### Unclassified ENV/JM/MONO(2004)11

Organisation de Coopération et de Développement Economiques Organisation for Economic Co-operation and Development 24-Jun-2004

___________________________________________________________________________________________

_____________ English - Or. English ENVIRONMENT DIRECTORATE JOINT MEETING OF THE CHEMICALS COMMITTEE AND THE WORKING PARTY ON CHEMICALS, PESTICIDES AND BIOTECHNOLOGY

OECD SERIES ON EMISSION SCENARIO DOCUMENTS Number 6

EMISSION SCENARIO DOCUMENT ON ADDITIVES IN RUBBER INDUSTRY

JT00166668

Document complet disponible sur OLIS dans son format d'origine Complete document available on OLIS in its original formatENV/JM/MONO(2004)11UnclassifiedEnglish - Or. English

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3 

## OECD Environmental Health and Safety Publications

Series on Emission Scenario Documents No. 6



# EMISSION SCENARIO DOCUMENT ON ADDITIVES IN RUBBER INDUSTRY

Environment Directorate

Organisation for Economic Co-operation and Development

June 2004

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4 ABOUT THE OECD

The Organisation for Economic Co-operation and Development (OECD) is an intergovernmental organisation in which representatives of 30 industrialised countries in North America, Europe and the Pacific, as well as th e European Commission, meet to co-ordinate and harmonize policies, discuss issues of mutual concern, and work together to respond to international problems. Most of the OECD's work is carried out by more than 200 specialised Committees and subsidiary groups composed of Member country delegates. Observers from several countries with special status at the OECD, and from interested international organisations, attend many of the OECD's Workshops and other meetings. Committees and subsidiary groups are served by the OECD Secretariat, located in Paris, France, which is organised into Directorates and Divisions.

The Environmental Health and Safety (EHS) Division publishes documents in eight different series: Testing and Assessment ; Good Laboratory Practice and Compliance Monitoring ; Pesticides ; Risk Management ; Harmonization of Regulatory Oversight in Biotechnology ; Chemical Accidents ; Pollutant Release and Transfer Registers; and Emission Scenario Documents

. The Environmental Health and Safety Programme co-operates closely with other international organisations. This document was produced with in the framework of the Inter-Organization Programme for the Sound Management of Chemicals (IOMC).



### The Inter-Organization Programme for the Sound Management of Chemicals (IOMC) was established in 1995 by UNE P, ILO, FAO, WHO, UNIDO and the OECD (the Participating Organizations), following recommendations made by the 1992 UN Conference on Environment and Development to strengthen co-operation and increase international co-ordination in the field of chemical safety. UNITAR joined the IOMC in 1997 to become the seventh Partic ipating Organization. The purpose of the IOMC is to promote co-ordination of the policies and activities pursued by the Participating Organizations , jointly or separately, to achieve the sound management of chemicals in relation to human health and the environment.

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5 

## This publication is available el ectronically, at no charge.

For the complete text of this and many other Environmental Health and Safety publications, consult the OECD’s

World Wide Web site (h ttp://www.oecd.org/ehs/)

or contact:

OECD Environment Directorate, Environmental Health and Safety Division

2 rue André-Pascal 75775 Paris Cedex 16 France

Fax: (33-1) 45 24 16 75

E-mail: ehscont@oecd.org

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6 Explanatory notes

Purpose and background

This OECD Emission Scenario Document (ESD ) is intended to provide information on the sources, use patterns and release pathways of chemicals used as additives in rubber industry to assist in the estimation of releases of chemicals to the environment.

This ESD should be seen as a ‘living’ document, which provides the most updated information available. As such, an ESD can be updated to take account of changes and new information, and extended to cover the industry area in countries ot her that the lead (Germany). Users of the document are encouraged to submit comments, corrections, updates and new information to the OECD Environment, Health and Safety Division ( env.riskassessment@oecd.org ). The comments received will be forwarded to the OECD Task Force on Environmental Exposure Assessment, which will review the comments every two years so that the lead country can update the document. The submitted information will also be made available to users within the OECD web-site ( www.oecd.org/env/riskassessment ).

How to use this document

The user of this ESD needs to consider how the information contained in the document covers the situation for which they wish to estimate releases of chemicals. The document could be used as a framework to identify the information needed, or the approaches in the document could be used together with the suggested default values to provide estimates. Where specific information is available it should be used in preference to the defaults. At all times, the values inputted and the results should be critically reviewed to assure their validity and appropriateness.

For the estimation of the emissions of chemicals used as additives in the rubber industry the following data and information should be available:

• function of the additive

• type of rubber product

• amount of rubber product produced per day (default)

• percentage of additive introduced into the rubber product

• fraction of additive remaining in the rubber product (default).

Coverage

This ESD describes the life cycle stages of rubber additives in formulation, use, and service life (tyre abrasion), and provides emission estimations to local surface waters, air and soil. The industry categories, use categories and biocidal product types relevant to this document are as follows.

Industry category Use Category Biocidal product type 11 – polymer industry 20 – fillers 22 – flame retardants and fire preventing agents 49 – stabilisers 53 – vulcanising agents

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7 How this document was developed

In the year 1999, Umweltbundesamt (UBA Germany) commissioned the Institute for Environmental Research, University of Dortmund (INFU) (contract no 360 01 27/3; http://www.oekopro.de ) to develop this ESD. In 2001, Umweltbundesamt integrated comments received from RIVM (The Netherlands) and adjusted the nomenclature to the agreed EU nomenclature ( http://ecb.jrc.it - biocides). This ESD was published in the European Union Technical Guidance Document on Risk Assessment [EU 2003, Part IV].

Germany (Umweltbundesamt) as the lead country submitted this draft to OECD, and the draft was circulated to the member countries in February 2002. Comments were received from the following organizations and institutions: UK (Environment Agency and Health and Safety Executive), US EPA and US industries, Canada [OECD, 2002]. Umweltbundesamt incorporated these comments in consultation with the Institute for Environmental Research, University of Dortmund (INFU) and the Association of the German Rubber Industry and amended the document with two new sections:

• Emission scenario for formulation and processing to air and soil

• Emission scenario for use of rubber products by tyre abrasion (service life).

Releases from leachates in landfill and to sea or fresh water are not covered yet and need to be considered in the next version.

The OECD Task Force for Environmental Exposure Assessment concluded at its 10 th 

### session (8 April 2003) that this ESD is to be subsumed unde r the Industry Category 11 “Polymer Industry” new subsection “rubber additives”.

