Chemicals in politics and everyday life

Chemicals in politics and everyday life EU’s chemicals regulation REACH, endocrine disrupting chemicals, nanomaterials and cocktail effects

Chemicals in politics and everyday life EU's chemicals regulation REACH, endocrine disrupting chemicals, nanomaterials and cocktail effects

The Danish Ecological Council May 2014

Contents

Preface Introduction to chemicals in society 1 EU and REACH How is the EU structured?

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47

Brominated flame retardants

54

3 Chemicals in everyday life Chemicals in food

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50

7 8

How can the EU be influenced?

10

Chemicals legislation in the EU

12

Risk assessment

57 60

15

Chemicals in clothing and textiles The horror show – are we hormonal ticking

Limit values

16

time bombs?

64

How large concentrations can humans tolerate?

17

REACH –Step-by-step

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Registration

19

4 Cocktail effects and Nanomaterials Cocktail effects

68

Evaluation

19

Nanomaterials

72

Autorisation

20

"Right to know”

22

5 Hazardous chemicals can be replaced

77

Classification and labelling

25

Legislation deficiencies

27

Substitution of hazardous chemicals What is a substitution and why do it?

78 78

2 Endocrine disrupting substances

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Warning lists and substitution Substitution portals and networks

Intro. to endocrine disrupting substances

30

Consumer role

79

Parabenes

34

Phthalates

39

Glossary

81

Phthalates in hospitals

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Chemicals in politics and everyday life – EU’s chemicals regulation REACH, endocrine disrupting chemicals, nanomaterials and cocktail effects 1. edition, May 2014 ISBN: 978-87-92044-43-3 Text by: Lone Mikkelsen – The Danish Ecological Council (unless otherwise stated) Translation by: Karen Bahn Kristensen, Maria Lund Jensen Design and layout: Birgitte Fjord | Grafisk design Front page photo: wragg

Ph o to R T i ma g es

Bisphenol A Fluorinated substances – PFOA/PFOS

This publication can be downloaded free of charge from the Danish Ecological Council’s website: www.ecocouncil.dk

Quoting, copying and other use of the content of this publication is permitted and encouraged as long as credit is given to its source.

Published by: The Danish Ecological Council – with funding from the Villum Foundation The Danish Ecological Council Blegdamsvej 4B DK-2200 Copenhagen N Tel. +45 3315 0977 email: info@ecocouncil.dk web: www.ecocouncil.dk

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PREFACE

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Preface

In this teaching material, we discuss the problems relating to the so-called endocrine disrupting substances, cumulative effects of chemicals – often referred to as cocktail effects – as well as nanomaterials. These different types of chemicals are present in a large number of products that surround us in our everyday lives and are an important part of our modern lifestyle.

Many of the products containing these chemicals have made our lives easier or smarter, but far too many of these substances have not yet been sufficiently studied for potential harmful effects on human health, animals, and the environment. Experts suspect endocrine disrupting substances of affecting a large number of processes in our body, for instance, the age where children/young people reach puberty and, later, their ability to have children. In addition, the substances are under suspicion of causing cancer and genital abnormalities. Recently, these substances have also come under suspicion of having an impact on obesity and development of diabetes, the latter gradually becoming one of the major lifestyle diseases. Nanomaterials have also been in focus for a long time. Not only due to their extremely modest size, but also in particular due to the fact that, in line with endocrine disrupting substances, they are under suspicion of harming human health and the environment.

Many substances are already regulated by the common European chemicals legislation, REACH. However, many of the permitted chemicals on the market are still suspected of having endocrine disrupting effects and of contributing to cocktail effects. It is the producer’s and/ or industry’s responsibility to prove that the substance produced or used in their products is not hazardous for consumers. However, since there are still no criteria for how to establish whether a chemical is an endocrine disruptor these substances will slip through the safety net of legislation. To secure consumers against any health hazard it is important that these substances are better regulated. Therefore, it is necessary to increase focus on chemicals altogether.

In this electronic publication, we explain the structure of the European Union (EU) and how legislation adopted at EU level is implemented and enforced at national level. In addition, we discuss the contents of

the common European chemicals legislation in general.

Subsequently, the most important groups of endocrine disrupting substances are described with a review of how we are exposed to these substances every day and what impact this might have for our health and the environment. Furthermore, cocktail effects and nanomaterials are described. Each of these sections include examples of what each of us can do in our everyday lives to reduce the risk of being exposed to hazardous chemicals.

The contents of this electronic publication may be rather complicated and contain difficult terms, so at the end of the text you can find a glossary with explanations. When terms included in the glossary appear in the text, they are marked in italics. However, they are not marked in those sections dealing with the specific term and in places where we find that detailed explanations are superfluous. In addition, some terms appear so often that any marking would disturb the reading (e.g. terms like “chemical” and “the EU”).

This electronic publication is produced with the aim of being used within several different subjects and teaching courses, as well as in interdisciplinary projects. You may use it from beginning to end or select sections applicable to specific teaching subjects. Each section is written so it can stand alone, but refers to supporting sections if specific passages need further explanation.

We wish you a pleasant reading!

INTRODUCTION

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Introduction to chemicals in society

Chemicals are present everywhere in our society and they come as both natural and industrial substances. At all times, humans and the environment have been exposed to chemicals. Whether they are natural or man-made has nothing to do with their potential harmful effects on human health and the environment.

Incorrectly, many believe that if a substance is natural, it has no harmful effect. Regrettably, this is not the case!

There are many examples of naturally occurring chemicals being harmful. To give just one example, think about natural aromatics (fragrances). There are no less than 2,500 fragrances, which are combined endlessly in the manufacture of perfumes, personal care products, cleaning agents, etc. A perfume may easily consist of up to 300 different fragrances. Of these 2,500 fragrances at least 100 are suspected of being allergenic, while 26 have been proven to be so. When a substance has been proven to be allergenic it must be mentioned by name in the informative label of the product. This means that if it says ‘perfume’ followed by a name, you know that the product contains a fragrance known to be allergenic.

Furthermore, cosmetics often contain preservatives to ensure longevity of the products. There is an ongoing discussion whether the use of preservatives for, in particular, skin care products such as body lotion is really necessary. Lotions in pots, for instance, are problematic.

When our fingers – more or less contaminated with bacteria – daily are in direct contact with the entire content there is a major need for preservation with antibacterial agents to prevent the lotion from developing mildew.

However, using closed packages such as tubes can largely solve this problem.

It is a fact that we cannot avoid chemicals in our everyday lives, since many of them occur naturally; however, we can control to what extent we are exposed to them, by avoiding those that are really not necessary.

Still today, the harmful consequences these chemicals have for humans and the environment are not fully known. This fact alone should be sufficient for acting according to the precautionary principle. Using the precautionary principle means that chemicals may only

be used when it is necessary for social and/or economic reasons 1. An example of a social argument for using a certain chemical substance that is harmful to our health is a vaccine, which due to heat, only can be preserved in tropical climates if mercury is used as a preservative. In this case, it is more important for an infant to have the vaccine – which may mean survival – than to protect it against a minor quantity of mercury. For such considerations, however, specific analyses must be made before making a final decision. In our part of the world we can most often do without hazardous substances (or at least use less hazardous alternatives).

Every day we are in contact with a range of products without knowing whether they are full of hazardous chemicals such as endocrine disrupting substances and/or allergenic and carcinogenic compounds.

Moreover, our knowledge about most of the chemicals that we use today is extremely limited. As consumers, we should feel sure that there are no substances of high concern in the products we use every day, whether they are manufactured in the European Union (EU) or imported from other countries. Quite simply, it is not acceptable that hazardous substances are allowed in products when alternatives that are less harmful to human health and the environment are available.

Chemicals are a natural part of the material wealth and comfort we live with today and many of us would rather not be without them; but they have also created enormous health and environmental problems. Today, a number of manufactured chemicals have been spread all over the world and are found in water, air, and soil.

It has been proven that these chemicals – even in very small quantities – can affect eco-systems and animals, leading to problems such as accumulation of pollutants in polar bears and whales with ensuing health impacts.

Furthermore, hermaphroditic fish and snails have been found, among other places, in Denmark and herma- phroditic alligators have been found in the US, suspected to be caused by an increasing exposure to man made (hormone disrupting) chemicals.

1 A socio-economic analysis is a well established method for balancing pros and cons of an action for society as a whole.

INTRODUCTION

Many scientific surveys have shown that girls today reach puberty earlier 2 and in Denmark an increasing number of boys are born without descended testicles (cryptorchidism) or with a penis malformation with an abnormal ventral opening of the urethra (hypospadias)3.

In addition, Denmark shares the world record with Norway when it comes to the number of people with testicular cancer (see Figure 1). An increasing number of researchers confirm that these health impacts are caused, entirely or partly, by exposure to endocrine disrupting substances.

In 2004, the WWF (World Wildlife Fund) conducted a well-known survey in which blood samples from the ministers of the environment and health from 13 EU countries were tested. The blood samples were screened for a range of industrial (manufactured) chemicals that may have a negative impact on health and the environment and are present, among others, in ordinary consumer goods such as electronics, carpets, furniture, pizza boxes, and packages for microwave popcorn. On

Figure 1 Denmark and testicular cancer

The graph shows that Denmark is the EU country with the largest rate of testicular cancer incidences. The columns show how many have been diagnosed with testicular cancer. The lowest axis shows the number of persons per

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average, 37 chemicals per person were found among the 103 persons tested. In the blood of the former Danish Minister for the Environment (Hans Christian Schmidt) 36 chemicals were found. Of the substances found, some were banned several decades ago, but many of them are still in use or present as pollutants in the surrounding environment presenting a threat against our health and nature. Many of the chemicals found in the ministers’ blood are persistent, bio accumulative and toxic (poisonous) – called PBT substances.

In addition, many of them can disturb the endocrine system of animals and humans. The problem relating to PBT substances is their persistency in our environment, even after production and consumption has stopped.

PBTs cannot degrade or only do so very slowly; in addition, large quantities accumulate in the fatty tissue of animals and humans, as they are liposoluble. An example is polychlorinated biphenyls (PCBs), which are a group of industrial chemicals developed in the 1920s.

They were in particular used in the electronics industry due to their insulating properties and low flammability.

Later it was discovered that these substances might lead to, among other things, brain damage and today they are banned almost all over the world.

Sweden was one of the countries that adopted a ban already back in 1972.

It is assessed that some 2 million tonnes of PCB has been produced.

Some of this PCB has been incinerated or landfilled. However, a large part is still present in our surroundings, for instance, in buildings and electronics.

The rest has been discharged into the oceans and has entered nature’s cycle.

The result is that animals and humans will be exposed to these substances in generations to come. PBTs are found in seals and polar bears in the Arctic, an area where the substances never were used but have been transported by water and air. To avoid similar problems in the future it is crucial that the chemicals legislation becomes stricter! We have to regulate the chemicals before they enter the market.

100,000. Source: http://info.cancerresearchuk.org/cancerstats/types/testis/incidence/uk-testicular-cancer-incidencestatistics. (2008).

2 Danish Environmental Protection Agency. ”Langtidseffekter af prænatal pesticideksponering” (Long-term effects of prenatal exposure to pesticides): http://www2.mst.dk/Udgiv/publikationer/2012/06/978-87-92779-71-7.pdf 3 Gabel, P. et al. 2011. The risk of cryptorchidism among sons of women working in horticulture in Denmark: a cohort study. Environmental Health: A Global Access Science Source, 10: 100

P ho t o P i et ro N aj - Ol ea ri

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EU and REACH

EU AND REACH > HOW IS THE EU STRUCTURED?

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How is the EU structured?

Since 1973, Denmark has been a member of the European Union (EU). Consequently, many aspects of our everyday life are subject to a number of common laws and regulations that are enacted and managed at EU level. It affects such different aspects as what you eat, what you wear, how large CO2 emissions our countries may have, and in which parts of the oceans fishermen may catch fish.

The EU primarily legislates in fields where problems are best solved in union. When it comes to chemicals, for instance, it is evident that all countries wish to protect their citizens against harmful chemicals. However, it would be much more expensive if each country has its own set of rules for which substances may be present in different consumer goods such as toys, electrical appliances, and cosmetics. In addition, each country alone would not have the capacity to regulate the many thousands of substances and products that are produced and imported from all over the world. Common rules mean that companies may benefit from producing their goods in much larger quantities and that more companies compete. At the same time, countries together are

in a better position to adopt common rules, request risk assessments of the multitude of substances, and assess all the data to be submitted by the producers. In order to regulate all these different fields the EU institutions adopt rules that must be followed in the member states according to a set of guidelines depending on the type of ‘act’ to be introduced. These new acts or rules come in the form of regulations, directives, decisions, recommendations, and opinions. The difference among them is primarily the way in which they are handled in the member states.

• A regulation applies directly all over the EU. This means that it is binding in all details and applies to all member states as soon as it has been adopted.

• A directive is binding for each member state regarding the objective – such as a ban on a chemical substance – but the national authorities can implement it in their national legislation as they see fit.

• A decision is binding in all details. When it is stated to whom it is directed it is only binding to those mentioned.

• Recommendations and opinions are not binding.

The EU has 28 member states. The newest member is Croatia, which joined in the summer of 2013. EU institutions are primarily located in Brussels in Belgium, but Luxembourg City and Strasbourg also have important EU institutions.

EU AND REACH > HOW IS THE EU STRUCTURED?

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Figure 2 The European Union

European Commission Has the right of legislative initiative

European Parliament

Council of the European

Organized in 8 political groups.

Union

Adopts or rejects legislative pro-

Shares legislative and

posals together with the Council

budgetary powers equally

through the co-decision procedure

with the Parliament

European Court of Justice Interprets EU law to make sure it is applied in the same way in all EU countries Structure of the European Union with its four key institutions; the European Commission, the European Parliament, the Council of the European Union, and the European Court of Justice.

The most important institutions in the EU are the European Commission, the European Parliament, the Council of the European Union, and the Court of Justice of the European Union, normally referred to as the European Court of Justice (see Figure 2).

The European Commission consists of a political management with one commissioner from each member state as well as officials. Each commissioner runs a department. The departments are known as DirectoratesGeneral (DGs). The Commission proposes acts and rules for the entire EU so any country is treated fairly. In addition, it is the responsibility of the Commission that all member states comply with the common legislation.

If it finds that violations take place, it may bring a case against a specific member state before the European Court of Justice.

When the Commission has submitted a legislative proposal, it must be adopted in the European Parliament and the Council of the European Union. Together, these two institutions have the legislative power in the EU. They cannot submit legislative proposal themselves, but they adopt, amend, or reject the proposals of the Commission.

You may say that the Parliament is the spokesperson of the Europeans since it consists of directly elected politicians. Denmark has 13 members of the European Parliament, representing different political parties. By

contrast, the Council of the European Union consists of a number of ministers with responsibility for a given area, for instance the Council of Environment and the European Council that consists of the Heads of State or Government of the 28 member states.

To distribute influence and power as equally as possible between the European institutions it is the role of the Parliament to control the Commission. For instance, the members of Parliament must approve a new Commission when the member states have designated new commissioners 4.

In view of creating dynamics in the EU, the Council is presided over for a period of six months by each member state in turn. This is called the EU presidency. The country holding the EU presidency has two main tasks: 1. To organise and chair the meetings in the different

configurations of the Council. For instance, the Danish Minister for the Environment chairs meetings in the Council of Environment when Denmark holds the presidency. The presidency must always act in a neutral and impartial manner.

2. To represent the Council towards other EU institutions, not least the European Parliament and the European Commission. Here, the presidency is the other member states’ spokesperson in negotiations with the Parliament and the Commission.

4 The EU and the Danish Folketing (Parliament): http://www.eu-oplysningen.dk/upload/application/pdf/4fb582d3/EU%20og%20Folketinget_2010%20pdf.pdf

EU AND REACH > HOW CAN THE EU BE INFLUENCED?

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How can the EU be influenced?

Many players seek to influence decisions in the EU. These players may be a large private corporation, a company, a trade union, an environmental organisation, or a local player such as a Danish regional council. The environmental organisations, for instance, normally seek to promote their own case, while large companies and trade organisations often hire lobbyists. A lobbyist is a person representing a specific interest towards politicians and officials, seeking to influence legislative work in the EU in the desired direction. Lobbyism takes place in all stages of the EU decision-making process and towards all parties. Many interest organisations, companies, and regions and municipalities in Denmark have staff members located in Brussels. They seek to influence decision-makers in the EU institutions by presenting their interests; and they gather knowledge early in the decision-making process. This knowledge is communicated back home to be used by the ‘mother organisation/company’ in the Danish decision-making process. Actually, lobbyists are an indispensable part of the democratic law-making process in both Denmark and the EU. Lobbyists inform politicians about possible consequences of specific decisions and legislative proposals. This gives politicians a better decision-making basis.

An estimated 15,000 lobbyists work in Brussels.

Around 60 % of the lobbyists represent private industry and 21 % represent the public sector. The

remaining 19 % represent other organisations such as trade unions, consumer and environmental groups (including several NGOs 5), churches, and think tanks 6.

There is clearly an unequal distribution of interest organisations. This is primarily due to the fact that companies and industrial organisations have by far the largest financial resources. Another reason is historical facts. The EU is the continuation of what started as the European Coal and Steel Community (ECSC) and it was thus primarily an economic cooperation. This meant that major specific interests were at stake for private industry in particular when legislation was designed.

In the different member states, there is more or less democratic influence on how votes are cast in the EU. When Denmark votes for or against a proposal in the Council it is done on the background of a thorough decision-making process – the EU coordination process.

First, Government reaches an agreement and then it makes sure not to have a majority in the Danish Parliament against their view on the specific case. The European Affairs Committee does this giving its mandate to Government on how to vote. In other countries, the national parliament has far less influence on their government’s policy in the EU. When a law has been finally adopted at EU level, it must be implemented in the different member states.

Lobbyism may influence votes in the European Commission, the Parliament, and the Council of the European Union.

5 Non-governmental Organisation (NGO); an organisation that is neither supported nor controlled by government 6 Source: EUropa på vej (EUrope on the road) by Mads Dagnis Jensen and Julie Hassing Nielsen

EU AND REACH > HOW CAN THE EU BE INFLUENCED?

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The European Parliament has gained increasing influence on the EU environmental policy up through the years. The Parliament is the European institution working with the largest degree of openness and thus, the easiest institution to influence. In the Danish debate, it has often appeared as if it is impossible to get any influence on the EU decision-making processes.

However, the experience of, for instance, environmental organisations, is that it is equally difficult to influence EU decisions and the Danish Parliament. However, it is a prerequisite that groups cooperate across borders.

There are some general trends in relation to the votes in environmental issues among the different groups of parties in the European Parliament; thereby it is important how to plan lobbying. The green group in the Parliament naturally gives high priority to environmental issues. In addition, the Social Democrat group – the progressive alliance of socialists and democrats – and other left-wing groups have some emphasis on

In the US, there are laws to control lobby activities, while in the EU there is basically free scope for how the different organisations choose to influence politics.

However, to secure a meaningful discussion about how to set up the framework for lobbying at EU level it is necessary to define a basic framework for the interplay between EU institutions and lobbyists. In this regard, the European Commission has drawn up a basic guideline presented in the Green Paper 'European Transparency Initiative’ 8, which was launched in 2006 and followed up in 2007:

environmental problems. The large conservative and Christian democrats groups are normally more reluctant and much more willing to focus on short-term financial interests of industry. The liberal group is often positioned in-between while the right-wing groups have the least environmental focus.

tention of the European institutions. In some cases, the Community offers financial support in order to ensure that views of certain interest groups are effectively voiced at European level (e.g. consumer interests, disabled citizens, environmental interests etc.).

3. At the same time, undue influence should not be exerted on the European institutions through improper lobbying.

4. When lobby groups seek to contribute to EU policy development, it must be clear to the general public, which input they provide to the European institutions. It must also be clear who they represent, what their mission is and how they are funded.

5. Measures in the field of transparency must be effective and proportionate.

Nature, environment, and consumer organisations in the EU member states cooperate closely. Greenpeace and the World Wildlife Fund (WWF) are genuine international organisations and in addition, there are umbrella organisations in which the different national organisations cooperate. The largest umbrella organisation is European Environment Bureau (EEB) that operates broadly with working groups within, for instance, chemicals policy, nanotechnology, and air pollution.

There are also more specialised umbrella organisations such as Pesticide Action Network (PAN-Europe) focusing on the reduction of pesticides. These organisations have their offices in Brussels where they follow EU’s work closely, and there is lively e-mail communication between these offices and the associated organisations in all EU member states. The same is true for the consumer organisations that have joined forces in the umbrella organisation BEUC (The European Consumer Organisation) in Brussels. Many parliamentarians 7 – including many of the Danish ones – are very aware that they are overwhelmed with arguments from industry organisations (industry, agriculture, hauliers, airlines, etc.) and are therefore open for arguments from the green organisations to create a balanced basis for decision-making.

1. Lobbying is a legitimate part of the democratic system, regardless of whether it is carried out by individual citizens or companies, civil society organisations and other interest groups or firms working on behalf of third parties (public affairs professionals, think tanks and lawyers).

2. Lobbyists can help bring important issues to the at-

In an attempt to create more openness around decisionmaking processes and the role of lobbyists in the EU, the European Commission introduced a voluntary transparency register in June 2008. This is a first step, but it is still not transparent who is walking around the corridors. The problem of a voluntary scheme may be that only ‘the good guys’ sign up. To be able to control lobbyism to the benefit of all EU citizens it would be extremely advantageous to know who the lobbyists are and how many of them are around. A mandatory transparency register may be the solution to this problem. At the same time, it would give decision-makers a chance to know who they are dealing with and which interests have been heard in a case.

7 Members of the European Parliament, who are democratically elected, are called parliamentarians.

8 http://ec.europa.eu/transparency/eti/index_en.htm#one; Green Paper 'European Transparency Initiative’, European Commission, May 2006

EU AND REACH > CHEMICALS LEGISLATION IN THE EU

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Chemicals legislation in the EU In December 2006, the EU adopted a new common chemicals regulation: REACH. REACH came into effect on 1 June 2007, replacing some 40 previous directives.

Since the adoption of REACH, chemical producers and importers are responsible for acquiring information about the properties of substances, including any risk in their use, before they can be approved. Before REACH took effect it was up to the authorities to prove that a chemical was hazardous if they wanted it removed from the market. The purpose of the regulation is to secure that the around 100,000 different chemicals used in the EU are tested regarding safety for humans and the environment and that they are used safely. With REACH, it was established that the chemicals legislation in Europe is based on the precautionary principle. Before that, all existing chemicals could be used freely unless an authority had proven a risk posed by a specific chemical product and subsequently banned its use. Only for substances placed on the market after 1981 tests were automatically required. With REACH, it is the industry that must prove that they produce and use chemicals in a safe manner. REACH covers individual substances (the chemical substance), substances in chemical preparations, and substances in articles (see definitions below). The regulation also means that the use of particularly problematic substances (often called SVHC-substances; Substances of Very High Concern) will in due time require a permit.

The most hazardous of these substances must be substituted (replaced) if suitable alternative substances or technologies are available.

In connection with the implementation of REACH, the European Chemicals Agency (ECHA) was established.

ECHA plays a key role in the general process relating to guidelines for the use of chemicals. ECHA is located in Helsinki, Finland and is the institution that receives registration of existing chemicals. All registrations are scrutinised and selected substances are then assessed by the authorities of the EU member states who can either approve or set limits for chemicals that they find will pose a health risk to consumers. This is done to secure coherent legislation all over the EU. Each member state may in periods draw up special national rules. For instance, Denmark has done this with the ban on Bisphenol A in baby’s bottles, using the precautionary principle (see section ’BISPHENOL A’). When

REACH – a brief introduction

• REACH is the extensive EU chemicals regulation and is short for: Registration, Evaluation, Authorisation of CHemicals.

• The aim of REACH is to secure a high level of protection of human health and the environment and to increase competitiveness and innovation in companies.

• After the introduction of REACH the responsibility for acquiring information about the substances’ properties and the risks associated with their use in connection with permitting is vested with the chemicals producers and importers.

Definitions – chemical substances, products, mixtures and articles Chemicals is a general term for chemical substances and mixtures of these .

A chemical substance is a chemical element and its compounds in the natural state or obtained by any manufacturing process, including any additive necessary to preserve its stability and any impurity deriving from the process used, but excluding any solvent, which may be separated without affecting the stability of the substance or changing its composition.

A chemical product/mixture is a mixture or solution composed of two or more substances. A chemical product can be solid, liquid or gaseous.

An article is an object which during production is given a special shape, surface or design which determines its function to a greater degree than does its chemical composition.

EU AND REACH > CHEMICALS LEGISLATION IN THE EU

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Figure 3 REACH timeline Deadline of registration : Substances > 1 ton/year Deadline of registration: Deadline of registration:

Substances > 100 tonnes/year

Substances > 1000 tonnes/year R50/R53 substances > 100 tonnes/year CMR substances category 1 and 2 > 1 ton/year Public announcement of pre-registered substances by ECHA. Start of registration Pre-registration REACH enters into force

1/6 2007

1/6-30/11 2008

1/1 2009

1/12 2010

1 /6 2013

1/6 2018

Time line of full implementation of REACH. Even though

find suitable alternatives to those chemicals that will be

this chemicals regulation came into effect already back in

banned with REACH, and that retailers must have time to

2007 it is seen here that it will not be fully implemented

replace parts of their assortment. R50/R53 substances:

until 2018. This is due, among other causes, to the fact

classified as harmful to the environment.

that producers and companies must have a chance to

an EU member state uses this rule the specific case is discussed at EU level and subsequently the rule will apply all over the EU or the country in question will be told to withdraw the ban in order to have identical rules for all EU member states. If not complied with, the country in question may be brought before the European Court of Justice for breach of the Treaty. If a country has been found guilty of infringement of the Treaty, it may be sentenced with a fine if it continues to disobey the same rules.

Before REACH came into force a time line was made for its full implementation (see Figure 3), as many years will be needed to register, evaluate, and authorise the around 100,000 chemical substances that are believed to be on the market in the EU 9. The time line has been designed in a way that registration prioritises the most health-hazardous substances, the so-called CMR substances 10 together with environmentally

hazardous substances, and substances produced in the largest quantities (> 1,000 tonnes/year). Then there is a registration deadline for substances produced in quantities over 100 tonnes/year and finally registration must be made of substances with a production of more than 1 tonne/year. All quantity limits apply to a single company’s production or import of a given substance into the EU. It is a key objective of REACH to promote substitution (replacement) of particularly hazardous chemicals with safer alternatives – so far, however, this has only been the case for very few substances. However, just the mere existence of the REACH authorisation process sends a clear message to companies to the effect that they should go through all the chemicals they are using and start replacing hazardous substances with safer alternatives. The intention is that this legislation will promote innovation and lead to safer processes and the use of alternative techniques. Whether this intention

9 The European INventory of Existing Commercial chemical Substances (EINECS): http://esis.jrc.ec.europa.eu/index.php?PGM=ein 10 CMR means Carcinogenic (causes cancer), Mutagenic (changes genes) and Reprotoxic (harms reproduction), applies to production > 1 tonne/year/producer..

