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TABLE OF CONTENTS

1 INTRODUCTION AND OBJECTIVES .............................................................................4

2 AFR SUITABLE FOR CO-PROCESSING IN CEMENT KILNS...................................6

3 WASTE PRE-PROCESSING TO AFR.............................................................................14 3.1 General .........................................................................................................................14 3.2 Pre-processing of waste for co-processing in cement kilns ...........................................15

3.2.1 General ............................................................................................................15 3.2.2 Pre-processing before co-processing as AFR .................................................15

4 PROCEDURES FOR PRE-PROCESSING WASTE DERIVED AF.............................17 4.1 General .........................................................................................................................17 4.2 Analyses of wastes .........................................................................................................17 4.3 Transport of waste ..........................................................................................................18 4.4 Arrival of waste ..............................................................................................................18 4.5 Unloading waste .............................................................................................................19 4.6 Waste storage units.........................................................................................................20 4.7 Health and safety handling waste...................................................................................20

4.7.1 Fire and explosion protection..........................................................................20 4.7.2 Workers protection..........................................................................................24

5 PRODUCTION PROCESSES OF AFR BASED ON WASTE .......................................26 5.1 Solid alternative fuel (SAF) ...........................................................................................26 5.2 Liquid alternative fuel (LAF) as such ............................................................................28 5.3 LAF by fluidification .....................................................................................................29 5.4 LAF by emulsification ...................................................................................................30 5.5 Pre-processing plant examples .......................................................................................32

5.5.1 Energis, Holcim Group, in Albox, Spain ........................................................32 5.5.2 Ecoltec, Mexico...............................................................................................34 5.5.3 Recent waste deal between Shanks and SRM of Castle cement, UK .............36

6 ENVIRONMENTAL ISSUES ............................................................................................37 6.1 Consumption of resources ..............................................................................................37 6.2 Emissions to air ..............................................................................................................37 6.3 Volatile organic carbon (VOC) and smell......................................................................38 6.4 Impact on surface and ground water ..............................................................................39 6.5 By-products and wastes generated .................................................................................40 6.6 Noise .........................................................................................................................40

7 TECHNIQUES TO INCLUDE IN BAT DETERMINATIONS......................................41 7.1 Preventive measures and reduction techniques for dust.................................................41 7.2 Preventive measures and reduction techniques for VOC and smell ..............................42 7.3 Preventing pollution of surface and ground water .........................................................45 7.4 By-product recovery and waste treatment......................................................................46

8 BEST AVAILABLE TECHNOLOGIES (BAT)...............................................................47 8.1 General .........................................................................................................................47 8.2 Preventive measures for dust, VOC and smell emissions ..............................................47 8.3 VOC emission capture and treatment.............................................................................47 8.4 Water emission prevention and treatment ......................................................................48 8.5 Used packaging ..............................................................................................................48

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9 HEALTH AND INDUSTRIAL HYGIENE.......................................................................49

9.1 General .........................................................................................................................49 9.2 Industrial hygiene (IH) ...................................................................................................49

9.2.1 Terminology....................................................................................................49 9.2.2 Recognizing factors and stressors ...................................................................49 9.2.3 Evaluations ......................................................................................................50 9.2.4 Control measures.............................................................................................50

9.3 Chemical hazards and controls.......................................................................................50 9.3.1 General ............................................................................................................50 9.3.2 Chemicals and compounds..............................................................................50 9.3.3 Air contaminants .............................................................................................54 9.3.4 Chemical hygiene plan ....................................................................................59 9.3.5 Hazard communication ...................................................................................59 9.3.6 Respiratory protection.....................................................................................59

9.4 Physical hazards and controls ........................................................................................61 9.4.1 General ............................................................................................................61 9.4.2 Noise and hearing conservation ......................................................................61 9.4.3 Pressure extremes............................................................................................64 9.4.4 Radiation and control ......................................................................................64 9.4.5 Thermal hazards ..............................................................................................65

9.5 Ergonomic hazards and control......................................................................................67 9.5.1 General ............................................................................................................67 9.5.2 Body systems at risk........................................................................................67 9.5.3 Evaluation .......................................................................................................68 9.5.4 Controls ...........................................................................................................68 9.5.5 Training ...........................................................................................................68

9.6 Biological hazards and controls .....................................................................................68 9.6.1 General ............................................................................................................68 9.6.2 Bio-aerosols.....................................................................................................69 9.6.3 Blood borne pathogens (BBP) ........................................................................70 9.6.4 Zoonotic diseases ............................................................................................70

10 AFR FEED POINTS IN CEMENT KILNS ......................................................................72

11 CONCLUSIONS ..................................................................................................................74

12 REFERENCES.....................................................................................................................75

ABBREVIATIONS .....................................................................................................................77

APPENDIX 1: LIST OF WASTE MATERIALS SUITABLE FOR AFR.............................79

APPENDIX 2: MATERIAL SAFETY DATA SHEET OF LINDANE..................................86

APPENDIX 3: MATERIAL SAFETY DATA SHEET (MSDS) OF DDT.............................92

APPENDIX 4: RISK PHRASES................................................................................................94

APPENDIX 5: SAFETY PHRASES..........................................................................................98

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1 INTRODUCTION AND OBJECTIVES This report is a part of the Sino-Norwegian project “Environmentally Sound Management of Hazardous and Industrial Wastes in Cement Kilns” running from 2007 through 2009 (Karstensen and Justnes, 2007). The project comprises co-processing of waste in cement kilns. It has two major advantages; the society gets rid of waste in a safe manner and the cement industry save energy if the waste has a calorific value (alternative fuel, AF) or save raw material (alternative raw material, AR) if the waste has a fraction that remains solid after burning (Justnes and Engelsen, 2007). Sometimes it is difficult to distinguish the two latter benefits since many wastes have a calorific value and a remaining solid component. Waste for co-processing is, therefore, often referred to as alternative fuel and raw material (AFR). Another aspect of the project is to use cement kilns to destruct hazardous waste in a safe manner. The objective of the present report is to elucidate operational health and safety issues when handling hazardous waste for destruction or when pre-processing industrial waste to make AFR for co-processing in cement kilns, but also to inform about technology for pre-processing operations transforming waste to AFR. Some terms are important to define and definitions 1-5 are taken from the GTZ-Holcim “Guidelines on co-processing waste materials in cement production” (2006): 1) Waste: The EC Framework Waste Directive 75/442/EEC, Article 1 defines waste as “any substance or object, which (a) the holder discards or intends or is required to discard or (b) has to be treated in order to protect the public health or the environment.” Waste material can be solid, liquid, or pasty. Any waste material can be defined by its origin (industry, agriculture, mining etc.), hence a proper list should always be established at national level to help create a common understanding and define a legal framework. Where no specific list has been defined, the EC Waste Catalogue might serve as a reference. 2) Hazardous and non-hazardous waste: The EC Directive 91/689/EC on Hazardous Waste defines hazardous waste by reference to two Annexes that evaluate the level of danger of a material (harmful, irritating, combustible etc.). However, legislation can vary greatly between countries (except within the EU), leading to differences in determining whether a waste is hazardous or not. For countries where no classification of waste exists, either the Waste List of the Basel Convention1 or the EC Waste Catalogue2 is recommended. 3) Co-processing: This refers to the use of waste materials in industrial processes, such as cement, lime, or steel production and power stations or any other large combustion plants. Even though the EU calls this process co-incineration, for the purpose of this report, co-processing means the substitution of primary fuel and raw material by waste. Co-processing is a recovery of energy and material from waste. Waste recommended for co-processing is listed in Appendix 1 (GTZ, 2006). 4) AFR (Alternative Fuel and Raw Materials): This refers to (pre-processed) waste materials used for co-processing. Such wastes typically include plastics and paper/card from commercial and industrial activities (e.g. packaging waste or rejects from manufacturing), waste tires, waste oils, biomass waste (e.g. straw, untreated waste wood, dried sewage sludge), waste textiles, residues from car dismantling operations (automotive shredder residues), hazardous industrial 1 http://www.basel.int/text/con-e-rev.pdf 2 http://www.vrom.nl/get.asp?file=/docs/milieu/eural_engelse_versie.pdf

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waste (e.g. certain industrial sludges, impregnated sawdust, spent solvents) as well as obsolete pesticides, outdated drugs, chemicals and pharmaceuticals. 5) Pre-processing: Transforming waste to AFR requires certain standards. AFR does not always consist of a specific waste stream (such as tires or solvents) but must be prepared from different waste sources before being used as fuel or raw material in the cement plant. The preparation process is needed to produce an AFR stream that complies with the technical and administrative specifications of cement production and to guarantee that environmental standards are met. Cement is one of the most widely used substances on earth. Making cement is an energy and resource intensive process with both local and global environmental, health and safety impacts. Recognizing these facts, several cement companies initiated the Cement Sustainability Initiative (CSI) as a member-sponsored program of the World Business Council for Sustainable Development (WBCSD). Currently, sixteen cement companies, who together represent more that half the worldwide industry outside China, sponsor the Initiative. Recently the CSI Conference Board (http://www.conference-board.org/aboutus/about.cfm) published a research report: R-1334-03-RR, ‘Driving Toward “0”’, Best Practices in Corporate Safety and Health, in which it collated Best Practice gems of wisdom from a wide range of industries. The findings can be found in the full document at the URL: http://www.conference-board.org/publications/describe.cfm?id=724 For more general information concerning “Safety Management and Organization” as well as “Effective Safety Practices” in the cement industry, that also are relevant for waste processing plants or any other process industry, it is referred to Kirk (2004a) and Kirk (2004b), respectively. This report focuses on the more specific hazard and health aspects of waste handling and pre-processing, as that this often is done by another company than the cement plant. The waste pre-processing plant will then deliver ready AFR to the cement plant.

