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					Green Chemistry and the Consumer
Newsletter
Issue 5 - November 2005
REACH - now the work begins
The most important chemicals legislation of modern times is progressing through the European approval labyrinth and will come into force in 2007. At the time of writing REACH has passed its first reading in the European Parliament by a comfortable majority although many NGOs believe that it has been unacceptably diluted (notably through a relaxation on registration requirements for some lower volume chemical substances). This is, however, only the beginning of the approval process (with further stages including approval by member states) and further changes can be anticipated before its progress to complete. Whatever its precise final form it is clear that the chemical world - and that is the world we all live in - will be different as a consequence of REACH. An unprecedented level of chemical testing with an associated enormous quantity of information about chemicals, a substantial and vital new European Chemicals Agency, a likely significant degree of ‘partnering’ to share information and costs and the inevitable authorisation, control and probable prohibition of numerous chemical substances, will dramatically change the chemicals landscape in Europe and, by extension of the rules to imported substances and other consequences, in the rest of the world. It is unfortunate, although perhaps inevitable, that these critical final phases of the REACH approval process are resulting in extreme views being expressed and an apparent polarisation of the stakeholders. I have attended two recent meetings which gave me hope and despair; at a meeting in Copenhagen on Chemical Safety organised by International Chemical Secretariat, I was delighted to hear so many of the invited delegates agree that Green Chemistry and specifically research and development of greener products, is the most important issue we face today. In contrast, at a meeting organised by Envirowise in England, I heard views reminiscent of those voiced repeatedly over the years when REACH has been debated, that the added burden of legislation and associated costs will drive the chemicals industry from Europe. The media has suddenly woken up to the new legislation but sadly many articles in the newspapers have concentrated almost entirely on chemical hazards with emotive reporting about ‘toxic’ chemicals being found in the blood of children and claims that some politicians and industry associations are threatening our health by either their inaction or by their causing dilution of REACH. It’s a pity that with chemicals now more in the public eye than ever before, the media can take advantage of the debate and topicality to produce a series of scare stories. Excuse my naivety, but wouldn’t it be wonderful if we could use the current high profile of chemicals to make people more aware of the intrinsic role chemicals play in everyone’s lives, to show that the authorities (encouraged by NGOs and other stakeholders) are Breakthroughs now seeking to make their essential role less risky to people and the Greener Fabrics to Dye for: Making natural dyes more effective 2 environment, and that more than ever we need research and Reducing the complexity of metal complex dyes 2 stakeholder incentives to give us new products that are ecoNovel eco-friendly binders for pigment printing 2 compatible and provide all the healthcare, subsistence and lifestyle Sustainable Furniture 3 Green Materials from Soy 3 benefits which a growing number of people on the planet require.
Biodegradable Surfactants Preserving food naturally

We must redouble our efforts to increase the amount of research on greener chemical products - by showing academics the potential for 5 applying their skills to a vital and exciting area and by persuading the 6 funding agencies to set up appropriate funding initiatives. Greener substitutes must have green lifecycles (we must be wary of an News and Views Risk Assessment and the Proactive Management of apparently greener chemical that actually hides unacceptable process Chemicals through the Supply Chain or raw material steps) but also come with a good degree of
Focus Articles Flame Retardants - A Burning Issue! From Wax to Riches David Buszard, Chemtura Corporation News Snippets 3rd GC&C Symposium 7 9 10 (Continued on page 2)

4 4

Green Chemistry Solutions for Sustainable Product Supply Chains
1

understanding of their actions - in too many cases today we face the challenge of finding replacements for important substances whose role is not well understood. For example, it is quite likely that we will replace chromate as a primer before its mechanism of action was ever understood! We must also find ways to convert the research to the supply chain and ensure that all of the stakeholders are aware of the innovative opportunities. The Green Chemistry and the Consumer project, which Louise leads with such diligence, enthusiasm, intelligence and dogged determination, is our small contribution to make this happen but with authorisation likely to impact on one or more substances in a multitude of everyday articles, we must do more! James Clark, York, November 2005

Here we describe some recently reported exciting breakthroughs in research on greener chemical products

We include for each of the inventions a mini lifecycle assessment (LCA) based on our knowledge and understanding of the science*

Greener fabrics to dye for
We live in a colourful world of textiles, with the clothes we wear and the soft furnishings in our homes. The dyeing of fabrics requires the application of a wide variety of chemicals, some of which have hazards associated with their use and disposal. The volume of research on more environmentally friendly dyes and dyeing processes is however beginning to increase, as is highlighted below in three recent papers from the journal Dyes and Pigments.