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8 

## Contents

1. INTRODUC TION ................................................................................................................... ............... 9

2. INDUSTRY SUMMARY AND BACKGR OUND.............................................................................. 10

3. MAIN PROC ESSES................................................................................................................. ............ 12

3.1 Natural- and sy nthetic Rubber.................................................................................................. ... 15

3.1.1 Mastication and Creat ion of Mixtures .................................................................................... 15 3.1.2 Shaping ........................................................................................................................ ........... 16 3.1.3 Vulcanisation / Curing ......................................................................................................... ... 16 3.2 Latex.......................................................................................................................... .................. 17 3.3 Rubber-Me tal ................................................................................................................... ........... 17 3.4 Chemicals and Additives........................................................................................................ ..... 17

4. EMISSION SC ENARIOS ............................................................................................................. ....... 21

4.1 Definition of the gene ric Point Source........................................................................................ 2 2 4.2 Emission Rate Estimation ....................................................................................................... .... 24 4.3 Emission Scenario for Formulation and Processing to Wastewater............................................ 25 4.4 Emission Scenarios for Formulation a nd Processing to Air and Soil.......................................... 30 4.5 Emission Scenario for Use of Rubber Products by Tyre Abrasion ............................................. 31 4.6 Emissions fro m Leachates....................................................................................................... .... 32

5. EXAMPLES OF EMISSI ON ESTIMATION...................................................................................... 33

5.1 Emissions from Formulation and Processing to Wastewater...................................................... 33 5.2 Emissions from Formulation and Pr ocessing to Ai r resp. Soil.................................................... 35 5.3 Emission from Abrasion of Tyres ............................................................................................... 3 5

6. REFERE NCES ..................................................................................................................... ................ 36

7. GLOSSA RY ....................................................................................................................... .................. 37

8. ABBREVIAT IONS .................................................................................................................. ............ 39

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9 1. INTRODUCTION

1. This document provides guidance for estimation of emissions from chemicals used as additives in the rubber industry (IC-11 Polymer industry), including additives like vulcanising agents (UC-53), anti ageing agents, fillers (UC-20), pigments, stabilizer (UC-49), plasticisers, processing aids, flame retardants (UC-22).

2. The emissions during “industrial use” depend on th e type and formulation of the additive and the processes. The two life-cycle phases “formulation” and “industrial use” can often not be separated and are therefore combined for this emission estimation. The processing steps taken into account are:

• the creation of the rubber mixture

• the mastication

• the shaping

• the vulcanisation

• the finishing

3. Additives may enter the environmental compartments water, air, and soil. The major pathway is the entry into water. This occurs in those processes, where water is used as cooling or heating medium, in vulcanisation, where water has direct contact with the rubber mixture. Releases to water can also occur in cleaning steps throughout these processes. The water pathway is the predominant one and is described in this document by a generic point source. For most additives, the air pathway is of minor importance.

4. A regional scenario of tyre abrasion describes the phase „service life“ with subsequent leaching into surface water and soil. The phase “waste disposal” means the leaching potential by rainwater to the soil and water compartment or when used tyres are in contact with fresh or marine water. Mainly volatile monomers and plasticisers escape to the air compartment. A waste disposal scenario is not covered in this document.

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10 2. INDUSTRY SUMMARY AND BACKGROUND

5. The EU produces only synthetic rubber. The total production of synthetic rubber amounted to 2.51 million tonnes in the year 2001 (International R ubber Study Group 2003). This is about 25% of the world production. Unlike natural rubber, synthetic rubbe r is subject to strong fluctuations in the amount used and produced. This raw material was used to produce about one million tonnes of tyres and about 530.000 tonnes of rubber products (“technical and other elastomer products”) in 1995. Table 1 shows the production of different EU countries, and Table 2 provide s the market share of different synthetic rubber types characterised by the monomers used in the production. The world production of natural rubber grew from 3 million tonnes (1980) to 7.13 million tonnes in 2001 (International Rubber Study Group 2003).

Table 1 Production and Consumption of Rubber (1996)



### Country synthetic rubber production [1000 tonnes] synthetic rubber consumption [1000 tonnes] natural rubber consumption [1000 tonnes] Spain 83.7 0 124.9 Italy 317.2 349 119.4 Turkey 40.1 0 0 France 565.8 403.6 209.7 Belgium 139.6 0 51.9 Germany 573.4 611.3 211.8 Netherlands 215.7 0 66.6 United Kingdom 306 268.9 140.4 

### Source: Rubber Statistics, Rubber Statistical Bulletin Vol. 51, No 10 (1997). http://www.rubberstudy.com 

### - Statistics.

Table 2 Market Shares of different synthetic Rubber Types in the EU



### Rubber type Market share [%] Styrene butadiene rubber (SBR) 58 butadiene rubber (BR) 14 ethylene propylene diene rubber (EPCM) 10

Isoprene rubber (IR) 1 Isoprene isobutylene rubber (IIR) 5 acrylonitrile butadiene rubber (NBR) 7 poly-2-chlorobutadiene (CR) 5 

### Source: Rubber Statistics, Rubber Statistical Bulletin Vol. 51, No 10 (1997). http://www.rubberstudy.com 

### - Statistics.

6. The following Table 3 presents different rubber products and their percentages of uses. This distribution does not fluctuate over the years; it is assumed to be valid for all EU countries.

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11 Table 3 Distributions of Rubber Products in Germany 

### Rubber products Percentage [%] form products, rubber-metal-compounds 24 Technical tubes and profiles 23 glues, mixture, repair material 13 other rubber products 11 foam, micro cellular and cellular rubber products 10

Conveyor belts, flat and vee-belts 9 other technical products 5 sole material 3 sheet material, punching products 2 Sum 100 Source: Association of the German Rubber Industry 1990: leaflet

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12 3. MAIN PROCESSES

7. It is helpful to define three terms that are used in the rubber industry [Ullmann 1993]:

• Rubber (raw rubber) is a non-cross-linked, but cross-linkable (curable, vulcanisable) polymer with rubber-elastic properties at room temperature. At higher temperatures and/or, if exposed to deforming forces, rubber demonstrates an increasing tendency for viscous flow. Therefore, it can be formed under appropriate conditions.

• Elastomers are polymeric material that is cross-linked (vulcanised). They are hard and glassy at low temperature and do not exhibit viscous flow even at high temperature. Rubber elastic behaviour is characterised by a relatively low shear modulus with comparably low temperature dependency.

• Vulcanisation is a process in which rubber, through a change in its chemical structure (for example, cross-linking) is converted to a condition, in which the elastic properties are conferred or re-established or improved or extende d over a greater range of temperature.

8. Natural rubber differs from synthetic rubber. Natural rubber is made from the milk of the rubber tree. This rubber milk is also called latex and is a colloidal dispersion in an aqueous medium. The latex concentration after tapping is about 30%. Only a small percentage is used directly; the greatest part is processed into harder rubber. This is done throug h evaporation, hydro extracting, creaming and electro decanting. Thailand is the most important producer of natural rubber. The raw rubber material is exported into the processing countries in the solid form.

9. Natural rubber demonstrates a balanced combination of physical attributes resulting in a broad range of possible uses [Ullmann 1993]. A certain synthe tic rubber surpasses every single attribute of a natural rubber. If these attributes are specifically required, the appropriate synthetic rubber will be used instead of the natural rubber.

10. The most important types of synthetic rubber are shown in Table 2 in relation to their market shares. Almost two thirds of the total rubbers currently used in industry are synthetic. These rubbers are made from monomers like butadiene, styrene, acrylonitrile and isobutene. Table 4 characterises the attributes of these rubbers. There are many more synthetic rubbers than shown in the Table [Baumann and Ismeier 1998; Ullmann 1993].

11. Depending on the production procedure, one differentiates between polymerisates, polycondensates and polyaddition products. According to DIN ISO 1629 rubbers in the form of hard rubbers and latex are divided into groups depending on the chemical structure of the polymer chains. The rubber types are divided by their attributes [Lüpfert 1990] and their functions [Rentel et al. 1991]. A rubber is made mainly of [Lüpfert 1991]

• polymers (elastomers)

• fillers

• plasticisers

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13 • anti ageing agents

• linking systems.

12. Additives are added before and during processing. After the initial composition the mixture is created with an internal mixer, a rolling mill, a batch- off-facility and an extruder. The shaping of the semifinished product is made with an extruder, a plunger type injection moulder, through calendaring, the spreading machine and assembly.