EU AND REACH > CHEMICALS LEGISLATION IN THE EU

comes true will be seen in the coming years’ administration of the regulation. If substitution of the mentioned substances is not possible for technical reasons (e.g. there is no suitable substance on the market that can replace the hazardous one) or if it is estimated that the alternative substance is too expensive, substances will only be permitted when the socio-economic benefits exceed the risks. This means that the social and economic benefits compared with human health should be larger than the risk associated with the use of the chemical. To give an example, it could be chemicals used for treatment of water in developing countries here it is more important that people get clean water than to protect them against a small amount of chemicals, even if the substances used may be suspected of being endocrine disrupting or carcinogenic.

Some substances are exempt from registration under REACH. For instance, pesticides and biocides (regulated under Statutory Order on plant protection products), substances used in medicinal products for human and veterinary use and substances used in food or feeding stuffs. In addition, cosmetics are not covered by the REACH scope. Earlier cosmetics were regulated under the special cosmetics directive, which was implemented in Danish law in the form of the Statutory Order on cosmetics. In June 2013, this changed to a regulation on cosmetic products. However, all cosmetic products must be registered under REACH, but the chemical safety report is not required to cover evaluations of risks for human health.

The above clearly shows how many exemptions are contained in REACH – and these are just a few examples.

Before describing the regulation in detail below (”REACH – Step by step”) we should be familiar with a few terms. For instance, that a distinction is made between an article and a product – and that different rules apply to them 11.

•

•

A chemical substance is a chemical element and its compounds in the natural state or obtained by any manufacturing process. In technical and legal terms a chemical substance is defined as ‘the substance as it occurs or as it is manufactured’.

A chemical product/mixture is a uniform mixture or solution composed of two or more substances. A chemical product may be solid, liquid, or gaseous. Paints and detergents are examples of chemical products.

11 Website of the Danish Environmental Protection Agency: www.mst.dk

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•

An article is an object, which during production is given a special shape, surface or design, which determines its function to a greater degree than does its chemical composition. Examples of articles are cars, textiles, batteries, wallpaper, and electronic equipment.

When we use the word ‘chemicals’ in this text it covers both chemicals and mixtures of chemicals. It is often seen that only the terms ‘chemicals’ and ‘articles’ are used, but you should be aware of the statutory differences, where a distinction is made between the four terms described above.

EU AND REACH > RISK ASSESSMENT

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Risk assessment When you wish to examine whether chemicals have hazardous effects on human health and the environment, you make a so-called risk assessment.

However, making risk assessments is not a walk in the park. You must be familiar with many factors in order for it to become a satisfactory analysis and in addition, you often make separate assessments for humans (human risk assessment) and the environment (ecotoxicological risk assessment). The human risk assessment is generally the least complicated and in many cases the most precise, since only one species – man – is being studied. In the ecotoxicological risk assessment it is the impact on the environment in general that is assessed and this includes obviously thousands of species. The purpose of a risk assessment is to gather all existing knowledge into a uniform presentation in order for decisions on regulation, if any, to be made in a consequent and clear manner where all scientific data is taken into consideration.

seek to describe all possible ways in which people and the environment may be exposed to a substance. The process is extremely time consuming and this is one of the reasons why regulating chemicals is a very slow process. Therefore, environmental groups and trade unions often request that substances must be regulated based on the hazardous properties and not wait for a risk assessment.

The risk assessment is an important requirement in EU legislation in connection with control of production, use, and discharge of chemicals. The statutory risk assessment is very comprehensive. It is described in ”The Technical Guidance Document” (TGD) 12, where the primary objective is to look at possible effects from individual chemicals on human health and the environment. The risk assessment is a prerequisite for environmental and health effects of a given substance to be implemented and regulated in specific legislation.

Normally, extensive scientific work and documentation will be available to be used by an authority - such as the Danish Working Environment Authority - for making a risk assessment. An example of such may be researchers having studied how lead affects human health. They may for instance have made tests, for carcinogenic effects, effects on the cardiovascular system, teratogenic effects, behavioural effects, and allergenic effects. The results from all these tests are then studied in order to end up with a risk assessment with the broadest possible coverage.

The disadvantage of a risk assessment is that the procedure becomes very comprehensive – because you

12 http://ihcp.jrc.ec.europa.eu/our_activities/public-health/risk_assessment_of_Biocides/doc/tgd

EU AND REACH > LIMIT VALUES

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Limit values A limit value of a substance determines how large a quantity of the substance may be present, for instance, in food or in soil. Limit values reflect how much experts believe we can ingest every day thoughout life without having an increased risk of diseases etc. Therefore, minor exceedances of the limit value for short periods of time have no health effects.

When setting a limit value for chemicals contents in food, experts must first find out how much of the substance a person can tolerate. Then they must know how much we typically eat of different foodstuffs.

Against this background, a limit value is set of how large a quantity of the substance may be found in each foodstuff.

have been exposed to endocrine disrupting substances for a long period or in particularly sensitive periods of our life, for instance at the embryonic stage.

There is no guarantee that the assessment of the health effects of a substance will not change. Limit values may change if new knowledge shows that this is called for. For instance, new research results may show novel properties of the substance.

Despite much research in endocrine disrupting substances, we know very little about these substances’ impact on human health in the quantities we are exposed to in everyday life. The endocrine system generally restores itself after short external impacts, but we do not know whether this is also true when we

We know several examples where the development of animals has been affected after prolonged contact with endocrine disrupting substances. Fish and snails with gender disorder have been found, and in several cases, it has been substantiated that the disorders were due to contamination with endocrine disrupting substances. In other cases, the cause has not been found. In addition, it has been established through animal tests that certain chemicals affect the hormonal balance of animals and thus their normal gender development.

This indicates that it might be beneficial for human health and the environment if we could work in the direction of having limit values for different endocrine disrupting substances. Alternatively, the substances should be phased out completely if it turns out that it is impossible to set a lower limit value under which the substance has no effects on human health and the environment.

Acute effects of a chemical are normally tested by making so-called LD50 tests. In such tests, test animals (e.g. mice) are exposed to such high doses of a given substance that many of them die. The purpose is to find

Response

Response

Figure 4 Dose-response curves

Dose

Dose

Dose-response curves as they are generally presented. To

the right is a linear curve. This describes, for instance, a

the left is a sigmoid curve, which is the most common one.

carcinogenic substance where no threshold value can be

Here, there will be a lower threshold value where expo-

set, under which exposure to the substance does not lead

sure to a given substance does not lead to harmful effects;

to higher risk of developing cancer. No matter how small a

after this, higher doses will lead to higher response. To

dose you are exposed to it increases the risk of disease.

EU AND REACH > LIMIT VALUES

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the dose, by which 50 % of the exposed animals die, also called the LD50 value.

For carcinogenic substances, there is no lower limit value. This means that you cannot be exposed to even the slightest concentration of the substance without having a somewhat higher risk of developing cancer.

When this is the case, the term ‘lifetime risk’ is often used. In Denmark, we generally tolerate a lifetime risk of 10 -6. This means that we tolerate one additional case

Phot o C at heri ne Lane

In the establishment of limit values researchers uses a number of scientific tests to assess whether or not a limit value of the chemical substance can be found.

Finding a limit value means that if you are exposed to concentrations of the substance that is below this limit it will not have harmful effects; by contrast, exposure to higher concentrations may lead to damage to human health and/or the environment.

Experts decide, based on scientific data, the quantities of various substances allowed in our food. This is to ensure, that the population is not exposed to health risks from normal intake of food and drinks.

of cancer based on exposure to the given substance for each one million people during a normal lifetime, which has been set at 70 years.

How large concentrations can humans tolerate?

The health risk of chemical substances in foodstuffs is assessed based on scientific studies that cover, among other things, feeding tests on animals such as mice and rats. In most cases, these assessments of additives, contaminants, and natural toxins in food are made by international scientific committees such as the EU Scientific Committee for Food or in the UN by the FAO/ WHO Joint Expert Committee on Food Additives (JECFA).

The Danish Veterinary and Food Administration also has the expertise to make these assessments and has participated actively in international work for many years.

In the assessment of substances, an Acceptable Daily Intake (ADI) or a Tolerable Daily Intake (TDI) value is often established. These values are very similar, as both are expressions of the highest amount of a given substance that we can be exposed to without any health effects (see below). According to the FAO/WHO JECFA expert committee this quantity is normally one hundredth of the highest dose that a test animal can ingest daily throughout life without observed damage (in animal tests this factor is called NOAEL – ”No Observed Adverse Effects Level”). The safety factor of 100 varies according to the substance in question. This factor takes into consideration the variation between

different species, for instance between mice and humans and the variations from one person to another, for instance the physical variation between children and adults. This means that if an animal test has shown that a given substance does not have harmful effects to health in a concentration of 4.5 mg/kg body weight/day you find the corresponding ADI/TDI with the calculation:

So on the basis of this animal test it will be assessed that a person can tolerate an intake of 45 μg/kg body weight/day of the given substance.

ADI is short for “Acceptable Daily Intake" and is normally used for substances that may be used in the production of foodstuffs, but will need an evaluation before they are permitted. This means that a chemical substance is deliberately added to attain a desired effect despite the negative side effects that may occur.

ADI is a measurement for how large a quantity of the substance a person can ingest throughout life without any health risk. Examples of substances with an ADI value are additives, including colorants, preservatives, and sweeteners.

All approved additives are included in the so-called ‘ positive list’. From this list, it appears which additives may be added to which foodstuffs and in which quantities.

EU AND REACH > LIMIT VALUES

TDI is short for “Tolerable Daily Intake" and is used for substances whose presence in foodstuffs cannot be completely controlled and as a consequence have to be tolerated to some extent. This is the case, for instance, for heavy metals and dioxins that are found as pollution in the environment. The tolerable daily intake is the quantity of the substance that a person is assessed to be able to ingest every day throughout life without any health risk. Examples of substances with a TDI value are lead and cadmium. Often a safety factor is used significantly below 100 as mentioned above – mostly due to the diffuse pollution that cannot be removed.

ADI and TDI are established based on our knowledge about the toxicity of the specific substance. This knowledge comes, among other sources, from animal tests. Any impacts in the long-term perspective are also considered; for instance, whether a substance can cause cancer. Experts furthermore request results from so-called reproduction tests clarifying the effect from the substance on test animals’ fertility and health over several generations. If knowledge is available about a substance’s effect on humans, for instance from the use in medicine or from chemical contamination incidents this is also considered in the evaluation.

It is important to note that ADI and TDI are not a hazard limit, nor an absolute limit value, but an expression of an expert evaluation based on scientific data about what you may ingest all your life without any risks.

Even if it is not desirable, minor exceedances of the established values for short periods will have no health effect due to the safety factor. If this is significantly below 100, however, it may still be problematic. Not least because the cocktail effects, where several substances are present in the same product, have not been taken into consideration. Therefore, it is possible that the safety factors used in the establishment of ADI and TDI do not always give the intended level of protection.

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EU AND REACH > REACH – STEP-BY-STEP

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REACH –Step-by-step Figure 5 How to understand REACH

R (egistration)

E (valuation)

A (uthorisation of)

CH (emicals)

REACH is the European regulation on chemicals and their safe use. As explained in the figure the name is an abbreviation.

Registration Registration is the first phase of the REACH regulation.

Producers are requested to submit specified health and safety information about all substances produced or imported and thereby present on the European market. Health information must be based on research for which specific tests and analyses, agreed upon in the EU, must be applied. The obligation of registration applies to all chemicals produced or imported as substances or as part of a mixture in quantities above one tonne per year per producer/importer (see, however, the time line for implementation, Figure 3).

Furthermore, producers and importers must register if there is an intended release of one or more chemicals from the article. An example of an article with an intended release is an eraser or a tissue with a scent.

In the latter case, there will be an intended release of fragrance.

The report on health and safety data must be submitted to ECHA in Helsinki. A pre-registration of substances, which were already on the market when REACH entered into effect, took place during 2008 and resulted in a list of more than 140,000 substances. The pre-registration was necessary in relation to companies continued use of the substances they had used hitherto and it applied to all companies producing or importing a

chemical substance in quantities above 1 tonne/year.

If a company had not pre-registered a substance by 1 December 2008, it would not later on be able to register its substances within the deadlines established in REACH. Thereby the so-called “no data – no market” rule applies with the consequence that the company will have to interrupt its production, import, and/or marketing of the substance or the chemical product in which the substance is an ingredient. The reasoning behind this pre-registration was among other things a desire to reduce companies’ costs in connection with subsequent registrations. In the pre-registration companies only had to state the identity of the substance, the name of the company, and similar data. By the end of the pre-registration period all companies were divi-ded into groups with other companies using the same substances. In this way they were invited to join forces in the actual registration so that, for instance, animal tests were not repeated unnecessarily, thereby redu-cing the use of laboratory animals. In the end the costs were, as mentioned, reduced for everybody.

Evaluation In view of standardising the evaluation of the registered substances, the European Chemicals Agency

EU AND REACH > REACH – STEP-BY-STEP

ECHA reviews the submitted data and estimates the hazardousness of substances in cooperation with the authorities of the member states. ECHA is in charge of the practical management of the registrations, evaluation of proposed tests, and of monitoring that the registrations comply with requirements. ECHA also handles the practical administration of the authorisation scheme, as well as preparation of guidelines to industry and authorities about how best to comply with the requirements associated with REACH. A registration application as a minimum goes through two consecutive evaluations with each their purpose.

First, the Agency carries out a completeness check.

Here it is assessed whether all necessary items in the application are correctly filled in, but the correctness and quality of data are not assessed. Then, at random sampling level, a control of correctness of submitted data is made – a so-called compliance check. This control may lead to a request to the company having submitted the registration that it submits further information if the original data are insufficient for ascertaining that the substance does not pose a risk to human health and the environment.

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Authorisation The authorisation process is the last phase of REACH. You can say that the ECHA “Candidate List” is the key of the entire authorisation process. The substances on this list comply with the criteria for “substances of very high concern”. Both member states and EU authorities may designate hazardous chemicals for entry on the Candidate List. A substance belonging to the group of substances of very high concern complies with one or more of the following criteria: • • •

is classified as a CMR substance in category 1 or 2 (An EU categorization system) is a PBT substance or a vPvB substance there is scientific documentation of other probable serious impacts on human health or the environment. This applies, for instance, to endocrine disrupting substances.

CMR substances: Carcinogenic, mutagenic and/or reprotoxic PBT substances: Persistent, bioaccumulative and toxic vPvB substances: Very persistent, very bioaccumulative

The EU chemicals regulation REACH was adopted in 2006 and entered into force in 2007.

CMR is short for carcinogenic, mutagenic and reprotoxic.

This abbreviation is used for substances that are carcinogenic, may cause mutations in our genes, and/ or are harmful to our reproductive system (harms the ability to reproduce).

PBT is short for persistent, bioaccumulative, and toxic.

Persistent means that the substance decomposes very slowly in nature. Bioaccumulative means that it accumulates in living organisms, as certain pollutants, such as PCB and mercury are known to do. In addition, it is toxic (poisonous) and thus has several harmful properties effecting human health and the environment. In contrast to the CMR substances, for which just one of the properties must be present, all three properties must be met for a substance to be called PBT. When we talk about vPvB substances things get a lot worse.

It means very Persistent and very Bioaccumulative – and it may even not decompose at all. In return, these substances do not need to be toxic, but may be poisonous to a minor degree – the high persistence makes them very problematic anyhow.

EU AND REACH > REACH – STEP-BY-STEP

An entry on the Candidate List is the first step towards a substance being included in the so-called authorisation list. Once a substance appears on this list it means that companies still wishing to produce, import, or use the substance must apply for an authorisation/permit within a specific deadline 13. The application for authorisation must normally be submitted no later than 18 months before this date. An authorisation to continued production, import, or use of the substance is only given if the benefits of continued use of the substance outweigh the risks or if the potential risks are considered limited or under ”adequate control”. This means that the substances in the future can only be used for purposes approved by the authorities. However, the notion of ”adequate control” is controversial. For instance, it may mean that a substance is used in so-called closed systems – it may be substances chemically bound in plastics – and then requirements are not nearly as strict. However, history has shown that systems originally considered as closed are often not so in practice – for instance, when the products in question are to be disposed after the end of their useful life. In addition, it is not certain when a substance is so hazardous that it must be subject to the full authorisation scheme. For example, REACH stipulates that this is only the case for endocrine disrupting substances, if no threshold value under which they can be considered safe exists.

According to the plan, this should have been decided in the EU before June 2013, but the decision has been postponed. Still there is much uncertainty and discussion whether such threshold values can be established.

An extensive report has been published describing all the research implying that it is not possible to establish a threshold value for endocrine disrupting substances, since they may be harmful to health even at very low concentrations, even though we do not see the same effects at high concentrations of the same substance 14.

The responsibility for applying for authorisation is solely with the producer or the importer of a substance and in this way, the consumer should (in theory) be protected against hazardous chemicals. An authorisation is not given to a substance as a whole, but to a specific application of the substance for a specific applicant. To protect the European consumers further authorisations are re-evaluated within a given deadline. Furthermore, an authorisation can be revoked at any time if the conditions for the original authorisation have changed in a way that influences the risk, the socio-economic

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consequences, or the possibilities of substituting the substance with a less hazardous alternative.

At least twice a year the Candidate List is updated with new substances. Proposals for new substances come from ECHA or individual member states, but substances are not included in the list until ECHA has submitted it for a public consultation and found a majority among the member states. Once a substance has entered the Candidate List, it will not be removed, even if it becomes subject to authorisation.

Despite the fact that REACH took effect in June 2007, the first substances did not appear in the authorisation scheme until early 2011. Today (early 2014) there are 151 substances on the Candidate List and 22 substances on the Authorisation List. One of the most important objectives of REACH is that all substances of very high concern (SVHC) must be on the list by 2020 in order to decide whether to substitute them with less hazardous substances. It is estimated that around 1,500 SVHCs are on the market. If the EU does not speed up their work this group of hazardous substances will not be on the list until at least 2060.

Figure 6 The stepwise structure of REACH

REACH works step by step, as indicated in the figure.

Once a chemical product has been registered with ECHA it must be evaluated to decide on its further fate on the European market. If the substance is dangerous to human health and the environment its production and use will be regulated or banned.

13 This deadline is called the “sunset date” and refers to the date after which the use of the substance must cease.

14 Hormones and Endocrine-Disrupting Chemicals: Low-Dose Effects and Nonmonotonic Dose Responses, Vandenberg L et al., Endocrine Reviews, June 2012.

EU AND REACH > REACH – STEP-BY-STEP

The authorisation process is very expensive and time consuming. First, an extensive survey of the chemical must be made and subsequently a detailed documentation of the chemical risks and hazards for human health and the environment must be drawn up. In addition, there is no guarantee that an authorisation will be given, so a company may have spent many resources in the form of time and money to defend a chemical that may not be authorised in the end. This motivates competitors and other third parties to present a solution with less hazardous substances, which is a benefit for consumer safety. Furthermore, under REACH, ECHA must consider other available information about alternative chemicals when they decide on authorisations.

The purpose is to reduce the risk associated with substances of very high concern and preferably substitute these chemicals whenever it is economically and technically feasible.

The authorisation scheme rests on the principle of substitution stating: “hazardous substances should be substituted where a safer alternative is available”. The alternatives may be less harmful chemicals, technical changes of processes, or implementation of alternative technologies in the production.

When a company applies for authorisation to use a substance of very high concern it must provide an analysis of possible suitable alternatives. Industry must substitute the most hazardous substances if suitable alternative substances are available. For other substances of high concern that are assessed to be used “sufficiently safely”, industry must prepare a plan for substitution with suitable alternatives, but they are not obliged to follow it.

In Denmark, the Danish Environmental Protection Agency is the supervisory authority in relation to compliance with the rules of the EU chemicals legislation, which includes around 50 different Statutory Orders, Regulations, and Circulars; among them REACH. In practice, a special unit in the Danish Environmental Protection Agency – the Chemical Inspection Service – carries out practical monitoring and supervision to ensure that importers, producers, and distributors of chemical substances comply with the regulations.

Whether you are a consumer or an importer/producer/ retailer, the Chemical Inspection Service is the unit to contact if you wish to report a product you suspect of not complying with the chemicals legislation.

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"Right to Know” When a substance is on the Candidate List the consumers have the right to know whether the substance in question is found in a given product. The duty of information to customers applies to chemical mixtures as well as to products in solid form, including ordinary consumer products such as clothing, shoes, electronics, kitchenware, toys, and furniture. These products are defined as articles under REACH, and all purchasers of these goods must according to REACH be in a position to acquire information about the contents of Candidate List substances. This is the case for articles produced in the EU or imported from non-EU countries. Therefore, as a consumer you can enter a clothes shop and ask whether there are hazardous chemicals in the pants you consider buying. The retailer (or the producer/importer) must be able to provide this information within 45 working days after the request.

REACH is undoubtedly a large step towards higher safety for European citizens. In addition, the regulation ensures that Europe cooperates to reduce the risks from hazardous chemicals for human health and the environment by harmonising legislation and thereby avoiding unfair competition between member states.

At the same time, the REACH process is very tedious and changes often take a long time. It may take years from a chemical product comes under suspicion of being hazardous until it is subjected to legislation and maybe banned. In an attempt to influence the process of having hazardous chemicals added on the Candidate List several European organisations have drawn up their own suggestions for a list of chemicals that they believe have a proven harmful effect on human health and/or the environment. Examples of such lists are given below.

SIN list: The purpose of the SIN list (Substitute It Now), which is drawn up by the Swedish environmental organisation ChemSec, is to speed up the transition to a world free of hazardous chemicals. The third version of the list (SIN List 2.1) consists of 626 chemicals that ChemSec has identified as Substances of Very High Concern based on the criteria established by REACH. The SIN list is based on the very simple concept: replacing hazardous chemicals with safer alternatives. ChemSec finds that there is an urgent need to reduce exposure of people and animals to endocrine disrupting substances.

When they launched SIN List 2.1 intensive media work was used to invite the European Commission and

EU AND REACH > REACH – STEP-BY-STEP

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at ministerial conferences in international organisations such as the UNEP (United Nations Environment Programme) under the UN, or they may be made at a world summit. When a global environmental agreement has been finally adopted, the Danish Environmental Protection Agency is responsible for its implementation and compliance in Denmark.

There are specific agreements that deal with welldefined groups of chemicals. Below we briefly describe the two most important global agreements:

Phot o t oos

•

Several global agreements have been made to attain

the convention covered twelve substances or substance groups, but it has subsequently been extended with another ten POPs.

increased protection of human health and the environment in relation to chemicals.

The convention has been signed by 150 governments, including the EU member states and the EU Council of Ministers on behalf of the entire union.

This was done at a conference in Stockholm in 2001. However, the convention did not come into effect until 17 May 2004. It bans the production and use of particularly hazardous substances.

Today (ultimo 2013) the list covers 22 substances such as PCB and a number of pesticides such as DDT 16. For some of the substances, however, there are a number of exemptions.

New substances may be included in the list if there is scientific data for persistence, bioaccumulation and potential for spreading (whether they are spread, for instance, through air and water pollution) as well as adverse effects on human health and the environment. Relevant data are acquired through a scientific committee. If the criteria for inclusion are met, the committee studies further information and prepare an evaluation of risk management if needed. Then the committee presents a recommendation about how to include the new substances in the convention. The final decision is made by what is called the conference

the EU member states to prioritise regulation of these substances through REACH and companies were urged to start phasing out the substances.

ETUC list (The Trade Union Priority List): In addition, the European Trade Union Confederation (ETUC) has drawn up a list of substances of very high concern (SVHC) that should be prioritised for inclusion in the Candidate List from a trade union’s point of view. The list contains 334 chemicals (early 2014). The purpose is to enhance REACH and urge industry to develop safer substances so that REACH can combine higher competitiveness for European industry with a higher protection of workers, consumers, and the environment.

Global agreements: In addition to the European environmental legislation, which all EU member states must comply with, there are a number of global agreements setting up rules for all countries in the world in relation to various chemicals and other environmental issues. Decisions on starting negotiations about an international agreement in the environmental field are normally made

The Stockholm Convention – is a global convention regulating the POP substances 15. POP is short for persistent organic pollutants, which means that they do not decompose in the environment, but accumulate in the food chain. The purpose of the convention is to protect human health and the environment against the POP substances. Originally,

15 http://chm.pops.int/Home/tabid/2121/mctl/ViewDetails/EventModID/871/EventID/230/xmid/6921/Default.aspx POP is short for Persistent Organic Pollutants, which means that they decompose extremely slowly. There is therefore a great risk that these substances remain in our environment and in the worst case scenario accumulate in the food web.

16 PCB is short for Polychlorinated biphenyl. The substance used to be present in construction materials, but was banned in 1977 when harmful effects were seen on human health and the environment. DDT is short for dichlorodiphenyltrichloroethane. This chemical was also banned due to its severe side effects.

EU AND REACH > REACH – STEP-BY-STEP

of the parties – composed of the Parties to the Convention (the signatory countries) and their potential observers. The conference of the parties sets up procedural rules and makes all the important decisions.

Every five years all signatory countries must prepare an updated national implementation plan describing the POP situation in the country and plans for implementation of the country’s duties under the convention.

•

The Rotterdam convention (also called the PIC convention: Prior Informed Consent) 17 – is a global environmental agreement with the purpose of protecting human health and the environment by sharing information about hazardous chemicals, including how safely to store, transport, use, and dispose these chemicals. Member states must be

able to decide which harmful substances they wish to import, and in particular, developing countries must be able to protect themselves against the import of particularly hazardous chemicals.

Negotiations on the PIC convention were concluded at a conference of diplomats in Rotterdam in 1998.

The convention covers export of chemicals that are banned or severely regulated in the country of export. Before export, the country of export must ensure that the authorities of the country of import are informed about the restrictions placed on the substance in question in the country of export.

In addition, the convention sets requirements for labelling and classification of the PIC chemicals.

Today (early 2014), the list covers 47 chemicals whereas 33 are pesticides.

