 4-tert-butylcyclohexanol.
Due to its low alkyl chain-length, 4-tert-BP is not suitable for the production of surfactants and
butylphenol is not used to produce butylphenol ethoxylates (CEPAD, 2012).
2-sec-Butylphenol
The compound 2-sec-butylphenol (= o-sec-butylphenol, CAS No 89-72-5) is registered with an im-
ported and manufactured tonnage in the 1,000-10,000 tonnes range. The substance is indicated as

raw material for the production of fungicides and other plant protection products (ECHA, 2012e) in
the registration.
o-tert Butylphenol
o-tert butylphenol was produced in quantities of <1000 t/y in 2010 according to CEPAD (2011).
Together with other ortho-substituted alkylphenols, they are chemical intermediates for the produc-
tion of herbicides, plastic additives, or - after hydrogenation - for the fragrance industry.
3.2.5 Dibutyl- and tributylphenols

Dibutylphenols
Four dibutylphenols are registered. For both 2,4-di-tert-butylphenol (CAS No 96-76-4) and 2,6-di-
tert-butylphenol (CAS No 96-76-4) more than one registrant has registered a production or import
in the 100-1,000 t/y range. According to CEPAD (2011), the total production is >1,000 t/y for both
compounds and they are used as chemical intermediates for the production of plastic additives
(antioxidants and UV-light stabilizers). According to the registrations they may also be used as fuel
additives and lubricant additives used both by professionals and consumers (ECHA, 2012e). The
consumption of the two substances in 1999 was 13,000 and 15,000 t/y (Environment Agency,
2005b).
Two dibutyls are registered for usage as intermediate only: di-sec-butylphenol, mixed isomers (CAS
No 5510-99-6) and di-sec-butylphenol (CAS No 31291-60-8). According to CEPAD (2011), both are
manufactured in a quantity of <1,000 t/y and used as intermediate for the production of plastic
additives (antioxidants and UV-light stabilizers).
Tributylphenol
The substances 2,4,6 tris-tert butyl-phenol (TTBP) (CAS no 732-26-3) is registered for usage as
intermediate. CEPAD indicates that the production is <1,ooo t/year and that the substance is used
as intermediate for the production of plastic additives. In Norway the main flow of TTB-phenol was
due to its potential use as a fuel additive (Lambert et al., 2010). In Norway, it was only found in
imported fuel, and would be present at a level of approximately 0,027%. With normal use, TTBP
will burn and environmental emission will not be of any significance (Lambert et al., 2010).
3.2.6 2,6-Di-tert-butyl-p-cresol
2,6-Di-tert-butyl-p-cresol (BHT, CAS No 128-37-0) is registered as manufactured and imported in
the 10,000-100,000 t/y tonnage range. The substance is registered by at least three manufacturers
or importers.
The substance is not included in the presentation on major uses of AP/APEO submitted by CEPAD.
According to the OECD SIDS Initial Assessment Report from 2002 (OECD, 2002a), the world pro-
duction capacity of BHT in 2000 amounted to about 62,000 t/y. The substance was manufactured
by four companies in Western Europe with a production capacity of 25,000 t/y.
BHT is registered for usage as a stabilizing (antioxidant) component for many applications. As an
antioxidant, it finds many applications in a wide variety of industries (OECD, 2002). It is used in
ground vehicle and aviation gasolines; lubricating, turbine, and insulation oils; waxes, synthetic and
natural rubbers, paints, plastics, and elastomers (synthetic rubbers). It protects these materials
from oxidation during prolonged storage. Highly purified grades are suitable for use in foods to
retard oxidation of animal fats, vegetable oils, and oil-soluble vitamins. It is also used in cosmetics
and food packaging materials such as waxed paper, paper board, and polyethylene. It is important
in delaying the onset of rancidity of oils and fats in animal feeds, and in preserving the essential
nutrients and pigment-forming compounds of these foods (OECD, 2002). The worldwide distribu-
tion by end-applications for year 2000 was: rubber (27%), plastics (27%), mineral oil/food additive

(17%), foodstuff/pharmaceuticals/cosmetics (12%), animal feed / pet food (11%) and printing
inks/miscellaneous (6%).
The substance is authorised for use as food additive and as cosmetic ingredient under the name
butylated hydroxytoluene (BHT).
3.2.7 Other alkylphenols

The use in the EU of a number of other alkylphenols is summarised in Table 9. The substances are
either used in small quantities or mainly used as intermediates.
TABLE 9
AVAILABLE INFORMATION ON A NUMBER OF OTHER ALKYLPHENOLS
Substance CAS No Import Registered Main application areas *2

and manu- quantity
facture in t/y
2010
t/y *1
4-tert amylphenol 80-46-6 <1,000 n.r. Production of phenolic resins and lacquers
o-tert amylphenol 3279-27-4 <1,000 n.r. Production of herbicides, plastic additives, or - after
hydrogenation - for the fragrance industry
2-isopropylphenol 88-69-7 >1,000 n.r.
2,4-dinonylphenol 137-99-5 <1,000 n.r. Production of polycarbonates and phenolic resins and
lacquers
2,4-di-tert amylphe- 120-95-6 <1,000 n.r. Plastic additives

nol
Phenol, isopropylat- 90480-88-9 n.i. intermediate use Chemical intermediate

ed only
2-tert-butyl-p-cresol 2409-55-4 n.i. intermediate use Chemical intermediate

only
6-tert-butyl-m-cresol 88-60-8 n.i. intermediate use Chemical intermediate

only
C14-16-18 alkylphe- 931-468-2 n.i. intermediate use Chemical intermediate

nol only
Thymol 89-83-8 n.i. 1,000 - 10,000 Cleaning agents

Use of scented articles
o-pentylphenol 136-81-2 n.i. Available in Production of phenolic resin

confidential Germicide
4-pentylphenol 14938-35-3 n.i.
annex to Crane Vulcanizing agent
m-pentylphenol 20056-66-0 n.1. et al. (2008)
*1 Source: CEPAD, 2011.

*2 Source: Registrations (ECHA, 2012e).
n.r: Not registered; n.i.: not indicated.
3.2.8 Summary on the use of AP/APEO in the EU

A summary of the use of AP/APEO in the EU is provided in Table 20 together with the summary of
the use of the substances in Denmark.

3.3 Manufacture and use of AP/APEO in Denmark
The following sections examine manufacture and use of AP/APEO in Denmark.
3.3.1 Manufacture, import, export and consumption of AP/APEO on its own and
in mixtures
Alkylphenols and alkylphenol ethoxylates are not produced in Denmark.
Import/export statistics
The import of butylphenol, octylphenol and nonylphenol and salts thereof as retrieved from Euro-
stat is shown in the table below. Other AP/APEOs are included in aggregated commodity groups
which also include other phenols. The net import in 2011 of octylphenol and nonylphenol on their
own was 1.6 tonnes, while the net import of 4-tert-BP was 4.5 tonnes.
The imported 1.6 tonnes of nonylphenol, octylphenol and their salts is a relatively small quantity
compared to the 34 tonnes registered in total for the two substances in the Danish Product Register
(shown in next section). Considering that the average for the period 2006-2010 was 0.08 tonnes, it
clearly indicates that nonylphenol and octylphenol are mainly imported in mixtures. The imported
mixtures may partly consist of raw materials for production of mixtures in Denmark, and partly of
mixtures for end-use in Denmark.
The imported quantities of 4-tert-BP is of the same size as the quantities registered in the Product
Register. No indication of the application of the 4-tert-BP on its own has been obtained. Consider-
ing 4-tert-BP is generally used for the production of phenolic resins, it is likely that the substance
could be used for this application in Denmark.
TABLE 10
DANISH IMPORT AND EXPORT OF 4-TERT BULTYLPHENOL, OCTYLPHENOL AND NONYLPHENOL AND SALTS
THEREOF (EUROSTAT, 2012A)
CN code Text Import, t/y Export, t/y
Average 2011 Average 2011

2006-2010 2006-201o
2907 13 00 Octylphenol, nonylphe- 0.08 1.6 0 0

nol and their isomers;
salts thereof
29071910 4-tert-butylphenol 5.3 4.5 0 0.06
Data from the Danish Product Register

Data on AP/APEO registered in the Danish Product Register were retrieved in July 2012 on the
basis of the gross list of AP/APEO shown in Table 1. For a few of the substances identified at a later
stage of study implementation, data have not been retrieved from the Product Register, but a search
in the SPIN database of the Nordic Product registers has indicated that the substances are not regis-
tered in the Danish Product Register.
The Danish Product Register includes substances and mixtures used occupationally and which
contain at least one substance classified as dangerous in a concentration of at least 0.1% to 1% (de-
pending on the classification of the substance). Of the AP/APOE, nonylphenol, 4-octyl phenol and
thymol are classified as dangerous. For the other non-classified substances, the registration will
only occur if they are constituents of mixtures which are classified and labelled as dangerous due to
the presence of other constituents. The data consequently do not provide a complete picture of the

presence of the substances in mixtures placed on the Danish market. On the other hand, for sub-
stances included in mixtures used for formulation of other mixtures in Denmark (e.g. those includ-
ed in raw materials used for production of paint), the quantities may be double-counted as both the
raw material and the final mixture in the register. As stated above, the amounts registered are for
occupational use only, but for substances used for the manufacture of mixtures in Denmark the data
may still indicate the quantities of the substances in the finished products placed on the market
both for professional and consumer applications.
Data on AP/APEO in mixtures registered in the Danish Product Register are summarised in Table
11. In total, 39 AP/APEO within the scope of this study were registered. The total production and
import was 392 tonnes and the total consumption (content of mixtures placed on the Danish mar-
ket) was 330 tonnes. Of this, nonylphenol (substances with non-confidential data only) and
nonylphenol ethoxylates accounted for 52% and 2,6-di-tert-butyl-p-cresol for 36%. It should be
noted that 2,6-di-tert-butyl-p-cresol often is not included in the group of AP/APEO. The substance
was present in 1,156 registered mixtures.
TABLE 11
AP/APEO IN MIXTURES PLACED ON THE DANISH MARKET IN 2011 AS REGISTERED IN THE DANISH PRODUCT REG-
ISTER
CAS No Chemical name No of Registered tonnage, t/y

mixtures Produc- Export Consump-
tion + tion
import
Nonylphenol
25154-52-3 nonylphenol 84 32.513 3.651 28.862
84852-15-3 phenol, 4-nonyl-, branched 7 0.091 0.000 0.091
104-40-5 4-nonylphenol Conf. - - -
Total ( excl. confidential) 32.604 3.651 28.953
Nonylphenol ethoxylates
9016-45-9 nonylphenol, ethoxylated 186 119.711 11.109 108.602
26027-38-3 4-nonylphenol, ethoxylated 13 0.014 0.004 0,010
37205-87-1 poly(oxy-1,2-ethanediyl), α-(isononylphenyl)-ω- 41
5.041 0.283 4,758
hydroxy-
68412-54-4 2-{2-[4-(2,4,5-trimethylhexan-3- 103
44.064 17.558 26,506
yl)phenoxy]polyethoxy}ethanol
127087-87-0 4-nonylphenol, branched, ethoxylated 8 0.467 0.192 0,275
Total 169.298 29.146 140.152
Octylphenol
140-66-9 4-(1,1,3,3-tetramethylbutyl)phenol Conf. - - -
3884-95-5 o-(1,1,3,3-tetramethylbutyl)phenol Conf. - - -
Octylphenol ethoxylates
9002-93-1 poly(oxy-1,2-ethanediyl), α-[4-(1,1,3,3- Conf.
- - -
tetramethylbutyl)phenyl]-ω-hydroxy *5
9036-19-5 poly(oxy-1,2-ethanediyl), α-[(1,1,3,3-
104 12.650 2.032 10.619
tetramethylbutyl)phenyl]-ω-hydroxy
Dodecylphenol
104-43-8 4-dodecylphenol 16 0.051 0.001 0.049
27193-86-8 decylphenol 4 0.044 0.000 0.044
121158-58-5 Phenol, dodecyl-, branched 105 4.355 0.419 3.935
210555-94-5 phenol, 4-dodecyl-, branched (not pre-registered ) Conf. - - -

CAS No Chemical name No of Registered tonnage, t/y
mixtures Produc- Export Consump-
tion + tion
import
57427-55-1 Tetrapropylenphenol (not pre-registered ) Conf. - - -
Dodecylphenol ethoxylates
74499-35-7 phenol, (tetrapropenyl) derivs. 41 2.426 0.003 2.423
9014-92-0 Dodecylphenol, ethoxylated Conf. - - -
Butylphenols
88-18-6 2-tert-butylphenol 5 0.184 0.027 0.157
98-54-4 4-tert-butylphenol 61 8.339 5.515 2.824
28805-86-9 butylphenol Conf. - - -
68610-06-0 phenol, isobutylenated Conf. - - -
2,6-di-tert-butyl-p-cresol
128-37-0 2,6-di-tert-butyl-p-cresol 1156 137.556 18.764 118.792
128-39-2 2,6-di-tert-butylphenol 58 19.605 1.322 18.282
497-39-2 4,6-di-tert-butyl-m-cresol Conf. - - -
732-26-3 2,4,6-tri-tert-butylphenol 5 0.670 0.067 0.603
17540-75-9 4-sec-butyl-2,6-di-tert-butylphenol Conf. - - -
Other monoalkylphenols
25429-37-2 ethylphenol Conf. - - -
1987-50-4 4-heptylphenol Conf. - - -
119-42-6 2-cyclohexylphenol 59 0.335 0.016 0.319
1131-60-8 4-cyclohexylphenol 59 0.046 0.002 0.044
68025-37-6 bis(tert-butyl)dodecylphenol 6 1.573 0.000 1.573
Other di- and trialkylphenols
89-83-8 thymol 44 0.002 0.000 0.002
96-76-4 2,4-di-tert-butylphenol 13 0.295 0.074 0.221
1323-65-5 dinonylphenol Conf. - - -
1879-09-0 6-tert-butyl-2,4-xylenol 10 0.023 0.000 0.023
2409-55-4 2-tert-butyl-p-cresol 5 0.001 0.000 0.001
4306-88-1 2,6-di-tert-butyl-4-nonylphenol 23 0.196 0.030 0.165
Total (incl. confidential) 392.062 61.077 330.986
Conf.: Data are confidential due to a low number of mixtures or registrants.
Information on use areas by main substance groups is described below. This description is followed
by a description of the main use areas across the substance groups. Please note that the total sum of
mixtures for each substance group is higher in the following tables compared to what would result
from calculation by summing up the data in Table 11 (for nonylphenols e.g. 100 vs. 91). The reason
is that more of the substances may be used in the same mixtures. The total for each substance in
Table 11 has been generated by the data retrieval and represents the correct total number of mix-
tures for each substance. The total number of mixtures may be slightly overestimated in all other
tables.

Nonylphenol, octylphenol and their ethoxylates
NP and NPEO accounted for the majority of those substances traditionally considered AP/APEO.
The registered consumption of one of the nonylphenols (CAS No 25154-52-3) by application area is
shown in Table 12. Data for other alkylphenols are confidential.
The main application area of this NP was paint, lacquers and varnishes, which accounted for ap-
proximately 70% of the total. Other applications were hardeners, adhesives, sealants and filling
agents and joint-less floors. None of these applications are included in the list of restricted applica-
tions. The hardeners are probably the hardener components of two-component systems e.g. for
epoxy or phenolic plastic. The use in the other mixtures is further discussed in the later description
of the application areas across the different substances groups.
The registered consumption of octylphenol was confidential.
Paint and varnishes was also among the main application areas of NPEO (Table 13). The major
application area of the nonylphenol ethoxylates, however, was cleaning agents, polishes and
maintenance agents. The use of NPEO is restricted in cleaning agents and some of the registered
applications such as car shampoo, “general cleaning agents” and “other cleaning agents“ are proba-
bly within the scope of the restriction as further discussed below. The maintenance agents may be
outside the scope of the restriction, but they account for a smaller part of the total within this group.
TABLE 12
CONSUMPTION OF ONE NONYLPHENOL (*1) REGISTERED IN THE DANISH PRODUCT REGISTER, 2012
Application area Consumption (production +

import – export) *1
n *2 t/y %
Paints, lacquers and varnishes 42 19.6 69
Adhesives 6 0.5 2
Sealants and filling agents 7 5.6 20
Hardeners 10 0.2 1
Joint-less floors 4 0.5 2
Other (mainly confidential or substances with the appli- 15 2.1 7

cation area not indicated)
Total (including confidential) 84 28.5 100

*1 CAS No 25154-52-3, nonylphenol.
*2 Number of mixtures.
TABLE 13
CONSUMPTION OF TWO NONYLPHENOL ETHOXYLATES REGISTERED IN THE DANISH PRODUCT REGISTER, 2012
Application area Consumption (production + import – export) *2
n*1 t/y %
Paints, lacquers and varnishes 96 12 9
Lubricants and oils 32 1 1
Biocidal products 13 13 10
Cleaning agents, polish and

maintenance agents 91 53 39
Other 28 55 41
Total (including confidential) - 135 100


*2 Sum of CAS No 9016-45-9 and 68412-54-4 (each with >3 mixtures for each application area)
The main part of the octylphenol ethoxylates were for confidential applications or applications not
indicated in the Product Register. The main non-confidential application accounting for 25% of the
use of CAS No 9036-19-5 was for paints, lacquers and varnishes.
Butylphenols
4-tert-butylphenol was mainly used in paint, lacquers and varnishes and as hardeners for plastics,
i.e. as a constituent of the hardener component of two-component plastics such as epoxy and phe-
nolic plastics. The tonnage registered in the Product Register is lower than the import registered in
the trade statistics. As the substance is not classified as hazardous, mixtures with the substance will
only be registered in the Product Register if the mixtures contain other substances which are classi-
fied as hazardous. An import, for example for use in the manufacture of phenolic plastics, would not
result in a notification of the Product Register.
The consumption of other butylphenols by application area is confidential.
TABLE 14
CONSUMPTION OF 4-TERT-BUTYLPHENOL REGISTERED IN THE DANISH PRODUCT REGISTER, 2012
Application area Consumption (production + import – export)
n *1 t/y %
Paints, lacquers and varnishes 18 2.0 71
Adhesives 17 0.04 1
Sealants and filling agents 4 0.01 0.3
Hardeners 10 0.57 20
Other (incl. confidential) 13 0.2 7
Total (including confidential) - 2.8 100

2,6-di-tert-butyl-p-cresol
As described in the section on use of the substance in the EU, 2,6-di-tert-butyl-p-cresol (BHT) is
widely used as an antioxidant in various mixtures. The substance is registered in nearly 1,200 dif-
ferent mixtures, and the function is usually as an antioxidant. The substance is in general not con-
sidered together with the long-chain APs such as NP, OP and DP.
The substance is used as an antioxidant in food and cosmetics and may be imported in various mix-
tures not registered in the Danish Product Register. The substance is widely used in consumer
products. The total manufacturing capacity in the EU was about 25,000 tonnes in the year 2000. If
it is assumed that the total EU consumption in 2011 was in the range of 15,000-30,000 t/y and
Denmark accounted for 1% if the total EU consumption, the consumption in Denmark would be in
the 150-300 t/y range. The registered tonnage is somewhat lower, but still in the same order of
magnitude.

TABLE 15
CONSUMPTION OF 4-TERT-BUTYLPHENOL REGISTERED IN THE DANISH PRODUCT REGISTER
Application area Consumption (production + import – export)
Number of mix- t/y %

tures
Paints and lacquers 593 0.1 0.1
Inks 11 12.9 11
Adhesives 36 1.8 2
Sealants and filling agents 32 0.002 <0.1
Lubricants and oils 127 3.0 2
Joint-less floors 21 0.1 <0.1
Pesticides and biocidal products 10 0.003 <0.1
Cleaning agents, polish and

maintenance agents 45 6.0 5
Surface active agents, defoamers 21 0.02 <0.1
Raw materials for synthesis 48 21.5 18
Other (confidential and applica-

tions not indicated) 251 73.4 62
Total - 118.8 100
Substances mainly registered as fuel additives and lubricants

A number of the substances are mainly registered as used in fuel additives and lubricants, as further
described in the next section.
Of these substances, the highest quantities are for 2,6-di-tert-butylphenol where the total registered
consumption is 18.3 tonnes, used mainly in lubricant, hydraulic oils and fuel additives. The use in
lubricants and fuel additive is in accordance with the information from registrations under REACH
(ECHA, 2012e).
At EU level, 99% of dodecylphenol is used to prepare lubricant additives. This is also the main non-
confidential application area registered in the Product Register for these substances. A survey of the
use of dodecylphenol and 2,4,6 –tri-tert-butylphenol in Norway found that the concentration of
dodecylphenyl was typically 0.15% in those lubricants, whereas the MSDS indicates that do-
decylphenol was present in the lubricants (Lambert et al., 2010).
The main uses of one of the dodecylphenol ethoxylates (CAS No 74499-35-7) with non-confidential
application were lubricants and oils which accounted for 61% of the total consumption of 2.4 t/y.
2-Cyclohexylphenol and 4-cyclohexylphenol

These substances are used in small quantities for many applications including paint, lacquers and
varnishes. The total registered consumption was 0.3 tonnes.
3.3.2 Consumption of AP/APEO by main application areas

In this section the use of AP/APEO in Denmark is described by main application areas. Possible
import of the substances in articles and mixtures is briefly discussed, although a thorough survey of
such import has not been carried out.

Paint, lacquers and vanishes
Paint, lacquers and vanishes constitute one of the main application areas of the AP/APEO. The
trade organisation for the paint and adhesives industry in Denmark, DFL, has been contacted in
order to obtain more information of the use of AP and APEO in paint and adhesives produced in
Denmark. The trade organisation has carried out a survey among the members and the general
answer is that the substances are not used on their own in the production of paint and adhesives in
Denmark, but may be present in imported raw materials used in production. The same was report-
ed by the trade organisation in 2005 (Kjølholt et al., 2007). The relatively small import of
nonylphenol and octylphenol on their own confirms that the substances are mainly imported in raw
materials and other mixtures.
Nonylphenol is mainly used in hardeners for paint and lacquers, probably for two component speci-
ality lacquers. NPEO and OPEO are used as surfactants, which reduce the surface tension of water,
allowing easier spreading, wetting, and better mixing of paints.
In paints and printing inks, nonylphenol ethoxylates are typically used in concentrations of 0.6 to
3%. (ECHA 2012b). Nonylphenols or their ethoxylates are mainly used in paints used on wet-room
floors, water-based paints and varnishes for indoor use, printer’s ink, concrete floor paint, metal
coating and anticorrosive paints (ECHA 2012b).
As the nonylphenol and nonylphenol ethoxylates are classified as hazardous, the majority of the
mixtures imported or manufactured containing these substances are expected to be registered in
the Product Register.
The compound 2,6-di-tert-butyl-p-cresol is used in small concentrations and quantities as antioxi-

dant in a large number of mixtures.
The paint, lacquers and vanishes may be used for consumer, professional and industrial applica-
tions. No data are available to estimate how much of the total consumption is used for consumer
applications.
TABLE 16
CONSUMPTION OF AP AND APEO IN PAINT, LACQUERS AND VARNISHES REGISTERED IN THE DANISH PRODUCT
REGISTER, 2012
Substance Number of reg- Consumption t/y % of total

istered mixtures
Nonylphenols 49 20.0 53
Nonylphenol ethoxylate 119 12.7 34
Octylphenol ethoxylates 53 2.6 7
4-tert-butylphenol 18 2.01 5
2,6-di-tert-butyl-p-cresol 593 0.1 0.3
Cyclohexylphenols 42 0.02 0.1
Other - <0.001 -
Total - 37.4 100
Lubricants and oils

Many of the small-volume alkylphenols have their main application in lubricants and fuel additives.
The total registered consumption for lubricants, oils and fuel additives is 22.4 tonnes (Table 17 and
Table 18).

This is in accordance with the general information on the use of the substances in the EU.
Lubricant additives are complex mixtures of synthetic chemicals. They are combined with highly
refined lubricant base oils to blend lubricants or are added to petroleum fuels to achieve a particular
end-use or level of performance (e.g. two-cycle oils) (Environment Agency, 2005). If the substances
are added to fuels they would be combusted with the fuel. Used otherwise they would typically be
disposed of with the waste oil, but spill may occur.
The lubricants and oils may be used for consumer, professional and industrial applications. The
consumer applications of these types of lubricants (e.g. crankcase lubricants) is considered too be
very limited.
TABLE 17
CONSUMPTION OF AP AND APEO IN LUBRICANTS AND OILS REGISTERED IN THE DANISH PRODUCT REGISTER, 2012
Substance Number of regis- Consumption t/y % of total

tered mixtures
Nonylphenol ethoxylates *1 40 1.7 13
Octylphenol ethoxylate *2 6 0.05 0.4
2,6-di-tert-butyl-p-cresol 127 3.0 16
Dodecylphenol *3 108 2.1 12
Dodecylphenol ethoxylate* 4 32 1.5 21
2,6-di-tert-butylphenol 40 2.7 2
2,6-di-tert-butyl-4-nonyl-phenol 15 0.2 12
Other - 1.5 13
Total (incl. confidential) - 12.9

* Sum of CAS No 68412-54-4 and 9016-45-9 (each with >3 mixtures).
*2 CAS No 9036-19-5.
*3 Sum of CAS No 104-43-8 and 121158-58-5 (each with >3 mixtures).
*4 CAS N0 74499-35-7.
TABLE 18
CONSUMPTION OF AP AND APEO IN LUBRICANTS, OILS AND FUEL ADDITIVES REGISTERED IN THE DANISH PROD-
UCT REGISTER, 2012
Substance Number of regis- Consumption, t/y % of total

tered mixtures
2,6-di-tert-butylphenol 9 6.7 71
Other - 1.8 29
Total (incl. confidential) - 9.5 100
Cleaning and maintenance agents

In spite of the restriction on the use of nonylphenol ethoxylates for the majority of cleaning agents,
still, some 54 tonnes were registered for this application area. A part of this total may be for applica-
tions exempt from the general restriction or e.g. maintenance agents not within the scope of the
restriction, but the majority is registered for usage in general cleaning agents. The reason may be
that the companies have not updated their registrations for many years so that the registered vol-
ume is outdated, or that some companies are not in compliance with the legislation.

In addition to the 54 tonnes registered as cleaning and maintenance agents, 13 tonnes were regis-
tered as disinfectants and other biocidal products for private use and use in the medical sector,
which may in fact be cleaning agents within the scope of the current restriction.
According to the Association of Danish Cosmetics, Toiletries, Soap and Detergent Industries (SPT),
the members of the Association have not used the nonylphenol ethoxylates since the late 1990s
when the association made a voluntary agreement with the Danish EPA.
Apparently, the NPEO has not been replaced by OPEO and other alkylphenol ethoxylates in the
cleaning agents.
2,6-di-tert-Butyl-p-cresol was used as an antioxidant in a number of mixtures, and may likely be

used in more mixtures which are not registered in the Product Register.
The use of cleaning agents with NPEO for consumer applications is prohibited, but NPEO may still
be present in some maintenance agents used by consumers
TABLE 19
CONSUMPTION OF AP AND APEO IN CLEANING AND MAINTENANCE AGANTS IN THE DANISH PRODUCT REGISTER,
2012
Substance Number of mixtures Consumption t/y % of total
Nonylphenol ethoxylates *1 100 54.0 90
Octylphenol ethoxylate *2 5 <0.000 -
2,6-di-tert-butyl-p-cresol 45 6.0 10
Other - <0.000 -
Total 60.0 100

*1 Sum of CAS No 9016-45-9, 37205-87-1, 68412-54-4 (each with >3 mixtures)
*2 CAS No 9036-19-5.
Sealant and fillers

Sealant and fillers contained mainly NP and NPEO with total consumptions of 5.6 and 0.8 tonnes,
respectively. According to information obtained from the trade organisation FSO (Fugebranchen),
AP and APEO are not used on their own in the production of sealant and fillers in Denmark, but
may be included in the raw materials. The main application of the two substances in these mixtures
is probably the same as described for paint: NP is mainly a constituent of hardeners of two compo-
nent systems and APEO is a surface active agent.
The sealant and filler may be used for both consumer and professional applications. No data are
available to estimate how much of the total consumption is used for consumer applications.
Textiles
In the EU, NP and NPEO are not regulated for use in the manufacturing of textiles and leather mix-
tures in concentrations above 0.1% unless the processing takes place in closed systems (Annex XVII
to the REACH Regulation). Textiles and leather produced in closed systems may still contain resid-
uals of NP and NPEO.
Furthermore, import of textiles and leather products with NP and NPEO is not restricted and the
substances may be used outside the EU and be present in imported textile and leather products.
NPEO is still used in textile production outside the EU as detergent and auxiliaries such as dispers-
ing agents for dyeing, emulsifiers and spinning lubricants (ECHA, 2012b ).