dyed cotton and therefore improves their properties as textile dyes. D. Cristea & G. Vilarem, Dyes and Pigments, 2006, 71, 39 Feedstocks
Combines natural dyes with (some) natural additives

Process

Product

~
Salt waste is produced

~
Encouraging preliminary results

Making natural dyes more effective
Natural dyes have been around since prehistoric times but their use has declined since the discovery of synthetic dyes in the mid-18th century. However in recent years interest in natural dyes has heightened due to increasing demands on manufacturers to produce more environmentally friendly alternatives to petrochemical derived dyes. One main issue associated with the use of natural dyes in the colouring of textiles is their tendency to have poor to moderate light fastness. Scientists in Toulouse have been studying the ability of certain additives to improve the light fastness, and hence effectiveness, of three natural dyes – madder, weld and woad, which were used to produce red, yellow and blue colours respectively in Europe, America and Asia until the 19th century. UV absorbers, used to prevent photodegradation of polymeric materials by UV-rich sunlight and artificial light, and antioxidants, used to retard autooxidation and prolong the useful life of oxidisable organic materials, were applied to the dyed cotton yarn before determining the rate at which they fade. It was found that the natural additives Vitamin C (ascorbic acid) and gallic acid (found in sumach, tea leaves, oak bark and many other plants) were most effective in reducing the rate of fading in madder, weld and woad2

Reducing the toxicity of metal complex dyes
Metal complex dyes have an important role in the textile industry and are frequently used for dyeing dark shades on wool and nylon. The metal, typically chromium [Cr(III)] or cobalt [Co(III)], acts as a mordant (which comes from the Latin word meaning ‘to bite’). The metal links or ‘fixes’ the dye molecule to the fabric and improves the colour fastness properties of the dye in particular to light and washing. Due to the known ecological and toxicological issues surrounding the use of chromium and cobalt, research has been carried out into their substitution with more environmentally benign metals such as iron and aluminium. A group of scientists at North Carolina State University are continuing to build upon their previous success in developing iron-complexed azo and formazan dyes, which exhibit lower toxicity than the corresponding Cr and Co analogues. (Azo and formazan dyes are synthetic dyes that contain the azo functional group [-N=N-]). The new azo and formazan dye ligands (the term given to the molecule that complexes with the metal) were synthesised in good yields and readily form 1:2 iron complexes with good colour strengths and light fastness. However to completely assess the ‘greenness’ of these dyes, green chemistry metrics would need to be applied to the synthetic route

*These are initial views and are by no means comprehensive. Thorough investigation would obviously be necessary to determine the true environmental impact
at each of the stages in the lifecycle.

employed to make them. M. Szymcyzk et al., Dyes and Pigments, 2006, 71, 206 Feedstocks Process Product

Little difference in resources compared to traditional

~
Reduces some of toxic inputs but synthesis still complex & involves hazardous substances

~
Improvement in terms of metals but complex organics have unknown ecofate

Novel eco-friendly binders for pigment printing
Pigment printing is the oldest method of printing and also one of the most important and widely used methods of dyeing textiles. Its main advantage is its versatility as it is applicable to almost all textiles. The use of kerosene or mineral turpentine as a solvent in the process, which is released to the atmosphere during the curing (drying) stage and is rarely recovered, is an environmental concern. The process also requires the use of binders to fix the pigment to the textile, for which formaldehyde is sometimes used. Researchers at the National Research Centre in Cairo and the Institute for Textile Chemistry and Chemical Fibres in Germany have developed novel binders for use in pigment printing that negate the need for volatile organic solvents. The binders are oligomers (polyethylene glycol or glycerol ethoxylate-copropoxylate) that are mixed with water, the pigment dye and other additives to form the pigment paste that is used to treat the fabric. The oligomers solvate the pigment and carry it to the surface of the fabric, where during the curing process the oligomers are polymerised to fix the pigment to the fabric. Using these binders, high colour strengths and good fastness properties were obtained compared to commercial binder for all the fabrics tested including cotton, viscose, wool, nylon 6,6 and polyester, thus providing an effective, versatile and VOC free method of pigment printing all types of textile fabrics. M.M. El-Molla & R. Schneider, Dyes and Pigments, 2006, 71, 258 Feedstocks Process Product