In addition, an increasing number of countries copy the REACH Regulation into their own legislation. This is mainly due to the fact that countries having significant exports to Europe – not least China and India - must comply with many of the REACH rules in order to continue exportation. Thus, Chinese companies must submit detailed information about classification and labelling, hazardous properties of chemicals, including possible effects on human health and the environment, as well as area of use and safety procedures, almost as if China was also subjected to REACH. Finally, there is a global chemicals strategy: Strategic Approach to International Chemicals Management

17 http://www.pic.int/

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(SAICM). This strategy is meant to play the role as the key global instrument in the efforts to attain the objective of the UN Summit in Johannesburg in 2002: by 2020, chemicals must be used and produced in a way that minimises significant adverse impacts on human health and the environment. It is positive that we now have a global agreement, but unfortunately, compliance with it is voluntary for the countries. There are no statutory obligations and this obviously means that some countries will do nothing. The US, among other countries, was a strong opponent to the strategy and managed to weaken the agreement in several important fields. As an example the precautionary principle and the principle of substitution, both of which are key issues in REACH, were not included.

EU AND REACH > CLASSIFICATION AND LABELLING

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Classification and labelling Hazardous chemicals and products must be classified. The purpose of classification and labelling is to inform and warn the user about the hazardous properties of chemical products. In 2009, new rules on classification and labelling came into effect. The new Regulation on classification, labelling and packaging is known as the CLP Regulation. The purpose is to create a global harmonised classification of chemicals ensuring that the same hazards will be described and labelled in the same way all around the world. Meaning, when a chemical is classified as a carcinogenic in Europe it will have the same classification in, for instance, Japan.

effect in 2010, which is based on a globally harmonised system (GHS). This system will over time be extended to cover the entire world, and the harmonisation of the global hazard labelling will help users of chemicals understand their hazardous properties no matter where in the world you find the chemical. The hazard labelling will appear on the label of the package. In addition to the new symbols, the label will also state information about the nature of the hazard and precautions during use. Furthermore, the label will state a signal word, which may be “warning” or “danger”, the latter being placed on the most hazardous products.

Most people are familiar with the orange hazard symbols. However, a new classification system came into

Figure 7 Global hazard labellings for chemical products

Health hazard: Chemicals that may cause skin or eye irritation, skin sensitization, respiratory tract irritation, or narcotic effects. Examples of products carrying this label are toilet cleanser, antifreeze, and decalcifier.

Corrosive: Chemicals that have a skin corrosive effect, may cause serious eye damage, or have corrosive effect on metals. Examples of products are hydrochloric acid and drain cleaner.

Flammable: Flammable substances and their vapours, gases, aerosols, and solid matter.

Examples of products are spirits, nail polish remover, and motor fuel.

Environment hazards: Chemicals that are hazardous for the environment. Examples of products are paints, petrol, and turpentine.

Chronic health hazard: Chemicals that cause chronic damage such as cancer, are harmful to the genetic material and to reproduction. It also covers chemicals that are allergenic by aspiration, or cause organ damage or lung damage by aspiration. Examples of products are petrol, turpentine, and lamp oil.

Oxidising: Chemicals that may cause or contribute to the burning of another material.

Examples of products are bleaching agents and oxygen used for patients with breathing problems.

Box continues on the following page

EU AND REACH > CLASSIFICATION AND LABELLING

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Acute toxic: Chemicals that are acute toxic by ingestion, skin contact, and/or aspiration.

Chemicals carrying this pictogram may be potentially lethal. Examples of products are certain pesticides and methanol (wood alcohol).

Gases under pressure: Gases that are stored in containers under pressure (2 bar or higher). Examples of products: oxygen bottles and welding gas.

Explosive: Explosive chemicals and articles. Examples of products are nitroglycerine, ammunition, and fireworks.

Packages containing a chemical substance or product/mixture classified as hazardous must carry a hazard labelling 18.

The purpose is to secure users of the products against damage. Here the nine hazard symbols are explained with examples of products carrying the label.

18 Danish Environmental Protection Agency. Leaflet on new hazard pictograms (in Danish).

EU AND REACH > LEGISLATION DEFICIENCIES

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Legislation deficiencies When REACH came into effect in 2007, it was in many ways a giant step on the way to a more toxic-free Europe, but we must also admit that the regulation in many ways is insufficient. Industry has exemptions and loopholes, and several important decisions, for instance regarding endocrine disrupting substances and nanomaterials, have been postponed for future revisions of the regulation (a revision opens up for amendments in the legislative text).

There are a number of critical fields in the regulation 19.

Some of them are discussed below: Endocrine disrupting substances were just about to be included in the regulation in line with for example carcinogenic substances. There was a majority for the proposal in the Council of the European Union and it was backed vividly be several political groups in the European Parliament. Still, vehement discussions between the Council of the European Union, the EU Commission, and the Parliament meant that the decision whether or not to include these chemicals was postponed until 2013. The Commission has still not presented a proposal for a solution.

If endocrine disrupting substances from the outset had been put on the same footing as carcinogenic substances in REACH they should have been substituted with less hazardous chemicals by now, unless producers/importers could prove, that they were used in a quantity that is not harmful or that they were used in a closed system and thereby were under “adequate control”.

Denmark is a frontrunner in the fight against endocrine disrupting substances, and in 2011, the Danish Environmental Protection Agency submitted a proposal to the EU Commission concerning criteria for identification of endocrine disrupting substances and possible options for regulation. In the proposal, the Danish Environmental Protection Agency has focus on the following criteria for identification of endocrine disrupting substances:

19 Navigating REACH; Published August 2007

1) they must be scientifically based.

2) they must rest on recent knowledge, but also consider new knowledge when available.

3) they must cover health and the environment alike.

4) they must cover all applications across the legislation.

In both the US, Japan, and the EU we have major research programmes on endocrine disrupting substances. The more knowledge we have – the more we find evidence that endocrine disrupting substances also affect human health. However, so far we have limited knowledge about the effects of the substances and the concentrations causing an effect.

Internationally accepted test methods specifically for endocrine disrupting substances are yet to be developed. Therefore, only very few existing chemicals are accepted as being endocrine disrupting – despite the fact that animal tests indicate that a far larger number has this adverse property.

Chemicals considered as being of very high concern and therefore in principle should be phased out are subject to a specific authorisation scheme (see section ”REACH – Step-by-step”). For hazardous substances for which it has been assessed that they are used in a sufficiently safe manner, industry must prepare a plan for substitution, but is not under any obligation to follow it. This means that “safe use” – which is not specified in further detail in REACH – can replace “the principle of substitution”. In worst-case this may lead to that even when safer alternatives are available, companies can continue to import, produce, and use many hazardous substances that may cause cancer, congenital malformation, reproductive diseases, and hormonal imbalances.

Cocktail effects of chemicals are also a problem that has only been briefly considered in the legislation.

Today, risk assessments are based on the effects of the individual chemicals despite the fact that it is generally accepted that we are exposed to a “chemical cocktail” of many different substances on a daily basis. To secure a high level of protection against hazardous chemicals it

EU AND REACH > LEGISLATION DEFICIENCIES

28

thus, they will not be examined for harmful effects on human health and the environment. Due to the lack of registration and control there is a general lack of knowledge about who produces what, why, and in how large quantities.

The problem can be solved either by changing the REACH text or by developing a so-called “stand-alone� legislation establishing how REACH tools and provisions must apply to nanomaterials. The first option does not seem possible at present since the EU Commission does not wish to open for changes in the REACH text for quite some time ahead.

When regulating harmful chemicals the pros and cons concerning business, human health and the environment are weighted.

is therefore important to consider how cocktail effects can be covered by the European chemicals legislation.

Since there are thousands of chemicals on the market, we must acknowledge that it is not possible to study all combinations. However, recognized calculation models exist to estimate effects from mixtures based on knowledge about the different chemicals. Therefore, political initiatives are now called for to ensure that legislation (e.g. REACH, CLP, and the regulation on cosmetic products) will cover cocktail effects in order to protect human health and the environment against the harmful effects of mixtures.

Nanomaterials are regulated under a number of existing statutory instruments of which REACH is the most important one. All of these instruments, however, have their limitations when it comes to efficient treatment of this substance group. First of all, we need a clear definition of nanomaterials. Today, the wording is so broad that it is unclear whether a nanomaterial with other physical and chemical properties than the same chemical material in a larger form (normally above 100 nm) must be assessed separately. In practice, this means that it is up to producers whether they choose to follow the rules, including the registration procedure in connection with nanomaterials. This is a barrier to any effort of applying REACH as a regulation instrument for monitoring the use of these substances. In addition, REACH has the so-called tonnage limits entailing that substances produced or imported in smaller quantities than 1 tonne per year per producer/importer are not covered by the duty to register. This is a problem since many nanomaterials, due to their limited size, are not produced in quantities exceeding this tonnage limit and

REACH registration only applies to some 30,000 of the more than 100,000 chemicals believed to be on the European market today. This is due to the fact, that registration only covers substances that are produced or imported in quantities above 1 tonne/year/producer or importer – and not until 2018 this many chemicals will be included (see the time line in Figure 3). In addition, for 60 % of the 30,000 chemicals we expect a lack of information due to the loopholes in the system, even if the authorities have the right to request more complete information. The result will probably be an insufficient amount of data to decide whether a substance is hazardous or not. Hence, far too many substances will remain on the market despite risks for human health and the environment.

2

P ho t o h id e sy

Endocrine disrupting substances

ENDOCRINE DISRUPTING SUBSTANCES > INTRODUCTION

30

Introduction to endocrine disrupting substances The EU legislation defines an endocrine disrupting substance as an exogenous substance that alters function(s) of the endocrine system and consequently causes adverse health effects in an intact organism, or its progeny, or (sub) populations.

What is an endocrine disrupter?

An exogenous substance that alters function(s) of the endocrine system and consequently causes adverse health effects in an intact organism, or its progeny, or (sub) populations.

In other words, an endocrine disrupting substance is a chemical that affects our natural hormonal balance in various ways. Hormones control a large number of processes in our organism and are decisive to metabolism, the nervous system – including the development of the brain, growth, and reproduction. Therefore, it is evident that changes in the hormonal balance can have very serious consequences. In addition, we are particularly sensitive to endocrine disrupting substance in certain life stages. This applies to the embryonic stage where the embryo is affected through the mother, the period just after birth, and the infant stage. In these periods, we only produce very little sex hormones ourselves and are therefore particularly vulnerable to impacts on the endocrine system. During the embryonic stage, our body’s detoxification system is underdeveloped and therefore the embryo can only to some extent, secrete the chemicals. Moreover, the blood–brain barrier does not exist and thus the chemicals have easy “access” to the brain and the rest of the body when they are carried around with the blood.

Endocrine disrupting substances are among others linked to low fertility, genital malformation, and breast and testicular cancer. The substances can also cause obesity and several studies indicate that some can harm several generations after the first exposure. This means that also children and grandchildren are affected by an exposure that took place many years before their birth. Despite much research in well-known endocrine disrupting substances, very little about these substances’ impact on human health in the quantities we are exposed to in everyday life is known. So the final proof that the chemicals cause these effects in people

is still lacking. However, there is general agreement among researchers, authorities, and politicians that we have sufficient indications to act based on the so-called precautionary principle, i.e. legislation and regulation based on reasonable suspicion.

According to the Danish Environmental Protection Agency, exposing test animals to endocrine disrupting substances may lead to an increased occurrence of genital deformation, undescended testicles, lower sperm quality among adult males, and precocious puberty among the females 20. And it does not look much better for humans.

The Department of Growth and Reproduction of Rigshospitalet (the largest hospital in Denmark) suspects, among others, endocrine disrupting substances of contributing to the following 21: •

•

one of five Danish males between 18 and 20 have a sperm quality below the normal value set by the WHO. in Denmark we have seen a large increase in testicular cancer in the last 60 years, and Denmark is with Norway the countries in Europe with the highest incidence of this type of cancer (see Figure 8). Almost one percent of Danish men risk getting testicular cancer during their lifetime.

20 Identification of chemicals in consumer products. Number 103 2009 “Combined effects on two year old children – The Toddler’s chemical cocktail” http://www.mst.dk/ NR/rdonlyres/FE3B1D94-B3F2-4CBD-ABC4-D1B24158C26F/0/65000_english.pdf 21 Sources: Niels Erik Skakkebæk, Professor, Rigshospitalet and Ph.d. and doctor at Rigshospitalet Lise Aksglæde: see among others (Danish only) http://www.tidsskriftet.no/?seks_id=1659942 and http://videnskab.dk/content/dk/krop_sundhed/forskere_slas_om_unge_pigers_bryster

ENDOCRINE DISRUPTING SUBSTANCES > INTRODUCTION

31

Figure 8 Testicular cancer in the Nordic countries

Testis Incidence: ASR (World) Age 0-85+

A statistical view of the development of testicular cancer

with a standard age structure. Age-standardisation is

in Denmark, Finland, Norway, and Sweden. The x-axis

necessary in order to compare figures for incidences/

shows time and the y-axis shows the rate of incidences

mortality between population groups with different age

per 100,000 persons. The rate expresses the number of

composition since age is a very important factor in terms

new incidences per 100,000 persons per year. An age-

of getting cancer. Source: NORDCAN © Association of the

standardised rate is the rate as it would be in a population

Nordic Cancer Registries (7.1. 2014).

•

In March 2013, WHO and the UN Environment Programme (UNEP) published an updated version, where endocrine disrupters were described as a 'global threat'. The final conclusion of the report was that exposure to endocrine disruptors give reason for global concern for people and the environment.

•

•

Nine percent of Danish boys are born with cryptorchidism (undescended testicles). This is a significantly higher number than in the 1960s.

Cryptorchidism is correlated with higher risk of low sperm quality and testicular cancer.

The testosterone level in Danish men’s blood is decreasing. Men born after the 1930s-40s have a lower testosterone level than their fathers and grandfathers had at comparable ages.

Danish girls reach puberty earlier by as much as one year compared to 15 years ago.

The World Health Organization WHO has previously studied all the knowledge available on endocrine disrupting substances. At that time, no definitive proof was found that it is detrimental for humans to be in contact with the substances despite the fact that it affects development, for instance, in mice and rats.

However, if the suspicion that the substances disturb the endocrine system and thereby human development and reproduction is true, it may have serious consequences for humanity in the long-term perspective. Therefore, it may be necessary to act under the precautionary principle to protect consumers, also when the proof is not definitive.

Most often, we are exposed to hormone disrupting chemicals through our food, such as residues of plant protection products (pesticides), other substances from

ENDOCRINE DISRUPTING SUBSTANCES > INTRODUCTION

pollution, natural phyto-oestrogens (“phyto” comes from Greek and means plant) and animal oestrogens, but we also absorb small amounts through our skin (e.g. through cuts and rashes). We find the endocrine disrupting substances in multiple places. For example in the external environment, where the burning of organic materials, among others, releases dioxin, which is a very harmful substance for humans and animals. During long-time exposure, this toxin leads to increased risk of cancer, reproductive disturbances, reduced immunity, neurotoxic effects, and endocrine disorders. In addition, we are exposed to endocrine disrupting substances in consumer products such as plastics, toys, cosmetics, electronics, clothing, and many others.

32

are very different, but common to them all is that they can be bound to the body’s hormone receptors just like the body’s own hormones. They can also affect formation, transport, and excretion of the body’s own hormones. The hormonal effects are caused by many different mechanisms, such as: • • •

•

• Innumerable substances are found to either have endocrine disrupting effects or are being suspected of having it. Chemically, endocrine disrupting substances

imitating the effects of natural hormones blocking the effects of natural hormones affecting the body’s metabolism of natural hormones. Can result in hormones remaining in the body for longer or shorter periods than intended. affecting the synthesis (formation) of natural hormones in a way that the body is exposed to a too high or too low concentration of hormones affecting the transport of natural hormones. Can result in specific hormones not being transported to their target organs.

Hormones and receptors In order to work, a hormone needs to bind to a receptor, whereby a signal is released. A hormone can have one specific or several different receptors that is suited for binding.

When the hormone binds to a receptor on a cell membrane, a reaction is initiated in the cell via the receptor. This may include an activation of specific enzymes, which in turn controls other reactions in the cell, for example phosphorylation of proteins for the formation of cyclic nucleotides, e.g. cyclic adenosine monophosphate (cAMP; part of cell energy metabolism). The cyclic nucleotides serve as intracellular signaling molecules (second messengers), which for instance activate enzyme systems. In this way, the body gets different signals via hormones.

The problem with endocrine disrupting substances is that they can affect the body in the same way as our natural hormones. This can be critical, as the body's own

Agonist

hormones are very carefully expressed, i.e. in very precise doses and at very specific times in our lives. Therefore, even very small changes can have a significant impact on our health.

An agonist is a substance that has the same effect as the natural ligand. This means that the agonist will bind to the same receptors and exert the same effects as the natural ligand. Put in a very simplified way, it can be compared to the way a key (the agonist) fits in a lock (the receptor).

In contrast, an antagonist favors and binds (not necessarily to the same site) to the receptor, thereby inhibiting the receptor from binding the natural ligand. In this manner, the activity is turned off so to speak, and the body cannot receive the signals that its natural hormones should start.

Antagonist

Cell membrane

Response

- Response

ENDOCRINE DISRUPTING SUBSTANCES > INTRODUCTION

These mechanisms are divided into three main groups: 1) They can imitate the effect of a naturally produced hormone such as oestrogen or testosterone and thereby cause similar reactions in the body (Agonism).

2) They can block the receptors in the cells receiving the hormones and thereby prevent the normal hormones from working (Antagonism).

3) They can affect synthesis, transport, metabolism, and/or excretion of hormones and thereby change the concentration of natural hormones. The endocrine disrupting chemicals can mimic the body's natural hormones in different ways:

33

heating, and waste incineration. Dioxin is a generic description of a group of chlorine-containing toxins that are formed in the burning of organic materials in the presence of chlorine.

Endocrine disrupting substances have very different decomposition rates in living organisms. Phthalates, for instance, decompose very quickly and are then excreted in the urine, while other substances such as PCB compounds are heavily decomposable and accumulate in the fatty tissue. For the same reason heavily decomposable substances can still be measured in humans, for instance in mothers milk and fat, many years after the industry has phased them out.

oestrogen-like effect: The naturally occurring female sex hormones are oestradiol, oestril, and oestrone, overall referred to as oestrogens.

Hormones work by binding to their specific recep-

Some of the most discussed endocrine disrupting substances are parabens, phthalates, bisphenol A, fluorinated substances (in particular PFOA and PFOS), and brominated flame retardants. These substances

tors. When this binding occurs in the right way, a response is triggered. Chemicals with oestrogenlike effects may especially be harmful to male embryos, as they only tolerate a very low concentration of oestrogen.

Examples of substances with oestrogen-like effects are bisphenol A, certain phthalates, methoxychlor (a chlorine-containing pesticide), DDT and its decomposition products, and certain conversion products of the industrial chemical PCB. antiandrogen effect: Chemicals with this effect mechanism prevent testosterone and other male sex hormones from working in the way they should. This effect is especially critical for male embryos as it may cause incomplete development of, particularly, reproductive organs.

Substances that may have an antiandrogen effect are, for instance, the phthalates BBP, DBP, DEHP, and DINP. thyroid gland effects: Chemicals that may have a disturbing effect on the transport and decomposition of the hormones of the thyroid gland (thyroxine and triiodothyronine). For example, this may affect the development of the brain of embryos whose mothers are exposed to these substances and predispose the embryo to obesity. The latter is due to hormones with a negative effect on the production of thyroxine, which causes a reduction of the resting metabolic rate, which in turn may affect the energy expenditure.

Examples of substances with an effect on the thyroid gland are PAHs and dioxins. PAH is formed in the incomplete burning of organic materials.

The most significant sources are traffic pollution,

are discussed below.

ENDOCRINE DISRUPTING SUBSTANCES > PARABENS

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Parabens

By Claus Jørgensen, The Danish Consumer Council

Most consumers today have heard about parabens and have probably also heard that they are suspected of having endocrine disrupting effects. This is largely due to the fact that parabens and their hormone-like effects have been discussed for almost 20 years in the media and because there is still no consensus about the potential harmful effects.

What are parabens?

The term ‘parabens’ covers a number of chemicals that all consist of a benzene ring with a hydroxy group and an alkyl group. What distinguishes one paraben from another is the number of carbon atoms on the alkyl chain.

In Figure 9, the most common parabens are shown with their respective structural formulas: butyl, ethyl, isobutyl, isopropyl, methyl and propyl parabens.

Figure 9 Chemical structures of the six most common parabens

Butylparaben

Ethylparaben

Isobutylparaben

Isopropylparaben

Methylparaben

Propylparaben

Source: forbrugerkemi.dk

Info on parabens Parabens are commonly used preservatives, e.g. used in cosmetics and lotions as well as certain types of food and medical products to prevent bacterial and fungal growth, thus improving the durability. There are several types of parabens, which are often used in the same product in order to preserve as efficiently as possible.

Parabens have been shown to have the ability to slightly mimic estrogen in most types of cell-based experiments and in animal studies. It has previously been shown in animal experiments that exposure to potent estrogenic compounds can be toxic to reproduction in both female and male rats. In adult women the estrogen levels, by nature, is so high that you can think that the doses you are exposed to from outside sources, will only be a drop in the ocean. In contrast, normal estrogen levels are very low in fetuses and children, so here the exposure can have a very big impact.

The substances are used as preservatives in cosmetics and drugs; they preserve the products and inhibit bacterial growth in lotions, shampoos, sunscreens, headache tablets, and anti-smoking preparations.

Two of the parabens; ethyl and methyl paraben and their salts are also permitted in foodstuffs 22 with the E numbers: E214, E215, E218 and E219.

Parabens are artificial compounds manufactured in laboratories and are primarily used in cosmetics. The substances are also used in cosmetics manufactured for children, which was documented in a survey from the Danish Environmental Protection Agency in 2007 23.

It showed that all the mentioned parabens were used in products for children – propyl paraben was found in 70 products and butyl paraben in 48 products. In 2009, the Danish Consumer Council asked consumers to report products containing one or more substances on the EU list of substances having shown endocrine disrupting effects in animal tests, including several parabens. Of the more than 1,200 products reported up to March 2012, 92 % contain one or more parabens.

22 Danish Veterinary and Food Administration: http://www.foedevarestyrelsen.dk/SiteCollectionDocuments/25_PDF_word_filer%20til%20download/06kontor/Positivlisten%202011%20-%20netudgave%20_01.08.pdf 23 Danish Environmental Protection Agency: www2.mst.dk/common/Udgivramme/Frame.asp?http://www2.mst.dk/Udgiv/publikationer/2007/978-87-7052-634-4/html/helepubl.htm

ENDOCRINE DISRUPTING SUBSTANCES > PARABENS

According to the National Allergy Research Centre 24, parabens are also used in other types of products such as glue, shoe polish, and industrial products. Here, they are referred to with synonyms (see box) and it may be hard for consumers to navigate through the jungle of chemicals when the substances occur with different names depending on the product in which they are used.

Even though two parabens (ethyl- and methylparaben) are permitted in foodstuffs, Danish consumers rarely find them on the shelves, primarily because of a Danish tradition for not using them in food production. In the past, propylparaben (E216) was permitted, but the EU banned the substance in 2006 due to its endocrine disrupting properties 25. According to the Danish Veterinary and Food Administration the two permitted parabens may be used in confectionery products (candy), snacks, surface treatment of dried meat products, and jelly layer on meat products and patĂŠs

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Synonyms for parabens when used in products other than cosmetics and food Methyl 4-hydroxybenzoate Methyl paraoxybenzoate Ethyl 4-hydroxybenzoate Ethyl paraoxybenzoate Propyl 4-hydroxybenzoate Propyl paraoxybenzoate Butyl 4-hydroxybenzoate Butyl paraoxybenzoate Isopropyl 4-hydroxybenzoate Isopropyl paraoxybenzoate Isobutyl 4-hydroxybenzoate Isobutyl paraoxybenzoate

with the exception of liver patĂŠ.

Good preservatives According to the Danish Asthma and Allergy Association26 the cosmetics sector only started using parabens in the 1920s and the food sector started some 20 years later. Parabens are the best-studied preservatives on the market. They are good at preserving, i.e. preventing bacteria growth and putrefaction, and allergic incidences are rarely seen with this group of substances. They are active towards many different types of bacteria and are gentle to the skin, which makes them suitable, for instance, in lotions, deodorants, and other cosmetics used on the skin.

On the other hand, the National Allergy Research Centre describes preservatives as slightly allergenic, which is confirmed by the Danish Environmental Protection Agency 27. However, the latter states that parabens, in contrast to other preservatives, rarely cause allergic reactions when used in cosmetics.

Parabens must be declared in cosmetics and foodstuffs allowing consumers to see which substances they are exposed to. The permitted paraben content in cosmetics is regulated at EU level; a product cannot contain more than 0.4 % methylparaben, 0.4 % ethylparaben, 0.19 % propylparaben, and 0.19 % butylparaben.

Oestrogen-like effects Parabens are extensively used in cosmetics and are believed to be among the least allergenic preservatives.

Despite this fact, the debate about parabens is very intense and visible, since both in vitro and in vivo studies have shown that parabens may have oestrogen-like effects and thus affect the hormonal balance. In 2007, the EU published a list of substances having documented effects in in vitro and/or in vivo tests 28. On this list, most of the parabens are present.

However, already back in the 1990s the endocrine disrupting effects of butylparaben came into focus. In their tests of cosmetics and care products, the Centre of Green Information dismissed products containing butylparaben. The Centre referred to some of the first scientific articles describing environmentally harmful and endocrine disrupting effects from the use of butylparaben. Later, scientific tests have documented that the other parabens have similar, although weaker, endocrine disrupting effects.

In the report 29 behind the EU list of substances having shown endocrine disrupting effects the authors have gathered examples of the effects found in tests using animals or cells. A selection of parabens with shown oestrogen-like effects is listed in Table 1.

24 National Allergy Research Centre: www.videncenterforallergi.dk 25 Danish Veterinary and Food Administration: http://www.foedevarestyrelsen.dk/Foedevarer/Tilsaetningsstoffer_og_teknologi/Tilsaetningsstoffer/Sider/parabener.aspx 26 Danish Asthma and Allergy Association: www.astma-allergi.dk 27 Danish Environmental Protection Agency: http://www.mst.dk/Borger/Kemikalier/Kosmetikguiden/Hvordan+er+det+lige+med/parabener.htm 28 EU Commission: http://ec.europa.eu/environment/endocrine/documents/final_report_2007.pdf 29 EU Scientific Committee: http://ec.europa.eu/environment/endocrine/documents/final_report_2007.pdf

ENDOCRINE DISRUPTING SUBSTANCES > PARABENS

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Table 1 Selection of parabens with proven oestrogen-like effects in animal tests

Substance

Oestrogen-like effects found in

Ethylparaben

Rats, mice, and fish

Propylparaben

Rats and fish

Butylparaben

Mice and fish

Methylparaben

Mice

Source: DHI, 2007 – Study on enhancing the Endocrine Disruptor priority list with a focus on low production volume chemicals – ENV.D.4/ETU/2005/0028r

Parabens are regulated continuously and the permitted concentration in cosmetics has been reduced. Back in 2005, the first of a number of scientific evaluations

In Denmark it is not permitted to use butyl, propyl-, isobutyl-, and isopropylparabens or their respective salts in cosmetics and care products for children below

from the EU Scientific Committee on Consumer safety (SCCS) was published. It concluded that parabens could not be linked to breast cancer 30. It was followed by evaluations concluding that the use of methyl- and ethylparaben was safe in the permitted concentrations, and the committee requested more information about the other parabens 31. In 2006 and 2008 further evaluations from SCCS were published in which the scientific committee rejected the materials submitted by the cosmetics sector 32,33. The committee insisted that it could not say anything about the safety of several of the parabens. However, methyl- and ethylparaben were still claimed to be safe.

the age of three 35. A majority in the Danish Parliament decided this in spring 2011. Denmark is the only EU member state having a ban on these parabens. It is now up to the EU to assess whether the ban, which is based on the precautionary principle, should be extended to cover all EU member states, or whether Denmark must withdraw this special ban.