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2 AFR SUITABLE FOR CO-PROCESSING IN CEMENT KILNS Although waste suitable for alternative fuel (AF) is treated in a separate report by Karstensen in this project and alternative raw materials (AR) recently was reported in detail by Justnes and Engelsen (2007), overviews of the utilization of alternative fuels (AFs) in the European and AFR in the Japanese cement industry are given in Table 1 and 2 respectively, while utilization of alternative raw materials (ARs) in the European cement industry is listed in Table 3. The recommended exclusion of certain waste materials (GTZ, 2006) grouped 1-8 from co-processing can be justified as follows (also summarized in Table 4): 1. Electronic waste Electronic waste is composed of computer and accessories, entertainment and communication electronics, toys but also white goods such as kitchen devices or medical apparatus. A recent study3 of the Swiss environment agency BAFU reveals that average electronic scrap consists of 45% of metals in terms of weight, with the highest portion on heavy metals and rare metals. With 23%, plastic ranges second in the composition, and compounds of picture tubes are at 20%. The average composition shows that electronic scrap contains on one hand substances harmful to health and the environment such as Cl, Br, P, Cd, Ni, Hg, PCB and brominated flame retardants in high concentration, often higher than threshold limit values as fixed in the permits. On the other hand, the scrap contains so much scarce precious metals that all efforts have to be undertaken to recycle it. Co-processing of the plastic parts of the electronic waste would be an interesting option, but requires disassembling and segregation first. Table 1 Utilization of AF in the European Cement Industry in 2002 Alternative fuels (AFs) Amount

(1,000 ton/year)Energy(1012J)

Substitution rate (%)

Animal meal / bone meal /animal fat 760 15,000 2.0 Tires 500 13,200 1.8 Other hazardous waste 360 6,500 0.9 Plastic 210 5,000 0.7 Paper / cardboard /wood / PAS 180 2,800 0.4 Impregnated sawdust 165 1,900 0.3 Coal slurries / distillation residues 110 1,650 0.2 Sludges (paper, fibre, sewage) 100 970 0.1 Fine /anodes / chemical coke 90 1,600 0.2 Refuse Derived Fuel (RDF) 40 530 0.1 Shale / Oil shale 15 130 < 0.1 Packaging waste 12 260 < 0.1 Agricultural & organic waste 10 170 < 0.1 Other non-hazardous waste 730 14,100 1.9 Subtotal solid AF (75%) 3,282 63,810 8.5 Waste oil and oiled water 380 13,500 1.8 Solvents and other organic liquids 260 3,900 0.5 Other hazardous liquid AF 170 4,300 0.6 Subtotal liquid AF (25%) 810 21,700 2.9 Total AF 4,092 85,510 11.4

3 Schriftenreie Umwelt Nr. 374, BUWAL, 2004

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Table 2 Utilization of waste for AFR in the Japanese cement industry (2001) Type of waste Use at cement plant Mass (1,000 tons) Blast furnace slag Raw material, mixing material 11,915 Coal ash Raw material, mixing material 5,822 By-product gypsum Raw material (additive) 2,568 Low quality coal from mine Raw material, Fuel 574 Non-iron slag Raw material 1,236 Revolving furnace slag Raw material 935 Sludges etc Raw material, Fuel 2,235 Soot and dust Raw material, Fuel 943 Foundry sand Raw material 492 Used tires Fuel 284 Waste oils Fuel 353 Spent activated carbon Fuel 82 Waste Plastics Fuel 171 Others Raw material, Fuel 450 Total AFR 28,061 2. Entire Batteries Batteries can be classified as automotive batteries, industrial batteries and portable (consumer) batteries. Automotive batteries are mainly lead-acid batteries; industrial batteries comprise both lead-acid batteries and nickel-cadmium batteries. The portable battery consists of general purpose batteries (mainly zinc-carbon and alkaline manganese batteries), button cells (mainly mercury, zinc-air, silver oxide, manganese oxide and lithium batteries) and rechargeable batteries (mainly nickel-cadmium, nickel-metal hydride, lithium ion and sealed lead-acid batteries). Most of these substances are harmful to health and the environment. Co-processing of batteries would lead to an undesirable concentration of pollutants in the cement and the air emissions. Also, some battery contents, such as mercury, nickel or cadmium, exceed any limit value for AFR (see Table 5, 6 and 7). In addition, commercially viable battery recycling plants have been successfully introduced. Table 3 Utilization of AR in the European cement industry (2002) Main clinker substitution

Alternative raw material

Amount (1,000 tons/year)

Substitution rate (%)

Foundry sand 131 2.2 Silicon (Si) Sand 93 1.6 Ca-sources 396 6.7 Calcium (Ca) Waste limestone 438 7.4 Fe-containing materials 699 11.8 Blastfurnace & converter slag 215 3.6

Iron (Fe)

Pyrite ash 438 7.4 Al-containing materials 150 2.5 Aluminium (Al) Industrial sludge 137 2.3 Other Si-Al-Ca rich materials 247 4.2 Fly ash 1,140 19.3

Si-Al-Ca

Others 1,823 30.8 All Total 5,907 -

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3. Infectious and biologically active medical wastes Infectious and biologically active hospital wastes are generated in the hospitals, in veterinary care and in research. Examples are used blood transfusion bags, blood contaminated bandages, dialysis filters, injection needles, and also parts of the body and organs. Biologically active hospital wastes include pharmaceuticals. The disposal requires special hygienic and work safety requirements on handling, packaging and transportation. See also Chapter 9 on Health and Industrial Hygiene. The conditions in the cement kiln would be appropriate to treat infectious and biologically active hospital wastes, but would require special precautions on occupational health and safety (OH&S) in the supply chain of this type of waste. As the required OH&S conditions can not be fully assured, co-processing is presently not recommended. However, the problem of inadequate handling of medical waste has persisted for years, especially in developing countries. Although it is well known that segregating waste at the source is the most important step in managing medical waste, this principle is not yet sufficiently applied. Even less attention is given to the ultimate safe storage and final treatment (sterilization or microwave) of infectious waste. Small medical waste incinerators have been promoted and introduced in the past in many countries as a decentralized solution. However, experience that this technology in many cases is not appropriate due to absence of qualified personnel and high costs associated with building, operating, maintaining and monitoring such facilities. As a consequence, the release of unwanted emissions (such as Polychlorinated dibenzodioxins (PCDDs) and Poly-chlorinated dibenzofurans (PCDFs), hydrochloric acid or heavy metals) in relatively high concentration must be considered. As the problem persists and might become even more severe with a wider spread of infectious diseases (such as AIDS, SARS, Bird flu, Ebola etc.) co-processing might become part of the solution for final treatment, but only if defined pre-conditions in hospitals and health care centres have been introduced. Future cooperation and research between international organizations such as the WHO and the cement industry could result in joint activities, such as the definition of standardized handling procedures. Table 4 Overview of waste materials not recommended for co-processing and reasons why Enrichment

of clinker pollutants

Emissionvalues

OH&S Recyclingpotential

Landfilling better option

Negative impact on kiln operation

Electronic waste

x x x

Entire batteries

x x x x

Infectious and biological active medical waste

x

Mineral acids and corrosives

x x x

Explosives x x x Asbestos x x Radioactive waste

x x

Unsorted municipal waste

x x x x

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4. Mineral acids and corrosives Mineral acids are derived from inorganic minerals. Examples are hydrochloric acid, nitric acid, phosphoric acid and sulphuric acid (e.g. automotive batteries). The inorganic minerals such as S and Cl that are the main component of the acid have a negative impact on the clinker process (also P if P2O5 > 0.5% of clinker) and product quality and may lead to unwanted waste gas emissions. Acid may corrode and damage the production facilities. Beside mineral acids, substances that can cause severe damage by chemical reaction to living tissue, or freight, or the means of transport are prohibited, as are all corrosive substances. Well known examples are aluminium chloride; caustic soda; corrosive cleaning fluid; corrosive rust remover/preventative; corrosive paint remover. These types of materials should be excluded from co-processing due to the upstream collection, transport risks and handling hazards. 5. Explosives Explosives are any chemical compound, mixture or device capable of producing an explosive-pyrotechnical effect, with substantial instantaneous release of heat and gas. Examples are nitro-glycerine, fireworks, blasting caps, fuses, flares, ammunition, etc. Reasons to exclude them from co-processing are occupational safety due to the risk of uncontrolled explosions during pre-processing activities such as transportation, handling, shredding etc. Explosive reactions in the cement kiln would have a negative impact on process stability. 6. Asbestos Asbestos is a name given to a group of minerals that occur naturally as masses of long silky fibers. Asbestos is known for its unique properties of being resistant to abrasion, inert to acid and alkaline solutions, and stable at high temperatures. Because of these attributes, asbestos was widely used in construction and industry. Asbestos fibers are woven together or incorporated within other materials to create many products. Airborne asbestos fibres are small, odourless and tasteless. They range in size from 0.1 to 10 microns in length (a human hair is about 50 microns in diameter). Because asbestos fibres are small and light, they can be suspended in the air for long periods. People whose work brings them into contact with asbestos may inhale fibers. Once inhaled, the small, inert asbestos fibers can easily penetrate the body‘s defences. They are deposited and retained in the airways and tissues of the lungs and can cause cancer. Due to this negative health impact, the use of asbestos has been forbidden for around 25 years. Asbestos-containing materials can be classified into one of three types: Sprayed or trowelled-on material (e.g. ceilings or walls), thermal system insulation (e.g. plaster cement wrap around boilers, on water and steam pipe elbows, tees, fittings, and pipe runs), or miscellaneous materials (e.g. floor tile, sheet rock, ceiling tiles, automotive friction products). Millions of tons of asbestos products will become waste material in the future, especially in developing countries, and not all countries have national regulation on handling and final disposal of this significant waste stream. Asbestos-containing products could be treated in specially equipped rotary kilns at a temperature > 800°C for a certain time. The asbestos minerals would be transformed into other minerals like Olivine or Forsterite. Therefore co-processing could be, from a technical point of view, an option for treatment of asbestos waste. However, sanitary landfilling must be regarded as the most appropriate way of final disposal as the material can be disposed undisturbed and does not provoke the release of unwanted fibers into the air. Once safely dumped, the asbestos waste does not have further negative environmental impacts. As the availability and new installation of sanitary landfill become more and more a problem, requests for co-processing asbestos might arise in the future. However before cancelling asbestos from the banned list, detailed