13. The compression process, the transfer moul ding, and injection moulding are used for vulcanisation (curing) in presses. A continuous vulcanisation is made with the rotational vulcanisation, the steam pipe vulcanisation, the hot-air vulcanisation with microwave preheating, the boiling bed vulcanisation and the salt-bath vulcanisation. In addition to these, vulcanisation can also be accomplished in an autoclave.

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14 Table 4 Rubber Type and Additives


### Abbreviation Rubber Type Mixture
NR Natural Rubber proteins (cis-1,4-polyisoprene) aliphatic acids vulcanisation agents (sulfur) resins vulcanisation accelerators ash anti ageing agents sugar fillers Water plasticisers processing aids

SR Synthetic Rubber SBR styrene butadiene rubber monomers (1,3-butadiene, styrene) vulcanisation agents (sulfur) vulcanisation accelerators anti ageing agents fillers plasticisers factices resins processing aids BR butadiene rubber monomers (1,3-butadiene) vulcanisation agents (sulfur) vulcanisation accelerators anti ageing agents fillers plasticisers processing aids NBR Acrylonitrile butadiene rubber monomers (1,3-butadiene, acrylonitrile) vulcanisation agents (sulfur) vulcanisation accelerators anti ageing agents fillers plasticisers factices processing aids CR poly-2-chlorobutadiene monomers (chloroprene) (polychloroprene) vulcanisation agents (sulfur) vulcanisation accelerators anti ageing agents fillers plasticisers factices processing aids EPDM ethylene propylene diene rubber monomers (ethylene, propylene) vulcanisation agents vulcanisation accelerators anti ageing agents fillers plasticisers processing aids IR isoprene rubber monomers (isoprene) vulcanisation agents

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15 Abbreviation Rubber Type Mixture vulcanisation accelerators anti ageing agents fillers plasticisers processing aids IIR isoprene isobutylene rubber monomers (isoprene, isobutylene) vulcanisation agents vulcanisation accelerators vulcanisation activators anti ageing agents fillers plasticisers processing aids OTHER Special monomers vulcanisation agents vulcanisation accelerators anti ageing agents fillers plasticisers processing aids



### 3.1 Natural- and synthetic Rubber

3.1.1 Mastication and Creation of Mixtures

14. The mastication is a process, in which the length of the polymer chains is decreased to lower the viscosity. This is necessary to get a better workability of the rubber (extrusion, calender and others) and to spread the rubber chemicals throughout the matrix. Rubber additives like anti ageing agents, fillers, plasticisers are discussed in Subsection 3.4. Their functions are shown in Table 5.

15. An optimised viscosity is especially important for the production of rubber blends, since a homogenous distribution of the constituents is only possible within an equal viscosity. Unlike synthetic rubber, which can often be processed without a previous mastication, natural rubber is usually offered as a relatively hard product with little plasticity, making mastication a requirement.

16. The mastication can be achieved in a purely mechanical process, in a mechanic-thermal process, physically by adding plasticisers and/or processing agents as well as chemically.

17. Machines like rolling mills, the internal mixer or the gordon-plasticator masticate the rubber substance but also serve as mixers, for cooling, to finish the mixing of half ready rubber mixtures and to preheat finished rubber mixtures. A possible contam ination of the water compartment during the mixing process can happen through the cooling process, if water is used as a direct cooling agent. Finally sulfur is added to the mixture. The finished mixture is taken off as a rough sheet. This rough sheet is cooled by immersion in water to which an anti tack-agent has been added (rolling mill). Especially in larger companies, the internal mixer replaced the rolling mill. An internal mixer can hold 15 to 650 litres. For the homogenisation, cooling and working into sheets rol ling mills are still used. In modern installations, a batch off machine is responsible for taking off the sheet s and immersing them in a bath of water or a bath with an anti tack-agent.

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16 3.1.2 Shaping

18. Rubber mixtures are usually not immediately reprocessed after the mixture was created, but are stored in a cool and dry environment. For the shaping, processes like extrusion, calendering, form moulding and transfer moulding are used.

19. Injection machines (extrusion plants) form rubber mixtures into bars, tubes, profiles, treads of tyres or sheets or encase cables and wires. In a continuous process, the rubber mixture is cured immediately after extrusion. If reprocessing as a semi-finished product is planned, the mixture is dusted and drawn through an adherent bath. Calendering is used to create sheets for the rubberisation of technical weaves (fractioning) and to coat weaves with a thin rubber sheet (skimming).

20. Formed articles are mass articles like stoppers, bottle caps, soles, packing rings, collars, membranes, valve balls, buffers and tyres. Processes like pressing, transfer moulding, flashless-processes and the injection-moulding process are characterised by shaping and vulcanisation in one step. An assembly line takes an important role in this context.

21. After the forms were used in a transfer moulding process over time, organic residues from the rubber mixture or from the anti tack-agents deposit as incrustation or carbonisation. A chrome sulfur bath (60°C) is used to clean the forms. The actual cleani ng takes place in a lapping machine with a suspension of quartz flour. Water is used for rinsing the cleaned forms.

3.1.3 Vulcanisation / Curing

22. Vulcanisation is a chemical process to link the polymer structure. The term vulcanisation is used for a linking procedure, during which the macromolecules of the rubber are linked to each other over linking bridges. The linking is achieved with vulcanisation agents, usually sulfur, sulfur producers or peroxides as well as energy rich radiation.

23. If uncured, rubber is thermoplastic. The molecu les are not connected to each other. During vulcanisation the rubber changes from the thermoplastic to the elastic condition. The number of links depends on the amount of linking substances, their activity and reaction time. The following procedures are used for vulcanisation:

• liquid curing method (LCM-Vulcanisation)

• boiling bed vulcanisation

• hot air vulcanisation after UHF-preheating

• vulcanisation in hot steam under high voltage (under lead).

24. The LCM-vulcanisation is commonly used for extruded profiles, tubes and similar processes. It is continuous and takes place in a liquid bath. The duration of the bath depends on the vulcanisation speed, the injection performance of the extrusion plant, the temperature of the heating bath and other factors. Eutectic salt mixtures (as well as glycerin, silicon oils, polyalkyleneglycole, metal mixtures) are used as a heating medium. For the boiling bed vulcanisation, small glass beads are used through which gas flows to lift them.

25. The HF vulcanisation uses a pressure-free continuous process. The vulcanisation in steam pipes is used almost exclusively in the cable industry. Immedi ately after coating, the cable is guided into a pipe,

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17 in which the steam pressure is usually between 0,5 and 1,2 MPa (max. 2 MPa). To reduce deformations, the vulcanisation is sometimes performed under a lead coating, this coating protects from the hydrolytical effect of th e steam. After cooling with water, the lead coat is removed.

26. The vulcanisation of calendared products can be achieved with rotational vulcanisation or in vulcanisation presses. A high frequency preheating is possible. Assembled rubber products are vulcanised free (not in a mould) in an open heater (hot air vulcanisation).

27. To decrease the vulcanisation time, a steam heater is used. When using saturated vapour, in which water and steam are in balance, the temperature transference is more even. To avoid condensation spots, spreading agents are used. When vulcanising in water, the temperature transfer is extremely good compared to a medium of air or steam. This process will be used for big parts. It is used rarely for example for the vulcanisation of large rolls due to the complexity of the process. Vulcanisation can also be achieved through cold vulcanisation or energy rich radiation.