petrochemical resources. They also contain the residual hazardous chemicals such as V O C s a n d formaldehyde, and while this has led to legislative pressure to reduce VOCs in some parts of the world, many of the substitutes are still petroleum-derived leaving major questions over their long-term sustainability. Various bio-based alternatives have been suggested but usually with reduced performance properties. Polysaccharides are perhaps the most promising category of renewable bio-based adhesives and numerous starch-and chitinbased adhesives have been reported but performance characteristics remain lower than is desirable. A collaborative research project involving academic and industrial scientists in the US has led to a new family of microbially derived polysaccharide adhesives. These are characterised by improved performance over other bio-based adhesives including high sheer strengths. Water-tolerance is a limitation and while the researchers show this can be improved with chemical modification, the actual chemistry they describe is not acceptable environmentally and would need “greening”. With such improvements, these adhesives could well be suitable for indoor furniture. (A. P. Haag et al., Int. J. Adhesion and Adhesives, 2006, 26, 177) Feedstocks
Totally sustainable source

Process
Chemical processing involves some hazardous reagents

Product
Products may well be bio-compatible

Green Materials from Soy
The quest for novel, sustainable, biodegradable, but also structurally robust materials is gaining momentum as legislative, consumer and economic drivers build up. Longlasting plastics and composite materials derived there from are likely to become less and less acceptable as landfill sites fill, public pressure and industry demand grows, and oil prices rise. The use of soy as a raw material for construction has a venerable history as Henry Ford used soy plastic to construct various car parts in an effort to demonstrate his belief that ‘farms are the factories of the future’. Seventy years later this view seems more relevant than ever. A group of scientists based at Cornell University and Georgia Institute of Technology in the US have now reported 3

~
Avoids need for traditional solvent but does have new input materials which may need to be made renewable

~
Avoids VOC release but new process hazards would need to be evaluated

?
New materials (polymer/ pigment mixtures) will be released into environment & need to be assessed for ecotoxicity

Sustainable Furniture
Adhesives are an integral component of wood products and the world market is worth several billion €/year. Unfortunately while wood is sustainable, most wood adhesives are based on non-renewable,

new composite materials derived from soy flour and flax resin. Quite cleverly the soy flour’s mechanical properties can be much enhanced by a ‘cross-linking’ reaction with glutaraldehyde, a chemical that is derivable from bio-feedstocks. Materials produced have good mechanical properties (though their longterm stability may be an issue) which, coupled with their sustainable feedstock and green processing credentials, should give them value as structural materials for indoor applications. (S. Chabba et al., Green Chemistry, 2005, 7, 576) Feedstocks
Totally sustainable raw materials including reagents

Feedstocks
Starch-derived and other sustainable starting materials

Process
Chemical reactions involve hazardous reagents

Product

?
Promising but true eco-compatibility needs to be demonstrated

Preserving food naturally
The development of new, safe and naturally derived antioxidants for applications in areas including food is a major goal in green product design. Synthetic antioxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) continue to be widely used despite concerns over their toxicity and long-term availability. Numerous compounds and mixtures of compounds derived from edible and nonedible plant materials have been reported as natural antioxidants. These include substances derived from ginger, peanut hulls and various herbs and spices. Recently, a research group in Pakistan has discovered the antioxidant properties of citrus peel extract. The extracts proved to be effective in preserving corn oil at room temperature and above. Larger quantities of the natural product may be required to achieve the same effect as synthetic antioxidants but the added safety and sustainability of the natural extracts may compensate for this. The chemistry of the preparation of these natural antioxidants could be improved – notably the replacement of VOCs as extraction solvents with for example, supercritical carbon dioxide (which is nontoxic, safe and very easy to remove and reuse) would reduce the overall environmental footprint of the new process and product. (Zia-ur-Rehman, Food Chemistry, 2006, article in press) Feedstocks
Sustainable raw material

Process
Uses benign chemicals

Product

~
Long term stability not yet proven

Biodegradable Surfactants
Surfactants are remarkably ubiquitous substances in modern society being used in common products i n c l u d i n g detergents and many personal care products. Ther e have been several iterations in the improvement of detergents over the years including environmental improvements and especially their biodegradability: the original alkylbenzene sulfonates (LABS) following major pollution problems especially in colder regions where the surfactants accumulated in rivers causing enormous problems for aquatic life. LABs became the major surfactant in the world but the quest to develop more biodegradable surfactants continues. In a new article, a Taiwanese engineering group have reported new surfactants based on dextrins which are saccharides that can easily that can easily be derived from starch. Saccharides are highly biodegradable (they are the natural foods of bacteria found in sewage and untreated rivers). By reacting dextrins with fatty acids and their derivatives, new sustainable and biodegradable surfactants have been formed. They have highly desirable physical properties including low foaming, good wetting and whitening ability, as well as excellent biodegradability. The article describes some chemical transformations that use quite hazardous reagents and the chemical processes will need to be improved if the green credentials of these promising new surfactants are to be enhanced. (H-J. Wang & K-M. Chen, J. Applied Polymer Science, 2005, 98, 711) 4

Process
Some aspects need to be improved including use of VOCs

Product
Expect product to be fully biocompatible

Natural Sources of Antioxidants The food and agricultural products processing industries generate substantial amounts of byproducts rich in phenolic compounds, providing a potentially valuable source of antioxidants. An interesting review of this area in the journal Food Chemistry (N. Balasundram et al., 2005, in press) covers their occurrence, antioxidant activity compared to synthetic antioxidants and potential uses for anyone that would like to learn more.