A recent survey of NP and NPEO in textiles undertaken for the Danish EPA (Rasmussen et al., in
press) has reviewed the literature and summarised the results of tests undertaken by a range of
organisations in Denmark, Norway, Sweden, and the UK. In a total of 139 tests, the average NPEO
concentration was 670 mg/kg with a median value (geometric mean) of 66 mg/kg and the 95th
percentile at 2,440 mg/kg. The maximum value was 14,100 mg/kg (1.4%). The average NP concen-
tration was 5.9 mg/kg with a median value of 0.7 mg/kg and 95th percentile of 22.9 mg/kg. The
maximum value was 49 mg/kg.
In the survey, 15 pieces of clothing and bed linen were furthermore tested for the presence of NP
and NPEO. The NP concentration ranged from 0.7 to 3.7 mg/kg with an average of 1.6 mg/kg. The
total NPEO concentration ranged from <2 to 311 mg/kg with an average of 96 mg/kg. The NPEO
concentration was measured for three types of NPEO with various numbers of ethoxy groups:
NPEO1, NPEO2 and NPEO3-15 (number of ethoxy groups in subscript). It was assumed that the aver-
age number of ethoxy groups in the NPEO3-15 group was 9. The average concentration for the three
groups was 1.6, 1.7 and 92.8 mg/kg, clearly demonstrating the dominance of the NPEO with more
than two ethoxy groups. Using the specific molar weight of the three groups of ethoxylates, the
NPEO concentration could be recalculated to NP equivalents, NP-s. The total average content of NP-
s was estimated at 37 mg/kg.
In 8 of the samples the concentration of OPEO was below the detection level of 0.2 mg/kg textile
and the maximum concentration measured was 10 mg/kg. The average for all samples was less than
1.6 mg/kg; less than 2% of the average NPEO concentration.
Five pieces of clothing were washed at 40˚C and one piece of bed linen was washed at 60 ˚C. In the
clothing, the concentration decreased by 29 to 82 % in the process of one washing cycle, while the
concentration decreased by 99% in the bed linen sample washed at 60 ˚C. The results further indi-
cate that some of the long-chained NPEO were degraded to shorter-chained NPEO during the wash.
The Swedish Society for Nature Conservation has analysed NPEO in imported towels and t-shirts.
In 20 towels the concentration of NPEO ranged from <1 to 10,608 mg/kg with an average of 652
(Hök et al., 2007). The dataset is included in the reviewed data mentioned above. On the basis of
the results, the report estimates that 2-9 tonnes of nonylphenol originating from imported textiles
reach the waste water treatment plants of Stockholm and constitute the likely source of the 1.6
tonnes of NP in the waste waster inlet to the waste water treatment plants measured in 2006.
In the UK, the Environment Agency (2012) tested 100 pairs of underpants. Twenty-eight of the 100
samples analysed contained NPEO, ranging from 3.3 mg/kg to 1759.7 mg/kg. Further testing on six
pairs of underpants showed that NPEO was released from all samples, with an average release of
over 99.9% after two washes at 40ºC using liquid biological detergent. It was estimated that im-
ported underpants could account for up to 1.5 tons of NPEO emissions to the water environment in
the 2011 in the UK. No clear relationship could be established between the presence or concentra-
tion of NPEO and a number of factors: price, country of manufacture, retailer type, colour, and
intended end consumer.
In textiles imported to Denmark, an indication of the total content of NPEO and the equivalent NP-s
may be obtained by multiplying the average content of the textiles with the total tonnage. The ana-
lysed textiles reviewed originate from countries outside the EU and may not be representative for
textiles produced within the EU. The total import of apparel and other textiles (Combined Nomen-
clature codes G_61, G_62 and G_63) from countries outside the EU (nearly 100% from Asia) in
2011 was 145,000 tonnes, while 44,000 tonnes was imported from other EU Member States. The
tree commodity codes also include some accessories and articles which may not be comparable to
the tested articles. If it is assumed that the 120,000 tonnes had an average NPEO concentration of
96 mg/kg the total import of NPEO in textiles can be estimated at 12 tonnes. Considering the uncer-

tainties, the actual value is likely in the range of 6-20 tonnes/year. The total NP content can similar-
ly be estimated at 0.2 tonnes. Using the average NP equivalent content of 37 mg NP-s/kg, the total
NP equivalent in the imported textiles can be estimated at 4.4 t/y NP-s .
During washing the NP and NPEOs are released to wastewater and the estimated quantities of NP
and NPEO in imported textiles indicate that textiles would be one of the main sources of NP and
NPEO to waste water in Denmark.
Pesticides
The industry and the Danish authorities have made a voluntary agreement of phasing out OPEO
and NPEO in pesticides sold in Denmark since 2000 (Krongaard et al., 2008). The content of OPEO
and NPEO in pesticides is frequently controlled. The Chemicals Inspection Service at the Danish
EPA conducts non-laboratory control and the Danish Centre for Environment and Energy (former
National Environmental Research Institute), Aarhus University, conducts the laboratory control of
pesticides in assistance to DEPA. In 2008 none of the tested pesticides contained OPEO, whereas
one product contained NPEO (Krongaard et al., 2008).
Import of APOE in other types of articles

As mentioned above, APEO may be present in leather products imported from countries outside the
EU. Before the restriction, the consumption of NPEO for leather auxiliaries in the EU was at the
same level as the consumption for textiles. No data on the import of NPEO with leather articles have
been indentified, but the total quantity may be at the same level as the import with textiles. A part of
the NPEO may be released to waste water from the washing of leather, but it is assumed that the
majority of the NPEO is disposed of as solid waste together with the leather.
NPEO was before the restriction used in the production of paper and pulp, and may be present in
low concentrations in paper and boards. No data on the possible import of NPEO in paper and
board from countries outside the EU have been identified.
Residual content of 4-NP, 4-t-OP and 4-tert-BP in articles

Products manufactured from 4-NP, 4-t-OP and 4-tert-BP may contain small amounts of residual
APs. No data on the actual import to Denmark of the substances in articles have been identified.
The EU Risk Assessment for 4-nonylphenol mentions that the main issue regarding residual 4-NP
and consumer exposure is residual 4-NP in trisnonylphenylphosphite (TNPP) which is used as an
antioxidant to stabilise polymer coatings used as food contact materials against degradation by
ultraviolet light. TNPP is used in four types of food-contact polymers: polyolefin, rubber modified
polystyrene, PVC films and rubber (ECB, 2002). The residual level of 4-NP in TNPP is typical 1-2%.
The report does not indicate the 4-NP content of the materials and neither does the UK risk reduc-
tion strategy for NP (Footit, 1999). No data on the possible import to Denmark of NP in articles with
TNPP have been identified.
As described in section 3.2.2 an average EU tyre contains between 0,007 % and 0,012 % of 4-t-OP
(ETRMA, 2011). With a total import of tyres to Denmark of about 45,000 t/y (based on collection
data, DBFR 2012), in total some 3-5 t/y of unreacted 4-tert-OP is imported with tyres. A significant
part of this may be released to the environment by the wear of the tyres.
The EU Risk Assessment for 4-tert-butylphenol states that the potential consumer exposure is via
direct use of mixtures with phenolic resins or epoxy resins containing residual 4-tert-BP monomers,
or via use of the final articles containing residual concentration of 4-tert-BP (ECB, 2008). The main
exposure from final articles is expected to be from adhesives (residual content of 0.1-1%), canned
food, polycarbonate used for food contact material and drinking water from drinking water reser-
voirs or pipelines. According to the risk assessment the residual content of 4-tert-BP in polycar-

bonates is indicated at < 5 mg/kg while the concentration in final articles other polymers is indicat-
ed as much lower than 3%. The risk assessment does not quantify the total amounts of 4-tert-BP as
residual content of materials and mixtures based on the substance.
3.4 Summary on the use of AP/APEO in Denmark and the EU
The available information on the use of AP/APEO in the EU and in Denmark is summarised in the
table overleaf.
No updated inventory of the consumption in the EU has been identified, but based on the available
information, the total consumption within the EU of the substances within the scope of this survey
is likely in the 130,000-260,000 t/y range. The total production and import of AP/APEO in mix-
tures registered in the Danish Product Register was 392 tonnes and the total consumption (content
of mixtures placed on the Danish market) was 330 tonnes. This is less than ¼ of what could be
expected if the consumption in Denmark resembled the EU consumption on a per capita basis
(Denmark represents about 1% of the population in the EU). The relatively low registered volume is
discussed below.
Three APs with consumption volumes of > 10,000 t/y, nonylphenols, octylphenols and 4-tert-
butylphenol are mainly used for production of phenolic resins and other resins/plastics in the EU.
The registered consumption of these substances in Denmark is relatively low compared to the EU
total, which reflects that only very small amounts of AP-based resins are manufactured in Denmark.
Import data from the trade statistics confirms that the substances are used in relatively small vol-
umes in Denmark. The main registered application area for these substances in Denmark is paint,
varnishes and lacquers.
Three other high-volume APs, dodecylphenols, 2,6-di-tert-butylphenol,and 2,4-di-tert-butylphenol

are mainly used for manufacturing of additives for lubricants and fuels. For these substances, the
registered consumption in Denmark as compared to the EU total is low as well, reflecting that no
major producers of these additives are located in Denmark. The major application areas of the sub-
stances in Denmark are as additives in/for lubricants and fuels.
The tonnage of 2,6-di-tert-butyl-p-cresol (BHT) is high both in the EU and Denmark, reflecting the
general use of this substance as an antioxidant in food and a wide range of mixtures.
Among the APEOs, NPEO represented 93% of the total registered consumption in the Danish Prod-
uct Register, while OPEO and DPEO accounted for the remaining part of the total of approximately
150 t/y. The main use of NPEO was as surfactants cleaning agents, and it is unclear to what extent
the registered quantities of NPEO are due to inadequate update of the notifications, exempted uses
or applications that are not in compliance with the current restrictions. The second main use area
and the main application of the OPEO was paint, varnishes and lacquers. Notably, there is no indi-
cation that OPEO has substituted in a significant manner for NPEO in cleaning and maintenance
agents. The total production of OPEO in the EU is less than 1% of the consumption of NPEO before
the introduction of the EU-wide restriction on the NPEO. DPEO was used for lubricants and oils
and some confidential applications in Denmark.
The remaining AP/APEOs represent less than 1% of the total consumption of the 330 t/y registered
in the Danish Product register.

The most important data gaps are:
• Updated information on current uses and on the significance of the potential sources of
NP/NPEO releases of to waste water and the environment is missing.
• Information on the current uses of NPEO in cleaning and maintenance products in Denmark
calls for a clarification of actual uses.
• For some of the substances, information on the total manufacture and import to the EU in the
registrations is not in accordance with information obtained from the industry and calls for a
clarification.

TABLE 20
SUMMARY OF THE USE OF AP/APEO IN THE EU AND DENMARK
Substance Registered EU Denmark

group tonnage, t/y
Most recent assess- Main application areas Registered con- Main application areas Remark
ments sumption in the (excl. confidential uses
Product Register, only)
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
Monoalkylphenols and alkylphenolesthoxylates
Nonylphenols (NP) 10,000-100,000 78,590 *1 1999 2011: 29.0 Paints, lacquers and var- The registered consumption
Production of phenolic resins nishes is small considering the EU
25,000- 2011 Production of(4-nonylphenyl) Sealants and filling agents consumption, probably
50,000 phosphite Hardeners because of low use of the
Catalyst in epoxy resin production Joint-less floors, surface substance as intermediate
Production of plastic stabilizer active agents, confidential
Production of phenolic oximes applications. The main application areas
Production of NPE are as component of harden-
ers in various mixtures
Nonylphenol ethox- 2,000-20,000 118,000 *1 1999 2011: 140.2 Cleaning agents, polish The majority of the regis-
ylates (NPE) Paint and varnishes and maintenance agents tered use as cleaning agents
2,000-20,000 2011 Acrylic esters used for specialist Paints, lacquers and var- may be due to missing up-
coatings, adhesives and fibre bond- nishes date of the notifications or
ing Disinfectants and other uses not in compliance with
Metal working fluids (specific biocidal products for the restriction
exemptions) private use and use in the Significant import of NPEO
medical sector with textiles
Adhesives, sealants and
filling agents, hardeners,
lubricants and oils, joint-
less floors, confidential
applications

group tonnage, t/y
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
Octylphenols (OP) 10,000-100,000 22,900 2001 Production of phenolic resins and Confidential Confidential OP may be imported as
tackifiers (98%) residual OP content of tyres
Production of OPEO (2%)
Octylphenol ethox- n.r. 1,000 2001 Emulsion polymerisation (52%) 10.6 Paints, lacquers and var- -
ylates (OPEO) Textile and leather auxiliaries nishes
(14%) Sealants and filling agents,
Agriculture (10%) joint-less floors.
Paints (5%) The majority of the con-
Production of octylphenol ether- sumption is confidential
sulfates (24%)
Dodecylphenols 10,000-100,000 50,000 2004 Oil and lubricant additives (99%) 4.0 Lubricants and oils The registered consumption
Production of phe- Fuel additives is small considering the EU
nol/formaldehyde resins consumption, likely because
Production of dodecylphenol the lubricant additives are
ethoxylates produced in Denmark in
limited amounts
Dodecylphenol eth- n.r. <1000 2004 Anti-rust agents in lubricants 2.4 Lubricants and oils
oxylates

group tonnage, t/y
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
4-tert-butylphenol Intermediate 27,351 2001 Production of phenolic resins 2.8 Paints, lacquers and var- The registered consumption
CAS No 98-54-4 (>1,000 t) nishes small considering the EU
Production of polycarbonates Hardeners consumption, probably
(>1,000 t) Adhesives because of low consumption
Production of epoxy resins Sealants and filling agents as intermediate
(>1,000 t)
Production of alcohols through The main application areas
hydrogenation (>1,000 t) are as components of hard-
eners in paints, lacquers and
varnishes and for plastics
Import of 3.4 tonnes of the

substance on its own is
probably for production of
resins
2-sec-butylphenol 1,00o-10,000 1,00o-10,000 2011 Production of fungicides and other 0 - -

CAS No 89-72-5 plant protection products
o-tert butylphenol n.r. <1000 2011 Production of herbicides, plastic o - -

CAS No 68610-06-0 additives, and substances for the
fragrance industry.
2-tert-butylphenol n.r. n.i. - - 0.2 Fuels additives -

CAS No 88-18-6
Other butylphenols n.r. n.i. - - confidential confidential -

28805-86-9

group tonnage, t/y
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
Cyclohexylphenols n.r. n.i. - - 0.4 Surface active agents

CAS No 119-42-6,
1131-60-8
bis(tert- n.r. n.i. - - 1.6 Lubricants

butyl)dodecylphenol
CAS No 68025-37-6
Phenol, isopropylat- intermediate use n.i. *1 - Chemical intermediate 0

ed only
CAS No 90480-88-9
Dialkylphenols and trialkylphenols
2,6-di-tert-butyl-p- 10,000-100,000 25,000 2002 Antioxidant for many applications 118.8 Antioxidants, antiozonanes, and The substance is used
cresol (BHT) in a wide variety of industries "other additives for food and as an antioxidant for a
CAS No 128-37-0 feedstuff" wide range of products
Raw materials for synthesis and the total con-
Inks sumption is likely
Various products higher than registered
2,6-di-tert- 100-1,000 15,000 1999 Fuel and lubricant additive 18.3 Lubricants and oils The registered con-
butylphenol Intermediates for the production Fuel additives sumption is small
CAS No 128-39-2 of plastic additives (antioxidants Confidential considering the EU
and UV-light stabilizers) consumption, likely
because the lubricant
2,4-di-tert- 100-1,000 13,000 1999 Fuel and lubricant additive 0.2 Lubricants and oils
additives are produced
butylphenol Intermediates for the production Fuel additives
in Denmark in limited
CAS No 96-76-4 of plastic additives (antioxidants
amounts
and UV-light stabilizers)

group tonnage, t/y
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
2,4,6 tris-tert butyl- intermediate use <1000 t 2011 Chemical intermediate 0.6 Confidential
phenol only
CAS no 732-26-3
Thymol 1,000 - 10,000 n.i. Cleaning agents <0.01 Perfumes, fragrances, various Probably used in
CAS No 89-83-8 Use of scented articles products various products not
registered in the Prod-
uct Register
6-tert-butyl-2,4- n.r. n.i. - - 0.02 Confidential -

xylenol
1879-09-0
2,6-di-tert-butyl-4- n.r. n.i. - - 0.2 Lubricants -

nonylphenol
4306-88-1
4-tert amylphenol n.r. <1,000 2011 Production of phenolic resins and 0 - -

CAS No 80-46-6 lacquers
o-tert amylphenol n.r. <1,000 2011 Production of herbicides, plastic 0 - -

CAS No 3279-27-4 additives, or - after hydrogenation
- for the fragrance industry
2-isopropylphenol n.r. >1,000 2011 0 - -

CAS No 88-69-7
2,4-dinonylphenol n.r. <1,000 2011 Production of polycarbonates and 0 - -

CAS No 137-99-5 phenolic resins and lacquers

group tonnage, t/y
Total con- Year
2011 data, t/y
sumption, t/y
(excl. confidential
uses)
2,4-di-tert amylphe- n.r. <1,000 2011 Plastic additives 0 -

nol
CAS No 120-95-6
2-tert-butyl-p-cresol intermediate use n.i. Chemical intermediate <0.01 confidential -

CAS No 2409-55-4 only
6-tert-butyl-m-cresol intermediate use n.i. Chemical intermediate 0 - -

CAS No 88-60-8 only
C14-16-18 alkylphe- intermediate use n.i. Chemical intermediate 0 - -

nol only
CAS No 931-468-2
n.i.: No information besides the information from registrations (ECHA, 2012e) has been available.
n.r.: Not registered

4. Waste management
The main issue regarding AP/APEO in the waste steam concerns releases of the substances from
waste water treatment and disposal of sludge on agricultural land.
4.1 Waste from manufacture and industrial use of AP/APEO

Discharges of AP/APEO with waste water is the main waste issue with regard to the manufacture
and industrial use of AP/APEO. No overview of AP/APEO in waste waster from industrial sources
has been identified, but the risk assessments and risk reduction strategies include some data on
releases of some of the substances from industrial processes.
The total releases of NP in 1977 to surface water and waste water from manufacturing and formula-
tion of NP and NPEO was estimated at 0.3 t/y NP and 1.1 t/y NPEO, accounting for a small part of
the total releases of the substances (ECB, 2002). The releases will today be lower due to the de-
crease in the manufacture of NP and NPEO.
The UK risk reduction strategy for 4-tert-OP indicates the total discharges from industrial sources
in the UK in 2005 at 0.4 t/y of 4-tert-OP and 7.9 t/y of OPEO (Nwaogu, 2006). No data on dis-
charges at EU level are provided. The discharges from industrial sources are not compared to other
sources.
For 4-tert-BP the total releases to WWTP and surface water from manufacturing of the substances
in 2001 is estimated at 310 g/day while the total releases from down stream industrial uses is about
400 g/day (ECB, 2008), corresponding to total discharges of about 0.3 t/y. The discharges from
industrial sources are not compared to other sources.
The risk reduction strategy for DP indicates that the releases of DP from manufacture and formula-
tion is a few kg/year and very small compared to the releases from the use and disposal phases.
(Brooke et al., 2007)
4.2 AP/APEO in waste and releases from disposal of solid waste

The substance flow analyses for NP/NPEO and OP/OPEO shown in Annex 4, prepared as part of
the COHIBA project (COHIBA, 2012), show that the quantities released from solid waste treatment
and recycling are very small compared to the quantities released from municipal waste water treat-
ment plants.
AP/APEO in solid waste would mainly be due to:
• AP/APEO in articles, either from intentional use of the substances or as residual content of
plastic parts made from AP.
• AP/APOE on paints, sealants and adhesives on building materials or metal scrap.
Apart from the OP, the majority of the articles containing AP/APEO would be disposed of to munic-
ipal solid waste incinerators (MSWI) in Denmark. No data on the fate of AP/APEO by incineration
have been identified, but most probably the substances would be nearly 100% destroyed by the
incineration process, based on similarities with other non-persistent substances.

A significant quantity of OP is present as residuals in tyres, and would be disposed of with the tyres
for recycling in Denmark. The Environment Agency (2005a) reviews various studies on releases
from tyres used for civil engineering (e.g. bulk fill application, noise barriers, artificial reefs, etc.).
The assessment concludes that overall, the picture appears to be that 4-t-OP may be leached from
tyre materials in civil engineering uses. Where tyres are used whole or baled, and especially where
the use is underground or in seawater, the potential for losses appears to be low. There may be
greater potential for losses in situations where shredded materials are used, but there is currently
not enough information to make estimates of the potential for releases from this route. However,
considering the relative concentrations measured in road runoff and in infiltration water, it is ex-
pected that the contribution from subsequent use in construction work will be lower than that from
tyre wear during their original lifetime (the latter is estimated to be 83 tonnes 4-t-OP per year in the
UK).
According to Environment Agency (2005a), by the use of OP in printing inks, the ink production
process actually involves some reaction between the components. Hence there are no significant
traces of 4-tert-octylphenol left in the finished inks and no significant releases from the printing
process, or from the recycling of paper printed with these inks.
AP/APEO present on steel scrap and other metal scrap is assumed to be destroyed by the heating of
the scrap by the melting down of the scrap.
AP/APEO may be present in small quantities in paint on building waste which is disposed of for use
in civil engineering or disposed of to landfill.
4.3 Waste oil disposal

Waste oil which is not disposed of properly has been identified as the main source of environmental
emission of dodecylphenols (DP) in Norway (Lambert, 2010). As a worst case scenario it was esti-
mated that 3.8 t/y of DP in Norway have an unknown fate and was potentially released directly to
the environment (Lambert, 2010). The estimate is based on a worst case total import of DP in lubri-
cants of 25 y/y.
The UK risk evaluation report for DP (Brooke et al., 2007) estimates the total releases from the use
and disposal stage of the use of DP in lubricants at 23.4 t/y to waste water, 3.35 t/y to surface water
and 22.6 t/y to soil for the EU as a whole. It is not specified how the DP in the lubricants ends up in
waste water and the environmental compartments, but it is in the assessment assumed that spillage
and leakages to soil and surface water correspond to 1% of the total use of the substances for crank-
case lubricants. Releases from the use and disposal phase for other applications of the DP are esti-
mated to be low compared to the releases due to the use in lubricants.
In both the Norwegian and the UK study, the releases are assumed to be due to spill, leakages and
waste oils not disposed of properly.
Releases to the environment from use and disposal may also occur for other APs used as fuel addi-
tives but no data have been identified.
No data on the potential releases of APs from spill and disposal of waste oils in Denmark have been
indentified.
4.4 AP/APEO in waste water and sewage sludge

A wealth of literature on the fate of NP and NPEO in municipal waste water treatment plants
(MWWTP) exists, whereas literature on other AP/APEO is limited, reflecting that NP/NPEO are the
dominant AP/APEO in waste water.

NP and NPEO in waste water
Nonylphenol ethoxylates reach sewage treatment works in substantial quantities where they biode-
grade into several by-products including nonylphenol.
The trends in discharges of NP and NPEO from MWWTP over the period 2000 to 2010 are shown
in Table 21. The concentration of NPs in outlets from MWWTP measured in 2010 was lower than
previous years for which data are available. According to the authors it is on basis of the data not
possible to determine if the decrease is significant (Boutrup and Svendsen, 2012).
TABLE 21
TRENDS IN CONCENTRATIONS OF NP AND NPEO IN OUTLETS FROM MWWTP 2000-2010 (BOUTRUP AND SVEND-
SEN, 2012)
Year Nonylphenols NP1EO NP2EO
Mean 95% ft % Mean 95% ft % Mean 95% ft %

µg/L µg/L above µg/L µg/L above µg/L µg/L above
d.l. d.l. d.l.
2000 0.24 0.57 58 0.08 0.18 11 0.12 0.35 11
2001 0.35 0.68 65 0.66 1.71 14 0.55 1.40 15
2002 0.43 1.60 70 0.52 1.44 13 0.54 1.40 9.8
2003 0.30 0.60 32 0.07 0.20 7.9 0.05 0.10 5.4
2010 0.06 0.30 17 n.d. n.d. n.d. n.d. n.d. n.d.
Ft: Fractiles; d.l.: detection limit; n.d.: not detected.
The fate of NP and NPEO in MWWTPs in Denmark was analysed by Pedersen and Bøvadt (2002).
The long chained NPEO, NPEOn, was degraded to short-chained substances and NP under both
aerobic (with oxygen present) and anaerobic (without oxygen) conditions. In one plant, NPEOn
accounted for 31% of the inflow, whereas in the other it accounted for 11%. In both plants the NPE-
On was nearly 100% degraded and accounted for 0 and 2%, respectively, in the sludge from the two
plants. The degradation was most pronounced under aerobic conditions. Under anaerobic condi-
tions the substances were mainly degraded to mono-NPEO (NP1EO) and NP. These degradation
patterns have been demonstrated in many MWWTP across Europe (Soares et al., 2008).
The Danish national surveillance programme for the aquatic environment (formerly NOVA 2003,
now NOVANA) has included monitoring of trace elements and organic xenobiotics in discharges
from sewage treatment plants (STPs) and other point sources since 1998. With the objective of
enabling the use of the resulting information in the planning of future surveillance programmes and
for assessment of the total amount of substances discharged from Danish sewage treatment plants,
the point source data on metals and xenobiotics for the period 1998-2009 were analysed (Kjølholt
et al., 2011). Based on about 327 samples for the NPEOs and 62 samples for NP, "Nation Mean
Concentrations" (NMCs) for substance concentrations in inlets and outlets from STPs were derived
(see Table 22). Furthermore, possible correlations with relevant variables were identified. On the
basis of the mean concentrations, the total discharge in 2010 was estimated at 41 kg for nonylphe-
nol monoethoxylates and 120 kg for nonylphenol, while the discharge of nonylphenol diethoxylates
could not be estimated as the measured concentrations in outlets were below the detection level.
Considering the reduction factors, the total inlet to the waste water treatment plants can be esti-
mated at 1.6 t/y for NP and 2.1 t/y for nonylphenol monoethoxylates. The study did not establish
mean concentration of the substances in sludge from the waste water treatment.

The study did not establish national mean concentrations of NPEO with longer chain lengths,
NPEOn, which may account for a significant part of inflow as demonstrated by Pedersen and Bøvadt
(2002).
The total discharge of nonylphenol from municipal sewage treatment plants in 1998-2003 was
estimated as slightly higher at 228 kg/y based on an average concentration of 0.3 µg/L (Boutrup et
al., 2006).
TABLE 22
NATION MEAN CONCENTRATIONS OF NP AND NPEO IN INLET AND OUTLETS OF MUNICIPAL SEWAGE TREATMENT
PLANTS IN DENMARK (KJØLHOLT ET AL., 2011)
Substance Inlet, µg/L *1 Outlet µg/L Reduction fac- Discharge,

tor, % kg/year
Nonylphenol 2.9 (2.2 - 4.2) 0.057 (0 - 0.13) 98.03 41

monoethoxylates
Nonylphenol 0.67 (0.31 - 0.98) 0 (0-0.10) not indicated not indicated

diethoxylates
Nonylphenols 2.2 0.2375 89.20 170
*1 Figures in brackets represent 65%-85% fractiles. Please note that the key national mean concentration,
which represents the average, typically is close to the 75% fractile.
In accordance with the Danish experience, COHIBA (2011a) states that the removal efficiencies for
NPEO from the water phase in WWTP is higher than 95%.
According to the COHIBA substance flow analysis for NP/NPEO, the NP and NPEO emissions into
the Baltic environment mainly come from industrial sources in Lithuania and Poland, whereas in
the other countries municipal waste water treatment plants (MWWTPs) are the dominant sources
(COHIBA, 2012) . The upstream sources of NP and NPEO to the MWWTPs are mainly in the prod-
ucts’ service life category and are dominated by emissions from washing of textiles containing
NPEO (about 40% of total emissions to wastewater). This is followed by the use of NPEO in indus-
trial and institutional cleaning (about 15-30% of total emissions to wastewater depending on the
scenario), which was not expected to be a significant source at present as the use of NP and NPEO
in this application is restricted under REACH (Regulation (EC) No 1907/2006). Other important
sources of emissions to wastewater were car washes and emissions due to private use of detergents.
A recent Danish report estimates that washing of textiles may contribute 86% of the total sources of
NPEO to MWWTPs (Rasmussen et al., in press). Imported textiles as sources of NP/NPEO to waste
water are further described in section 3.3.2.
No actual data on the releases to waste water from the use of AP/APEO in paint have been identi-
fied. An OECD report on techniques for estimating releases from products includes a summary of
emission factors for different NP/NPE uses in products (OECD, 2011 ). For paint, an emission fac-
tor of 0.5% of the NP to waste water is indicated while the emission factor is 1% for adhesives. No
emission factors for NPE from these products are indicated. The Resource Compendium makes
reference to an unpublished Swedish case study, and does not provide details about how the emis-
sion factors are derived. If a factor of 0.5% is applied for the 20 tonnes NP used per year in Den-
mark (Table 12), the release to waste water from the application of paint can be estimated at 0.1 t/y
which is low compared to the estimated NP equivalent content of imported textiles of 4.4 y/y (sec-
tion 3.3.2). This should be considered a first very rough estimate, and a more detailed study would
be necessary to quantify the actual sources of NP/NPEO to waste water in Denmark.

A range of measures for reduction of emission of NP/NPEO and OP/OPEO from waste water treat-
ment plants are described in COHIBA (2011).
OP and OPEO in waste water

Measurement of OP and OPEO is included in the national environmental monitoring and assess-
ment programme NOVANA, but data has not been published in recent years. In 2003 OP was de-
tected in concentrations above the detection limit of 0.1 µg/L in 8% of 190 inlet samples and in 1%
of 191 outlet samples. No median or average values were calculated. Compared to the concentration
of NP/NPEO, the concentration of OP was at least a factor of 10 lower.
According to the COHIBA substance flow analysis for OP/OPEO, the emissions were dominated by
releases of OP from the product service life category, where the main source was emissions from
abrasion from tyres, which represents almost 100% of the reported emissions in this category
(COHIBA, 20). The emissions from MWWTP accounted for a small percentage of the total emis-
sions. The main source of OP and OPEO to MWWTP is washing of textiles, which is estimated to
account for 30-50% of the total releases to waste water (COHIBA, 2012b).
The fate of octylphenol ethoxylates (OPEOs) by waste water treatment is described by the Environ-
ment Agency (2005a). Longer chained OPEO are degraded by the treatment of waste water by the
same mechanisms as described for NPOs. From the available data for APEOs (predominantly for
NPEOs), reasonable worst-case assumptions for the fate of OPEOs during anaerobic wastewater
treatment are estimated to be (based on % weight): Mineralised/highly degraded (45 %), released as
OP1EO/OP2EO/OPnEC (OP carboxylate with n ethoxy units) in effluent (25 %), released as OPnEO
(n > 3) (8%), released as OP in effluent (2.5%) and OP in anaerobically digested sludge (19.5%). The
study of OP in effluent from WWTP in the UK showed that concentration was measured at 0.5 µg/L.
A study of the flow of 4-t-OP (and other substances) in two MWWTP in Germany showed influent
concentrations in the range of 0.0 39-1,4 µg/L while the measured effluent concentration < d.l.-
0.39 µg/L. The elimination efficiency varied between 73% and 93% (Höhne and Püttmann, 2008).
The maximum concentration for NP was about 10 times higher than the maximum for OP.
Other AP/APEO in waste water

No data on other AP/APEO in waste water and sewage sludge in Denmark have been obtained.
Remberger et al. (2005) have screened for the 30 phenolic substances in the environment, industri-
al sources and waste water and sewage sludge in Sweden. The concentration of the substances in the
influents is typically a factor of ten higher than the concentration in effluents in accordance with the
expected reduction factors. The concentration of NP/NPEO is a factor of ten to one hundred higher
than the concentration of the other AP/APEO.
Relatively high concentrations are found for 2,6-di-tert-butyl-p-cresol (BHT), which has wide-
spread use as an antioxidant in food and other products. It has been concluded by the OECD
(2002a) that more information on actual releases and environmental exposure to this substance is
needed.

FIGURE 6
CONCENTRATION OF AP/APEOO IN INFLUENTS AND EFFLUENTS OF MWWTP IN SWEDEN. PLEASE NOTE LOGA-
RITHMIC X-AXIS (BASED ON REMBERGER ET AL., 2005, ORIGINAL FIGURE INCLUDE DATA ON METHYLPHENOLS)
No data on dodecylphenols in municipal waste water have been identified. A provisional UK envi-
ronmental risk assessment of dodecylphenols estimated that the main source of releases to the
environment was releases of DP to waste water from lubricant use and disposal (Brooke et al.,
2007).
AP/APEO in sludge from MWWTP

NP and NPEO
Gawlik and Bidoglio (2006) reviewed data on NP and NPEO in sewage sludge from a number of EU
Member States reported during the period from 1994 to 2003. The concentrations varied consider-
ably and different parameters were reported, which makes a comparison across the Member States
difficult. Mean values (averages) of the total for NP+NPEO were reported from Sweden (2003) and
Germany (2003) at 3.9 and 11.7 mg/kg while median values from Austria (2001) and Denmark
(1997) were 13 and 8 mg/kg, respectively. Two surveys in Germany both reported a median value of
5 and 18 mg/kg in 2003, illustrating a relatively large variation in the concentrations.
The most recent assessment of NP/NPEO in Danish sewage sludge (Danish EPA, 2009) reports that
the weighted average concentration decreased from 1997 to 2005 by approximately 80 percent from
27.2 mg/kg dw in 1997 to 7.8 mg/kg dw in 2005. This is, according to the assessment, in part due to
the voluntary agreements made with industry in the late 1980s aimed at reducing the use of NPEO
in products. In 2oo5 the average concentration of NPEO in all sludge was 7.8 mg/kg. In sludge
disposed of to agricultural soils the concentration was 4.5 mg/kg. The total quantity of sludge in
2005 was 58,200 tonnes and the total NPEO content of the sludge is estimated at 0.45 tonnes.
The limit value for NP/NPEO in sludge applied to farmland in Denmark is 10 mg/kg TS. In 2005,
6.4% of all analysed sewage sludge samples exceeded the limit value for NP/NPEO.