The cosmetics sector was then asked to submit data showing that the parabens were safe; so far, this has not been done. When the most recent evaluation from the committee was published in 2011, it was assessed that the permitted concentrations of butyl- and propylparaben were to be lowered and that several other, not very common, parabens were to be banned. Again, the committee concluded that the use of ethyl- and methylparaben was safe 34.

Today, parabens are still permitted in limited quantities in the official EU regulation, but their use is still questioned, among others by Denmark that has introduced a special ban beyond EU legislation.

The background for the Danish ban is a report published by the Danish Environmental Protection Agency in autumn 2009 in which it was studied how many endocrine disrupting substances a two-year old child gets into contact with during one day. In the study, the risk of a two-year old child’s daily exposure to endocrine disrupting substances, exceeding the maximum acceptable level, (defined bythe Danish Environmental Protection Agency), was calculated. Based on the report, the former Minister for the Environment Troels Lund Poulsen (Liberal) recommended that parents avoid care products containing propyl- and butylparaben.

In the report, the authors used a measuring method attempting to evaluate the cocktail effects of the many endocrine disrupting substances the two-year old child is exposed to on a daily basis. It was the result of this work, which led the Minister to state, that precaution is needed in the use of the two mentioned parabens.

30 EU Scientific Commitee: http://ec.europa.eu/health/archive/ph_risk/committees/04_sccp/docs/sccp_o_00d.pdf 31 EU Scientific Commitee: http://ec.europa.eu/health/archive/ph_risk/committees/04_sccp/docs/sccp_o_019.pdf 32 EU Scientific Commitee: http://ec.europa.eu/health/archive/ph_risk/committees/04_sccp/docs/sccp_o_074.pdf 33 EU Scientific Commitee: http://ec.europa.eu/health/archive/ph_risk/committees/04_sccp/docs/sccp_o_138.pdf 34 EU Scientific Commitee: http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_o_041.pdf 35 Danish Environmental Protection Agency: www.mim.dk/Nyheder/2010/20101220_forbudparabener.htm

ENDOCRINE DISRUPTING SUBSTANCES > PARABENS

37

REMEMBER

NGO opinion In Denmark and the rest of the world, consumer and environmental groups have pointed out for years that regulation of endocrine disrupting substances is deficient 36. New research on cocktail effects of chemicals has further increased concern among NGOs about the substances. Therefore, they continue to put pressure on the authorities and producers in order to have substances regulated in a way that considers all known factors.

that NGO is short for ”non governmental organisation”, meaning that it is not subsidised by government.

This means that such groups only work for funds raised among different donors or from member contributions; thereby they are not dependent on state opinions.

by consumers, if they cannot use parabens. If the demand for products without hazardous chemistry were to increase, producers would see a competitive benefit in substituting preservatives harmful to health with substances without any adverse health effects. In addition, more generally it would be possible to pack care products in tubes instead of, for instance, in pots with a lid. When a product is sold in a tube, the direct contact

Parabens are not seen as being worse than other substances suspected of being endocrine disrupting for humans and animals. But since ’paraben’ is easy to remember for consumers and journalists - by contrast to, for instance, ethylhexyl methoxycinnamate or 4-Methylbenzylidene Camphor, and since they are extremely common in cosmetics, the media often have this substance group in focus.

between the product and bacteria from, for instance, our hands (a very large source of contamination) will

Some organisations, such as the Danish Asthma and Allergy Association, are not very concerned about parabens; they believe that the health effects are so weak that they are actually not harmful to humans 37.

Industry associations for producers and retailers also do not share the concern of the NGOs 38.

It is a fact, however, that there are a number of permitted preservatives 39 (56 are approved for cosmetics) that could be used instead. Many of them have adverse allergenic effects and would not be suitable as substitutes, while others seem to have no health effects.

So why are parabens not replaced by other less harmful substances? According to SPT (Soap and Perfumery Manufacturer Association), you cannot just replace a preservative with an alternative, since substances have different properties and therefore are suitable for different products. Therefore, producers face the challenge of making a similar product as the one preferred

Ph o to i cy i ma g e

Alternatives to parabens The advantage of parabens is that they are thoroughly tested and benign for allergy. Other more recently developed preservatives cause larger allergy problems and are at worst not tested as thoroughly as parabens.

It is more important to add preservatives such as parabens when care products are sold in open containers as the product will be contaminated with bacteria more easily, for instance from our hands.

36 In Denmark: The Danish Consumer Council, the Ecological Council, and Greenpeace; Internationally: European consumer groups ANEC and BEUC, the European organisation of green NGOs EEB, Greenpeace and ChemSec, among others.

37 Danish Asthma and Allergy Association: http://dinhverdag.astma-allergi.dk/deklarationer/forbruger/parabener 38 http://politiken.dk/tjek/sundhedogmotion/forbrugerkemi/ECE846125/kosmetikindustrien-forbrugerraadet-lyver/ and http://spt.dk/frame.cfm/cms/id=1013/sprog=1/ grp=9/menu=4/ 39 https://www.retsinformation.dk/Forms/R0710.aspx?id=12915#B5

ENDOCRINE DISRUPTING SUBSTANCES > PARABENS

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Figure 10 The Nordic Ecolabel

New research shows that exposure to a “cocktail” of several endocrine disrupting substances, even in very low concentrations, can have effects that are harmful to health – even when no effects are seen of the individual substances in higher concentrations. However, with today’s legislation we only consider whether each substance is harmless at its specific limit value – so possible cocktail effects are not considered. You can read more about this type of effect in the section ”COCKTAIL EFFECTS”.

The Nordic Ecolabel (also known as the Nordic Swan) is one of many ecolabelling schemes. You can read more in the section “Chemicals in clothing and textiles”.

be reduced, thereby reducing the risk of developing mold. This would reduce or even eliminate the need for adding preservatives to various care products.

For many years, it has been possible to produce care products and cosmetics in such a careful way that producers can obtain an ecolabelling. The Nordic Swan has set up criteria for labelling of cosmetics. One of the criteria is that the product must be produced without the use of parabens. Just like all other substances on the EU list of endocrine disrupting substances parabens are banned from Swan labelled products. It is thus possible to have a production without using substances suspected of being endocrine disruptors, which is clearly seen from the number of Swan labelled products on the Danish market. So far, 27 deodorants, 69 facial care and cleansing products, 82 baby care products, and 54 hair styling products are approved under the Nordic Swan label.

Parabens – also in the future?

Today, it is generally agreed that we have scientific proof of the correlation between parabens and endocrine disrupting effects. However, when we wish to determine the importance of these effects on humans there are many different opinions.

Denmark is a pioneer in the fight against cocktail effects.

Only time will show whether the EU will follow suit and ban butyl- and propylparaben. In Denmark the Danish Environmental Protection Agency has focus on the problem, for instance by informing consumers in campaigns. The latest campaign was based on a major survey focusing on products for pregnant women and giving tips and guidance for women trying to get pregnant. In addition, the Danish government put hormone chemistry and cocktail effects on the agenda under the Danish EU Presidency in the first semester of 2012.

Much work is being done to develop methods to tackle cocktail effects, for instance at the Technical University of Denmark (DTU). Undoubtedly, we will see new methods for calculating risks from chemicals and this may mean that parabens will disappear completely from consumer products: maybe even before we see a direct ban. Already today, we see more and more cosmetics and care products on the Danish market without parabens – and often carrying the Nordic Swan label 40. On top of the consideration for human health and the environment this may be due to the fact that producers see a competitive benefit from being in front and that consumers increasingly demand products free from chemicals suspected of harming humans and the environment.

Authorities and producers are still very much of the opinion that there are no problems related to the substances as long as the limit values are respected. Today parabens are therefore permitted in limited amounts apart from the number of parabens banned in Denmark in products for children below the age of three.

40 The Danish Consumer Council published in March 2012 a list of 52 brands/companies no longer using substances on the EU list of endocrine disrupting substances, including Matas and COOP that have phased out substances from their own brands. http://taenk.dk/nyheder/kosmetikproducenter-dropper-hormonkemi

ENDOCRINE DISRUPTING SUBSTANCES > PHTHALATES

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Phthalates

By Eline Aggerholm Kristensen, The Danish Ecological Council

Polyvinyl chloride (PVC) is a plastic consisting of many vinyl chloride molecules on a long chain (see Figure 11). PVC is a very hard material and therefore needs to get more flexible and soft. For this purpose, the so-called phthalates are often used. Phthalates is a common term for different esters of phthalic acid; they are formed from a simple condensation reaction41 between alcohol and carboxylic acid splitting off water.

What are phthalates?

Phthalates are manufactured from mineral oil. They have no or only a weak odour and are increasingly lipophilic (dissolves in fats) depending on the length

of their chain. Phthalates have many different chain lengths but generally, the long-chained phthalates are used as plasticisers while the short-chained are used in cosmetics. Generally, they are used to improve flexibility, adhesion, or bendable properties of many consumer products. The plasticising effect means that they permit movement in and between the polyvinyl chloride chains of PVC (see Figure 11). Primarily, phthalates are used to soften PVC plastics used in, among other things, rainwear, rubber boots, electronics, floor coverings, toys, binders, shower curtains, oilcloth, and T-shirt prints. Phthalates are also added to other products such as cosmetics, pharmaceuticals,

Figure 11 PVC consists of many vinyl chloride molecules (CH2=CHCl) on a long chain. At the right-hand side of the figure the structure of a phthalate is shown

Standard formulas for PVC and phthalate

Vinyl chloride:

CH2 = CHCl

Polyvinyl chloride:

-CH2-CHCl-CH2-CHCl-CH2-CHCl

PVC

Phthalate

The binding of phthalates to PVC The phthalates are bound to the PVC through weak electrical forces. These forces occur because both the PVC and the phthalates have some imbalances in the distribution of electrons. The atomic oxygen in the phthalates and the atomic chlorine in the PVC pull in those electrons that are shared with their neighboring atoms, whereby

Example of a partial electrical bond between two molecules wherein atomic oxygen pulls the electrons from a neighboring atom leading to partial charges.

partial negative and partial positive charges occur. The partial negative charges in the phthalates are attracted to the partial positive in the PVC and vice versa. Such weak electrical bonds between neutral molecules are called Van der Waals forces. Flexible PVC products contain up to 40% of phthalate.

Phthalate Polyvinyl chloride

41 A condensation reaction is a chemical reaction in which two molecules or functional groups combine into one molecule splitting off a smaller molecule (very often water).

ENDOCRINE DISRUPTING SUBSTANCES > PHTHALATES

and paints; here they are primarily used due to their adhesive properties. Humans are generally exposed to many phthalates as they are released from the products we use. Phthalates readily release since they are only attached to the PVC through weak electrical forces that decrease gradually throughout the lifetime of the products (see box). The softer the PVC product the more phthalates it contains (up to 40 %) and the more it can release.

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is how to use them, because results from animal tests cannot be transferred directly to humans (see section about “LIMIT VALUES“).

Harmful effects of phthalates

There are many differences between laboratory tests and the real world. Humans are exposed to a mixture of substances, whereas test animals are often exposed only to the specific chemical under scrutiny.

Furthermore, we decompose phthalates in a different way than other animals, and the disease mechanisms among different species are not always the same.

However, animal tests may indicate which effects the phthalates may have on humans.

Another way to determine whether phthalates have harmful effects on human health is biomonitoring studies. In these studies certain biomarkers, such as the level of specific enzymes in our blood, and the decrease/increase of body weight of humans known to have a high concentration of phthalates in their

Extensive research on the harmful effects of phthalates has been carried out. Thousands of animal tests (in vivo) have been made to elucidate different aspects of exposure, such as type of phthalate, exposure method (through skin, food, mother's milk, inhalation etc.), determination of harmful concentrations, duration of exposure (acute or long-lasting for months/ years/generations), type of test animal, life stage etc.

However, even when results are available the question

blood, are monitored. Epidemiological studies on an entire population are also popular due to the very high number of “test persons”, which makes the results very robust. Such a population of humans may be an entire community known to have been exposed to a specific chemical pollution – for example a chemical release from a nearby factory. Several epidemiological studies have revealed possible relations between exposure to phthalates and male reproductive

The phthalate molecules are released gradually to the surrounding environment such as air, water, skin, or foodstuffs. With time, this results in the PVC products becoming less flexible, harder and finally brittle. And as studies show, large quantities of phthalates released from PVC products such as vinyl flooring end up in ordinary house dust.42

Table 2 Examples of phthalates with their short names and structural formulas

Name

Acronym

Structural formula

Dimethyl phthalate

DMP

C6H4(COOCH3)2

Diethyl phthalate

DEP

C6H4(COOC2H5)2

Di-n-propyl phthalate

DPP

C6H4[COO(CH2]2CH3)

Di-n-butyl phthalate

DBP

C6H4[COO(CH2]3CH3)

Diisobutyl phthalate

DIBP

C6H4[COOCH2CH(CH3)2]2

Benzyl butyl phthalate

BBP

CH3(CH2)3OOCC6H4COOCH2C6H5

Butyl decyl phthalate

BDP

CH3(CH2)3OOCC6H4COO(CH2)9CH

Di(2-ethylhexyl) phthalate

DEHP

C6H4[COOCH2CH(C2H5)(CH2)3CH3]2

Diisononyl phthalate

DINP

C6H4[COO(CH2)6CH(CH3)2]2

Diisodecyl phthalate

DIDP

C6H4[COO(CH2)7CH(CH3)2]2

42 Report from ChemSec and Swedish Society for Nature Conservation (2011): http://www.chemsec.org/images/stories/2011/chemsec/home_sweet_home_lowres.pdf

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Table 3 Examples of suspected harmful effects by ptalates

Hypospadias

incomplete development of the urethra so that the opening of the urethra is at varying distance from the top of the penis head. Malformation is accompanied by split foreskin and in some cases of curvature of the penis

Cryptorchidism

a condition in which the testes are not yet in the scrotum at birth

Reduced sperm quality

40 % of young otherwise healthy Danish men have decreased sperm quality, which can lead to fertility problems. 6 % have such poor sperm quality that they cannot have children without being helped

Testicular and breast cancer

hormone-related diseases

Obesity and insulin resistance

there has been shown a connection between these conditions and the level of metabolites (products from metabolism) from phthalates in men. It is suggested that especially exposure to phthalates – and other endocrine disruptors – in the fetal stage, increases the risk of obesity later in life

Feminisation

effects of endocrine disrupting chemicals seen in rodents, fish and amphibians - e.g. reduced distance between the anus and the root of the penis

Some health effects have been demonstrated in animal tests (e.g. cryptorchidism and various kinds of cancer) while others are suspected of being caused by phthalates and other endocrine disrupting substances (e.g. reduced sperm quality).

disorders 43, low sperm quality44 and fertility45, precocious puberty among girls46, asthma47, obesity48, and effects on the thyroid gland49.

In vitro testing is another option to test harmful effects of different chemicals. For example by screening, where a general impression of many chemicals is obtained by testing them on a (human) cell line – e.g. cells from the lungs if you wish to examine what happens when the substances are inhaled. Such tests are advantageous since they are fast and cheap and use no or only few test animals. They give an idea of how the substance affects certain specific biological endpoints (such as lung cells in this case) and may further give an indication of whether the chemical substance is harmful to health. What should have particular focus in in vitro screenings is that this kind of test only looks at the specific cell type and thus can’t exclude other effects (such as the blood vessels being damaged when inhaling a specific substance, even when the lung cells are not). In vitro tests can thereby not acquit a chemical substance of being harmful to health just because

we do not see any effects on the specific endpoint measured.

The extensive research on phthalates have revealed several effect mechanisms – they may behave like oestrogens in the body and bind to the oestrogen receptors or act as antiandrogens by blocking the male sex hormone effects or its production.

Table 3 gives some examples of possible carcinogenic, mutagenic, reprotoxic, and endocrine disrupting effects of phthalates.

It is generally agreed, that exposure during the embryonic stage increases the risk of serious and permanent changes in humans and animals more than exposure of adults. The endocrine system plays a key role throughout our life, but a well-working endocrine system is of utmost importance for the normal development of an embryo and a child.

Another problem that gets increasing attention is the risk of so-called cocktail effects of different chemicals.

In brief, cocktail effects arise when we are exposed

43 Swan et al. 2005. Decrease in Anogenital Distance among Male Infants with Prenatal Phthalate Exposure. Environ Health Perspect, 113(8): 1056–1061 44 Duty et al. 2003. Phthalate Exposure and Human Semen Parameters. Epidemiology 14:269 –277 45 Tranfo et al. 2012. Urinary phthalate monoesters concentration in couples with infertility problems. Toxicol Lett. 213(1):15-20 46 Wolff et al. 2010. Investigation of Relationships between Urinary Biomarkers of Phytoestrogens, Phthalates, and Phenols and Pubertal Stages in Girls. Environ Health Perspect 118(7): 1039–1046 47 Just et al. 2012. Children's Urinary Phthalate Metabolites and Fractional Exhaled Nitric Oxide in an Urban Cohort. American Journal of Respiratory and Critical Care Medicine, 186:9 830 48 Teitelbaum et al. 2012. Associations between phthalate metabolite urinary concentrations and body size measures in New York City children. Environmental Research, 112:186-93 49 Whyatt et al. 2012. Maternal Prenatal Urinary Phthalate Metabolite Concentrations and Child Mental, Psychomotor, and Behavioral Development at 3 Years of Age. Environmental Health Perspectives, 120:2 290-295

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simultaneously to several different chemicals, such as when children are playing on the floor and inhale house dust, which generally contains a mix of chemicals from the household electronics, furniture etc. The effect of this exposure may be different (worse) than the effect of each chemical alone (read more in the section “Cocktail effects“).

Phthalates are everywhere in our surroundings. The Danish Veterinary and Food Administration made a study in 2003 estimating the total daily exposure of DEHP, DBP, BBP, DINP and DIDP to be 96.8 µg/kg body weight/day for adults and 927 µg/kg body weight/day for infants between 6 and 12 months. The much higher exposure of infants compared with adults is primarily due to the fact that they often move about on the floor where dust is accumulated and have much “hand-tomouth” contact.

In 2006, Greenpeace studied the blood of a number of famous Danes for selected chemicals. On average, they found three types of phthalates in each blood sample.

Other studies have shown the presence of phthalates and their metabolites in urine, blood from the umbilical cord, amniotic fluid, saliva, mother's milk, and placental tissue.

Phthalates decompose relatively easily into their metabolites, so-called phthalate monoesters, and are readily secreted from the organism. Therefore, it takes a daily exposure to maintain a measurable content in, for example, blood and urine.

Phthalates in the environment Phthalates and their metabolites ultimately end up in the environment and thereby also in the food chain.

Discharges take place through rain or wastewater where the substances are led to the aquatic environment or found in sludge from wastewater treatment plants. On the sea floor, the lipophilic phthalates will bind to organic particles and settle, while in the wastewater treatment plant they will bind to sewage sludge that is later used as a fertiliser on agricultural land. Therefore, soil and sediment will often contain relatively large quantities of phthalates. Some phthalates are bioaccumulative and are found in aquatic organisms. In this context, we have examples of feminisation in the form of development of ovaries instead of testicles in male fish, frogs, and other amphibians living in phthalate contaminated aquatic environments. All these damages are suspected of being caused by the endocrine disrupting effects of phthalates.

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Reduction of phthalate exposure – phasing out, taxation, legislation There is a solution to the phthalate problem, since quite many alternatives are on the market that may replace the traditional PVC and phthalate products. It is beneficial for the environment if not just phthalates, but also the PVC plastics, are replaced. PVC is neither suitable for recycling due to the content of heavy metals; nor for landfilling due to the long-term leaching of phthalates; nor for incineration due to formation of, among other things, hydrochloric acid and dioxin. The hydrochloric acid is neutralised in Danish incineration plants, but it generates a residue that must be landfilled in special deposits to prevent pollution of the groundwater. By far, most dioxin is decomposed or captured in filters.

However, even small amounts of dioxin are extremely toxic for humans and thus constitute an undesired and unacceptable pollution. The alternative plasticisers may also be released from PVC. Substitution therefore requires extensive research to secure that we do not just replace one endocrine disrupting substance with another harmful substance.

The largest problem regarding alternatives to phthalates is that there are relatively few on the market and they are in general more expensive than phthalates.

For producers to see the advantage of developing alternatives they must have some certainty that they can sell their products. Right now, the market for alternative products is limited by their higher price compared with traditional phthalate-containing products. This is a barrier to further development and competition in this field. For instance, it is important for hospitals that the medical equipment complies with the highest technical standards and that the economy is healthy. If the phthalate-free products are inferior to the traditional products, such as being less flexible, and also more expensive, these products are not selected. There are, however, many good alternatives to PVC products, for instance polyethylene, polyester, and silicone. These are already used in products with a ban on certain phthalates – such as toys.

Increased competition on the market will promote product development and ensure products of a high standard at competitive prices. One of the ways of accelerating this process is by levying green taxes.

In 2000, Denmark introduced a PVC and phthalate tax. The tax amounts to DKK 2/kg PVC and DKK 7/kg phthalates. The purpose of the tax was to reduce the consumption of phthalates and it has been successful within several fields, such as in cable production. The Danish company “nkt cables” has developed cables

ENDOCRINE DISRUPTING SUBSTANCES > PHTHALATES

Figure 12 Symbol on plastic products, which indicates the type of plastic – this indicates PVC

Soft plastics of the type PVC are normally softened with phthalates. Some of the phthalates are endocrine disrupting or suspected of being so. Much plastic, particularly packaging, is labelled with three arrows forming a triangle with a number in the centre. This labelling is not mandatory in Denmark.

substituting polyvinylchloride (PVC) that was stabilised with lead and softened with phthalates. Their NOPOVIC® cable type is based on a mixture of halogenfree polymers containing non-flammable minerals such as magnesium and aluminium hydrates. They are competitive since they are exempt from the taxes levied on PVC and phthalates, and furthermore the company can promote themselves as eco-friendly.

In a report from 2006, the Danish Environmental Protection Agency showed a decreasing trend concerning the use of phthalates 50. However, the tax has not had the intended effect regarding hospitals. If the phthalate tax was increased, the alternatives would have an additional cost reduction and there would thus be no savings from using the phthalate-containing products. On the other hand, there are examples that a phthalate-free purchasing policy does not necessarily constitute an additional cost. In the Dutch ’Westfriesgasthuis’ Hospital, all phthalate-containing products have been replaced in the children’s care unit, apart from blood bags, without having entailed additional costs.

Since phthalates are found in many product types, they are regulated under several different pieces of legislation. These include the EU chemicals legislation REACH, the directives on toys and medicinal products, the directive on medical devices, the Cosmetics Regulation and legislation regarding food contact materials.

Di 2-ethylhexyl phthalate (DEHP) is one of the most common and discussed phthalates. The substance

50 http://www.ft.dk/samling/20051/almdel/mpu/bilag/343/267804/index.htm

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appears on many warning lists, including the European Candidate List under the REACH regulation, the Danish Environmental Protection Agency’s list of undesirable substances, and the EU priority list of possible endocrine disrupting substances. Common to all products containing DEHP is, however, that they must be marked.

In 2011, the Danish government prepared a scientifically based proposal for a Danish ban on the use of four phthalates – DEHP, DBP, BBP and DIBP – and a proposal to have them banned in the longer-term perspective all over the EU. This was done based on the health effects from the substances when they appear in mixtures (so-called cocktail effects). However, medical devices, among others, are exempt from the proposal.

The first assessment of the proposal (June 2012) was made by two of the European Chemicals Agency’s (ECHAs) scientific committees – the Committee for Risk Assessment (RAC) and the Committee for SocioEconomic Analysis (SEAC). Their recommendation to ECHA was that there was not sufficient data to substantiate the proposal. Therefore, it is expected that the Commission will reject the proposal. However, the Danish government chose initially to take the case further and introduce a national ban on the four phthalates in a variety of product lines. The national prohibition was scheduled to enter into force in December 2013, but the government decided to postpone the proposal for two years after pressure from the industry.

In the EU, special rules for phthalates in toys for children aged 3-14 have applied since 2007. The phthalates DEHP, DBP, and BBP are banned in toys and articles for infants in concentrations above 0.1 % (weight); in addition, the phthalates DINP, DIDP, and DNOP are forbidden in toys (same limit value as above), if they can be put in the mouth. In addition, Denmark has had special rules since 1999 for phthalates in toys and articles for infants. There is a ban on the import, sale, and use of phthalates in toys and articles for infants aged 0-3 if the articles contain phthalates in concentrations above 0.05 % (weight). In addition to ordinary toys, it also applies to other products for infants, such as nursing pillows, baby slings, soothers, and bathing gear. Any person producing, importing, or selling toys and articles for infants is responsible for compliance with the above rules. In other words, the companies must make sure that the articles do not contain banned phthalates. Due to the stringent Danish special rules, Danish importers must be particularly aware when they import from other EU member states.

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Phthalates in hospitals Endocrine disrupting substances are present in many places in hospitals despite 30 years old knowledge that phthalates are released from medical devices 51.

Most medical devices made of PVC have a phthalate content of 20-40 % (weight), while PVC tubes may contain as much as 80 %. Primarily bis(2-ethylhexyl) phthalate (DEHP) is used for this purpose. Devices include bags for blood, infusions, and nutrition mixtures, tubes, catheters, single-use gloves, and much more. In addition to medical devices phthalates are also found in more ordinary products at hospitals, such as vinyl floors, shower curtains, carpets, curtains, windows, and construction materials.

In which ways are patients exposed?