3.2 Latex

28. Natural latexes and synthetic latexes (as are created during the emulsion polymerisation) are processed, among other things into thin-walled products. The mixture is prepared by kneading the required chemicals into the latex solution. The coagulation process is used to create thick-walled products. The form is submerged in an alcoholic solution of a coagulation substance. This results in a thicker coagulum on the form as in other submerging processes. The vulcanised products must then be thoroughly rinsed with water to remove the coagulation substance.

29. For foam rubber, steam or hot water is used as a medium for the vulcanisation. The spinning process for the creation of latex strings also requires water to rinse out the coagulator.

30. Products made from unwoven textiles are made from bonded fabrics impregnated with a latex mixture. The unused adhesive is pressed out and the da mp fabric dried and vulcanised. Leftover chemicals (emulsifying agents, stabilisers) are removed by washing.

3.3 Rubber-Metal

31. Metal working takes place in the rubber industry wherever composite parts made of rubber and metal are needed. One example is the tyre, which, in addition to a multitude of rubber mixtures, includes stabilising material like steel, textiles or plastic. Other rubber-metal parts for the automobile industry are shock absorbers, elastomere springs, coupling parts, hangers and others. Rubberised parts, like rolls are used in other areas. For the preparation of composite parts, spray- and degreasing plants are used.

3.4 Chemicals and Additives

32. The rubber industry uses hundreds of different substances. The finished product gains the required attributes only by adding fillers, plasticisers, vulcanisation chemicals, anti ageing agents and adhesives. Table 5 lists the most important process steps for the production of rubber and the most important substance classes used in each step.

33. The rubber industry uses a special unit for expressing the components of a rubber mixture. They are presented in relation to 100 mass parts total rubber (parts per hundred rubber [phr]) or in wt-% (cf. Table 9)

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18 Table 5 Functions of Additives in Rubber Processing Steps



### Process Step / Additive Description Function of the Chemicals used

Mastication plastification of the rubber 1. mastication agents before working the molecular 2. activators (Boosters) chain splitting through oxidative breakdown (usually aromatic or heterocyclic mercaptan). By using activators, the mastication can be shifted to a lower temperature spectrum (inner complex salts). Vulcanisation For linking the rubber molecules Vulcanisation agents And creating linking bridges Vulcanisation accelerators (usually sulfur, Vulcanisation activators Vulcanisation Sulfur producers, peroxides) Vulcanisation retarders Anti-ageing agents finished product with protection against damaging influences. 1. antioxidants

2. anti fatigue agents 3. anti ozonants 4. light protection agents 5. anti hydrolysis agents 6. agents against metal poisoning 7. desactivators 8. reversion protection agents 9. anti cyclisation agents

Fillers substances which are insoluble inorganic fillers towards the rubber matrix, organic fillers non-volatile and inert towards the polymer. The fillers define the attribute of the vulcanisate. They extend and strengthen the vulcanisate. Plasticisers plasticisers serve as extensions, they improve the fluidity, they distribute the fillers, improve the workability and the adhesiveness. They influence the physical attributes of the rubber like expansion and elasticity. Primary plasticisers have a loosening effect and lower the viscosity of non-vulcanisated rubber mixtures. Secondary plasticisers serve as lubricants and improve the shapeability. Plasticisers (categories: mineral oils, natural substances, synthetic plasticisers)

Pigments/ pigments are in rubber de facto 1. inorganic pigments: Colourants insoluble, organic or inorganic, a) white pigments coloured or white substances . b) coloured pigments  !

" organic pigments

Processing aids processing aids ease the working of the material: 1. lubricants are used mainly in the extrusion and the injection moulding
processes 1. lubricants

# Metal soaps (like zinc-, calcium-soaps)

# Aliphatic acids, Aliphatic acid ester

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19

Process Step / Additive Description Function of the Chemicals used

2. tackifiers serve to increase the assembly adhesion 2. tackifier

Processing aids 3. among others to improve the stability, the injectability and calendrability 3. factice

Processing aids 4. by using fillers activators, the activity of the fillers can be improved 4. fillers activators, adhesion agents

5. blowing agents are used to produce porous rubber articles (decompose under gas splitting) 5. blowing agents 

$ " inorganic 

$ " organic 6. bonding agents increase the adhesion of rubber on strengthening material (weaves, metal) 6. bonding agents

other agents 1. anticyclisation agents serve to prevent unwanted cyclisation during mastication 1. anti cyclisation agents

2. with the aid of replastication agents slightly vulcanized mixtures can be returned to a workable condition (desulfuring of the rubber mixture) 2. replastication agents

3. emulsifier disperse systems 3. emulsifier 4. flame retardant lower the flammability of the rubber 4. flame retardant

5. in solvent adhesives, in solvent dipping processes, for cleaning 5. solvents

6. for refining the surface 6. surface treatment agents 7. to increase the hardness of the vulcanisate 7. hardeners

8. to nuance, neutralize and cover the rubber smell 8. odorants

9. to increase the electronic co nductibility 9. antistatic agents 10. to kill microorganisms 10. microbiocides 11. to prevent the spreading of germs 11. anti termite agents

Latex- to add pulverised additives into 1. dispersion agents chemicals the aqueous colloidal latex 2. emulsifier Solution 3. stabiliser 4. wetting and foaming agents 5. foam stabilisers 6. thickeners 7. coagulating agents 8. preservatives 9. vulcanisation chemicals Latex- 10. anti ageing agents chemicals 11. fillers 12. plasticisers

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20

Process Step / Additive Description Function of the Chemicals used

Release agents 1. prevent non-vulcanised rubber mixtures from adhering during storage 1. release agents for non- vulcanised rubber mixtures (anti tack agents) 2. prevent rubber from sticking to the forming tools 2. mould release agents

3. release agents are added to the rubber mixture, migrate to the surface and improve the removability of the vulcanisate from the form 3. mandrel release agents

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21 4. EMISSION SCENARIOS

34. This document describes three generic emission scenarios:

• formulation and processing: emissions to wastewater

• formulation and processing: emissions to air and soil

• private use of rubber products by tyre abrasion: emissions to surface water and soil.

35. The contamination of water in the rubber industry takes place in several phases of the rubber production, whenever water comes into direct contact with the rubber product. This happens during cooling-, heating-, vulcanisation- and cleaning operati ons. Examples are direct cooling during the extrusion or direct contact of the material vulcanised with the steam in the vulcanisation processes.

36. The sources and possible contaminations of wastewater are presented in Table 6. The water can contain zinc (zinc compounds are often used in anti tack agents), cadmium, copper and lead from vulcanisation. Storing, weighing, mixing are other possible sources of exposure.

37. By using wastewater free procedures (indirect cooling, circulation systems, dry cleaning) releases to water can be avoided. A cascading arrangement of the rinsing baths and an optimised water flow can also decrease the volume of wastewater. The remaining wastewater is treated, if the pollutant concentration makes it necessary. Degreasing is accomplished with chlorinated hydrocarbons and complex builders like EDTA. The reduction or prevention of hazardous substances from the cleaning operations can be accomplished by degreasing on an aqueous basis.

Table 6 Water Contaminatio n of different Sources in the Rubber Industry [in mg.L -1 ] (Association of the German Rubber Industry 1999) 1

Source COD 2 C 3 SLS 4 AOX 5 BTX 6 NO 2 P total Pb Cu Zn Cd

direct cooling water and anti tack agent contact after mixing 3000 (RP) 1.5 (RP) 0.54 (TI) 1.0 (RP) <0.005 (TI)

1 This table gives an overview about individual situations of special rubber manufacturers. It is not a generalisation of the emission situation.

