HAZARDOUS CHEMICALS CAN BE SUBSTITUTED

HAZARDOUS CHEMICALS CAN BE SUBSTITUTED – DEVELOPMENTS SINCE 2006

MAY 2012

CONTENTS 1

INTRODUCTION · 3

2

WHY SUBSTITUTE AND WHAT IS SUBSTITUTION? · 4

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LEGISLATION IN DENMARK AND IN THE EU · 5 REACH – a brief introduction · 5 Warning lists and substitution · 7 Substitution portal and networks · 9

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E X A M P L E S O F S U B S T I T U T I O N · 10 Fourteen Danish companies - developments since our 2006 report Brødrene Hartmann · 11 Danfoss · 13 Danisco · 15 Nakskov Sugar Mill · 20 nkt-cables · 21 Fujitsu · 24 Poul E. Meier · 28 Dana Lim · 29 Kymi Rens · 32 Logstor · 34 Frigor · 36 Abena · 38 Novadan · 39 Kompan · 42 New examples - from Denmark and abroad · 44 Melitek - PVCFreeBloodBag · 47 Substitution at hospitals – Westfriesgasthuis (NL), Karolinska (S), Sygehus Sønderjylland (DK) · 50 Bisphenol A substitution · 52 Boston shoecare · 54

5 . S U M M A R Y · 55 6 . R E A D M O R E · 57 Warning and priority lists · 59

Hazardous Chemicals Can Be Substituted – Developments since 2006 1st issue, May 2012 ISBN: 978-87-92044-45-7 Text by: Eline Aggerholm Kristensen, Christian Ege Translation: Karen Bahn Kristensen, Eline Aggerholm Layout: Hanne Koch / DesignKonsortiet Printed by: KLS Grafisk Hus A/S

The publication can be downloaded from The Ecological Council’s website: www.ecocouncil.dk. Quoting, copying and other use of the content of this publication is permitted and encouraged so long as credit is given to its source.

Published by: The Ecological Council - with funding from the Velux Foundation The Ecological Council Blegdamsvej 4b 2200 Copenhagen N · Denmark Ph.: (+45) 3315 0977 E-mail: [email protected] www.ecocouncil.dk

1 INTRODUCTION This pamphlet is a follow-up to the publication “Hazardous Chemicals Can Be Substituted” published in 2006. Substitution is still a hot topic, and we see more and more companies choosing this approach. The drivers are the desire to be ahead of chemicals legislation, to meet their social and environmental responsibility, and to attain or maintain a good reputation in their sector. A major milestone since

our last publication was the adoption of the European Union chemicals legislation called REACH. REACH consolidates chemicals legislation for the entire EU and will - ultimately strengthen the entire chemicals field. This, however, does not eliminate the need for companies themselves to take initiative and perform substitutions.

PUBLICATION FROM

2006

BY

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2 WHY SUBSTITUTE AND WHAT IS SUBSTITUTION? According to the principle of substitution, dangerous chemical substances used in products or processes should be substituted with less dangerous alternatives. These alternatives may be less harmful chemicals, technical changes of processes, and implementation of alternative technologies in the production. By phasing out the use of a dangerous chemical substance the exposure of both humans and the environment stops completely – this is a good example of how to use the precautionary principle. There may be many reasons for a company to opt for substitution. One reason may be requirements or demands from customers, 4

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another may be new knowledge about production methods and alternative ingredients, and there may also be new legislation in the field. Companies may also seek to be ahead of the chemicals legislation. They may get a competitive advantage by creating a green image, thereby getting publicity and reaching more consumer groups.

3 LEGISLATION IN DENMARK AND IN THE EU In Denmark, we must comply with the chemicals legislation REACH. REACH is a regulation and therefore applies directly to all EU Member States. REACH is an abbreviation of Registration, Evaluation, and Authorisation of Chemicals. It was introduced in 2007, as it became clear that the chemicals regulations in force at that time were insufficient in terms of protecting man and the environment against harmful substances. In 1981 the EU introduced requirements to the effect that new substances were to be examined before being placed on the market. However, there were no requirements for examining the approximately 100,000 chemical substances that were already on the market in 1981. This was one of the drivers behind the reform that started in 1998, when the EU Commission published an

analysis of the law in force, pinpointing a large number of serious shortcomings. REACH now replaces more than 40 former EU directives and provisions. REACH - a brief introduction REACH consists of three basic elements: Registration, Evaluation, and Authorisation, and it rests on the principle of ”no data, no market”. There are around 100,000 chemicals on the European market, of which 30,000 fall within the scope of REACH. Substances not covered by REACH are mainly chemicals used as a food additive and in medicinal products as well as substances used in relatively small quantities (less than 1 tonne/producer/year), such as laboratory chemicals. In the field of bans and authorisation many substances are

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Registration deadline: Substances > 1 tonne/year Registration deadline: Substances > 100 tonnes/year Registration deadline: Substances > 1,000 tonnes/year R50/R53 substances > 100 tonnes/year CMR substances categori 1 and 2 > 1 tonne/year Publication of the substances pre-registered by ECHA. Commencement of registration Start of the pre-registration phase REACH comes into effect

1. 6. 2007

1. 6. - 30.11 2008

1. 1. 2009

covered by other directives and are therefore not included in that part of REACH. This applies to groups such as cosmetic products, pesticides and biocides, and medical devices. REACH covers chemicals used in a quantity exceeding 1 tonne a year. It includes chemicals produced, imported, used as an intermediate, or placed on the market as a chemical, in preparations (such as paints), and in articles (such as furniture). The deadline and the extent of information required in the registration of chemicals depend on the quantity produced. For chemicals produced in quantities exceeding 10 tonnes a year, a Chemical Safety Assessment (CSA) and a Chemical Safety Report (CSR) must be drawn up. However, a phase-in period of eleven years has been introduced for existing chemicals produced and sold before 1981, and many substances under REACH will thereby not be registered until 2018. Substances produced in large quantities (more than 1,000 tonnes/producer/year), and substances that have carcinogenic, mutagenic, or toxic for reproduction (CMR) properties or are toxic to

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1. 12. 2010

1. 6. 2013

1. 6. 2018

the aquatic environment and are produced in quantities exceeding 100 tonnes had to be registered by 2010. Other substances produced/imported in quantities exceeding 100 tonnes must be registered by 2013. Finally, substances produced/imported in quantities exceeding 1 tonne must be registered by 2018. For chemicals produced in quantities between 1 and 10 tonnes/year the registration requirements are less stringent and only consist of very basic safety information or available existing information. It may not be sufficient in all cases to classify a substance as being harmful or not to the environment and human health. After registration, the European Chemicals Agency - ECHA - in cooperation with the Member State authorities goes through submitted data in a prioritized order, assessing the potential for harm of the substance. Substances assessed to be of very high concern – SVHC – are included in the candidate list. Consumers may at any time contact a producer or an importer of a product and within 45 days be informed whether it contains a

substance from the candidate list in a concentration above 0.1 % weight by weight. So far, only 73 substances have been included in the list. Substances included in the candidate list may eventually be included in the priority list of substances to be authorised, thereby undergoing an authorisation procedure (Annex XIV). When a substance has been included in the authorisation list, it is necessary to apply for authorisation to use the substance, and the applicant must analyse possible alternatives. If such alternatives are available, the applicant must present a substitution plan. Dangerous substances not qualifying for this list are treated according to a less stringent procedure. They can be used in industrial production or processes considered as “under adequate control” - this is typically closed loops. The problematic aspect of this is that if a substance is placed in this category it is due to the fact that knowledge about its hazardousness is insufficient. Much experience shows that chemical substances considered as under adequate control have caused critical exposure of man and the environment, for instance due to closed loops not being closed and substances having entered the environment in the waste management stage. Under REACH there is also a list of substances with restrictions and prohibition of use - the restricted substances list (RLS), also called Annex XVII. Here, a number of bans are gathered that used to be included in directives and statutory orders, but new rules have also been adopted since the introduction of REACH. RLS is divided into two categories. One category includes substances with a restricted use or a restricted content in certain products. For instance, the mass fraction of benzene must not exceed 5mg/kg in toys or parts of toys,

and polybrominated biphenyl (PBB) must not be used in textiles such as underwear, blankets, clothing, and other materials coming into contact with the skin. The other category is a restriction on all uses and covers substances such as asbestos, dichloro[(dichlorophenyl)methyl]methylbenzene and monomethyldibromodiphenylmethane. The REACH regulation includes a timeline with important events. These events include a recast of REACH in 2012, and in 2013 it will be decided whether substances having endocrine disrupting properties should fall under REACH. Warning lists and substitution Many of the companies substituting chemicals are using the candidate list as a guideline for which substances to avoid. They do so to avoid having to go through another substitution when the substance eventually will be subject to authorisation. REACH in itself is thereby a good guidance for companies, since it provides an insight into which substances are problematic and worthwhile to substitute and which are a bad choice to substitute into. In Denmark the Danish Environmental Protection Agency has drawn up a list of undesirable substances, which is a signal list and a guideline for manufacturers, product developers, purchasers, and other players regarding chemicals whose use will be restricted or completely stopped in the future. Only substances used in Denmark in quantities exceeding 100 tonnes are included in this list. Another and more extensive list is the list of effect, which is a good supplement in a substitution case. This list shows all substances that have one or more of the problematic characteristics that are defined according to the same criteria as for substances on the list of undesirable subHAZARDOUS CHEMICALS CAN BE SUBSTITUTED

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stances. In addition, the list of effect has no quantitative limit, and therefore all substances of high concern are included, whether or not they are used in Denmark. The list of effect consists of around 19,500 substances selected according to the following criteria: > problematic characteristics on the ”EU list of harmonized classification” > problematic characteristics according to computer-based model calculations on the ”Danish Environmental Protection Agency’s Advisory list for self-classification of dangerous substances” (QSAR1-list) > identified persistent and bioaccumulating substances - in the EU called PBT/vPvB > substances on the EU priority list of potential endocrine disruptors The list of effect is thereby significantly more extensive than the candidate list and the list of undesirable substances, and it is a very good tool for companies aiming to avoid substances with similar hazardous effects when they are looking for better alternatives in a substitution case.

list”, covering the most dangerous chemicals according to EU regulation. The SIN list contains substances complying with the criteria for SVHC under REACH. These are substances that may be carcinogenic, change DNA, have endocrine disrupting properties, 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. The SIN list covers today 378 substances whereas the candidate list only covers 73 substances.

Swedish NGO ChemSec has published the”SIN

1 QSAR=Quantitative Structure Activity Relations. A computer programme that can derive with relatively high certainty the hazardous properties of chemical substances based on a comparison of their chemical structure. The degree of certainty varies, however, between different hazardous properties.

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Substitution portal and networks Business networks exist in which companies involved in substitution meet and share experience with other companies wishing to reduce their consumption of dangerous chemicals. Sweden is home to a ’ChemSec Business group’ covering, among others, Boots, Dell, IKEA, and Sony Ericsson, and in the USA 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 containing resources to help finding alternatives to dangerous chemicals. It is not just a source of information on alternative substances and technologies; 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 really important that good tools are available. Warning lists, networks, and portals may help companies getting started, thereby promoting the entire field of substitution.

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4 EXAMPLES OF SUBSTITUTION Fourteen Danish companies – developments since our 2006 report This section presents the substitution projects that were described in the publication “Hazardous Chemicals Can Be Substituted” from 2006. We have contacted the companies and asked how the substitution cases proceed

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and whether they have made other substitutions or have plans to do so. Some companies are really active in their substitution efforts, while others have felt the financial crisis through the customers’ increased focus on cheap goods at the expense of less harmful products.