Normally, when we speak about exposure to phthalates and other substances we mean impacts through scratches or through the respiratory system. Various barriers in the body (such as skin, pleura, and cellular membranes) affect and partly reduce the assimilation of phthalates. Some of the substances pass the barriers and reach the blood; subsequently they are transported around the body and cause various harmful effects. Some phthalates even accumulate in the uterus and are transferred to the foetus during pregnancy. However, at hospitals there are more channels of exposure. The most significant one adding to the normal channels of exposure is intravenous exposure, for instance through nutrition mixtures.

The reason humans and animals can assimilate phthalates is as earlier mentioned that phthalates are not chemically bound to PVC and thus are released

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from the plastic when the equipment gets in contact with liquids, fats, and/or heat. The phthalate DEHP is lipophilic, and is therefore primarily released to fatty dissolutions such as blood and nutrition mixtures.

Situations at the hospital where patients are particularly exposed to phthalates are in connection with long-term and repeated hospitalization. In addition there are areas where much equipment is naturally required, such as blood transfusions, haemodialysis (see below), and infusion of nutrition. Patients receiving dialysis are among the most exposed persons.

The function of the kidney is to clean the blood, and when the kidneys can no longer assume this function, patients receive dialysis. This may be in the form of haemodialysis where the blood is led through a pipe out of the body into an artificial kidney where it is cleaned before being led back into the body. This entails long-lasting contact between blood and tubes and thereby the possibility of an increased content of phthalates in the treated blood. Another example of a patient group that is particularly exposed are premature babies. This scenario will be discussed in the below “case study” on neonatal care units.

Legislation Medical devices are covered by three EU directives that have been up for revision in 2012 and 2013, and will be made into regulations in 2014. At present, the directives do not contain any restrictions on the use of phthalates and other endocrine disrupting substances.

In addition, chemical substances found in medical devices are regulated by REACH, but as mentioned, there is only labelling obligations for the use of DEHP. In the above-mentioned Danish ban, medical devices

Exposure to phthalates has many sources.

Due to phthalates in medical devices patients receiving dialysis, among others, risk getting large quantities of phthalates

F o to Pi cs f i v e

directly into their blood through tubes.

51 Kevy et al. 1981. The need for a new plasticizer for polyvinyl chloride medical devices. Trans Am Soc Artif intern Organs, 27:386-390

ENDOCRINE DISRUPTING SUBSTANCES > PHTHALATES

are exempted. Amendments to the current proposal for the new regulations have been adopted by the EU Plenary in October 2013. The amendments include a ban on hazardous chemicals in medical devices, and applies to chemicals that are carcinogenic, mutagenic and reprotoxic (CMR substances) and chemicals which have endocrine disrupting properties – and which are contained in invasive medical devices, or devices that come into contact with the patient or are used to administer, transport or store medicines, body fluids or other substances. The amendment allows the hazardous chemicals to remain in medical devices for a maximum of four years during an exemption process.

Why are phthalates and PVC used so extensively in medical devices?

PVC and phthalates have many useful properties. This is why they are used extensively all over the world.

In some fields, it is difficult to find good alternatives complying with the standards set by the traditional products. Blood bags are a good example. Here, PVC meets many functional requirements, for instance in terms of flexibility, transparency, centrifuging, handling, and weldability.

Other aspects also contribute to maintaining phthalate-containing PVC equipment for medical use.

An extensive infrastructure has been developed for manufacture of the material. It is a relatively cheap product; it is well tested and complies with current legislation.

Many companies today offer phthalate-free alternatives to medical devices or alternative plasticisers.

One example is a non-toxic plasticiser developed by Danisco on the basis of castor oil. Another example is a phthalate-free plastic granulate for use in medical devices from Danish Melitek. Many hospitals already use phthalate-free products. At the Southern Jutland Hospital in Denmark, there is a general focus on procurement of products without DEHP. At the neonatal care unit, they use DEHP-free catheters, intravenous tubes, tongue depressors, nutrition tubes, soothers, and bandages. At the Dutch Westfriesgasthuis Hospital, the entire child-care unit is PVC and phthalate-free, apart from blood bags. More examples can be found in publications from Health Care Without Harm and on the Danish website http://www.eco-forum. dk/medicoartikler/ from the Danish Environmental Protection Agency.

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In a present EU project named PVCFreeBloodBag, running up to 2015, a PVC and phthalate-free blood bag is being developed. Blood bags are one of the only products to which no good alternatives to the phthalates presently used have been found. The project covers many producers, among others Danish Totax Plastics A/S and Melitek A/S, Italian Haemotronic S.p.A., and Finnish Wipak Medical. Blood transfusions are one of the medical treatments that save most lives, and requirements to blood bags are high. The plastic material must not affect the quality of the blood, it must withstand temperatures up to 70 °C and sterilisation. In addition, it must withstand centrifuging in ultracentrifuges working at speeds of up to 5,000 times the relative centrifugal force (5,000*g). An additional advantage of the traditional blood bags is that DEHP has a stabilising effect on the membrane of the red blood cells, thereby reducing haemolysis52 and osmotic structural weakness53. Unfortunately, the blood lipids cause the lipophilic DEHP to be released from the PVC plastic and the harmful substances can thereby be transferred to the person receiving blood.

Case study – Neonatal care units Premature babies in intensive care often need extensive help to survive, as they are not fully developed at birth. Some babies may need help to breathe and are placed in a respirator with a tube through the mouth down the trachea. In many premature babies, a

As yet, there are no alternatives to the phthalates used in blood bags, but the EU supports a project with the purpose of developing a product by 2015.

52 Hemolysis refers to the situation in which red blood cells release hemoglobin (and other contents) to the surrounding fluid because the cell membrane is damaged.

53 To equalize the concentration difference between the red blood cell's internal environment and the external environment (osmosis), fluids will penetrate into the cells and the membrane will weaken. In worst case, the membrane may rupture when the cell is unable to expand further.

ENDOCRINE DISRUPTING SUBSTANCES > PHTHALATES

venflon is inserted 54. This intravenous access is used to administer liquids (such as electrolyte liquids) and medicine directly into the bloodstream. Other procedures include blood transfusion, oxygenation of the blood in a machine – a technique called Extra Corporal Membrane Oxygenation (ECMO) – and feeding of nutrition mixtures through probes. Premature babies are thereby exposed to phthalates in many different ways and in many cases, they get the substances directly into the blood, which poses a larger risk than dermal exposure (assimilation through the skin). In hospital equipment – also for premature babies - DEHP is the preferred type of phthalate. Unfortunately, also an endocrine disrupting chemical affecting, among other things, reproduction and development.

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of this enzyme. The concentration of phthalates in babies’ bodies ends up higher – particularly among the premature babies – than in adults, since the quantity of children’s body fat is much lower.

The endocrine system plays a decisive role in the early developmental stages, and premature babies are thereby particularly vulnerable, as they are still

Through the medical equipment used in the treatment of premature babies they may be exposed to concentrations of DEHP far exceeding the concentration for ”no observed adverse effect level” (NOAEL), i.e. the level below which no harmful effects to health have been seen in animal tests (read more in the section “Cocktail effects“). Tests have shown that tubes for lung ventilation (endotracheal tubes) release 6-12 % DEHP during use 55. This release presumably accumulates in the lungs; an argument that is substantiated by the discovery of DEHP in the lungs of babies after mechanical ventilation. In addition, studies have shown that while a normal exposure to DEHP is 3-30 µg/kg body weight/day, premature babies that are fed

developing. They have less efficient blood-brain and blood-testicle barriers and substances thereby move easier from the bloodstream to the brain and testicles, respectively. Premature babies also have more difficulty secreting phthalates and their decomposition products, as their metabolic detoxification routes are still not sufficiently developed. Lipase (an enzyme decomposing lipids) from the pancreas is the primary detoxifier, and premature babies have very low levels

by one of the two methods mentioned in Figure 13, are exposed to 40-140 µg/kg body weight/day (enteral nutrition) and 2500 µg/kg body weight/day (total parental nutrition), respectively. Such exposures may be up to several hundred times higher than recommended by the authorities. In the light of the fact that gavage feeding often takes place over a long period of time, this single exposure route can cause a very high DEHP load, which is a health hazard for the newborn babies.

Figure 13 Phthalates are transferred to the blood

Different types of treatment involving PVC products and thereby a risk of having phthalates transferred into the blood.

ECMO: ExtraCorporeal Membrane Oxygenation – a heart-lung machine that takes over the heart-lung functions while the organs fully develop.

Electrolyte infusion: is done to stabilise liquid and ion balance.

Enteral nutrition: nutrition by tube directly into the gastrointestinal tract.

Total parenteral nutrition: nutrition given through the blood – is only used when nutrients cannot be ingested, digested, or absorbed.

54 A venflon is a thin plastic catheter that is introduced in a vein of a patient.

55 Latini et al. 1999. Materials degradation in endotracheal tubes: a potential contributor to bronchopulmonary disease (letter). Acta Paeditr, 88: 1174-1175

ENDOCRINE DISRUPTING SUBSTANCES > BISPHENOL A

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Bisphenol A Bisphenol A (BPA) is an industrial chemical.

It is an organic substance consisting of two phenol molecules (See Figure 14). Every year around 700,000 tonnes of BPA is manufactured in the EU, of which the major part is used in the manufacture of polycarbonate – hard impact-resistant plastic. Polycarbonate has several applications, for instance plastic containers for food and drinks such as baby bottles, cans, water coolers, etc. as well as electronic equipment and in cars.

In addition, BPA is used in paints, varnish, glues, and flooring. Several different organisations have studied a selection of food and drinks in cans and have found BPA in all samples; this indicates that the substance leaks from the package into the contents. The concentrations found in the different foodstuffs are very low and thereby hardly harmful to health, if the consumer only eats the foodstuff in question. If, however, the total intake over an entire day, consisting of many different food and drinks together, is considered together with other exposures, e.g. from receipts on thermal paper, the total load may give reason to concern.

In 2006, EFSA (European Food Safety Authority) decided upon a limit value for tolerable daily intake (TDI value) of BPA of 50 μg/kg body weight/day. There has been much discussion whether, and to which extent, BPA has a harmful effect on health when ingested in quantities below this limit. Conclusions seem to depend on the design of the different tests. Certain research results indicate that the substance may have an endocrine disrupting effect on fish and snails, even in concentrations lower than TDI. Tests with mammals have shown that the substance has an endocrine disrupting oestrogen-like effect and reduces fertility. So even if the substance does not accumulate much in the organism (animal and human data suggest that it tends to be rapidly metabolized, with elimination thought to be virtually complete within 24 hours of acute exposure), the endocrine disrupting effects still give reason to concern. In 2007, a scientific article described how concentrations had been found in human blood, urine, placenta, umbilical cord, amniotic fluid, and breast milk 56. This shows that the substance may be

Figure 14 Structural formula for 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A).

transferred from mother to foetus during pregnancy and through breastfeeding.

In addition to the oestrogen-like effect, cellular tests also have shown anti-androgen effects (hampering the biological effects of male sex hormones such as testosterone) of BPA. BPA is suspected, among others, of having health effects contributing to obesity, diabetes, cardiovascular diseases, behavioural changes in children, etc. In addition, the substance is suspected of being a contributory cause of the increasing instances of infertility, malformation of the reproductive organs, as well as breast and prostate cancer that have occurred for the last 50 years in Europe and the US. A scientific article from 2010 states that more than 150 studies describing a negative effect on animals exposed to a BPA dose lower than the established TDI of 50 μg/kg body weight/day exist 57.

This is especially a reason for concern in relation to foetuses, newborn babies, and infants, since the brain and other organs are particularly vulnerable to exogenous hormones in the development stage.

One may wonder why BPA is approved as a food contact material in the EU when so many studies indicate that the substance may have major consequences for human health and the environment. In recent years, however, limited bans on BPA have been introduced after pressure from NGOs and researchers around the world, particularly in products for infants. BPA is subjected to category 1 on the EU priority list of

56 Vandenberg LN, Hauser R, Marcus M, Olea N, Welshons WV. Human exposure to bisphenol A (BPA). Reprod Toxicol 2007;24:139-77 57 Vandenberg LN, Chahoud I, Heindel JJ, Padmanabhan V, Paumgartten FJR, Schoenfelder G. Urinary, circulating and tissue biomonitoring studies indicate widespread exposure to bisphenol A. Environ Health Perspect, online 23 March 2010.

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suspected endocrine disrupting substances. Category 1 contains 194 substances and for this group of substances the endocrine disrupting effects have been documented in at least one survey of living animals.

In addition, BPA appears on the Danish Environmental Protection Agency’s list of undesirable substances.

This list contains chemicals and substance groups that the Agency regards as having undesired health and/ or environmental effects, or that deserve special focus based on suspicion of problematic properties. The list is a guideline for producers, product developers, purchasers, and other players and is intended to be a signal about which chemicals will be restricted or completely phased out in the future.

Despite the fact that BPA appears in many consumer products, Denmark has actually been a frontrunner in terms of limitations for many years. Former Minister for Food, Agriculture and Fisheries, Eva Kjer Hansen, invited the EU Commission to initiate further surveys of BPA's potential harmful effects to health in September 2008. On 30 March 2010, Denmark as the first EU country (Canada was already ahead, see below) adopted legislation banning BPA in food contact materials for infants 0-3 years of age based on the precautionary principle. The ban covers baby bottles and feeding cups as well as packaging (e.g. cans and lids for jars) destined for contact with food for infants aged 0-3 years. Special rules at the National level can only be temporary, since all EU member states must follow the common European legislation, in this case primarily REACH and the Safety of Toys Directive.

When a country makes a national special rule the case is discussed at EU level and subsequently the rule will apply all over the EU or the country in question will be told to withdraw the ban in order to have identical European legislation. If not, the country in question may be brought before the European Court of Justice for breach of the Treaty. If a country has been found guilty of breach of the Treaty, it may be sentenced with a fine if it continues to disobey the same rules.

In this case, Denmark won the case, and since 1st July 2010 it has not been allowed to sell baby bottles containing BPA all over the EU. France will be the first country worldwide to introduce a much more extensive ban on BPA. The ban, which will be fully enforced on 1st January 2014, covers all materials that get into contact with food. This ban will be a major challenge for producers of preserves and soft drinks since BPA as mentioned is a constituent of the epoxy that makes the inner lining in close to all cans containing food and drinks as well as many lids for

Cans contain the endocrine disrupting substance bisphenol A that is readily transferred to foodstuffs and thereby through the diet to humans.

glass containers. Until the ban enters into effect cans and other products for pregnant women and infants must be marked that they contain BPA. The French ban protects all population groups, young and old, and it is important that Denmark and, preferably, the entire EU follow suit to secure the entire population. EU now has to decide if they support the ban and thereby introduce a general EU regulation on the substance or if France must redraw it.

At the global level, particularly Canada is advanced in its protection of the population against exposure to BPA. Canada was the first country in the world to ban the substance in baby bottles and a number of measures have been launched to control the BPA contents in foodstuffs, especially for children, as well as releases to the environment.

In addition, more and more producers worldwide phase out BPA on a voluntary basis. This may partly be due to the fact that they see a competitive benefit as still more consumers demand BPA-free products due to the uncertainties related to the health effects; it may also be a benefit to be abreast of legislation. As an example, Campbell's, the world 's largest soup manufacturer in 2012 announced that the company would start phasing out BPA from their packaging material. The decision

ENDOCRINE DISRUPTING SUBSTANCES > BISPHENOL A

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was made after Campbell's had received more than 70,000 letters from consumers as a reaction to a survey in which 12 preserved products from different companies were tested for their release of BPA. Campbell’s produced the four products with the highest BPA levels.

In addition, Tupperware, which primarily produces plastic containers for the storage of food, has chosen completely to phase out BPA – this, however, only applies to production in the US and Canada. Many of the Tupperware products are already BPA-free and for certain other products the substitution is progressive.

Alternatives to bisphenol A As a direct consequence of the BPA ban in baby bottles in many countries, several alternatives to polycarbonate have appeared on the market. However, many of the alternatives found on the European market are just other forms of bisphenols (S, F, B, and E), of which some also seem to have endocrine disrupting effects. In addition, BPA has been found in plastic types that are not made of polycarbonate, where it may have been used as a subsidiary material. This fact reflects deficient legislation. Producers should not be allowed to replace one harmful chemical substance with another harmful one, and according to legislation, they must document that there are no dangers from using a given material. The problem is that endocrine disrupting substances are not sufficiently covered by the chemicals legislation. Therefore, producers may find loopholes in the law so they do not need to test the substances further.

Today, the best way for consumers to avoid BPA is to use glass bottles and containers wherever possible.

For cans, it is almost impossible to be sure, unless they contain foodstuffs for infants aged 0-3 where the use is banned.

Denmark was the first EU country to ban bisphenol A in baby bottles. Since then, the ban has been extended to cover all EU member states.

ENDOCRINE DISRUPTING SUBSTANCES > FLUORINATED SUBSTANCES – PFOA/PFOS

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Fluorinated substances – PFOA/PFOS Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are synthetic fluorine-containing substances that have a very long decomposition time in nature. PFOS contains a linear perfluoroalkyl chain58 on eight carbon atoms and a sulphonic acid or its salt as a functional group (see Figure 15).

The fluorinated substances can be divided into two main groups: perfluorinated and polyfluorinated.

However, as a whole these two substance groups are called PFC substances (perfluorinated substances).

They all consist of a chain of carbon atoms (C) – a tail – where all (or almost all) hydrogen atoms (H) are replaced by fluorine (F) or with at least three fluorine atoms. The tail can be of varying length (typically between 4 and 12 carbon atoms) and the strong C-F bond makes it nearly non-decomposable. The strong C-F bond also obstructs PFCs from making strong as well as weak bonds to other substances and therefore does not dissolve in oil or water. Instead, they float on the surface like sulphone in water and are thus called a surfactant.

Figure 15 Chemical structure of A) PFOA and B) PFOS.

A.

B.

Per- and polyfluorinated substances In the perfluorinated substances all the atomic hydrogen (H) on the carbon molecule (C) are replaced with fluorine (F).

In the polyfluorinated substances, there are at least three atomic fluorine, but there is still atomic hydrogen at some of the carbon atoms, which make substances able to further decompose - often to perfluorinated substances.

Examples of polyfluorinated substances are fluorotelomer

alcohols (precursors for the design of other substances) and di-PAPs (impregnating substances). In contrast to PFOA and PFOS, the fluorinated tail and head of the acid-containing di-PAPs are linked to a phosphate ester bond, which makes the bond susceptible to degradation by enzymes that are common in nature. Di-PAPs can among others be degraded to PFOA.

Di-PAPs Fluorotelomer alcohol

58 An alkyl consists of carbon and hydrogen atoms. An example of a simple alkyl is methyl (-CH3).

ENDOCRINE DISRUPTING SUBSTANCES > FLUORINATED SUBSTANCES – PFOA/PFOS

The fluorinated substances are found in innumerable products and function both as a water and fat repellent.

They appear in almost all impregnations causing stains to be wiped off easily from, for instance, flagstones, tablecloths, sofas, and nursing pillows. The substances also secure that water does not penetrate your shoes and coats when you have treated them with a Gore-Tex spray. PFCs are also present as coatings (Teflon) on non-stick cookware where water and fat are seen as small pearls, and on the paper and cardboard packages that contain hot food without absorbing fat as would happen with normal paper. The PFCs are so useful and fancy that we actually do not wish to know other than that it works. For what if it means that we cannot use these substances due to the unexpected harmful effects to health?

Not surprisingly, there is a correlation between the fact that when a substance has remarkable effects in products, it also has it in our bodies or the surrounding environment. In addition, when the substances appear in numerous products and do not decompose in nature we now find high concentrations of them all over the environment and in animals and humans. For instance, PFOA has been found in all pregnant Danish women who were tested. When fluorinated substances are tested on rats, the animals develop cancer, grow fat, and die prematurely. Spray products with these substances destroy the rats’ lung function and they die shortly after. Luckily, humans are not rats, but the many harmful effects should lead us to think again before uncritically permitting and using the substances. In humans, PFOA has been found accumulated in blood cells, liver, kidneys, and other organs where the substance is suspected of harmful effects 59. In addition to concerns about the substances’ potential harmful effects on our organs, several fluorinated compounds have also been shown to be endocrine disrupting and others are suspected of being so. For instance, PFOA exposure can lead to early puberty in girls 60. Other PFOA studies indicate that women have difficulties getting pregnant and that men have lower sperm quality61. A study of 1,240 Danish women showed a connection between a high content of PFOA and PFOS in the blood

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and difficulties getting pregnant - it took them between 6 and 12 months longer. The same high chemical concentrations in the mother also affected the birth weight of babies and increased the risk of premature birth62.

Furthermore, other recent studies indicate a correlation between a high content of PFC substances in human blood and increased cholesterol levels and obesity, as well as higher risk among women for diseases in the thyroid gland, i.e. diseases that impairs the energy metabolism in the body and thus may lead to obesity63.

Finally, a study has shown that prenatal exposure (i.e. the baby is exposed to the chemical at the embryonic stage) to PFOA increases the risk of obesity at the age of 20 64.

The fluorinated substances have been used for more than 50 years, but in recent years, they have become more widespread. It is only within the last eight to ten years they have come in focus due to harmful effects to health. How the substances actually disturb the body is still not known, but a number of studies have been made – mostly on rats – seeking to clarify the mechanisms. There are indications that proteins binding to fluorinated substances are prevented from functioning as intended.

The perfluorinated substances are the most well-studied.

However, a general property of PFC substances is that they are both fat and water repellent and therefore do not accumulate in fatty tissue nor are excreted with urine. In fact, the perfluorinated substances are so stable that the body's normal excretion mechanisms – which otherwise makes substances to be excreted, water soluble - does not work. Instead, PFC substances accumulate and bind almost exclusively to proteins in the blood, liver, kidneys, lungs and other organs.

PFC substances are extremely bioaccumulative and have the longest half-lives (half of the substance has been degraded) of all known chemicals in humans – as much as four to eight years. This means that if you are exposed to these substances on a regular basis the concentration in the blood and the body’s organs steadily increases.

Moreover, we are exposed constantly, because PFCs

59 Lau C et al., 2007. Perfluoroalkyl acids: a review of monitoring and toxicological findings. Toxicol. Sci. 99 (2): 366–94 60 Fletcher, T. et al., 2010. Status report Patterns of age of puberty among children in the Mid-Ohio Valley in relation to Perfluorooctanoic Acid (PFOA) and Perfluorooctane Sulfonate (PFOS).

61 Fei, C. et al., 2009. Maternal levels of perfluorinated chemicals and subfecundity. Human Reproduction, Vol.1, No.1 pp. 1–6.

62 Fei C. et al., 2010. Perfluorinated Chemicals and Reproductive and Child Health Outcomes in Humans: A Study within the Danish National Birth Cohort. Afhandling, 128 pages 63 Melzer D. et al., 2010. Association between Serum Perfluorooctanoic Acid (PFOA) and Thyroid Disease in the U.S. National Health and Nutrition Examination Survey.

Environ Health Perspect, 118:686-92 64 Halldorsson T.I. et al., 2012. Prenatal Exposure to Perfluorooctanoate and Risk of Overweight at 20 Years of Age: A Prospective Cohort Study. Environ Health Perspect, 120:668-73

ENDOCRINE DISRUPTING SUBSTANCES > FLUORINATED SUBSTANCES – PFOA/PFOS

occur in all possible places: indoor, outdoor, in soil, groundwater and surface water. Even in the Pacific at 1 km. depth traces of the substances have been found. In addition, polar bears, minks, birds, humans, and aquatic animals such as fish, seal, otter, sea lion, and dolphin have been tested positive for PFCs. Humans are presumably primarily exposed to PFC substances through food, but the concentrations in question are not yet fully known. For instance, measurable, but relatively low concentrations of the simple PFC substances with one alkyl chain are found in fish from the Baltic Sea, but this is not the major source to human exposure. Many other and larger fluorinated substances are found in the impregnation agents used in paper and cardboard packaging for foodstuffs, but their possible harmful effects on health are hardly investigated. However, studies have shown that packaging, such as bags for microwave popcorn, release many chemicals (including PFCs) to the packed food - in this case the popcorn. It is believed today that food contact materials are the most significant source of PFC exposure. The box below illustrates the problem.

The University of Copenhagen-LIFE, the Technical University of Denmark-FOOD, and the University of Toronto have studied the PFC level in 74 samples of paper and cardboard intended for packaging of food or containing food products. The samples were taken in Danish, Swedish, and Canadian stores, and 42 of the 74 samples tested positive for PFC impregnating agents (di-PAPs). Particularly high concentrations of these substances were found in packaging intended for fat foodstuffs, high temperatures, or long shelf lives.

Di-PAPs are polyfluorinated substances decomposing in the body into perfluorinated acids such as PFOA (see box on per- and polyfluorinated substances). It is very unfortunate that we are exposed to such high doses of PFC substances every time we eat, for instance, microwave popcorn.

However, the problems are not over yet; when PFCs are used in paper and cardboard production they will continue to pollute when the paper ware is recycled or incinerated, because of their persistence.

We can also be exposed to fluorinated substances if we work in an environment where they are used. For example, when we spray a coat, shoes, or a sofa with impregnation agents, or treat flagstones or our cars with fluorine wax.

It is not completely clear whether PFCs can penetrate the skin. Nevertheless having it on the skin possesses a risk of getting it into our mouth when we eat, drink or smoke.

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The packaging contains fluorinated substances!

Paper and cardboard packaging for food products increasingly contains fluorinated substances.

A Danish study found PFC substances in 42 out of 71 samples of paper and board for food packaging! One example of these high levels was seen in the packaging for microwave popcorn.

American studies have shown that a person who eats a bag of microwave popcorn ingest 0.11 mg of fluoride compounds. This dose is twice as high as what the limit value (TDI = 0.0015 mg fluoride compounds/kg body weight/day) allows a child of 35 kg (approximately a 10-year-old child) to ingest per day.

TIPS! • Be aware of the type of packaging your food is wrapped in, and the one you use yourself • Use the packaging for what it is intended for - paper towel for example, is not approved as a food contact material • Use glass and ceramics instead of plastic and paper – especially in the oven.

In addition, especially infants, but also others, may be exposed through house dust when the substances are worn off furniture and accumulate in the dust.

Legislation PFOS were banned in May 2009 with Annex B of the Stockholm Convention (read more about this convention in the section ”REACH -Step-by-Step”) on persistent organic pollutants (POP-substances). Therefore, PFOS is now completely phased out globally except in situations where it has been found that a substitution is not possible for social or economic reasons. PFOA on the other hand is still not banned, neither in the EU

ENDOCRINE DISRUPTING SUBSTANCES > FLUORINATED SUBSTANCES – PFOA/PFOS

nor in other parts of the world, and there are hardly any restrictions on its use. However, this chemical is barely used in Danish industry. In addition, it appears on the list of undesirable substances of the Danish Environmental Protection Agency and the SIN list due to the fact that the substance is carcinogenic, reprotoxic, persistent, and is found all over our environment and in humans. However, compounds such as di-PAPs, which are decomposed into PFOA in the body, are completely unregulated today.