2 Chemical oxygen demand

3 Hydrocarbons

4 Semivolatile lipophilic substance

5 Adsorbable organic halogen compounds

6 Benzene, Toluene, Xylene

### ENV/JM/MONO(2004)11

22 Source COD 2 C 3 SLS 4 AOX 5 BTX 6 NO 2 P total Pb Cu Zn Cd

direct cooling water after extrusion 5 (RP) <0.05 (RP) 0.06 0.12 0.052 0.084 (TI) <0.1 (RP) <0.001 (TI) <0.005 (TI) <0.02 (RP)

wastewater from the waste air treatment during the production and processing of solutions after pretreatment (stripping) ca. 6000 35000 I 1000 (RP) 0.1 O (RP) 0.03- 0.2 (RP) 0.1 I 8.1 O

wastewater from vulcanisation in forms as well as subsequent washing and cleaning
processes 282 (TI) 0.065 (TI) 0.14 (TI) 6.8 (TI)

wastewater from vulcanisation in autocl aves as well as subsequent washing and cleaning processes 65 (RP) 1100 (RP) 301 (RP) 233 (RP) 0.23 (RP) 0.05 (RP) 3.3 (TI) 0.2 (RP) <0.03 (TI) 0.16 (RP) 0.02 (RP) 0.05 (RP) 0.22 (RP) 0.87 (RP) <0.002 (RP) ca. 0.05 (RP)

wastewater from vulcanisation i n a salt bath as well as subsequent washing and cleaning processes 1500 (RP)

wastewater from general cleaning of production tools 540 (TI) 2000 I 1200 O (RP) 87 (TI) 0.05 O (RP) 28 O (RP) 80 (TI) >3.0 I <1.0 O (RP) <1 (TI) 41 I 6.6 O 5.8 I 0.01 O (RP) 2.2 I 0.02 O (RP) 38.5 I 0.2 O (RP)

I: inflow, O: outflow of the waste water treatment plant TI = tyre industry, RP = rubber products



### 4.1 Definition of the generic Point Source

38. The generic point source for the rubber industry derived in this sub-chapter is related to the German situation. However, it is believed that the size of a typical manufacturer in the EU Member states is comparable, because of the general structure of the rubber industry. This generic point source is the reasonable worst case used in the environmental exposure assessment. Similar considerations can be followed in deriving the generic point sour ce in non-EU Member states of the OECD.

39. The emissions of the generic point source are deri ved from a survey of the wastewater discharges in the rubber industry. This total wastewater stream can be divided into the following component waste streams: sanitary, rainwater, metalworking, rubber working and others. The total quantities discharged each day are shown in Figure 1. The Association of the German Rubber Industry (1999) provided these discharge volumes and the following assumptions.

### ENV/JM/MONO(2004)11

23 sanitary rainwater metal working rubber processing other indirect discharge direct discharge

0 1 2 3 4 5 6 7 8 91000 m3/d

Figure 1 Volume of Component Wastewater Streams of direct and indirect Discha rge for Members of the Association of the German Rubber Industry (1999) 

### 40. The Association of the German Rubber Industry (1999) recorded these wastewater data for 18 direct dischargers (facility owned sewage treatment plant) and 70 indirect dischargers (via the municipal sewage treatment plant), 88 companies in total. It shou ld be noted, that three companies discharged 75% of the total volume directly, and one indirect discharger made up for 30% of the corresponding discharge. This wastewater volume covers not only the rubber processing, but also the sanitary, metalworking and other areas. It is assumed that 37 % of the wastewater is attributed to rubber processing. Table 7 lists the statistical wastewater data for determining the generic point source.

Table 7 Statistical Data for de termining the gen eric Point Source 

### Quantity of Wastewater (1) Flow rate [m 3 

### .d -1 

### ] Q wwat 

### (arithmetic average) 184 Q wwat 

### (minimum) 10 Q wwat 

### (maximum) 1154 Q wwat 

### (90-percentile) 438 (1) Sample size of 84 companies



### 41. Direct and indirect discharges were combined. The EU standard sewage treatment plant with a flow rate of 2000 m3.d -1 

### was used to eliminate from this sample those companies with a higher flow rate. 84 companies were below this threshold and discharged in total about 15000 m3.d -1 

### . Four very large companies that were above this threshold and discharged in total also about 15000 m3.d -1 

### . These four companies were eliminated in the evaluation of the 90 percentile. The 90 percentile value is 438 m3.d -1



### .

42. It was further assumed that about 3 m 3 

### water are needed to produce one tonne of rubber goods. This water consumption accounts only for the rubber production.

### ENV/JM/MONO(2004)11

24 43. With the assumption that the water consumption of the rubber production is 37% of the value for the 90-percentile of the wastewater volume, a daily generic production (Q prod 

### ) of about 55 tonnes per day is derived as the reasonable worst-case generic point source:

Q prod 

### (generic point source) [t.d -1 

### ] = Q wwat 

### (90 percentile) [m3.d -1 

### ] * 0.37 / 3 [m3.t -1 

### ] Q prod 

### (generic point source) [t.d -1 

### ] = 438 m3.d -1 

### * 0.37 / 3 m3.t -1 

### = 55 t.d -1



### 44. A further assumption is that the production ratio for tyres: rubber products is 60 : 40. This assumption is presented in Table 8. The quantities compiled in this table are also used in example calculations (Section 5).

Table 8 Product Type and Amount pr oduced at the ge neric Point Source



### Product type Amount Q prod 

### [kg.d -1 

### ] Tyres 33000 tyres total 26400 car tyres 11600 Truck tyres 14800 re-treading 6600

rubber products 22000 technical tubes, profiles 5320 form products, rubber-metal compounds 5190 glues, mixtures, repair materials 2840 foam-, micro cellular- and cellular rubber products 2110 conveyor belts, flat- and vee belts 1940 sole material 550 sheet material, punching products 460 other technical products 1150 other rubber products 2440 Sum 55000 Source: Association of the German Rubber Industry (1999)



### 4.2 Emission Rate Estimation

45. The emission scenarios are presented in the following way.

Input [Variable/parameter (unit)] [Symbol] [Unit] [Origin: A/D/O/P]

These parameters are input to the scenario. The A, D, O, or P classification of a parameter indicates the
status: A Parameter must be present in the input data set for the calculation to be executed. The applicant delivers it. Normally, there is no default value. D Parameter is a standard default value. O Parameter is the output from a calculation. P Parameter is chosen from a “pick-list” of values.

### ENV/JM/MONO(2004)11

25 Output [Symbol] Description

4.3 Emission Scenario for Formulation and Processing to Wastewater

46. The following information is needed for the emission calculation of the releases to wastewater:

• function of the additive (Table 9)

• product type and amount produced per day [kg/d]. The default values for tyres and different rubber products and their sub-divisions are presented in Table 8.

• additive introduced. This figure is either given in weight percent [wt-%] or in parts per hundred rubber [phr]. The latter figure is a special term used in the rubber industry (cf. Table 10). This figure can either be delivered by the applicant (A) or can be taken as default (D) from Table 9.

• fraction of additive remaining in the rubber product. This figure can either be provided by the applicant or be taken as default from Table 9.