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investigations are required in particular on OH&S in the whole supply chain. Further, asbestos-specific regulations have to be introduced and enforced by the national authorities. 7. Radioactive waste Radioactive waste is normally excluded from “classical” waste management, and therefore specific regulations have to be applied according to international agreements. This means that radioactive waste can not be treated under the regulations of municipal and household waste and special permissions for its treatment are required. The procedure is normally stipulated in national nuclear laws. Cement plants are not suited to handle radioactive waste. However, there is a borderline case for low radioactivity wastes (e.g. waste from research, cleaning devices or in medical entities). Following the recommendations from the International Atomic Energy Agency and other organizations, many countries define waste as low radioactive if the radiation of this material to humans does not exceed 10 μSv (micro Sievert) per year. For this case a restricted or even an unrestricted clearance for handling this waste within an integrated waste management scheme could be given. At the international level, there is still a big discrepancy on procedures for clearance, and no uniform levels are given. As it is very difficult for most companies and/or authorities to guarantee that the threshold limit value (TLV) of 10 μSv could be assured at any time, co-processing of any kind of radioactive waste is not recommended. 8. Unsorted municipal waste Municipal waste is a heterogeneous material and consists in developing countries mainly of native organic (e.g. kitchen refuse), inert (e.g. sand) and post-consumer (e.g. packing material) fractions. Valuable recycling goods such as cardboard, plastic, glass or metal are often sorted out by the informal (waste pickers) or formal (cooperatives) sector. Despite recent efforts by local authorities in keeping their cities cleaner, the problems persist with the final disposal of the waste if no sanitary landfill sites can be made available due to protests by citizens or the high costs of the transport to a suitable site. In order to escape from this bottleneck, local and national decision makers opt for co-processing of the collected mixed waste material and to shift the responsibility of final treatment to the cement industry. However, from an ecological, technical and financial point of view, the co-processing of unsorted municipal waste is not recommended. Mixed municipal waste must be sorted in order to obtain defined waste streams of known quality. For selected materials, co-processing should be regarded as an integrated part of municipal solid waste management. There are a number of limitations in different countries for wastes to be used in co-processing and for AFR. These are listed in Tables 5, 6 and 7.

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Table 5 Limit values in different permits and regulations for waste for co-processing in

Austria, Switzerland and Germany

Austria Switzerland Germany

General combustible waste1

High calorific fraction of common waste

Solvents, spent oil, waste lacquers

General combustible waste2

Other waste for disposal

High calorific fraction of common waste3

Solvents, spent oil

Maximum values (mg/kg) As 15 15 20 15 - 13 15Sb 5 20 (200)4 100 5 800 120 20Be 5 - - 5 - 2 2Pb 200 500 800 200 500 400 150Cd 2 27 20 2 5 9 4Cr 100 300 300 100 500 250 50Cu 100 500 500 100 600 700 180Co 20 100 25 20 60 12 25Ni 100 200 - 100 80 160 30Hg 0.5 2 2 0.5 55 1.2 1Tl 3 10 5 3 - 2 2V 100 - - 100 - 25 10Zn 400 - - 400 - - -Sn 10 70 100 10 - 70 30Cl- 10,000 20,000 - - - 15,000 -PCB 50 - 100 - - - -1Net calorific value 25 MJ/kg. 2Net calorific value 18 MJ/kg. 3PET. 4PET, polyester. 5Special case, flue gas cleaning for Hg

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Table 6 Examples of limit values for AF for different countries based on individual permits Parameter Unit Spain1 Belgium2 France2

Calorific value MJ/kg - - - Halogens (given as Cl-) % 2 2 2 Cl % - - - F % 0.2 - - S % 3 3 3 Ba mg/kg - - - Ag mg/kg - - - Hg mg/kg 10 5 10 Cd mg/kg 100 70 - Tl mg/kg 100 30 - Hg + Cd + Tl mg/kg 100 - 100 Sb mg/kg - 200 - Sb + As + Co + Ni + Pb + Sn + V + Cr

mg/kg 5,000 2,500 2,500

As mg/kg - 200 - Co mg/kg - 200 - Ni mg/kg - 1,000 - Cu mg/kg - 1,000 - Cr mg/kg - 1,000 - V mg/kg - 1,000 - Pb mg/kg - 1,000 - Sn mg/kg - - - Mn mg/kg - 2,000 - Be mg/kg - 50 - Se mg/kg - 50 - Te mg/kg - 50 - Zn mg/kg - 5,000 - PCBs mg/kg 30 30 25 PCDDs / PCDFs mg/kg - - - Br + I mg/kg - 2,000 - Cyanide mg/kg - 100 - 1Limit values set by authorities for individual permits for cement plants in Spain 2Voluntary self-commitment of the cement industry with authorities and concerned ministry

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Table 7 Examples of limit values for waste to be used as AR in different countries Parameter Unit Spain1 Belgium2 France2 Switzerland3

TOC mg/kg 20,000 5,000 5,000 -Halogens (given as Cl) % 0.25 0.5 0.5 -F % 0.1 - - -S % 3 1 1 -Hg mg/kg 10 - - 0.5Cd mg/kg 100 - - 0.8Tl mg/kg 100 - - 1Hg + Cd + Tl mg/kg 100 - - -Sb mg/kg - - - 1Sb + As + Co + Ni +Pb + Sn +V + Cr

mg/kg 5,000 - - -

As mg/kg - - - 20Co mg/kg - - - 30Ni mg/kg - - - 100Cu mg/kg - - - 100Cr mg/kg - - - 100V mg/kg - - - 200Pb mg/kg - - - 50Sn mg/kg - - - 50Mn mg/kg - - - -Be mg/kg - - - 3Se mg/kg - - - 1Te mg/kg - - - -Zn mg/kg - - - 400PCBs mg/kg 30 - - 1pH - - - - -Br + I mg/kg - - -Cyanide mg/kg - - - -1Limit values set by authorities for individual permits for specific cement plants in Spain 2Voluntary self-commitment of the cement industry with authorities and concerned ministry 3Limit values for AR, BUWAL 1998. Guidelines disposal of wastes in cement plants, Table 1

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3 WASTE PRE-PROCESSING TO AFR

3.1 General Waste recovery and disposal treatment often need a pre-processing step. This may be a single operation or the combination of several processes (grouping/reconditioning, pre-processing). These operations may be processed on the waste production site, on specific dedicated locations or integrated with the final process. The aim of waste pre-processing before recovery or disposal (i.e. including use as AFR) is to:

1. Facilitate a recovery access or to improve dedicated treatment for wastes such as stabilisation for landfilling (in order to decrease long term impact of the hazardous waste), homogenisation for an incinerator feed (used in order to improve combustion conditions) etc.

2. Improve safety for waste treatment (decrease hazardous characteristics, facilitation of handling etc.)

3. Rationalise the logistic cost The combination of treatments used in waste preparation and in pre-processing operations depends on the specifications of final treatment. At the end of the pre-processing, the pre-processed waste has to comply with chemical and physical specifications that are fixed by the end users. Most of the operation linked with waste treatment may be divided into regrouping / reconditioning and pre-processing. In regrouping / reconditioning the aim is to group wastes in small or medium quantities, when they have the same nature, and when they are compatible. The resulting waste has still to be processed. The vocation of regrouping is to have more important and homogeneous volumes. In pre-processing the aim is to adapt the waste to the type of recovery and/or disposal final treatment. Pre-processing may develop several aspects. It can be defined as the operations that lead to homogenisation of chemical composition and/or physical characteristics of the wastes. Pre-processing produces an adapted waste, which is different from the initial ones, but not from the regulatory point of view. This adapted waste has still to be treated in a recovery and/or in a disposal plant. The main processes used in waste preparation activities are

• Re-grouping / re-conditioning • Homogenisation and blending • Crushing • Sieving • Fluidification • Sorting for solid wastes • Phase separation for liquid wastes: settling, centrifugation, extraction etc. • Drying • Washing

Pre-processing activities are integrated in the treatment of wastes. So, they have both to comply with waste regulations (knowledge of wastes, traceability, follow up of wastes stream etc.), industrial and environmental regulations (environmental impact assessment and public

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consultation, permit with adapted specifications such as risk prevention, specifications for soil, water and air protection etc.), as well as related health and safety regulations.

3.2 Pre-processing of waste for co-processing in cement kilns

3.2.1 General The history of the co-processing (mainly co-incineration in cement kiln) started in the mid seventies when the petroleum crisis had increased drastically the cost of the fuel oil and when, in different countries, new regulation was issued on waste disposal. As a large amount of energy rich waste (mainly solvents) were available, the co-processing of waste in cement kilns was the most logical answer to the situation on both environmental and economical points of view. Then, in order to increase the energy saving, more and more sophisticated pre-processes have been developed, first to produce liquid alternative fuel (LAF) and in the nineties to produce solid alternative fuel (SAF). Alternative fuel is sometimes referred to as “substitution fuel”. The use of waste derived fuel in European cement kilns saves fossil fuels. This represented in 2003 3.15 million tons of coal per year. In addition to energy recovery, there is a corresponding greenhouse gas saving, mainly CO2 emissions (7.4 million tons CO2) not released to the atmosphere. This waste may contain mineral components that will be recovered in the kiln as alternative (also referred to as “substituted”) raw material. The advantages of utilizing a cement kiln for treatment of hazardous wastes can be summarised as follows:

• high flame temperature (1,800-2,000°C) • 5 to 6 seconds of residence time above 1,200°C • excess of oxygen during and after the combustion • complete destruction of organic compounds • neutralisation of acid gases, sulphur oxides and hydrogen chloride, by the active lime in

the kiln load, in large excess to the stoechiometry • embedding of the traces of heavy metals in the clinker structure with very stable bonds • no production of by-products such as ashes or liquid residues from gas cleaning • reduction of fossil fuel and/or raw material uses • total recovery of energy and mineral content of the wastes (raw material and fossil fuel

saving)

3.2.2 Pre-processing before co-processing as AFR The aim of the pre-processing is to adapt the waste to enable fuel and raw material recovery by means of co-processing. The basic principles of waste derived fuel production are the following:

• The chemical and physical quality of the fuel shall meet regulatory specifications and/or standards ensuring environmental protection, cement kiln process and cement quality.