BRØDRENE HARTMANN Interview with Ms Charlotte Brix Merlin, EcoDesign and Product Safety Manager At Skjern Paper Mill Brødrene Hartmann substituted the intumescing agent Sursol*VL with Rheocol ACP further to a customer request. Hartmann assessed the chemical and since they found it harmful to occupational health and the environment they contacted the customer and planned to look for a better solution. Despite its poorer quality Rheocol ACP was chosen to substitute the substance with harmful effects. Brødrene Hartmann furthermore acquired a Brazilian factory that had a number of challenges regarding chemicals. The challenges were surveyed and a number of changes made; among others, powder dyes were replaced with water-based dyes. Today, Brødrene Hartmann no longer owns Skjern Paper Mill and the Brazilian factory. However, the company continues to follow the same approach regarding chemicals and an ABC system (a tool used to pinpoint chemicals where substitution should be considered). They do not use the Danish Environmental Protection Agency’s list of undesirable substances, since they no longer find it relevant due to the REACH regulation. They now have a

policy of not using chemicals appearing on the European candidate list and thus being categorized as substances of very high concern according to REACH. To improve the opportunities of using environmentally friendly dyes, Brødrene Hartmann have implemented a new dye dosing system in their facilities that increases the flexibility regarding which pulp dyes to use. The company substitutes continuously and has, for example, substituted the cleaning agent ’P3-Clint KF’ that contains nitrilotriacetate (NTA), a suspected carcinogen. Instead, the company now uses ’P3 Topactive LA’ containing presumably harmless alkylpolyglycosides (APG). Furthermore, the company has substituted the process oil ’Q8 Puccini 19 P’, which contains dimethyl sulfoxide (DMSO) with ’Q8 Medicinal white oil’, a white mineral oil. This substitution was made due to the fact that products are suspected of being carcinogenic at contents exceeding 3 % of DMSO. Furthermore, Brødrene Hartmann has carried out a number of occupational health related substitutions, and the company has substituted a number of dyes due to their flammability.

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Facts on Sursol*VL Sursol*VL is used to soften cardboard. Sursol are ethers formed by ethoxylated- or propoxylated aliphatic alcohols with 12 – 18 carbon atoms. The alcohols are primarily linear. The structure of the propoxylated, linear, primary alcohol with 12 carbon atoms is shown below: CH3 – (CH2)10 – CH2 – O – CH2 – CH2 – CH3 Sursol*VL is classified as dangerous for environment. It is severely toxic to organisms living in water, and it is suspected to cause long-term damage to water environments. Furthermore, Sursol*VL affects humans, as it may cause skin irritations, and it is therefore classified as irritant. It is recommended that people working with Sursol*VL carry protective clothes and eyewear, and avoid inhalation.

Facts about nitrilotriacetic acid Nitrilotriacetic acid (NTA) is a polyamino carboxylic acid and is used as a chelating agent which forms complexes with metal ions (chelates), such as Ca2+, Cu2+ or Fe3+. NTA is used in detergents and is suspected of being carcinogenic.

O OH HO

N O

O

HO

Facts about dimethyl sulfoxide Dimethylformamide (DMF) is a liquid which can dissolve both organic and inorganic substances. DMF is a common solvent for chemical reactions and is used as a solvent for plastics and coatings. (CH3)2SO DMSO is used in medicaments, as it penetrates the skin and other membranes without damaging them and is able to transport drugs into a biological system. DMSO can cause allergies and is irritating to skin, eyes and the respiratory system. If a product contains more than 3% DMSO, it has to be labeled as carcinogenic.

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DANFOSS Interview with Ms Lone Damm, Senior Approval Consultant Danfoss produces thermostats etc. They substituted a large number of their chlorine-containing cooling lubricants in favour of phosphorus and zinc compounds, vegetable and animal oils, and some sulphur compounds. The problematic substance in cooling lubricant is medium and long-chain chlorinated paraffins. The company used to have 7-8 chlorinecontaining oils that are now substituted with 5-6 oils not containing chlorine. Consumption of chlorine-containing lubricants has been on a steady decrease; in 1989 it was at 250 tonnes/year, in 2006 7 tonnes/ year, and today Danfoss has reached a consumption of 2-3 tonnes/year. The reduction that has taken place from 2006 to 2012 is due

to several facts, for instance process substitution, in which Danfoss has gone through their production processes and further developed them. In addition, the reduction is due to substitution of products not containing chlorine as well as a reduction in the production itself. Substitution projects are continuously launched, and they are selected according to substances being included in their negative list. This negative list is based on legislation in force, including the list of undesirable substances from the Danish Environmental Protection Agency and the European candidate and authorisation lists under the REACH regulation. Danfoss also uses German TRGS (technical rules for dangerous substances) to avoid the use of secondary amines that readily form carcinogenic nitrosamines.

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Facts on chlorinated paraffins Chlorinated paraffins are a group of chemicals used in coolants and lubricants, in paint, plastics and flame-retardants. Chlorinated paraffins are aliphatic hydrocarbons with chlorine bound to part of the carbon atoms. They are divided into short-chained (having 10-13 carbon atoms), medium-chained (having 14-17 carbon atoms) and long-chained (having 18-30 carbon atoms). A distinction is made between. Below is shown an example of a short-chained chloroparaffin (12 carbon atoms) containing more than 50% chlorine: Cl H H H Cl H H H Cl H H H H–C–C–C–C–C–C–C–C–C–C–C–C–H H Cl Cl H H H Cl Cl H H H Cl Chlorinated paraffins found in coolant are medium- and long chained. They are added because of their lubricating properties at high pressures and temperatures. When coolants containing chlorinated paraffins are used, the substances will be spread widely in the external environment including in wastewater and in contaminated soils. It is estimated that around 25% of the total amount of coolants used will remain on the metal chips used to produce new steel, and the chlorinated paraffins will consequently be burned. The waste is treated at Kommunekemi (a plant for incineration of hazardous waste). When chlorinated paraffins are burned, dioxins and dibenzofurans are released. Dioxins and dibenzofurans are chlorinated aromatic compounds, which may be acute toxic; have carcinogen effects and may cause other adverse health effects. Besides, dioxins and dibenzofurans can accumulate in breast milk. At the production stage, workers are exposed to the chlorinated paraffins through skin contact or inhalation of dust or mist. At the stage of waste removal, the substance may be absorbed through skin, which may cause skin irritations or eczema. Chlorinated paraffins are found on the Danish EPA’s list of undesirable substances. Short-chained chlorinated paraffins have been risk assessed by the EU, and they are on the list of prioritized substances in the field of aquatic environment, including the water framework directive. Furthermore, they are on the REACH candidate list. Restrictions are imposed on the use of short-chained chlorinated paraffins. They must not, for instance, be used in coolant. Furthermore, they are classified as PBT (persistent bio-accumulating toxic) substances, and short-chained chlorinated paraffins are classified as carcinogenic and dangerous to the environment, and are nominated for inclusion in the Stockholm Convention. They are also on the SIN list. The EU is currently risk assessing the medium-chained chlorinated paraffins, and long-chained chlorinated paraffins are currently undergoing a voluntary risk assessment in the EU.

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In addition, the company draws on its own experience with some of the groups of chemicals it has worked with such as cooling lubricant; in this connection formaline releasers and kathon have been included in the negative list. Presently, Danfoss is working on removing boron from their products due to a new classification requirement for products containing

more than 5.5% of certain boron-containing compounds. Danfoss has in this case chosen to state that the company does not wish to manufacture products with boric acid. In general, Danfoss is substituting in an effort to improve environmental issues - both regarding occupational health and the external environment.

DANISCO Interview with Mr Bjarne Nielsen

new raw materials, and some interesting characteristics in the castor oil appeared.

American Dupont acquired Danisco in 2011. The former Danisco’s division for emulsifiers developed a substitute for phthalates based on American castor oil, called SOFT N SAFE™. It was developed as at one point Danisco’s research centre was running some tests with

One of the major challenges for Danisco has been the approval of SOFT N SAFE™. It was a new material, and the effect on human health and the environment had to be surveyed in a number of toxicological and ecotoxicological studies. All studies show that SOFT N SAFE™

CASTOR OIL SEEDS

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Facts on phthalates The name phthalates refers to a group of different esters of phthalic acid (see formula below). They are mainly used to soften PVC. Some phthalates are used to make nail varnish flexible or to make perfumes linger longer. Others are used in adhesive plaster, sealings and in artificial colourings – to make them stronger. Phthalates are also found in products such as raincoats, rubber tubes, medical devices (e.g. tubing and bags), textile printings, children’s toys, cables and glue. The phthalates are released from the products during the production process and during the use and discharge of the products. When added to PVC, the phthalate-molecules bind to vinyl molecules after which the molecules begin to slide against one another but without losing strength. After a period of time has elapsed, there will be a certain migration of phthalates from the PVC. The content in soft PVC can be up to 60%. Phthalates are the most commonly used plasticizers in the world. There are many different kinds of phthalates and they vary in size and structure. The most commonly used are: COOH

Phthalic acid COOH

DEHP (Bis(2-ethylhexyl)phthalate) – used to soften different kinds of flexible PVC products including medical devices, shower curtains, cables and children’s toys.

CH3 O

CH2

C – O – CH2 – CH – CH2 – CH2 – CH2 – CH3 C – O – CH2 – CH – CH2 – CH2 – CH2 – CH3 O

CH2 CH3

O

DINP (Diisononyl phthalate) – used in garden hoses, shower curtains, children’s toys etc.

C – O – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH – CH3 C – O – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH – CH3 O

DIDP (Diisodecyl phthalate) – used in garden hoses, shower curtains, PVC flooring, electrical cables etc.

O

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CH3

CH3

C – O – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH – CH3 C – O – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH – CH3 O

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CH3

CH3

O C – O – CH2

BBP (Butylbenzylphthalate) – used in PVC flooring, paint, lids etc.

C – O – CH2 – CH2 – CH2 – CH3 O

DBP (Dibutylphthalate) – used primarily in cellulose polymers, plaster, ink and seals. Also used in small amounts in cosmetics and nail polish.

O C – O – CH2 – CH2 – CH2 – CH3 C – O – CH2 – CH2 – CH2 – CH3 O

DEPH is the most commonly used phthalate. As phthalates are widely used and used in large quantities, they have been thoroughly tested for environmental and health effects. DEHP has been classified by the EU as harmful to embryos (teratogenic) and as a cause of infertility (group 2). This means that animal testings have indicated that DEHP may cause harm to an unborn child and that it may be the cause of human infertility. This classification is founded on test results showing damages in embryos in mice and rats and damages to testicles in rats. This documentation represents sufficient evidence to conclude that humans may risk infertility and damages to embryos if exposed to DEHP. There has been an increase in the use of DINP since the classification of DEHP. Both DINP and DIDP show signs of having harmful effects on embryos and fertility, but only when very high concentrations are used. Therefore, classification is not relevant in relation to these effects. But also DINP is found on the EU priority list of potential endocrine disruptors. Tests on rats have shown that DINP may have anti-androgenic effects – that is, inhibiting the effects of male sex hormones. Both DBP and BBP have damaging effects on embryos and on sexual reproduction when tested on animals. DBP has been classified and is found on the EU list of harmonized classification. A risk assessment of BBP suggests that the substance be classified as teratogenic in category 2 and as a cause of infertility in category 3. Phthalates are degradable if oxygen is present, but in the environment, the degradation is a very slow process – especially for DEHP, DIDP and DINP, whereas DBP is easier degradable. Phthalates can be found frequently and in all compartments of the environment, and they bind to sediments or soil. When phthalates are absorbed in living organisms, they are transformed into other metabolites and finally discharged. Especially, some of the metabolites are reported to be hormone disturbing. As a result of the abundant uses of the phthalates and their wide distribution, humans living in the industrial societies will regularly carry noticeable concentrations of phthalate-metabolites in their blood veins.