47. The emission rate [kg/d] into wastewater is calculated from equation (1) as shown: 

# ( ) remaining recipe additive prod water 

### F F Q Q Elocal

− ⋅

⋅ ⋅ = 1 100 (1)



### Parameter:

Explanation Symbol Value Unit Origin Remarks Input Amount of the product type produced per day prod 

### Q [kg.d -1 ] P see Table 8. If no detailed information is available the default of 55000 kg.d -1 is used Parts of additive introduced additive 

### Q [wt-%] or [phr] A/P from applicant or Table 9

Recipe factor recipe 

### F 2
resp.

1 A 2, when content is given in phr 1, when content is given in wt- % (see Table 10) Fraction of additive remaining in the rubber product F remaining [-] A/P from applicant or Table 9

Output Emission of substance to waste water treatment plant Elocal water [kg.d -1 ] O



### 48. Table 9 lists for various additives the content in rubber products and tyres mostly expressed in parts per 100 rubber parts [phr]. For worst-case calculations the upper range is used. If the content of the additive in the mixture is not specified, then the figure in the overall class (the gray field) can be used. The last column presents the fraction of the additive assumed remaining in the rubber product and therefore not being subject to emissions during processing.

49. These figures should not be seen as a possible recipe. The actual amount used depends on the function of the mixture and can vary within the ranges given. A tyre for example is composed of 10

### ENV/JM/MONO(2004)11

26 different rubber mixtures and is made up of 48 wt-% natural and synthetic rubber, 23 wt-% carbon black, 18 wt-% steel, 3 wt-% woven glass fabrics and 8 wt-% additives

[Association of the German Rubber Industry (1999)].

Table 9 Functions and Content of Rubber Additives
Rubber additive Use in rubber products [phr] Use in tyres [phr] F remaining

Mastication agents / peptiser 0.1-0.5 wt-% (NR), 1-3 wt-% (SR) 0.5 0.995

Activator no data 4

vulcanisation agents 0.25-5 (soft)
25-40 (hard) up to 2 1.0

sulfur-containing cross-linking agents 2 2

Vulcanisation accelerator 0.1-2 0.2-2.0

Accelerator activator 1.5-5 1.3

sulfur-free cross-linking agents 0.001-1 no data

coagents for sulfur-free cross-linking agents 0.5-2.0 2.0

other cross-linking agents 0.001-2.0 0.001-2.0

vulcanisation retarders 1.5-2 0.3-2

scorch inhibitors 0.1-1 0.5

anti ageing and antiflex-cracking agents / antidegradants 0.8 0.8 0.98 (RP) 0.99 (TI)

Antioxidants 0-3 0.25

Antifatigue agents 1-5 0.2

Antiozonants 1-7 0.2-1

light protection agents 0-3 0.2

anti hydrolysis agents 0.5-3 0,2

heat protection agents 0.5-3 1

agents against metal poisoning 0.5-3 0.2

Deactivators 0.5 0.3

### ENV/JM/MONO(2004)11

27 Rubber additive Use in rubber products [phr] Use in tyres [phr] F remaining

reversion protection agents 0.5-3 no data

anticyclisation agents 0.5 no data

Quencher 0.5 no data

other anti ageing agents 1.5-3.0 no data

fillers and pigments 7 8 Up to 30 up to 40 0.99

Fillers 10-30 40

Pigments 1-5 No data

Plasticiser Up to 20 Up to 3.8 0.95 9

plasticiser, natural 10-20 2.4-3.8

plasticiser, synthetic 10-20 2.4-3.8

Processing aids Up to 15 1-5 0.995

lubricants and flow improvers 5-15 No data

Tackifier 5-15 No data

Factices 5-15 No data

filler activator 5-15 No data

blowing agents 5-10 3 0.999

bonding agents 1-4 3-4 0.999

Stabiliser 1,5-3 1,5-3

other agents 0.1-3 0.1-3 0.95

7 After formulation, fillers are not removed from the rubber matrix.

8 Some fillers act as pigments and vice versa.

9 Plasticisers do not enter into a chemical bonding wi th the rubber; migration to the surface is possible.

### ENV/JM/MONO(2004)11

28 Rubber additive Use in rubber products [phr] Use in tyres [phr] F remaining

anticyclisation agents No data No data

replastication agents No data No data

Emulsifier 0.1-0.5 No data

flame retardant 2-3 No data

Solvents No data No data

surface treatment agent 2-43 2

Hardeners No data No data

odour agents 0.25-0.1 No data

Antistatic agents 0.1-0.6 5

Microbiocides No data No data

Antitermite agents No data No data

Reinforcing agent No data No data

Homogeniser No data No data

latex-chemicals Up to 5 0.95(RP)

dispersion agents 1-2

Emulsifier 1-5

Stabilizer 1-2

wetting and foaming agents 1-2

foam stabilizers 1-5

Thickeners No data

coagulation agents No data

Preservatives No data

vulcanisation chemicals 0.5-2

anti ageing chemicals No data

Fillers No data

### ENV/JM/MONO(2004)11

29 Rubber additive Use in rubber products [phr] Use in tyres [phr] F remaining

Plasticisers No data

release agents 10 up to 30 Up to 30 0.95

for non-vulcanised rubber 0.5-5 0.5-5

mould release agents 5-30 5-30

mandrel release agents 5-30 5-30

Others Up to 5 Up to 5 0.95

cleaning agents No data No data

other rubber chemicals No data No data
TI = tyre industry; RP = rubber products



### 50. An example for a recipe is presented to demonstrate the introduction of the F recipe 

### -factor for information about the composition in phr.

Table 10 Example for a Recipe [Sablowski Datacom 1996] 

### Compound constituent Recipe [phr] Recipe [wt-%] Synthetic rubber butadiene (SBR) 80.28 43.63 Butadiene rubber (BR) 19.72 10.72 fatty acid 1.97 1.07 Plasticiser 11.97 6.50 Waxes 1.69 0.92 zinc oxide 3.10 1.68 carbon black 60.56 32.91 anti ageing agent 1.69 0.92 Accelerator 1.20 0.65 Sulfur 1.83 0.99 Sum 184.01 99.99

10 These substances are not a part of the rubber mixture, but will be treated so

### ENV/JM/MONO(2004)11

30 4.4 Emission Scenarios for Formulation and Processing to Air and Soil

51. Hardly any monitoring data for air and soil emissions of rubber additives are available. A simple emission scenario based on the A-Tables (emission fa ctors) of the European Union Technical Guidance Document (TGD) [EU 2003] from IC-11 (polymer indus try) life cycle phase ”polymer use” is presented here. For air emissions, the OECD Emission Scenario on “Additives in the Plastics Industry” (Draft July 2001) may be consulted.