Focus on Flame Retardants
Flame retardants – A burning issue
Halogenated versus Halogen free.
In recent years the heightening demands of consumer safety and increased fire safety regulations have prompted the widespread use of Flame Retardants (FRs) in many consumer products. In improving the flame retardancy of materials they provide inherent safety to a vast range of items. Their use and application is extensive and ranges from electronic and electrical equipment to fabrics, textiles, wood, plastics and polymers. The safety margin added to a material on incorporation of a flame retardant is significant! The total quantities of toxic gases released from FR protected materials have been shown to be a third of that given off from non-FR products! Flame Retardants provide up to 15 times more available escape time from fires. Damage to materials is considerably reduced as typically 50% less material is consumed by fire when Flame Retardants are used (www.ceficefra.com). The benefits of Flame Retardants are clear, they significantly reduce the number and extent of fires. In short, they save lives and protect property! There are a number of different types of Flame Retardants, which act to prevent the spread of fire by inhibiting the combustion process either by physical or chemical means. The main families of Flame Retardants are based on compounds containing one or more of the following, halogens (bromine, chlorine), phosphorous, nitrogen, (melamines), intumescent systems and minerals. One important distinction exists and that is between halogenated and nonhalogenated. The former have been by far the most commonly used type. Brominated Flame Retardants (BFRs) have traditionally been the most effective, efficient and most favourable on a cost basis. However environmental concerns raised by NGOs prompted an investigation into their environmental and human health effects. Risk assessments on some of the most prolifically used BFRs resulted in the banning of polybrominated biphenyls (PBBs) and penta and octa bromo diphenyl ethers (PBDE and OBDE) under WEEE and RoHS legislation in electronic and electrical equipment. They were found to be persistent, bio-accumulative and toxic. BFRs have been detected in human breast milk, the fatty tissues of polar bears and seals and were found to have potential endocrine disrupting properties in rats. Deca bromo diphenyl ether (DBDE) another member of the BFR family has also received much attention of late, with endless debate as to whether it should be banned along with PBDE and OBDE. It has not been banned as of yet, due to limited evidence of toxicity and health effects. Alongside legislative drivers a number of voluntary Eco labels also exist such as the Nordic Swan, Blue Angel and the European White flower. These prohibit the use of BFRs in various consumer products. So a combination of regulation, market drivers and consumer pressure has prompted an industry-wide move from halogenated FRs to more environmentally and socially acceptable alternatives, principally nonhalogenated. The most widely marketed and available non-halogenated alternatives are based on phosphorous compounds such as phosphonates, phosphinates and phosphorous esters. Although on the face of things they appear to be environmentally more attractive than the halogenated predecessors in that they are not persistent in the environment, they do not appear to accumulate in mammalian tissues or appear to be toxic to human or wildlife, they do have their drawbacks. Limited environmental data is available for many of these new formulations and so their true potential health effects are relatively unknown. They are also less effective than their brominated counterparts and so require far higher loading (40-60% compared with 5-20% for brominated FRs), which can increase their cost. Many producers are reluctant to abandon their proven halogenated FR products for such alternatives due to inherent economic risk and uncertainty over performance. Research and development into novel solutions is ongoing but slow. One such emerging technology is that of nano-composites, materials based on layers of silica clay which are being investigated for their flame retardancy in various widely used polymers and plastics (polyurethane resins for example). Another interesting area is research into polymer siloxanes that may have inherent flame retardant properties. This of course would be ideal as it could potentially eliminate the need for FR addition, avoiding the problem altogether. In the short term it is unrealistic to demand a total ban of halogenated Flame Retardants as there are limited feasible ‘drop-in’ alternatives currently available. It is likely that brominated constituents will be phased out slowly. As new, promising technologies become commercially available BFRs will be replaced. In the near future it will be vital to ensure that there is transparency and information dissemination right down the supply chain from producer to retailer and consumer. Increased awareness of the risks associated with such halogenated compounds, methods of safe handling, use and disposal will be necessary to ensure their adverse environmental and health effects are managed successfully. The matter is a complex one and there is no quick fix, gradual phase out together with continued R&D will be vital. Rachel Cahill, University of York 5