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for instance silicone for impregnation of textiles. In addition, Teflon, used as kitchenware coating, can be replaced with titanium and good alternatives are also available within other product groups, such as paints and varnish.

Hardcore and ambitious legislation is needed for entire groups of substances if the fluorinated compounds are to be phased out. The fluorinated substances have so many chemical formulas working together that it is totally insufficient to legislate on one substance at the time. Unfortunately, even despite harsher legislation the fluorinated substances are here to stay. Even if we stop their manufacture completely tomorrow, they will never disappear. The only way to remove them is by incineration, but this process entails a risk of CFC gas (short for Chloro-Fluoro-Carbon) formation that depletes the ozone layer and is strong greenhouse gases, so there is really no good solution. In the best case, we can hope the substances bind to sediment encapsulated in the sea floor and/or in soil over time. Meanwhile, chemical industries keep on working to develop socalled ”biodegradable fluorinated substances” (shorter fluorine chains), which may be less harmful to health.

There are no specific limit values to PFC substance exposure and toxicological tests are sparse and do not necessarily survey endocrine disrupting effects. For impregnation agents containing the more complex PFC substances, hardly any analysis methods can be used to determine the total exposure and possible effects on human health and the environment. The reason is partly that clean substances cannot be acquired and partly that chemical manufacturers for confidentiality reasons will not inform about their fluorinated industrial mixtures for research analysis. The EU may force producers to hand over their PFC mixtures, but this process is laborious especially when there are no specific limit values for the substances. In practice, companies are free to use risky chemicals, thereby literally turning humans into test animals.

At the global level, the manufacture of polyfluorinated substances is estimated to 10,000 tonnes a year 65.

However, there are many possible substitutions,

65 Source: Ministry of the Environment: http://www2.mst.dk/common/Udgivramme/Frame.asp?http://www2.mst.dk/udgiv/publikationer/2008/978-87-7052-843-6/ html/kap01.htm

ENDOCRINE DISRUPTING SUBSTANCES > BROMINATED FLAME RETARDANTS

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Brominated flame retardants As the name implies, “Brominated flame retardants” are chemicals often added to different products, especially electronics, because they reduce the risk of fire during use. The content of bromine increases the ignition temperature so the product does not catch fire so easily. If the material catches fire anyway, bromine acid will form (HBr) and hinder free radicals (e.g. H+) from reacting with oxygen resulting in a mitigating effect on continued burning (See Figure 16).

year. The substance tetrabromobisphenol A, TBBPA, (see Figure 17) and its derivatives account for almost half the consumption – a total of 47 %.

Around 70 different chemicals are used as brominated flame retardants. Around 40 of these are used extensively mostly in electronic equipment. None of these

Brominated flame retardants may constitute as much as 22 % of the material in which they are used.

TBBPA has been found in the blood of eight out of ten computer technicians66, 67. A Swedish survey has also shown that employees in the WEEE (waste electrical and electronic equipment) sector have up to 70 times higher contents of brominated flame retardants in their blood than other citizens. As mentioned, the substances are found in the blood and they are persistent,

substances are produced in Denmark, but at least 13 of the brominated flame retardants are used in manufacturing processes in Danish companies. It is estimated that between 300 and 600 tonnes are imported each

which means that they do not – or only very slowly – decompose in nature or in organisms. Due to this, the concentration will increase constantly up through the food chain and be highest in predators, including

Figure 16 How does brominated flame retardants work?

When a fire is about to break out, for instance in a TV,

process (hydrogen ion, H+ and hydroxide ion, OH-), and

the high temperatures causes the plastic material – here

bromine acid is formed (HBr). The ensuing chain reaction

with polyethene as an example – to decompose into shorter chains. At the same time bromine (Br-) will be

will prevent the free radicals from reacting with oxygen,

released from the brominated flame retardants causing

could otherwise catch fire.

the product not to burn easily. Bromium will combine with

Source: Jensen C.B., Økotoksikologi (Ecotoxicology), 2008.

thereby keeping the temperature low in the TV, which

the free radicals that have formed during the ignition

66 Dansk Kemi (Danish Chemistry), 86, No. 8, 2005. TBBPA, valg mellem pest eller kolera (TBBPA, a choice between pest and cholera).

67 Jakobsson K.; Exposure to polybrominated diphenyl ethers and tetrabromobisphenol A among computer technicians; 2002; Chemosphere 46:709–716

ENDOCRINE DISRUPTING SUBSTANCES > BROMINATED FLAME RETARDANTS

Figure 17 Structural formula of TBBPA

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exposed to the substances for a long period, than what we have seen so far in animal tests. There is thus reason to suspect that brominated flame retardants are hazardous, both to human health and the environment. The health hazard is best documented for two types of brominated flame retardants, PBB (polybrominated biphenyls) and PBDE (polybrominated diphenyl ethers). In addition, the Danish Environmental Protection Agency has assessed TBBPA to be toxic for aquatic organisms and to cause harmful long-term effects in the aquatic environment.

Structural formula of the flame retardant tetrabromobisphenol A (TBBPA). The substance consists of bisphenol with four bromium atoms attached; it is derived from bisphenol A.

humans. With a fancy word, this is called biomagnification. Biomagnification was observed already in the 1950s and 60s with mercury and DDT, among others.

Regrettably, we repeat the same mistakes today, just with other substances with a similar effect.

When we use and dispose products containing brominated flame retardants the substances may be released into the surroundings. In our homes, the substances bind to for example dust and when the products are thrown away the flame retardants may end up in the environment.

Adverse health effects of brominated flame retardants Brominated flame retardants have a number of negative effects on human health and the environment. Studies on mice and rats have shown that these substances may affect the development of the foetus, reduce reproductive capacity and cause neurological changes. They also affect the function of the thyroid gland and are suspected of being carcinogenic. The concentrations needed to cause the above effects are higher than what we see in humans. However, there is much reason for concern, not least as brominated flame retardants accumulate in the fatty tissue (they are lipophilic). They will therefore be present in the organism for a very long time (they are bioaccumulative). This also means that in real life the substances will remain in the body for much longer than in the animal tests that have shown effects. Therefore, there may be more and/or other health effects when

Therefore, it is important to be aware of how to treat waste electronics. You should not just throw your used electronics in the waste bin. It is a statutory requirement that waste electronics (WEEE) must be disposed of in an environmentally safe manner. In practice, this means at the nearest recycling centre.

From here, WEEE is transported to a factory dismantling it into components that are sent for reprocessing so that raw materials can be recycled. Some years back a survey among 2,000 homes in the municipalities of Copenhagen and Frederiksberg (Denmark) showed that much WEEE ends up in the waste bin68. Every week households in these two municipalities discarded an average of 83 kilograms of small electronic items in their waste bin. If these figures are converted to the national level it corresponds to thousands of tonnes of WEEE that are sent for incineration every year, without any kind of recycling of raw materials.

Subsequently, experiments have been introduced in different city districts where every home gets a little box for collection of small WEEE. The box is picked up similar to other schemes for paper, glass, and cardboard.

In 2012, the Danish Environmental Protection Agency made a survey of domestic waste showing that annually in Denmark 19.4 tonnes of mobile phones and 25.4 tonnes of energy-saving bulbs are discarded with the domestic waste 69. Nine of ten used mobile phones end up in the bin instead of the recycling centre where the hazardous waste can be treated correctly, so that it harms human health and the environment as little as possible. This is most likely less of a problem today because of the increase in the resale of used mobile phones.

68 Petersen, Claus (2006): Sammensætning af dagrenovation i København og Frederiksberg. (Composition of domestic waste in Copenhagen and Frederiksberg) Report prepared by Econet AS for: City of Frederiksberg, City of Copenhagen and R98 69 Danish Environmental Protection Agency (2012): Kortlægning af dagrenovation i enfamilieboliger. (Survey of domestic waste in single-family dwellings) http://www2. mst.dk/Udgiv/publikationer/2012/05/978-87-92779-94-6.pdf

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and phased out the use of PVC and brominated flame retardants. This has been possible, among other reasons, due to reduced energy consumption in their products – thereby less heat is developed and the risk of fire is reduced. Apple has also replaced the typical plastic surface with aluminium.

Most electronics on the market still contain brominated flame retardants, which are increasingly suspected of

Electronics without brominated flame retardants are available today. The selection is still not very large, but if a consumer demands goods – such as PCs, printers, and copiers – with either the Nordic Swan label, the EU-Flower or the German Blue Angel he can avoid many hazardous substances. As requirements become stricter, the problematic brominated flame retardants will disappear completely from ecolabelled products.

being endocrine disrupting.

As a consumer, you also have the right to know the content of “substances of very high concern” in the goods you acquire. You must ask for this information Legislation Different pieces of legislation exist that are meant to reduce the problem of hazardous chemicals in electronics and electronic waste. However, there have been a variety of difficulties in the implementation of effective rules and conventions in the waste sector.

Furthermore, there are problems with the collection of the waste. Still, there are special rules for hazardous substances in this group of products, namely the RoHS directive (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) and the WEEE directive (Waste Electrical and Electronic Equipment). In pursuance of the RoHS directive, PBB and PBDE have been banned from electrical and electronic equipment from 1st July 2006.

In the EU, there is also a general ban on two of the most problematic brominated flame retardants: penta-BDE and octa-BDE. The ban entered into force mid-2004.

Unfortunately, studies indicate that consumers are more concerned about design and price, than about health and the environment, when buying electronics. However, it seems that the RoHS directive has changed the trend among producers on the market.

Several large producers have increased their focus on hazardous chemistry. This is to the benefit of consumers, the environment, and the companies as well, which can market less hazardous and environmentally harmful products and also be at the cutting edge of any subsequent more severe legislation where the hazardous chemicals may be banned. Apple is one of the producers that have taken the first step

yourself, where after the retailer is obliged to reply within 45 days whether the product contains one of, so far, 151 substances (January 2014) that the EU assesses to be of very high concern (appearing on the so-called Candidate List). However, TBBPA is not on this list and it will not be included as it stands today.

Therefore, regarding brominated flame retardants, consumers are not sufficiently protected by this ”right to know” rule.

3

Fo t o V nl it

Chemicals in everyday life

CHEMICALS IN EVERYDAY LIFE > CHEMICALS IN FOOD

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Chemicals in food We are extensively exposed to chemicals through our food in the form of pesticides, parabens, bisphenol A, and dyes and fragrances, but there is much we can do ourselves to reduce this exposure. Especially candy, snacks, and soft drinks are filled with additives.

Additives are used in food due to their special properties. Some properties prolong the shelf life, others give a certain consistency or colour. Many foodstuffs would not last in a sales process, all the way from production, through transport to supermarket, if no preservatives were added. Therefore, these substances may in some cases be necessary, but it is important that they are used moderately. Generally, there is no difference

is whether consumers should be exposed to a possible risk just to give the sausage the “right” red colour.

in terms of health effects of additives whether they are synthetic or natural. Many people consider plant products – “natural additives” – as harmless and healthy, but this is far from the entire truth, since these products also can pose a health risk. Essential oils (e.g. lavender or lemon oil) are a frequent cause of allergies. Before additives can be used in foodstuffs, they must be permitted in the EU and appear on the so-called positive list. However, for many substances professionals constantly disagree whether specific additives have been investigated sufficiently for possible toxicological effects, even when they have been successfully through a permit procedure.

their sodium salts. These parabens are on the EU list of substances suspected of being endocrine disruptors and are classified as Category 170.

Azo dyes are mostly known from textiles but these dyes are also used extensively in foodstuffs. Azo dyes are a group of synthetic dyes that all contain the socalled “azo group” (See Figure 18).

Figure 18 Structural formula of an azo group

Fo t o Pg i a m

Many additives are suspected of being carcinogenic.

Nitrite is used as a preservative, for instance, in wine and sausages and also enhances the colour and taste of the product. Unfortunately, nitrite is very poisonous, if it is ingested in too large quantities (much larger quantities than what is found in foodstuffs), and can be transformed into substances called nitrosamines known to be highly carcinogenic. We still do not know all the consequences of this. In the organic food production, this uncertainty has been taken into consideration to the benefit of consumers. It is not permitted to add nitrite at all to organic products. The continued use of nitrite illustrates a problem – we still use specific substances that are suspected of being harmful to health, despite the fact that we can do without them in food production. Nitrite is not indispensable in food preservation and the question

Parabens, which most people normally only associate with care products such as shampoos, body lotion, and similar, are also widely used in foodstuffs, where they have a preserving effect. It is even more difficult to establish whether parabens are present in foodstuffs or not, than in care products, since food is only labelled with E numbers. Four parabens are permitted in foodstuffs: E214, E215, E218, and E219.

Occasionally, the names are stated instead as ethylp-hydroxybenzoate, methyl-p-hydroxybenzoate and

Azo dyes are found in many different foodstuffs but mainly in candy, soft drinks, and juices. Foodstuffs containing the five mostly used azo dyes must in the future be marked with this ominous phrase; “May have an adverse effect on activity and attention in children”.

70 Category 1: Substances with documented endocrine disrupting activity in at least one study of a living organism. These substances have top priority for further studies.

CHEMICALS IN EVERYDAY LIFE > CHEMICALS IN FOOD

Ten different azo dyes are permitted in limited quantities in a large number of foodstuffs in the EU. Again, a way to avoid these chemicals is to buy organic food. All azo dyes have been shown to cause allergenic symptoms, such as asthma and hay fever.

In addition, aggravation of hyperactivity in children has been observed repeatedly71. Before the introduction of a common European chemicals legislation, we did not add colorants to basic food such as yoghurt or food specifically intended for children in Denmark.

There has long been demands that azo dyes should be banned completely in the EU, and thereby also be phased out from the Danish market, but so far unsuccessfully. However, in 2008 it was decided that azo dyes in foodstuffs, including candy, soft drinks, and cakes - had to be labelled. The EU decision came into effect in 2010 and in practice it means that foodstuffs containing the six most used azo dyes must be marked with the ominous phrase; “May have an adverse effect on activity and attention in children”. The argument for not banning the substances completely is that we need more scientific proof despite the abovementioned research results. On the other hand, the existing results should be sufficient for EU decisionmakers to make use of the precautionary principle of the Treaty and to give the consumers the benefit of doubt regarding the harmful effects. Especially because there are suitable and unproblematic alternatives to the azo dyes.

When it comes to risk assessment of food and feed safety in the EU, the responsibility lies with the European Food Safety Authority – EFSA. In 2002, EFSA was established as part of an extensive programme to improve food safety in the EU, to guarantee a high degree of consumer protection and to re-establish and maintain confidence in food supply in the EU. The entire food production “from soil to table”, i.e. from the primary production (including feed safety) to delivery of food to consumers, is the responsibility of EFSA. If there is a risk that humans get too much contamination through food, it is first and foremost important to reduce the source of the pollution, as this is the most efficient measure. For example, the use of unleaded petrol is one of the main reasons that in particular vegetables and fruit, but also meat, contain significantly less lead today than some years back.

For pesticides and other processing aids, only the most hazardous substances have been banned in

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conventional production, but the authorities have made rules for how to use the unbanned materials in order to reduce residues in foodstuffs. Organic producers avoid pesticides completely.

Concerning natural toxins and environmental pollution, limit values are calculated and established against the background of total dietary composition.

Thereby the contribution from different foodstuffs to total intake of the substance in question is accounted for. Tolerable daily intake (TDI) is generally measured in micrograms (µg). TDI indicates the quantity of a chemical a person can ingest through the diet every day, throughout life, without any negative health effects (see the section ”Limit values”). The TDI value is, so to speak, distributed throughout all food. The intake of a certain pollutant in an average diet can therefore in principle not exceed TDI, when the limit values are complied. Unfortunately, we do not have official TDI values for a large number of important chemicals. This applies, among others, to brominated flame retardants; an expert committee of the World Health Organization (WHO) concluded in 2005 that the available information and data were too sparse to set up TDI values.

The largest problem associated with a TDI value is that it does not consider cocktail effects. Today it is generally known and accepted that it may have health impacts that we are exposed to many different chemicals on a daily basis. However, there are still no guidelines for how to tackle this problem. This means that the traditional way of calculating TDI values may lead to a significant underestimate of the risk.

For natural ingredients or pollutions that, among other sources, origin in the manufacturing processes, it is not always possible to set up a limit value. Instead, information and guidance is provided to the consumers to secure them against health risks. For example, we have dietary guidelines for pregnant women, including that they should not eat more than 100 grams of predatory fish a week, since predatory fish may contain mercury.

As a general rule, a varied diet is important to avoid a high intake of a single pollutant.

71 Assessment of the results of the study by McCann et al. (2007) on the effect of some colours and sodium benzoate on children’s behaviour - Scientific Opinion of the Panel on Food Additives, Flavourings, Processing Aids and Food Contact Materials (AFC) - http://www.efsa.europa.eu/en/efsajournal/doc/660.pdf

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Chemicals in clothing and textiles Textiles are also covered by REACH and therefore consumers have the right to get information about any contents of substances on the Candidate List, if they ask for it. Unfortunately, legislation is not very extensive in this field and children and adults may be exposed to dyes, preservatives, and other chemicals through their clothes. The extent of chemicals in clothes production can be illustrated by the fact that 0.5-1 kilogram of chemicals is used for the manufacture of one T-shirt72.

For this reason, you should always wash new clothes before use, to reduce the release of these substances on the skin73. However, this does not solve the problem relating to the use of hazardous chemicals. Chemicals washed out of the clothes end up in the aquatic environment where they obviously also do much harm, while other chemicals will remain in the clothes, even after wash. Particularly phthalates, some heavy metals, and antibacterial agents are not washed from the textiles in household washing. However, phthalates, and to some extent heavy metals, can to a certain degree be avoided by buying textiles marked with ecolabels or health labels such as the Nordic Swan or the EU-flower.

Consumers have problems relating to chemicals in textiles, but another group of people are affected much

Part of the Danish Environmental Protection Agency’s campaign use a well-known Danish children’s song (slightly modified) to convey their message.

more severely. In the working environment, there is extremely high exposures to chemicals, where many workers are at great risk of getting sick of fumes from and through direct contact with harmful chemicals.

Report from Greenpeace led to major mindset changes in the textile industry

P ho t o R o b e rt o Gen naro

brands, such as Nike, Adidas, Puma, Calvin Klein and H&M. One month later a follow-up report 'Dirty Laundry 2: Hung Out to Dry' was launched. Here they had tested 78 newly purchased items of clothing from 15 international brands. In two thirds of the clothes were found nonylphenol, which is a toxic, non-degradable and endocrine disrupting chemical particularly used in the dyeing of textiles.

In July 2011, Greenpeace released the report 'Dirty

A few weeks after the publication of the report, PUMA announced that the company will eliminate all hazardous chemicals from their production by 2020. Shortly thereafter Nike and Adidas followed that statement. Also the Swedish fashion giant H&M has promised to phase out the use of

Laundry', where they revealed textile factories release of toxic chemicals into rivers in China. These factories are suppliers to some of the major multinational clothing

hazardous chemicals and furthermore to publish data of pollution from the factories where their clothing are produced. Source: Greenpeace www.greenpeace.org/denmark

72 Danish Environmental Protection Agency: http://www.mst.dk/Borger/Kampagner/toejkemi/ 73 Danish Environmental Protection Agency campaign ”Kemikalier i tøjet er hverken for børn eller voksne”: http://www.mst.dk/Borger/Kampagner/toejkemi/toejkemi.htm (Chemicals in clothes are no good for children and adults”)

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Carcinogen found in bags sold in Denmark

Phot o Pas t i cci o

lining of the bag and the amount exceeded the threshold limit more than 33 times. Such large quantities of the dangerous substance led to the withdrawal of the bags from the market and were subsequently handled and disposed as 'hazardous waste' – bags, that many consumers had already bought. The Danish Environmental Agency wrote to the clothing group: "This azo dye is a highly potent (strong) carcinogen and both direct skin contact with the colored lining as well as indirect skin contact through spillovers from the lining to food, hands, lipstick, creams, etc. should be avoided."

In the summer of 2011, the azo dye Azobenzene, which by the Environmental Protection Agency is described as "a very potent carcinogen", was found in a fashion bag sold from Danish stores. The substance was found in the

This is not least the case in developing countries where working conditions might be extremely poor. Today, almost all production takes place in low-pay areas that have low or no requirements for discharges of wastewater and use of chemicals, including China, Bangladesh, and India. H&M is a frontrunner in terms of phasing out hazardous chemicals in textiles. In autumn 2011 the same clothing company made an ambitious commitment to all the citizens of the world and their descendants: “H&M is committed to continuously eliminate the use of all hazardous chemicals and hence achieve zero discharge in all production procedures associated with the making and using of H&M products, at the latest by 2020”. For example, the fashion chain has already introduced a ban on the use of PFOA and PFOS and PFOS-related substances.

In addition to chemical residues in conventional clothing, some clothes items also have plastic prints (so called plastisol print). The prints are often made from polyvinyl chloride (PVC) softened with phthalates that are suspected of having endocrine disrupting effects. Particularly in children’s clothes, this may be a problem, since young children tend to suck and chew on their clothes, which puts them in direct contact with the chemicals. Many of the substances used for the manufacture of clothing are furthermore allergenic. Particularly the black colorant p-Phenylenediamine (PPD), which is found in black and very dark clothes, is strongly allergenic. Another very problematic chemical product is formaldehyde, which is used to make the product “wrinkle-free”. In the US formaldehyde is now included on the list of substances causing cancer

It is worthwhile to be a critical consumer, and for instance ask the supplier if a product or its packaging contains any of the so-called Substances of Very High Concern (substances on the EU Candidate List).

in the human organism, but its use is still permitted in small concentrations. In the EU, the maximum permitted concentration of formaldehyde in finished products is 0.2 % and any product containing more than 0.05 % must carry a mention that the product contains formaldehyde. Only specific ecolabelling schemes have completely banned the use of formaldehyde in textiles. In general, the probability of chemical residues in textiles is increased in those with special properties. This group includes water repellent and windbreak textiles (typically impregnated), anti-bacterial textiles, which may contain silver in nanometre size, and flame retardant textiles containing brominated flame retardants. Table 4 shows an outline of chemicals in new clothes. In addition, the general purpose of the chemical is described along with the harmful effects to health.

In 2010, a large consumer survey showed that price is the key factor when Danes buy textiles or clothing for their children and themselves. If you, on the other hand, want to consider health and the environment when buying clothing and other textiles, you may use the following tips: • buy organic textiles • look for one of the official ecolabels: GOTS, the Nordic Swan, or the EU-Flower • avoid plastic prints made from PVC • avoid rainwear and wellies made from PVC • avoid using impregnation agents with fluorated compounds (PFCs) • avoid clothing with a smell of chemicals or perfume The fragrance may be added to hide the chemical smell

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Table 4 Tips from the Danish Environmental Protection Agency on how to avoid undesired chemicals in your clothes

Type of chemical

What are the chemicals used for? What is the problem?

What can you do?

Antibacterial agents

Antibacterial agents such as triclosan and nanosilver are added to clothing to kill bacteria and thus prevent odours.

The agents are used in e.g sportswear, outdoor clothing, and stockings.

Triclosan may be skin irritant. In addition, there is a risk that the antibacterial agents may promote resistant bacteria. Antibacterial agents may be very toxic to the aquatic environment.

Do not buy clothing treated with antibacterial agents. Therefore avoid words like “antibacterial” and “odourless”.

Colorants

In the colouring of textiles, a large number of different colorants are used. Some colours contain heavy metals such as chromium, copper, nickel, zinc, cadmium, and lead.

A number of colorants are considered to be allergenic. Some also of being carcinogenic and many are toxic to the aquatic environment. Especially heavy metals are problematic for both health and environment.

Wash your clothes before use.

Optical brighteners

Optical brighteners are used to make textiles appear whiter.

Optical brighteners are heavily decomposable and very toxic to the aquatic environment. They may also be skin irritant.

Wash your clothes before use.

Avoid detergents containing optical brighteners.

Flame retardants

Some textiles are treated with flame retardants to prevent them from catching fire. Textiles in question are typically furnishing fabrics, textiles in cars and clothes used for special purposes, such as clothes worn by professionals.

Flame retardants may be problematic since they accumulate in the environment and they are suspected of reducing reproduction and causing congenital malformation and cancer. Some of the brominated flame retardants have been banned from textiles since 2004.

Do not buy clothing treated with flame retardants.

Phthalates

Prints on clothing and textiles may be of PVC softened with phthalates. In Denmark, phthalates are banned in toys and articles for infants below the age of 3, but are permitted in ordinary clothes – also for children.”

Some of the phthalates are endocrine disrupting or suspected of being so – and they are suspected of reducing reproduction.

Do not buy clothing with PVC prints (also called plastisol prints or rubber prints) containing phthalates. Ask in the shop.

Impregnation agents

Impregnation agents are used to give a water and dirt repellent effect.

The agents may contain fluorinated substances suspected of being both carcinogenic and endocrine disrupting. Several, however, are banned in the EU while others are still permitted. Fluorinated substances are heavily decomposable and accumulate in the environment.

Avoid impregnation with fluorinated compounds.

Formaldehyde

Formaldehyde is added to textiles to prevent them from shrinking and wrinkling, to fix colour and repel dirt. In addition, formaldehyde is used as a preservative to prevent clothes from rotting during transport over long distances.

Formaldehyde may cause skin irritation and allergenic reactions. In addition, formaldehyde is carcinogenic by inhalation - in particularly high doses that will typically only occur in the working environment during production and use of formaldehyde.

Wash your clothes before use.

Source: Danish Environmental Protection Agency 2011

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Figure 19 A selection of labelling schemes

The Nordic Swan

The EU-Flower

Fairtrade

Oeko-Tex®

A selection of labelling schemes that can help consumers

types of labels: Organic labels, ecolabels, fair trade labels,

avoid many chemicals. Generally, there are four different

and health labels. They are described below.

• avoid buying antiwrinkle clothing (often contains formaldehyde) • avoid clothing described as antibacterial, mildew resistant, or similar (most probably contains nano-silver).

Clothes with the Nordic Swan label don't contain substances that are suspected of being endocrine disrupting.

The EU-Flower has requirements for the manufacturing process from the cotton arrives at the factory until it

There are many labelling schemes for clothing that help consumers buy goods that are either less harmful to health, the environment and/or to those producing it (See Figure 19).

ends up in Danish shops, including requirements for use of chemicals. However, the EU-Flower does not have requirements for organic raw materials, but does have rules for the kinds of pesticides used in the fields.

Both the Nordic Swan and the EU-Flower ban the use of PVC prints on the clothes, and colorants causing allergy or that are suspected of causing cancer may not be used.