• Energy and mineral contents must remain stable to allow optimal feed in the kiln. • The physical form must allow safe and proper handling, storage and feeding.

Several derived fuels can be prepared according to the different waste markets:

• Solid alternative fuel (SAF) based on absorbents, solid and pasty wastes.

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• Liquid alternative fuel (LAF) based on solvents, oils, emulsions or other organic liquids. • Sludges.

Note that some hazardous wastes, produced in stable processes, may comply without any preparation with the requirements of the co-processing plant. Due to that, they are often delivered directly to the co-processing plant (e.g. used oils, used solvents etc), these streams, their control modalities and their storage specifications are not integrated in this document. Data for SAF based on pre-processing plants production in 2001 in France, Belgium, Holland, Germany, Italy, Switzerland, Spain, Portugal, Poland, Norway and Slovakia: The average size of a SAF pre-processing plant is 18,000 tons/year, with capacities ranging from 2,000 tons/year to 70,000 tons/year. The total production of SAF was 465,000 ton/year in 26 plants. Data for LAF (excluding oils) based on regrouping and pre-processing plants in France, Belgium, Holland, Germany, Italy, Switzerland, Spain, Portugal, Ireland, England, Sweden, Norway, Czech Republic and Slovakia: The size of a LAF pre-processing plant varies widely, from 5,000 tons to 100,000 tons/year. For regrouping facilities, the typical size of a plant ranges from 1,000 tons to 20,000 tons/year. The total production of LAF was 806,000 ton/year in 117 plants.

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4 PROCEDURES FOR PRE-PROCESSING WASTE DERIVED AF

4.1 General This chapter is about all operations which are common to all types of alternative fuel (AF) production.

4.2 Analyses of wastes Each step of the hazardous waste management (and not only waste recovered fuel production) requires knowledge and control of the waste. The aim of this sub-chapter is to present the different types of controls and analyses which are carried out, during the waste recovered fuel process, from the waste production to the final treatment. Acceptance analyses When a waste producer contacts a waste management company (WMC) in order to treat his wastes, a very complete and preliminary analysis will be done by the WMC. Based on the results of these analyses, and according to the permit and the technical specifications (pre-processing facilities and final users), the WMC decides to accept (or reject) the waste on its pre-processing facility and delivers «an acceptance certificate». This certificate is regularly reviewed (one to five years). The main parameters which are analysed in order to prepare a waste useful for energy recovery in co-processing are listed in Table 8. A sample is taken under the responsibility of the producer by himself or by the WMC commercial representative. Reception analyses For each reception of wastes on the pre-processing site, analyses are done in order:

• to be sure that the waste complies with the permit requirements, • to define as well as to decide if pre-processing is possible, • to provide a stable quality of the prepared fuel, • to ensure compliance with internal OH&S requirements (employee’s protection), • to keep records for (potential) future requests, inquiries or allegations

The main parameters which are analysed at reception are listed in Table 8. In specific cases, some sites may develop simplified procedures for regular wastes with constant quality. This particular procedure may be developed under quality procedure and with the agreement of the authorities. The procedure of sampling before unloading is made by dedicated personnel. Adequate sampling equipment must be available at each sampling station. The sampler must receive extensive training in occupational health & safety aspects and preventive / protective measures, in addition to training in the regular sampling procedures. Recommended sampling tools are the following:

• For liquids use standard aluminium or copper sampling tubes (2.5 and 1.2 m length, around 20-30 mm diameter) with ball valves at one end.

• For solids and pasty materials use an aluminium shovel (capacity around 0.5-1 litre) or drilling devices.

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Automatic sampling of liquids during unloading of trucks enables higher accuracy and reduced OH&S risk for the sampler. If the sample is not available prior to unloading, the waste has to be unloaded in a separate buffer tank and analysed prior to further treatment. The samples can be stored in glass or plastic bottles (PE or PTFE) of different volumes (250, 500, 1,000 ml), in plastic bags (various size) or in metallic cans. Written instructions (sampling procedures) must be available for the sampler taking into consideration:

• The physical nature (liquid, solid, pasty) and the volume of the material. • The containment of the waste deliveries (trucks, containers, drums, cans etc.). • OH&S risk of the material.

When the pre-processing unit is separated from the co-processing facilities, new analysis, with or without adapted procedure, can be requested and will be similar to the preceding reception analyses. Process analyses During the waste pre-processing, specific analyses are undertaken to monitor the quality of the processed wastes. The main parameters which are analysed are listed in Table 8. Sampling is according to the type of processes and installations. Expedition analyses At the completion of the pre-processing, analyses are made in order to ensure compliance with respect to all parameters and specifications which are necessary (regulatory or technical parameters) for the final treatment. The main parameters which are analysed are listed in Table 8. Sampling is according to the type of alternative fuel produced. External analyses Supplementary analyses can be done under the control of the authorities.

4.3 Transport of waste

• Wastes are conditioned in trucks, container, drums or other types of containers. • Transport of drums or containers has to be done properly, especially in case of hazardous

wastes: They must be in good state, closed, and the content has to be identified. • Transport of hazardous wastes has to comply with the relevant Regulations on the

Transportation of hazardous substances, so called ADR: Special equipped trucks have to be used, transport documents have to be in order and the driver must be properly trained for this type of transport.

• Usually wastes are brought to the pre-processing plants by trucks. Ship and rails transport should be promoted whenever economically and environmentally feasible.

4.4 Arrival of waste

• At the arrival on the plant, the driver has to give all the administrative required documents, such as:

o Certificate of acceptance

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o Administrative document which follows the waste way, from the producer to the

plant, via the collectors or transport companies o Transport authorisations, according to national regulations o Waste analyses from the producers in some cases

• If these administrative requirements are not met (after checking with a producer), the truck is sent back to the producer, and local authorities will be informed.

• A control of the aspect of the truck and its loading is made by the personnel of the plant. If some non-conformity is noticed, the producer/collector is immediately informed.

• After these controls of both administrative documents and loading, the truck is weighed, and sampled. The reception analysis follows (see chapter 4.1). In the case of packaged wastes, trucks are unloaded before analysis.

Table 8 Recommended parameters for different analyses of waste Parameters Acceptation Reception AF preparation

process* Expedition

Density Yes Optional Optional Optional Viscosity Optional Optional Optional Optional Flash point Yes Yes Optional Yes Low calorific value (LCV) Yes Yes Yes Yes Vapour pressure Optional Optional Optional Optional Water content Yes Yes Optional Yes pH Yes Yes Optional Yes Ash content Yes Optional Optional Yes Ash composition Optional Optional Optional Optional Chlorine Yes Yes Yes Yes Fluorine Optional Optional Optional Optional Bromine Optional Optional Optional Optional Iodine Optional Optional Optional Optional Volatile heavy metals (Hg, Tl, Cd) Yes Yes Optional Yes Other heavy metals Yes Yes Optional Yes Polychlorinated biphenyl (PCB) Yes Yes Optional Yes PCP Optional Optional Optional Optional Sulphur Yes Optional Optional Optional Alkalis Optional Optional Optional Optional Corrosion test Optional Optional Optional Optional Compatibility test Yes Yes - - Radioactivity Optional Yes - Optional * function of the type of production. Optional: Function of type of wastes, operating processes (liquid or solid alternative fuel preparation) and according to requirements specifications of the final users. Parameters in italic characters: Minimum controls required in standard procedure.

4.5 Unloading waste After the laboratory has given its approval for unloading, the truck will proceed to the unloading area. Wastes delivered in bulk are unloaded:

• In pits for solid and pasty wastes, • On sealed concrete floors for solid and pasty wastes • In tanks for liquid wastes.

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Wastes delivered in drums, containers or other types of conditioning are unloaded on a specific area, dedicated to conditioned wastes. Each load which is clearly identified by the laboratory has to be properly and separately stored, per producer, type of waste, etc.

4.6 Waste storage units Storage capacities have to be designed to ensure a continuous service to the waste producers, in case of shutdown of the co-processing facilities which use the pre-processed wastes as an alternative fuel. Sludges and solid wastes can be stored in a closed building in pits or on a sealed concrete floor according to the physical aspect and flash point. The installations have to be waterproof and resistant to the waste composition (notably corrosion and abrasion). Appropriate ventilation is required. Packed wastes are stored on a covered concrete area, with retention. Liquid wastes are stored inside closed tanks. Sawdust and/or waste which may be used as adsorbents are stored in a closed area with concrete floor, in silos, containers, hoppers or big bags. Note that some installations are equipped to produce their own sawdust by shredding waste wood. Sawdust comes from the first use of wood (sawmill or furniture production), but also from the recycling of waste wood (tiny particles that can not be reused in the wooden panel industry). Surfactant products may be used in some alternative fuel production (e.g. to make emulsions). They are stored in separate tanks.

4.7 Health and safety handling waste This sub-chapter presents standardised procedures applied for all types of treatment or pre-processing of hazardous wastes, being for co-processing or for incineration.

4.7.1 Fire and explosion protection Since wastes generally are transformed to AFR for their calorific value (combustible), and wastes for simple destruction often is of organic nature, fire and explosive risks are highly relevant issues. Fire prevention measures are an appropriate combination of the following points:

• Waste knowledge (to detect potentially exothermic reactions) • The plant have to be protected from direct and indirect lightning impacts • Prevention of electrostatic electricity discharges (e.g. establish equipotential connections

between metallic masses and trucks) • A fire permit has to be established for all works which request a flame • Adapted and regular electricity controls are requested

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• Workers training against fire in order to know how to use protection measures • Development of an adapted plant control with cameras, temperature and flame detection,

etc • Use of technical measures such as firebreak wall, water curtain, etc

According to Kirk (2004b) safe storage and handling practices of waste will minimize hazards and the likelihood of fire. Best practices for handling flammable and combustible materials include:

1. Storing flammable gases away from oxidizers 2. Storing combustible and flammable liquids in labelled safety cans with a spring-closing

lid, spout cover and flame arrestor screen 3. Storing safety cans and aerosol cans in approved, designated storage cabinets 4. Storing solid fuels in compacted piles to reduce the chance of spontaneous combustion 5. Posting warning signs prohibiting smoking, flames and open lights wherever flammables

or combustibles are used, stored or handled 6. Controlling and promptly cleaning up spills, leaks and waste before large quantities

accumulate 7. Turning OFF internal gasoline-powered internal combustion engines when refuelling 8. Using hot-work permits and fire watches when welding or oxy-fuel burning near

combustible materials 9. Providing fire suppression sprinklers in critical work and storage areas.