Focus on Wheat Straw
From Wax to Riches
Wheat straw is an abundant and inexpensive coproduct of the agricultural industry. In the UK alone, 10 million tonnes of wheat straw (ca. £20-30/T) are produced annually of which 4 million tonnes have no commercial market. Thus, alternative uses would be Box 1: extremely valuable to the agricultural industry especially when incomes for farming are at a record low. Similar to wood, wheat straw is composed of three major components (cellulose, hemicellulose and lignin - ca 90-95% of material) that form the basis of its physical structure. The remaining part of the plant is comprised of minor non-structural components, commonly named ‘extractives’, which can be extracted using water or organic solvents. Also, close examination of the surface of wheat straw using a microscope reveals tubular wax crystalloids, which act as a vital barrier for the plant in defence against bacterial and fungal attacks. Preliminary studies undertaken at the Biocomposite Centre, Bangor have demonstrated that this wax can also become very valuable to us! Wheat straw waxes extracted by organic solvents (i.e. hexane, benzene, chloroform) have been tested in lipstick formulations and exhibited ideal properties to the cosmetic industry. This is especially relevant considering that the most widely used industrial plant waxes Carnauba wax and Candelilla wax are produced in hot climates. From a UK perspective, the distance such waxes travel and the security of supply mean that such sources of waxes are far from sustainable. In addition, the high volume UK source of natural wax lanolin (sheep wool wax) is currently facing consumer reluctance. Since the BSE breakout, a few very large global cosmetic companies have initiated plans to completely remove all animal derived materials from their products as a consequence of consumer concerns. Consequently, it would be of great benefit to supply natural waxes with the desired performance characteristics from a cheap, readily available and renewable non-animal source, i.e. wheat straw. However, the classical method of extraction presents many disadvantages. Apart from the environmental and toxicological problems of using solvents such as benzene and chloroform, the extraction is unselective co-extracting a large number of unwanted compounds including pigments, polar lipids, and free sugars. Further research carried out at the University of York has showed the tremendous potential of supercritical carbon dioxide as a more selective and environmentally friendly alternative to traditional solvent extraction.

By definition, a supercritical fluid is a substance above its critical pressure (PC) and critical temperature (TC) where the distinction between liquid and gas phases no longer exists. Many substances can be used to perform supercritical extractions such as carbon dioxide, water, ammonia, nitrous oxide and fluoroform to name a few. However, carbon dioxide is by far the most widely used compound as it has the best overall combination of properties, being non-toxic, nonflammable, readily-available (by-products of many processes), can be easily recycled and leaves no
O O
OH

10 µm
Fatty Alcohols

Wax esters
OH

Free Fatty Acids

O

Alkanes
HO

Sterols / Steryl Esters

Typical SEM picture of wheat straw leaf
6

Major chemical compounds present in wheat straw wax

residues. Low impact technology supercritical CO2 offers very attractive extraction properties and is currently employed in a wide range of applications including decaffeination of coffee and extraction of hops for the beer industry. As part of a successful i n d u s t r i a l collaboration with Botanix Ltd, The University of York has re cen t l y scaled up the supercritical carbon dioxide extraction of Commercial plant at Botanix, Kent wheat straw to plant scale (> 75kg of wheat straw). This trial has led to the isolation of over 0.5 kg of wax product that will be further tested in finished product formulations such as lipsticks in collaboration with Croda (a speciality chemical company). This study has also demonstrated that by adjusting the supercritical CO2 conditions, wheat straw waxes can be fractionated into more valuable products. For example, at relatively low pressures, a wax fraction containing high proportions of alkanes ( u s ef u l as i ns e c t Wheat straw waxes semiochemicals, i.e. natural insecticide) can be recovered whereas higher pressures leads to the extraction of a product enriched in long chain aliphatic alcohols so called ‘polycosanols’ (widely used as a ‘cholesterol reducing’ dietary supplement). This process would represent the first step of a single integrated facility (commonly named the Biorefinery) that extracts the high value components and subsequently transforms the Process in Brief residue into ‘platform Wheat straw molecules’ or bioproducts, bio-fuel, • Renewable and bio-energy in • Natural and plantorder to maximize the derived value of the • Readily-available and feedstock. This inexpensive methodology could obviously be applied Supercritical CO2 to other crops or any other process by• Non-toxic products and wastes. • Non-flammable • Readily-available Fabien Deswarte, • Easily recycled Green Chemistry • Leaves no residues Associate, • Selective extraction and University of York fractionation