A risk assessment of contaminants in sewage sludge applied to Norwegian soils by the Norwegian
Scientific Committee for Food Safety reached the conclusion that even though the PEC (predicted
effective concentration) exceeded the PNEC (predicted no effect concentration) for OP and NP
immediately after the application, the committee considers OP and NP to be of low concern (VKM,
2009). The explanation is that these substances are rapidly degradable (t1/2 in soil = 8-10 days)
where the highest concentrations were found immediately after application of sewage sludge fol-
lowed by a rapid decrease.
Other AP/APEO
The average concentration of OP in 45 samples of sewage sludge from Danish MWWTP analysed in
2003 was 0.049 mg/kg, less than 1% of the concentration of NP. The maximum value was 0.4
mg/kg (Danish EPA, 2004). No data for other AP/APEO in sewage sludge from Denmark have been
obtained.
Data from the screening of AP/APEO in sewage sludge in Sweden is shown in the figure below. The
concentration of NP and NPEO is two orders of magnitude higher than the concentration of the
other substances. The relatively high concentrations found for 2,6-di-tert-butyl-p-cresol in influent
shown in Figure 6 is not reflected in high concentrations in sludge, probably because the substance
is degraded during the waste water treatment.
FIGURE 7
CONCENTRATION OF AP/APEO IN SEWAGE SLUDGE FROM MWWTP IN SWEDEN. PLEASE NOTE LOGARITHMIC X-
AXIS (BASED ON REMBERGER ET AL., 2005, ORIGINAL FIGURE INCLUDE DATA ON METHYLPHENOLS)
4.5 Summary for waste management

The main issues with regard to management of waste and waste water containing AP/APEO is dis-
charges from municipal waste water treatment plants. Most available data are on NP/NPEO and
OP/OPEO.
The concentration of NP/NPEO in waste water in Sweden was around 2005 a factor of ten to one
hundred higher than the concentration of the other AP/APEO. In Denmark the concentration of NP
has decreased and the concentration in 2010 was at 25% of the level in 2000. No data on the trends
of NPEO have been available. The major source of NP/NPEO to municipal waste water today is
considered to be imported textiles and a recent Danish report estimates that washing of textiles may
contribute 86% of the total sources of NPEO to municipal waste water treatment plants. Even the

reduction factor in the waste water treatment plants is about 90-95%, effluents from waste water
treatment plants are considered the dominant sources of NP/NPEO to the Baltic Sea. The limit
value for NP/NPEO in sludge applied to farmland in Denmark is 10 mg/kg TS.
The weighted average concentration of NP/NPEO in sludge decreased from 1997 to 2005 by ap-
proximately 80 %. In 2005, 6.4% of all analysed sewage sludge samples exceeded the limit value for
NP/NPEO. No newer data have been available.
The concentration of OP/OPEO is considerably lower that the concentration of NP/NPEO and dis-
charges from waste water plants are estimated to be a small source of releases to the Baltic Sea as
compared to the releases of OP from tyres. The concentration of OP/OPEO in sewage sludge is more
than a factor of 10 lower than the concentration af NP/NPEO.
In a Swedish study relatively high concentrations of 2,6-di-tert-butyl-p-cresol were found in waste

water. The substance has widespread use as an antioxidant in food and other products. It has been
concluded by the OECD (2002a) that more information on actual releases and environmental expo-
sure to this substance is needed.
Apart from OP in tyres, the majority of AP/APEO in solid waste is disposed of through municipal
solid waste incineration. No data on the fate of AP/APEO by incineration have been identified, but
most probably the substances would be nearly 100% destroyed by the incineration process.
OP residues in tyres may be released from the tyres by disposal of the tyres depending on the actual
disposal operations. A UK assessment indicated that releases may in particular occur when shred-
ded tyres are used for civil engineering work. However, considering the relative concentrations
measured in road runoff and in infiltration water, it is expected that the contribution from waste
disposal work will be lower than that from tyre wear during their original lifetime.
For a number of the APs the main application area is as additives to lubricants. A Norwegian and a
UK study conclude that the main releases of dodecylphenol (DP) to waste water and the environ-
ment are due to spill and leakages of lubricants and waste oils not disposed of properly. It may be
the situation for some of the other APs as well, but no data on the potential releases of other APs
from spill and disposal of waste oils have been indentified.

5. Environmental effects and
fate
As described in previous chapters, alkylphenols are a group of chemicals comprising a substantial

number of substances ranging from cresol (C1-alkylphenol) to phenols with up to four linear or
branched constituent groups of varying chain lengths. However, the ethoxylated versions of al-
kylphenols of any commercial significance (detergents, emulsifiers) are in reality limited to C8-, C9-
and C12-compounds with a few C4- C7-compounds being possible future substitutes for some of the
long-chain alkylphenols.
C1-, C2- and C3-alkylphenols are, contrary to the long chain alkylphenols, typically ready biode-
gradable and only moderately toxic in the environment, as e.g. reflected by their lack of environ-
mental classification by notifiers (see Annex 3). They are also different from the long-chain al-
kylphenols with regard to other properties and their technical uses; therefore, they are not included
in the following environmental review. The emphasis of the review will be on the important C8-, C9-
and C12-alkylphenols and their ethoxylates together with examples of possible technical alterna-
tives among the C4-to C7-alkylphenols.
5.1.1 Nonylphenol and nonylphenol ethoxylates
Fate in the environment

Abiotic degradation
Nonylphenol does not undergo hydrolysis to any appreciable extent while phototransformation in
water may occur to some extent under favourable conditions (DT50 = 10-15 hours under lab condi-
tions). This mechanism is, however, considered to be of minor quantitative importance only for the
overall dissipation of the substance in the aquatic environment (ECHA, 2012b).
Photodegradation in the atmospheric compartment is an important mechanism of degradation in

air. The atmospheric half-life of nonylphenol is estimated to be 0.3 days (EHCA, 2012b).
Biodegradation
Nonylphenols are biodegradable in the environment at rates that vary with the degree of branching;
the higher the branching, the lower the biodegradability. A screening study on n-nonylphenol indi-
cates that this substance may even be easily biodegradable 2 in water under aerobic conditions
whereas the branched nonylphenols may only be considered inherently 3 biodegradable. The degra-
dability under anaerobic conditions is low. The standard TGD value for biodegradation of inherent-
ly degradable substances in surface waters corresponds to 150 days. This is consistent with reported
measured values (ECB, 2002).
Nonylphenol ethoxylates are degraded to nonylphenol in the environment according to the overall
reaction pathway shown in Figure 8.
2 I.e. undergo significant degradation within 28-days in one of OECD's screening test methods for ready biodegradability.
3 Undergo less but still some degradation in a 28-days OECD test.

FIGURE 8
DEGRADATION PATHWAY FOR ETHOXYLATES OF NONYLPHENOL AND OTHER HIGHER ALKYLPHENOLS (UBA, 1998)
Dissipation rate in soils depends on soil properties, environmental conditions and on the degree of
branching of the nonylphenol studied. Most studies only report on the dissipation of the parent
compound, not on the subsequent degradation eventually leading to full mineralization. The prima-
ry degradation step typically takes place with a half-life of 20-30 days and the results of one study
indicate that full mineralization of n-nonylphenol could take place with a half-life of about 100 days.
However, branched nonylphenols probably degrade more slowly and, for the EU risk assessment, a
half-life of 300 days (TGD for inherently degradable substances with Kp >100 4) is recommended
(ECB, 2002).
Adsorption, distribution and bioconcentration

The Log Kow 5 is 5.76 for linear 4-nonylphenol and 5.4 for branched 4-nonylphenol (ECHA, 2012b).
The E1-E4 ethoxylates of nonylphenol have somewhat lower Log Kow values (4.17 - 4.30, decreasing
with increasing number of ethoxylate units) (Ying et al., 2002).
4 A standard measure of the partitioning between particulate matter (e.g. soil or sediment) and water.
5 A standard measure of the partitioning between a lipid phase (octanol) and water (octanol-water partitioning constant)

The Kp in soils is in the range >100 - <1,000 and Log Kow values are in the range 4.35 - 5.69 (ECB,
2002).
The distribution in environmental compartments is as shown in the table below applying a MacKay
Level III fugacity model, a model predicting the distribution of a substance between the various
main environmental compartments (ECB, 2012b).
TABLE 23
PREDICTED DISTRIBUTION OF NONYLPHENOL IN THE ENVIRONMENT (ECB, 2012b)
Value (percent)*
Fraction to air 0.26
Fraction to water 12.2
Fraction to soil 66.0
Fraction to sediment 21.5

* EPI suite v4.10, standalone version.
The available data suggest that nonylphenol bioconcentrates in aquatic organisms and values up to
BCF = 1,300 in fish (on a fresh weight basis) have been reported. The EU RAR mentions that more
reliable measured values with a mean of 741 have been reported. The EU RAR recommends, howev-
er, to use a calculated BCF of 1,280 (fish) for the aquatic risk assessment (ECB, 2002).
Environmental effects
Nonylphenol is classified as R50-53 or, according to CLP, Aquatic Acute 1 + Aquatic Chronic 1.
The EU's RAR on nonylphenols (ECB, 2002) summarizes the traditional endpoints for aquatic spe-
cies as shown in

Table 24. It appears from the data that nonylphenols are highly toxic to all three main "standard"
groups of aquatic organisms; fish, invertebrates and algae.
The most sensitive species in acute studies appear to be the freshwater invertebrate Hyalelle azteca
(EC50 (96 h) = 20.7 µg/L) while the most sensitive species in long-term studies is the green freshwa-
ter alga Scenedesmus subspicata (EC10 = 3.3 µg/L).
The PNECwater is calculated to be 0.33 µg/L using an assessment factor of 10. Based on the aquatic
toxicity data a PNEC for sediment = 0.039 mg/kg sediment has been calculated by the equilibrium
partitioning method.
A PNECsoil = 0.3 mg/kg soil wet wt was determined based on reproduction effect data for earth-
worms (EC10 = 3.44 mg/kg soil wet wt) and applying an assessment factor of 10.
The most sensitive soil dwelling species is the earthworm Apporrectodea caliginosa with a 21 day
EC10 ("NOEC") for reproduction = 3.44 mg/kg soil. PNECsoil is calculated to be 0.3mg/kg (ECB,
2002).
No experimental data are available on avian species but a PNECoral = 10 mg/kg food has been calcu-
lated based on a mammalian NOAEL = 15 mg/kg bw for reproductive effects (ECB, 2002).
It is widely accepted today that nonylphenol is an endocrine disruptor. Several tests, in vitro as well
as in vivo, have demonstrated the estrogenic potency of nonylphenol. Especially the estrogenic
effect in fish is well documented through tests on a number of standard species in which clearly
endocrine mediated effects start at concentrations between 1.05 µg/L and 15 µg/L.
There are indications of endocrine (estrogen-like) effects also on anuran amphibians and aquatic
invertebrates including molluscs too but the evidence is less clear and ECHA's Annex VX Dossier
for nonylphenol does not reach a clear conclusion on this (ECHA, 2012b).
The relative estrogenic potency of nonylphenol compared to the natural estrogen 17β-estradiol is
low in in vitro studies but in in vivo studies with fish relative potencies of 0.019 (sheepshead min-
now) and 0.050 (medaka) have been reported (Soares et al., 2008).
Nonylphenol ethoxylates
Nonylphenol ethoxylates have traditionally been the major source of nonylphenol in the aquatic
environment due to their widespread uses as detergents and emulsifiers. Their specific, individual
properties depend on the length of the ethoxy chain but they all degrade to nonylphenol by succes-
sive de-ethoxylation (e.g. in wastewater and sewage treatment plants) until nonylphenol is formed
as the, more persistent and potentially bioaccumulative, end product.
Data on the environmental toxicity of nonylphenol ethoxylates are relatively sparse. However,
Warhurst (1995) provides an environmental review of alkylphenol ethoxylates and alkylphenols in
which he presents data showing that alkylphenols (most data are on nonylphenol) are generally
more than 10 times more acutely toxic to aquatic organisms than the corresponding ethoxylated
compounds (LC50's typically 0.1 mg/L for alkylphenols and 1.5 mg/L for the corresponding ethox-
ylates).

TABLE 24
SUMMARY OF AQUATIC TOXICITY OF NONYLPHENOL (ECB, 2002)
Trophic level Species End point Concentration Reference *1 Validity

(mg/l)
Freshwater fish Fathead minnow 96hr LC50 0.128 Brooke (1993a) Valid
33 day NOECsurvival 0.0074 Ward and Boeri Valid

Pimephales promelas
(1991b)
Saltwater fish Sheepshead minnow 96hr LC50 0.31 Ward and Boeri Valid
Cyprinodon variegatus (1990d)
Freshwater Ceriodaphnia dubia 96hr EC50 0.069 England (1995) Valid

invertebrates
7 day NOECreproduction 0.0887 Valid
Daphnia magna 48hr EC50 0.085 Brooke (1993a) Valid
21 day NOECsurviving 0.024 Comber et al. Valid

offspring (1993)
Hyalella azteca 96hr EC50 0.0207 Brooke et al. Valid

(1993)
Saltwater Mysidopsis bahia 96hr LC50 0.043 Ward and Boeri Valid
invertebrates (1990c)
28 day NOEClength 0.0039 Ward and Boeri Valid

(1991c)
Fresh water Selenastrum 96hr EC50(Cell growth) 0.41 Ward and Boeri Valid
algae capricornutum (1990b)
Scenedesmus 72hr EC50 (Biomass) 0.0563 Kopf (1997) Valid

subspicatus 72hr EC10 (Biomass) 0.0033
72hr EC50 (Growth rate) 0.323
72hr EC10 (Growth rate) 0.0251
Saltwater algae Skeletonema costatum 96hr EC50 (Cell growth) 0.027 Kopf (1997) Valid
Mesocosm 20 day NOEC 0.005 Liber et al. Use with

study 20 day LOEC 0.023 (1999) care
*1 See ECB (2002) for fulle reference
5.1.2 Octylphenol and octylphenol ethoxylates

Much less scientific environmental literature exist on octylphenols (and -ethoxylates) than on
nonylphenol (and -ethoxylates). However, octylphenol (most often as the branched 4-tert-
octylphenol) is chemically closely related to (branched) nonylphenol. Therefore with regard to envi-
ronmentally relevant properties, there are also similarities. Hence, in the absence of specific studies
on octylphenol the corresponding studies on nonylphenol can be used to fill the data gaps and be
used for environmental risk assessment of octylphenol without introducing too much uncertainty
(effect levels typically within a factor of 3 (Environment Agency, 2005a).

Abiotic degradation
Similar to nonylphenol, octylphenol is not expected to be degradable by hydrolysis, while dissipa-
tion in surface water with a half-life of about 14 hours under favourable conditions has been report-
ed. However, as for nonylphenol, photolysis in water is considered only to be of minor quantitative
importance for the overall dissipation of the substance in the aquatic environment (Environment
Agency, 2005a).
Photodegradation in air is an important removal mechanism for octylphenols released to the at-
mospheric compartment. The estimated half-life for the reaction of hydroxyl radicals with 4-tert-

octylphenol is 0.25 days, which is so fast that the substance will most likely not be transported far
from its emission sources before being degraded (Environment Agency, 2005a).
ECHA (2012d) reports on the photodegradation of 4-tert-octylphenol ethoxylates that the trans-
formation rate increases with the length of the ethoxy-chain; therefore e.g. OP2EO has a half-life in
air of 7.2 hours while the half-life of OP10EO is only 2.3 hours.
Biodegradation
Screening tests for ready biodegradability in water have given varying results ranging from one test
where 62 % was degraded in 28 days (i.e. fulfilled the 60 % ThOD pass level but failed the 10 day
window) to test where virtually no material was fully mineralized after 28 days. In summary, 4-tert-
octylphenol is not readily biodegradable but there are indications of some degree of biodegradation,
in particular following a period of adaptation. In simulation tests ,octylphenol shows a small poten-
tial for biodegradation in aerobic conditions whereas practically no dissipation was observed under
anaerobic conditions (DT50 >83 days in sediment) (ECHA, 2012c). The British Environment Agency
(2005a) describes 4-tert-octylphenol as inherently biodegradable.
No data on the degradation/dissipation of octylphenols in soil have been obtained (Environment

Agency, 2005a).
The corresponding ethoxylates are not readily biodegradable either. Primary degradation of the
higher ethoxylates will take place, especially if the inoculums are adapted, but apparently stable
metabolites are formed and full mineralization cannot be expected in sewage treatment plants. In
surface waters, degradation will take place slowly with a primary degradation DT50 of several days.
Similarly, de-ethoxylation leading to OP itself is slow in both sediment and soil (ECHA, 2012d).
Adsorption, distribution and bioconcentration

The log Kow for 4-tert-octylphenol has been reported as in between 3.7 and 4.12. Based on this, the
KOC is estimated as 1,376-2,740 L/kg. The E1-E4 ethoxylates of octylphenol have slightly lower
log Kow values (4.10-3.90, decreasing with increasing number of ethoxylate units) (Ying et al.,
2002).
The environmental distribution of octylphenol is assessed using a Level III fugacity model, a model
predicting the distribution of a substance between the various main environmental compartments
(ECHA, 2012c) as shown in the table below.
TABLE 25
PREDICTED DISTRIBUTION OF OCTYLPHENOL IN THE MAIN ENVIRONMENTAL COMPARTMENTS AFTER ORIGINAL-
LY BEING RELEASED TO EITHER AIR, WATER OR SOIL (ECHA, 2012C)
Release to air Release to water Release to soil
Air 26.0 % 1.2 % <0.1 %
Water 5.1 % 77.9 % 0.3 %
Soil 67.7 % 3.1 % 99.6 %
Sediment 1.2 % 17.8 % 0.1 %
Based on a Log Kow = 4.12, a worst-case BCF = 634 is calculated. Measured bioconcentration fac-
tors in a number of fish species are all lower than this, with the BCF = 471 in rainbow trout (O.
mykiss) being the highest experimental value (ECHA, 2012c).
4-tert-Octylphenol is classified R50-53 or Aquatic Acute 1 + Aquatic Chronic 1.

The most sensitive standard endpoints for aquatic species, among the studies considered reliable
(with some reservations regarding salt water species), are shown in Table 26
TABLE 26
THE MOST SENSITIVE ACUTE AND CHRONIC ENDPOINTS FOR 4-TERT-OCTYLPHENOL TOWARDS FISH, INVERTE-
BRATES AND ALGAE (ENVIRONMENT AGENCY, 2005A)
Trophic level Species End point Concentration (µg/L)
Freshwater Fathead minnow (Pimephales prome- 96-hour LC50 290

fish las)
Rainbow trout (Oncorhynchus mykiss) 6-day LC50 170
Rainbow trout (Oncorhynchus mykiss) 60-day post-hatch early life stage NOEC 6.1
Freshwater Freshwater shrimp (Gammarus pulex) 96-hour EC50 (immobilisation) 13.3

invertebrates
Water flea (Daphnia magna) 48-hour LC50 270
21-day NOEC (juvenile production by 62

surviving adults)
Freshwater Scenedesmus subspicatus 72-hour EC50 (growth rate) 1100

algea (use with care)
72-hour EC50 (growth rate) 300

(use with care)
Based on the above data (in particular the lowest NOEC = 6.1 µg/L for rainbow trout, O. mykiss)
and an assessment factor of 50, a PNECwater = 0.122 µg/L has been calculated.
A provisional PNECsediment has been calculated to be 0.0074 mg /kg ww while a provisional PNECsoil
based on the surface water effect value and equilibrium partitioning approach is 0.0059 mg /kg ww.
However, the latter value deviates highly from the PNECsoil for nonylphenol = 0.3 mg/kg, which is
based on experimental data and therefore needs careful consideration (Environment Agency,
2005a) as in most cases the experimental toxicities of octylphenol and nonylphenol are within a
factor 3 of one another.
Like nonylphenol, octylphenol is commonly accepted to be an endocrine disruptor with estrogen-

like effects (EU Cat 1, see section 7.1.1). In in vitro tests, the relative endocrine disruption potency of
4-tert-octylphenol compared to 17β-estradiol is 0.001 or lower for most parameters studied, but a
few exceptions up to a relative potency of 0.01 compared to 17 natural estrogens (Environment
Agency, 2005a). The lowest NOEC from a valid study assessing the endocrine disrupting effects in
fish was 1.6 µg/L for vitellogenin induction in adult male rainbow trout, O. mykiss. Other species of
fish are slightly less sensitive but most of them still have NOECs in the relatively low µg/L range.
The lowest NOEC for endocrine effects in fish based on fully valid studies is, however, 12 µg/L (En-
vironment Agency, 2005a).
The ethoxylates of 4-tert-octylphenol also show estrogenic activity in in vitro tests but with a lower
potency than octylphenol itself (0.0088 compared to OP). Longer chain ethoxylates show only very
weak estrogenic activity. Assessment of the in vivo activity is based on results for NPEO, generally
showing about 10-fold lower activity of the short-chain ethoxylates compared to NP itself (ECHA
2012d).
5.1.3 AP/APEO of a chain length of less that eight

4-tert-butylphenol will be used to exemplify the environmental properties of AP/APEO with chain
lengths from C4 to C7. This substance has been mentioned as a possible substitution candidate for
nonylphenol in the production of phenolic resins (Environment Agency, 2005b).

4-tert-butylphenol is, like the long-chain alkylphenols, stable to hydrolysis and abiotic degradation
in water is not considered a significant mechanism of degradation whereas in air phototransfor-
mation takes place with a half-life of 3.2 hours thus suggesting that this is a significant removal
process in the atmospheric compartment (Environment Agency, 2005b). In the EU Risk Assess-
ment of 4-tert-BP a half-life of 0.4 days or less is stated (ECB, 2008).
Conflicting results of aquatic degradation screening tests are available but the British Environment
Agency (2005b) concludes that the substance should be characterized as readily biodegradable not
fulfilling the 10 day window criterion. This implies using a half-life of 50 days in surface water and
90 days in soil for environmental risk assessment (ECB, 2008).
The Log Kow of 4-tert-BP is 3.29 leading to an estimated KOC of 582. A QSAR estimation with
Episuite gives a KOC of 1912 (Environment Agency, 2005b).
TABLE 27
ENVIRONMENTAL DISTRIBUTION OF 4-tert-BP USING A MACKAY LEVEL III FUGACITY
MODEL (ENVIRONMENT AGENCY, 2005B)
Release Release Release
Compartment
100% to air 100% to water 100% to soil
Air 39.7 % 0.2 % 0.0 %
Water 23.3 % 95.3 % 0.4 %
Soil 35.9 % 0.2 % 99.6 %
Sediment 1.1 % 4.4 % 0.0 %
A bioconcentration study with the fish Leuciscus idus melanotus gave a measured BCF of 120,
which is comparable to estimated BCFs and is suggested to be used for risk assessment (Environ-
ment Agency 2005b).
4-tert-butylphenol is less acutely toxic to fish than the long-chain alkylphenols. The lowest valid
LC50 reported is 5.1 mg/L for P. promelas and O. latipes. The toxicity to invertebrates is very similar
to a 48 hour EC50 =3.9 mg/L for D. magna. The EC50 to algae (S. capricornutum) was found to be
14 mg/L (ECB, 2008).
A valid long term NOEC (21 day reproduction study with D. magna) gave a NOEC = 0.73 mg/L
while the NOEC in the study with the green alga S. capricornutum resulted in a NOEC = 0.32 mg/L.
The latter is the most sensitive traditional endpoint reported and leads to a calculated PNECwater of
6.4 µg/L using an assessment factor of 50 (ECB, 2008). A PNECsediment has not been derived.
PECsoil is estimated to be 73 µg/kg ww based on the aquatic data (ECB, 2008).
In the table below, the toxicity of some of the short chain alkylphenols to D. magna (96 hour
NOEC) is compared to the toxicity of the long chain alkylphenols OP and NP.

TABLE 28
COMPARISON OF TOXICITIES OF C4-C9 ALKYLPHENOLS TO D.MAGNA
SOURCE: ENVIRONMENT AGENCY, 2005B)
Substance No effect concentration (mg/l)
4-sec-Butylphenol 9.7
4-tert-Butylphenol 8.6
4-tert-Pentylphenol 1.8
4-tert-Octylphenol 0.19
4-Nonylphenol 0.3
2,4-Di-tert-butylphenol 0.85
Overall, the general toxicity data indicate that aquatic organisms appear to be more sensitive to the
longer chain alkylphenols than to the shorter chain alkylphenols.
4-tert-pentylphenol is another possible nonylphenol substitute for production of resins (Environ-

ment Agency, 2005b).
This substance appears to be somewhat more toxic to aquatic organisms than 4-tert-butylphenol
with a lowest acute LC50 = 1.7 mg/L (Crangon septemspinosa) and a long term NOEC = 0.063
mg/L (Environment Agency, 2005b).
The Log Kow is 4.03, the BCF is 531, and the substance is not considered to be readily biodegrada-
ble. The atmospheric half-life is estimated at 3.1 hours.
Other short-chain APs

A detailed assessment of all short-chain APs is beyond the limits of this survey. One of the sub-
stances, 2,6-di-tert-butyl-p-cresol (BHT) is used in relatively high quantities as an antioxidant and
found in relative large concentrations in waste water (section 4.4). For this reason BHT is briefly
mentioned here. An OECD SIDS Initial Assessment Report for BHT (OECD, 2002a) concludes:” In
the environment, BHT is rapidly decomposed forming several, partly unidentified, metabolites.
BHT is not readily biodegradable, a moderate to high bioaccumulation potential has to be as-
sumed. The NOEC from the long-term toxicity to daphnids was 0.07 mg/l, resulting in a PNEC of
0.0014 mg/l. Therefore, the performance of an environmental risk assessment is recommended.
Especially the questions concerning exposure, bioaccumulation as well as toxicity of the metabo-
lites should be clarified”. The substance is not among the substances proposed for priority in the
Prioritisation of Alkylphenols for Environmental Risk Assessment from Environment Agency
(2005b). A risk assessment of BHT has to the knowledge of the authors not been undertaken.
5.1.4 AP/APEO of a chain length of more than nine

The only commercially important substance group of a chain length of more than nine is the do-
decylphenols. The following data originates from ECB's summary fact sheet (undated, PBT List No.
55).

Dodecyl phenol is classified R50-53 by the producers, and in its PBT-assessment No. 55, ECB con-
siders it to meet the T criterion, likely to meet the P criterion but not meeting the B criterion, i.e. the
substance is not a PBT (ECB, undated).

In a screening test, 10 % degradation was achieved over 56 days based on CO2 production. The
result indicates that dodecylphenol is neither readily nor inherently biodegradable.
The Log Kow of dodecylphenol is 7.17 and a valid bioconcentration study in fish gives a worst case
steady state BCF = 823 (ECB, 2011).
Level III fugacity modelling predicts the environmental distribution of dodecylphenol shown in the
following table.
TABLE 29
ENVIRONMENTAL DISTRIBUTION OF PARA-C12-ALKYLPHENOLS (BROOKE ET AL., 2007)
Compartment Mass %
Release to air Release to water Release to soil
Air 0.03 0.001 <0.001
Water 0.005 0.91 0.003
Soil 99.5 4.54 94.7
Sediment 0.49 94.5 0.32
Environment Agency (2007) reports a lowest acute (96 h) aquatic toxicity value (EC50) of 17 µg/L
for aquatic invertebrates and a 21 day NOEC (reproduction, invertebrates) = 2.0 µg/L.
ECB (2011) mentions that a valid 21 day reproduction study with Daphnia magna according to
OECD (2011) gave a NOEC = 3.7 µg/L. In view of uncertainties over the actual exposure levels in the
study, the results were re-calculated based on time-weighted means to give a NOEC = 2.0 µg/L .
A PNECwater = 0.04 µg/L has been calculated (Brooke et al., 2007) and a PNECsediment = 96 µg/kg wt
estimated using the equilibrium partitioning approach and aquatic effect data.
Dodecylphenol is believed to exhibit endocrine (estrogenic) disrupting properties like nonylphenol

and octylphenol; however reliable appropriate screening data are lacking (Brooke et al., 2007).
5.2 Summary of environmental effects

The British Environment Agency (2005b) provides a comparative overview of the environmental
fate and effects properties of some of the most relevant alkylphenols described in the preceding
sections; see Table 30. Further, an overview of environmental classification of the various alkylphe-
nols is provided in Chapter 9 (Table 44).
The data show that the short chain alkylphenols (C4, i.e. butylphenols) have a significantly lower
potential for bioaccumulation than the long chain (C8-C12) alkylphenols, as demonstrated by their
lower log Kow values and lower bioconcentration factors (BCF) in fish as well as their relatively high
water solubilities. Further, they appear to be readily biodegradable (i.e. non persistent) thus posing
a lower risk of accumulation in sediments and soil and of surface water mediated long range
transport compared to the long chain compounds, which are, at best, inherently biodegradable.
Finally, the short-chain alkylphenols are less acutely toxic to aquatic organisms than the long chain
correspondents. Branched chain alkylphenols tend to be more persistent and have higher
log Kow/BCF than the linear alkyl chain homologues.

TABLE 30
COMPARATIVE OVERVIEW OF ENVIRONMENTAL FATE AND AQUATIC EFFECT PROPERTIES OF A NUMBER OF ALKYLPHENOLS (EN-
VIRONMENT AGENCY, 2005B)
2-tert- 4-tert- 4-tert- 4-tert- Nonyl- Dodecyl- 2,4-Di- 2,6-Di-

Butyl- Butyl- Pentyl- Octyl- phenol phenol tert- tert-
phenol phenol phenol phenol (bran- butyl- butyl-
ched) phenol phenol
Physicochemical properties
Water solubility
700 (meas) 610 (meas) 37 19 (meas) 6 (meas) 1 12 4.11
(mg/l)
Octanol-water
partition coefficient 2.7-3.5 3.3 4.03 4.12 4.48 5.5 5.19 4.5
(log Kow)
Persistence
Readily Readily Not readily Inherently Inherently Not readily Not readily Not readily
Biodegradation biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable biodegradable
Bioaccumulation
Highest fish BCF value 188 (est) 120 531 (est) 634 (est) 1,280 9,440 (est) ~660 (est) 660
Toxicity
Aquatic Acute 2.4 3.4 1.7 0.013 0.085 0.093 1.8 0.076
toxicity No data
(mg/l) Chronic 0.042 (est) 0.73 0.063 0.006 0.025 0.008 (est) 0.019 (est)
available
With regard to the endocrine disrupting properties of alkylphenols and their ethoxylates, it has
clearly been demonstrated in in vivo studies, in particular with fish, that the long chain alkylphe-
nols have an endocrine effect potency to cause estrogen-like effects that is not negligible while the
corresponding ethoxylates and the short chain alkylphenols appear only to be weakly estrogenic, if
at all. No firm conclusion (e.g. in the form of EC criteria) as to the actual environmental significance
of these findings has been reached as yet, but there is concern that the endocrine disrupting potency
of the long chain alkylphenols in combination with their persistence and observed concentrations in
the aquatic environment implies a risk of estrogen-like effects occurring as a result of organisms
being exposed to alkylphenols, in particular nonylphenol and octylphenol. Nonylphenol and 4-tert-
octylphenol are included on the EU list of suspected endocrine disrupting compounds in Cat 1 while
4-tert-butylphenol is a Cat 2 substance on that list. None of the other alkylphenols mentioned in
Table 44 are currently on the list.
In December 2011, 4-tert-octylphenol was included on ECHA's list of SVHC while proposals for
inclusion have been submitted also for the corresponding ethoxylates as well as for 4-nonylphenol
and for dodecylphenol. None of the substances meet all the criteria to be classified either PBT or
vPvB but are proposed as SVHC with reference to Article 57 (f) of the REACH Regulation, i.e. sub-
stances with an "equivalent level of concern having probable serious effects on the environment"
due to EDC properties in combination with persistence and bioaccumulative properties not fulfilling
the criteria specified in Annex XIII of the Regulation.
Most probably the short-chained APs, with the exception of 4-tert-BP and 4-tert amylphenol, would
not be considered SVHC. For dodecylphenol, 4-tert-BP and 4-tert amylphenol, a closer assessment
would be needed for a conclusion as to whether they may be considered SVHCs.