Kirk (2004 b) emphasises further that gases, oils, greases, paper products and other flammable or combustible materials should not be stored or allowed to accumulate in:

1. Pyro-processing areas or other locations where high temperatures or open flames are common or likely

2. Areas where spillage of hot dust may occur 3. Near potential electrical ignition sources.

Automatic sprinklers or fire suppression systems are recommended in storerooms or warehouses where large quantities of combustible materials are stored. Belt conveyors used for transporting hot materials, such as clinker, should be rated for high temperature use, monitored by remote sensors and protected by sprinklers. Explosions release tremendous amounts of energy in the form of heat, light, sound and pressure. Pressure waves can rise at the rate of 13,800 kPa/sec to reach 620-760 kPa with air velocities in excess of 320 km/h. Potential explosion damages include:

1. Human injury or fatality 2. Secondary explosions 3. Fires 4. Damage to equipment or building structures 5. Damage to or interruption of process systems, utilities or communications systems.

Explosion prevention measures are an appropriate combination of the following points:

• Closed areas with canalisation of exhaust air with effective ventilation • If necessary, development of spraying measures or use of inert nitrogen atmosphere (in

mixers, crushers, etc.)

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• Definition of explosion risk areas in order to put signals on and to equip them with adapted

detection means • Use of anti sparks equipment • Avoid any sources that could cause local heat release

Catalytic and infrared detectors are used to spot explosive atmospheres. The calibration of the detector needs particular attention. According to Kirk (2004b), explosions can occur only when the following five factors exist together simultaneously:

1. Finely divided fuel 2. An ignition source 3. Oxygen 4. Suspension 5. Confinement.

Best practice is to prevent explosions by eliminating or controlling one or more of the preceding five factors. Immediate repair of flammable and combustible materials leaks is advised, such as when coal-handling systems leak in a cement plant. Good housekeeping will minimize the quantity of fuel that could be involved in a secondary explosion. Other control methods include use of oxy-fuel burning and welding gases with a narrower explosive range, less volatile solid fuels (such as coke instead of coal), limiting heat or eliminating ignition sources, reducing oxygen or using inert process gases, etc. According to Kirk (2004b) explosion protection methods include:

1. Containment; relying on the strength of process equipment to retain the post-explosion atmosphere

2. Isolation; stopping the spread of the explosion from the point of origin 3. Suppression; minimizing the destructive ability of an explosion by injecting pressurized

nitrogen or powdered agents such as mono-ammonium phosphate or sodium hydrogen carbonate into the incipient explosion area

4. Venting; reducing pressure to a safe level by releasing the burning process material and excessive pressure into a safe area (Chatrathi and Siwek, 1996.) Redundant systems are recommended.

In a cement plant (Kirk, 2004b), explosion and fire potential exists in kiln fuel preparation, dust collection and firing systems (especially those using gas or stored pulverized coal), and in electrostatic precipitators of the kiln exhaust cleaning system where combustible gases like carbon monoxide (CO) or combustible pulverized coal particulates may accumulate. Written procedures should be prepared and followed regarding fuel preparation and safe operating parameters of precipitator. Particular attention should be given to periods of non-standard operating activities such as start-up, shut-down, equipment malfunctions and equipment maintenance periods. These are the times of highest probability of sparking or collection of oxygen-rich gases in the system. Gases used for heating, drying and ground fuel transport in coal mills should be inert, having oxygen levels incapable of supporting combustion, certainly less than 12%, preferably less than 8%. Rising temperature and incipient explosion sensors and analyzers for oxygen and combustible gases should be tied to automatically acting control systems. When oxygen-displacing materials such as liquid or vapour CO2, or N2 gas, are used to control combustion or explosion, best practices are to:

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1. Protect the inert gas storage tanks from damage and subsequent unintentional leakage into

the work environment 2. Add an odour that personnel can sense if leakage does occur 3. Employ gas detection devices to sense concentrations that might be of immediate danger

to life and health, and couple them with visible and audible warning alarms 4. Provide lockable valves in the gas piping and delivery systems to prevent unintended

discharge into equipment or vessels occupied by persons performing inspections or maintenance

5. Consistently use lockout and confined space entry procedures. Where explosion rupture vents are used, they should be located away from areas where personnel travel or congregate and away from critical equipment, preferably directed to the outside of buildings. Workers should not be permitted near explosion vents during operation. Explosions could potentially involve vehicles transporting or discharging flammable or combustible liquids or gases (gasoline, fuel oil, oxy-fuel burning gases). Procedures should, therefore, be developed to control these activities in the plant. Explosion of accumulated hydrogen gas at battery charging stations may be prevented by collecting the gas and venting it safely outside, and by eliminating sparks or open lights in the vicinity. Typical principles of fire detection equipment are listed in Table 9. Table 9 Principles of fire detection Signal Fire Detection Equipment Temperature increase

Thermo-fusibles, sprinklers with fusible heads, temperature probes, linear detection of temperature

Smoke Optical smoke detector, laser detector CO (carbon monoxide)

CO detection is only actual when active carbon is used for gas treatment

Flame Three wavelength infra-red detector Incandescent particles

Detector with infra-red principle

According to Kirk (2004b), fire fighting facilities should: 1) provide strategically located hydrants, hoses and extinguishers of appropriate size and rating, and inspect and test them at intervals at least as frequently as specified by regulatory agencies, 2) maintain clear access in front of extinguishers, hydrants and hose reels, and 3) train employees on proper use of fire fighting equipment. Emphasis should be placed on procedures to be followed when a fire is discovered. Best practices include exercising these steps in this order to: 1) rescue any persons at risk, 2) alarm or alert others to the fire, 3) contain the fire by closing doors and windows, and 4) extinguish the fire, in a safe manner. The first letters of this procedure spells RACE. Combustion produces intense heat and toxic gases, so fire fighting should be attempted only when personal safety is not at-risk. Specially trained and experienced fire fighting teams, protective clothing and special equipment should be used as conditions warrant. Typical principles of fire extinguishing equipment depending on location in a waste processing plant are given in Table 10.

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Table 10 Principles of fire extinguishing Location - part of the plant

Fire extinguishing equipment

Liquid waste storage Injection box of foam inside storage, cooling ring system (foam or water) on storage circumference, foam diffusers inside retentions capacity

Drum storage Adapted sprinkler systems (foam solution, powder or CO2-systems depending on waste stored)

Pasty waste reception pit Foam diffusers Solid alternative fuel final storage

Foam diffusers

Conveyer belts Sprinkler system with foam Crushers Powder or foam injection Dust filters CO2 or nitrogen injection Active carbon treatment CO2 or nitrogen injection Rotary screener Sprinkler systems

4.7.2 Workers protection a) Identification of the properties of the waste It is requested to get the Material Safety Data Sheet (MSDS) or all available information on the hazards (corrosive, flammable, toxicity, etc.) of the waste presented for treatment. These can be obtained from the producer of the waste or by analysis of the physico-chemical properties of the waste and can be compared with data on industrial toxicology. b) Compliance of the properties of the waste with the installations Some properties as corrosion effects, flammability and possibility of dust emission, reaction with other components, etc have to be checked before formal acceptance of the waste in the installation. c) Separation of workers and waste The concept of the installation and the organisation of storage and handling of the waste have to be planned in order to limit the workers exposure to the waste, vapours or dust (keep the hazard far from the worker). d) Storage and treatment in closed area In order to limit emissions and dispersions, storage and treatment of the waste should occur as far as possible in closed buildings, with appropriate ventilation. Keeping the waste in closed areas reduces drastically the risk of contact, inhalation or absorption by the workers. e) General safety rules Due to the variety of waste and hazard properties, it is necessary to simplify as far as possible the safety instructions and safety rules for the workers. This is why it is recommended to have general safety instructions such as the obligation to wear individual protections e.g. helmets, safety shoes, gloves and glasses, as well as masks for dust or organic vapours (for this last element, depending of the kind of waste which is handled). Specific instructions and adapted procedure have to be applied only for some wastes presenting special hazard characteristics.

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f) Personal information and training - The workers have to be trained for fire intervention and for first aid action if requested. - Appropriate emergency plans have to be set up, explained to the workers and training for emergency situations has to be enforced. - Each time that a new risk occurs due to a new waste, special information is requested for the workers. - Workers must not work alone in isolated parts of a plant and must always be equipped with appropriate communication tool to report any problem. g) Personal protection Individual protections have to be always available and have to be changed each time that a contamination is identified (overall, gloves, mask-filters, etc.) h) Controls of

• Atmosphere Controls of the atmosphere to which the workers could be exposed should be done once a year or more regularly if the levels of contaminants are near a MAC limit value. Appropriate ventilation or filter systems can be added.

• Quality of the waste Analyses are always requested to ensure that the qualities of the delivered waste correspond to the specifications of a former acceptation. Adaptation in the processing method, safety rules or rejection of the waste has to be examined when a deviation is detected.

• Safety requirements The composition and the risk of waste received are presented to the doctor who is in charge of the health of the workers. He will identify what appropriate tests have to be done to control their health. He will eventually recommend protection measures.

• Health of the workers In the case of exposure to hazardous components, a medical check-up of the worker is done every 6 month by the doctor. The examination is done on general health aspects, but also on the research of components or metabolites in blood and urine.