Organic labels: If you wish to buy organic clothing there are several labels you can look for. Some organic labels only have requirements that the material, e.g. the cotton, is organic while others also have environmental and health requirements for the production stage. Some of these labels comply with the criteria for Global Organic Textile Standard (GOTS), which is the closest we get to a global standard for organic clothing. GOTS requires that the clothes are manufactured from organic raw materials and that it is processed in an environmentally correct manner at the factory. In addition, it must not contain phthalates. There are a number of other organic labels for clothing in Denmark, including Demeter and Soil Association.

Environmental labels: When you buy ecolabelled clothing or furnishing fabrics, particularly such labelled with either the Nordic Swan or the EU-Flower you choose one of the least environmentally harmful products on the market.

The criteria for these labelling schemes are normally strengthened every three years to secure that the labelled products are always in the best category when it comes to environmental and health considerations.

At the same time, the labels guarantee that the quality and function of the product are at least as good as for comparable, non-labelled products.

Fairtrade label: The Fairtrade label, which used to be known as Max Havelaar, is also used on clothing and is an international labelling scheme. The label guarantees that farmers and workers in developing countries have decent working conditions and get a minimum price for their products. The farmers are paid a special supplement for organic farming if they have converted their production, but there is no requirements for organic farming in the Fairtrade labelling since it would exclude some of the weakest farmers. Around 75 % of Fairtrade labelled products on the Danish market are also organic, and if so this will appear from an organic label next to the Fairtrade label.

Health labels: “Confidence in Textiles” – Oeko-tex® is the world’s leading health label for textiles, but it entails no environmental requirements. It guarantees that the clothes contain a minimum of a large number of substances of high concern. For instance, there are rules for how many chemical residues, pesticides, and formaldehyde the textiles contain. By contrast, it says nothing about how and with which substances the textile has been manufactured. For example, there is no general ban on the use of phthalates in the clothes.

CHEMICALS IN EVERYDAY LIFE > THE HORROR SHOW

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The horror show – are we hormonal ticking time bombs?

A case story On a daily basis, more than 100 substances that affect our endocrine system one way or the other surround us. If on top of that we are exposed to several different harmful chemicals simultaneously, the result may be the so-called cocktail effects. We are exposed to the substances around the clock, but we can make many choices that reduce exposure.

Already when we go through our regular morning routines, we are exposed to large quantities of endocrine disrupting substances. In the shower, they are found in the care products we use such as shampoo, conditioner, and shower gel. Later, when we use body lotion and – as many girls and women do – put on make-up, we can again be exposed to harmful substances. As explained in the above section (See ”Chemicals in clothing and textiles”) exposure increases when we start dressing.

Breakfast and other meals during the day can also contain endocrine disrupting substances and other undesired chemicals as can food packagings. Actually, it is presumably through our diet that exposure is highest.

When we read our newspaper, we are potentially exposed to harmful chemicals from the printing ink and when we check our e-mail before leaving home, we are exposed to brominated flame retardants from the computer and some of our furniture. In addition to all these exposures, a person inhales large quantities of air during a day. In kilograms this is much more than what we eat and drink in one day, and the air is most probably also polluted with hazardous chemicals.

This scenario clearly illustrates that there is a large risk of exposure to numerous chemicals during a day – often in concentrations that by far exceeds the limit values set up to protect human health and the environment.

Also, cocktail effects of all these chemicals may arise when we are exposed to many different chemicals at the same time (read more about this issue in the section ”Cocktail effects”).

Naturally, we cannot do without chemicals in our daily lives, but we can phase out the most harmful ones.

Many consumer products contain unnecessary endocrine disrupting chemicals that can easily be replaced or left out completely, such as some preservatives in care products. For example, if we keep lotions and hair wax in tubes instead of open cans they preserve fine without harmful chemicals. In many other products, the most hazardous chemicals can be substituted with other substances that are thoroughlytested and scientifically proven harmless. This is the case, for instance with the plasticisers phthalates, which can be replaced by polyester and silicone.

The Swedish Society for Nature Conservation together with other NGOs have tested dust from bedrooms in a large number of European, African, and Asian countries 74. In September 2011, the Society published a report showing that a hazardous mixture of endocrine disrupting substances is hidden under our beds regardless of the country of origin of the house dust. The chemicals are present in levels that are much higher than previous findings. These results cause concern, since endocrine disrupting substances are increasingly suspected of being the cause of a number of health problems. For instance, a rising number of boys are born with genital deformation and still more women get breast cancer. In addition, it has been seen that the male part of the population in many countries has reduced fertility. Women therefore take longer to get pregnant, must receive treatment to get pregnant, or cannot have babies at all.

Europeans spend up to 90 % of their time indoors 75 where exposure to chemicals may be up to 1,000 times higher than outdoors (see Figure 20 with possible sources of chemicals released in our homes). This much higher rate of exposure is due to the fact that decomposition of organic chemicals is very limited indoors due to the often very dry air and the absence of microorganisms and sunlight (UV radiation accelerates decomposition). The circulation of air in modern insulated buildings, as they are in our cool climate, is also limited, contributing to a very long decomposition

74 ”Home sweet home - dusty surprises under the bed”; 2011; http://www.chemsec.org/images/stories/2011/chemsec/home_sweet_home_lowres.pdf 75 www.bolius.dk

CHEMICALS IN EVERYDAY LIFE > THE HORROR SHOW

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Figure 20 We are surrounded by chemicals

COUCH

ELECTRONICS WOODEN FURNITURE

CABLES FLOOR

A small selection of chemicals that may be released from the items we have in our homes. BF: brominated flame retardants; DS: disinfecting substances; FA: formaldehyde; PS: polyfluorinated substances.

time for chemicals in the indoor environment.

Generally, young children spend even more time in their homes than adults. Other factors affecting exposure are associated with physiology and behaviour. Children spend much time on the floor and young children often have “hand-to-mouth contact”, which means that they generally ingest more dust than adults do. A poor indoor environment may cause symptoms such as irritated eyes, headaches, tiredness, and allergy – and in the worst case more serious diseases such as cancer and cardiovascular diseases. Therefore, it is not hard to imagine that relatively high concentrations of chemicals suspected of being endocrine disrupting may threaten our health conditions.

According to the Swedish report, the endocrine disrupting substances found in the dust included brominated flame retardants, phthalates, bisphenol A, parabens, polychlorinated biphenyls (PCB), alkylphenols, perfluorinated substances (PFCs), and pesticides. Most of these substances and their names are not familiar to many people, but most of us have them in our homes in various concentrations - first in consumer products and later on in dust. This is due to the fact, that endocrine disrupting substances are released from many of the products in which they occur, due to either heating or

wear. In addition, they are found in products that are normal in our homes, including furniture, electronics, cosmetics, and toys (see Figure 20). As described above, it is possible to replace the most hazardous chemicals with less hazardous or harmless substances in many of these products. However, since there is no ban on their use it is difficult to make producers replace a substance that is already part of their production.

This is often due to economics – it may be expensive to change production or the new substance may be more expensive – but ignorance about suitable alternatives may also be a reason. Therefore, it is necessary to have these substances included in the European chemicals regulation in order to have a level playing field. This will entail larger demand for the alternative less harmful substances and thereby decreasing prices. In addition, it will balance the distortion of competition that arises if one producer chooses to take the lead to ensure that his products are harmless to human health and the environment. The way it is today a company that takes the lead regarding substitution of hazardous chemicals risks to be priced out of the market.

Multitudes of guides are available on the Internet helping us to become greener consumers. In addition, various campaigns are made to help ordinary consumers

CHEMICALS IN EVERYDAY LIFE > THE HORROR SHOW

act reasonably in relation to their health. For instance, the Danish Ministry of the Environment makes many campaigns that are often directed at specific target groups, such as teenagers, parents of young children, pregnant women, etc. In many cases, a scientific survey is behind the campaigns that thus also can be used in European/international contexts. For instance, Denmark has used such scientific data in a legislative proposal aiming to ban bisphenol A in baby bottles (read more in the section �Bisphenol A�). As from July 2010, this ban took effect all over the EU.

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4

Pho t o Lao s hi

Cocktail effects and Nanomaterials

COCKTAIL EFFECTS AND NANOMATERIALS > COCKTAIL EFFECTS

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Cocktail effects

Every day humans and the environment are exposed to Foto D an Brandenburg

a cocktail of all the chemicals that surrounds us in our everyday lives. The chemicals are released from e.g. electronics, furniture, clothing and food packaging.

Just as people are exposed to chemicals from many different sources (discussed in the section ”The Horror Show – are we hormonal ticking time bombs?”) exposure also affects the environment. This may be in the form of pesticides from agriculture, discharges and sludge from wastewater treatment plants and overflow from sewers, as well as atmospheric accumulation of heavy metals and various chemicals transported by the wind. Both people and the environment are therefore exposed to many different chemicals on a daily basis and no existing legislation protects us from adverse effects from this chemical cocktail.

A cocktail effect is also referred to as a combined effect or a synergetic effect. It means that all chemicals found in a mixture contribute to the total effect of that mixture. A cocktail effect may arise from many scenarios, but people are primarily exposed through their diet or the air we breathe. Such scenarios may be: • exposure to several different pesticides occurring in the same food product which are thereby ingested with the diet.

• exposure to many different kinds of chemicals occurring in consumer products such as parabens from cosmetics and care products and phthalates and fluorinated substances from clothes.

• exposure to house dust, where chemicals released from ordinary consumer products in the home accumulate. These are, for instance, brominated flame retardants from electronics, PVC and phthalates from vinyl floors, and disinfectants from furniture.

Particularly young children are exposed in this way as they crawl on the floor.

Today we know that chemicals that individually and at low concentrations are harmless to human health and the environment may have harmful effects if they occur in mixtures. Thus, it may seem evident that assessments should consider the toxicity of chemical mixtures as a whole. However, with today’s procedure, we study the toxicity of each single chemical substance in a given mixture separately, and the responsibility lies with the producer. One of the problems with chemical mixtures is that they come in overwhelming numbers.

With around 80,000-100,000 chemicals76, 77 in mass

76 EU definition: Chemicals are the common term for chemical substances and mixtures whereas a chemical substance is defined as ‘the substance as it occurs or as it is manufactured’.

77 http://ec.europa.eu/environment/chemicals/exist_subst/einecs.htm

COCKTAIL EFFECTS AND NANOMATERIALS > COCKTAIL EFFECTS

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The problem of chemical mixtures concerns all groups of chemicals such as carcinogenic substances, allergenic substances and endocrine disrupting substances.

But only for the latter – the endocrine disrupting substances – has research on cocktail effects been made. Danish research has shown that when test animals are exposed to mixtures of endocrine disrupting substances it may cause serious reproductive disturbances 78. This has been seen in concentrations so low that each chemical separately would not cause measurable health effects.

Many pesticides are used in agriculture. Therefore, foodstuffs can contain a large number of different chemicals that humans are exposed to through their diet. The chemical cocktail we are exposed to may have adverse health effects.

production, there are more potential combinations than could ever be tested for toxicity. In addition to the number of potential mixtures, also the number and concentrations of chemicals in a chemical mixture have an impact on the toxicity of the mixture. Furthermore, which organism is exposed to the chemical mixture also matters. A mixture may have one effect on plants, another one on humans, and a third effect on fish.

Therefore, it is not sufficient to assess chemicals one by one. However, there are still discussions about how best to calculate the risks associated with mixtures of chemicals and who should prepare the risk assessments. With the risk assessment methods available today it is almost impossible to assess the risks associated with all possible chemical mixtures. Furthermore, it is difficult to set up realistic scenarios in scientific tests, since it is not possible to use humans as test organisms when serious effects are tested. Limit values for chemicals found as additives in foodstuffs, softening phthalates in toys, or in the working environment, are often established based on a concentration found harmless, for instance, in animal tests. This “safe” concentration is further divided by a safety factor (in many cases 100), which is assumed to be sufficient in order to protect human health and the environment.

Subsequently, when doing risk assessments, it is tested, on the basis of this limit value, how much the overall exposure is for each substance. This is done without considering that humans and the environment are actually exposed to many different chemicals from many different sources at the same time, not considering the cocktail effects.

To minimise the risk of these cocktail effects as much as possible there has in recent years been an increasing focus on research where effects of mixed contaminations (where many different chemicals were at play) have been studied. Increasingly, these test results indicate that in most cases it is possible to calculate the cocktail effects of mixtures by two relatively simple concepts: Concentration Addition (CA) and Independent Action (IA). CA presupposes that the different chemicals in a mixture have the same effect mode, while IA presupposes that the different chemicals in a mixture have different effect modes, for instance one chemical affects the liver while another affects the blood vessels. Both methods are based on precise knowledge about the quantitative and qualitative composition of the mixture, so it is decisive to have single substance assessments of high quality.

Concentration Addition The method is based on the assumption that all chemicals in a given mixture have the same effect mechanism, but the strength of the effect may be different for the different chemicals. The concentrations causing exposure are simply added and thereby the total effect is found.

It can be explained by comparing with the intake of alcohol. Everybody knows that you do not get drunk from half a beer. Nor from a small glass of wine. One Gin & Tonic does not make you stumble. And one whiskey will not knock you out. However, if we drink all of these one after the other, most of us would feel a certain effect of the total amount of alcohol. Very simply, in this case, the concentrations of each drink are added and the total effect of the “cocktail” is inebriation. Here different substances with the same effect mechanism individually have no or only very little effect, but the sum of them has a harmful effect to health.

78 Hass U et al., 2012. Adverse effects on sexual development in rat offspring after low dose exposure to a mixture of endocrine disrupting pesticides. Reprod Toxicol.

34(2):261-74.

COCKTAIL EFFECTS AND NANOMATERIALS > COCKTAIL EFFECTS

Independent Action This method is based on the fact that chemicals in a given mixture have different effect mechanisms, i.e. they work on different targets in the organism; but all chemicals in general contribute to the same type of effect – e.g. it is fatal or affects reproduction or growth.

In this method, the effects of the different substances are added to find the total effect of a mixture. This method has the fundamental problem that the total effect is calculated from observed effects of individual substances. Therefore, a given mixture effect will be missed if a chemical occurs in a concentration that is lower than the “zero effect concentration” (a defined limit under which the given substance has no harmful effect).

It is a key assumption of both methods that the individual substances in a mixture do not affect each other mutually with regard, for instance, to assimilation, transport, metabolism, or excretion. In addition, the substances are not supposed to affect each other’s effect mode in the exposed organisms.

Both models have their uncertainties, since they rest on assumptions that would rarely be seen 100 % satisfied in reality. Generally, the Concentration Addition method tends to slightly overestimate the effect of mixtures with different effect mechanisms, while it seems that Independent Action often underestimates the effects of chemicals with the same effect mechanisms. In other words, if the choice is between the two models for risk assessment, Concentration Addition will give a higher degree of protection than Independent Action.

Three types of cocktail effects Cocktail effects come in different ways: 1. Additive effect 2. Antagonistic effect 3. Synergistic effect Additive effect. The total effect of several different substances corresponds to the sum of the different substance effects. This type of effect thereby corresponds to what you can calculate with the above-mentioned Independent Action model.

However, it is not as transparent as it may sound; for instance, you add the four effects seen/measured in the four different chemicals. In that case, the effect could be stated as 0+2+0+1 = 3. Here it seems that two of the chemicals have no effect. However, all chemicals have an effect - some of them are just not measurable.

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Therefore, the two effects that seem to have zero effect may have one when they are added, and the additive effect of the four chemicals might thus be four or five instead of three. In other words, for some substances the concentration we are exposed to from the single substance may be so low that it would not cause any harmful effects to health. However, if you are exposed to the same concentration of the substance in combination with other substances, then it may have an effect.

It is believed, that additive effects are the most common form of cocktail effect.

Antagonistic effect. Chemicals occurring together sometimes neutralise or reduce the effects of each other. In this type of interaction, it is less hazardous to be exposed to several substances at the same time than what should be expected based on knowledge about the effects of each individual chemical substance. In other words, 2+2 = 3. The antagonistic effect is only seen when the chemicals react with each other (affect each other). They can do this by either precipitation or by increasing each other’s turnovers (metabolism). In such a case, neither the Concentration Addition nor the Independent Action model can be used as the model for calculation of cocktail effects.

Synergistic effect. In this type of effect chemicals in a mixture enhance each other’s effect. The effect of the substances in combination is thus larger than expected based on the effects of the individual substances. In this case, the risk of health effects from the chemicals is higher when you are exposed to a mixture of the substances than when you are exposed to the individual substances.

An example of substances that may have synergistic effects are certain fungicides that are known to reduce the activity of the enzymes that decompose xenobiotics, in humans among others. If a person is exposed to these fungicides, other xenobiotics getting into the body cannot decompose and will thus remain in the body for a longer time. This will presumably increase the toxicity. A mixture of a fungicide and a toxin where the fungicide impedes the decomposition of the toxin will therefore release a synergistic effect.

So far, synergistic effects have had most focus, as it is evidently the most alarming. In addition, the synergistic effects are different from one chemical mixture to another and from one organism to another; thereby it is very difficult to determine their effect. However, it is also very important to have focus on additive effects as the individual chemicals in a chemical mixture often

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will be present in so small concentrations or have so low an effect that they are considered harmless. However, in mixtures even apparently harmless concentrations and/or effects may turn out to be harmful after all.

From the sparse knowledge available on synergistic effects, they seem to occur very rarely. Generally, synergism would not be a problem if only this effect was exploited by using smaller quantities of these substances to attain the same effect. However, the problem arises because legislation is based on the potential for harm of individual substances. Thereby, substances causing synergistic effects are often not identified.

Even small concentrations of pesticides in our food has

The Technical University of Denmark, DTU-FOOD published in 2009 a study79 showing that the impact from a simultaneously exposure to several different endocrine disrupting substances multiplies greatly the hormonal damage in male rats. By contrast, only few effects were seen in rats exposed to the individual

been shown in some cases to have adverse health effects

substances one by one. Some test groups of pregnant rats were exposed to one endocrine disrupting chemical while other groups of pregnant rats were given very low doses of several endocrine disrupting chemicals that individually have no harmful effect in small doses.

The effects on the offspring of the latter groups of animals were alarming. The male offspring had, inter alia, severe malformation of the reproductive organs, caused by sex hormone (testosterone) disturbances.

The article concludes that the principles can most probably be transferred to humans, as testosterone also is crucial for development in the embryonic stage of male babies.

legislation REACH, which entails a major risk for European citizens. So far, authorities set up limit values for individual substances only. However, legislation should take into account that we are exposed to many different chemicals at the same time on a daily basis.

This has become a priority area for the Danish government, and during the Danish EU presidency in spring 2012, it was decided to prioritise this area in the next ten years; this has subsequently been included in the so-called 7th EU Environment Action Programme. In the Environment Action Programme the EU environmental policy is adopted for a ten-year period. It contains fields of special attention in the EU, where improvements are called for.

when they occur in combination.

effects are not included in the European chemicals

In an expert report 80 from 2009 it was concluded that ”with the knowledge attained in recent years it is both possible and necessary to include the risk of cocktail effects in the risk assessment of endocrine disrupting substances”.

Legislation Fortunately, there is an increasing focus on the problems relating to chemical mixtures, but it is important that the research community, authorities, and ultimately politicians work with determination. We need to develop new and better tools, including new and better laboratory methods and mathematical models for prediction of cocktail effects. In addition, legislation should be more stringent. As it is today, cocktail

79 Christiansen S. et al., 2009. Synergistic Disruption of External Male Sex Organ Development by a Mixture of Four Antiandrogens. Environmental Health Perspectives.

Volume 117 number 12:1839-1846 80 Ministry of the Environment. “Expert workshop on combination effects of chemicals”. http://www.mst.dk/NR/rdonlyres/C59693B7-2421-4748-89F05937496E0A28/0/BILAG_2_Expertworkshop.pdf

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Nanomaterials Figure 21 How small is a nanoparticle?

The size of a nanoparticle compared with a football and the globe. The difference in size between a nanoparticle and a football corresponds to the difference in size between a football and the globe.

Nano refers to the size of the particles or the material in question. The word nano comes from Greek and means ‘dwarf’. A nanomaterial is defined as having one or more external dimensions in the size range 1 - 100 nm. Mathematically, nano means one-billionth and since a nanometre thus is one-billionth of a metre, these materials are far smaller than what can be seen with the naked eye. For instance, we can compare with a human hair, which is 80,000 times thicker than a nanometre, or we can compare a nanometre, a football, and the globe. Here the difference between a nanometre and a football corresponds to the difference between a football and the globe (see Figure 21).

Nanomaterials can be used in a wide range of different products, including: • nanostructures that improve the performance of computers and other electronics • active nanoparticles in catalytic converters in vehicles contributing to removal of harmful gases from the exhaust • nanomedicine that can be targeted at specific organs • antibacterial treatment of sportswear • sun tanning filters of titanium dioxide(TiO2) in sun tanning products • water repellent surface treatment products for stain resistant sofas and similar textiles

• carbon nanotubes that improve the strength of light-weight materials such as rackets, bicycle frames, and windmills • pigment in paints • and several other products....

Clearly, nanomaterials are used in very different types of products many of which are covered by different pieces of legislation and hence make it difficult to protect both human health and the environment in general. The issue is further complicated by the fact that so far nanomaterials are not covered by any legislation. Instead, they are treated as the same substance at a larger scale. This means that nanosized silver, which is used among others in sportswear to prevent odour, is regulated in the same way as silver in larger forms, as we know it from jewellery.

A nanomaterial can be manufactured from a known chemical substance or from a completely new chemical compound and it may consist of one or more substances. Nanosized chemicals can be exploited technologically in new contexts, since the size alone can give the material special properties. One reason being that nanomaterials with the same mass as the original substance have a surface that is much larger than the same particles of ‘normal’ size. Nanosized materials can in this way have inexpedient physical, chemical, and

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TiO2 as photocatalyst In the presence of UV light, titanium dioxide (TiO2) is a very efficient photocatalyst. In atmospheric air, there is always a naturally occurring water film on almost any surface.

The water molecules are split by catalytic TiO2 to the very reactive hydroxyl radicals (.OH), which can break down organic molecules. Oxygen O2 from the air can also be split

by TiO2. Under the influence of UV light, the CO2 is split to superoxide molecules (O2·-), which also participate in the decomposition of organic molecules.

and organic dirt, which in then rinsed off the hydrophilic ("water-loving") surface.

Both molecules are potent antioxidants, and the primary degradation products after complete oxidation of an organic molecule are CO2, water and NO2 (see figure). Despite the fact that the reaction products are comparable to a complete combustion, the reaction mechanism is very different.

The figure is a schematic illustration of the photocatalytic effect of TiO2. In the presence of sunlight (or other UV radiation) TiO2 splits H2O and O2 to the very reactive hydroxyl radicals (.OH) and superoxide molecules (O2·-). The radicals degrades both nitrogen oxides (NOx) from air pollution

biological properties, since the surface of the particles often trigger an effect, such as a photocatalytic effect (see box), which in some cases can cause damage to the environment.

Even if a material is harmless in a larger form, it may be hazardous when it occurs in nanosize. For instance, gold and silver jewellery is harmless, while nanoparticles of the same materials both are more reactive and so small that they may penetrate the cells of humans, animals, and plants (see Figure 22). One of the special features of nanoparticles is that they can penetrate into the deepest regions of the lungs – the alveoli – where they cannot be removed easily (see Figure 24).

Larger particles cannot penetrate further down than to an area of ciliated epithilium. Cilia move together and carry out mucus of the respiratory tract. Particles of larger size will stick to the mucus. When nanoparticles end up in the alveoli they will remain there for such a long time that inflammation might develop. This phenomenon is a contributory factor to the development of cancer and cardiovascular disease. Research from The Danish NanoSafety Centre, at the University of Copenhagen, and the National Research Centre for the Working Environment, among other institutions, have shown that these damages can occur at concentrations that humans are exposed to in the working environment.

Therefore, due only to their size, nanomaterials have some new features, which means that we cannot automatically assume that they are harmless, merely based on the fact that their larger 'siblings' are. This illustrates the necessity for nanomaterials to be seen as an individual substance group, for which specific Figure 22 Routes of exposure

Nanoparticles are absorbed through the mouth, the skin (especially in wounds and cuts), and by inhalation through the respiratory tract.

COCKTAIL EFFECTS AND NANOMATERIALS > NANOMATERIALS

legislation should be subjected ensuring that human health and the environment are not harmed.

The health uncertainties relating to the use of nanoparticles are primarily found in the production stage where the staff may be under constant exposure to free nanoparticles, i.e. particles that are not bound to other materials and thereby occur free in the air. When the product is finished, the nanoparticles will normally be bound or encapsulated in the product. However, also here a risk of exposure exists, since the nanoparticles may be released, for instance, by wear of the product or in the waste management stage.

It is important that we become capable of including considerations about risks and environmental impacts when we use and develop nanoproducts. Hence, more research is needed in so-called nanotoxicology, where scientists study the toxicity of nanosized materials.

When we wish to know whether there is a risk associated with the use of a substance there are two main questions to be answered: 1. To which degree are we exposed to the substance?

2. How hazardous is the substance?

To begin with, if we are not exposed to a substance it is not dangerous. However, it is rather hard to find a product that contains nanomaterials where there at no time of its lifecycle (production, consumption, waste disposal) exists a risk of exposure for humans or the environment.

It is said, that the sum of the exposure and the hazard related to the substance determines the total risk of using the substance. This is illustrated in Figure 23.

Figure 23 The risk of chemicals

EXPOSURE

R I S K

HAZARD

How exposure and hazard can entail a risk of use of a given substance.

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Undoubtedly, nanoparticles have many fine properties, when they are added to consumer products and products for industry, but their potential health impacts are not yet fully understood and therefore caution is needed.

We have several examples from the past where it was realised too late that the use of a given substance had severe consequences. An example known to most is the use of asbestos. Asbestos was used in the 19th and 20th centuries as a construction material due to its fireproofing and insulating properties. Not until the 1980s was asbestos banned completely in Denmark and today it is not permitted to manufacture, import, or use asbestos or asbestos containing materials of any kind. More than 40 countries have a similar ban, including most countries in the European Union. However, it is permitted to remove asbestos from buildings, for instance, but this work is subject to major safety precautions.

Asbestos is a health hazard especially because of its small size. When we inhale asbestos fibres, they can penetrate into the remotest parts of the lungs, as they are much smaller than 3 Îźm, which is the diameter of the thinnest branches of the lungs. Therefore, asbestos dust will accumulate in the lungs and cannot be removed. Inhalation of asbestos dust increases the risk of cancer in the lungs, the pleura, the ovaries, the peritoneum, and the throat. Moreover, some studies indicate that asbestos increases the risk of cancer in the intestines and the gullet.