Table 11 Emission Factors [EU 2003, A- Table for IC-11 “Polymer Industry”)

Type of additive Conditions Emission factor

Air F air Vapour pressure [Pa] Boiling point [°C] Additives Pigments Colorants Fillers Processing aids < 1

1-100

>100 < 300 / unknown > 300 < 300 / unknown > 300 < 300 / unknown > 300 0.001 0.0005 0.0025 0.001 0.01 0.005 Plasticisers < 400 / unknown > 400 0.01 0.005 Vulcanising agents <100 100-1000 1000-10000 >10000 0.075 0.15 0.25 0.35 Soil F soil Additives Pigments Colorants Fillers 0.0001

Processing aids 0.0005 Vulcanising agents 0.0001



### 52. The emission rate [kg/d] into air resp. soil is calculated from equation (2) as follows:

air recipe additive prod air 

### F F Q Q Elocal



### ⋅

⋅ ⋅ = 100 (2)



### Parameter:

### ENV/JM/MONO(2004)11

31 Explanation Symbol Value Unit Origin Remarks Input Amount of the product type produced per day prod 

### Q [kg.d -1 ] P see Table 8. If no detailed information is available, the default 55000 kg.d -1 is used. Parts of additive introduced per parts of 100 rubber additive 

### Q wt-% or [phr] A/P from applicant or Table 9

Recipe factor recipe 

### F 2
resp.

1 [--] A 2, when content is given in phr 1, when content is given in wt- % (see Table 10 

### Example for a Recipe [Sablowski Datacom 1996] ) Emission factor to air resp.

Emission factor to soil F air

F

soil [--] A/D from applicant or Table 

### 11

from applicant or Table 

### 11 Output Emission of additive to air resp. To soil Elocal air

Elocal soil [kg.d -1 ] O



### 4.5 Emission Scenario for Use of Rubber Products by Tyre Abrasion

53. Tyres for motor vehicles cause tyre abrasion that is deposited as particles or dust on streets and roads and on nearby soil [Baumann and Ismeier 1998, p. 307-353]. These particles are exposed to wind transport and weathering so that hydrolysis, leaching, and biodegradation of tyre constituents can take place. Photo transformation by light is unlikely to play a major role on degradation. The following persistent leaching products were identified, when tyres were kept in water (pH 7) or acid rain water (pH 4) for eleven months [Baumann and Ismeier 1998, p. 341] (Table 12).

Table 12 Laboratory Experiments: long-term Leaching Products of Tyres in distilled and acid rain Water, [Baumann and Ismeier 1998, p. 341] 

### Substance Abbreviation Concentration [mg/L] 2-Mercaptobenzothiazol MBT < 0.5 Benzothiazole BT 15 – 1972 2-Methylbenzothiazol MeBT < 2 2-Methylthiobenzothiazol MeSBT < 2 Aniline 5.9 – 294 Dicyclohexylamine < 35 – 218 Cyclohexylamine < 1 – 423



### 54. These and other additive substances were identified in monitoring studies of street run-off water and urban sediments. These monitoring studies [Baumann and Ismeier 1998; p. 342 - 343; Schmegel 1995, p. 75; Spies et al. 1987; Kumata et al. 2000] show that tyre abrasion contributes significantly to run-off releases of persistent breakdown products of rubb er additives, e.g. benzothiazole and methylated benzothiazole.

55. An approach to calculate the annual regional em ission rate [kg/a] of a rubber additive or its breakdown product via tyre abrasion is presented in equation (3).

### ENV/JM/MONO(2004)11

32 product breakdown additive abrasion prod ann product breakdown 

### MW MW F Q Eregional

_ _ _ 

### ⋅ ⋅ = (3)

Parameter:

Explanation Symbol Value Unit Origin Remarks Input Amount of the additive produced per year in defined region prod ann 

### Q

_ [kg.a -1 ] A The region needs to be defined.

Emission factor for abrasion from tyres F abrasion 0.12 [--] D Hartung and Koch 1989 p. 33 Ahlers et al. 1996, p. 73 Molecular weight of additive MW additive [g.mol -1 ] A Molecular weight of breakdown product MW breakdown_pr

oduct [g.mol -1 ] A

Output Emission rate of breakdown product (or additive) from tyre abrasion in defined region Eregional [kg.a -1 ] O The quotient of molecular weights is one, if the additive is considered.



### 56. The regional emission rate can be the input parameter in any Mackay level III fugacity model (e.g. SimpleBox) for calculating the regional concentrations in surface water and natural soil.

4.6 Emissions from Leachates

57. Considerable amounts of used tyres (about 30%) are disposed off in landfills. In Germany this amount was 135 000 t.a -1 

### in 1987 [Hartung and Koch 1989, p.81]. Rubber additives and their breakdown products may find their way into leachates of the landfill. Used tyres are used as bumpers in fresh water and marine habours. Rubber constituents and breakdown products leach to water. The emission rates of such leachate processes are not quantified yet.

### ENV/JM/MONO(2004)11

33 5. EXAMPLES OF EMISSION ESTIMATION

5.1 Emissions from Formulation and Processing to Wastewater

A Calculation of the emissions of a plasticiser Additive in the manufacturing of a tyre; emission occurs during cooling after extrusion (equation 1).

Input Data

Q

prod = 33000 kg.d -1 Q additive = 3.8 phr F recipe = 2 - F remaining = 0.95 -
Output Data

Elocal water = 31.35 kg.d -1



### B Calculation of the emissions of an antioxidant Additive in the manufacturing of a rubber product (equation 1).

Input Data Q

prod = 22000 kg.d -1 Q additive = 0.4 phr F recipe = 2 - F remaining = 0.99 - Output Data Elocal water = 0.4 kg.d -1



### C Calculation of the emissions of an anti-ageing agent Additive in the manufacturing of a truck tyre (equation 1).

Input Data Q

prod = 14800 kg.d -1 Q addtivie = 0.5 wt-% F recipe = 1 - F remaining = 0.99 -
Output Data Elocal water = 0.7 kg.d -1



### Example for the determination of the Clocal water 

### with the data of example B Additive in the rubber industry. Calculation of PEClocal for the aquatic compartment. The EU default values for the waste water treatment plant and the dilution factor are us ed. Other OECD Member countries may use other default values. Site specific values may also be used.

### ENV/JM/MONO(2004)11

34 Chemical: Example:

Amount of the product produced per day Q prod = 22000 kg.d -1 (from Table 8):

Parts of additive introduced in Q additive = 0.4 phr parts of 100 rubber:

Recipe factor: F recipe = 2

Fraction of additive remaining in the product: F remaining = 0.99

Fraction of emission directed to water (100% assumed): Fstp water = 100 % (SimpleTreat Model [EU 2003])

Capacity of sewage treatment plant (STP) [EU 2003]: EFFLUENTstp = 2000 m 3 .d -1

Dilution factor [EU 2003]: DILUTION = 10

Factor (1+Kp*SUSPwater) [EU 2003]: FACTOR = 1

Emission per day

recipe

remaining additive prod 

### F F Q Q
∗ − ∗ ∗ = 100 ) 1 ( Elocal water Elocal water = 0.44 kg.d -1

Influent concentration

Clocal inf = 

### p EFFLUENTst Elocal water Clocal inf = 0.22 mg.L -1

Effluent concentration

Clocal eff = Clocal inf * Fstp water Clocal eff = 220 μg. L -1

Concentration in surface water:

Clocal water = 

### F ACTO R D ILUTIO N Clocal eff



### ∗ Clocal water = 22 μg. L -1

PEClocal water = Clocal water if PECregional water = 0

### ENV/JM/MONO(2004)11

35 5.2 Emissions from Formulation and Processing to Air resp. Soil

A Calculation of the emissions of a plasticiser Additive in the manufacturing of a tyre; emission occurs during cooling after extrusion (equation 1).

Input Data Q

prod = 33000 kg.d -1 Q additive = 3.8 Phr F recipe = 2 - F air = 0.01 -
Output Data Elocal air = 6.27 kg.d -1



### 5.3 Emission from Abrasion of Tyres
Example: N-Cyclohexylbenzothiazol-2-sulfenamide (CBS ) is degraded to the persistent Benzothiazol (BT). Production of this vulcanisation accelerator in Germany is used.