6. Human health effects
6.1 Introduction to human health effects of AP/APEO

As described in previous chapters, alkylphenols (AP) belong to a large and diverse group of related
chemical substances with shorter or longer, branched or unbranched alkyl chains. Some alkylated
phenols occur naturally in e.g. crude oil (Ioppolo-Armanios et al., 1992) but the commercial prod-
ucts that are of importance are mostly complex mixtures of isomers or homologues. Commercial
nonylphenol can, for example, consist of a variable mixture of about 20 isomers.
For some phenols with a short alkyl group, there may be specific and relevant human health data
from occupational exposures available, but for non-tested commercial mixtures with unknown
content, a health assessment may be difficult or impossible. However, all phenols should be consid-
ered hazardous substances.
The classification and labelling of a few alkylphenols (methyl phenols (cresols), dimethyl phenols
(xylenols), tert-octyl phenol and nonyl phenols) are harmonized in the EU and more alkylphenols
are self classified (see Annex 2). In general, alkylated phenols are acutely toxic or harmful, a charac-
teristic which decreases with the length of the alkyl chain, and irritating to skin, eyes and mucous
membranes. In addition, nonylphenol and other long-chain alkylphenols are endocrine disruptors
and demonstrate reproductive toxicity.
The nonyl phenol ethoxylates (NPEO) are a group of commercially important derivatives, where the
phenol group is substituted by polyethylene glycol. Only ethoxylates of nonyl-, octyl- and dodecyl
phenols are commercially important. Because of the large polymeric size, such chemicals have re-
duced bioavailability. An ether group is much less reactive than a phenolic hydroxyl group; there-
fore, nonyl ethoxylates have lower toxicities, and such chemicals are not as corrosive as nonylphe-
nol is but only mild skin irritants.
6.2 Nonylphenol and nonylphenol ethoxylates

As mentioned in previous chapters, nonylphenol is phenol substituted in either the ortho- or para-
position by a linear or branched alkyl group consisting of nine carbons (C9); therefore, it is not one
single chemical. Most toxicity data on nonylphenol (NP) are about commercial products of variable
composition, a situation which causes analytical difficulties. Very little information exists for
nonylphenol ethoxylates other than from self classification and for nonaethylene glycol 4-
nonylphenyl ether (nonoxynol-9), used as a spermicide in pharmaceuticals.
Toxicokinetics
In experimental animals radiolabelled nonylphenol was used to determine the toxicokinetics. It was
found that the absorption via the oral route in rats was almost complete with 76% of the adminis-
tered dose excreted with faeces and 19% via the urine as glucuronic acid conjugates during the first
4 days (Knaak et al., 1966). The potential for bioaccumulation was limited. For three ethoxylates
studied, the excretion in the urine was greater and in the faeces it was smaller (Knaak et al., 1966).
The absorption through the skin in an in vitro test system was poor: less than 1% (Monteiro-Riviere
et al., 2000).

The absorption and excretion of nonylphenol was investigated in human volunteers (Müller, 1997).
After oral administration of a single dose of 5 mg nonylphenol the absorption was about 20% of the
dose, the blood level peaked after one hour, and nonylphenol was present as 86 ng conjugate/g
blood. The concentration of the free nonylphenol was 100-fold lower. About 10% of the oral dose
was excreted in the urine free or as conjugate. The excretion via faeces was low.
There are no data on the toxicokinetics of nonylphenol following inhalation exposure, but on the
basis of the oral absorption data and high partition coefficient, it would be prudent to assume that
significant absorption via the inhalation route can occur.
There is no information about the metabolism of nonyl phenol or of the nonyl phenol ethoxylates,
but once absorbed, NPEOs are likely metabolised to nonylphenol.
Acute toxicity
The acute oral toxicity of nonylphenol is moderate to low with estimated LD50 values in rats ranged
from about 1200 to 2400 mg/kg for males and 1600 to 1900 mg/kg for females. The 95% confi-
dence intervals in these studies were generally relatively tight, suggesting that the dose-response
curve is steep. Clinical signs of toxicity included excessive salivation, diarrhoea and lethargy. At
necropsy, erosion of the mucosal surface of the stomach was seen in some of the animals (EU
2002). The toxicity of nonylphenol in mice may be greater since a LD50 in male mice was reported
to 300 mg/kg (Gaworski et al., 1979). The oral rat LD50 for NPEO with an ethoxylate side chain
length of 9 was 2.6 ml/kg (Smyth and Calandra, 1969).
A dermal LD50 of 2031 mg/kg bw was determined in rabbits after an exposure period of 24 hours
(Smyth et al., 1969).
Irritation
No information is available from human studies but skin irritation caused by some technical
nonylphenol substances of unknown composition has been investigated in a number of animal
studies. Most of these studies have not been published in peer-reviewed papers, but rather in labor-
atory reports, and the reactions vary with substance and test. Some studies reports severe erythema,
thickening, necrosis and ulceration of the skin, severe eye irritation and burns, but only mild irrita-
tion of the respiratory tract (ECB, 2002).
Sensitisation
No information is available from human studies or inhalation but the skin sensitization potential of
nonylphenol has been investigated in several animal studies, including the guinea pig maximization
test, without showing significant skin sensitizing potential (ECB, 2002). There are two papers
claiming contact dermatitis from exposure to nonylphenol ethoxylate (Nethercott and Lawrence
1984; Meding, 1985).
Repeated dose toxicity

There are no human toxicity studies and few animal studies of oral administration of nonylphenol.
In a 28-day study, groups of five male and five female Sprague-Dawley rats were exposed to
nonylphenol via incorporation in the diet at nominal dose levels of 0, 25, 100 or 400 mg/kg bw/day
(Hüls, 1989). At the highest dose level, the body weight gain was reduced and for the males there
were slight differences in comparison with the controls for certain clinical chemical parameters. A
NOAEL of 100 mg/kg bw/day for 28-day exposure was determined.
In a 90-day study, groups of fifteen male and fifteen female Sprague-Dawley rats were exposed to
nonylphenol via incorporation in the diet at concentrations of 0 (control), 200, 650 or 2000 ppm
(mg/kg in the diet) (Cunny et al., 1997). Calculated nonylphenol intakes were about 0, 15, 50 and
140 mg/kg bw/day, respectively. There were no treatment-related mortalities or clinical signs of

toxicity. At the highest dose of 140 mg/kg/day only, there were minor adverse effects on bodyweight
gain, the amount of food consumed and food utilisation throughout the dosing period, and some
evidence of morphological changes in the liver and possibly kidneys. In this 90-day sub-acute study
the NOAEL for nonylphenol was determined to be 50 mg/kg bw/day. Various nonylphenol ethox-
ylates were tested in a 90-day feeding study with rats, and the LOAELs for increased liver weight
were determined to 40-200 mg/kg/day (Smyth and Calendra, 1969). Dogs receiving 0.64% NPEO
in the feed for 90 days had retarded weight gain.
Further information on repeated dose toxicity can be derived from a good-quality multigeneration
study (NTP, 1997). Groups of thirty male and thirty female Sprague-Dawley rats were exposed to
nonylphenol in the diet at concentrations of 0 (control), 200, 650 or 2000 ppm over three genera-
tions. Calculated nonylphenol intakes were, respectively, about 0, 15, 50 and 160 mg/kg bw/day
during non-reproductive phases. The F0 generation was exposed for 15 weeks, the F1 and F2 genera-
tions from soon after birth to about 20 weeks of age and the F3 generation from birth to about 8
weeks of age. Evidence of general toxicity was seen in adults of all generations, although there were
no treatment-related clinical signs, mortalities or adverse effects on food consumption. Histopatho-
logical examination revealed an increase in the incidence of renal tubular degeneration and/or
dilatation in adult males from all generations and all nonylphenol treated groups and for some
adult females. Therefore, the LOAEL for histopathological changes in the kidneys after repeated
exposures to nonylphenol was considered equal to the lowest dose of 15 mg/kg/day (ECB, 2002).
Long-term feeding of rats with 0.2 g NPEOs/kg bw/day in 2 years resulted in increased liver weight
in female rats, and in dogs when they received 0.27% NPE= in the diet (Smyth and Calandra, 1969).
In addition, focal myocardial necrosis was observed in dogs and guinea pigs exposed to a high mo-
lecular weight NPEO-20 at 0.04 g/kg/day. NPEO-9 was half as potent in dogs and NPEO-15 a fifth.
Mutagenicity and cancer

Mutagenicity data are available from in vitro test systems and animals. No mutagenicity of
nonylphenol was detected in the Ames test with several Salmonella typhimurium strains and in
Escherichia coli in the presence and absence of metabolic activation (Shimizu et al., 1985; Bo-
yacioglu et al. 2007). An in vitro gene mutation test with Chinese hamster V79 cells was negative
(Hüls, 1990). Micronucleus studies with mice were also negative for nonylphenol (Hüls, 1999). No
cancer studies of humans or animals were available.
Effects on reproduction, hormones and fertility

There are some newer data on reproductive effects in humans. Low doses of pure 4-n-nonylphenol
are able to affect cytokine secretion in human placenta which may result in implantation failure,
pregnancy loss or other complications (Bechi et al., 2010).
The estrogenic activity of nonylphenol in various quantities has been investigated in a number of
studies using recombinant yeast, estrogen sensitive MCF-7 cells or a rodent uterotrophic assay
response. 4-Nonylphenol was tested for estrogenic activity in an in vitro assay using a recombinant
strain of yeast (Saccharomyces cerevisiae), which contains an estrogen-inducible expression sys-
tem (Routledge and Sumpter, 1997). Nonylphenol was active but 30 000 times less potent than a
17ß-estradiol standard. The estrogenic activity of nonylphenol has also been assessed in an in vitro
assay involving estrogen-sensitive human breast tumor MCF-7 cells (Soto et al., 1991). In this test
system the estrogenic potency of 17ß-estradiol was 3 000 000 times greater than that of nonylphe-
nol.
The estrogenic activity of nonylphenol has been assessed in several studies using an assay based
upon the uterotrophic response in the rat. Absolute uterus weight and bodyweight-related uterus
weight were statistically significantly increased in a dose-dependent manner by nonylphenol. The

NOAEL was 9.5 mg/kg bw/day. Estradiol was about 1000 times more potent in this assay than
nonylphenol.
In the multi-generation study mentioned above (NTP, 1997) fertility and mating performance were
not adversely affected by nonylphenol treatment. However, there were changes, albeit relatively
slight, in the estrous cycle length, timing of vaginal opening, ovarian weight and sperm/spermatid
count. The effects on the estrous cycle were seen in both the F generations (not assessed in F males)
and the timing of vaginal opening was influenced in all three generations; this consistency provides
firm evidence of a relationship with treatment. These effects were possibly related to the estrogenic-
ity of nonylphenol. There is some uncertainty about the relationship to nonylphenol treatment with
respect to the ovarian weight reduction, because this effect was apparent after adjusting for body-
weight in only one generation and did not correlate with any histopathological changes; neverthe-
less, it is compatible with the anticipated direct effects of exogenous estrogenic activity. Also, there
is uncertainty regarding the cause of the apparent reduced sperm/spermatid numbers in the F2
generation. This study provided evidence that nonylphenol exposure over several generations can
cause minor perturbations in the reproductive system of offspring, which are compatible with the
predictable or hypothesised effects of exogenous estrogenic activity, although these perturbations
do not cause functional changes in reproduction of the rat at the dose levels tested. A NOAEL for
these changes of 15 mg/kg/day was identified.
Another study (de Jager et al., 1999) provided evidence of nonylphenol-related testicular toxicity at
exposure levels which also cause mortality. A LOAEL for testicular toxicity of 100 mg/kg/day was
established.
Developmental toxicity
In a rat developmental toxicity study of timed-mated females of the Wistar strain were adminis-
tered by oral gavage corn oil solutions of nonylphenol from days 6 to 15 of pregnancy at dose levels
of 0, 75, 150 and 300 mg/kg/day (Lee, 1998). There was clear evidence of maternal toxicity at 300
mg/kg/day, manifested as a reduction in bodyweight gain and food consumption, mortality of two
females and the macroscopic organ changes in the kidney and spleen. Similar macroscopic changes
were seen occasionally at 150 mg/kg/day. No maternal toxicity was seen at 75 mg/kg/day; there-
fore, the maternal NOAEL was 75 mg/kg/day, and the fetal NOAEL was 300 mg/kg/day.
Tolerable daily intake

Based on a NOAEL value of 15 mg/kg bw/d in experimental animals the tolerable daily intake (TDI)
for nonyl phenol in humans has been calculated at 5 µg NP/kg bw (Nielsen et al., 2000).
6.3 Octylphenol and octylphenol ethoxylates

Similar to nonylphenol, octylphenol is also a group name for various phenols substituted in either
ortho- or para-position by a linear or branched alkyl group consisting of eight carbons (C8). The
most well-studied isomer is called 4-tert-octylphenol with the systematic name 4-(1,1,3,3-
tetramethylbutyl)phenol and short form 4-t-OP. A REACH Annex XV dossier on 4-tert-octyl phenol
has been published in 2011 (ECHA, 2011). No information about the toxicity of octylphenol ethox-
ylates was available other than self classifications (see Annex 2).
Toxicokinetics
After oral application in rats 4-tert-octylphenol is rapidly absorbed and quickly released into the
blood. The absorption of 4-t-OP dissolved in various solvents and administered by gavage was 10-
50% of the dose depending on the rat strain, and the blood half-life ranged from 5 to 38 hours (EC-
HA, 2011).
The highest absorption was observed in a newer study, where 4-tert-octylphenol was dissolved in
propylene glycol, bioavailability ranged from 26-38% in male animals and to 46-55% in females,

and the 4-tert-octylphenol blood half-life ranged from 5-16.6 hrs in male animals and 8.3-37.9 hrs
in females (Hamelin et al., 2009).
After a single oral administration the highest concentrations were found in liver and fat, followed by
kidneys and ovaries, and the lowest concentrations were found in muscle tissue. No significant
differences occurred between the tissue concentrations from single and repeated treatment, indicat-
ing no bioaccumulation of 4-tert-octylphenol, and tissue concentrations appeared to be higher in
female animals than in males (Hamelin et al., 2009).
When rats were fed 4-tert-octylphenol it had a direct inhibitory effect on cytochrome P450 activities,
causing decreased levels of testosterone hydroxylating CYP activities in the liver, where 4-tert-
octylphenol is transformed to its glucuronide and its sulfate and further excreted into the bile and
faeces (Hüls, 1996).
An oral intake of 4-tert-octylphenol at 200 mg/kg bw/day is in excess of a level shown to saturate
liver metabolic capacity (Tyl et al., 1999).
In a rat study 4-tert-octylphenol ethoxylate was poorly absorbed by oral administration, since about
90% was excreted in faeces within 24 hrs and only 1% in the urine (Larson et al., 1963). The oral rat
LD50 increased with the length of the polyether-chain from 1.7 to >28 g/kg bw. No adverse effects
were observed in rats exposed to 1.4% of the ethoxylates for up to 2 years.
Repeated dose toxicity

There are no available human studies but numerous studies are available on repeated administra-
tion of 4-tert-octylphenol to adult rats of different strains of both sexes, with various routes (oral,
subcutaneous and intraperitoneal injection) of administration. The only route relevant with regard
to human health assessment and exposure is through oral exposure.
The sub-acute toxicity of 4-tert-octylphenol (purity 98.2 %) was determined in a 28 day gavage
study with rats exposed to 0, 15, 70, and 300 mg/kg/day (ECHA, 2011). Increased urine volume was
evident in females and males at the highest dose. Urinalysis showed decreases in specific gravity
and in concentrations of sodium, chloride and potassium. Slight but statistically significant increas-
es in kidney weights were found in the high-dose males and females and in liver weights in the high-
dose females. The high-dose males and females showed greyish kidney patches as gross findings,
and regeneration of renal tubules as microscopic findings. The NOAEL was reported as 15 mg/kg
bw/day. In asimilar study the NOAEL was the same and the LOAEL was estimated at 150
mg/kg/day; in a third study, a concentration of 500 mg/kg bw/day was lethal for about half of the
exposed animals during the treatment period (ECHA, 2011).
In a 3-month study the toxicity of 4-tert-octylphenol (purity 93.1 %) has been investigated in rats
exposed daily to concentrations of 30, 300, or 3000 ppm 4-tert-octylphenol in the diet - corre-
sponding to an intake of 2.3, 23, 230 mg/kg bw/d (Suberg et al., 1982). No treatment related death
occurred and no clinical signs were observed throughout the study. Food consumption was unaf-
fected. Slightly increased water consumption was observed in females receiving the highest 4-tert-
octylphenol dose. The body weight gain was slightly decreased in male and female animals receiving
300 ppm and markedly decreased in animals receiving 3000 ppm 4-tert-octylphenol. Absolute
organ weights were decreased in the highest dose group in male animals (thyroid, thymus, heart,
lung, spleen; but not kidney, adrenals, testes or brain) and female animals (thymus, heart, lung,
liver, spleen, kidney, adrenals; but not thyroid, ovaries or brain). Histopathological investigations
were carried for organs of 5 male and 5 female animals each in the control and highest dose group;
no treatment related effects were observed. Based on the results of this study, a NOAEL of 30 ppm
(2.3 mg/kg bw/d) and a LOAEL of 300 ppm (corresponding to 23 mg/kg bw/d) were determined.

Mutagenicity and cancer
Octylphenol was mutagenic in Ames test with Salmonella typhimurium strains TA98 and TA100 in
concentration of 20-40 µg/L (Boyacioglu et al., 2007). No cancer studies have been published.
Effects on female reproduction and fertility

In a study comparing estrogenic activities of various environmental estrogens, adult female rats
were treated orally (gavage) with 0, 50, 100 or 200 mg 4-tert-octylphenol/kg bw or 0.01 or 0.1 mg
ethinylestradiol/kg bw for a period of 25 days (Laws et al., 2000). Ethinylestradiol significantly
reduced the number of 4- to 5-day cycles during the exposure period, and oral exposure to 200 mg
4-tert-octylphenol/kg bw induced a similar response.
In a study on 35 day old female rats , daily gavage administration of saline (negative control), pro-
pylene glycol (vehicle control), or 4-tert-octylphenol at dosages of 25, 50, or 125 mg/kg bw were
given for 35-41 days (Sahambi et al., 2010). No significant differences were seen on body weights or
on organ weights across groups. There were no significant differences in serum estradiol concentra-
tions and all animals continued to cycle throughout the monitoring period.
Effects on male reproduction and fertility

In a study focusing on effects on testicular functions, groups of male rats were given daily gavage
administration of 0, 50, 150 or 450 mg 4-tert-octylphenol for 30 days (Bian et al., 2006). In the
animals of the high dose group (450 mg/kg bw/d) body weight gain was suppressed. Weights of
testes, epididymis and prostate were statistically significantly lower in comparison to controls. His-
topathological examinations of testes revealed alterations in rats administered 450 mg/kg bw/d
with seminiferous tubules markedly reduced in size and disturbance of normal spermatogenic cell
organization and total number of germ cells inside the tubules markedly reduced. Electronic micro-
graphs of testicular cells revealed more intracellular vacuoles, lipofuscin and showed degeneration.
Testicular sperm counts revealed statistically significant decreases of sperm head count and daily
sperm production in rats treated with 450 mg/kg bw/d.
A study had been performed to determine the effects of 60 days’ exposure to various doses of 4-tert-
octylphenol on male reproductive parameters in rats exposed to 25, 50, or 125 mg 4-tert-
octylphenol/kg bw/d by gavage (Cyr and Gregory, 2006; Gregory et al., 2009). 60 days represent-
ing approximately 1.5 cycles of spermatogenesis. In the 4-tert-octylphenol-treated rats there was a
tendency toward decreased body weight, relative to controls, with a statistically significant decrease
in mean body weight at the highest dose. There were no effects on organ weights of testes, epididy-
mis, ventral prostate, and seminal vesicles between experimental groups.
In a 4 month study the effects on the reproductive system of 4-tert-octylphenol exposure via drink-
ing water were investigated in adult (2 month old) male rats (Blake et al., 2004). No effects were
seen on total mixed germ cell yield, on flow cytometric distribution of spermatogenic cells or on
testicular sperm concentration per g testis or per organ. Mean epididymal sperm head count per
gram tissue was slightly decreased to ~700 million in comparison to controls (~800 million) at 10-5
M drinking water concentration. Mean percentage of sperm tail abnormalities (n=6 males/group)
was slightly higher (~10-12 %) in treated groups as compared to the control group (~7 %).
Developmental toxicity
Pregnant female Wistar rats were given 4-tert-octylphenol daily by gastric intubation at a dose of
15.6, 31.3, 62.5, 125, 250, and 500 mg/kg bw on pregnancy days 0 (sperm plugs detected) through 8
of pregnancy (Harazono et al., 2001). In the high dose group, all rats died by day 6 of pregnancy,
and one-third of the rats treated with 250 mg/kg bw/day died during the administration period.
Clinical signs such as diarrhea and loss of fur were seen in animals treated with > 62.5 mg/kg bw/d.
The body weight gains from dose groups > 31.5 mg/kg bw/day during the treatment period and on

days 0-20 were significantly lower than those of control groups. Net weight gain of the dams, how-
ever, did not differ significantly from that of the control group. The food consumption on days 0-9
and on days 0-20 of pregnancy was significantly decreased in all treated groups (> 15.6 mg/kg
bw/day) compared with control values. There were no significant differences in the pregnancy rate
between treated animals and the control group. The numbers of corpora lutea, implantation sites
and pre-implantation loss per litter in the treated animals were not significantly different from the
control group. A significant decrease in the numbers of live foetuses per litter was observed at 31.5
and 125 mg/kg bw/day, and a significant increase in the incidence of post-implantation loss at dos-
ages of > 31.3 mg/kg bw/day. The sex ratio of live foetuses was comparable across all groups as well
as body weights of male and female. No significant increases in the incidences of foetuses with ex-
ternal malformations were observed. The LOAEL for maternal toxicity was estimated as 15.6 mg/kg
bw/day based on reduced food intake, and the NOAEL for developmental toxicity was 15.6 mg/kg
bw/day based on statistically significant increased percentage of post-implantation loss.
4-tert-Octylphenol has been investigated for developmental effects in offspring in several studies of
lower quality using oral or other application routes to pregnant dams in various species. In rats,
intrauterine exposure to 4-tert-octylphenol caused a significant decrease in the numbers of live
foetuses and a significant increase in the incidence of post-implantation loss. The NOAEL for that
was 15.6 mg/kg bw. However, these effects occurred at doses that also caused maternal toxicity,
including death, reduced body weight gain and reduced food consumption (ECHA, 2011).
Multi-generation toxicity studies

A two-generation reproduction toxicity study was conducted with rats fed with dietary concentra-
tions of 0, 0.2, 20, 200, and 2000 ppm 4-tert-octylphenol in their diet, leading to a daily intake of
0,034-0.011, 3.3-1.05, 32.6-10.9, and 369-111 mg/kg/d depending on the age and sex of the animals
and the phase of the study, according to a OECD guideline. The test protocol involved parental
dosing of the F0 generation (30 animals/sex/dose group) during the 10 weeks pre-breeding, mating
and gestation period (Tyl et al., 1999).Treatment-related systemically toxic effects were limited to
consistent and persistent reductions in body weights and weight gains in both sexes in the F0, F1,
and F2 generations at 2000 ppm. Feed consumption was unaffected, and there were no clinical
effects observed. Body weights during gestation were unaffected and were reduced during lactation
in F0 and F1 females at 2000 ppm. At necropsy, F0 and F1 parental and F2 retained male absolute
and relative organ weights were unaffected for liver, kidneys, adrenal glands, spleen, and brain.
There were no treatment- or dose related gross or microscopic findings for the examined organs, for
F0 and F1 parental animals, and for F2 retained adult males. No effects on reproductive parameters,
testes weights or morphology, epididymal sperm counts or morphology, daily sperm production,
efficiency of daily sperm production, or prostate or dorsal prostate weights or histopathology were
observed. Furthermore, no estrogen-like effects on males or females and no low-dose effects were
evident. In that study, the NOAEL for systemic toxicity/postnatal toxicity was 200 ppm in feed (11-
33 mg/kg bw/d), and NOAEL for reproductive toxicity was as high as 2000 ppm (111-369
mg/kg/d). It has to be noted that the exposure duration was limited.
Endocrine disruption in screening systems

4-tert-Octylphenol has been studied in many different in vitro test systems, and the relative estro-
genic potency has often been related to 17β-estradiol, ethinylestradiol or DES (ECHA, 2011). In the
MCF-7 Cell proliferation test, the relative potency to 17β-estradiol was for instance 10-6-10-3.
4-tert-Octylphenol has been screened for androgenic/anti-androgenic activity in the Hershberger

bioassay, and the impact on testosterone biosynthesis/testicular steroidogenic competence was
investigated in vitro in neonatal Leydig cells derived from 6-7 days old neonatal rats. Overall, the in
vitro and in vivo screening tests indicate that 4-tert-octylphenol has some but low estrogenic poten-
tial in mammals.

4-tert-Octylphenol features some inherent potential for being toxic to reproduction, probably in
relation to female sexual maturation and female fertility in combination with unrealistically high
doses or using artificial and non-human relevant routes of administration.
6.4 AP/APEO of a chain length of less than eight

Monoalkylphenols with a short alkyl chain have different properties than the longer chain homo-
logues and are used for other purposes and not as ethoxylates. The most important are the three
methylphenols (o-, m- and p-cresols – out of study scope), and 4-tert-butylphenol.
6.4.1 4-tert-Butylphenol
Regarding toxicokinetics the available information is rather sporadic. In an experimental study of
rats exposed by gavage to 147 µg/kg bw of 14C-labelled 4-tert-butylphenol once daily for three days
it was found that after 7 days about 27% of the applied dose was excreted via feces and about 73%
via urine, thus the absorption must have been complete (Freitag et al., 1982). In another rat study it
was shown that after intravenous injection of 14C-labelled 4-tert-butylphenol about 70% of the ap-
plied dose was excreted as glucuronide and about 20% as sulfate (Koster et al., 1981).
There exist some older biomonitoring studies of workers handling 4-tert-butylphenol and being
exposed by inhalation and through the skin. It was reported that the absorption of the phenol was
close to complete but most was excreted again within 24 hrs as glucuronide- and sulfate conjugates
(ECB, 2008).
The acute toxicity of 4-tert-butylphenol has been determined in some animal experiments and
appears to be insignificant. The inhalation rat LC50 was very low at >5000 mg/m3. Lethality was not
observed among rats exposed to saturated 4-tert-butylphenol vapours for 6-8 hrs. The acute dermal
toxicity in rabbits and guinea pigs appear also to be low at >2000 mg/kg bw. Finally, the oral rat
LD50 is low at >2000 mg/kg bw (ECB, 2008).
Although the lethality of 4-tert-butylphenol is low for skin application, it can be severely irritating
and also corrosive to skin of rabbits with erythema, oedema, fissuring, desquamation and necrosis.
It is also highly irritating to rabbit eyes (e.g. Klonne et al., 1988). In addition, dissolved in DMSO
and in propylene glycol, 4-tert-butyl phenol has shown strong skin depigmentation potency in guin-
ea pigs (Gellin et al., 1970). Skin depigmentation has also been observed in workers handling 4-tert-
butyl phenol in industry. A systemic LOAEL of 103 mg/kg bw/day for skin depigmentation in orally
exposed mice has been developed (ECB, 2008).
4-tert-Butylphenol had no sensitisation potential in a modified Magnusson-Kligman test with guin-

ea pigs but some cross-reactivity between 4-tert-butyl phenol and 4-tert-butyl catechol was ob-
served (Zimerson, 1999). A 2% solution of 4-tert-butylphenol dissolved in petrolatum caused an
allergic reaction/skin sensitisation in at least 1% of groups of contact dermatitis patients (Jordan
and Dahl, 1972; Rudner, 1977) but apparently no reaction in healthy people.
The toxicity of 4-tert-butylphenol has been studied in the OECD 422 Combined Repeated Dose and
Reproductive/Developmental Toxicity Screening Test with administration by gavage. In the initial
dose-finding activity, daily doses of 250 mg/kg bw and higher during 14 days were causing respira-
tory distress. In the main study 8-week old male and female Sprague-Dawley rats (13 males and 13
females per dose level) were administered 4-tert-butylphenol by oral gavage in 0.5 % methyl cellu-
lose at daily doses of 0 (vehiclecontrol), 20, 60 and 200 mg/kg bw. The males were administered 4-
tert-butylphenol for 6 weeks, whereas the females were exposed from 14 days prior to mating to day
4 of lactation. Some females of the highest dose group showed respiratory stress with dyspnea but
no compound-related morphological changes were observed during pathological examination of
parental animals. However, there was high lethality in the offspring. In males there was a slight
increase in mean relative liver weight. Based on respiratory distress in exposed females and effects

on several blood parameters in male rats, the NOAEL for 4-tert-butylphenol in the study was estab-
lished at 60 mg/kg bw/day.
A two-generation reproduction study was carried out in Sprague-Dawley rats with 4-tert-
butylphenol given orally in the diet at the following concentrations: 0, 800, 2500 and 7500 ppm,
corresponding to approximately 0, 70, 200 and 600 mg/kg bw/day. In the parental generation, 28
rats per sex and group were used. The animals were exposed for 10 weeks prior to mating and until
termination of lactation. No treatment related clinical signs were reported but at the two highest
doses there was a decrease in body weight gain compared to controls (Clubb and Jardine, 2006). At
the termination of the experiment in the highest dose group, a statistically significant increase in
the weights of the kidneys and liver in males was reported, and in females a statistically significant
decrease in the weight of the adrenal gland and ovaries was reported following covariance analysis
with the body weight as the covariate. There was a significant increased incidence of minimal to
mild vaginal atrophy in high dose females and an increase in the incidence of primordial follicles. At
200 mg/kg bw/day a statistically significant decrease in the relative weights of ovaries was reported
in females, as well as reduced relative weights. The NOAEL for repeated dose toxicity was consid-
ered to be 70 mg/kg bw/day (800 ppm) from this study, based on a dose-dependent reduction of
relative weights of ovaries and adrenal glands in females. The results indicated that 4-tert-
butylphenol had no effect on fertility and induced no embryotoxicity or teratogenicity at the dose
levels tested. The NOAEL for fertility and developmental toxicity derived from this study was there-
fore ≥ 200 mg/kg bw/day.
The mutagenicity of 4-tert-butylphenol is likey to be absent. It was not observed in some in vitro
mutagenicity tests using Salmonella typhimurium strains TA100, TA1535, TA98, and TA1537
(Ames test), as well as using Escherichia coli WP2 uvrA. In addition, 4-tert-butylphenol had no
significant mutagenic potential in the mouse lymphomaTK+/- locus assay in L5178Y cells. It was
also not genotoxic in the in vivo mammalian erythrocyte micronucleus test (i.p. injection). Howev-
er, 4-tert-butylphenol induced chromosomal aberrations in Chinese hamster lung cells in the pres-
ence of an exogenous metabolic activation system (ECB, 2008).
Sufficient animal cancer studies are missing; however, 4-tert-butylphenol has, as many other phe-
nols, a promoting effect. After initiation with N-methyl-N’-nitro-N-nitrosoguanidine (MNNG) 4-
tert-butylphenol induced forestomach squamous cell carcinoma in F344 male rats.
4-tert-Butylphenol is a very weak endocrine disruptor. In the E-screen 4-tert-butylphenol induced

proliferation in human estrogen receptor-positive MCF-7 breast cancer cells but was 10 -30 times
less potent than nonylphenol and >100 000 times less active than the reference substance 17β-
estradiol (Soto et al., 1991, Körner et al., 1998).
“The recombinant Yeast screen assay” is an estrogen-inducible strain of yeast, Saccharomyces cere-
visia, expressing the human estrogen receptor. In this study 4-tert-butylphenol was shown to be a
weak estrogen disruptor and approximately 1,500,000 times less potent than 17β-estradiol to bind
to the human ER receptor. In comparison, 4-nonylphenol was 30,000-fold less potent than 17β-
estradiol (Routledge and Sumpter, 1997). The data indicated that both the position (para > meta >
ortho) and branching (tertiary > secondary = normal) of the alkyl group affect estrogenicity. Opti-
mal estrogenic activity requires a single tertiary branched alkyl group composed of between 6 and 8
carbons located at the para-position on an otherwise unhindered phenol ring.
6.5 AP/APEO of a chain length of more than nine

Among APs longer than nine, the most important is dodecyl phenol and its ethoxylates. Very little
toxicological information exists for this chemical; however, there is self classification information,
which indicates that…...