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All the phthalates mentioned here (except DIDP) are on the SIN list. Phthalates are found on the Danish EPA’s list of undesirable substances. In Denmark it is illegal to use phthalates in toys produced for children below the age of 3. There is a similar EU law against the use of phthalates in toys, although in this case the law merely covers toys intended to be put in the mouth. In October 2011, Denmark introduced a proposal to ban DEHP, DBP, BBP and DIBP in articles intended for indoor use and products that may come into direct contact with the skin or mucous membranes. This proposal is so far the strictest approach for an EU-wide regulation regarding the restriction of phthalates in everyday products. The proposal is based on the indication that exposure to the four phthalates may cause combination effects (cocktail effects)* In 2005, the EU put a ban on the use of three phthalates (DEHP, DBP, BBP) in all toys and other products aimed at children, and in addition introduced a full ban on the use of the three other phthalates (DINP, DIDP, DNOP) in toys made for children under the age of 3. The phthalates DEHP, DBP, BBP and DIBP are on the authorisation list under REACH, and must be phased out of products by 21st of February, 2015 (with some exceptions) * Combination effects might change the risk of adverse effects. This means that even though exposure to a particular dose of a single chemical does not in itself constitute a risk of effects, there could be a risk if there is simultaneous exposure to other substances at the same time.

has no effect on human health and the environment. A particularly positive aspect is that there are no endocrine disrupting effects, which is exactly the largest problem associated with some of the phthalates that SOFT N SAFE™ can substitute. The product has been approved, among other uses, for use in plas-

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tics without any restrictions or any specific migration limit (how much may be released) according to Directive 2005/79/EC. Danisco states that the positive profile has strengthened their position on the market due to the fact that SOFT N SAFE™ is based on nat-

EMPLOYEES FROM DANISCO SHANGHAI

urally occurring raw materials. The company’s original SOFT N SAFE™ target groups within foodstuff contact, toys, and medical devices have developed in new directions, and they now see fields of application, where SOFT N SAFE™ can be chosen as a supplement to existing products and be launched in a new brand. Focus is here on product safety and the content of bio-based renewable materials. Specifically, in vinyl flooring SOFT N SAFE™ meets much interest, since it is less volatile than phthalates and thereby contributes to a better indoor climate. The use of SOFT N SAFE™ has expanded to also cover the USA, where the material has three approved fields of application under the FDA (Food and Drug Administration). An FDA approval is the key to increased sales in the USA in the approved applications, but it also contributes to showing the market that there are alternatives to phthalates with a positive assessment from the FDA.

The use of SOFT N SAFE™ has increased steadily, thereby reducing manufacturing costs. However, SOFT N SAFE™ is still around 2-2.5 times more expensive than most phthalates. Danisco’s objective is not to match phthalates, but to bring down costs to a level reducing the barrier for the change. Concretely, Danisco in cooperation with the Technical University of Denmark and the University of Aarhus runs a project under the Danish National Advanced Technology Foundation focusing on how to manufacture SOFT N SAFE™ or similar substances in a cheaper way. Phthalates are still extensively used, also in medical devices such as blood bags and tubes - uses where the risk of human exposure to endocrine disrupting properties is particularly high. Danisco sees many positive prospects, since the demand for secure bio-based alternatives to the fossil based and endocrine disrupting plasticisers is on a steep increase.

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NAKSKOV SUGAR MILL Interview with Mr Ture Kliving, SHEQ (safety, health, environment and quality) coordinator In the past, Nakskov Sugar Mill used nitric acid to clean production equipment, but substitut-

ed it with citric acid and acetic acid. This substitution still works fine. Nakskov Sugar Mill has a general goal to reduce the number of hazard-labelled chemicals in their production - in view of both simplicity and a better occupational health.

Facts on nitric acid Formula: HNO3 Nitric acid is a strong acid that reacts with most metals. Therefore it is often used in metallurgic processes and in the refining of metals etc. In addition, it is a strong oxidizer and those two features combined makes it suitable for cleaning equipment and containers in the food industry. Iron as well as aluminium both stand up to nitric acid because a protective layer of oxides is formed on the surface of the metal, and this protects it from being attacked by the acid. 100% nitric acid, also called fuming nitric acid, releases the toxic gas, NO2, and it reacts strongly with almost any organic material. Sometimes this process even starts a fire. Combustion of coal and oil releases a mixture of nitrogen oxides, which then reacts with water to form nitric acid. Nitric acid is thus one of the chemical compounds found in acid rain, and it is partly responsible for the acidification of soil and water. Nitric acid is on the EU list of harmonized classification, classified as corrosive.

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NKT CABLES Interview with Mr Jens Thiesen; Environmental Director nkt cables has developed cables substituting polyvinylchloride (PVC) that was stabilised with lead and softened with phthalates. Their NOPOVIC® cable type is based on a mixture of halogen-free polymers such as polyethylene (PE), polypropylene (PP) and ethylene vinyl acetate (EVA) copolymers containing nonflammable minerals such as magnesium and aluminium hydrates. The cables are not eco-labelled, since no criteria have been set up for eco-labels for electric cables as stand-alone products in the Nordic eco-label the Swan and the EU label the Flower. nkt’s PVC and phthalate free products, however, earn points under the Swan label criteria for small houses and are thereby a good choice in sustainable construction aiming for the Swan label. Consumption of the NOPOVIC® plastic has increased from 1997 to 2012 from next to

nothing to around 10,000 tonnes. Now after ten years, the PVC and phthalate free installation cables constitute 80% of their sale in Denmark while only some 10% is exported. nkt cables states that originally customers were quite reluctant, but now it is a huge success in the field of installations. However, PVC is still preferred in the professional field (the OEM field) where cables are used as components in other products. In the latest revision of the EU RoHS directive on electronic and electrical equipment the EU Commission proposed limits on the use of PVC, but during the reading in Parliament the PVC restrictions were removed and were not included in the final version. Today, everybody at nkt cables agrees that the substitution was a good idea. It has contributed to maintaining the view among customers that nkt cables is a serious company showing respect for the environment. The substitution has contributed to maintaining nkt as the market leader in Denmark. As a result of the success and the increasing consumption, the production of compounds (production of

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Facts on plastic Plastics are polymers. All plastic types are primarily made of carbon and hydrogen - and sometimes chlorine. Plastics are defined as organic materials made of macromolecules – polymer chains of monomers. (CH2-CH)n | X The X in the formula indicates: Hydrogen (H), Chlorine (Cl) or Methyl (CH3) according to the type of plastics, namely Polyethylene (PE), Polyvinylchloride (PVC) or Polypropylene (PP), respectively. These are produced either by processing natural products or they are synthesised from primary substances of oil, natural gasses or coal. There are three types of plastics: 1) Thermoplasts. This name refers to the fact that the materials become plastic when heated and hard again when cooled down. This quality is used in the manufacturing of plastic products, as the material is heated, moulded and subsequently cooled down. Accordingly, thermoplast waste and old products can be melted and re-used. Themoplasts make up 85% of the total plastics consumption. Examples of thermoplasts are: PE (polyethene), PP (polypropylene), PVC (polyvinylchloride), PS (polystyrene) and EVA (ethylvinylacetate). 2) Duroplasts. Unlike thermoplasts, duroplasts cannot be melted once it has been moulded and hardened. And therefore it cannot be re-used. Instead, duroplasts will, when heated at high temperatures, be charred. 3) Elasts are characterised by having macromolecules bound in such a way that, when affected by a light force, the material is capable of being deformed several hundred percent and resume to its original form afterwards. This material is, for example, used in sponges. Plastic raw materials, which are delivered by the supplier to the plastics processing plant, usually contain several different substances – additives - whose purposes are to make the moulding process easier and to improve the final product. The additives assist in the processing of the plastic end product and make it possible to produce tailor-made plastic products. Some of the most important additives are: Surface treatments give the material extra strength. Plasticizers make the materials flexible. Colour pigments give it colour. Stabilizers protect against ultra-violet radiation and thermic degradation. Antistatics prevent static electricity. Fire-retardants retard fire. And fillers for plastics make the material stretch longer – these could be chalk or dolomite.

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PVC is a common form of thermoplast. It consists of carbon, hydrogen and chlorine. It is a hard form of plastic and therefore a softener needs to be added before it can be moulded. In this way, the created plastic material is given strength and flexibility, and at the same time it becomes long-lived and cheaper. Worldwide, PVC makes up 20% of the total plastic consumption. In Denmark, it makes up 15% of the total consumption. There are no Danish manufacturers of raw PVC. PVC causes several different environmental problems. When burned, hydrochloric acid is released; and subsequently this needs to be neutralised using a considerable amount of alkaline material, e.g. chalk. Heavy metals contained in the PVC (e.g. lead and cadmium – although these are banned in an increasing number of applications) will, in the course of the incineration process, be concentrated in the solid residues. PVC contains up to approximately 50% chlorine and several additives (as mentioned above) to which different environmental issues are related. The waste product weighs more or less the same as the original PVC. And it contains a large amount of chalk, which makes it unstable, and therefore it must be deposited in a special manner. Moreover, it contains heavy metals and organic toxins – such as dioxin. PVC-containing waste, which is incinerated, may contribute to the creation of dioxin. However, to which extent the creation of dioxin is affected by the content of chlorine in the PVC remains unclear, considering that chlorine will always be present in mixed waste material – in wasted food, wood etc. Alternatives to PVC are PE, PP and EVA etc. PE makes up around 45% of the total plastics consumption in Denmark, whereas PP makes up around 15%. If we compare the different plastic materials in terms of energy use during the manufacturing processes and pollution during the production and waste removal processes, the result will be that PE and PP are to be preferred. None of them have seriously damaging effects on the environment beyond the oil usage and the release of CO2, which is part and parcel of all plastic products. This means that only water and CO2 are released during a total combustion. This presupposes that the products in question are without additives. MS-polymers (Modified Silane Polymer) stand out from the plastic types mentioned above by having silicon (Si) as one of their main elements. They are mainly used in fillers and they are characterised by being free from isocyanate and silicone (polymers based on chloro-silane), of which especially isocyanate (monomers contained in polyurethane) is severely hazardous to human health. MS-polymers have features that combine those of silicone and polyurethane.

polymer and added substances) was outsourced a few years ago. nkt still works with substitution and phasing out. As a new objective, the production is to be entirely talc-free. When cables are fitted in plugs and switches, the cable ends must be stripped to access the copper conductor. To

facilitate the work of the electrician a small amount of talc is traditionally introduced between the insulated conductors (the lodes), fill cap, and outer cap. This talc is a dust nuisance in both production and fitting. nkt cables has succeeded in developing plastic mixtures without talc for a number of installation cables that electricians find easy to strip. HAZARDOUS CHEMICALS CAN BE SUBSTITUTED

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FUJITSU Interview with Mr René von Staffeldt Beck, Product Manager - Work Place Systems Fujitsu Siemens has developed the Green Scenic PC containing a number of substitutions. For instance, lead was substituted with soldering pewter and PVC, cadmium, mercury, and partially brominated flame retardants were removed. Fujitsu no longer produces the Scenic PCs, but most of their portables (LIFEBOOK), stationary computers (ESPRIMO), and workstations (CELSIUS) come in ProGreen versions. This entails zero watt power supply that exploits more than 93 % of the power. Fujitsu now also has screens that turn off completely when not in use instead of turning to power-consuming standby. The last few years have been tough for Fujitsu in Denmark, but demand is starting to increase. However, the company calls on the public authorities to go for environmentally friendly products in their procurement. No new competitors have appeared for the green PCs of Fujitsu. Customers are slowly starting to assess whether they can get a financial benefit from choosing green equipment, either directly through less power consumption or by attaining a green image.