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5 PRODUCTION PROCESSES OF AFR BASED ON WASTE

5.1 Solid alternative fuel (SAF) The goal of SAF preparation is to prepare a tailor-made, homogeneous, and free flowing alternative fuel to be used in co-processing. The following list (a-d) is an indicative one and should not be considered as exhaustive: a) Pasty wastes: High viscosity solvents, oil sludges, distillation residues, sludges from the treatment of industrial sludges (mechanical industry, chemical industry, pharmaceutical industry, etc), paints and varnishes sludges, ink sludges, polyol, glues, resins, grease and fats and other pasty wastes. b) Powder wastes: Carbon black, toner powder, paints, spent catalysts, surfactants and other powders. c) Solid wastes: Polluted polymers, impregnated sawdust, sludges from waste water treatment, resins, paints, glues, spent activated carbon, polluted soils, hydrocarbon sludges, polluted absorbents, organic residues from the chemical and pharmaceutical industries, spent plastic packaging, waste woods and other solid wastes. d) Liquid wastes that are not suitable for Liquid Alternative Fuel (LAF) production (due to polymerisation risks, etc.). Between 20% and 40% of absorbents per ton of SAF produced are used, depending on co-processing specifications. The kinds of absorbents are fresh sawdust, sawdust from wood recovery, polyurethane, papers by-product, textile, etc. There is a permanent research for other absorbents in order to replace the fresh sawdust. General processes and production steps for SAF can be divided into (a-h): a) Feeding of the waste from the storage to the production units. Pre-homogenisation of the incoming wastes is realised based on physical and chemical characteristics. This step is critical for ensuring the compliance of the SAF with the final users’ specifications. Solid waste and adsorbents (as such or premixed together) can be taken back for treatment with a bulldozer, a crane, a travelling crane or a walking floor. The transport to the mixing unit can be done by a conveyor belt, a screw, an elevator, etc. Pasty wastes (as such or premixed with adsorbents) are handled by a crane or pumped to the mixing unit. b) Shredding and/or sieving of coarse particles Wastes that could contain big particles need to be shredded or sieved before introduction into the mixing unit. Types of shredders are 1) Slow motion shredder used for flammable and low flash point wastes (mono-rotor or bi-rotor with large knives), 2) Hammer shredder used for wood pieces, polluted packaging, and/or plastics, etc. and 3) Dedicated shredders used for specific wastes (e.g. cryogenic shredder, etc). Types of sieves used for big particles separation are 1) Vibrating sieve, 2) Static sieve and 3) Rotary sieve.

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c) Feeding of the mixing unit Concrete pump, endless screw, elevators, bulldozers or conveyor belts are used for the transport from the shredder to the mixing unit. d) Mixing operations These operations are made in closed areas to prevent emissions of dust and volatile organic compounds (VOC). Types of mixing systems are: 1) Mixing with a crane in a dedicated pit. 2) Closed mixer with a range of propellers or screws on a horizontal axis with low speed rotation. This system is efficient for waste without hard particles bigger than for example 25 cm (e.g. concrete, hard wood, steel, etc) that could block or damage the propellers or screws. 3) Closed mixer with a “turn-cup” and an axis with knives. The safety of the mixing devices can be ensured by using nitrogen as inert atmosphere. The reduction of oxygen (working conditions between 6 to 8 % of oxygen) by the injection of nitrogen allows the mixing of waste with flash point lower than 0°C. Materials are fed directly or through a hopper to stabilise, regulate and control the quantity of waste introduced in the mixing unit. A conveyor belt is used after the mixing operation to bring the SAF to the sieve. e) Scrap extraction Standard magnetic separator on the conveyor belt is used to extract iron and steel particles. Depending on the desired output, a vibrating sieve can be used to clean the scrap from remaining sticking residues. In some cases, Foucault current systems could be added to remove non-ferrous metals. f) Sieving operations These operations are made in closed systems to prevent emissions of dust and VOC. The kinds of sieves are 1) Rotary sieve and 2) Vibrating sieve. The dimensions, as well as the design of the sieve mesh depend on the granulometry specifications and the off-specification products (different fractions are possible on some installations, depending on the possibilities of reuse of the big particles). Off-specifications fractions can be reprocessed in the production, treated in a dedicated shredder, and/or treated in incineration or dedicated co-processing units. g) Storage of SAF before loading Storage capacities have to be designed to ensure a continuous service. SAF quality is controlled during the production phase either by automatic or manual sampling before storage. If the quality does not fulfil the specifications, the product is reprocessed. It is necessary to store the SAF in a closed area like 1) Closed building with appropriate ventilation and retention where the SAF is handled with a crane, travelling crane or conveyor belt or 2) Silo (cylindrical or parallel piped) with a screw or a walking floor to extract the SAF. The type of storage will depend on the need for homogenisation in the storage unit. h) Expedition of the SAF The loading of the trucks (or potentially of train or ships) is done by crane, conveyor belts or bulldozers.

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5.2 Liquid alternative fuel (LAF) as such These operations can consist of grouping of small quantities and/or pre-processing activities such as phase separation or settling. The aim of this operation is to blend and homogenise compatible wastes from several producers and / or sources. The purpose of this operation is to:

• Provide a proximity service to producers having small quantities of organic liquid wastes • Rationalise the logistic organisation (transports, etc.) • Develop an adapted solution for packed wastes with several phases (liquid/pasty or solid) • Separate the different phases (water, organic liquid, sludges or solid) from a composite

waste in order to optimise the recovery • Prepare homogeneous and stable wastes with specifications in accordance with

environmental protection and co-processing processes or dedicated incineration processes Wastes suitable for LAF are typically;

• Solvents • Xylenes, toluenes, white-spirit, acetone • Cleaning and degreasing solvents • Petroleum residues • Distillation residues • Off specification organic liquid product

General processes and production steps for LAF can be divided into (a-c): a) Unloading and grouping 1) Liquid wastes in bulk After filtration and/or settling, organic liquids are sent with a centrifuge or membrane pump to metallic cylindrical-conical tanks equipped with blending devices in order to avoid settling or phase separation (pendular mixer or pumping system which blend the top and the bottom of the tank by continuous circulation). If necessary, storage will be made inert with nitrogen. Each storage tank is put in a waterproof retention area and equipped with a level indicator. Gas effluent from events are collected and treated. 2) Packed wastes (drums, etc.). Before grouping, the packaging is emptied with techniques adapted to their physical-chemical characteristics. Generally, two phases exist; a liquid and a pasty (and sometimes solid) in the bottom of the drum. For liquid wastes the drums are put in a ventilated emptying area. After opening, the liquid phase is pumped to a small buffer tank. A compatibility test is carried out before transfer to the final storage. Pasty and solid wastes present in the bottom of the drums will be processed in solid alternative fuel production (see chapter 5.1). This step can be carried out manually or in an automated emptying station. b) Preparation This step can consist as operation such as settling, grinding, filtration and blending. A stirring propeller or a re-circulation system is used in order to keep the wastes homogeneous. Sometimes, a grinding system is used with re-circulation technique in order to decrease granulometry of solid particles which may be in the liquid waste.

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c) Expedition Before loading, the liquid preparation is filtered through a 3 mm mesh. The loading of the trucks is done with all the security systems needed.

5.3 LAF by fluidification Fluidification means processes where liquid, pasty and solid wastes are homogenised and shredded together in order to produce liquid alternative fuel (LAF) for co-processing. Typical acceptable wastes for fluidification are;

• Pasty organic wastes (ink sludges, paint sludges, adhesives wastes, etc.) • Oil residues • Pulverulent wastes such as paint powder • Filter cakes • Residues from organic chemical synthesis • Oil and fat • Spent ion exchange resins • Distillation residues • Wastes from cosmetic industries

The fluidification process is composed of 4 main sections (a-d). In order to prevent emissions into the environment, the first section of operations are done under controlled ventilation. This measure allows to trap VOC and dusts and to treat them with air filters. The last 3 sections of the process are run in closed vessels and pipes. For this part, VOC emissions are very low (exhaust gas of the vessels and tanks) and are treated with other VOC on a dedicated equipment. a) “Calibration” of pasty part This step consists in both shredding coarse particles and extracting of foreign metallic parts blended accidentally with chemical waste, and transfer of this pasty product into the mixing tank. Shredders used are 1) Slow motion shredder for flammable and low flash point waste (mono-rotor or bi-rotor rotary shears) or 2) Dedicated shredders for specific waste (e.g. cryogenic shredder, etc). Over-bands are necessary for extracting foreign metallic bodies from chemical waste. Technologies based on Foucault current are also used for isolating nonferrous metals. Vibrating sieves and / or static grates can also be used in this conditioning step to remove big particles in order to facilitate the operation of the shredder. The product can be transferred by: 1) Endless screw as the cheaper solution. It requires a limited slope from screw bottom to mixing tank inlet (less than 15° for the screw) and a by-pass for liquid (from screw bottom to mixing tank). 2) Pump (e.g. a concrete pump). A simpler design is beneficial for lower investments (small capacity unit) or when the wastes are prevented by strong by-product (e.g. waste from distillation). In this case, the product may be transferred into the mixing step by shredding. A rotary filter may be installed to remove large quantities of by-products. b) Dissolution and screening The aim of this step is to dissolve and emulsify pasty parts into a solvent phase to reach a homogeneous product.

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The dissolution of solid organic compounds in the liquid phase composed of solvents and / or waste water is carried out by special mixers, rotary screens and buffer tanks. The mixers must respond to the constraints of sticky material containing strong and voluminous solids in suspension. They pulverise the solids between rotor and stator and blend them into the liquid phase. Once the dissolution of hydrocarbons is achieved, the liquid mixture is admitted inside a rotary screen which extracts the pieces of plastic lining fragmented by the shredder of the prior step. A buffer tank collects the product at the end of this step. c) Grinding and emulsifying This step consists in finely grinding the solid particles remaining in suspension in the liquid phase. It consists also in making a fine emulsion between the aqueous and hydrocarbons phases constituting the alternative liquid fuel. The stability and the quality of combustion of the fuel depend directly on both, its homogeneity and the size of fragmentation of the solids in suspension. Those criteria require high velocity technologies of grinding / emulsifying protected by magnetic separators and mechanical filters. The equipment must be flexible enough in order to accept fluctuations of viscosity, density and nature of the solids in suspension. Risks of fire / explosion inside this section are prevented by a hydraulic guard inside the buffer tank of the previous section. This guard prevents any penetration of oxygen inside the machinery. The alternative fuel quality is controlled at this step, during filling up of the buffer tank. Some parameters such as pH and viscosity can be controlled continuously. Other parameters such as LCV, composition, flash point, are controlled from samples taken during the production. If the quality doesn’t meet the specification, the fuel must be reprocessed before being transferred to the storage unit. A simpler design is possible for lower investments (small capacity unit) where steps b and c may be done at the same time. In this case the mixing and buffer tank are the same and the grinding line runs into the mixing tank. d) Storage and dispatching Once a high level is reached inside the buffer tank, the liquid alternative fuel can be transferred by pump into the final storage. During this transfer, a latter adjustment of the quality of the fuel can be carried out by means of grinders and filters operating on the transfer line. The storage capacity is generally composed of vertical cylindrical-conical tanks with blending equipment. Two technologies of blending are appropriate to homogenise the liquid fuel: 1) A long marine mixer installed on the roof of the tank, or 2) A pumping system which blends the top and the bottom of the tank by loop circulation. The technology of a vertical agitator without any bearing inside the tank is the most efficient. Dispatching to the cement kilns is carried out by a truck loading station. This loading station is fed by the storage unit mentioned above.