Risk Assessment and the Proactive Management of Chemicals through the Supply Chain
Dr David Buszard Chemtura Corporation European Brominated Flame Retardants Industry Panel, VECAP Project Director
The risk assessment (RA) of chemicals is a relatively new science. It was introduced into the European regulatory system through the process for the registration of new chemical substances, ELINCS (http://ecb.jrc.it/new-chemicals/), and the Existing Substances Regulation priority lists for risk assessment (http://ecb.jrc.it/existing-chemicals/). So far relatively few chemicals have been through the full process, which covers both human health and environmental assessments*. However the new EU chemical regulations, REACH (Registration, Evaluation, Authorisation, and restrictions of Chemicals ) (http://ecb.jrc.it/REACH/), which are currently under discussion in the Council and European Parliament, will require all chemicals to go through such risk assessments covering not only the chemicals themselves but their downstream uses. Risk assessment is an enlightening process in that it forces chemical manufacturers and users to consider products, processes and applications in a different manner to that which they have previously been accustomed. Following the RA process, manufacturers then need to deal with the consequences of the findings. Decabromodiphenyl Ether (Deca-BDE), an important flame retardant for electrical and electronic equipment, construction products and textiles, has been subjected to a concluded Risk Assessment under the EU Existing Substances Regulation. This was a process that took 10 years with some 588 studies taken into consideration. It was finally concluded in May 2004. No risks were identified by the RA and no restrictions were placed on the use of this chemical. There were concerns though; although Deca-BDE is non-toxic and not bioaccumulative, it is very persistent. This means that when it gets into the environment it doesn’t degrade at any significant rate, it just stays there. There was also evidence that levels in the environment were increasing and it had been detected in certain birds’ eggs at albeit at low levels. Even before the Risk Assessment was concluded the DecaBDE manufacturers began working closely with the *At the time of writing, risk assessment conclusions have been
reached by the EU authorities for 70 existing substances

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supply chain to address this issue. Significant routes for emission were identified particularly for textile applications with lesser ones for other, mainly plastics applications. In response to these findings the brominated flame retardant industry started an ambitious programme aimed at minimising the potential environmental impact of its products. The programme, known as VECAP (Voluntary Emissions reduction and Control Action Programme) (http://bsef.com/product_stew/ vecap/), was developed in partnership with a selected group of downstream users in the UK. It was initially focussed on Deca-BDE in textile applications but has since been extended to all applications and is currently being extended to a wider range of flame retardants. The three main manufacturers of Deca-BDE, Albemarle, Chemtura and ICL-IP, developed a practical process to reduce industrial emissions to the environment through the industry’s trade association, EBFRIP (European Brominated Flame Retardant Industry Panel) in cooperation with Deca-BDE using industries. These BFR manufacturers have committed to implement VECAP voluntarily and jointly with user industries and industry associations such as the Textile Finishers Association, (TFA) and British Plastics Federation (BPF) in the UK, Euratex, PlasticsEurope and European Plastics Converters (EuPC) across Europe. Flame retardants, such as Deca-BDE, give people up to 15 times more escape time when there is a fire. Brominated flame retardants are used in textiles for upholstered furniture, seating in transport, public buildings and domestic furniture in some EU Member States. They are also used in the plastic casing for televisions and other applications to flame retard. According to the UK Government they have saved at least 1000 lives in the United Kingdom in the first 10 years following the introduction of the UK (1988)

Furniture and Furnishings Fire Safety Regulations (Effectiveness of the Furniture and Furnishings (Fire) (Safety) Regulations 1988, Consumer Affairs Directorate, DTI, June 2000). Flame retardants are therefore an important and effective contribution to the safety of modern materials and products in everyday life. However it is important to take positive steps through the various productions stages that they are where they are needed and not inadvertently released into the environment. The programme’s principles are contained in a Code of Good Practice, which the managers of the participating companies sign to show the companies’ commitment to the programme. VECAP is built on the principles of ISO 14001 and EMAS, but stripped to essentials so that it can readily be applied by an SME processor. There are two Codes of Practice and operating toolkits to reflect specific operating conditions in textile (aqueous based processes) and plastics (dry processes). Once a company commits to participating in VECAP, they enter a cycle of assessment and improvement (see Fig 1). This starts with a refinement of their actual working procedures to take account of the key elements in the Code of Good Practice. Then the company critically analyses its product flow and processes to identify the potential for emissions. Two ‘Toolkits’ have been devised to assist the Company in the examination of their processes and identifying potential uncontrolled emissions. Measuring and recording the relevant data will identify the plant’s actual emissions baseline throughout the entire production process. Once this emissions balance is known, an emissions report can be drawn up. When this has been done users will take appropriate actions to improve process control and reduce identified emissions and update their working procedures. This first cycle is very important for the DecaBDE user as it normally raises their awareness