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Facts on heavy metals Heavy metals are found in nature. They are generally defined as metals with a specific density higher than 5g/cm3, but a most often seen characteristic is that they are metals which are hazardous even in small doses. The problem with heavy metals is that most are toxic and non-biodegradable, and they may accumulate in the food chain in the fatty tissue or in organs of humans and animals. Heavy metals may hamper recycling of waste products such as slag, fly ash, residues from gas cleaning, sludge and compost. Three of the most important toxic heavy metals are described below. Other hazardous metals are arsenic, nickel and chromium. Lead (Pb) Of all the heavy metals lead is the one most commonly found in nature. Lead binds easily to soil and therefore it is possible to find soils which still show traces of past lead contamination. In larger cities, we see an extensive, diffuse lead pollution. Especially since up until the mid-1980s petrol contained organic lead compounds. Lead may be found in many different products: electronics, electric components, roof tiles etc. Lead is absorbed into the human body if we are exposed to it via the air, dust or our food. Lead is a toxic substance affecting the nervous system. High concentrations of lead cause severe deterioration of learning abilities and changes in the reproductive system. It has recently been discovered that even very small concentrations of lead may cause child learning disabilities. Lead will have both acute and chronic toxic effects on vegetation, animals and micro-organisms. Lead is on the Danish EPA’s list of undesirable substances. Lead and lead compounds are classified as CMR substances belonging to the categories 1 and 2. In Denmark it is illegal to use lead in consumer products, and from September 2004 it became illegal as a constituent in cosmetics in the EU. Lead is regulated by executive order No 1012 of November 13, 2003 on the ban on sales and import of lead-containing products. There are certain exceptions like lead accumulators. Lead may still be a problem in waste because it may contain old traces of the substance. Lead is on the EU list of harmonized classification, as it is very toxic to aquatic organisms (R50), may cause long-term adverse effects in the aquatic environment (R53), may cause harm to the unborn child (R61) and presents a possible risk of impaired fertility (R62). Restrictions regarding leadcarbonates and leadsulfates are described in Annex XVII No.16 and No. 17 of REACH. Cadmium (Cd) Cadmium is found in nature in relatively small quantities. The metal can be found in products such as electric components, plastics, batteries, accumulators, colour pigments etc. Cadmium and cadmium-containing chemicals may have acute toxic effects on both humans and animals. Moreover, there are good reasons to fear cadmium since it may accumulate in the human

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body – especially in the kidneys. Other long-term effects are changes in the reproductive system, reduced growth, and kidney and liver diseases. Furthermore, cadmium prevents us from absorbing important and necessary substances. Most cadmium compounds are found on the EU list of harmonized classification. It is illegal to use cadmium in Denmark with a few exceptions (batteries included). Most cadmium containing batteries have now been substituted with e.g. nickel-metal hydride. Cadmium and cadmium dioxide are presently undergoing risk assessments within the EU. From December 2011 cadmium was regulated through REACH. For example, the allowed amount of cadmium in certain product types is only 0.01 %. The Regulation is described in Annex XVII, no.23 of REACH. Mercury (Hg) Mercury is found in products such as batteries, dental fillings, fluorescent tubes, electrical switches and computers. Mercury is easily absorbed into the body and it affects the brain and cause visual disorders, motor and balance disabilities. Furthermore, mercury may affect embryos and in severe cases it may lead to brain damage in the newborn child. Animals at the top end of the food chain will contain most mercury due to the fact that the amount of the substance is accumulated up the food chain. Therefore it is recommended that pregnant women refrain from eating certain kinds of fish (large predatory fish) or fish caught in certain, relatively contaminated waterways – e.g. the Baltic Sea and some freshwater systems in Scandinavia. Mercury and mercury compounds are on the EU list of harmonized classification. Mercury is covered by Annex XVII, No. 18a of REACH and the Danish directive No. 627 of 1st July 2003 prohibiting the import, sale and export of mercury and mercury containing products.

Facts on brominated flame-retardants Brominated flame-retardants belong to a group of substances used to hinder or delay fire in electronic equipment, building materials, furniture etc. They are organic compounds containing bromine and they are often formed by two linked phenyl rings with variable numbers of bromine atoms attached. In electronic equipment the brominated flame-retardants are found in the compartment, printing plates and switches. There are around 40 different brominated flame-retardants. The most common groups are as follows: Br HO

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Br

C Br

•

CH3

CH3

Br Br

Br Br

Br

OH Br

TBBPA (Tetrabromobisphenol A)

THE ECOLOGICAL COUNCIL

Br

Br

•

Br Br

Br

PBB (Polybrominated biphenyls)

Br

Br

Br

Br

Br

Br Br Br

O

Br Br Br

•

Br

Br

Br

Br

PBDE (Polybrominated diphenylethers)

•

Br

HBCD (hexabromine cyclododecan)

The most problematic groups are PBB and PBDE, and the most commonly used are HBCD and TBBPA. Brominated flame-retardants may either become a part of the material they are protecting from fire through chemical reactions, or the substances are mixed with the material as an independent component – an additive. They are most easily released from the material when they are used as additives and not chemically bound. When the products are produced, used or disposed of, the hazardous substances may be released and subsequently inhaled by humans or enter into the environment via rain or dust. Brominated flame-retardants are – in various degrees – slowly degradable and will never disappear completely after they have entered into the human body or the environment. Based on animal testing results, researchers suspect that the substances may affect embryo formation and the reproduction system, that they may cause cancer and that they affect the function of the hormone thyroxine. Thyroxine helps regulate growth and development of embryos and of the newborn. Its structure is quite similar to that of PBDE. Several American, Swedish and Japanese studies have detected brominated flame-retardants in breast milk. Especially high concentrations were found in breast milk from American women. Brominated flame-retardants were also found in animals – e.g. in whales. In their mobility and distribution patterns in theenvironment brominated flame-retardants are comparable to the insecticide DDT and to the synthetic oil and plasticiser PCB. Like DDT and PCB, they consist of linked phenyl rings to which halogen atoms are attached – only bromine instead of chlorine atoms. Both DDT and PCB have harmful effects on humans and on the environment, they both degrade very slowly and they are stored in fatty tissue and accumulate in animals at the top end of the food chain (humans included) - just like brominated flame-retardants. Other less used flame-retardants are: vinyl bromide that may cause cancer, and 2,4,6 – tribromophenol that may affect the liver and cause damages to embryos. Penta-BDE (penta-bromidediphenylether) is classified as irritant, harmful and as environmentally hazardous. In 2006 the substance was – like octa-BDE (octa-bromidediphenylether) - banned in electronic products in the EU. Furthermore PBB is included in the EU directive No 2002/95/EC banning its use in electronic and electric products from July 1st, 2006. Deca-BDE was included in the ban in 2008. The industry has voluntarily removed PBB from the market. Deca-BDE and TBBPA are undergoing risk assessments within the EU. HBCD is on the EU candidate list.

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POUL E. MEIER Interview with Mr Poul E. Meier and Mr Jesper Quist, export manager of Perform Poul E. Meier substituted lead in roof flashing, thereby developing the product Perform. Perform is a composite consisting of a robust aluminium lattice cast into rubber/plastic of the type MS polymer. Perform sells well and around 70 % is exported today. Demand fluctuates heavily, however, in line with the price of lead. Denmark has a very broad ban on lead including a ban on import and sale of lead-

containing roof flashing. There are many competitors on the market with other flashing solutions, including producers from Germany, England, and the Netherlands. However, no competitors sell products with the same properties as Perform. Poul E. Meier is no longer actively involved in Perform, and he has now started developing products in the field of climate and energy.

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DANA LIM Interview with Mr Erik Andersen, Laboratory Director Dana Lim (‘Dana Glue’) has substituted a number of substances in their sealing compound, including phthalates, oximes, and polyurethane (PU). Dana Lim still manufactures products containing PU, but have alternative products based on MS polymers (functionalized polyether with methoxysilane terminal groups) for all their product groups. The company sees a decrease in the sale of wood glue and sealing compound containing PU while the sale of PU foam remains unchanged. The oxime substitution in sealing compounds has been successful, as the company has come below the limit value set for the release from sealing compounds upon hardening. The company works to phase out oximes completely, but still manufactures a few products where butanonoxime is split off during hardening. However, quantities are very low, and the products are socalled “low-oxime”. The oxime substitution succeeded thanks to a shift to completely different formulations using another type of

binder. Thereby, a completely different product was developed solving the same task. The positive aspects of the new product are that it is eco-friendlier and easier to paint over. Phthalate sealing compounds are still manufactured, but the number is limited and only di-isononyl phthalate (DINP) is used. This decision was made after the publication of a status report from the EU risk assessment programme for chemical substances that stated that DINP is not top priority and does not require labelling. Dana Lim wishes to avoid going through one more temporary solution and thereby puts off the substitution of DINP in the last products. All phthalates have been removed from glue products, but they still exist in supplementary products, and primarily in products for industrial purposes. Dana Lim still substitutes, but in recent years substitution activities have been on stand-by. This is due to REACH, among other reasons, since the company cannot see the effect of the regulation at present. So they hold back due to the fact that a substitution process may be prolonged and expensive, and Dana Lim wishes to avoid a situation where they substitute with a substance that may in the near future be subject to restrictions or authorisation. Erik Andersen states that it is difficult to carry out substitution without basing decisions on legislation.

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Facts on polyurethane Polyurethanes are polymers formed by diisocyanates and polyalcohols – that is alcohols containing more than one OH-group. Both components vary to the extreme and many different compounds with many different characteristics. Polyurethanes are used in foam, lacquers, joint fillers and insulating materials. An example of a simple diisocyanate: OCN – (CH2)6 – NCO An example of a simple polyalcohol: HO – (CH2)4 – OH Polyurethane with ”n” isocyanate elements, formed by the compounds mentioned above, has the following formula: H – (O – (CH2)4 - O – CO – NH – (CH2)6 – NH – CO - )n – O – (CH2)4 - OH The reactive isocyanates give rise to health problems. Therefore, the production of polyurethane causes problems in the working environment. If inhaled, the substance may create coughing, chest paints and other respiratory problems. It may cause irritation to the eyes, nose and throat. If absorbed through skin, the substance may cause problems such as dryness, rash and blisters. Allergies such as respiratory allergies and skin allergies may occur if you are exposed to diisocyanates. Allergies such as these are chronic. Polyurethane is particularly dangerous during the manufacturing process. But isocyanate is released also when the product is heated (e.g. during welding). Special precautions must be taken when working with polyurethane. Facts on oxime The name oxime refers to a group of chemical compounds formed by aldehydes and ketones in reaction with hydroxylamines. Butanonoxime is one example:

CH3 | C = N – OH | CH2 – CH3

Oximes are contained in different types of joint fillers and it may be released during the hardening process. Oximes may cause allergic reactions and is an eye irritant. Moreover it may cause cancer.

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Furthermore, their stand-by is caused by the financial crisis. Many raw material suppliers have rationalized or merged. Also, many raw materials are no longer available. And the company has feared that many substances will disappear due to REACH. Some of Dana Lim’s products have been discontinued, which Erik Andersen finds positive. The least eco-friendly products disappear first due to possible future restrictions. Dana Lim has also felt the financial crisis among their customers who have now more focus on competitiveness and survival than in 2006. When economy was booming customers were more generous with eco-friendly solutions. Dana Lim now has increasing focus on indoor climate and food packaging where products are subject to substitution. As a supplier to the packaging industry the company is subject to the Danish ‘smiley scheme’ (four different smileys signal how well the enterprise complies with food regulations), and this has been positive since an expert from the scheme has given good advice and made a systematic review of relevant raw materials. The company has the Finnish indoor climate label M1 on their filler - this is a statutory

requirement for exports to Finland. M1 is short for the Finnish voluntary classification of emissions of volatile organic compounds (VOCs) from construction materials. To have the label, products were tested and found to comply with the emission requirements after substitution of a preservative that caused too high VOC figures. Dana Lim furthermore has just been upgraded under the German EMICODE® label. This is a quality assurance scheme giving labels to construction materials that are found to be modern, free of solvents, and with low VOC emissions. The scheme uses a range where EC1PLUS has the lowest permitted emission. EC1 requires, among others, that after three days the product has an emission of all its VOCs not exceeding 1000μg/m3. For EC1PLUS total emissions after three days must not exceed 750 μg/m3. A control test showed that Dana Lim products labelled with EC1 were actually better than that, so it was possible to upgrade to the EC1PLUS label. All in all, Dana Lim has high focus on substitution and consultants have been engaged to convince customers to purchase the ecofriendlier products that have been subject to

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substitution.