No toxicokinetics studies of these substances are available. The acute toxicity of dodecyl phenol is
low, determined as an oral rat LD50 of >2100 mg/kg and a dermal LD50 of >3000 mg/kg (Brooke et
al., 2007).
Dodecylphenol (90% p- and 10% o-) applied undiluted to rabbit skin for 24 hrs was severely irritat-
ing, and a moderate eye irritation was exhibited (Randall and Robinson, 1990)
A repeated exposure study of rats fed 500, 2500 and 5000 mg/kg dodecylphenol in the diet for 1
month showed decreased food intake and body weight and some blood changes in the two highest
groups. Males of the highest dose showed harmful effects on testes. The low dose of 500 mg/kg diet
was reported as the NOAEL value. Calculated as intake it was 33 mg/kg bw/d in males and 41
mg/kg bw/d in females (USEPA, 1989; Hass et al., 1994).
Dodecylphenol is not mutagenic in the Ames test with Salmonella typhimurium and in Chinese
hamster ovary cells and not active in a chromosome aberration test (USEPA, 1987; Hass et al.,
1994).
In a study of developmental toxicity, where pregnant rats were exposed to dodecyl phenol by gavage
in ten days during gestation, an embryotoxic effect was evident by an increase in the incidence of
uterine resorption. Foetotoxicity was evident by lower foetal weight and an increased incidence of
foetuses with ossification variations; however, these effects may be secondary to maternal toxicity
(USEPA, 1987; Hass et al., 1994).
6.6 Assessment across the groups

The shorter chain monoalkylphenols are more reactive substances than the longer-chain com-
pounds, potentially irritating and corrosive to skin, eyes and mucous membranes. These substances
are used as pure chemicals directly as intermediates in the process industry, while the longer chain
alkylphenols are complex mixtures of isomers and more used as their ethoxylates, which have dif-
ferent chemical, physical and toxicological properties, being glycol ethers and not phenols. Howev-
er, the ethoxylates may degrade and be transformed back to the phenols.
There is little information about the toxicities of the ethoxylates but because they are large mole-
cules, the availability for uptake in the body, and therefore also the toxicity, is low.
A main reason for the selection of alkylphenols for LOUS is likely the endocrine disruptive effects of
the long-chain members of the family. Alkylphenols with alkyl groups of more than C2 attached at 4-
(para-) position of the phenol showed properties very similar to that of estrogen. The available data
indicate that both the position (para > meta >ortho) and branching (tertiary > secondary = nor-
mal) of the alkyl group affect estrogenicity. Optimal estrogenic activity requires a single tertiary
branched alkyl group composed of between 6 and 9 carbons located at the para-position on an
otherwise unhindered phenol ring. It should therefore be underlined that the para- (4-) mono-
substituted homologues seem to be most active as endocrine disruptors, and 4-nonyl phenol and 4-
tert-octylpenol are the most potent of these.
In one study, phenol derivatives were examined by means of gene expression profiling based on
DNA microarray assays (Terasaka et al., 2006). For the data analysis a total of 120 genes were se-
lected, contributing to the statistical reliability. Among the alkylphenols tested, technical nonylphe-
nol - a mixture of NP with branched alkyl groups - showed the most activity, and exhibited stronger
estrogenic activity than straight chain 4-nonylphenol. Significantly high correlations to the profile
for estrogen were observed for 4-n-heptylphenol, 4-tert-octylphenol, and nonylphenol. p-Cresol
and 4-n-ethylphenol were not estrogenic. Therefore, the scientific documentation for keeping the
other alkylphenols on the list appears to be insufficient.

An estrogen receptor (ER) competitive-binding assay has been used to determine the ER relative
binding affinity for a large, structurally diverse group of 188 chemicals including alkylphenols of
various qualities (Blair et al., 2000). The data for alkylphenols are extracted and shown in Table 30
with estradiol as a reference.
TABLE 31
RELATIVE ESTROGEN RRECEPTOR BINDING AFFINITY AND MEAN INHIBITION CONCENTRATION OF ALKYLPHE-
NOLS AND ESTRADIOL
Substance Mean IC50 *1 Relative binding af-

Purity (%)
(M) finity (%)
17β-Estradiol Not available 8.99 x 10-10 100
4-Nonylphenol 95,6 2.40 x 10-6 0.037
4-Nonylphenol Tech 2.60 x 10-6 0.035
4-Nonylphenol 85 2.90 x 10-6 0.031
4-Nonylphenol Tech 3.05 x 10-6 0.029
4-Nonylphenol 85 4.73 x 10-6 0.019
4-Dodecylphenol 99,7 4.85 x 10-6 0.019
4-tert-Octylphenol 97 6.00 x 10-6 0.015
4-Octylphenol 99 1.95 x 10-5 0.005
4-n-Nonylphenol 98 2.80 x 10-5 0.0032
4-tert-Amylphenol 99 1.65 x 10-4 0.0005
4-sec-Butylphenol 96 2.10 x 10-4 0.00043
2-sec-Butylphenol 98 3.15 x 10-4 0.00029
4-tert-Butylphenol 99 3.68 x 10-4 0.00024
4-Ethylphenol 99 1.34 x 10-3 0.00007
*1 IC50 is the concentarion with 50% inhibition
Compared to estradiol, all alkylated phenols are weak endocrine disruptors in this test system.
Nonylphenol is the most active alkylphenol. The various mixtures/qualities (isomers, impurities) of
nonylphenol seem to have considerable effects on the activity. The ER activity declines with shorter
chain length and substances with ≤ C5 had insignificant activity.
The EU strategy for endocrine disruptors includes the task of compiling a candidate list of potential
endocrine disruptors that must be evaluated further for endocrine disrupting effects. In order to
prioritize the efforts, the substances on the list have been subdivided into a number of categories.
Nonylphenol and 20 other alkylated phenols as well as two nonylphenol ethoxylates are on the
candidate list in the EU of endocrine disruptors. The AP/APEOs included in the EU list are shown
in Table 32. For many of the substances no or insufficient data were available (CAT 3b) for the as-

TABLE 32
AP/APEO LISTED IN THE EU PRIORITY LIST OF POTENTIAL ENDOCRINE DISRUPTORS (EC, 2012)
CAS No No. of C Chemical name (as indicated in the Human Wildlife Overall
in alkyl chain list) health category
99-71-8 4 4-sec-Butylphenol CAT2 CAT2 CAT2
98-54-4 4 4-tert-Butylphenol CAT2 CAT2 CAT2
80-46-6 5 4-(tert-Amyl)phenol, 4-tert- - - -

Pentylphenol
87-26-3 5 2-sec-Pentylphenol, 2-(1- CAT3b - CAT3b

Methylbutyl)phenol
1131-60-8 6 4-Cyclohexylphenol CAT1 CAT3b CAT1
949-13-3 8 2-Octylphenol CAT3b CAT3b CAT3b
1806-26-4 8 4-Octylphenol CAT 1 CAT 1 CAT 1
11081-15-5 8 4-Isooctylphenol CAT 1 CAT 1 CAT 1
26401-75-2 8 2-sec-Octylphenol CAT3b CAT3b CAT3b
27214-47-7 8 4-sec-Octylphenol CAT3b - CAT3b
27193-28-8 8 Octylphenol (mixture of tert- CAT 1 CAT 1 CAT 1

Octylphenol isomers)
140-66-9 8 4-tert-Octylphenol, 4-(1,1,3,3- CAT 1 CAT 1 CAT 1

Tetramethylbutyl)phenol
3884-95-5 8 2-tert-Octylphenol, 2-(1,1,3,3- CAT3b CAT3b CAT3b

Tetramethylbutyl)phenol
27985-70-2 8 (1-Methylheptyl)phenol, (mix of iso- CAT3b CAT3b CAT3b

mers)
18626-98-7 8 2-(1-Methylheptyl)phenol CAT3b CAT3b CAT3b
1818-08-2 8 4-(1-Methylheptyl)phenol CAT3b CAT3b CAT3b
17404-44-3 8 2-(1-Ethylhexyl)phenol CAT3b CAT3b CAT3b
3307-00-4 8 4-(1-Ethylhexyl)phenol CAT3b CAT3b CAT3b
3307-01-5 8 4-(1-Propylpentyl)phenol CAT3b CAT3b CAT3b
37631-10-0 8 2-(1-Propylpentyl)phenol CAT3b CAT3b CAT3b
25154-52-3 9 Nonylphenol (mixture of isomers) CAT1 CAT1 CAT1
104-40-5 9 4-Nonylphenol (4-NP) CAT 1 CAT 1 CAT 1
9016-45-9 9 Nonylphenol ethoxylates (NPEO, CAT2 CAT1 CAT1

mixture, polymeric)
20427-84-3 9 4-Nonylphenol diethoxylate (NP2EO), CAT2 CAT2 CAT2

2-[2-(4-nonylphenoxy)ethoxy]ethanol
CAT 1: Evidence of endocrine disrupting activity in at least one species using intact animals.
CAT 2: At least some in vitro evidence of biological activity related to endocrine disruption
CAT 3b: No or insufficient data available.

6.7 Summary on human health effects
Most available data have been generated from animal studies with oral administration and from in
vitro tests. Some data are rather old and of low quality. There are no data on the toxicity of al-
kylphenol ethoxylates but these polymers are less bioavailable and therefore not toxic; however,
they may be metabolised to the alkylphenols.
The short-chain alkylated phenols are highly acutely toxic, with toxicity decreasing with the length
of the alkyl chain, and nonylphenol is only moderately acutely toxic. All the alkylphenols are irritat-
ing or corrosive to the skin, eyes and mucous membranes. 4-tert-Butylphenol may cause skin
depigmentation.
The available toxicity data for long-chain alkylphenols other than nonylphenol are rather limited,
and data on the ethoxylates are nearly absent. Only 10-20% of an administered dose of nonylphenol
is absorbed following oral exposure. It accumulates in the fat and the major metabolic pathways are
likely to involve glucuronide- and sulfate conjugation and excretion with faeces and urine. Humans
and animals differ with having more excretion via urine and faeces, respectively.
The critical effects for nonylphenol and other long-chain alkylphenols are endocrine disruptions
and effects on reproduction and fertility. There is evidence that nonylphenol, 4-tert-octylphenol and
dodecylphenol has in vitro and in vivo estrogenic activity but is 3-6 orders of magnitude less potent
than estradiol. The effects of nonylphenol on fertility and reproductive performance have been
investigated in a good quality oral (dietary administration) multi-generation study in the rat. This
study provided evidence that nonylphenol exposure over several generations can cause minor per-
turbations in the reproductive system of offspring, namely slight changes in the estrous cycle length,
the timing of vaginal opening and possibly also in ovarian weight and sperm/spermatid count, alt-
hough functional changes in reproduction were not induced at the dose levels tested. The NOAEL
for these changes was 15 mg/kg/day. The observed perturbations in offspring are compatible with
the predictable or hypothesised effects of exogenous estrogenic activity. Data also indicate that
specifically pure 4-n-nonylphenol may have an effect on the function of the placenta.
The main data gaps concern:
• Toxicity data for long-chain alkylphenols other than nonylphenol are limited and data on al-
kylphenol ethoxylates are nearly absent;

7. Monitoring data and expo-
sure
7.1 Monitoring of AP/APEO in the environment in Denmark and re-

leases from point sources
The national environmental monitoring and assessment programme, NOVANA, includes measure-
ments of six AP/APEO substances or substance groups in point sources and streams and three sub-
stances in groundwater (Table 33).
TABLE 33
AP/APEO INCLUDED IN THE NATIONAL MONITORING AND ASSESSMENT PROGRAMME FOR THE AQUATIC AND
TERRESTRIAL ENVIRONMENT, NOVANA 2011-2015 (NOVANA, 2011)
Substance Point sources Streams Ground water
Nonylphenols , ∑ x x x
4-nonylphenol x x
Nonylphenol monoethoxylates x x x
Nonylphenol diethoxylates x x x
Octylphenols, ∑ x x
4-tert-octylphenol x x
The monitoring of ground water and water from water work wells carried out by the Geological
Survey of Denmark and Greenland (GEUS) includes measurements of NP and for some years NPEO
(GEUS 2009; 2011).
7.1.1 AP/APEO in the environment
Results from the NOVANA programme

The most recent data on AP/APEO from the NOVANA programme are summarised in Table 34.
In 2008, nonylphenol was found in all samples of lake sediment at concentrations where the sub-
stances may have an environmental effect as the concentration exceeded the predicted no-effect
concentration (PNEC) (Nordemann Jensen et al., 2009). The median concentration was 0.57
mg/kg dw. Octylphenol was found in most samples but at a significantly lower concentration. The
concentration of nonylphenol was higher than reported in previous NOVANA reports. The reports
for 2001 and 2o03 both indicate a median concentration of 0.1 mg/kg while the maximum values
were 0.34 mg/kg and 0.27 mg/kg, respectively (Jensen et al., 2003, 2004).
In marine sediments the median concentration of NP was measured at 0.063 mg/kg dw, nearly 10
times lower than the concentration in the lake sediments. The concentration of NPEO is reported to
be at the same level as the NP while the concentration of OP was significantly lower (Petersen and
Hjort, 2010). The exact figures are not reported.

In stream sediments the concentration of nonylphenol monoethoxylates and diethoxylates were
below the detection level of 0.1 mg/kg while octylphenols and 4-tert-octylphenol were found in 5 of
11 samples at 0.036 and 0.0035, respectively (Wiberg-Larsen, 2010). The concentrations were not
compared to PNEC values.
TABLE 34
MOST RECENT MONITORING DATA FOR AP/APEO IN THE ENVIRONMENT FROM THE NATIONAL MONITORING AND
ASSESSMENT PROGRAMME, NOVANA
Substance Medium Number of Median (maxi- PNEC value Year Source

samples *1 mum) concentra- mg/kg dw
tion, mg/kg dw
Nonylphenol Lake sediment 25 (25) 0.57 (4.2) 0.039 *2 2008 Nordemann Jen-
sen et al., 2009
Nonylphenol Sea sediment 29 (13) 0.063 (0,69) not reported 2009 Petersen and
Hjort, 2010
Octylphenol Lake sediment 25 (25) 0.004 (0.088) 0.063 *2 2008 Nordemann Jen-
sen et al., 2009
Nonylphenol Stream sedi- 21 (0) all samples <0.1 not reported 2009 Wiberg-Larsen,
mono- ment 2010
ethoxylates
Nonylphenol Stream sedi- 21 (0) all samples <0.1 not reported 2009 Wiberg-Larsen,
di-ethoxylates ment 2010
Octylphenol Stream sedi- 21 (5) not reported not reported 2009 Wiberg-Larsen,
ment (0,036) 2010
4-tert- Stream sedi- 21 (5) not reported not reported 2009 Wiberg-Larsen,
octylphenol ment (0,0035) 2010
*1 Number of positive samples in brackets

*2 Reference is in made to the EU Risk Assessment Report (ECB, 2002) in Nordemann Jensen et al. (2009).
7.1.2 Groundwater
The limit values for the sum of NP and OP in ground water in Denmark are 20 µg L (Danish EPA,
2010). For other phenol compounds the limit value is 0.5 µg/L for each.
In 730 samples from water works wells from the period 1993-2003 APs were found in concentration
above the detection limit in 4% of the samples (GEUS, 2004). In none of the samples the concentra-
tion exceeded the limit values. In 839 samples of water from water works wells from 2007-2010,
nonylphenol was found in concentrations above 0.5 µg/L in 13 samples (GEUS, 2011). In 585 sam-
ples of ground waste from 2007-2008 NPEO was not found in a concentration above the detection
limit in any of the samples (GEUS , 2010). Data for other APs in ground water in Denmark have not
been identified.
A pan-European survey of the occurrence of other selected polar organic persistent pollutants in
ground water from 2011 presents data for nonylphenol (NP), tert-octylphenol and nonylphenoxy
acetic acid (NPE1C) (Loos et al., 2010). NPE1C is a transformation product of NPEO. The survey
includes ground water samples from Denmark and 22 other EU Member States from a total of 164
locations, but the data are not presented by country.
NPE1C was among the most relevant compounds detected, with a frequency of detection of 42%,
and a maximum concentration level of 11.3 mg/L. The monitoring results on NPE1C in ground water

supports according to the authors, findings by other studies and show that the NPEO carboxylates
(NPECs) are persistent chemicals wide spread in European ground waters (Loos et al., 2010). In a
sister study of the same pollutants in rivers, NPE1C was above the detection limit of 2 ng/L in 97%
of the samples and the median concentration of 553 ng/L was the highest for the analysed organic
persistent pollutants (Loos et al., 2009).
TABLE 35
OCCURENCE OF NP, 4-TERT-OP AND NPE1C IN GROUND WATER ACROSS THE EU (LOOS ET AL., 2010)
Chemical Limit of Freq. of Max Average Median 90th per-

detection, detection ng/L ng/L ng/L centile
ng/L (%), ng/L
Nonylphenol (NP) 30.0 11.0 3,850 83 0 39
4-tert-Octylphenol 0.4 23.2 41 1 0 2
Nonylphenoxy acetic 0.5 41.5 11,316 263 0 127

acid (NPE1C)
7.1.3 AP/APEO in point sources

The most recent monitoring data concerning municipal waste water treatment plants (MWWTP),
industrial sources and rainwater outlets from the NOVANA programme are shown in the table
below.
TABLE 36
MOST RECENT MONITORING DATA FOR AP/APEO IN OUTLET FROM POINT SOURCES FROM THE NATIONAL MONI-
TORING AND ASSESSMENT PROGRAMME
Substance Point Number of Average Median Year Source

source samples *1 µg/L µg/L
Nonylphenols MWWTP 35 (10) 0.065 < d.l. 2007-2009 Naturstyrelsen,

2010
Nonylphenols MWWTP 6 (1) 0.06 < d.l. 2009-2010 Naturstyrelsen,

2011
Nonylphenol monoeth- MWWTP 36( 3) 0.007 < d.l 2007-2009 Naturstyrelsen,

oxylates 2010
Nonylphenol monoeth- Industrial 25 (n.i) 1.77 < d.l. 2006-2009 Naturstyrelsen,

oxylates 2010
Nonylphenol diethox- Industrial 26 (n.i) 1.97 < d.l. 2006-2009 Naturstyrelsen,

ylates 2010
Nonylphenols Rainwater 49 (n.i) 0.04 < d.l. 2007-2010 Naturstyrelsen,

outlets 2011
Octylphenol MWWTP 190 (8%) not reported not re- 2003 Danish EPA,
93% of sam- ported 2004
ples below o.1
*1 Number of positive samples in brackets

<d.l. : Below detection level. n.i.: not indicated

National mean concentrations based on the results from the Danish national environmental moni-
toring programme (NOVANA) for the period 1998-2009 are described in section 4.3 on releases
from waste water treatment plants. Compared with the nation mean concentrations shown in Table
22, the average NP concentration of 0.06 µg/L is significantly lower than the national mean of 0.24
µg/L. Also for the nonylphenol monoethoxylates the measured average is below the nation mean of
0.057 µg/L. Both could indicate a decreasing trend in the concentration.
7.2 European Pollutant and Transfer Register (E-PRTR)

The European Pollutant Release and Transfer Register (E-PRTR) contains annual data reported by
some 28,000 industrial facilities in 27 EU Member States as well as Iceland, Liechtenstein, Norway,
Serbia and Switzerland. NP/NPEO and OP/OPEO are among the 91 pollutants covered by the re-
porting. The requirements for reporting are established by the PRTR Regulation (Regulation (EC)
No 166/2006).
Data from the E-PRTR for NP/NPEO show that waste and waste water management account for 61
t/y of the total registered release to water in the EU27 of 63.6 t/y. Other main sources are the ener-
gy sector (0.3 t/y) and production and processing of metals (0.7 t/y).
For OP/OPEO the E-PRTR data show similarly that releases from waste and waste water manage-
ment account for nearly 100% of the registered 13.2 t/y released to water from point sources in the
EU27 in 2010. The registered emissions from all other point sources including the chemical indus-
try total less than 0.1 t/y. The registered emissions to air and soil are 0.
The E-PRTR does not included point source data from any point sources in Denmark.
7.3 AP/APEO in the Baltic Sea and North Sea environments

The status of nonylphenol, 4-n-octylphenol and 4-tert-octylphenol in sediment, biota and water in
the Baltic Sea has been reviewed by HELCOM (2010). The primary source of NP found in the Baltic
environment is considered to be NPEOs, which can break down into NP in wastewater treatment
plants or in the environment. Sediment measurements showed that concentrations of 4-iso-
nonylphenol or unidentified NPs in the surface sediment exceeded the PNEC (predicted no effect
concentration) level in the Northern Baltic Proper and the South Western Baltic Sea. As it appears
from the maps shown in Figure 9, the concentration of NP in sediments from the Inner Danish
Waters is generally significantly higher than the concentration in the Baltic Sea. Concentrations of
octylphenol in surface sediment were high compared to the threshold concentration, with 50% of 4-
n-octylphenol samples and 65% of 4-t-octyphenol samples exceeding the threshold concentration
for the substance suggested in the context of the Water Framework Directive (see reference in figure
caption). The deep sediments in the Northern Baltic Proper contained levels 30 times higher than
the threshold concentration.
Fish is not an appropriate matrix for monitoring nonylphenol, octylphenol and their ethoxylates
because they are metabolized in fish (HELCOM, 2010).
The report ”Hazardous substances of specific concern to the Baltic Sea” from HELCOM (2009)
includes a broader review of NP/NPEO and OP/OPEO production and use, discharges, concentra-
tions in the environment, data gaps, etc. The conclusions regarding data gaps are exactly the same
for NP/NPEO and OP/OPEO. For OP/OPEO the conclusion reads: “In general, there should be
more measured data on OP/OPE levels both in discharges in the catchment area, and in sea wa-
ter, biota and sediment of the Baltic Sea to examine if OP/OPE causes harmful effects on the ma-
rine environment. While few available data indicate that the OP levels in biota (fish) are not high,
the levels in the sediment may have adverse effects on the Baltic marine environment. In general,
the measured OP levels in treated municipal wastewater may cause both acute and chronic effects
in recipient waters. Thus information on both the occurrence of OP (and OPE) in the in sea water,
biota and sediment of the Baltic Sea and its presence in discharges (e.g. WWTPs, landfills and
waste sorting sites) in the Baltic Sea catchment area is greatly needed. There is also need for eco-

toxicological data on sediment dwelling organisms in order to better define the OP PNEC estimate
for the benthic community.”
FIGURE 9
STATUS OF NONYLPHENOL, 4-N-OCTYLPHENOL AND 4-TERT-OCTYLPHENOL IN SEDIMENT, BIOTA AND WATER IN THE INNER DANISH
WATERS AND THE BALTIC SEA. THE THRESHOLD CONCENTRATIONS FOR SEDIMENT AND BIOTA ARE FROM
ANON. (2005), AND FOR WATER FROM THE EU PRIORITY SUBSTANCE DIRECTIVE (DIRECTIVE 2008/105/EC) (HELCOM, 2010)
Screening of selected phenolic substances in the Nordic environment

A screening of selected phenolic substances in the Nordic environment was initiated by the Nordic
Chemicals Group and financed by the Nordic Council of Ministers. All six Nordic countries partici-
pated in the project that included the sampling and analysis of 120 samples from different environ-
mental compartments (Hansen and Lassen, 2008). The study included the analyses of 13 different
phenolic compounds including tert-butylphenols, di-tert-butylphenol, octyl-, nonyl- and dodecyl
phenols) octyl- and nonylphenol mono-ethoxylates. The results are shown in Annex 4 and summa-
rised as follows by Hansen and Lassen (2008).
Overall, recipient water and background water samples did, however, have relatively low concentra-
tions of most substances. NP-mix, dodecylphenol and nonylphenol monoethoxylate were present in
detectable amounts, and surface water from Tórshavn had the highest estimated concentrations of
NP-mix.
In the background sediments samples from Kattegat and Oslo fjord, NP-mix, NP, 4-tert-BP and
NP1EO was found in concentrations above the detection limits. In some sample sediments from
recipient environments, other substances could be found in relatively high concentrations of several
hundred µg/kg.
The NP-mix (various nonylphenol isomers), dodecylphenol, 4-tert-octylphenol and nonylphenol

monoethoxylate were those AP/APEO substances found in highest concentrations in all sewage
water samples.

The sludge samples demonstrated the highest content of the analysed substances, and in terms of
the sewage water samples, NP-mix and dodecylphenol were detected in the highest concentrations,
whereas the ethoxylates had been significantly reduced. Compared to sludge, both soil from landfill
sites and sediments were low in concentrations of most AP/APEO.
Sources of AP/APEO to the Baltic Sea

Within the framework of the multilateral project “Control of Hazardous Substances in the Baltic Sea
Region”, sources of NP, NPEO, OP and OPEO to the Baltic Sea environment have been analysed
(COHIBA, 2012). Substance flow diagrams for the four substances are shown in Annex 4.
According to the study, the majority of the emissions of NP and NPEO to the Baltic environment are
distributed to surface waters. The NP and NPEO emissions into the Baltic environment mainly
come from industrial sources in Lithuania and Poland, whereas in the other countries, municipal
waste water treatment plants (MWWTPs) are the dominant sources (described in section 4.2).
According to the COHIBA study, a small fraction of the emissions of OP and OPEO in the Baltic
area is distributed to air and the main part is rather evenly distributed to surface waters and land
areas. The yearly loads differ significantly between countries, also on a per capita basis. The emis-
sions were dominated by releases of OP from the product service life category, where the main
source was emissions from abrasion from tyres, which represent almost 100% of the reported emis-
sions in this category. Industrial sources include the use of OP-based resins in insulation varnishes
(about 50% of the industrial emissions) in Poland and Germany and the manufacture of OP-based
resins (about 10% of the industrial emissions) in Poland and perhaps Estonia.
Emissions from MWWTPs were of some relevance for OP and OPEO in all of the Baltic countries.
The emissions to wastewater primarily originate from private washing of textiles containing OPEO,
which represents 30-50% of the total emissions to wastewater.
The North Sea Environment

Three alkylphenols on the OSPAR List of Chemicals for Priority Action, nonylphenol, octylphenol
and 2,4,6-tri-tert-butylphenol. OSPAR chemicals identified for priority action have most recently
been assessed in the OSPAR quality status report of 2010 (OSPAR, 2010), but the report does not
include a summary for the APs.
The updated OSPAR background document for NP from 2009 states that recent monitoring data
about the occurrence of AP/APEO in the aquatic environment in the North Atlantic were hard to
find in the literature (OSPAR, 2009).
A background document for 2,4,6-tri-tert-butylphenol was developed in 2006 (OSPAR, 2006). In

response to the call for a monitoring strategy, the UK as a lead country for the substance has devel-
oped a strategy and carried out a one-off survey on 2,4,6-tri-tert-butylphenol in sediments in indus-
trial estuaries around the UK coast. A number of samples were below the detection limit, but there
were also several positives ranging from 0.01 to 0.09 mg/kg of dry sediment (OSPAR, 2009).
7.4 Human exposure and biomonitoring
7.4.1 Intake of AP/APEO

Tolerable daily intake
A tolerable daily intake (TDI) value has not been established at EU level. Nielsen et al. (2000) from
the Danish Institute of Food Safety and Toxicology, Danish Veterinary and Food Administration
(now DTU Food – National Food Institute) have set health based TDI values for NP at 0.005 mg/kg
b.w./day and for NPEO at 0.013 mg/kg b.w./day.