5.4 LAF by emulsification The aim of this liquid alternative fuel process is to produce homogeneous and stable products which comply with environmental protection and co-processing specification. The origin of this process comes from the theology comportment of pasty preparation for clinker production. The installations used to produce this type of LAF are similar to those used for the pasty raw meal

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preparation for clinker production. This process is based on the control of blending by means of chemical or surfactants addition. The following list of wastes suitable for emulsification is indicative and should not be considered as exhaustive:

• Oils emulsions from mechanical and metallurgy industries • Wastes and sludges containing oil from petroleum refining, from collection and storage of

oil products • Wastes from oil distillation and regeneration • Waste from production failure (off-spec products) • Pasty wastes such as grease, ink and adhesives wastes • Pulverulent waste such as paint powder, washing powder wastes etc • Used bases such as sodium hydroxide • Used oils

General processes and production steps for LAF by emulsification can be divided into (a-f): a) Feeding of the waste from the storage to the production units Before introduction into the production process, wastes are de-conditioned with equipment adapted to their physical characteristics. Pasty wastes extracted form drums are put in special pits. They are first handled by mean of a mechanical shovel to a homogenisation pit. Then, they are transferred to a hopper in order to be introduced to the production process by a screw conveyor or a concrete pump. Pulverulent wastes such as paint and washing powder are received in big-bags. They are directly put in the production process with adapted equipment which will capture dust emissions. Liquid wastes are handled by pump. Pumping technologies (centrifuge pump, volumetric pump with outer rotor, etc) must be able to accept fluctuation of viscosity and presence of particles in suspension. b) Formulation According physical-chemical characteristics of the waste stored, the laboratory defines specifications including nature and quantities of wastes which are to be put in the production processes. Compatibility tests are also developed. Such tests are carried out at every operation, in order to comply with the LAF co-processing specifications. c) Production process The production process is a batch one. It is carried out by special mixers (called “delayers”), closed in order to prevent VOC emissions. The different components are introduced in the mixer according to laboratory specifications. An agitator provides a stable emulsion production. During this step, several parameters are monitored, such as viscosity, pH, temperature and motor specification. One of the purposes of this monitoring is to detect polymerisation reaction. d) Screening Once the emulsion is achieved, it is circulated again with a centrifuge pump to the mixer and through a curved screen providing particle retention above 4 mm.

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e) Sand extraction When the mixer is emptied and before being sent to the storage capacity, the LAF is pumped to a concrete pit with a sedimentation area. The aim is to separate through density mineral solid particles (e.g. sand) which may be present in the LAF production. f) Storage and dispatching The LAF is transferred by centrifugal pump to the storage. The capacity of storage is generally composed of concrete or steel vertical cylindrical tanks with blending equipment. Three technologies of blending are appropriate to keep the homogeneity; 1) a submerged agitator, 2) a low agitator with scraper in order to avoid sedimentation and 3) a pumping system which blends the top and the bottom of the tank with high flow (around 250 m3/hour) loop circulation. The LAF quality is controlled in order to be sure that its characteristics comply with the cement kiln specifications. In some specific cases, addition of energetic waste may be done if the calorific value is considered too low. Dispatching to the co-processing factories is carried out by a truck loading station. A final screening (through a mesh of 3 mm size) is done whilst loading.

5.5 Pre-processing plant examples

5.5.1 Energis, Holcim Group, in Albox, Spain Energis was created in 1997 as a subsidiary of Holcim Spain. The purpose of the company is to add value to Holcim Spain’s cement operations by providing waste management solutions to industry and communities through co-processing of waste in Holcim cement kilns. To directly access the waste market, Energis established the pre-processing plant at Albox in 2003. The plant, located in south-eastern Spain, transforms a wide range of solid, pasty, and liquid wastes into impregnated sawdust and liquid alternative fuels. Energis at Albox has two main production lines: (1) a shredding and mixing line in which solid and pasty waste are mixed with sawdust to produce impregnated sawdust and solid alternative fuel (SAF), and (2) a liquid storage and blending line for liquid alternative fuels (LAF). The lines are designed to produce 60,000 tons of SAF and 20,000 tons of LAF per year. Half of the sawdust used in SAF production must be fresh, and substitutes may be mixed with the sawdust. The main impregnation substitute material is compressed cellulose. Moisture content varies significantly among deliveries and suppliers, and greatly affects the impregnation capability of sawdust. This in turn affects the percentage of sawdust required for SAF production. About 90% of Energis’ waste is delivered in drums, 10% is transported in bulk by tanker or container truck, and a small amount is delivered in large bags. Waste for SAF include contaminated earth and sand, resin, paint, distillation residues, sludges of ink, glue, varnish and oil, mastic, filter cake, grease, soap, used catalysts and alumina sludge. Waste for LAF includes waste oil, polluted water and halogenated as well as non-halogenated solvents, etc. In July 2005 Spain introduced a law banning organic waste in landfills. This gave Energis at Albox more opportunities to find organic waste on the market. Only waste from authorized producers or collectors is accepted. To become authorized, the waste producer must submit a sample for analysis to the on-site laboratory, and permit Energis representatives to visit the producer and collect information about its manufacturing process. If the producer and the waste meet Energis’ requirements, Energis at Albox issues a certificate. To prevent contamination, each delivery undergoes rigorous quality control.

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Energis at Albox does not treat wastes such as pressed drums and metal separator residues, which are sent to a foundry for recycling. Pallets are taken back by the sawdust supplier, non-polluted scrap metal is sold to a local scrap dealer, and waste that cannot be processed – such as drums that cannot be shredded – is sent to a third party for treatment. Thanks to preliminary testing, a strong external communications policy, detailed analysis and a strict refusal policy, the percentage of refused waste is low. The plant’s success ensures a sustainable flow of AFR to Holcim Spain offers an innovative and practical solution to waste producers and, above all, benefits the cement industry as a whole. The design of the pre-processing plant at Albox (see Fig. 1) is similar to an earlier plant in Belgium: Scoribel. Energis at Albox profited from the many lessons learned at Scoribel. But market conditions in Spain and Belgium differ: 90% of the waste in Belgium is transported in bulk, whereas 90% of the waste in Spain is transported in drums. Each drum must be sampled as part of the quality assurance program, and properly handled and stored, which increases operational costs. The plant at Albox faced the problem of shredder fires caused by friction between the drums, their contents and the machinery during shredding. To reduce this risk, nitrogen was used as inert gas during the shredding operation, which increased the overall pre-processing costs. Over the past two years, Energis at Albox has got these problems under control. It has improved its sourcing of critical spare parts, and developed a special course to teach workers how to prevent shredder fires.

Fig. 1 Scheme of AFR production at the pre-processing plant of Energis at Albox. The legends

CSSf and CCS g in this case stands for fine and coarse SAF, respectively.

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5.5.2 Ecoltec, Mexico Ecoltec has facilities that process all types of waste. Agreements with the customers regulate the packaging and the collection/delivery conditions of waste materials. Transport is done in tanks or barrels or as bulk material by an external company. Liquid waste (e.g. waste oil, solvents, etc.) is mixed and stored in tanks before being fed into the cement kiln. Solid waste (e.g. plastic packaging, chipped tires, waste textiles etc.) and sludgy waste (e.g. paint residues, distillation sludges, oil sludge, etc.) are mixed with clean sawdust (see Fig. 2) and then shredded. During the sieving process, the fine, solid mix is separated from the coarse mix and then forwarded via conveyer belt to the storage building. The AFR is now ready to be transported by truck to the cement plant. A sketch of the pre-processing plant for SAF is reproduced in Fig. 3. Quality control is an essential part of pre-processing activities. First, clinker production requires that the used AFR fulfils certain requirements concerning calorific value, pH-value, humidity, chlorine and sulphur content. Second, accumulation of pollutants in the cement and excessive air emissions must be avoided. Quality control takes place in the internal laboratory, where test samples of incoming waste and of AFR are held ready to be fed into the cement kiln. The test samples and records of the results of the analysis are stored for security and reference purposes. The results are reported to the authorities on a regular basis.

Fig. 2 Handling impregnated saw dust at Ecoltec, Mexico. Note worker protection. The pre-processing activities are organized by Holcim Apasco’s pre-processing subsidiary, Ecoltec. It offers complete waste disposal solutions to customers, independent of whether the waste is suitable for co-processing or not. Waste not suitable for co-processing is forwarded to companies with adequate treatment facilities. For the transport of certain wastes, plastic or steel barrels are used. The plastic barrels are shredded and used as AFR. The steel barrels are forwarded for recycling once waste is removed. The barrels are squeezed flat with a special machine before recycling.