KYMI RENS Interview with Mr Michael Porsmose, Director Kymi Rens (‘Kymi Dry Cleaning’) substituted perchloroethylene as the cleaning agent with AquaClean, CO2 cleaning and GreenEarth, which is a silicone-based cleaning method. Perchloroethylene is still used as the primary cleaning agent by most of Denmark’s dry cleaners despite the fact that it is suspected of several health and environmental effects, and is on several warning lists. Since our last publication Kymi Rens has substituted the silicone system GreenEarth with SYSTEMK4 from German supplier Kreussler. The company states that the silicone system was actually fine, but discussions were starting about endocrine disrupting effects associated with silicone, so they decided to switch to the

new system. K4 uses a halogen-free solvent (SOLVONK4), which is unproblematic for the environment. It is marked as highly inflammable, but not harmful to human health or the environment according to the Globally Harmonized System (GHS) of classification and labelling of chemicals. SYSTEMK4 is a very efficient system, and the process consumes considerably less energy. The company has acquired a machine dedicated to SOLVONK4, and in October 2011 the new method was launched. In addition, the silicone machine was converted into a K4 machine with very fine results. When cleaning, the company divides items into what needs to be wet cleaned (using water) and what needs CO2 cleaning. These two methods cover most needs. What cannot be treated here is put in K4, which is thus only

Examples of symbols in GHS2 Inflammable: This pictogram covers inflammable substances and their vapours, gases, aerosols, and solid matter. Examples of products carrying this label are spirits, nail polish remover, and motor fuel. Chronic health hazard: This pictogram covers 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 inhalation, or cause organ damage or lung damage by inhalation. Examples of products carrying this label are petrol, turpentine, and lamp oil. Acute toxic: This pictogram covers chemicals that are acute toxic by ingestion, skin contact, and/or inhalation. Chemicals carrying this pictogram may be potentially lethal. Examples of products carrying this label are some pesticides and methanol (wood alcohol). 2 Danish Environmental Protection Agency pamphlet on new hazard pictograms.

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operated a few times a week, causing low operating costs. Director Michael Porsmose has not heard of the use of K4 with other dry cleaners, and more than 50 % of Danish dry cleaners still use perchloroethylene. In the long-term perspective Kymi Rens is opting for the CO2 method. The company has invested

in one more CO2 machine, and it is the primary cleaning method, since it has the lowest energy consumption and is most environmentally friendly. However, still very few customers demand environmentally friendly cleaning. Kymi Rens has substituted since they wish to survive in the sector in the longer term, and environmental considerations are an important part of that objective. They wish to be at the cutting edge of developments in the chemicals field.

Facts on chlorocarbon and perchlorine (perchloroethylene) Chlorocarbons are hydrocarbons with a maximum of one chlorine-atom attached to each carbon atom, whereas all hydrocarbons are replaced by chlorine in perchlorine compounds. ‘Perchlorine’ is commenly used as the name for perchloroethylene (tetrachloroethylene). Both chlorocarbons and perchlorines are mainly used in liquid forms and at room temperature. CH3CH2CH2Cl

1-chloropropane (a chlorocarbon)

Cl2C = CCl2

Tetrachloroethylene ( perchloroethylene)

Both chlorocarbon and perchlorine are – or has previously been - used in the dry cleaning industry. Chlorocarbons are dangerous when inhaled or swallowed. They may irritate skin, eyes and the respiratory system. In 1995 a law was introduced against the use of chlorocarbons in the dry cleaning industry. Perchlorine is still commonly used in dry cleaning. It is suspected to cause cancer (carcinogenic class 3) and it is damaging to water environments (R-51/53). It is listed on the Danish EPAs list of effect, the EU priority list of potential endocrine disruptors and on the SIN list. Denmark allows a maximum of 0.1 mg/m3 perchlorine in the air, which is considerably higher than the 0.006 mg/m3 recommended by the health authorities. Dry cleaners are typically found city areas and they are often located beneath flats. And perchlorine contained vapour may penetrate into the flats. For these reasons threshold limit values have been lowered and, consequently, many dry cleaners have closed down.

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LOGSTOR Interview with Ms Tina Thomsen, Chemical Support Manager Logstor produces pipes. They learned that their silica gel desiccant called Blågel (bluegel) was carcinogenic due to the addition of cobalt chloride. Blågel is only toxic when dried in the desiccator cabinet, but it is included in the Danish Environmental Protection Agency’s list of undesirable substances. Logstor substituted into another type of desiccant not containing the harmful substance. The substitution of desiccant is going very well and the company has found out that the new type of desiccant can absorb more moisture. This means that the drying process is only 50% of what it used to be. Logstor has substituted further in 2008 by phasing out dimethylformamide (DMF). This has been achieved by replacing some important foam machines from low pressure to high

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pressure machines. In a high pressure foam machine it is sufficient to clean the mixing head with a piston pushing reacted foam out of the mixing head - merely a mechanical cleaning. The low pressure foam machines were equipped with a rotating mixer in the mixing head, and after around four hours of continuous production this mixer had to be changed and cleaned in the solvent DMF. In other places using high pressure foam machines sprayer tubes fitted on the mixing head used to be cleaned in DMF. Now, most often a drill is used to drill out the foam, and in rare cases the sprayer tubes are introduced in a bath of Dowanol, which is a hydrophilic glycolether considered significantly less harmful than DMF.

Facts on silica gel Silica gel (or blue gel) is an adsorptive substance used to de-moisturize the atmosphere surrounding cameras and stereos etc. It is usually placed in small sachets in the packaging for these products. Silica gel is also used to control the moisture contents of grains and seeds during long-term storage. When the silica gel is dry, the colour is blue, but after the gel has picked up moisture from the air, it turns pink or becomes nearly colourless. Silica gel is a porous, solid material and has the chemical formula of silicon dioxide (SiO2). It has great water adsorptive power explaining its widespread use as a drying agent. Silicon dioxide is colourless both before and after the absorption of moisture, therefore cobalt chloride is added as a water indicator. Cobalt chloride (CoCl2) is pink, but turns blue when it is lightly heated and thoroughly dried. As Silica gel gradually absorbs water, pink cobalt chloride is reformed. Silicon dioxide is probably harmless, but cobalt chloride may cause cancer. Because cobalt chloride is not chemically bound to the silica gel, it is easily released and can then be inhaled. Commercial Silica gel is categorized as very toxic and harmful when inhaled.

Faktaboks om dimethylformamid Dimethylformamide (DMF) is a liquid which can dissolve both organic and inorganic substances. DMF is a common solvent for chemical reactions and is used as a solvent for plastics and coatings.

O C H

N

CH3

CH3

DMF is on the EU list of harmonized classification and labeled as R36 (irritating to eyes), R61 (may harm the unborn child) and R20/21 (harmful by inhalation and in contact with skin). DMF is also suspected of being carcinogenic and may impair fertility.

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FRIGOR Interview with Mr Karsten Fiil, Service Manager Frigor is a cold store brand. They substituted freon 134A with pentane in the foaming process,, and in most products the company replaced freon 134A with isobutane as the refrigerant. Freon 134A is a hydrofluorocarbon (HFC) and a potent greenhouse gas. Freon 134A and isobutane are still used as refrigerants, since the technique of using CO2 as a refrigerant is still too expensive for ordinary cooling and freezing. The advantage of the CO2 technique is that the lower limit for the temperature in a cold store can be reduced without significantly higher energy consumption. However, the technique requires special-

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ly designed freezers that can resist the higher system pressure caused by CO2 and the lower temperature. Frigor no longer has production in Denmark, as in 2007 the company Vibocold acquired Frigor and the right of the name, while ’Frigor Produktion’ is owned by Turkish UGUR. The cold store brands of Caravell and Derby are today owned by Metalfrio, and all three factories have moved almost entirely to Turkey.

Facts on freon (CFC, HCFC and HFC) Freon is a group of short-chained, halogenated hydrocarbons. They contain the elements carbon, fluorine and/or chlorine. Some also contain bromine. Freon are usually gases. The most common types of Freon can be divided into 3 different groups: CFC (ChloroFluoroCarbons), HCFC (HydroChloroFluoroCarbons) and HFC (HydroFluoroCarbons) CFCs are completely halogenated and therefore contain no hydrogen. They are used in can sprays, refrigerators, as degreasers, in dry-cleaning etc. The CFCs are severely stable and are only very slowly degraded in the atmosphere. CFCs contribute to the destruction of the ozone layer, as the chlorine atoms react with the ozone molecules and transform them into oxygen. For this reason, it is no longer legal to use CFCs in, for example, the production of new fridges. One example of a CFC-gas is: CF2 C2 (Freon 12) HCFC was introduced when the CFCs became illegal. Since they contain hydrogen, they stay for a shorter period of time in the atmosphere. Still, it turned out they contributed to the destruction of the ozone layer. One example of a HCFC gas is: CHClF2 (Freon 22) Originally, HFC was also developed as a substitute for CFC in the refrigerator industry. As HFC does not contain chlorine, it has no effect on the ozone layer. However, HFC is, like other halogenated hydrocarbons, a very strong greenhouse gas (a thousand times as strong as CO2), and it is toxic as well. HFC is found on the list of undesirable substances from the Danish EPA. Hence, in spite of the fact that HFC has no effect on the ozone layer, it is still not a suitable substitute for CFC. One example of a HFC gas is: CHF2CF3 (Freon 134a) The Montreal Protocol of Substances that Deplete the Ozone Layer was originally signed in 1987. The treaty covers approximately 40 different HCFCs of which only a small number is in use. The EU has set timeframes for phase-outs of CFCs and HCFSs (see regulation 2037/00). According to this, CFC’s should be phased out by 1995 and HCFCs by 2010. It is still legal to use HFCs in the EU. However, they are, together with other industrial greenhouse gasses, covered by the Koyoto Protocol and must be reduced just like CO2, methane etc. Denmark has introduced a national regulation covering the greenhouse gasses. In 2001 a tax on these gasses was introduced, and from 2006 a complete ban was implemented, cf. the European Parliament and Council Regulation (EC) No. 842/2006 of 17th of May 2006 on certain fluorinated greenhouse gases.

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ABENA PRODUCTION A/S Interview with Ms Mette-Sophie Thomsen, Quality Manager In the past, Abena has substituted a part of the superabsorbent in nappies. It used to be based on acrylic acid, but the company developed a superabsorbent based on wheat starch and granules. Abena is now again using a superabsorbent based on acrylic acid. The company states that the quality of the bio-friendly superabsorbent was not very good, so more raw materials had to be used to obtain the same quality. The company did not wish to do so, since this is not a good environmental choice. The company is still ISO 14001 certified.

They have not substituted in other fields, since the Swan label criteria have been changed and they can therefore opt for other solutions than substitution. Their primary environmental focus is on selecting the best raw materials. They will not use the most environmentally friendly raw materials, if it results in a product of lower quality, which would mean that the consumer uses more nappies, thus harming the environment in this way. Abena also seeks to reduce the consumption of raw materials by developing their products to avoid excess raw materials and by making materials as thin as possible without compromising the quality. They do not add unnecessary chemicals such as dye and perfume, and they are constantly seeking ways to optimize energy consumption in the process.