No other studies have been obtained.
TDIs for other AP or APEO have not been obtained.
AP/APEO in food
Alkylphenols and their ethoxylates are not included in the monitoring of chemical contaminants in
food in Denmark. No data on the content of nonylphenol or any other AP/APEO in food, or esti-
mates of the total intake of the substances with food in Denmark have been obtained.
The EU Risk Assessment for NP and NPEO states that no estimates of dietary exposure to
nonylphenol using EU data are available (ECB, 2002). The EU Risk Assessment for butylphenol
does not include monitoring data on butylphenol in food.
Guenther et al. (2002) analyzed NPs in 60 different food items commercially available in Germany.
The concentrations of NPs on a fresh weight basis varied between 0.1 and 19.4 µg/kg regardless of
the fat content of the foodstuff. Based on data on German food consumption rates and the analyses
of NPs in food, the daily intake of NP for an adult was calculated to be 7.5 µg/day. For infants exclu-
sively fed with breast milk or infant formulas daily intakes of 0.2 µg/day and 1.4 µg/day, respective-
ly, was estimated. For an adult of 60 kg the estimated TDI would correspond to an intake of 0.3 mg
NP/day which is 40 times more than the intake calculated by Guenther et al. (2002).
Gyllenhammer et al. (2012) has recently analysed NP in Swedish food and exposure of Swedish
nursing women. In food, NP was to some extent found at levels above limit of quantification (LOQ
20 µg/kg fresh weight) in fruits, cereal products, vegetables, and potatoes. The estimated mean NP
intake per capita was 27 μg/day (medium estimate) i.e. about four times higher than the intake
estimated by Guenther et al. (2002) but still significantly below the estimated TDI. In blood serum,
free NP above the limit of detection (limit of detection 0.5 ng/g) was detected in 46% of the study
participants while detectable levels of total NP (limit of detection 0.8 ng/g) were observed in 43%.
The results indicate according to the authors that there is a continuous source of exposure to NP
that is high enough for free NP to be detected in some consumers. A significantly higher total con-
sumption of fruits and vegetables was reported in questionnaires by participants with NP levels at
or above LOD than among women with levels below LOD. This result is supporting the market
basket results of relatively high NP levels in these types of food.
Ferrara et al. (2008) reports data on AP and APEO in seafood from the Tyrrhenian Sea. Of the
measured AP and APEO, NP was generally detected at the highest concentrations. On the basis of
the results of the study, the daily intake of NPs was according to the authors estimated to be much
lower than the TDI proposed by the Danish Institute of Food Safety and Toxicology.
A Norwegian risk assessment of contaminants in sewage sludge applied to Norwegian soils esti-
mates total intake with food from soils after 100 years’ use of sewage sludge but does not provide
data on the present situation (VKM, 2009).
Food contact materials

A significant source of the AP and APEO in food may be migration from food contact materials.
The Risk Assessment for nonylphenol (ECB, 2002) estimates that the main exposure to nonylphe-
nol from food contact materials is via 4-nonylphenyl phosphite (TNPP). Nonylphenol is used in the
production of TNPP, which is used as a co-stabiliser and as an antioxidant in the synthesis of vari-
ous polymers such as butadiene rubber, polystyrene, polyethylene and polyvinylchloride. It is also
used in the production of food contact plastics. Nonylphenol is present in TNPP as a residual impu-
rity and can be formed as a result of acid hydrolysis of TNPP. The Risk Assessment estimates the

worst case potential exposure from food contact materials at 0.06 mg NP/day. NPEO in paper and
paperboard (now restricted) was estimated to potentially contribute with another 0.08 mg NP/day.
The EU Risk Assessment for 4-tert-butylphenol (4-tert-BP; ECB, 2008) states that the potential
consumer exposure is via direct use of mixtures with phenolic resins or epoxy resins containing
residual 4-tert-BP monomers, or via use of the final articles containing residual concentration of 4-
tert-BP. The main exposure from final products is expected to be from adhesives and possibly
canned food. Consumers may also be exposed to 4-tert-BP in drinking water from drinking water
reservoirs or pipelines and from polycarbonate used for food contact material. Some exposure may
also occur from various consumer articles such as cosmetics, eyeglass frames, tooth- and hair
brushes, and hearing aids; however, exposure from these products is considered to be low. The
main routes of exposure to consumer products are by dermal contact (e.g. use of adhesives) and by
ingestion of food products into which 4-tert-BP has migrated from the food/water container or
packaging (e.g. food contact applications). For humans exposed indirectly from the environment,
the main exposure is expected to be from ingestion.
Other sources of exposure to NP

The EU Risk Assessment for 4-nonylphenol mentions that consumers may be exposed to low levels
of residual, unreacted nonylphenol NP in consumer products (ECB 2002). Furthermore, NP may be
present at very low levels in pesticides, cosmetics, spermicides and pharmaceutical preparations
(now restricted). The EU Risk Assessment concludes that even considering these exposures together
on a daily basis, there is no concern for human health.
AP/APEO used as food additives

Some of the short-chained APs are used as food additives and have been evaluated by the European
Food Safety Authority, EFSA. In a scientific opinion of EFSA Panel on Food Additives and Nutrient
Sources added to Food on the use of 2,6-di-tert-butyl-p cresol (BHT, butylated hydroxytoluene) the
Panel concludes that BHT is not of concern with respect to genotoxicity and that any carcinogenicity
would be thresholded (EFSA, 2012). On the basis of the present database the Panel derived an up-
dated Acceptable Daily Intake (ADI) of 0.25 mg/kg bw/day. Exposure of adults to BHT is unlikely
to exceed the newly derived ADI at the mean and at the 95th percentile. For exposure of children to
BHT from its use as food additive, the Panel noted that it is also unlikely that this ADI is exceeded at
the mean, but is exceeded for some European countries (Finland, The Netherlands) at the 95th
percentile.
Drinking water
The limit values for the sum of NP and OP in drinking water when leaving the water works in Den-
mark are 20 µg L (Statutory Order 1024 of 31/10/2011). The same value applies to ground water
(Danish EPA, 2010). For other phenol compounds the limit value is 0.5 µg/L for each.
In 730 samples from water works wells from the period 1993-2003 APs were found in concentration
above the detection limit in 4% of the samples (GEUS, 2004). In none of the samples the concentra-
tion exceeded the limit values. In 839 samples of water from water works wells from 2007-2010,
nonylphenol was found in concentrations above 0.5 µg/L in 13 samples (GEUS, 2011). In 585 sam-
ples of ground waste from 2007-2008 NPEO was not found in a concentration above the detection
limit in any of the samples (GEUS , 2010).
Data for other APs have not been identified.
7.4.2 Human biomonitoring data
No human biomonitoring data from Denmark have been obtained.

Alexandros et al. (2012) has recently reviewed trends in biomonitoring of bisphenol A, 4-t-
octylphenol, and 4-nonylphenol and the following is to a large extent extracted from this review, but
information from some of the original papers and on other AP/APEOs is added.
Studies concerning AP/APEO exposure assessment and epidemiology studies on human population
are limited.
Calafat et al. (2008) measured 4-tert-octylphenol (4-t-OP) in urine samples from a population of
2,517 subjects in the USA National Health and Nutrition Examination Survey (NHANES). The sub-
jects were above the age of 6 years. 4-t-OP was detected in 57.4% of the participants with total (free
plus conjugated species) concentrations ranging between 0.2 ng/mL and 20.6 ng/mL.
Tan and Mohd (2003) measured 4-t-OP in 180 cord blood samples collected during delivery at the
University Malaya Medical Centre in Malaysia; 4-t-OP was detected in 31 samples in concentrations
from <0.05 to 1.15 ng/mL.
Ademollo et al. (2008) studied the presence of 4-NP, 4-OP, nonylphenol monoethoxylate and two
octylphenol ethoxylates (OP1EO and OP2EO), in breast milk in samples from Italian women. NP
was the contaminant found at the highest levels with mean concentrations of 32 ng/mL, about two
orders of magnitude higher than OP (0.08 ng/mL), OP1EO (0.07 ng/mL) and OP2EO (0.16
ng/mL). On the basis of the concentrations found in the breast milk samples, a maximum NP daily
intake of 3.94 μg/kg bw/day was calculated (=0.004 mg/kg bw/day). This is only slightly below the
estimated TDI. No newer studies to confirm this result has been identified.
Chen et al. (2010) determined 4-NP and 4-OP in 59 human milk samples in Central Taiwan and
correlated findings with demographics and dietary factors. Women who consumed over the median
amount of cooking oil had significantly higher 4-OP concentrations (0.98 ng/mL) than those who
consumed less (0.39 ng/mL). NP concentration was also significantly associated with the consump-
tion of fish oil capsules.
Lopez-Espinosa et al. (2009) also determined 4-NP and 4-OP concentrations in adipose tissue of 20
non-occupationally exposed women living in Southern Spain. 4-NP and 4-OP were detected in
100% and 23.5% of subjects, respectively. The median level of 4-NP was 57 ng/g and that of 4-OP
was 4.5 ng/g of adipose tissue. The study found that body mass index was associated with 4-NP
levels.
7.5 Summary regarding monitoring and exposure

Monitoring data from recent years have demonstrated that the concentration of NP in lake sedi-
ments in Denmark and in marine sediments from the Baltic Sea and the Inner Danish Waters ex-
ceeded the predicted no-effect concentration (PNEC).
OP was found in both lake sediments and marine sediments, but at lower concentration. HELCOM,
however, concludes in the most recent assessment report that the concentrations of OP in surface
sediment were very high, with 50% of 4-n-octylphenol samples and 65% of 4-tert-octyphenol sam-
ples exceeding the threshold concentration for the substance suggested in the context of the Water
Framework Directive.
Other AP/APEO are not monitored but have been assessed as part of the Nordic survey. In general
the concentrations of the other AP/APEO are considerably lower than the NP concentration, but in
some recipient environments (e.g. close to towns) the level of the 4-tert-BP and DP may be in the
same range as the concentration of NP. In general limited data are available on the sources of 4-
tert-BP and DP to the aquatic environments and the possible environmental risks of the actual
concentrations.

A review from HELCOM concludes that in general, there should be more measured data on
NP/NPEO and OP/OPEO levels in discharges in the Baltic Sea catchment area, in sea water, biota
and sediment of the Baltic Sea to examine if the substances cause harmful effects on the marine
environment. There is also need for ecotoxicological data on sediment dwelling organisms in order
to better define the NP and OP PNEC estimates for the benthic community.
AP/APEOs are not included in the monitoring of chemical contaminants in food in Denmark and
very limited data on the intake with food is generally available. Daily intake estimated on the basis
of food data indicates that the intake of NP via food is well below the tolerable daily intake (TDI)
established by the Danish Institute of Food Safety and Toxicology. A recent Swedish measure rela-
tively high NP levels in fruit and vegetables and estimate to total daily intake with food to be higher
than reported in previous studies. Some estimates on the basis of biomonitoring data indicate that
the intake may be close to the TDI and further are needed to clarify if the total intake from all
sources is close to the TDI for NP.
For other AP/APEO hardly any data are available on the intake with food reflecting that AP/APEO
in food has not been of major concern.

8. Information on alternatives
Information on existing assessments of alternatives to AP/APEO is summarised in this chapter.
8.1 Alternatives to alkylphenol ethoxylates

The majority of the literature on alternatives to AP/APEO concern alternatives to the use of the
alkylphenol ethoxylates, particularly the NPEO and OPEO, which are responsible for the majority of
the releases of AP/APEO to the environment.
As described in chapter 2, the following uses of NPEO are restricted via Annex XVII to the REACH
Regulation, with exceptions for uses in closed systems: Cosmetics, cleaning agents, textiles and
leather processing auxiliaries, agricultural teat dips and pesticides/biocides, metal works, pulp and
paper, and other personal care items except spermicides. No restriction on the use of OPEO is in
force at EU level.
According to the OSPAR background document for NP/NPEO, the substitutes introduced for the
use area “detergents and cleaning agents” are mainly alcohol ethoxylates (OSPAR, 2009). In terms
of environmental risk, alcohol ethoxylates appear to present a clear advantage over NPEs, mainly
owing to issues of biodegradability. According to industry quoted by OSPAR (2009), the substitutes
in the use area ‘detergents and cleaning agents for domestic and industrial uses’ are mixtures of
anionic and nonionic surfactants, such as linear alcohol ethoxylates, fatty acids and derivatives,
fatty amines or unsaturated hydrocarbons. OSPAR (2009) reports that according to the paint indus-
try in Sweden, mostly fatty alcohol ethoxylates, but also esterified linseed oil, different kinds of
nonionic tensides, phosphate esters, and potassium polycarboxylates are used as alternatives to
alkylphenol ethoxylates in the binding polymer emulsion of water-based paints. According to the
adhesive industry, fatty alcohol ethoxylates are mostly used as alternatives in the polymer emulsion
of water- based adhesives. The major difficulties are in replacing NPEs in acrylic and chloroprene
rubber dispersions. According to the adhesive industry, fatty alcohol ethoxylates are mostly used as
alternatives in the polymer emulsion of water- based adhesives; the major difficulties are in replac-
ing NPEs in acrylic and chloroprene rubber dispersions. The document concludes that alternatives
seem to be available for many NPEO uses, though information was not found on specific alterna-
tives to some uses.
The US EPA Design for the Environment (DfE) Program presents a recent assessment of alterna-
tives to NPEOs (US EPA DfE, 2012). Based on information from surfactant and cleaning product
manufacturers who have partnered with US EPA's DfE programme, the NPEO alternatives selected
for assessment were comparable to NPEO in cost and performance, especially when viewed as part
of a detergent system. According to the study, formulators will often replace an NPEO surfactant
with a blend of two or more surfactants (e.g. a linear alcohol ethoxylate plus an alkyl glycoside).
Depending on product type, a change in surfactant may also prompt other ingredient or formulary
adjustments.
The US EPA DfE (2012) assessed nine alternatives to NPEO surfactants, one from each of the major
surfactant classes DfE has seen in its evaluation of detergent and cleaning products in its Safer
Product Labelling Program. Note that the surfactant uses involved also included uses which are
currently regulated in the EU though the use restriction in Annex XVII to REACH.

DfE selected the ten featured chemicals — NPEO9 (CAS No 127087-87-0 with 9 oxylate groups),
octylphenol ethoxylate (OPEO)10 (CAS No 9036-19-5 with 10 oxylate groups), and the eight alterna-
tives which are considered as safer representatives of their surfactant class and based on:
• the availability of an adequate dataset (i.e. sufficient experimental data to address all end-
points in the DfE Criteria for Safer Surfactants); and, except for NPEO9 and OPEO10,
• frequent use in DfE-recognized formulations, and/or inclusion on the CleanGredients® web-
site of safer surfactant alternatives.
The substances were assessed on the basis of the following environmental characteristics:
• rate of aerobic biodegradation,
• hazard profiles of the degradation products, and
• degree of aquatic toxicity of the parent compound and degradation products.
Since the surface active nature of surfactants causes toxicity to aquatic organisms, the criteria weigh
these characteristics holistically and require that surfactants with higher aquatic toxicity demon-
strate a faster rate of biodegradation without degradation to products of concern.
An overview of the assessment results from US EPA DfE (2012) can be seen in Table 37.
The alternatives in general have a better score in terms of degradation products of concern and
persistence in the environment. The acute and chronic aquatic toxicity of the alternatives are at the
same level of toxicity of the NPEO and OPEO or even higher. According to US EPA DfE (2012)
OPEO is more persistent in the environment than NPEO.
The report does not discuss the technical or economic feasibility of the alternatives for different
applications.

TABLE 37
OVERVIEW OF THE ASSESSMENT OF NPEO AND SELECTED ALTERNATIVES TO NPEO FROM EACH OF 9 SUBSTANCE
CLASSES (US EPA DFE, 2012)
Chemical CAS No Fate Aquatic toxicity1 Meets Synthesis

DfE
Surfac-
Aquatic toxicity
tant
Degradates of
Criteria
Persistance
Degradate
concern2
Chronic
Acute
Nonylphenol ethoxylates (NPEs)
Nonylphenol ethoxylate (9EO); NPE9
Nonylphenol is prepared from phenol
and tripropylene, yielding a highly
127087- branched, predominantly parasubsti-
M Y3 H M VH N
87-0 tuted alkylphenol. Reaction of
nonylphenol with ethylene oxide yields
NPE surfactants.
Octylphenol ethoxylates (OPEs)

Octylphenol ethoxylate (10EO); OPE10
Octylphenol is prepared from phenol
and diisobutylene, yielding a highly
branched, predominantly para-
9036-19-5 H4 Y5 H H VH N
substituted alkylphenol. Reaction of
octylphenol with ethylene oxide yields
OPE surfactants.
Linear alcohol ethoxylates (LAE)

C12-15 Alcohols, ethoxylated (9EO) Linear alcohols, derived from fatty
acids or alpha-olefins, are reacted with
ethylene oxide to yield LAE surfac-
68131-39-5 VL N VH H L6 Y
tants. Many detergent grade LAEs
make use of alcohols in the C10-C18
range.
Ethoxylated/propoxylated alcohols
Oxirane, methyl-, polymer with oxirane,
mono(2-ethylhexyl ether); Ecosurf EH-9
2-Ethylhexanol is reacted with eth-
ylene oxide and propylene oxide to
64366-70-7 L N M M L6 Y yield this product. Other surfactants in
this class use linear alcohols in place of
2-ethylhexanol.
Alkyl polyglucose (APG)

D-Glucopyranose, oligomeric, decyl octyl
glycosides
Fatty alcohols are reacted with glucose

in the presence of an acid catalyst.
68515-73-1 VL N M M L6 Y
Similar products may be prepared
from other sugars, such as sucrose.
Linear alkylbenzene sulfonates (LAS)

Benzenesulfonic acid, C10-13-alkyl derivs., Benzene is alkylated with a linear
sodium salt olefin (either internal or terminal) in
the presence of an acid catalyst, yield-
68411-30-3 VL N H H L6 Y
ing a linear alkyl benzene (LAB). The
LAB intermediate is sulfonated and
neutralized to yield a linear alkyl

Chemical CAS No Fate Aquatic toxicity1 Meets Synthesis
DfE
Surfac-
Aquatic toxicity
tant
Degradates of
Criteria
Persistance
Degradate
concern2
Chronic
Acute
benzene sulfonate surfactant.
Alkyl sulfate esters (AS)

Sodium lauryl sulfate Fatty alcohols are sulfated and neu-
151-21-3 VL N H H L6 Y tralized to yield alkyl sulfate ester
salts.
Alkyl ether sulfates (AES)

Polyoxy(1,2-ethanediyl), alpha-sulfo-
omegadodecyloxy-, sodium salt Linear alcohol ethoxylates are sulfated
9004-82-4 L N H H L6 Y and neutralized to yield alkyl ether
sulfate salts.
Sorbitan esters
Sorbitan monostearate
Fatty acid methyl esters are reacted
1338-41-6 L7 N H H L6 Y with sorbitan in the presence of a basic
catalyst to yield sorbitan esters.
VL = Very low hazard L = Low hazard M = Moderate hazard H = High hazard VH = Very high hazard - Endpoints in colored text (VL, L, M,
H, and VH) were assigned based on experimental data.
Endpoints in black italics (VL, L, M, H, and VH) were assigned using estimated values and professional judgment (Structure Activity Rela-
tionships). Y=Yes…N=No
Annotation: VL = Very low hazard L = Low hazard M = Moderate hazard H = High hazard VH = Very high
hazard. Endpoints in coloured text (VL, L, M, H, and VH) were assigned based on experimental data. End-
points in black italics (VL, L, M, H, and VH) were assigned using estimated values and professional judg-
ment (Structure Activity Relationships). Y=Yes…N=No.
Levels of 1,4-dioxane impurity in ethoxylated surfactants are limited to 100 ppm in the product formulation.
1. Acute toxicity data reviewed include 96-h LC50 assays in fish, 48-h EC50 or LC50 assays in invertebrates
and 72-96-h EC50 assays in algae. Chronic toxicity values are not required for rating if adequate acute data
are available.
2. Degradation products of concern for surfactants are compounds with high acute aquatic toxicity (L/E/IC50
≤ 10ppm) and a slow rate of biodegradation (greater than 28 days).
3. One potential degradation product, nonylphenol, raises concerns for its potential to affect the endocrine
system.
4. Half-life cannot be reliably determined from the available biodegradation data for octylphenol ethoxylates.
Based on biodegradation rate data, the time to achieve 50% degradation (as measured by oxygen demand)
appears to be somewhat longer than 60 days.
5. One potential degradation product, octylphenol, is more persistent and more toxic than the parent com-
pound.
6. According to available biodegradation studies, this chemical ultimately degrades to CO2, H2O, and mineral
salts, and therefore no aquatically toxic degradation product are expected.
7. The available biodegradation data do not include information on the 10-day window.
A Canadian assessment of alternatives to NPEO prepared for Environment Canada from 2002
(Campbell, 2002) states that linear alcohol ethoxylates (as alternatives to NPEO) have a wide range
of physical and nonionic properties for various applications and that they are excellent wetting
agents, emulsifiers, and detergents. They are generally moderate foamers - a desirable characteristic

for many of the applications in the current nonionic surfactant market. According to the study, the
cost of surfactants fluctuates with the price of raw materials, for example the cost of ethoxylates
fluctuates with the price of ethylene, and surfactants produced from oleochemical feedstocks fluctu-
ate with the price of, for example, plant-derived oils. In the years before 2o02, the price of the main
alternatives to NPEO had been, on average, ~20-40% higher than NPEO. The report identifies a few
applications for which there did not appear to be cost effective alternatives to NP/NPEO at that
time. These include:
• Emulsion polymerisation – NPEO used to produce polymer dispersions e.g. used in coatings
• The use of tris-nonylphenylphospite (TNPP) as an anti-oxidant and stabilizer for plastics/
resins.
The UK nonylphenol Risk Reduction Strategy from 1999 (Footit, 1999) indicates that the alterna-
tives to NPEO in emulsion polymerisation are often other APEs which pose a similar level of risk
while creating significant costs. NPEO and OPEO are used as apolymerization aids in the manufac-
ture of polymer emulsions. Emulsion polymerization is a type of polymerization that usually starts
with an emulsion incorporating water, monomer, and surfactant. The most common type of emul-
sion polymerization is an oil-in-water emulsion, in which droplets of monomer are in a continuous
phase of water. The surfactant (also known as emulsifier) stabilises the emulsion to prevent un-
wanted fusion or coagulation (Nwaogu, 2006). The end applications for the polymer dispersions
based on NPEOS and OPEOs include paints, paper, inks, adhesives and carpet backings (Footit,
1999; Nwaogu, 2006). For OPEOs it is indicated that the paint is the major end application
(Nwaogu, 2006). According to Nwaogu (2006) there are considerable difficulties in trying to differ-
entiate between the use of OPEOs in water-based paints and the use of OPEOs in emulsion polymer
manufacture used in water-based paints. Emulsion polymerisation and the uses of NPEO in paint,
adhesives and sealant are not covered by the current restriction. Emulsion polymerisation and the
use of NPEO in paint took up 12% (7,000 t/y) and 5% (4,000 t/y) of the total use of NPEO before
the restriction, likely still today two of the major uses of NPEO. Furthermore, in 2001, 550 tonnes of
OPEO at EU level were used as emulsifiers and 50 tonnes were used in binders for water-based
paints.
As part of the SOCOPSE project on priority hazardous substances under the Water Framework
Directive, Feenstra et al. (2009) give an overview of existing and emerging alternatives to NPEO in
the European context. The overview is to a large extent based on The UK nonylphenol Risk Reduc-
tion Strategy from 1999 (Footit, 1999) and Danish studies mentioned below, and do not include
much updated information. Alcohol ethoxylates are indicated as substitutes for NPEO in paints and
a number of other applications whereas, for emulsion polymerisation, OPEO is indicated as a sub-
stitute.
The UK Risk Reduction Strategy for OP/OPEO (Nwaogu et al., 2006) includes a discussion of the
possibilities for substituting OPEO in binders in paints and in emulsion polymer manufacture. The
considerations of Nwaogu et al. (2006) are summarised in Table 38.
The study does not provide information of the possible costs of alternatives and changes in manu-
facturing processes. Environmental and health effects of alternatives as compared with the
OP/OPEO are not assessed in the study.

TABLE 38
SUMMARY OF DISCUSSION OF ALTERNATIVES TO OPEO (BASED ON NWAOGU ET AL., 2006)
Alternative to Alternatives Remarks
OPEO use in binders in • Depending on paint type, the Styrenated resins used as co-binders in acrylic paints may
paints binders may be replaced with contain 4-tert-octylphenol.
other binders where OPEO is
not required Other alternatives to OPEO identified by industry in this
• Styrenate resin-free co-binders sector are based on C10–C15 alcohol ethoxylates.
in acryl latex paints
• Polyvinyl acetate binders
• Epoxy binders
• Polyurethane binders
• C10–C15 alcohol ethoxylates
OPEO use in emulsion • Fatty alcohol ethoxylates (Cas These alternatives are identified by industry. The alterna-
polymer manufacture - No 61725-89-1) tives in themselves are deemed inferior to OPEO as re-
Specifically formulation • Fatty alcohol ethoxylates (Cas gards performance, but this can be overcome by formula-
of PTFE emulsion No 65150-81-4) tion with other components. The unit cost of raw material
• Ethoxylated secondary alcohol to replace OPEO were expected to be twice that of the
(Cas No 25322-68-3) OPEO containing product in 2006. One time costs for the
substitution programme were estimated at around
£50,000 in technical support, sampling and staff time.
Work undertaken under the OECD SIDS programme
indicated that while some fatty alcohols may be toxic to
aquatic organisms, they do not bioaccumulate or have
endocrine disrupting effects and are not expected to be as
persistent as OP.
Experience from Danish studies

As regards the applications of NPEO and OPEO in binders for paints, wood preservatives, glues and
sealants, Rasmussen et al. (2003) identified the substance groups in Table 39 as tested and or
commercially applied alternatives to APEO in binders with the help of industry experts. The study
quotes a specific paint manufacturer successful in replacing APEO for the general water-based
paints and wood preservatives, but still used APEO for some niche products (not further specified).
The main part of the APEO was used in binders. It is indicated that the replacement of the APEO is
relatively resource consuming, but the study does not include an assessment of the economic feasi-
bility of the replacement.
The results of the assessment for environmental characteristics are depicted in the table with 1 as
the best score and 5 as the worst score. For health effects, 1 is the best score and 3 is the worst (see
reference for details). A broader group of substances, of which some were not tested or applied in
the involved companies, were identified as potential alternatives to APEO in binders. All substance
groups assessed in the study, and the related environment and health scores assigned are listed in
Table 40 and Table 41. These substance groups are presented as well known surfactants.

TABLE 39
ALTERNATIVES TESTED OR COMMERCIALLY APPLIED IN INVOLVED PAINT, WOOD PRESERVATIVES, ADHESIVES
AND SEALANTS INDUSTRIES AND SCORES FOR THEIR ENVIRONMENTAL AND HEALTH ASSESSMENT (FROM RAS-
MUSSEN ET AL. 2003)
Tested for Environmental

Used in the Health group
production of group
Group of substances production of General
paints and General
binders assessment
tinting pastes assessment
APEO 5 3
Alkyl sulfates (AS) x x 1-2 3
Alkyl ether sulfates x x 1-2 2-3
Alcohol ethoxylates x x 1-2 1 or 3
Alkyl mono ethanol

x x 1 1 or 3
amide ethoxylates
Alcohol alkoxylates x x 4-5* 1*
LAS x 1 3
Alkyl ether phosphates x 4* 1 or 3*

*Rating is based on inadequate data and large variations with regard to environmental properties may occur
within the tenside group, which is the reason why a few tenside compounds may differ considerably from the
stated environmental rating.
TABLE 40
ALL POTENTIAL ALTERNATIVES ASSESSED IN RASMUSSEN ET AL. (2003) FOR BINDERS USED IN PAINT, WOOD
PRESERVATIVES, ADHESIVES AND SEALANTS INDUSTRIES AND SCORES FOR THEIR ENVIRONMENTAL ASSESSMENT
Group of substances Environmental group

Subgroup Remarks
General assessment
APEO - 5
Alkyl sulfates (AS) Linear 1-2
Alkyl ether sulfates Linear 1-2
Some not readily degradable branched AES

Branched 1-2
belong to group 4 or 5.
Alcohol ethoxylates Linear < 20 EO 1-2
Linear > 20 EO 1
Some not readily degradable branched AES

Branched 1-2 belong to group 4 or 5. Several AES are not
degradable under anaerobic conditions.
Alkyl mono ethanol

- 1 Rating is based on inadequate data.
amide ethoxylates
Alcohol alkoxylates 2 and 1 respectively when readily degradable.

- 4-5
Data showed varying environmental properties.
LAS Not degradable under anaerobic conditions. On

- 1 the List of Undesirable Substances from the
Danish EPA.
Alkyl ether phos- General assessment is based on inadequate

- 4
phates data. 1 if readily degradable.

TABLE 41
ALL POTENTIAL ALTERNATIVES ASSESSED BY RASMUSSEN ET AL. (2003) FOR BINDERS USED IN PAINT, WOOD
PRESERVATIVES, ADHESIVES AND SEALANTS INDUSTRIES AND SCORES FOR THEIR HEALTH ASSESSMENT
Length of
Group of substances Ethoxylates units Health hazard group
carbon chain
APEO - - 3
Alkyl sulfates C12 - 3
Alkyl ether sulfates C9-15 >7 2

C9-15 2-3 3
LAS C9-14 - 3
Alkyl ether phosphates 13-18 - 3
Alcohol ethoxylates 5-20 3

-
> 20 1
Alcohol alkoxylates 3-9 EO and

- 1*
4-6 PO
Alkyl mono ethanol >12 1*

-
amide ethoxylates <5 3*
* Rating is based on inadequate data.
Hoffman et al. (2003) assessed selected alternative APEO-free raw materials for binders in the
manufacture of paints in cooperation with a Danish paint manufacturer. The technical test of alter-
natives was conducted in the laboratories of the paint manufacturer and demonstrated that it would
be possible to replace APEO and raw materials containing APEO. The substitution process would,
however, be time and resource consuming, as many raw materials with different functions in the
paint have to work together, while retaining as much of the original formulation as possible to avoid
complete reformulation. The identified alternatives are summarised in Table 42.
During the project the company replaced a number of raw materials containing APEO with alterna-
tives. The APEO-free raw materials were all based on three groups of surfactants: alkylsulfates,
alkylether sulfates and alcohol ethoxylates.
As regards the environment and health characteristics of the three alternatives applied by the com-
pany, Hoffman et al. (2003) stated the following: "These three groups of surfactants are in general
easily degradable under aerobic as well as anaerobic conditions and the surfactants are toxic or
very toxic to aquatic organisms. Alkyl sulfates and alkylether sulfates are not considered to be
bioaccumulating whereas a few alcohol ethoxylates (longchained with few ethoxylate units) have
a potential for bioaccumulation. The alkylphenol ethoxylates, which the above surfactants have
replaced, have on the other hand the problem that their degradation products (for instance
nonylphenol) are very toxic to aquatic organisms, are not easily degradable and have at the same
time a tendency to bioaccumulation. Even if the alternative surfactants in general are toxic or
very toxic to aquatic organisms too, they are on the other hand also quickly degradable in the
environment and for that reason there is an environmental advantage in substituting the APEOs,
which are hazardous to the environment, with these alternative surfactants. With regard to
health, there is furthermore the advantage of the substitution that the degradation product
nonylphenol is avoided. For this product, evidence for hormone disturbing effects is found."

TABLE 42
SURVEY OF APEO SURFACTANTS USED IN BINDERS IN PAINT MANUFACTURE AND CORRESPONDING ALTERNA-
TIVES (FROM HOFFMAN ET AL., 2003)
Alkylphenol ethoxylate Alternative
APEO Ethoxylated branched acid alcohol (C12-15) saturated
Fatty alcohol ethoxylated C9/11 saturated linear
Nonylphenol ethoxylate Styrene/maleic anhydride polymer
Surfactant?
Secondary ethoxylated alcohol (C12-14)
Ethoxylated acetylenic alcohol
Nonylphenol hydroxy polyoxy- Ethoxylated fatty acid alcohol

ethylene
Ethoxylated fatty acid alcohol - C16-18
Ethoxylated fatty acid - C12-14
Alkylphenol polyglycolether Ethoxylated linear fatty alcohol
Octylphenoxy polyethoxyethyl Sodium lauryl sulfate (alkyl ester sulfate C10-16)

phosphate
Polyoxyethylene tridecyl etherposphate
Octylphenoxy polyethoxyethanol
Tridecylpoly (ethyleneoxy) ethanol
Alkylaryl polyglycolether Alkylether sulfate, Sodium-salt (C10-16 7 EO)
Alkylether sulfate, Sodium-salt Ethoxylated lineær fatty alcohol
Octylphenol ethoxylat Surfactant?
Alkylaryl polyether octylphenoxy Secondary alcohol ethoxylate

polyethoxyethanol Secondary alcohols C12-14
Polyoxy ethandiyl nonylphenol Ethoxylated unsaturated fatty acid monoethanolamide
Ethoxylated fatty alcohol C12-14 (9.5 mol EO)
Alkylphenol alkoxylat Fatty acid derivate (can not be further specified)
Note: ’Surfactant?’ = information about surfactant in the APEO-free raw material has not been available.
New development
Most of the assessments are based on 10-year old data and new surfactants used as alternatives to
the APEO may have been developed in recent years. It has been beyond the scope of the current
assessment to prepare an updated alternative assessment, but a few websites of major manufactur-
ers have been accessed for the latest information. The websites in general indicate a number of
different surfactants as “APEO-free” or more specifically as APEO alternatives.
DOW Surfactants market a number of surfactants as alternatives to APEO in various applications

including cleaning product formulations, paints and coatings, and emulsion polymerization (DOW,
2012). The agents are based on specialty ethoxylated surfactants in the ECOSURF® series and sec-
ondary and branched alcohol ethoxylates similar to those assessed above. The product finder illus-
trates the complexity of the applications of surfactants and has as regards the product group “emul-
sion polymerization applications” suggestions for the following specific applications: Post-add
emulsifier, silicone emulsion stabilizers, acrylics-based systems, styrene/butadiene-based systems,
suspension polymerization of vinyl chloride, styrene/acrylics- based systems, rubber, polychloro-
prene, and PVC film applications.