Code of g o o d p rac ti ce

U se r P ro ce du re s Im p ro v e m e n t Im p le m e n ta tio n U s er S elf au d it S u p p lie r A u d it

C o rre c tiv e A c tio n s Nonco n fo rm i ty A s se ss m en t T h ird p a rty A u d it

E m iss io n s B ala n c e

A p p ro v ed M e tho d o lo g y P e riod ic S am p lin g

E m iss io n s R ep o rt E x te rn a l R e p o rtin g

M e tho d o lo g y V alid a tion

Figure 1: The VECAP Cycle
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of waste in their particular production processes. At this point they should have identified a number of low cost modifications they can make which result in making significant raw material cost savings, often on other chemicals used in addition to DecaBDE The user company has now been round the VECAP process cycle once. Then the user goes round the process again, checking to make sure that the changes made have resulted in the expected emission reductions and looking for further changes to reduce significant emissions. DecaBDE suppliers support users in building such a risk management system. If necessary an independent third party may audit the company to check process control and that reported emission data is correct. Experience from trials in the UK has demonstrated that in textile coating processes it has been possible to obtain emission reductions as high as 90% on the first VECAP cycle for minimal additional cost. VECAP’s main challenge is how do you convince companies, without legal enforcement to implement a series of environmental measures, particularly for a substance like Deca-BDE that is not classified as hazardous? Noble intentions are one thing, but product stewardship requires commitment. If companies can be convinced that it is in their longterm interests to participate in VECAP then they will do so. The key to the process is that it is in simple, logical and straight-forward steps. Experience has shown that where a company discovers it has a high emission then the savings made in preventing the emission losses quickly off-set any costs in reengineering their process. The next stage of the VECAP programme will be to work further down the customer chain with electronics and furniture manufacturers and retailers. In the future they will have an important role to play in product stewardship by ensuring that their suppliers are committed to the VECAP principles. Already one major retailer has incorporated VECAP participation into their purchasing guidance for suppliers, more are expected to follow. The programme was started to minimise emissions of the flame retardant Deca-BDE, but VECAP principles are already being extended to other flame retardant chemicals and their applications, such as HBCD and antimony trioxide in the UK textile industry. There is no reason in principle why it should not be applied more widely to other chemicals where it is important to minimise their release into the environment. The EU’s overhaul of the legislation governing the management of chemicals; better known as REACH, will require downstream users to have more information and prepare an assessment of the substances they use for their specific applications. In practice, there will need to be better communication up and down supply chains regarding the properties of substances, VECAP principles can help meet this goal.

Separating electronic waste is cost-effective A study commissioned by WRAP ahead of the impending WEEE legislation due to come into force next July has reported after its second stage that it is commercially viable to separate and treat brominated compounds from electronic waste rather than sending in to landfill or for incineration. This four-phase project is being undertaken by Axion Recycling Ltd, which aims to find a complete solution for the removal of BFRs (brominated flame retardants) from WEEE, currently one of the major technical barriers to recycling. Promising techniques include X-Ray based polymer chip sorting for bulk separation and two solvent-based BFR removal processes (Creasolv and Centrevap). For more information visit http://www.edie.net/news/ news_story.asp?id=10724&channel=0 Launch of new DecaBDE monitoring programme The Netherlands Institute for Fisheries Research has launched a programme to monitor levels and trends of DecaBDE and other brominated diphenyl ethers (BDEs) that are of known concern to the environment. Other partners in the ‘DecaMonitor’ programme are the Centre for Ecology and Hydrology (CEH) and the Centre for Environment, Fisheries and Aquaculture Sciences (CEFAS) in the UK and the Norwegian Polar Institute. Under this programme, monitoring will be carried out in sediment in the UK, Netherlands, Germany, France and Ireland as well as in sludge (UK, Netherlands) and bird eggs (UK, Norwegian Arctic). For more information visit http://www.rivo.dlo.nl/ New Detergents Regulation Detergents have recently been under the spotlight due to the new EU Regulation that came into force on the 8th of October this year. Regulation (EC) No. 648/2004 updates and consolidates existing European legislation on detergents, and covers the biodegradability of surfactants in detergents and product labeling. Aside from the provisions for ingredients information on packaging and websites, the most significant change for the surfactant manufacturers and the detergent industry is the new ultimate biodegradability requirements for all surfactants (anionic, non-ionic, cationic and amphoteric) used in detergents. Previous legislation required less stringent testing and did not include all surfactants within its scope. Under this legislation the European Commission is also required to carry out a review of phosphate use in detergents by April 2007 with a view to reduce usage, and by April 2009 the Commission may also submit proposals relating to anaerobic biodegradation of surfactants and the biodegradation of main non-surfactant organic detergent ingredients. For more information visit http://europa.eu.int/comm/enterprise/chemicals/ legislation/detergents/index_en.htm 9