Facts on acrylic acid (superabsorbent) Acrylic acid is an unsaturated, aliphatic carboxylic acid with the following formula: H2C = CHCOOH Due to its highly reactive double bond, acrylic acid is easily polymerized or taking part in polymerisation processes as basis for production of super absorbing materials. Polymerisation of acrylic acid: - CH2 – CH – CH2 – CH – CH2 | | COOH COOH Acrylic acid is corrosive and dangerous by inhalation, oral intake and dermal contact, and it is very toxic for aquatic organisms. Acrylic acid is listed as dangerous according to EU regulations. Acrylic acid being the basic raw material in the production of superabsorbent, it is primarily this process, which makes the hazards important and relevant in relation to workers as well as to the surrounding environment in cases of loss and/or emissions. Superabsorbent as separate material is a polymer in its own right, however not registered as toxic.

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NOVADAN Interview with Ms Lis Fleng Rasmussen, Development Manager Novadan produces washing, cleaning, and disinfection agents for many industrial markets. Substitution began when Novadan was invited to participate in a substitution project. They decided to substitute surface active agents (tensides) contained in their products and to develop less environmentally harmful washing agents for industry. The motivation for participating in the project derived partly from a requirement from the company’s own customers for supplying more environmentally friendly products, and the purpose of the project was to reduce the environmental burden from industrial laundries by substituting those washing active substances that were toxic,

bioaccumulating, and non-degradable. Novadan developed two alternative products to each of the original washing agents by finding alternatives to the surface active substances with the worst ecotoxicological profile. The most significant changes took place by replacing anionic tensides with nonionic ones, and they avoided substances marked with R50 (very toxic to aquatic organisms) and those marked with R53 (may cause long term adverse effects in the aquatic environment). Environmental assessments were made of their test products, and much attention was given to reducing the score of toxicity and degradability. Where data were not available for a constituent, QSAR estimates were used3. Novadan still produces these more environmentally friendly and Swan labelled products.

3 (Q)SARs are also referred to as computer models and they are used to predict the properties of chemical substances. Read more about QSAR models on the website of the Danish Environmental Protection Agency www.mst.dk HAZARDOUS CHEMICALS CAN BE SUBSTITUTED

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Facts on surfactants Surfactants are surface-active agents, and they can be divided into 4 different groups according to their charges in watery solutions. These 4 groups are: anionic (negative charge), non-ionic (neutral), cationic (positive charge) and amphoteric surfactants (positive or negative charge according to pH value). The different groups of surfactants have different properties considering aerobic and anaerobic degradability (oxygen containing or oxygen-free respectively) and toxicity. Often cationic surfactants are slowly degradable, while non-ionic surfactants are easy degradable under aerobic conditions. Moreover, the properties of the substances also differ within the same group, and therefore it is not, as such, possible to generalise on their properties. Surfactants – or detergents – are always partly hydrophilic (fat-loving and water repellent) and partly hydrofile (water-loving). The most commonly used anionic surfactants in Denmark are linear alkylbenzene sulphonates, also known as LAS. Less common are alkyl sulphates that are more toxic than LAS. Normally, both LAS and alkyl sulphates are easily degradable under aerobic conditions, but they are not 100% degradable, and therefore small amounts of anionic surfactants may be released from sewage treatment plants into the environment via cleansed waste water. LAS is used as surfactant in detergents and cleaning products. These substances are toxic to organisms living in water. Surfactants in detergents are released when the washing machine has finished washing. Surfactants help to remove fat and protein-containing stains from the laundry. Most surfactants will harm the environment. The ability of the surfactants to dissolve fat and proteins is the main reason for their toxic effects on organisms living in water – including bacteria, algae, crustaceans and fish. Furthermore, they react heavily with organic particles and therefore accumulate in wastewater sludge and sediment. The degree of the damage done to the environment depends on how fast they work and on whether the substance is degraded fully. One example of a structure of anionic surfactants is as follows: (CH2)11 – CH3 SO3-

Non-ionic surfactants consist mainly of the group of substances called alkylphenol ethoxylates (APEO). They improve the mixability of different substances with water and improve dispersing (fine distribution of pigments, for instance). The alkylphenol part of the APEO often consists of 8 16 carbon atoms and the degree of ethoxylation (EO) varies from 1 to 30, but normally stays within the spectrum 12 -13 EO. In paints, APEO works both as an independent raw material (e.g. as a dispersing agent) and as part of other raw materials (e.g. in binders or in pigment dispersers). APEO consists of a lipophilic alkylphenol part and a hydrophilic chain of ethoxylates. Partly due to their low acute toxicity, alkylphenol ethoxylates – especially nonyl and octyl versions – have a range of properties that makes them suitable as surfactants in a long list of products.

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An example of a structure for nonylphenol etoxylate: O – CH2 – CH2 – O – CH2 – CH2 – OH

CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH3

APEO can be found in detergents, cleaning products, paints and lacquers, cosmetics and as auxiliary components in pesticides. When APEO is biodegraded, alkylphenols – especially nonylphenols – may be created. These are toxic to organisms living in water. The degradation products of APEO are at least five times as toxic to aquatic organisms as APEO itself. Eventually, the degradation products may be completely degraded, but this only happens very slowly and only when placed in oxygen containing (aerobic) surroundings. They may have endocrine disrupting effects on living organisms. Even though the use of APEO is declining, APEO and its degradation products occur often and in somewhat high concentration in sludge from wastewater treatment plants, while low concentrations of these substances may occur also in the cleansed wastewater. APEO has been found in soil and aquatic environments in concentrations, which might lead to unwanted effects such as absorption of these substances into eatable plants, as well as bio-accumulation and toxic impact on living organisms. Because of the toxicity of the degrading product, APEOs have been eliminated gradually in cleaning products. In 1987, the Association of Danish Cosmetics, Toiletries, Soap and Detergent Industry (SPT) made a voluntary agreement with The Danish Environmental Protection Agency (DEPA) to begin a phase-out of APEO. The agreement included only nonylphenol ethoxylates (NPEO). According to information now received from the industry also octylphenol ethoxylates have been eliminated. APEO can be found on DEPA’s list of undesirable substances and NPEO is on the EU priority list of potential endocrine disruptors, cat.1. The use of nonylphenol and nonylphenol ethoxylates is in the EU framework regulated by REACH, Annex XVII No. 46 a and b. The substances must not be used in cleaning products, cosmetics or personal care products at concentrations greater than or equal to 0.1%. Nonylphenol is classified as harmful when inhaled, as corrosive and harmful to aquatic organisms, and the substance may have long-term hazardous effects in the aquatic environment. Octylphenols and octylphenol ethoxylates are undergoing risk assessments in the EU. A voluntary agreement states that APEO should not be used in new products, but the substances are not banned in ‘old’ products in the EU. In Denmark NPEO should not be used at all according to the agreement. APEOs do not require labelling. Cationic surfactants used today are often quaternary ester compounds. The toxicity of these towards aquatic organisms is quite similar to that of other synthetic surfactants. They are degradable under aerobic conditions.

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KOMPAN Interview with Mr Jesper Egelykke, Chief Supply Chain Officer Kompan is a manufacturer of playground equipment. They used a two-component epoxy filler to repair holes in plywood sheets, but substituted it with a water-based filler in powder form.

NEW EXAMPLES – FROM DENMARK AND ABROAD Substitutions take place constantly, both in companies and in public institutions. Below are presented new substitution examples, both from Denmark, Europe, and the USA. In the USA a programme was launched in 2006 with the aim to have large companies reducing their emissions and product contents of longchain perfluorinated chemicals (LCPFCs), including perfluorooctanoic acid (PFOA) and 42

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Kompan has outsourced their Danish production to the Czech Republic, and the company no longer uses plywood sheets in their products, but high-density polypropylene sheets. Thereby, this problem is no longer relevant.

perfluorooctanesulfonic acid (PFOS). LCPFCs are used in many production and industrial contexts and they are toxic, persistent, and accumulate in animals and humans. So far, the result is that four of eight companies - Daikin America Inc., DuPont, 3M/Dyneon, and Solvay Solexis have attained the intermediate aim. This aim is a decrease of emissions and product contents of 95%, and in addition the companies have developed more than 150 substitute chemicals. The ultimate aim is to completely phase out LCPFCs by 2015.

Facts on epoxy filling Epoxy filling is a two component epoxy-based material containing a number of substances carrying potential health risks. An epoxy compound can be seen as internal ether formed by two juxtaposed groups of alcohol. O

The simplest epoxy compound has the following formula: CH3

CH3

Epoxy compounds are extremely reactive. They easily enter a polymerisation process with other compounds – e.g. polyvalent aminos (compounds that have more than one amino group in the same molecule). When the epoxy is mixed with the hardener (the polyamine) the polymerisation will start, and the substance will start to harden. NH2

Epoxy filling contains the following hazardous substances:

CH

1.

3-aminomethyl-3,5,5-trimethylcyclohexylamine CH3

2.

trimethylhexamethylene-diamine

CH2

CH2

CH3

CH2

CH3 CH2 – NH2

H2N - CH2 - CH2 - CH2 - CH2 - CH2 - CH2 - NH2 CH2 OH

3. Benzylalcohol 4. Bisphenol-A-diglycidylether (epoxy compound) O

CH3

CH2 • CH • CH2 • O

C

O O • CH2 • CH • CH2

CH3

5. Salicylic acid

COOH OH

The substances listed above are classified as follows: 1 and 2 are both corrosive and may cause allergic reaction when absorbed through the skin. 3 is harmful. 4 is irritant, may cause allergic reactions when absorbed through the skin and is dangerous for the environment. 5 is harmful. Epoxies may be the cause of allergies for people working with the substances. Therefore anyone working with these substances must take special precautions – e.g. special training. The same goes for isocyanates and polyurethanes (see earlier facts box).

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There is also a large potential for substitution in construction materials. Construction Specialities has introduced a “healthy chemicals” strategy, after becoming aware of the problems associated with toxic waste. The substitution project was motivated by the desire to reduce quantities of toxic waste. Customers also demanded non-harmful products, for instance from Kaiser Permanente, who has the precautionary principle as part of their “safer alternatives” policy. Demand for and use of “green chemicals” is in general on the increase in the business to business trade. One example of this is Nike who has focus on using less dangerous chemicals in their production, and another example is Staples, who has developed a list of dangerous chemicals they wish to remove from their products. One such chemical is PVC that has already been removed from Staples’ packaging materials.