Input Data Q ann_prod (CBS in Germany) 2030 t.a -1

F abrasion 0.12 MW breakdown_product 264.50 g.mol -1
MW additive 135.18 g.mol -1 Output Data Eregional breakdown_product 124.5 t.a -1

### ENV/JM/MONO(2004)11

36 6. REFERENCES

Ahlers J, Beulshausen T, Diderich R, Maletzki D, Regelmann J, Riedhammer C, Schwarz-Schulz B, Weber C (1996). Bewertung der Umweltgefährlichkeit ausgewählter Altstoffe durch das Umweltbundesamt . Umweltbundesamt, UBA Texte, Vol.. 38/96. Berlin, p. 373. Association of the German Rubber Industry (1990), Wirtschaftsverband der Deutschen Kautschukindustrie (WDK). Leaflet of the WDK. Association of the German Rubber Industry (1999), Wirtschaftsverband der Deutschen Kautschukindustrie (WDK). information. Baumann W and Ismeier M (1998). Kautschuk und Gummi – Daten und Fakten zum Umweltschutz

, Springer Verlag, Berlin, ISBN 3-540-64044-4. Baumann W and Ismeier M (1998). Emissions from Tyres in dedicated Uses , Kautschuk, Gummi, Kunstoffe, 51, 3. EU (2003). Technical Guidance Document on Risk Assessment, European Commission, Joint Research Centre, Ispra/Italy, 2003; http://ecb.jrc.it

. Hartung H and Koch D (1989). Mengen, Verwertung und Entsorgung von Altreifen in der Bundesrepublik Deutschland (Amount, recycling and disposal of us ed tyres in the Federal Republik of Germany). Umweltbundesamt, research report UFOPLAN 103 03 220/01. Berlin, p. 117. International Rubber Study Group, Rubber Statistics (2003). Rubber Statistical Bulletin, http://www.rubberstudy.com - Statistics Kumata H, Sanada Y, Takada H, and Ueno T (2000). Historical trends of N-Cyclohexyl-2- benzothiazolamine, 2-(4-Morpholinyl)benzothiazole, and other anthropogenic contaminants in the urban reservoir sediment core, Environ. Sci. Technol. 34, 246-253. Lüpfert S (1990). Raw Material in the Rubber Industry in the Light of German and European Legislation

, Kautschuk, Gummi, Kunststoffe, 43(9), 780. Lüpfert S (1991). Environmental Protection versus Compounding , Kautschuk, Gummi, Kunststoffe 44(8), 771-779. OECD (2002). Compilation of comments on the dr aft emission scenario documents, Document TFEEA(2002)2 of 10 June 2002. OECD Paris. Rentel KH, Gmehling J, Lehmann E (1991). Stoffbelastung in der Gummiindustrie , Wirtschaftsverlag NW. ISBN 3-89429-139-7. Sablowski Datacom GmbH (1996). Rubber Doc. Schmegel C (1995). Struktur-Wirkungsbeziehungen in der prospektiven Analyse von Umweltgefährdungen am Beispiel der Substanzklasse der Benzothiazole . Fachbereich Biologie/Chemie der Universität Bremen. PhD dissertation, Bremen, p. 124. Spies RB, Andresen BD, Rice DW Jr. (1987). Benzothiazoles in estuarine sediments as indicator of street runoff . Nature 327, p. 697-699 Ullmann’s Encyclopedia of industrial Chemistry (1993), 5 th 

### edition, Chapter “Rubber” , Vol. A23, VCH Verlag, Weinheim, p. 221-472.

### ENV/JM/MONO(2004)11

37 7. GLOSSARY

Adhesion The strength of bond between cured rubber surfaces or a cured rubber surface and a non-rubber surface.

Anticoagulant (Natural Rubber Latex) A substance added to field latex to retard bacterial action, which would otherwise cause rapid coagulation of the latex. Note: The word "stabilizer" is often used in place of "anticoagulant" in latex terminology.

Antioxidant A chemical used to retard deterioration due to heat, light, oxygen, or combinations thereof.

Autoclave A pressure vessel into which materials or articles can be placed and exposed to steam under pressure. It is commonly used for vulcanisation.

Butyl rubber Isobutene-isoprene rubber (IIR), synthetic rubber, so ft rubber, chlorobutyl and bromobutyl rubber as variants containing halogens with modified properties, high chemical resistance and high resistance to permeation, resistant to ozone and weathering

Calendering Calendering is a process in tire manufacturing where steel or fabric is coated with rubber. Steel belts, body plies, cap plies and belt edge covers are all produced using the calendering process. Steel or fabric is placed between two large heavy rollers. Rubber is also in serted between the rollers at the top and bottom of the material being coated. As the material moved thr ough the rollers the pressure forces the rubber to permeate and adhere to the steel or fabric.

Compound A thorough mixture of natural and/or synthetic rubbers with various ingredients designed for each tire part.

Curing the act of vulcanisation; a description of a definite time and temperature of vulcanisation.

Emulsifier A surface-active substance used to facilitate the dispersion of an immiscible liquid compounding material in another liquid and to stabilize the emulsion thereby produced.

Extrusion Extrusion is a process used to manufacture shaped solid rubber. Treads, sidewalls and bead fillers are manufactured using extruders.

Filler A solid compounding material, usually in finely divided form, which may be added in relatively large proportions to a polymer for technical or economic reasons.

Mastication To dissolve the rubber in solvents a technology was developed which is capable of softening the rubber by shearing it between two rotors.

### ENV/JM/MONO(2004)11

38 Plasticiser A compounding material used to enhance the deformability of a polymeric compound.

Rubber Natural rubber or any synthetic, elastomeric material with physical properties similar to those of natural rubber.

Tack The ability to adhere to itself; a sticky or adhesive quality.

Tackifier Tackifier resins are processing aids, which help keep rubber components together prior to curing. They are especially useful in synthetic rubber compounds, which have low levels of inherent tack. Tackifiers are commonly incorporated into solvent base, water-base and hot melt adhesives with a base polymer such as natural rubber, styrenic block copolymer, ethylene vinyl acetate, polyethylene homopolymers, and butyl elastomers. The optimum type of elastomer will depend upon the final desired application and performance properties.

Thermoplastic Rubber Rubber that does not require chemical vulcanisation and will repeatedly soften when heated and stiffen when cooled; and which will exhibit only slight loss of its original characteristics.

Thickener A substance used to raise or control the viscosity of latex with out the necessity for major changes in the total solids content.

Vulcanisation An irreversible process during which a rubber compound through a change in its chemical structure (for example, cross-linking) becomes less plastic and more resistant to swelling by organic liquids and elastic properties are conferred, improved, or extended over a greater range of temperature.

### ENV/JM/MONO(2004)11

39 8. ABBREVIATIONS

BR butadiene rubber CR poly-2-chlorobutadiene DIN German Institute for Standardization EDTA ethylene diamine tetraacetate EPDM ethylene propylene diene rubber ESD Emission Scenario Document EU European Union HF high frequency IC industrial category IIR isoprene isobutylene rubber IR isoprene rubber LCM liquid curing method Max Maximum NBR acrylonitrile butadiene rubber NR Natural rubber PEClocal Predicted Environmental Concentration at the local stage phr parts per hundred rubber RP Rubber product SBR synthetic butadiene rubber SR synthetic rubber STP Sewage treatment plant TGD Technical Guidance Document of the European Union for Risk Assessment Chemicals and Biocides TI Tyre industry UC use category UHF ultra high frequency WDK Association of the German Rubber Industry