New Regulations for Paints On 1st November the new regulations for volatile organic compounds (VOCs) in paints, varnishes and vehicle refinishing products came into force. The Paints Directive establishes two sets of limit levels for maximum content of VOCs currently used as solvents in household paint and varnish, the first of which is effective from 1st January 2007 and the second more stringent limit which is to be put into place by 1st January 2010. It is believed that these compulsory measures will achieve an estimated 59% reduction in the current emissions of VOCs from paints. For more information visit http://europa.eu.int/comm/ environment/air/paints_directive.htm Impact of Biodegradable Packaging on Waste Management A review in the journal Industrial Crops and Products (G. Davis & J.H. Song, 2005, in press) discusses the potential impact of biodegradable packaging materials based on raw materials from crops on waste management compared to oil-based polymer packaging materials in terms of landfill, incineration, recycle/reuse and composting. The authors also provide recommendations for ways to improve the widespread use of biodegradable packaging, in particular citing the establishment of appropriate collection, transportation and treatment facilities to be crucial to their success. New eco-friendly coatings for grapes Aloe vera is a plant that is well known for its medicinal and therapeutic properties and is popular in the treatment of burns, scars and wound healing. Aloe vera gel is composed mainly of polysaccharides and scientists at the University Miguel Hérnandez in Spain have used this gel to develop a novel edible coating to preserve grapes and hence increase their shelf life. Typically untreated grapes have a shelf-life of just 7 days at 1ºC (plus 4 days at room temperature), whereas grapes treated with an aqueous solution of aloe vera gel remain fresh for up to 35 days. Sensorial analysis by a panel of testers also found no discernable difference in taste or smell of the grapes. This method of preserving grapes could be a potential environmentally friendly alternative to conventional preservatives such as sulphur dioxide (SO2) in a variety of different applications.
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3rd GC&C Symposium
Greener Products: Opportunities and Challenges Following the enthusiastic response to previous symposia, the GCN is holding its third Green Chemistry and the Consumer symposium on 28th February 2006 at the Society of Chemical Industry in London, “Greener Products: Opportunities and Challenges”. The programme for the day will include talks from representatives throughout the supply chain, government, research and NGOs, followed by breakout sessions, highlighting opportunities and challenges for greener products, with a particular focus on the area of surfactants. The symposium will provide an invaluable opportunit y to bri ng toget her representatives from throughout consumer product supply chains for mutual learning and technology transfer through the presentations and breakout sessions as well as the opportunities for networking. Speakers include: Lord Bach of Lutterworth Defra Minister responsible for Chemicals Stephen Johnson The Boots Group plc Peter Woodhead Selden Research Ltd Dr Bob Crawford Unilever Home and Personal Care R&D David Middleton Business Council for Sustainable Development (BCSD-UK) Dr Warren Smith National Non-Food Crops Centre (NNFCC) Dr Rich Liroff WWF-US For a registration form please visit http://www. chemsoc.org/networks/gcn/events.htm

Annual Report
The first annual report for the GC&C project is available to download on the GCN website http://www. chemsoc.org/networks/gcn/industry.htm#consumer For further information about anything contained in this issue of the GC&C newsletter contact: Louise Summerton Green Chemistry Network, University of York, Heslington, York, YO10 5DD Tel: +44 (0) 1904 434546 Fax: +44 (0) 1904 432705 Email: ls25@york.ac.uk
The GCN is not responsible for individual opinions and the contents of this newsletter do not necessarily express the views of the GCN.

Consultation on PFOS Perfluorooctane sulphonate (PFOS) has been demonstrated to be a chemical of high concern as it meets the criteria of persistence (P), bioaccumulative (B) and toxicity (T). A summary of the responses to the government’s consultation on the proposed national action to restrict the use of PFOS and substances that degrade to it can be found at http:// www.defra.gov.uk/corporate/consult/pfos/responsessummary.pdf 10


				
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