A green procurement policy is introduced in many places setting up procurement rules concerning contents and emissions of chemicals. A green procurement policy entails also that in your procurement you prioritize the respect for the climate and the environment. This means that you may choose procurement of IT equipment where waste disposal and energy consumption are taken into consideration, greener detergents, hospital equipment without endocrine disrupting substances, procurement of cars with particle filters, or ecofriendly energy purchase prioritizing wind or biofuels. In Cologne in Germany rules have been introduced for the procurement of the categories of toys, furniture, and sports equipment for municipal facilities, particularly kindergartens and primary schools. Banned chemicals

ELECTRONICS

THE COUCH

WOODEN FURNITURE PS

BF

Phthalates

Phthalates

BF DS

FA

BF

ELECTRIC CORDS Phthalates

FA

THE FLOOR Phthalates

PS

Figure 1 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. 44

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Facts on long-chain perfluorinated chemicals (LCPFCs) – also called perfluoroalkyl acids (PFAS) – including PFOA and PFOS The two most well-known LCPFCs are PFOS (Perfluorooctanesulfonic acid) and PFOA (perfluorooctanoic acid). F

F

PFOS

F

F

F

F

F

SO3H F F

F F

PFOA

F

F

F

F

F

F

F

F

F

F

F

F

F

F

F

F

F O

F OH F

F

F

PFOS is a perfluoro-C8-alkyl chain. The harmful effects of PFOS are so great that it July 2008 was placed on the restricted substances list (annex XVII in REACH), and can only be used for very specific purposes in the EU, such as fire fighting foam and aviation hydraulic fluids as well as in certain photographic processes. It used to be applied in a large number of industry and consumer products for impregnation of clothing, furniture cloth, and carpets. PFOS is also covered by the Stockholm convention, which is a voluntary agreement aiming to reduce amounts of POPs (persistent organic pollutants) in the environment. PFOS and PFOA are found everywhere in the air, soil, sediment, groundwater, rain and surface water, as well as in animals and humans. They are not lipophilic and do therefore not accumulate significantly in fat tissue in the body like other persistent organic pollutants, but are bound to proteins. Human exposure to PFAS primarily happens in the indoor climate. Substances come from impregnation of clothing, shoes, furniture, and carpets and in the form of dust released in wear of materials. Indoor air concentration of PFAS is around 3 ng/m3, which is 25 – 100 times higher than outdoors. Most people have PFAS in their blood where it binds to proteins and may accumulate in blood, liver, kidney, and spleen, and for some compounds in testicles and cerebral tissue. The substances are regarded as being moderately acute toxic, but in repeated exposure they are suspected of having properties similar to oestrogen and may cause cancer and congenital malformation with mammals. In animal experiments PFOS has caused cancer of the liver, while PFOA has caused testicular cancer. In addition, they are toxic to organisms living in water and may have long-term effects on the aquatic environment. There is no regulation in the field of PFOA despite the fact that it is suspected of many of the same harmful effects as PFOS. It appears on the SIN list due to the fact that it is carcinogenic and has endocrine disrupting properties, is persistent, and has been found to accumulate in humans and the environment.

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Facts on azo dyes Azo dyes are a group of synthetic dyes that all contain the so-called “azo group”. Azo compounds are compounds with the functional group of R-N = N-R ', where R and R' may be either aryl or alkyl.

R N

N R'

Azo dyes come in ten different dyes that are authorised in limited amounts in a large number of foodstuffs in the EU. It is not permitted to import, sell, and use a specific blue azo dye, azo dyes that may release carcinogenic substances, and certain goods containing azo dyes. The dyes just like all other additives must be labelled on the food they are used in. According to the Regulation on food additives 1333/2008/EC there are additional requirements for labelling of five azo dyes and 1 non-azo dye as from 20th of July, 2010. The dyes in question are: • E 102 Tartrazine • E 110 Sunset Yellow FCF • E 122 Azoruby

• E 124 Ponceau 4R • E 129 Allura red • E 104 Quinolin yellow (non-azo dye)

Food containing the dyes must be marked with the text: “may have an adverse effect on activity and attention in children”. They are all suspected of causing allergy symptoms such as hay fever, nettle rash, diarrhea, and asthma. Tartrazine, Sunset Yellow, Azoruby, and Ponceau 4R can also cause hyperactivity in children. The ban on import, sale, and use of azo dyes follows from Annex XVII, No. 43 of REACH.

Facts on formaldehyde At room temperature the substance appears as a toxic gas with a sharp, biting odour. Formaldehyde is used, among others, as an ingredient in synthetic materials that are used as preservatives in a number of construction materials. These materials release formaldehyde slowly to the surroundings and may thereby be concentrated in the indoor environment. In addition, the substance is used as a preservative in products for personal care and in textiles. Formaldehyde is carcinogenic by inhalation. It appears on the Danish EPAs list of undesirable substances, the SIN list, and on EU list of harmonized classification.

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include Bisphenol A in all categories and some phthalates, PAHs (polyaromatic hydrocarbons), and heavy metals in other categories. Emissions from wood products and textiles also have their own set of standards, and furniture made from PVC is banned. A green procurement policy contributes to increased demand for alternative products that are less harmful to health, and development of such products is thereby accelerated. At the same time it is a bonus for occupational health and indoor climate, health, and the environment.

dren aged 0-6 years must be without phthalates, brominated flame retardants, health hazardous heavy metals, organic solvents, carcinogenic azo dyes, formaldehyde, and perfumes and aromas. Toys bought for children aged 6-14 years must be without allergenic perfumes.

In Denmark measures are also being taken to enhance green procurement. The Ministry of the Environment has joined forces with six local authorities in the so-called “Partnership for Public Green Procurement” committing the local authorities to make an extra effort for the environment through their procurement. The measure includes targets that cars in the municipal home care have the lowest possible fuel consumption and the best possible particle filters, all packaging must be free from PVC and phthalates, and all toys bought for chil-

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MELITEK A/S Interview with Jesper Laursen, Business Manager MELITEK has for more than 20 years supplied material technology used to successfully replace soft plasticized PVC in medicinal applications such as infusion-, dialysis- and nutrition bags and more recently in medical device applications such as infusion- and transfusion sets, suction and urine catheters and different types of collection bags. Their materials are used by several original equipment manufacturers (OEMs) supplying these type of PVC free products in Europe and recently also in China where there also is a strong interest for PVCfree medical devices. Based on their extensive experience in offering PVC-free material solutions to the healthcare market, they have entered into two different EU funded projects aiming to develop and demonstrate that replacement of soft PVC used in blood bags is possible. So far, blood bags have proven to be the most difficult area for substitution of PVC and phthalates.

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The ‘PVCfreebloodbag’ project funded under EU Life+ program is aiming to show that PVCfree technology is a possible alternative for blood bags. A consortium consisting of Karolinska University Hospital in Stockholm and a group of companies that together build a complete supply chain from raw material compound to finish bags systems, have joined forces in the project. The project website is www.PVCfreebloodbag.eu. In another parallel project, ‘SafeBlood’ funded under Eurostar program, MELITEK is attempting to develop a new modified material that will have enhanced properties for blood storage. In this project they work together with the Danish Technological Institute and Rigshospitalet in Denmark to develop and evaluate the new enhanced material. They also partner with Haemotronic in Italy that is a producer of blood bags, -components and -tunings, and who has a long history supplying PVC-free systems to large OEMs in the medicinal industry. The main challenge in substituting soft PVC in blood bags lays in the fact that the key manufacturing technologies used to produce PVC blood bags needs to be changed to different

production technologies. This is why the consortium in both projects is teamed up with companies that have vast experienced producing PVC-free products for other demanding healthcare applications. Thus overcoming the technology shift in manufacturing via the partner companies. The project challenges are at the same time the conservativeness in the industry producing blood bags, along with a positive side effect of DEHP plasticizer. The effect is that DEHP leaches from the PVC, and that has a preservative effect on the red blood cells – thus giving it a longer shelf life. It has however been found in the early work in the PVCfreebloodbag project, that the shelf life for the red blood cells in PVC-free blood bags is likely not significantly shorter and can further be improved with additive solutions used in the blood bags.

years proven their merits in other medical applications. Combining the know how from the hospitals with partners that together build a complete supply chain, they think their chances will be good to overcome the challenges in replacing soft PVC and DEHP in blood bags. At the same time, there is an increasing demand for PVC-free products in the medical sector globally that will allow ‘first movers’ to gain good market share while offering improved products with better eco-profile and without use of harmful plasticizers (i.e. PVC-free material NOT containing substances listed on EU candidate list).

MELITEK has entered these two projects as they strongly believe that time is mature to replace soft PVC in blood bags and as their polyolefin based materials have already for

Facts on phthalates in medical devices Studies have found metabolites of phthalates in the urine from newborn babies hospitalized in intensive care units, and phthalates and their degradation products (metabolites) are found generally in urine, blood, umbilical cord blood, semen, mother's milk, uterine tissue, and amniotic fluid. The regulation of phthalates in medical devices is found in the directives on medical devices 93/42/EEC, 90/385/EEC, and 98/79/EC. These directives will be recast in 2012. Medical devices containing the phthalate DEHP are subject to labelling. In addition, it is not allowed to use DEHP in toys and articles for small children in the EU (1999/815/EC). DEHP is on the candidate list, the EU priority list of potential endocrine disruptors, and the SIN list. See fact box page 16 for more information on phthalates.

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SUBSTITUTION IN HOSPITALS Westfriesgasthuis (Gavin Ten Tusscher)(NL), Karolinska University Hospital (S), Sygehus Sønderjylland (DK) (Torben Mikkelsen). PVC materials containing phthalates (plasticizers) are increasingly avoided in medical devices. It has been known for 30 years that phthalates are released from PVC and thereby introduced into patients getting in contact with the products. Products are, among others, blood bags and tubes, catheters, and feeding tubes and mixing bags. Particularly bis(2-ethylhexyl)phthalate (DEHP) is used in concentrations up to 40-60 %. DEHP is suspected of damaging the unborn child, disturbing reproduction, harming various organs, and having endocrine disrupting effects. The most vulnerable persons are premature infants, infants, and children, as they are still developing and are particularly vulnerable to endocrine disruption. There are many alternative products on the market, and hospitals around the world are becoming increasingly aware of the problems. Many choose to substitute products containing

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phthalates with phthalate-free equipment however many have not yet done so. One example of a company having developed phthalate-free tubes is the medico company Gambro making products for diabetes treatment (kidney and liver dialysis) and other illnesses. They produce phthalate-free haemodialysis equipment using DEHA (diethyl-hexyl-adipate) as the plasticiser. The price of the blood tubes is the same as for products containing phthalates as the company has lowered the price along with higher demand and production. The phthalate-free equipment is radiated with electrons by contrast to the products containing phthalates, which are subjected to vapour sterilization. Gambro states that the sterilization method plays a major role in many hospitals and that vapour sterilization is preferred. The company is therefore working on the development of a phthalate-free tube that can resist vapour sterilization. The hospital Westfriesgasthuis in the Netherlands has chosen to set up an almost PVC and phthalate-free children’s section (apart from blood bags, see section on MELITEK). This has been possible without extra costs for the section.

At the neonatal section at Sygehus Sønderjylland in Denmark there is also much focus on phthalates. All products coming in contact with the newborn have been studied and phthalate-free products have replaced products containing phthalates. Originally, the frontrunner was an environmental employee and today the section has still large focus on phthalates in its procurement. Phthalate-free products include: intravenous (IV) catheters, IV administration sets, IV tubes, feeding tubes, gloves, pacifiers, and bandages. Karolinska University Hospital in Sweden has had focus on phthalates in medical devices since 2003, when a mapping was made of the use of soft PVC products in the various sections. In the phase-out period first priority was to replace PVC containing phthalates in products used over long periods in the most vulnerable groups of patients, including premature infants and dialysis patients. Substituted products include gloves, haemodialysis equipment, intravenous bags and tubes, urine bags, feeding tubes, and catheters.

Along with increasing demand, producers of alternative products can lower their price so that it does not entail extra costs for the hospitals to change to more safe alternatives. In Denmark this is supported by the fact that a tax on PVC and phthalates has been introduced amounting to DKK 2/kilogram of soft PVC and DKK 7/kilogram of phthalate. This tax helps balancing the price of products containing phthalates and alternative products. The tax was introduced in 1999, and a study from the Danish Environmental Protection Agency and the Ministry of Taxation estimated from the magnitude of the yield that the use of phthalates decreased by 15% from 2002 to 2004. A higher tax on phthalates would support the substitution processes for phthalates and PVC even more. Phthalates are still an issue for sewage sludge since the contents of phthalates are in some cases too high for sludge to be spread on agricultural soil. If so, sludge is incinerated and nutrients, particularly phosphorus, are wasted.