It is estimated that around 400 incidents of asbestos related cancer occur in Denmark every year, and this figure is not on the decrease despite the fact that asbestos has been banned for many years. This is, among other reasons, caused by the fact that cancer in the pleura takes about 25-30 years to develop.

Today, many opponents of the unregulated use of nanomaterials fear that the future will reveal similar adverse health impacts in humans exposed to nanoparticles.

Example of how animal tests can simulate the working environment In their working environment, painters are exposed to paints with nanoparticles added, for instance, as a pigment. These types of products are often not sufficiently studied in relation to potential harmful effects to human health and the environment. There are therefore concerns that paints containing nanomaterials may be a contributory cause of unforeseen industrial injuries for this profession. So far, a correlation between the

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Figure 24 Lung anatomy

Difference between mass and surface A calculated example of the difference between exposure to a specific mass (weight) of nanoparticles and a specific surface area of the same nanoparticles.

Many believe that it is the surface (or more precisely, what is attached to the surface) of the particles that might have adverse health effects.

Titanium dioxide large : the size is 288 nm and the surface area is 21 m2/g Titanium dioxide small: the size is 21 nm and the surface area is 107.7 m2/g Lungs with bronchial tubes and alveoli.

Source: National Institute on Alcohol Abuse and Alcoholism.

For titanium dioxide large:

Focus on the Lung.

frequency of nanoparticles in the working environment and hospitalisation has been found.

In Denmark, the limit value for airborne TiO2 (used as a white pigment in paints) in the working environment is 6 mg/m3 and ranges from 3 to 10 mg/m3 in the other European countries. In 2006, the International Agency for Research on Cancer (IARC) concluded that TiO2 might be carcinogenic for humans (Group 2B).

In an animal study, the aim was to simulate human inhalation of nanoparticles. Mice had TiO2 particles blown into their lungs (corresponding to humans inhaling particles) at a dose of 0.5 mg/kg body weight, which corresponds to a slightly higher dose than what we may be exposed to as a maximum at our workplace. This can be calculated in the following way: It is assumed that every day a person inhales 8 m3 air during his working hours and 100 % of the inhaled substance is deposited in the lungs – thereby the limit value corresponds to 0.64 mg/kg body weight for a person weighing 75 kg.

Mathematical models, however, have shown that only 10-20 % of the inhaled particles between 0.1 and 1 µm diameter (corresponds to 100 and 1000 nm, respectively) will reach the alveolar regions of the lungs (see Figure 24) from where they may be transferred to the bloodstream if they are sufficiently small.

In this study it was found that all the particles were 1 µm in diameter or smaller. Converted, this means that 0.064-0.128 mg/kg body weight of the TiO2 particles end up in the alveolar regions. This is described in detail in the box.

8 m3 * 6 mg/m3 75 kg

= 0.64 mg/kg body weight

(10 % of the inhaled particles will reach the lungs) 0.10 * 0.64 mg/kg body weight = 0.064 mg/kg body weight (20 % of the inhaled particles will reach the lungs) 0.20 * 0.64 mg/kg body weight = 0.128 mg/kg body weight This means that between 0.064 and 0.128 mg TiO2/kg body weight will reach the alveolar part of the lungs when exposed to 6 mg TiO2/m3, over an entire working day.

A mouse weighs on average 0.02 kg, which means that each mouse was exposed to: 0.5 mg TiO2/kg body weight * 0.02 kg body weight = 0.01 mg TiO2/mouse = 0.00001 g TiO2/mouse Converted to surface area, each mouse was exposed to: 21 m2/g * 0.00001 g = 0.00021 m2 = 2.1 cm2 titanium dioxide large The same can be calculated for titanium dioxide small , which gives a result of 10.8 cm2 titanium dioxide small This example clearly shows what the difference in size of nanoparticles can lead to regarding health effects. It can for example have a large impact if the surface area of the nanoparticle is highly reactive. And the smaller the nanoparticle, the greater an amount will reach deeply into the lungs, and thus result in a much larger surface area.

COCKTAIL EFFECTS AND NANOMATERIALS > NANOMATERIALS

The box illustrates that a given limit value for the exposure of nanoparticles cannot follow the traditional way of determining the value with mass (weight) as offset. As mentioned, the limit value for TiO2 at the workplace (occupational health limit value) is 6 mg/m3 in Denmark. However, the number of reactive nanoparticles that enter your lungs depends largely on the size of the particles and less on the quantity (by weight).

Therefore, the general limit value may not be expedient for nanoparticles. It is discussed whether it would be more accurate to calculate limit values for nanoparticles based on surface area.

If we instead had limit values based on the surface of particles in the working environment, the two particle types used in this study would give completely different results. The smallest particle was 21 nm and the largest 288 nm. This means, that even if the mice received the same mass (weight) concentration (0.5 mg/kg body weight), the mice exposed to the smallest particle type were exposed to particles with a much larger surface area compared to the mice exposed to the largest particles. It is assumed that the surface of nanoparticles is the most reactive and thereby the one that can cause most damage to human health and the environment. This example clearly indicates that nanoparticles should not be regulated in the same way as their larger “siblings�.

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5

env i ro m ant i c

Hazardous chemicals can be replaced

HAZARDOUS CHEMICALS CAN BE REPLACED > SUBSTITUTION

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Substitution of hazardous chemicals Much research is done to find harmless substances

P hoto A netta_R

that may replace hazardous chemicals.

What is a substitution and why do it?

Substitution means replacement of hazardous chemicals used in products or processes with less hazardous alternatives. These alternatives may be less harmful chemicals, technical changes of processes, or implementation of alternative technologies in the production. By phasing out the use of a hazardous chemical substance, a further exposure of both humans and the environment stops completely. The principle of substitution is incorporated in the EU chemicals legislation, REACH, which applies for substances of very high concern (SVHC). However, it has its limitations as situations are excluded where hazardous substances are used in industrial production or processes in a way that is considered “adequately controlled”. This applies to so-called closed systems (e.g. at production level) where humans and the environment are not exposed to the substances. Still, experience shows that such systems are often not as closed as they seem. One explanation is, that not the entire life cycle is considered when deciding if a chemical is “adequately controlled“ (e.g. the consumption and waste stages might be excluded) and thus, humans and the environment may be exposed to the hazardous chemicals.

There may be many reasons for a company to opt for substitution. One reason may be requirements or demands from customers. Another may be new knowledge about production methods and alternative ingredients, or there may be new legislation coming up. Companies may also seek to be ahead of the chemicals legislation. They may obtain a competitive advantage by creating a green image, thereby getting publicity and attracting more consumer groups. It may also improve the working environment of the company and reduce costs due to the fact that there will be less hazardous waste to handle.

Warning lists and substitution Many of the companies substituting chemicals are using the REACH Candidate List as a guideline for which substances to avoid. Thereby, they can get a jump-start that may pay off when a potential hazardous substance that is already substituted with time is subjected to authorisation and they often would have to substitute anyway. REACH in itself is thereby a good guidance for companies, since it provides an insight into which substances are problematic and worthwhile

HAZARDOUS CHEMICALS CAN BE REPLACED > SUBSTITUTION

to substitute and further which substances are poorly suitable substitutions. The disadvantage is that the Candidate List so far covers only 151 substances (January 2014) while it is estimated that at least 1,500 hazardous chemicals that should be characterized as SVHC are on the market. Therefore, it may pay off for companies also to include more extensive lists when considering substitution (see more about these lists in the section ”REACH – Step-by-step”).

In Denmark, the Danish Environmental Protection Agency has drawn up List Of Undesirable Substances (LOUS), which is a signal list and a guidance for producers, product developers, purchasers, and other stake holders, about which substances they can focus on in their work with substitution or stop the usage of.

It consists of 40 substances/groups of substances selected for their problematic effects according to criteria defined by the Danish Environmental Protection Agency. Only substances used in Denmark in quantities exceeding 100 tonnes/year are included in the list. A more extensive list is the List of Effect. This list contains substances, which are considered as problematic according to their effect on human health and the environment and should be avoided when substituting to other substances. The List of Effect consists of around 19,500 substances selected according to the following criteria: • having problematic characteristics according to the ”EU list of hazardous substances” • having problematic characteristics according to computer-based model calculations on the ”Danish Environmental Protection Agency’s Advisory list for self-classification of hazardous substances” (QSAR-list) • identified PBT/vPvB substances in the EU • substances on the “EU priority list of substances that must be further examined for endocrine disrupting properties”.

The List of Effect is a very good tool for companies aiming to avoid substances with harmful effects, when they are looking for better alternatives in a substitution case.

The Swedish NGO ChemSec has published the ”SIN list”, covering the most hazardous chemicals under EU law. The SIN list contains substances identified

by ChemSec and comply with the criteria for the

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Candidate List under REACH. The SIN list, however, contains far more substances than the Candidate List (at the moment 626 vs. 151) and is thereby a far more useful tool for companies. The list contains substances that may be carcinogenic, change DNA, have endocrine disrupting properties, and/or harm the reproductive system. It also covers toxic substances that are persistent and accumulate in nature with the ensuing potential of causing severe and long-term irreversible effects.

Substitution portals and networks There are networks in which companies involved in substitution processes meet and share experiences with other companies wishing to reduce their use of hazardous chemicals. Sweden is home to a ’ChemSec Business group’ covering, among others, Boots, Dell, IKEA, and Sony Ericsson. In the US there is a group ’BizNGO’ with Construction Specialities, Staples, Hewlett-Packard, and Method among their members.

Another tool for companies wishing to substitute is the substitution portal “SUBSPORT”, which is an EU LIFE+ supported project. SUBSPORT is an internet portal disseminating knowledge about substances and technologies that may be alternatives to hazardous chemicals. It also provides tools and advice in the evaluation of substances, as well as information about how to manage a substitution process. Starting a substitution process may be quite a challenge for a company – both in terms of finances and resources, so it is important that good tools are available. Warning lists, networks, and portals may help companies getting started, thereby promoting the entire field of substitution.

Consumer's role Consumers can do a great deal to reduce the contact with hazardous chemicals. You can look for ecolabelled goods – they are found within almost all product groups such as car care products, nappies, glues, paints, personal care products, furniture, candles, televisions, etc. There are many labelling schemes in Denmark and the rest of Europe – figure 25 shows a small selection.

The Nordic Swan is, as the name indicates, a Nordic label, while the comparable European label is named the EU-Flower. These labels set up a number of requirements for the producers as to the content of

HAZARDOUS CHEMICALS CAN BE REPLACED > SUBSTITUTION

Figure 25 Common ecolabels

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environmentally harmful products in consumption or production, taxes on the discharge of pollutants, and taxes on scarce natural resources.

Thanks to green taxes of the right magnitude the price of a product better reflects the entire resource usage associated with production, use, and final disposal of the product – and not only the resource consumption that should be paid by the producing company on the ordinary market. As a consumer, you are thereby financially encouraged to affect the production of consumer goods, since environmentally harmful products become more expensive. In general, this will increase motivation for choosing the environmentally less harmful goods.

Four of the most common and well-known ecolabels on the European market. The Nordic Swan label is only on the Nordic market, as the name indicates.

chemicals in their products. These requirements often go beyond REACH and Danish legislation.

The Danish Ø-label is for foodstuffs from organic farming without the use of pesticides. There is also a European organic label, the Euro-leaf, which is used increasingly on products on the Danish market.

In Denmark, “green taxes” have been levied since 1970 and made up 4.1 % of the gross national product (GNP) – or around 9 % of total tax revenues in 2012.

Green taxes are incentives for the market and consumers toward more eco-friendly behaviour and the development of green technologies. Ideally, the green tax corresponds to the environmental costs associated with producing, consuming, and disposing of goods.

However, often it is not possible to calculate these costs, so the tax is established in relation to what it takes to shift the consumption to more eco-friendly products. Examples of areas with green taxes are petrol, registration of vehicles, packaging, pesticides, wastewater, and PVC and phthalates. For every shower you take, you pay a tax. When you drive your car (instead of taking the bike) – and when you use disposable tableware (instead of an ordinary plate) you pay green taxes or environmental taxes. All these green taxes are meant to make you consume less.

Green taxes are divided into three categories: energy taxes, transport taxes, and environmental taxes.

Environmental taxes are further divided into taxes on

CHEMICALS IN POLITICS AND EVERYDAY LIFE > GLOSSARY

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GLOSSARY Accumulate Pile up or concentrate. When environmental toxins do not decompose, or only do so to a slight degree, there will be an accumulation in the upper parts of the food chain.

Agonism When a chemical substance imitates the effect of a naturally produced hormone and thereby causes similar reactions in the body. The substance is called an agonist. It may for instance, cause a too large oestrogen response, which may be critical to male foetuses.

Allergen A substance that may cause allergy. Commonly known allergens are nickel, for instance in jewellery, pet fur, and pollen.

Antagonism When a chemical substance is similar to a certain hormone, but does not have the same effect mechanism.

The substance is called an antagonist. The substance may, for instance, bind to receptors “belonging� to specific hormones and thereby block an important hormonal response from the real hormone.

Article (EU definition) An article is an object, which during production is given a special shape, surface, or design which determines its function to a greater degree than does its chemical composition. This may be clothing or a bicycle.

Authorisation Authorisation is an important term in the EU chemicals regulation REACH. For especially hazardous chemicals, companies must apply for authorisation to continue producing/dealing with these substances. The Candidate List plays a key role in the authorisation process.

Authorisation list EU list of chemicals for which companies must apply for authorisation if they wish to continue producing one or more of the substances on the list, or articles in which they are a constituent.

Bioaccumulation Continuous increase in the amounts of a substance in an organism. A term used when a chemical substance, such as a brominated flame retardant, accumulates in a living organism throughout a lifetime. If the organism assimilates more than it secretes, it is called bioaccumulation.

Bioaccumulation is both bioconcentration, i.e. the concentration of an environmental toxin grows more in a living organism than in its surroundings, and biomagnification, i.e. the accumulation of the environmental toxin may increase up through the food chain.

Biocide A chemical substance destined for the control of vermin, bacteria, fungi, etc. Biocide products must be approved by the Danish Environmental Protection Agency before being placed on the market.

Biomagnification When a substance accumulates in an organism through the food chain.

Bisphenol A Chemical substance used in the manufacture of certain types of plastics, such as single-use water bottles.

Suspected of endocrine disrupting effects. Is to some extent regulated in the EU. Brominated flame retardants Brominated flame retardants are bromine-containing, organic substances added to

electronic equipment, furniture, construction materials, textiles, duvets, toys, and much more to prevent or limit fire hazards. Some of the substances accumulate in the environment and are suspected of causing congenital malformation and cancer, among other diseases. In addition, suspected of being an endocrine disruptor.

Candidate List EU list of chemicals that are considered to be of very high concern. The problematic chemicals have harmful long-term effects on human health or they are harmful to the environment. Substances on this list are candidates for the authorisation list. You can always find the latest version of the list here: http://echa.europa.eu/chem_data/ authorisation_process/candidate_list_table_en.asp Carcinogen A substance that is carcinogenic i.e. increases the risk of developing cancer.

Chemical (EU definition) A common term for chemicals and chemical mixtures.

Chemical mixture (EU definition) A uniform mixture or solution composed of two or more substances. A chemical product may be solid, liquid, or gaseous.

Chemical substance (EU definition) A chemical element and its compounds in the natural state or obtained by any manufacturing process.

Circular An administrative communication that may assist in the interpretation of a statutory act. A circular is emitted, for instance by a ministry and is in itself not binding to citizens.

CLP regulation Classification, Labelling and Packaging. The purpose of the regulation is to create a global harmonised classification of chemicals in order for them to have the same labelling all over the world.

CMR substances: Substances that are Carcinogenic (causes cancer), Mutagenic (changes genes) and/or Reprotoxic (harms reproduction).

Cocktail effects All chemicals found in a mixture contribute to the total effect of that mixture on human health and the environment, such as toxicity. This means that chemicals that are harmless to human health and the environment individually and in low concentrations may have harmful effects if they occur together.

Council of the European Union Together with the European Parliament, it adopts the legislative proposals put forward by the Commission.

DDT In the past, it was used as an insecticide (a chemical used against insects). Unfortunately, it proved to have many inexpedient side effects and therefore today the use of DDT is banned or strongly limited in most parts of the world.

However, it is still used in many developing countries, especially in connection with the fight against malaria-carrying mosquitoes, as it has been estimated that the socio-economic benefits stand up for its continued use. In this case, the social benefits (fewer malaria cases) carry most weight.

CHEMICALS IN POLITICS AND EVERYDAY LIFE > GLOSSARY

Dioxin Generic description of a group of chlorine-containing toxins that are formed in the burning of organic materials in the presence of chlorine. Dioxin is very harmful to human health and the environment and leads, among others, to an increased risk of cancer, reproductive disturbances, and reduced immunity.

Directive A directive is one of the statutory instruments used in the EU. Directives are binding to all the member states. It generally addresses and establishes a target to be reached and then it is up to the member states to decide how to implement the directive. Directives must be implemented in national law before they take effect and this must be done before a certain deadline set up in the directive - often two years. When the implementation is complete, the EU Commission must be notified.

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European Court of Justice Decides in cases the EU Commission has brought against specific member states in, for instance, violations of current EU legislation.

European Parliament Together with the Council of the European Union, it adopts the legislative proposals put forward by the Commission. All EU member states have directly elected representatives in the Parliament.

Exposure Means “exposed to”. Concentration or amount of a substance to which a person or certain organisms or cells are exposed. We may be exposed to a substance by inhalation or through the skin, for instance, if chemicals occur in sun tanning products or similar.

ECHA (the European CHemicals Agency) Ensures that the EU chemicals regulation, REACH and the regulation on classification, labelling, and packaging (CLP) is implemented in a harmonised way in Europe. This institution receives registration of existing chemicals.

Fluorinated substances There are two groups of fluorinated substances: polyfluorinated and perfluorinated. The term polyfluorinated refers to the group of substances where there are several fluorine compounds on the carbon chain, replacing hydrogen. A fully fluorinated substance is an organic compound where all hydrogens on a carbon chain are replaced with fluorine.

These substances are called perfluorinated substances.

Perfluorinated substances are distinguished by containing as a minimum one other atom than carbon and fluorine.

The substances are suspected of having various endocrine disrupting effects in humans. They are furthermore suspected of being carcinogenic.

Endocrine disrupting substances An exogenous substance (e.g. industrially manufactured chemicals) that alters function(s) of the endocrine (hormonal) system and consequently causes adverse health effects in an intact organism, or its progeny, or (sub)populations.

Free radicals A radical or a free radical is the term used for an atom or a compound with an unpaired electron or an incompletely filled electron shell. Unpaired electrons are very reactive and radicals therefore easily become parts of chemical reactions.

Esther Series of chemical compounds formed in the reaction between a carboxylic acid (COOH) and an alcohol (common name for chemical compounds with a hydroxy group (i.e. an OH group) while splitting off water. Polyester is a category of polymers with the functional group of ester in their main chain.

Implementation Incorporation of a policy or an act in practice to have legal effect.

EC50 Effective Concentration 50 %. The concentration of a given chemical where a harmful effect to health is seen in 50 % of the test animals exposed to the substance. The effect may be, for instance, reduced growth, DNA damage, or damaging effects on embryos.

EU Short for European Union. Consists of 28 member states all situated in Europe. The citizens of the member states have the right to live, work, travel, and invest in the other member states. The EU has a number of common laws, including the chemicals regulation REACH. EU Presidency EU member states take turns in assuming the Council of the European Union for a period of six months.

The changing presidencies mean that each country to a certain extent has the possibility to influence the agenda of the EU. It also gives some dynamics to the EU cooperation and enhances the anchoring in the member states - the member states feel, so to speak, a stronger attachment.

Denmark has had the presidency seven times since we joined in 1972, most recently in the first semester of 2012.

European Commission The Commission proposes acts and rules for the entire EU so as to treat any country fairly.

In addition, it is the responsibility of the Commission that all member states comply with the common legislation.

In vitro tests Scientific tests made on cells. Tests are made outside the living organism – typically in a test tube or a petri dish.

In vivo tests Scientific tests made on a living organism typically on test animals, but they also include clinical tests on humans.

LD50/LC50 Lethal Dose/Lethal Concentration for 50 % of the test animals exposed to the substance. The amount (weight)/concentration of a toxic substance needed for half of a group of test animals to die while the other half survives.

LD50 is used when the test animals are actively given the substance (e.g. in their food) and LC50 is when the test organism are for example fish swimming in water with the given concentration.

Lipophilic Refers to the ability of a chemical compound to dissolve in fats. These substances bind to fat rather than water.

Metabolites Intermediates and products of the metabolism.

They are often referred to as decomposition products.

Mutagen A substance is a mutagen when it causes mutations. A mutation is a change in the hereditary material (DNA) and leads to changes in the expression of genes. For instance, some proteins will subsequently not be expressed.

CHEMICALS IN POLITICS AND EVERYDAY LIFE > GLOSSARY

Nano The word comes from Greek and means ‘dwarf’. 1 nanometre (nm) corresponds to 0.000000001 m (10 -9 m).

NGO (Non-Governmental Organisation) An organisation that is neither supported nor controlled by government.

PAH (Polycyclic Aromatic Hydrocarbons) A group of more than 100 substances found in different combinations of aromatic rings, so-called benzene rings. Several members of the substance group have been proven to be carcinogenic.

Most PAHs enter the environment via the atmosphere from a variety of combustion processes.

Parabens A group of chemical substances (preservatives) that make cosmetics and food products last longer. A varying number of carbon atoms binding to an ester group forms the different parabens. The substances are suspected of having various endocrine disrupting effects in humans.

PBT (Persistent, Bioaccumulating, Toxic) PBT substances are chemical substances with all three properties: Persistent – decomposes very slowly in nature; bioaccumulative - accumulates in living organisms throughout their lifetime. In addition it is toxic to human health and/or the environment.

For a substance to be classified as a PBT substance all three parameters must be met.

PCB (Poly Chlorinated Biphenyls): An industrial chemical (artificially made) that decomposes very slowly. In addition, it accumulates in the upper parts of the food chain and spreads over large distances in nature. Both oestrogenic and anti-oestrogenic effects have been proven from various PCB compounds. In Denmark, there has been a ban on the production and sale of PCB since 1986.

Persistent Decomposes very slowly in nature and in living organisms.

Pesticide A chemical substance used to control weed, protect crop against vermin attacks and fungi, or for affecting plant growth. Before a pesticide is permitted the producer must document that the pesticide residues, for instance in a food product, are not toxic to humans.

Phthalates A group of chemical substances that are used to soften and smoothen plastics. Phthalates are the term used for esters of phthalic acid.

They may be present in different consumer goods such as oilcloth, shower curtains, clothing (in plastic prints), wellies, etc. The substances are suspected of having various endocrine disrupting effects in humans.

Polymer A polymer is a natural or synthetic compound with a high molecular weight formed by linking together up to several million identical or at least comparable units (monomers). The linking process is called polymerisation. Polymers are often referred to as plastics, such as polyvinyl chloride (PVC), polyethylene, and polycarbonate.

POP substances (Persistent Organic Pollutants) Environmental toxins that decompose extremely slowly.

There is a great risk that these substances remain in our environment and in worst case accumulate in the food chain.

The substances are hazardous for human health and the environment.

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Precautionary principle One of the REACH cornerstones.

This principle makes it possible to react fast when there is a possible danger to the health of humans, animals, and plants, or to the environment. In cases where the available scientific data does not allow for a complete risk assessment, the precautionary principle can prevent the placing on the market of products that may be hazardous. It also makes it possible to withdraw such products from the market.

REACH The European chemicals regulation. REACH is short for Registration, Evaluation and Authorisation of Chemicals.

REACH is a regulation, which means that it applies all over the EU and that countries must comply with it. It is not allowed to introduce less stringent legislation in any EU member state.

Reactive When a particle/an atom has a huge impact, because of very reactive free unpaired electrons or an incompletely filled electron shell. This may cause an immediate launch of a chemical process under certain conditions.

Regulation A regulation is one of the statutory instruments used in the EU. A regulation is universal. This means that it is not directed at a certain group of persons or institutions, but to the entire population. Regulations apply directly in the member states, which means that they enter into force and have legal effect, once they are adopted in the EU. Unlike directives, they are not first to be implemented in the national legislation. Regulations are binding, and thus provide rights and duties just like national legislation.

SIN list (Substitute It Now). A list prepared by the Swedish environmental organisation ChemSec. The purpose is to promote the transition to a world free from industrial toxins by listing those chemicals ChemSec believes should be substituted by less hazardous substances. The substances on the list are selected in an evaluation against the REACH criteria for “substances of very high concern”.

Statutory Order A statute that applies further legislation to an existing act – often more detailed. The Statutory Order has the same effect as an act in relation to authorities and citizens.

Synergy Synergism or synergistic effect is the interplay between two or more chemicals, for instance in a mixture, that results in a larger effect than merely the sum of the effects given by each individual chemical.

TDI (Tolerable Daily Intake) A value stating how much of a chemical substance a person can tolerate every day throughout his life. The value is established based on scientific tests and generally a safety factor (e.g. 100) has been added. In addition, it has been taken into account that we are exposed to the given pollution from several sources, e.g. from both our diet and the inhalation of air.

Toxic Poisonous. vPvB (very Persistent, very Bioaccumulating) Used for a chemical substance that is heavily decomposable (may not decompose at all) and very bioaccumulating.

With this teaching material, we want to increase the focus on endocrine disrupting chemicals, the combination effects of chemicals – the so-called cocktail effects – and nano materials.

The common European chemicals regulation REACH regulates many of the chemicals produced today and thus increase the safety of people and the environment. Still, we surround ourselves with a wide range of consumer products that may contain substances suspected of having endocrine disrupting effects or that contribute to cocktail effects. Thus, there are gaps and shortcomings in the legislation that it is important to rectify.

In this electronic publication the construction of the European Union (EU) is clarified along with an explanation of how the individual member states suggest and follow legislation adopted at EU level. Furthermore, the common European chemicals legislation is explained in further detail, whereas legislation for specific product groups e.g. the Toys Safety Directive and the Cosmetic Products Regulation are briefly described where relevant. The most common groups of endocrine disrupting chemicals and our daily exposure to them are described and subsequently what this means for human health and the environment.

Cocktail effects and nanomaterials are examined separately, along with a description of the possibilities of replacing harmful chemicals with less hazardous substances. Each chapter provides examples of what you can do as a consumer to reduce the risk of exposure to hazardous chemicals.

This electronic publication is useful at several different educational levels and in different courses as well as for interdisciplinary projects – especially at university level and for project assignments in high school. It can be read from start to finish, or you can pick out sections in order to meet specific educational needs.

Each section is written to stand alone, but refers to a supporting section in case specific passages needs further explanation for better, or full, understanding.