According to Clariant (2012a) traditionally used NPO in emulsion polymerization applications can
be replaced by the company’s surfactants based on fatty alcohol ethoxylates in the Emulsogen®
LCN, Genapol® X, and Genapol® OX series, which are biodegradable and APEO-free. These agents
and agents based on a number of other surfactants are marketed as APEO-free agents for different
applications in paint manufacture e.g. wetting and dispersing agents and emulsifiers. A few of the
company’s agents for paint manufacture is not indicated as APEO-free (Clariant, 2012b).
8.2 Alternatives to 4-nonylphenol (NP), 4-tert-octylphenol and 4-tert-

butylphenol
4-Nonylphenol, 4-tert-octylphenol and 4-tert-butylphenol are used for some of the same applica-
tions and 4-tert-octylphenol and 4-tert-butylphenol may potentially substitute for NP for some
applications. As regards substitution of NP with OP, Nwaogu et al. (2006) considers that there is a
low possibility (and incentive) for companies to move from NP to OP due to costs.
Except for NPEO production, little information is available on alternatives for NP used for the pro-
duction of specific NP derivatives, where substitution is rather a question of substituting the deriva-
tives. An example is phenolic resins, where the only substitutes specifically identified are based on
other APs.
Footit et al. (1999) states that "During consultation with industry, few alternatives were identified
for replacement of NPs where they are used as an intermediate in the formation of other products.
The products in question include phenol/formaldehyde resins (PFR), tri (4-nonylphenol) phos-
phite, phenolic oximes, epoxy resins and other plastic stabilisers. These products generally owe
their properties to the use of NP in their formulation and such characteristics may be more diffi-
cult to duplicate using alternatives than appears to be the case with NPEs. The only alternatives
which have been suggested as suitable at present are other alkylphenol compounds, particularly
octylphenols. It is unlikely that these products would represent a suitable substitute because they
are so structurally similar to NPs and toxic effects may be expected to be of a similar magnitude."
Newer assessments of alternatives to NP have not been identified. Feenstra et al. (2009) give an
overview of existing and emerging alternatives to NP in the European context but base the assess-
ment on Footit et al. (1999).
Nwaogu et al. (2006) includes a discussion of the possibilities for substituting OP with a focus on
alternatives for the continued uses of 4-tert-octylphenol, i.e. in rubber formulation, insulating var-
nishes, printing inks, and marine and/or water-based paints. These three uses accounted for over
90% of the OP consumption in the UK. For textile finishing and plant/animal health products, a
discussion of alternatives were not provided in the study as industry had broadly indicated that the
availability of substitutes (amongst other factors) had resulted in a decrease in the use of OP in
these sectors. The evaluated alternatives may to some extent also be alternatives to NP.
The EU Risk Assessment for 4-tert-butyl phenol (ECN, 2008) does not include any information on
alternatives to the substance.

TABLE 43
SUMMARY OF DISCUSSION OF ALTERNATIVES TO 4-TERT-OCTYLPHENOL (BASED ON NWAOGU ET AL., 2006)
Alternative to Alternatives Remarks

OP-based resins in the − Rosin-based derivatives Rosins are the most widely known alternatives, and with
rubber industry (tacki- − Coumarone-indene res- modern formulations, adequate rubber quality can be
fiers) ins consisting of indene, achieved for some purposes at low cost. Rosin and terpene-
coumarone, styrene, etc. based tackifier resins are mentioned as of relevance for a
obtained from coal coke number of rubber and adhesive applications. Quality
oven light oils considerations and resources and time needed for tech-
− Aliphatic petroleum res- nical substitution make the manufacturers of automotive
ins made from unsatu- tyres reluctant to substitute phenolic resins. Rosin is a
rates obtained while solid form of resin obtained from pines and some other
cracking crude oil; plants, mostly conifers.
− Terpene oligomers of al-
pha- or beta-pinene ob-
tained from pine tree
stumps.
OP use in crosslinking − Epoxy resins The main alternatives to phenolic resins in insulating
agents in insulating varnishes identified to date are the epoxy resins. Recent
varnishes technology has made available a number of waterborne
epoxy dispersions which are attractive alternatives to the
solvent based resins. Most epoxy resins used today are
based on bisphenol-A; other types of dispersions are com-
mercially available including urethane modified epoxies,
rubbermodified epoxies and novolac epoxies.
8.2.1 Alternatives to other specific AP/APEO

Environment Canada (2009) states that while alternatives for 2,4,6-tri-tert-butylphenol are availa-
ble, the cost of alternatives is thought to be two to three times more expensive. The names of alter-
natives are not indicated.
No information was identified in the literature search on alternatives to the other APs and APEOs.
8.3 Conclusion on alternatives

Alkylphenol ethoxylates
Currently the largest use of APEOs is for paints and emulsion polymerization for various end uses
such as paints, inks, adhesives and sealants.
The assessments of alternatives have mainly focused on alternatives to NPEO and OPEO but the
identified studies that address the technical and economic feasibility of the substitution are about
10 years old.
The reviewed assessments of the environmental fate and toxicity of alternatives to NPEO reach the
same conclusion: that the alternatives in general are of less concern as regards persistence and
aquatic toxicity of degradation products. The acute and chronic aquatic toxicity of the alternatives
are at the same level as the toxicity of the NPEO and OPEO or even higher. Concerning health haz-
ards several of the alternatives have a similar score as NPEO.

The available information indicates that OPEO has in general not substituted for NPEO for the
applications where NPEO is currently restricted. OPEO cannot be considered a viable alternative to
NPEO.
For one of the main non-restricted applications of NPEO and OPEO, in paint varnishes and lac-
quers, the assessments reach different conclusions. A Canadian assessment indicated this applica-
tion area as an area where feasible alternatives are not available, whereas a Danish assessment
demonstrated that it would be possible to substitute APEO and raw materials containing APEO. The
substitution process would however be time and resource consuming, as many raw materials with
different functions in the paint have to work together, while retaining as much of the original for-
mulation as possible to avoid complete reformulation. One Danish study reported that NPEO could
be replaced in most water based paints.
A number of manufacturers of surfactants specifically market APEO-free surfactants for many dif-
ferent applications of emulsion polymerization and for paints. It is not clear from the available
information if the remaining uses (e.g. as registered in the Danish Product Register) are for niche
products.
EU, Nordic and German eco-labels target AP/APEOs for a number of product groups. Most of the
targeted product groups represent applications where NP/NPEO is today restricted, and probably
mainly replaced by non-AP/APEO alternatives. The ecolabels for indoor and outdoor paints and
varnishes and paper envelopes (the adhesives of the envelopes) target products groups which are
not covered by current restrictions. The fact that some products meet the ecolabels criteria indicates
that non-AP/APOE alternatives are available for at least some of the products within the groups,
but it cannot be used to conclude that alternatives are available for all types of products. It is e.g. in
the available alternative assessments indicated that APEO can be replaced for the general water-
based paints and wood preservatives, but is still used for some niche products.
A first step in an assessment of the technical and economic feasibility of alternatives to the remain-
ing uses of NPEO and OPEO would be to identify more specifically the remaining uses of the sub-
stances. The use may to some extent be for niche products where substitution could be relatively
costly, but it may also be the case that alternatives are readily available but not used due to margin-
ally higher costs, and that the NPEO and OPEO are used for low-costs bulk products.
Alkylphenols
Alternatives to the major uses of NP and OP in the production of phenolic resins, epoxy resins, etc.
are in general not available. The alternative solution would be to substitute phenolic resin or other
products. Possible alternatives to OP-based resins have been identified, but an assessment of the
advantages and drawbacks of using these alternatives is not available.

9. Overall conclusions
The results of the survey are summarised in the “Summary and conclusion” where the data are
summarised for each of the main substances groups going across all chapters in the report. It is
recommended to read this summary before this chapter.
A summary of the key consumption, environmental and health data on AP/APEO is provided in
Table 44.
Main issues
None of the substances are considered to be PBT or vPvB substances and the table consequently do
not have a row for indication of this. The substances are all biodegradable, but some are less biode-
gradable than others. For NP and OPEO, Annex XV SVHC dossiers have been submitted with the
scope of “equivalent level of concern” based on the estrogenic activity of the substances (in the case
of OPEO, the activity of the degradation products, OP). Table 44 indicates the endocrine disruptor
class of the substances, but most substances have not been involved in the EU evaluation pro-
gramme for endocrine disruptors (EC, 2012). As described in the chapter on health (which also
applies to the environmental effects) the available data indicate that both the position (para > meta
>ortho) and branching (tertiary > secondary = normal) of the alkyl group affect estrogenicity. Op-
timal estrogenic activity requires a single tertiary branched alkyl group composed of between 6 and
9 carbons located at the para-position on an otherwise unhindered phenol ring. Only the para- (4-)
mono-substituted homologues seem to be endocrine disruptors, and p-nonyl phenol and 4-tert-
octylphenol are the most potent ones. Based on this, most probably the short-chained APs in the
table (with the exception of 4-tert-BP and 4-tert amylphenol) would not be considered SVHC. For
dodecylphenol, 4-tert-BP and 4-tert amylphenol, a closer assessment would be needed for a conclu-
sion as to whether they may be considered SVHCs.
The self-classifications of the substances indicate that many of the substances are acute and chronic
toxic in the aquatic environment similar to those substances with a harmonised classification. None
of the self-classifications of the short-chain APs indicate that substances are carcinogenic, mutagen-
ic or toxic to reproduction.
The table indicated the consumption volume in the EU and to what extent the substances are used
for non-industrial applications that may be associated with wide-dispersive. Many of the short-
chain APs are used as intermediate or applications where relative small releases from the use phase
would be expected such as lubricants and fuel additives. Data on the presence of the substances in
waste water and the environment are scarce, but none of the available studies have demonstrated
high concentrations (similar to those of NP and NPEO) of any of the substances. One substance,
2,6-di-tert-butyl-p-cresol (BHT) are used in large quantities for purposes (as food additives, among
others) where significant emissions may occur, but available data from waste water treatment
plants have demonstrated BHT concentrations of at least one order of magnitude less than the con-
centration of NP.
The NPs and OPs are in general of most concern due to a combination of:
• The OPs and NPs are less biodegradable than other APs;
• They have a higher bioconcentration factor than most of the other APs;

• The substances are formed by degradation of the ethoxylates which are used for purposes with
relatively many wide-dispersive uses (resulting in releases to the environment);
• Evidence of high potency of endocrine disrupting activity;
• The substances and their ethoxylates are used in relatively high quantities, and
• NP is classified toxic to reproduction.
The main issues with regard to these substance groups identified are:
• One of the major applications of the substances and their ethoxylates as registered in the Dan-
ish Product Register is in paint, lacquers and varnishes. Alternatives to APEO have been as-
sessed for more than 10 years ago, but the substances are still used for some types of paint and
varnished. The substances are included in imported raw materials for production in Denmark,
and a substitution of the APEO would consequently imply a substitution of the raw materials.
• Textiles imported from countries outside the EU are major sources of releases of NP and
NPEO to waste water treatment plants. The problem will be addressed by a REACH restriction
dossier intended to be submitted by Sweden.
• A significant quantity of NPEO is still registered in the Danish Product Register as used in
cleaning agents and biocidal products, and it should be further clarified whether this is due to
inadequate updating of the notifications or is due to non-compliance.
• OPEO may be used for some of the applications where NPEO is restricted e.g. in textile and
leather auxiliaries. More information on the potential releases of OPEO from different uses of
the substances would be beneficial.
The dodecylphenols share some of the same properties as NP and OP and with a proposed classifi-
cation as toxic to reproduction it may be of similar concern. The registry of intentions does not
include any intentions of preparation of Annex XV SVHC or restriction dossiers for the substances.
It may be relevant to further assess whether the substance meets the SVHC criteria in the same way
as NP and OP/OPEO.
Some of the short-chain substances may be of some concern e.g. 2,4,6-tri-tert-butylphenol, which is
a priority substance under OSPAR; however, an assessment of the potential effects of the actual
concentrations have still not been undertaken.
Based on the available data it does not appear to be justified to target the short-chain substances as
one group together with the long-chain APs. Rather, it appears to make more sense to assess each of
the short-chain APs individually in order to identify any needs for measures to reduce the human
and environmental exposure.
Data gaps
The survey addresses a wide range of substances and for most of the substances limited data are
available on the life cycle releases of the substances, human health and environmental exposure and
concentrations in the environment. The most important data gabs identified, when considering
which substances are of major concern, are:
• Updated information on current uses and on the significance of the potential sources of releas-
es of NP/NPEO to the environment is missing.
• Information on the registered quantities of NPEO in cleaning and maintenance products in
Denmark calls for a clarification of actual uses.
• For some of the substances, information on the total manufacture and import to the EU in the
registrations is not in accordance with information obtained from the industry and calls for a
clarification.
• For many of the substances used in lubricants and oils, data on the potential releases from spill
and disposal of improper waste oil are missing.

• Relatively high concentrations of 2,6-di-tert-butyl-p-cresol are found in waste water and the
OECD has concluded that more information on actual releases and environmental exposure to
this substance is needed.
• A review from HELCOM concluded that in general, there should be more measured data on
NP/NPEO and OP/OPEO levels in discharges in the Baltic Sea catchment area, in sea water,
biota and sediment of the Baltic Sea to examine if the substances cause harmful effects on the
marine environment.
• The HELCOM review also concluded that there is a need for ecotoxicological data on sediment
dwelling organisms in order to better define the NP and OP PNEC estimates for the benthic
community.
• Human toxicity data for long-chain alkylphenols other than nonylphenol are limited and data
on alkylphenol ethoxylates are nearly absent.
• Updated information on the technical and economic feasibility of substitution of remaining
uses of NP/NPEO and OP/OPEO is missing, this concerns in particular:
− Use in emulsion polymerization and for paints which represent the major registered uses
of the substances in Denmark.
− Alternatives to 4-tert-BP, 4-tert-OP and 4-NP for manufacture of different types if resins.

TABLE 44
SUMMARY OF KEY CONSUMPTION, ENVIRONMENTAL AND HEALTH DATA ON AP/APEO
Substance Use Environment Human health
Total EU Non industrial Risk Biodegrada- Bioconcen- Hazard class *3 Endocrine Monitoring data Risk/hazard Hazard class*3 Endocrine disrup-
consumption, use *4 /hazard tion *2 tration disruptor class Denmark, Baltic assessment tor class *4
t/y assessment factor *4 Sea, North Sea identified
identified *1
Nonylphenols 25,000- Small EU RAR; Inherently 1,280 Harmonised CAT 1 Many data; EU RAR Harmonised CAT 1
(NP) 50,000 part:PSA; UK screen- Aquatic Acute 1 levels compared Repr. 2
Residuals in ing; UK Aquatic Chronic 1 to PNEC Acute Tox. 4 *
resin Env. risk Skin Corr. 1B
evaluation;
Annex XV
SVHC
Nonylphenol 2,000-20,000 Significant EU RAR Degrade to - Aquatic Chronic 2 CAT 1 Many data EU RAR Acute Tox. 4 CAT 1/CAT2 (for
ethoxylates (NPE) part NP Skin Irrit. 2 different NPs)
Eye Irrit. 2
Octylphenols (OP) 22,900 Small part: Annex XV Inherently 634 (est.) Harmonised CAT 1 (for Some data; OECD SIDS Harmonised CAT 1 (for OPs
(Ex. CAS No 140-66- PSA; Residu- SVHC; UK Aquatic Acute 1 OPS with levels compared Skin Irrit. 2 with available
9) als in resin screening; Aquatic Chronic 1 available data) to threshold Eye Dam. 1 data)
UK risk concentrations
evaluation,
OECD SIDS
Octylphenol eth- 1,000 Significant Annex XV Degrade to - Aquatic Chronic 2 Some data - Acute Tox. 4 -
oxylates (OPEO) part SVHC; OP Skin Irrit. 2
Eye Dam. 1
Dodecylphenols 50,000 Small part: UK risk Not readily 9440 (est.) Proposed - Few data from - Proposed -
(ex. CAS No 121158- lubricants evaluation; Aquatic Acute 1, Nordic envi- Skin Irrit.2,
58-5) UK screen- Aquatic Chronic 1 ronment Eye Irrit.2,
ing Repr. 2,
Dodecylphenol <1000 Significant UK screen- Degrade to - not classified - Few data from - Eye Irrit. 2 -
ethoxylates part: lubri- ing DP Nordic envi-
cants ronment

identified *1
4-tert-butylphenol 27,000 Very small EU RAR, Readily (in 120 Aquatic Chronic 2 CAT2 Few data from EU RAR ; Proposed CAT2
CAS No 98-54-4 part; Residu- UK scree- weeks- Nordic envi- CLH report STOT SE 3,
als in resin ning; OECD months) Proposed: not ronment and Skin irrit. 2
SIDS included WWTP Eye dam. 1
2-sec-butylphenol 1,00o-10,000 Intermediate UK screen- in weeks 48; 120; 174 - - no data - Skin Corr. 1B -
CAS No 89-72-5 only ing
o-tert butylphenol <1000 Intermediate - - - - - no data Skin Corr. 1B -

CAS No 68610-06-0 only Skin Sens. 1
2-tert-butylphenol n.i. ? : Fuels UK screen- in weeks 39-188 Aquatic Acute 1 - Few data from - Acute Tox. 4 -
CAS No 88-18-6 additives ing WWTP Skin Corr. 1B
Skin Irrit. 2
Cyclohexylphe- n.i. ?: surface UK screen- in weeks 902 Aquatic Acute 1 CAT 3b no data - Skin Corr. 1B CAT 1
nols active agents ing Aquatic Chronic 1 Eye Dam. 1
CAS No 119-42-6,
1131-60-8
bis(tert-butyl) n.i. ?: lubricants UK screen- in months 16 Aquatic Chronic 3 - no data - - -

dodecylphenol ing
CAS No 68025-37-6
Phenol, isopropy- n.i. *1 Intermediate UK screen- in weeks 67 no notifications in - no data - no notifications in -

lated only ing C&L inventory C&L inventory
CAS No 90480-88-9
2,6-di-tert-butyl- 25,000 Most applica- UK screen- Readily (in 2,500 Aquatic Acute 1 - Few data from OECD SIDS many suggestions -
p-cresol (BHT) tions ing; OECD weeks- Aquatic Chronic 1 WWTP both none by
CAS No 128-37-0 SIDS months) >50% of notifiers

identified *1
2,6-di-tert- 15,000 Some part: UK screen- Not readily 660 Aquatic Acute 1 - few data from OECD SIDS Skin Irrit. 2 -
butylphenol lubricants, ing; OECD (in weeks- Aquatic Chronic 1 Nordic envi-
CAS No 128-39-2 fuel additives SIDS months) ronment and
WWTP
2,4-di-tert- 13,000 Very small UK screen- Not readily 660 Aquatic Acute 1 - Few data from - Skin Irrit. 2 -
butylphenol part; lubri- ing (in weeks- Aquatic Chronic 1 WWTP Eye Irrit. 2
CAS No 96-76-4 cants months)
2,4,6 tris-tert <1000 t Intermediate UK screen- Not readily 23,200 Aquatic Acute 1 - Few data from - Eye Irrit. 2 -
butyl-phenol only ing (in months) Aquatic Chronic 1 WWTP
CAS no 732-26-3
Thymol n.i. Significant - - - Harmonised - no data - Harmonised -

CAS No 89-83-8 part Aquatic Chronic 2 Acute Tox. 4 *
Skin Corr. 1B
6-tert-butyl-2,4- n.i. ? OECD SIDS - - Aquatic Chronic 2 - Few data from OECD SIDS Acute Tox. 4 -
xylenol WWTP Skin Irrit. 2
1879-09-0 Eye Irrit. 2
2,6-di-tert-butyl- n.i. ?: lubricants UK screen- in weeks– 5,943 Aquatic Chronic 3 - no data - Skin Irrit. 2 -
4-nonylphenol ing months Eye Irrit. 2
4306-88-1 STOT SE 3
4-tert amylphenol <1,000 ? UK risk Not readily 12; Aquatic Chronic 2 - no data - Acute Tox. 4 -
CAS No 80-46-6 evaluation; (in 531 Skin Corr. 1B
UK screen- weeks–
ing months)
o-tert amylphenol <1,000 Intermediate UK screen- in 412 no notifications in - no data - no notifications in -

CAS No 3279-27-4 only ing weeks– C&L inventory C&L inventory
months

identified *1
2-isopropylphenol >1,000 Intermediate UK screen- in weeks 56 - - no data - Acute Tox. 4 -

CAS No 88-69-7 only ing
2,4-dinonylphenol <1,000 Intermediate UK screen- in weeks 99 Aquatic Chronic 3 - no data - Skin Irrit. 2 -
CAS No 137-99-5 only ing Skin Sens. 1
2,4-di-tert am- <1,000 Intermediate UK screen- Not readily 40,381 - - no data - Acute Tox. 4 -
ylphenol only ing (in weeks– Eye Irrit. 2
CAS No 120-95-6 months)
2-tert-butyl-p- n.i. Intermediate UK screen- in weeks - 501 - - no data - Skin Corr. 1B -

cresol only ing months
CAS No 2409-55-4
6-tert-butyl-m- n.i. Intermediate OECD SIDS - - - - no data OECD SIDS Acute Tox. 4 -
cresol only Skin Corr. 1B
CAS No 88-60-8
C14-16-18 al- n.i. Intermediate - - - no notifications in - no data - no notifications in -

kylphenol only C&L inventory C&L inventory
CAS No 931-468-2
*1 Based on Environment Agency, 2005, see original report for detailed notes; the wording is derived from the original wording of the report which does not seem to be totally consistent.
*2 EU RAR: EU Risk Assessment Report available. “UK screening”: (Environment Agency, 2005). OECD SIDS: SIDS Initial Assessment Reports available; please see reference list.
*3 Harmonised: classification according to the CLP Regulation. Proposed: submitted classification proposal intention. Other classification is based on the selfclassifications listed in Annex 2 – indicates
classification suggested by more than 50% of the notifiers
*4 “Intermediate”: intermediate use only. PSA: Paint, lacquers, varnishes, sealants, adhesives
*5* CAT1 : Evidence of endocrine disrupting activity in at least one species using intact animals. CAT 2: At least some in vitro evidence of biological activity related to endocrine disruption; CAT 3b:
No or insufficient data available. Substances marked with an “-“ have not been included in the evaluation programme.

10. Abbreviations and acro-
nyms
ADI Acceptable daily ntake

4-tert-BP 4-tert-butylphenol = p-tert-butylphenol = 4-tert-BP= ptBP
4-t-OP 4-tert-octylphenol = p-tert-octylphenol = 4-t-OP= 4-t-OP
AP Alkylphenol
APEO Alkylphenol ethoxylates
Aza Azadioxabicyclooctane
BCF Bioconcentration factor
BHT 2,6-di-tert-butyl-p-cresol
BIT 4-t, 1, 2-benzisothiazolin-3-one
CEPAD European Council for Alkylphenols and Derivatives
CEFIC European Chemical Industry Council
CLP Classification, Labelling and Packaging Regulation
COHIBA Control of hazardous substances in the Baltic Sea region
DEFRA Department for Environment, Food and Rural Affairs (UK)
DFL Trade organisation for the paint and adhesives industry in Denmark
DP Dodecylphenols
DT Degradation time
DTU Technical University of Denmark
ECn Effect concentration where n % of the species tested show the effect
ECB European Chemicals Bureau
ECHA European Chemicals Agency
EFSA European Food Safety Authority
EPA Environmental Protection Agency
E-PRTR European Pollutant Release and Transfer Register
EQC Equivalent level of concern
ETRMA European Tyre & Rubber Manufacturers' Association
EU European Union
FSO Fugebranchen, Danish trade organisation of the sealant industry
HELCOM The Baltic Marine Environment Protection Commission (Helsinki Commission)
Kow Octanol/water partitioning coefficient
Koc Organic carbon/water partitioning coefficient
Kp Partial pressure equilibrium constant
LC Lethal effect concentration
LOUS List of Undesirable Substances (of the Danish EPA)
MSWI Municipal solid waste incinerators
MWWTP Municipal waste water treatment plant
NMC Nation Mean Concentration
NOAEL No observable adverse effect level
NOEC No observable effect concentration
NOVANA Danish national monitoring and assessment programme
NP Nonylphenol

NPEO Nonylphenol ethoxylates
NP1EO Nonylphenol monoethoxylates
NP2EO Nonylphenol diethoxylates
NPnEO NP carboxylate with n ethoxy units
NPEO9 as well as OEPO10 s.93
OECD Organisation for Economic Co-operation and Development
OP Octylphenol
OPEO Octylphenol ethoxylates
OP1EO Octylphenol monoethoxylates
OP2EO Octylphenol diethoxylates
OPnEC OP carboxylate with n ethoxy units
OSPAR Convention for the Protection of the Marine Environment of the North-East Atlantic
PEC Predicted environmental concentration
PFR Phenol/formaldehyde resins
PHMB Poly(hexamethylene biguanide) hydrochloride
PNEC Predicted no effect concentration
PTFE Polytetrafluoroethylene
4-t-OP 4-tert-octylphenol = 4-tert-octylphenol = 4-t-OP
QSAR Quantitative Structure and Activity Relationship
RATG Risk Assessment Task Group of the American Chemistry Council’s Petroleum Addi-
tives Panel
RED Reregistration Eligibility Decision
REACH Registration, Evaluation, Authorisation and Restriction of Chemicals
SIDS Screening Information Data Sets
SOCOPSE Source control of priority substances in Europe (a project)
SPT Association of Danish Cosmetics, Toiletries, Soap and Detergent Industries
STP Sewage treatment plant
SVHC Substance of Very High Concern
TGD Technical guidance document
ThOD Theoretical oxygen demand
TDI Tolerable daily intake
TTBP 2,4,6 tris-tert butyl-phenol
TNPP tris nonylphenyl phosphite = 4-nonylpheyl phosphite
WE Western Europe

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Annex 1: Uses and tonnage bands according to registrations
The following information on uses and tonnage bands of registered substances has been extracted
from ECHAs website July 2012 (ECHA, 2012e). The information on cresols and xylenol is shown for
reference and the uses of these substances are not further discussed in the report.
CAS No Substance Tonnage band Registered uses

t/y
Monoalkylphenols and ethoxylates
Methyl phenols [cresols] (out of scope)
95-48-7 o-cresol 10,000 - 100,000 Use as a monomer in polymer production

Use as an isolated intermediate for chemical synthesis
Processing of solid polymers
Processing of liquid polymers
Solvent in electrical wire enamelling
Manufacturing of o-cresol
106-44-5 p-cresol 10,000 - 100,000 Use in polymer production

Use in processing of solid polymers
Use in processing of liquid polymers
Use as a solvent in electrical wire enamelling
Solvent in pharmaceutical industry
108-39-4 m-cresol 10,000 - 100,000 Use as a monomer in polymer production

Processing of solid polymers
Processing of liquid polymers
Solvent in electrical wire enamelling
Solvent in pharmaceutical industry
1319-77-3 cresol 1,000 - 10,000 Manufacturing of substance

Formulation and repacking
Industrial use of processing aids
Use as monomer - thermoset
Use as a monomer - thermoplastic
Use as intermediate
Use as reactive processing aid - wire enamelling
Use in laboratories
906-151-7* reaction mass of m-cresol and 1,000 - 10,000 Transportable intermediate

p-cresol Industrial manufacture of enamels
Electrical wire enamelling coating
Mixing into preparations (road surfacing)
Use as monomer for polymer production-solid
Propylphenol
90480-88-9 phenol, isopropylated intermediate use Site limited intermediate

only
Butylphenols

89-72-5 2-sec-butylphenol 1,000 - 10,000 Chemical intermediate
Plant protection products
Fungicide formulation
98-54-4 4-tert-butylphenol intermediate use

only
Octylphenols
140-66-9 4-(1,1,3,3- 10,000 - 100,000 Intermediate in production of ethoxylates and ether sulphates
tetramethylbutyl)phenol Coatings and inks - manufacture of organic solvent borne,
[4-tert-octylphenol, 4-t-OP] water borne and solvent-free products
Coatings, adhesives, inks and paint: manufacture, industrial
and professional application
Consumer application of adhesives, coatings and paint
Tackifier in manufacture of tyres and rubber products
Industrial end-use of paints containing octylphenol ethox-
ylates
Use as a monomer in production of polymers
Nonylphenols and ethoxylates
84852-15-3 Phenol, 4-nonyl-, branched 10,000 - 100,000 Industrial application of coatings or inks
Industrial intermediate
Formulation of paint
Production of polymers
68412-54-4 2-{2-[4-(2,4,5-trimethylhexan- 1,000 - 10,000 Industrial manufacture of NPEO

3- 1,000 - 10,000 Industrial formulation of mining products (flotation agents)
yl)phenoxy]polyethoxy}ethanol containing NPEO
440-740-5* 4-(4-trans- Intermediate use Chemical intermediate

propylcylohexyl)phenol only
Dodecylphenols
121158-58-5 Phenol, dodecyl-, branched 10,000 - 100,000 Chemical intermediate

monomer for synthesis of polymer
Intermediate use intermediate
only
Di- and trialkylphenols
Dimethylphenols [xylenols] and trimethylphenols (out of scope)
108-68-9 3,5-xylenol Intermediate use Chemical intermediate

only
576-26-1 2,6-xylenol 10,000 - 100,000 Chemical intermediate
905-287-4* reaction mass of 2,4-xylenol 1,000 - 10,000 Xylenol fraction as electric wire enamelling coating
and 2,5-xylenol Transported intermediate
2416-94-6 2,3,6-trimethylphenol 1,000 - 10,000 Chemical intermediate
89-83-8 thymol 1,000 - 10,000 End use of thymol in cleaning agents

Use of scented articles

Dibutylphenols, butyl methyl phenols, tributylphenols
96-76-4 2,4-di-tert-butylphenol Intermediate use Intermediate

only Fuel additives and additised fuels
100 - 1,000 Lubricant additives, lubricants and greases
100 - 1,000 Chemical intermediate
Plastic additive
Rubber additive
Stabilizing component in other products
128-39-2 2,6-di-tert-butylphenol 100 - 1,000 Intermediate

100 - 1,000 Fuel additives and additised fuels
Intermediate use Lubricant additives, lubricants and greases
only Chemical intermediate
Plastic additive
Rubber additive
Stabilizing component in other products
128-37-0 2,6-di-tert-butyl-p-cresol 1,000 - 10,000 Use as a stabilizing (antioxidant) component substance

1,000 - 10,000 Use in formulations (Food, Feed, Cosmetics, Pharmaceuticals,
Plant protection products)
Use in plastics
Use in adhesives, coatings, dyes, inks, printing dyes
Use in fuel (biodiesel)
Use as laboratory reagent
Use as a lubricant
10,000 - 100,000 Industrial coatings and inks
Paper industry
Lubricants
Polymers
Fuels
5510-99-6 di-sec-butylphenol, mixed intermediate use Chemical intermediate

isomers only
31291-60-8 di-sec-butylphenol intermediate use Chemical intermediate

only
732-26-3 2,4,6-tri-tert-butylphenol intermediate use Chemical intermediate

[2,4,6 -TTBP] only
2409-55-4 2-tert-butyl-p-cresol intermediate use Chemical intermediate

only
88-60-8 6-tert-butyl-m-cresol intermediate use Chemical intermediate

only
Other APs
931-468-2 C14-16-18 Alkylphenol intermediate use No manufacturing information

only
905-278-5 Reaction mass of 3,4-xylenol intermediate use Chemical intermediate

and 3,5-xylenol and 3- only
ethylphenol and 4-ethylphenol
906-550-6 Reaction mass of 2,3-xylenol 1,000 - 10,000 Transported intermediate

and 3,5-xylenol and 3- Xylenol fraction as electric wire enamelling coating
ethylphenol and 4-ethylphenol

Annex 2: Self classification of AP/APEO
The Classification & Labelling (C&L) Inventory database at the website of the European Chemicals
Agency (ECHA) contains classification and labelling information on notified and registered sub-
stances received from manufacturers and importers. The database includes as well the harmonised
classification. Companies have provided this information in their C&L notifications or registration
dossiers (ECHA, 2012e). ECHA maintains the Inventory, but does not verify the accuracy of the
information (ECHA, 2012).
Classification of AP/APEO listed in the database is shown in the table below.
For substances with a harmonised classification this is indicated.
TABLE A3
CLASSIFICATION INFORMATION ON NOTIFIED AND REGISTERED SUBSTANCES RECEIVED
FROM MANUFACTURERS AND IMPORTERS (C&L LIST)
Hazard
Carbon atoms Hazard Class and Number of
CAS No Substance name Statement
in alkyl chains Category Code(s) notifiers
Codes
Ethylphenols
90-00-6 2-ethylphenol 2 Total 266