4 Into a vein HAZARDOUS CHEMICALS CAN BE SUBSTITUTED

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BISPHENOL A SUBSTITUTION Bisphenol A (BPA) is a chemical that is primarily used in combination with other chemical products in the manufacture of plastic products and resins. BPA is primarily used in the production of polycarbonate, which is used for plastic bottles, food containers, roof windows, medical equipment, plastic tableware, and baby bottles. In addition, BPA is used in the production of epoxy varnish, which is used on the inner side of beverage cans for sealing of the top of the can and as a sealing of the inner side of food cans and tubes. The purpose of this is to avoid migration of metals to the food. BPA is also used in thermo paper, which is used for till receipts and fax paper. In several countries other materials are increasingly being used to replace BPA in cans

and other tinned goods. In the 1990s manufacturers in Japan started on a voluntary basis to use polyester coating and only use BPA as the underlying adhesive. In this way contents of BPA in foodstuffs and beverages fell significantly. Green Century Capital Management, a consultant on environmentally friendly investments, made a survey among 20 major food manufacturers in the USA about their use of BPA in food containers. Fourteen replies were received, and four companies stated that they wished to make an effort in the field of substitution.

Facts on bisphenol A Bisphenol A is a solid, white substance obtained by recombining phenol and acetone catalysed with hydrochloric acid. CH3

Bisphenol A

HO

OH CH3

BPA has an effect on the body similar to oestrogen and thereby falls under the category of endocrine disrupting substances. Experiments on animals indicate disturbances in reproduction, cancer, learning and behavioural disabilities, diabetes, and cardiovascular diseases. Almost all people in the developed world are exposed to BPA at a low, but constant level. BPA is permitted for use in food packaging in the EU (Regulation 10/2011/EU). In January 2011 the Commission adopted Directive 2011/8/EU with an EU ban on the manufacture of baby bottles containing BPA and a ban on import and sale in the EU of such products. BPA is on the EU priority list of potential endocrine disruptors and on the Danish list of undesirable substances, and the Danish Veterinary and Food Administration has introduced a temporary national ban on BPA in products aimed at children aged 0-3 years. The ban covers baby bottles and sippy cups and materials destined for contact with food for children aged 0-3 years. In addition, in October 2011 France chose to introduce a temporary national ban on BPA in all materials in contact with food, including packaging.

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The American producer of Eden Organic Beans has since 1999 used cans with a coating made from a mixture of plant based oil and resin. This was done on a voluntary basis and means extra costs of 14% for their cans. The new can is not yet used for tomatoes since this application has not yet been approved. In March 2009 Hain Celestial launched a BPAfree container for breast milk substitute, and the company is continuously developing and testing new coatings. Special efforts are made to find BPA-free packaging for baby food. Heinz no longer uses BPA in cans for baby food, and the company will remove the substances from glass lids for baby food in England. Heinz has also been involved in research and hopes to remove BPA-containing varnish from its other cans.

Alternatives to polycarbonate include high density polyethylene (HDPE), metallocene, polypropylene (PP), polyethylene (PE) naphthalene, and polyethersulfone. American Eastman Chemical Co. will, among other things, use their product ‘tritan copolyster’ to substitute polycarbonate in equipment for blood therapy and management of blood - such as haematology filters and containers. The company states that tritan copolyester has a good transparency, is resistant to chemicals, has good processing properties, and eliminates the need of hardening. Furthermore, substitution of BPA-containing polycarbonates with tritan copolyester can take place without major alterations in the production.

Nestlé has launched several projects to find alternatives to BPA.

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BOSTON SHOECARE Interview with Katarina Möllergren, Product Manager Boston Shoecare, as the name indicates, produces shoecare products. Products protecting against dirt and water (impregnation agent) often contain fluorinated compounds such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). These substances are persistent and accumulate in humans and the environment. Back in 2007 Boston shoecare developed its first products without any contents of PFOS and PFOA, and the use has now been completely phased out. In 2007 there were vivid discussions in Sweden about fluorinated compounds after a press release from a Swedish environmental NGO stating the harmfulness to human health and the environment of these substances. Boston had already developed the new products and they were launched shortly after. Boston now uses perfluorobutanesulfonic acid (PFBS), which is a short-chain perfluorinated compound. Boston bases their choice on results from studies indicating that the bioaccumulating properties and the hazardousness of the perfluorinated compounds increase along with the length of the alkyl chain. PFBS with its four carbon atoms thereby has a shorter chain than PFOA and PFOS with their eight 54

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carbon atoms. As an extra security for their customers the PFOA/PFOS free product has been designed in a way that it forms large particles in use. This means that the substance is less volatile, thereby decreasing the risk of inhalation. The company also studied the option of replacing PFOA and PFOS with silicone compounds. This option was however not found to give as good an impregnation and silicone behaves differently on textiles/shoes. Boston Shoecare has also developed a waterbased impregnation that is PFOS and PFOA free. In this way the company avoids using solvents, which are found in other types of products. The only difference in use is that this impregnation must dry 6-8 hours before use, whereas products based on solvents do not need to dry. Boston Shoecare finds that it is mostly young consumers who are aware of the issues associated with PFOA and PFOS, thus wishing to avoid the substances. In addition, it is mostly distributors who wish to sell harmless products - they have not felt the demand directly from customers. For more information about PFOS and PFOA, see facts box page 45.

5 SUMMARY More and more companies see the advantages to be gained from substitution. Many companies substitute to maintain or create a green image, while others do it to be one step ahead of legislation. When a chemical product gets bad mention and comes into focus in the media companies may see a large benefit from using the option of substituting away from the mentioned chemical, replacing it with a less harmful substance. Thereby they attract the growing consumer group that does not wish exposure of themselves or nature to unnecessary potential harm. However, it may be a long and costly process for a company to substitute, and the end products may turn out to be more expensive than the original ones. By contrast, the company will be in a good position in the market when legislation is introduced most often at EU level. At the same time, the company may solve an occupational health

problem and place itself at the forefront of environmental protection. For these reasons we see more and more innovative companies at the cutting edge of developments and keen to produce safer products both through the production processes and the finished products. However, it is still necessary to stimulate these developments. We are still exposed to many chemicals that may harm human health and the environment or that are poorly studied, which means uncertainty about their potential harmful effects. As an EU member Denmark cannot just introduce a ban on dangerous substances. But the above-mentioned substitution may take place, among others, through the introduction of a green procurement policy where the State, regions, and the local authorities set up

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requirements for the many goods and services procured - in Denmark alone this amounts to Euro 36 billion/year. Green procurement is already the official policy, but in practice there is still very large scope for improvement, since the decisions are left with the purchasers of the different institutions. The more environmentally friendly products will often have a higher price, but be beneficial in the long-term perspective. However, it is difficult for institutions to pay respect to this issue, since they have to follow a tight budget every year. Several companies having spent resources on substitution complain about the lack of interest from the customers, especially public institutions. Another way of stimulating substitution is to tax specific dangerous chemical substances. However, this instrument has not been in use in Denmark since the left-wing government in 1999 taxed PVC and phthalate plasticisers. Such taxes must be approved in the EU Commission, but if they do not discriminate imported products against domestic products, the Commission will normally accept such taxes.

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6 READ MORE THE ECOLOGICAL COUNCIL www.ecocouncil.dk • REACH og substitution i danske virksomheder (REACH and substitution in Danish companies), 2006 (in Danish) • ”Hazardous Chemicals Can Be Substituted”, 2006 (published in Danish and English) • Om bromerede flammehæmmere (About brominated flame retardants), 2006 (in Danish) • REACH – a leap forward for industry, made for Nordic Council of Ministers, 2004 • Kemikalier, miljø og sundhed (Chemicals, environment, and health), 2007 (in Danish) • Virkemidler til bæredygtig udvikling (grønne skatter, offentlig grøn indkøbspolitik og miljømærkning) (Instruments for sustainable development (green taxes, green procurement policy, and ecolabelling), 2002 (in danish) REACH CANDIDATE LIST http://echa.europa.eu/web/guest/candidatelist-table REACH AUTHORIZATION LIST http://echa.europa.eu/web/guest/addressingchemicals-of-concern/authorisation/recommendation-for-inclusion-in-the-authorisationlist/authorisation-list

REACH REGULATION http://eur-lex.europa.eu/LexUriServ/LexUriServ. do?uri=OJ:L:2006:396:0001:0852: EN:PDF SUBSPORT www.subsport.eu DANISH ENVIRONMENTAL PROTECTION AGENCY www.mst.dk • White Paper on Strategy for a future Chemicals Policy • How are chemical substances and products regulated DANISH WORKING ENVIRONMENT AUTHORITY www. at.dk Providing guidance, among other issues, on work with substances and materials ASSOCIATION OF DANISH COSMETICS, TOILETRIES, SOAP AND DETERGENT INDUSTRIES www.spt.dk Publishing, among other things, the chemicals database of the sector

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ASSOCIATION OF DANISH COLOUR AND PAINTS INDUSTRIES www.fdlf.dk Providing guidance, among other things, on the MAL code system THE INTERNATIONAL CHEMICAL SECRETARIAT, CHEMSEC www.chemsec.org

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WARNING AND PRIORITY LISTS

Candidate List A part of the EU chemicals legislation REACH. This is a list of substances of very high concern (SVHC). When chemicals are included on the list, manufacturers and suppliers have to meet certain requirements. This includes consumers, upon asking, having a right to be informed within 45-days if a substance from the candidate list is contained in a given product. Authorization List A part of the EU chemicals legislation REACH. In principle, the substances on the authorization list are banned, but if the producers get a special authorization, they can use them. The first substances will be banned in 2014. Annex XVII (Restricted Substances List) A part of the EU chemicals legislation REACH. When substances are included on this list, it means either it is forbidden to produce them, promote them or use them. Annex XVII brings together a series of prohibitions that were previously found in various directives and regulations, but also new prohibitions have been added since REACH was adopted. SIN-list The list is the environmental organization ChemSec’s (The Chemical Secretariat) bid at which substances should be on the list of candidates - as they fulfill the criteria for inclusion in the list, see www.chemsec.org / list EU list of harmonized classification (previously called ‘List of Hazardous Substances‘) Contains substances which are assessed and classified together in Europe. The list contains over 8000 chemical substances and substance groups. The Danish Environmental Protection Agency’s (EPAs) list of undesirable substances List of substances used in large quantities and where the EPA believes that in the longer term the use should be limited or stopped. The Danish EPAs list of effect A list of especially health and environmental contaminants, whereof those used in large quantities are also found on the list of undesirable substances. EU priority list of potential endocrine disruptors A list of substances to be further studied in detail for their endocrine disrupting effects. Substances are divided into four categories; Cat. 1 substances: Clear evidence in animal studies of endocrine-disrupting properties Cat. 2 substances: Potential endocrine disruptors. Cellular and animal studies indicate potential for endocrine disrupting properties Cat. 3a substances: Has not shown hormone-disrupting effects in experiments Cat. 3b substances: No data or insufficient data to rule out endocrine disrupting properties

HAZARDOUS CHEMICALS CAN BE SUBSTITUTED – DEVELOPMENTS SINCE 2006

More and more substances are studied and classified as hazardous to health or the environment, and an increasing number of companies choose to replace potentially dangerous substances - this is called substitution. Substitution is beneficial to both the environment and humans, but also for the company itself, as it can foster or create a green image and be innovative and at the forefront of development and legislation. This publication is a follow up to "Hazardous chemicals can be substituted" from 2006. The EU chemicals legislation REACH and the concept of substitution are explained, and Danish companies that have gone through a substitution process, report on their experiences and what has happened since 2006. Companies have, for example, replaced heavy metals, industrial greenhouse gases and endocrine disrupting phthalate plasticizers. Substitution does not only occur in Denmark, so also foreign examples are included in the new edition. The various chemicals, their effects and relevant legislation are presented in fact boxes, and warning and priority lists are explained. Substitution can be an extensive process and this publication can be used as inspiration for companies as well as a source of information for all other interested parties.