Acute Tox. 4 H302 159
Skin Corr. 1B H314 105
Skin Irrit. 2 H315 68
Eye Dam. 1 H318 98
STOT SE 3 H335 68
123-07-9 4-ethylphenol 2 Total 1024

Eye Dam. 1 H318 724
Eye Irrit. 2 H319 86
STOT SE 3 H335 68
Propylphenols
90480-88-9 Phenol, isopropylated 3 Total 5

Acute Tox. 3 H301 5
Acute Tox. 3 H311 5
Acute Tox. 3 H331 5
Muta. 2 H341 5
STOT RE 2 H373 5

Hazard
Codes
88-69-7 2-isopropylphenol 3 Total 51

Repr. 2 H312 9
Eye Dam. 1 H318 1
Acute Tox. 4 H332 6
Acute Tox. 4 H411 6
618-45-1 3-isopropylhydroxybenzene 3 Total 91

Eye Dam. 1 H318 1
Butylphenols
89-72-5 2-sec-butylphenol 4 Total 300

Eye Dam. 1 H318 116
Aquatic Chronic 2 H411 160
STOT SE 3 H335 48
98-54-4 4-tert-butylphenol 4 Total 2241

Slin Corr. 1B H314 446
Skin Sens. 1 H317 389
Eye Dam. 1 H318 877
Resp. Sens. 1 H334 75
STOT SE 3 H335 1607
11.1.1 Repr. 2 H361 510
11.1.2 STOT H372 1
RE 1 H410 15
Aquatic Chronic 2

Hazard
Codes

Eye Dam. 1 H318 116
STOT SE 3 H335 5
Aquatic Acute 1 H400 271
99-71-8 4-sec-butylphenol 4 Total 133

Acute Tox. 4 H302 1
Eye Dam. 1 H318 1

Eye Dam. 1 H318 53
1638-22-8 4-butylphenol 4 Total 68

Acute Tox. 4 H302 1
Acute Tox. 4 H312 1
Eye Dam. 1 H318 1
Acute Tox. 4 H332 1
27178-34-3 tert-butylphenol 4 Total 20

68610-06-0 Phenol, isobutylenated 4 Total 41

Pentylphenols

Hazard
Codes
80-46-6 p-(1,1- 5 Total 164

dimethylpropyl)phenol Acute Tox. 4 H302 71
Eye Dam. 1 H318 46
Acute Tox. 4 H332 3
87-26-3 2-(1-methylbutyl)phenol 5 Total 23

Eye Dam. 1 H318 23
1518-84-9 2-cyclopentylphenol 5 Total 23

STOT SE 3 H335 23
3279-27-4 2-(1,1- 5 Total 5

dimethylpropyl)phenol Acute Tox. 4 H302 4
Acute Tox. 4 H312 1
Eye Dam. 1 H318 4
Acute Tox. 4 H332 1
14938-35-3 4-pentylphenol 5 Total 27

Acute Tox. 3 H301 1
Eye Dam. 1 H318 1
Eye Irrit. 2 H319 1
Hexylphenols
119-42-6 2-cyclohexylphenol 6 Total 116

Eye Dam. 1 H318 23
STOT SE 3 H335 23
1131-60-8 4-cyclohexylphenol 6 Total 91

Eye Dam. 1 H318 91

Hazard
Codes
2446-69-7 p-hexylphenol 6 Total 139

Skin Corr. 1C H314 1
Eye Dam. 1 H318 1
Heptylphenols
1987-50-4 4-heptylphenol 7 Total 265

Eye Dam. 1 H318 1
140-66-9 4-(1,1,3,3- 8 Skin Irrit. 2 H315 Harmonised

tetramethylbutyl)phenol Eye Dam. 1 H318
Aquatic Acute 1 H400
1806-26-4 p-octylphenol 8 Total 81

18626-98-7 o-(1-methylheptyl)phenol 8 Total 50

Eye Dam. 1 H318 3
9002-93-1 Poly(oxy-1,2-ethanediyl), α- C8 ethoxylate Total 296

[4-(1,1,3,3- Acute Tox. 4 H302 193
tetramethylbutyl)phenyl]- Skin Corr. 1B H314 1
ω-hydroxy- Skin Irrit. 2 H315 198
Eye Dam. 1 H318 160

[(1,1,3,3- Acute Tox. 3 H301 26
tetramethylbutyl)phenyl]- Acute Tox. 4 H302 1354
ω-hydroxy- Skin Irrit. 2 H315 120
Skin Sens. 1 H317 1
Eye Dam. 1 H318 1458

Hazard
Codes
STOT SE 3 H335 1

(octylphenyl)-ω-hydroxy-, Acute Tox. 4 H302 45
branched 11.1.3 Skin H315 316
Irrit. 2 H318 45
11.1.4 Eye H319 316
Dam. 1 H335 316
11.1.5 Eye H411 45
Irrit. 2
11.1.6 STOT
SE 3
Aquatic Chronic 2
Nonylphenol and nonylphenol ethoxylates
25154-52-3 nonylphenol 9 Repr. 2 H361fd Harmonised

84852-15-3 4-nonylphenol, branched Acute Tox. 4 * H302
Skin Corr. 1B Aquat- H314
ic Acute 1 Aquatic H400
Chronic 1 H410
104-40-5 p-nonylphenol 9 Total 167

Eye Dam. 1 H318 86
Acute Tox. 4 Repr. 2 H332 1
H411 23
EC No 4-(4-trans-propyl- cylohex- 9 Total 1

440-740-5 yl)phenol Aquatic Chronic 4 H413 1
11066-49-2 isononylphenol 9 Total 77

Eye Dam. 1 H318 47
Repr. 2 H361 77
90481-04-2 Phenol, nonyl-, branched 9 Total 30

Eye Dam. 1 H318 30
9016-45-9 Nonylphenol, ethoxylated C9 ethoxylate Total 2218

Hazard
Codes

11.1.7 Skin H315 1405
Irrit. 2 H318 575
11.1.8 Eye H319 1509
Dam. 1 H335 131
11.1.9 Eye H361 56
Irrit. 2 H371 1
11.1.10 STOT H373 56
SE 3 H400 41
11.1.11 Repr. 2 H410 2
11.1.12 STOT H411 1875
SE 3 H412 93
11.1.13 STOT H413 48
RE 2
Aquatic Acute 1
Aquatic Chronic 1
Aquatic Chronic 2
Aquatic Chronic 3
Aquatic Chronic 4
20427-84-3 2-[2-(4- C9-ethoxylate Total 1

nonylphe- Skin Irrit. 2 H315 1
noxy)ethoxy]ethanol Eye Irrit. 2 H319 1
26027-38-3 4-nonylphenol, ethoxylated C9-ethoxylate Total 208

Eye Dam. 1 H318 23
11.1.14 Eye H319 160
Irrit. 2 H335 52
11.1.15 STOT H410 29
SE 3 H411 88
Aquatic Chronic 1
Aquatic Chronic 2
37205-87-1 Poly(oxy-1,2-ethanediyl), α- C9-ethoxylate Total 1004

(isononylphenyl)-ω- Acute Tox. 4 H302 628
hydroxy- Skin Irrit. 2 H315 145
Eye Dam. 1 H318 820
68412-54-4 2-{2-[4-(2,4,5- C9-ethoxylate Total 2815

trimethylhexan-3- Acute Tox. 4 H302 1480
yl)phenoxy]polyethoxy}eth Skin Corr. 1B H314 4
anol Skin Irrit. 2 H315 1345
Eye Dam. 1 H318 1535

Hazard
Codes

STOT SE 3 H335 2
127087-87-0 4-Nonylphenol, branched, C9-ethoxylate Total 925

ethoxylated Acute Tox. 4 H302 369
Eye Dam. 1 H318 350
STOT SE 3 H335 11
Repr. 2 H361 11
Dodecylphenol and docecylphenol ethoxylates
104-43-8 p-dodecylphenol 12 Total 16

Eye Irrit. 2 H319 1
H361 16
121158-58-5 Phenol, dodecyl-, branched 12 Total 503

Eye Dam. 1 H318 86
Repr. 1B H360 48
Repr. 2 H361 338
11067-80-4 isododecylphenol 12 Total 1

Eye Irrit. 2 H319 1
Repr. 2 H361 1
27193-86-8 dodecylphenol 12 Total 362

Repr. 2 H361 251

Hazard
Codes
9014-92-0 Dodecylphenol, ethoxylated C12-ethoxylate Total 144

Acute Tox. 4 H302 1
Eye Dam. 1 H318 46
STOT SE 3 H335 1
Pentadecylphenols
501-24-6 3-pentadecylphenol 15 Total 26

Skin Sens. 1 H317 2
STOT SE 3 H335 23
89-83-8 thymol 3+1 Acute Tox. 4 * H302 Harmonised

Skin Corr. 1B H314
499-75-2 carvacrol 3 +1 Total 971

3228-02-2 4-isopropyl-m-cresol 3+1 Total 81

Skin Sens. 1 H317 2
STOT SE 3 H335 26
3228-03-3 5-isopropyl-m-cresol 3+1 Total 23

STOT SE 3 H335 23
Di- and tri-propylphenols

Hazard
Codes
2078-54-8 disoprofol 3+3 Total 797

Acute Tox. 4 H312 6
STOT SE 3 H335 772
2934-05-6 2,4-diisopropylphenol 3+3 Total 24

STOT SE 3 H335 23
Butyl methyl phenols, butyl ethyl phenol, butyl dimethyl phenols, butyl tetramethyl phenol
88-60-8 6-tert-butyl-m-cresol 4 +1 Total 112

Repr. 2 H312 1
Eye Dam. 1 H318 53
STOT SE 3 H335 23
STOT SE 2 H371 1
STOT RE 2 H373 1
98-27-1 4-tert-butyl-o-cresol 4 +1 Total 23

2219-82-1 6-tert-butyl-o-cresol 4 +1 Total 88

Eye Dam. 1 H318 30
2409-55-4 2-tert-butyl-p-cresol 4 +1 Total 139

Eye Dam. 1 H318 37
Eye Irrit. 2 H319 4
STOT SE 3 H335 66

Hazard
Codes
1879-09-0 6-tert-butyl-2,4-xylenol 4+1+1 Total 441

Acute Tox. 3 H301 3
Skin Sens. 1 H317 1
STOT SE 3 H335 4
STOT RE 2 H373 21
879-97-0 4-tert-butyl-2,6-xylenol 4 +1+1 Total 23

Eye Dam. 1 H318 23
STOT SE 3 H335 23
96-70-8 2-tert-butyl-4-ethylphenol 4+2 Total 24

Eye Dam. 1 H318 23
Eye Irrit. 2 H319 1
96-76-4 2,4-di-tert-butylphenol 4+4 Total 777

Eye Dam. 1 H318 50
STOT SE 3 H335 222
STOT SE 2 H371 1
STOT RE 2 H373 81

Eye Irrit. 2 H320 7
Acute Tox. 5 H333 7
STOT SE 3 H335 6
STOT RE 1 H372 7

Hazard
Codes

5510-99-6 di-sec-butylphenol, mixed 4+4 Total 72

isomers Skin Corr. 1B H314 23
31291-60-8 di-sec-butylphenol 4+4 Total 105

128-37-0 2,6-di-tert-butyl-p-cresol 4 +4+ 1 Total 2810

STOT SE 3 H335 289
Muta. 2 H341 3
Carc. 1B H350 1
Carc. 2 H351 10
Repr. 2 H361 10
STOT SE 1 H370 1
STOT RE 2 H373 61
497-39-2 4,6-di-tert-butyl-m-cresol 4 +4+ 1 Total 32

616-55-7 4,6-di-tert-butyl-o-cresol 4 +4+ 1 Total 51

STOT SE 3 H335 23
732-26-3 2,4,6-tri-tert-butylphenol 4+4+4 Total 412

[2,4,6 -TTBP] Acute Tox. 4 H302 134
STOT SE 3 H335 5

Hazard
Codes
5892-47-7 2,4,6-tri-sec-butylphenol 4+4+4 Total 26

17540-75-9 4-sec-butyl-2,6-di-tert- 4+4+4 Total 319

butylphenol Acute Tox. 4 H302 1
Acute Tox. 4 H312 1
Acute Tox. 4 H332 1
Dinonylphenols
137-99-5 2,4-dinonylphenol 9+9 Total 27

1323-65-5 dinonylphenol 9+9 Total 78

Eye Dam. 1 H318 39
Other alkylphenols
16152-65-1 2-(1-methylcyclohexyl)-p- 7+1 Total 20

cresol Skin Irrit. 2 H315 20
77-61-2 6-(1-methylcyclohexyl)-2,4- 7 + 1+ 1 Total 30

xylenol Skin Irrit. 2 H315 30
120-95-6 2,4-di-tert-pentylphenol 5+5 Total 45

Acute Tox. 4 H312 1
Acute Tox. 4 H332 1
STOT SE 3 H335 14

Hazard
Codes
4130-42-1 2,6-di-tert-butyl-4- 4+4+2 Total 5

ethylphenol Skin Irrit. 2 H315 3
Eye Irrit. 2 H319 3
STOT SE 3 H335 2
4306-88-1 2,6-di-tert-butyl-4- 9+4+4 Total 24

nonylphenol Skin Irrit. 2 H315 24
STOT SE 3 H335 20
68025-37-6 bis(tert- 20 Total 288

butyl)dodecylphenol Aquatic Chronic 3 H412 288
* Source : Search Classification and Labelling Inventory at http://echa.europa.eu/web/guest/information-on-

chemicals/cl-inventory-database

Annex 3: Background information to chapter 3 on legal framework
The following annex provides some background information on subjects addressed in Chapter 3.
The intention is that the reader less familiar with the legal context may read this concurrently with
chapter 3.
EU and Danish legislation

Chemicals are regulated via EU and national legislations, the latter often being a national transposi-
tion of EU directives.
There are four main EU legal instruments:

• Regulations (DK: Forordninger) are binding in their entirety and directly applicable in all EU
Member States.
• Directives (DK: Direktiver) are binding for the EU Member States as to the results to be
achieved. Directives have to be transposed (DK: gennemført) into the national legal framework
within a given timeframe. Directives leave margin for manoeuvering as to the form and means
of implementation. However, there are great differences in the space for manoeuvering be-
tween directives. For example, several directives regulating chemicals previously were rather
specific and often transposed more or less word-by-word into national legislation. Consequent-
ly and to further strengthen a level playing field within the internal market, the new chemicals
policy (REACH) and the new legislation for classification and labelling (CLP) were implement-
ed as Regulations. In Denmark, Directives are most frequently transposed as laws (DK: love)
and statutory orders (DK: bekendtgørelser).
•
The European Commission has the right and the duty to suggest new legislation in the form of regu-
lations and directives. New or recast directives and regulations often have transitional periods for
the various provisions set-out in the legal text. In the following, we will generally list the latest piece
of EU legal text, even if the provisions identified are not yet fully implemented. On the other hand,
we will include currently valid Danish legislation, e.g. the implementation of the cosmetics di-
rective) even if this will be replaced with the new Cosmetic Regulation.
• Decisions are fully binding on those to whom they are addressed. Decisions are EU laws relat-
ing to specific cases. They can come from the EU Council (sometimes jointly with the European
Parliament) or the European Commission. In relation to EU chemicals policy, decisions are
e.g. used in relation to inclusion of substances in REACH Annex XVII (restrictions). This takes
place via a so-called comitology procedure involving Member State representatives. Decisions
are also used under the EU ecolabelling Regulation in relation to establishing ecolabel criteria
for specific product groups.
• Recommendations and opinions are non-binding, declaratory instruments.
In conformity with the transposed EU directives, Danish legislation regulate to some extent chemi-
cals via various general or sector specific legislation, most frequently via statutory orders (DK:
bekendtgørelser).
Chemicals legislation
REACH and CLP
The REACH Regulation 6 and the CLP Regulation 7 are the overarching pieces of EU chemicals legis-
lation regulating industrial chemicals. The below will briefly summarise the REACH and CLP provi-
6
Regulation (EC) No 1907/2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)
7
Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures

sions and give an overview of 'pipeline' procedures, i.e. procedures which may (or may not) result in
an eventual inclusion under one of the REACH procedures.
(Pre-)Registration
All manufacturers and importers of chemical substance > 1 tonne/year have to register their chemi-
cals with the European Chemicals Agency (ECHA). Pre-registered chemicals benefit from tonnage
and property dependent staggered dead-lines:
• 30 November 2010: Registration of substances manufactured or imported at 1000 tonnes or

more per year, carcinogenic, mutagenic or toxic to reproduction substances above 1 tonne per
year, and substances dangerous to aquatic organisms or the environment above 100 tonnes per
year.
• 31 May 2013: Registration of substances manufactured or imported at 100-1000 tonnes per
year.
• 31 May 2018: Registration of substances manufactured or imported at 1-100 tonnes per year.
Evaluation
A selected number of registrations will be evaluated by ECHA and the EU Member States. Evalua-
tion covers assessment of the compliance of individual dossiers (dossier evaluation) and substance
evaluations involving information from all registrations of a given substance to see if further EU
action is needed on that substance, for example as a restriction (substance evaluation).
Authorisation
Authorisation aims at substituting or limiting the manufacturing, import and use of substances of
very high concern (SVHC). For substances included in REACH annex XIV, industry has to cease use
of those substance within a given deadline (sunset date) or apply for authorisation for certain speci-
fied uses within an application date.
Restriction
If the authorities assess that that there is a risks to be addressed at the EU level, limitations of the
manufacturing and use of a chemical substance (or substance group) may be implemented. Re-
strictions are listed in REACH annex XVII, which has also taken over the restrictions from the pre-
vious legislation (Directive 76/769/EEC).
Classification and Labelling

The CLP Regulation implements the United Nations Global Harmonised System (GHS) for classifi-
cation and labelling of substances and mixtures of substances into EU legislation. It further speci-
fies rules for packaging of chemicals.
Two classification and labelling provisions are:
1. Harmonised classification and labelling for a number of chemical substances. These classi-
fications are agreed at the EU level and can be found in CLP Annex VI. In addition to newly agreed
harmonised classifications, the annex has taken over the harmonised classifications in Annex I of
the previous Dangerous Substances Directive (67/548/EEC); classifications which have been 'trans-
lated' according to the new classification rules.
2. Classification and labelling inventory. All manufacturers and importers of chemicals sub-
stances are obliged to classify and label their substances. If no harmonised classification is available,
a self-classification shall be done based on available information according to the classification
criteria in the CLP regulation. As a new requirement, these self-classifications should be notified to
ECHA, which in turn publish the classification and labelling inventory based on all notifications
received. There is no tonnage trigger for this obligation. For the purpose of this report, self-
classifications are summarised in Appendix 2 to the main report.

Ongoing activities - pipeline
In addition to listing substance already addressed by the provisions of REACH (pre-registrations,
registrations, substances included in various annexes of REACH and CLP, etc.), the ECHA web-site
also provides the opportunity for searching for substances in the pipeline in relation to certain
REACH and CLP provisions. These will be briefly summarised below:
Community Rolling Action Plan (CoRAP)

The EU member states have the right and duty to conduct REACH substance evaluations. In order
to coordinate this work among Member States and inform the relevant stakeholders of upcoming
substance evaluations, a Community Rolling Action Plan (CoRAP) is developed and published,
indicating by who and when a given substance is expected to be evaluated.
Authorisation process; candidate list, Authorisation list, Annex XIV

Before a substance is included in REACH Annex XIV and thus being subject to Authorisation, it has
to go through the following steps:
1. It has to be identified as a SVHC leading to inclusion in the candidate list8

2. It has to be prioritised and recommended for inclusion in ANNEX XIV (These can be found as
Annex XIV recommendation lists on the ECHA web-site)
3. It has to be included in REACH Annex XIV following a comitology procedure decision (sub-
stances on Annex XIV appear on the Authorisation list on the ECHA web-site).
The candidate list (substances agreed to possess SVHC properties) and the Authorisation list are
published on the ECHA web-site.
Registry of intentions
When EU Member States and ECHA (when required by the European Commission) prepare a pro-
posal for:
• a harmonised classification and labelling,

• an identification of a substance as SVHC, or
• a restriction.
•
This is done as a REACH Annex XV proposal.
The 'registry of intentions' gives an overview of intensions in relation to Annex XV dossiers divided
into:
• current intentions for submitting an Annex XV dossier,
• dossiers submitted, and
• withdrawn intentions and withdrawn submissions
•
for the three types of Annex XV dossiers.
International agreements
OSPAR Convention
OSPAR is the mechanism by which fifteen Governments of the western coasts and catchments of
Europe, together with the European Community, cooperate to protect the marine environment of
the North-East Atlantic.
8 It should be noted that the candidate list is also used in relation to articles imported to, produced in or distributed in the EU.
Certain supply chain information is triggered if the articles contain more than 0.1% (w/w) (REACH Article 7.2 ff).

Work to implement the OSPAR Convention and its strategies is taken forward through the adoption
of decisions, which are legally binding on the Contracting Parties, recommendations and other
agreements. Decisions and recommendationsset out actions to be taken by the Contracting Parties.
These measures are complemented by other agreements setting out:
• issues of importance
• agreed programmes of monitoring, information collection or other work which the Contracting
Parties commit to carry out.
• guidelines or guidance setting out the way that any programme or measure should be imple-
mented
• actions to be taken by the OSPAR Commission on behalf of the Contracting Parties.
HELCOM - Helsinki Convention

The Helsinki Commission, or HELCOM, works to protect the marine environment of the Baltic Sea
from all sources of pollution through intergovernmental co-operation between Denmark, Estonia,
the European Community, Finland, Germany, Latvia, Lithuania, Poland, Russia and Sweden. HEL-
COM is the governing body of the "Convention on the Protection of the Marine Environment of the
Baltic Sea Area" - more usually known as the Helsinki Convention.
In pursuing this objective and vision the countries have jointly pooled their efforts in HEL-
COM, which is works as:
• an environmental policy maker for the Baltic Sea area by developing common environmental
objectives and actions;
• an environmental focal point providing information about (i) the state of/trends in the marine
environment; (ii) the efficiency of measures to protect it and (iii) common initiatives and posi-
tions which can form the basis for decision-making in other international fora;
• a body for developing, according to the specific needs of the Baltic Sea, Recommendations of
its own and Recommendations supplementary to measures imposed by other international or-
ganisations;
• a supervisory body dedicated to ensuring that HELCOM environmental standards are fully
implemented by all parties throughout the Baltic Sea and its catchment area; and
• a co-ordinating body, ascertaining multilateral response in case of major maritime incidents.
Stockholm Convention on Persistent Organic Pollutants (POPs)

The Stockholm Convention on Persistent Organic Pollutants is a global treaty to protect human
health and the environment from chemicals that remain intact in the environment for long periods,
become widely distributed geographically, accumulate in the fatty tissue of humans and wildlife,
and have adverse effects to human health or to the environment. The Convention is administered
by the United Nations Environment Programme and is based in Geneva, Switzerland.
Rotterdam Convention
The objectives of the Rotterdam Convention are:
• to promote shared responsibility and cooperative efforts among Parties in the international
trade of certain hazardous chemicals in order to protect human health and the environment
from potential harm;
• to contribute to the environmentally sound use of those hazardous chemicals, by facilitating
information exchange about their characteristics, by providing for a national decision-making
process on their import and export and by disseminating these decisions to Parties.
• The Convention creates legally binding obligations for the implementation of the Prior In-
formed Consent (PIC) procedure. It built on the voluntary PIC procedure, initiated by UNEP
and FAO in 1989 and ceased on 24 February 2006.

The Convention covers pesticides and industrial chemicals that have been banned or severely re-
stricted for health or environmental reasons by Parties and which have been notified by Parties for
inclusion in the PIC procedure. One notification from each of two specified regions triggers consid-
eration of addition of a chemical to Annex III of the Convention. Severely hazardous pesticide for-
mulations that present a risk under conditions of use in developing countries or countries with
economies in transition may also be proposed for inclusion in Annex III.
Basel Convention
The Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their
Disposal was adopted on 22 March 1989 by the Conference of Plenipotentiaries in Basel, Switzer-
land, in response to a public outcry following the discovery, in the 1980s, in Africa and other parts
of the developing world of deposits of toxic wastes imported from abroad.
The overarching objective of the Basel Convention is to protect human health and the environment
against the adverse effects of hazardous wastes. Its scope of application covers a wide range of
wastes defined as “hazardous wastes” based on their origin and/or composition and their character-
istics, as well as two types of wastes defined as “other wastes” - household waste and incinerator ash.
The provisions of the Convention center around the following principal aims:
• the reduction of hazardous waste generation and the promotion of environmentally sound
management of hazardous wastes, wherever the place of disposal;
• the restriction of transboundary movements of hazardous wastes except where it is perceived
to be in accordance with the principles of environmentally sound management; and
• a regulatory system applying to cases where transboundary movements are permissible.
Eco-labels
Eco-label schemes are voluntary schemes where industry can apply for the right to use the eco-label
on their products if these fulfil the ecolabelling criteria for that type of product. An EU scheme (the
flower) and various national/regional schemes exist. In this project we have focused on the three
most common schemes encountered on Danish products.
EU flower
The EU ecolabelling Regulation lays out the general rules and conditions for the EU ecolabel; the
flower. Criteria for new product groups are gradually added to the scheme via 'decisions'; e.g. the
Commission Decision of 21 June 2007 establishing the ecological criteria for the award of the
Community eco-label to soaps, shampoos and hair conditioners.
Nordic Swan
The Nordic Swan is a cooperation between Denmark, Iceland, Norway, Sweden and Finland. The
Nordic Ecolabelling Board consists of members from each national Ecolabelling Board and decides
on Nordic criteria requirements for products and services. In Denmark, the practical implementa-
tion of the rules, applications and approval process related to the EU flower and Nordic Swan is
hosted by Ecolabelling Denmark "Miljømærkning Danmark" (http://www.ecolabel.dk/). New crite-
ria are applicable in Denmark when they are published on the Ecolabelling Denmark’s website (ac-
cording to Statutory Order no. 447 of 23/04/2010).
Blue Angel (Blauer Engel)

The Blue Angel is a national German eco-label. More information can be found on:
http://www.blauer-engel.de/en.

Annex 4 AP/APEO in the Nordic environment
The following tables are copied from Hansen and Lassen (2008) showing the results of a survey of
AP/APEO in the Nordic anvironment. (see text in Chapter 7 in main report).
For the water samples the following results were obtained:
For the solid samples the following results were obtained:
For the biological samples the following results were obtained:

Substance flow diagrams for the Baltic Sea region from the COHIBA (2012) project (see text in
Chapter 4 in main report).

Survey of alkylphenols and alkylphenol ethoxylates
This survey is part of the Danish EPA’s review of the substances on the List of Undesirable Substances
(LOUS). The report define the substances groups and present information on the use and occurrence of
the alkylphenols and alkylphenol ethoxylates, internationally and in Denmark, information on environ-
mental and health effects, on alternatives to the substances, on existing regulation, on monitoring and
exposure, waste management and information regarding ongoing activities under REACH, among oth-
ers.
Kortlægning af alkylphenoler og alkylphenolethoxylater

Denne kortlægning er et led i Miljøstyrelsens kortlægninger af stofferne på Listen Over Uønskede Stoffer
(LOUS). Rapporten definerer stofgrupperne og indeholder blandt andet en beskrivelse af brugen og
forekomsten af alkylphenoler og alkylphenoethoxylater, internationalt og i Danmark, en beskrivelse af
miljø- og sundhedseffekter af stofferne, og viden om alternativer, eksisterende regulering, moniterings-
data, eksponering, affaldsbehandling og igangværende aktiviteter under REACH.
Strandgade 29
1401 København K , Denmark
Tlf.: (+45) 72 54 40 00
www. mst.dk
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Survey of alkylphenols and alkylphenol ethoxylates. Part of the LOUS-review.

Technical Report · January 2013

Allan Astrup Jensen Frans M Christensen

SEE PROFILE SEE PROFILE

Chemical Risk Assessment and Risk Management View project

UN Life Cycle Initiative View project

The user has requested enhancement of the downloaded file.

Environmental project No. 1470, 2013

Survey of alkylphenols and alkylphenol ethoxylates 1

Survey of alkylphenols and alkylphenol Carsten Lassen 1

1 COWI A/S, Denmark

The Danish Environmental Protection Agency

Sources must be acknowledged.

2 Survey of alkylphenols and alkylphenol ethoxylates

Summary and conclusion .......................................................................................... 7

Sammenfatning og konklusion ................................................................................ 13

1. Introduction to the substance group ................................................................. 19

3. Manufacture and uses ...................................................................................... 45

4. Waste management .......................................................................................... 77

5. Environmental effects and fate ......................................................................... 85

Survey of alkylphenols and alkylphenol ethoxylates 3

6. Human health effects ....................................................................................... 97

7. Monitoring data and exposure ......................................................................... 111

8. Information on alternatives............................................................................. 121

9. Overall conclusions ........................................................................................ 133

10. Abbreviations and acronyms ........................................................................... 141

11. References ..................................................................................................... 143

Annex 1: Uses and tonnage bands according to registrations ....................... 155

Annex 2: Self classification of AP/APEO ..................................................... 158

Annex 3: Background information to chapter 3 on legal framework ............ 172

Annex 4 AP/APEO in the Nordic environment ............................................ 177

4 Survey of alkylphenols and alkylphenol ethoxylates

Background and objectives

Survey of alkylphenols and alkylphenol ethoxylates 5

• Sidsel Dyekjær, Danish EPA

6 Survey of alkylphenols and alkylphenol ethoxylates

Nonylphenols and nonylphenol ethoxylates

Survey of alkylphenols and alkylphenol ethoxylates 7

Octylphenols and octylphenol ethoxylates

8 Survey of alkylphenols and alkylphenol ethoxylates

Dodecylphenols and dodecylphenol ethoxylates

Short chain alkylphenols (with <8-carbon chains)

Survey of alkylphenols and alkylphenol ethoxylates 9

4-tert-Butylphenol is mainly used in a similar way as 4-nonylphenol and 4-tert-octylphenol as co-

10 Survey of alkylphenols and alkylphenol ethoxylates

Overall conclusion concerning the grouping of the substances

Survey of alkylphenols and alkylphenol ethoxylates 11

12 Survey of alkylphenols and alkylphenol ethoxylates

Denne kortlægning vedrører stofgruppen "alkylphenoler og alkylphenolethoxylater" (AP/APEO),

En sammenfatning af produktion og forbrug af 29 stoffer eller stofgrupper på EU niveau og i Dan-

Nonylphenol betragtes som et hormonforstyrrende stof og er klassificeret som reproduktionstoksisk

Survey of alkylphenols and alkylphenol ethoxylates 13

På EU-plan anvendes nonylphenoler hovedsageligt som råmateriale (co-monomer) til fremstilling

14 Survey of alkylphenols and alkylphenol ethoxylates

Koncentrationerne af OP/OPEO i kommunalt spildevand og spildevandsslam er betydeligt lavere

En af de vigtigste octylphenoler, 4-tert-OP, er inkluderet i kandidatlisten under REACH med be-

Et forslag til harmoniseret klassificering og mærkning af 4-(3,4,5-trimethylheptyl)phenol (en for-

Dodecylphenoler og dodecylphenol ethoxylater er ikke omfattet af nogen EU-regulering, er ikke