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The mixing process of sludgy waste with solid waste is done in an open building. The Volatile Organic Compound (VOC) emissions from the sludge must be drawn away to protect occupational health. A monitoring program assesses environmental impacts so managers can decide if further measures are required. VOC emissions are involved in the formation of summer smog. Common reduction techniques are nitrogen traps and biological treatment. The many different types of customers and the analysis of their different wastes require attention. Problems encountered in the transformation process from waste to AFR and in the clinker production due to unexpected pollutants in the waste, can be avoided by a frequent analysis of waste samples and securing the traceability of the waste from the customer to the cement kiln. The installation and running of pre-processing facilities requires development of strong relations with local communities. Their worries and fears about the negative effects of waste treatment need to be overcome, so Ecoltec held a series of open days for the public that included a plant tour. Beside general rules for pre-processing, special regulations are required for certain wastes (e.g. persistent organic pollutants, POPs). Although not critical from a technical point of view, public concerns remain about the formation of dioxins and furans during the combustion of POPs.

Fig. 3 Sketch of the SAF production at Ecoltec, Mexico.

Sieving

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5.5.3 Recent waste deal between Shanks and SRM of Castle cement, UK

The waste firm Shanks (www.shanks.co.uk/shanks/ ) has recently (February 2008) secured its second contract to supply solid recovered fuel (SRF) to the AFR pre-processing plant SRM, a subsidiary of Castle cement, UK. Under the Shanks contract, up to 50,000 tons of solid recovered fuel produced at mechanical biological treatment plants at Jenkins Lane and Frog Island in East London and Dumfries in Scotland will be sent to Castle Cement's Ketton works in Rutland. Here, the material will be shredded and blended by Castle's sister company SRM before being used to replace fossil fuels as AFR in the main kiln. For further information see

http://www.letsrecycle.com/do/ecco.py/view_item?listid=37&listcatid=217&listitemid=9666

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6 ENVIRONMENTAL ISSUES

6.1 Consumption of resources In terms of energy consumption, the electricity amount required to produce SAF varies from 5-25 kWh/ton, while the range for LAF is 5-20 kWh/t. The fuel consumption is from 0.15-3 litre per ton produced SAF and 0.05-2 litre per ton produced LAF. These data don’t include energy consumption for ventilation and air treatment. The large variation in electricity consumption is due to the different types of wastes, the packaging and the level of automation. For example, in the case of packaged drums to be shredded, the electricity consumption can reach 25 kWh/ton, while in the case of bulk wastes in a non-automated process line it will be 5-10 kWh/ton. Moreover, when the electricity consumption is high, the fuel consumption is usually on the low side. The fuel consumption is mainly for utilities vehicles and will decrease with the automation level. The total energy consumption represents less than 5% of the total energy content of the AF. Water is used for cleaning of installation, trucks and eventually drums, maintenance and spraying installations for dust abatement. The consumption is typical 5-20 litre per ton AF produced. On a general base, the water consumption is related to a good housekeeping of the AF production installation. It varies widely according to the type of wastes, the packaging and the eventual use of recovered rain water. If drums or containers need to be cleaned or rinsed for further use, an additional consumption of 2 to 20 l/ton AF can be anticipated. In some cases, nitrogen is used for making mixers, shredders or liquid storage inert. In such a case, the consumption of nitrogen may be 1-2.5 m3/ton AF produced. Other materials may be required for effluent treatment.

6.2 Emissions to air Dust is typically emitted during production of SAF during unloading and handling of absorbents and/or pulverulent wastes, processing and loading, but also during production of LAF by fluidification. Types of dust are absorbents (mainly from sawdust) and powdery wastes (paints, resins, washing powder, catalysts, etc.). Dust is monitored for

1. Canalised emissions: One control per year carried out by a certified laboratory 2. Air treatment systems: Follow up of the efficiency of the cyclone and bag filters by

pressure drop or opacity measures 3. Diffuse emissions: Can be followed by measurement with Owen gauge localised at the

site. Typical obtained values and limits for dust are listed in Table 11.

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Table 11 Typical dust emission values during AF production and limits SAF LAF After treating canalised emissions (daily average values) Achieved performance (mg/Nm3) Permit limit (mg/Nm3)

1-10

20-50

1-5

20-50 Emission from production site (mg/m2/day) < 100 m from emission source (depend on location of Owen gauge)

1.5-90 < 1

6.3 Volatile organic carbon (VOC) and smell Most accepted wastes contain organic compounds. In certain circumstance, according to vapour pressure and temperature, they are more or less volatile. These volatile organic compounds (VOC) could be potentially harmful for the environment and workers and could cause bad smell. This is why these emissions need a particular attention and follow up. The level of VOC emissions is a function of the nature of wastes, its flash point, vapour pressure of wastes components, and their concentration. VOC emissions are also influenced by the type of process and the climatic conditions. Emission of VOC and smell occurs during unloading operations (trucks, drums and containers) of both SAF and LAF, sieving of SAF and sampling of LAF. It can also occur under certain circumstances during storage of SAF and LAF, as well as during sampling of SAF. The nature and the concentration of VOC depend on the type of waste received at the site. Monitoring should be made of

1. Smell: Standardised tests for smell detection can be used to identify the influence of the process on the neighbours and workers environment. Bag samples may also be made for qualification and quantification of the pollutants in laboratory.

2. Diffuse emissions: Diffuse emissions are measured inside and outside workshops by taking samples. Quantitative and qualitative analyses can be carried out.

3. Canalised measures: VOC are measured either continuously by FID system or according to punctual measurements campaigns. Those conditions are defined in the permit.

Emissions values to ambient air in the working area have to comply with the national regulations. Canalised emissions after treatment are listed in Table 12. Table 12 Canalised emissions after treatment Daily average value SAF LAF Achievable performance Non-methane VOC (mg/Nm3)

4-50 10-110

Permit value Non-methane VOC (mg/Nm3)

20-1101 0-1101

1with water and oxygen content as achieved by the process

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6.4 Impact on surface and ground water Surface water can be contaminated by cleaning water from drum cleaning, truck cleaning, facilities cleaning and road tankers / ship cleaning and/or by process water from wastes settling during transport, from drying, etc. A synthesis of discharge limit values based on permits for 6 AF processing units in France and Belgium is presented in Table 13. These values have to be considered as examples. They are not indicative and depend on the water used. In some cases, water effluents are treated in an external and collective station. Specific values have to be defined from case to case. Waste water must be monitored before release. With the exceptions of major accidents, AF activities have no impact on groundwater. A piezometer network with analysis once or twice a year is generally used for survey. Table 13 Examples of waste water discharge limit values from 6 plants in France and Belgium Physio-chemical parameters

Limit values

pH 5.5-9.5 Maximum temperature (°C) 30-45 TSS (mg/l) 30-60 COD (mg/l) 50-300 BOD5 (mg/l) 30-40 N Kjeldahl (mg/l) NA2-40 N global (mg/l) 10-50 Total phosphate (mg/l) 1-10 Cr +VI (mg/l) 0.01-0.1 total Cr (mg/l) 0.02-0.5 free CN (mg/l) 0.1 Cu (mg/l) 0.03-0.5 Cd (mg/l) 0.05-0.2 F (mg/l) 10-15 Zn (mg/l) 0.3-2 Sn (mg/l) 0.01-2 Pb (mg/l) 0.05-0.5 Ni (mg/l) 0.05-0.5 Hg (mg/l) 0.05-0.15 Total metals1 (mg/l) 10-15 Total hydrocarbons (mg/l) 2-10

1 Sb + Co + V + Tl + Pb + Cu + Cr + Ni + Zn + Mn + Sn + Cd + Hg + Se + Te 2NA = not applicable

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6.5 By-products and wastes generated Generated by-products may be 1) Residues coming from the packaging of the delivered wastes - « Consigned » IBC, containers or drums - Metallic containers and drums - Plastic containers and drums - Palettes - Big bags - Plastic sheet 2) Production Residues - From the scrap extraction during the production stage: These residues are composed of metallic

parts which can be voluminous and massive - Rotating, vibrating and static sieve / screen rejects: These residues are composed of blocks of

different solid wastes (such as resins, paintings, glues, tars, bitumen, polluted soils, etc.), pieces of wood, sand, polluted plastics, lining and piece of textiles sheets.

3) Effluent treatment residues These residues can for instance be activated carbon from waste water and air effluent treatment. Generated wastes can be laboratory residues and rejected samples. Typical by-products from recovery (pallets, iron scrap etc.) can amount to 1.5-20 kg/ton AF. Other wastes for disposal can be about 0-3 kg/ton AF produced and laboratory residue around 0.015 kg/ton AF. The amount of by-products is strongly linked with the type of packaging. For example, in the case of small packaged wastes, the iron scrap fraction can reach up to 150 kg/ton AF. These data should be reported annually to the authorities.

6.6 Noise All the process lines and the equipment are designed and realised according to EU noise regulation for operators inside and for neighbours. Incoming and outgoing transports are the main source of noise around and inside the plants. Other noise sources can be: - Handling machines such as mechanical shovel, loader, and hydraulic shovels - Screeners - Shredders, grinders - Pumps - Agitators - Motors used for ventilation network - VOC treatment units Due to the relatively low noise level, no specific monitoring is usually requested. But, measures can be done for health and safety of workers and especially for environmental impact evaluation, notably when new equipment is commissioned.

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7 TECHNIQUES TO INCLUDE IN BAT DETERMINATIONS

7.1 Preventive measures and reduction techniques for dust This list of preventive measures against dust re-groups several measures which exist on the plant. It’s an indicative list and not an exhaustive one:

• Closing and under-pressure for all the reception, production and storage areas. • An atmospheric over-pressure at the working places (control room, vehicles cabin, etc)

ensures that no dust reaches the workers.* • Preparation and mixing operations have to be done in closed areas with canalised exhaust

air. • Pulverulent wastes have to be handled in closed areas.* • Dust retention net.* • Efficiently cover loads of fresh sawdust, pulverulent waste or SAF before transport* • Use of closed vessels / mixers / filters / screens / magnetic separators / homogenising

equipment.* • Spray / atomiser systems intended to moisturise ambient and confined air in order to

prevent dust emissions. Preventives measures marked with * in the above list could be applied on existing facilities without complete redesign of the facility. Emission treatment by filtration techniques comprises (a-d): a) Wet scrubber Principle: Gas flow is cleaned in a liquid phase which captures solid particles. Comments: This technique is not used in the existing LAF and SAF production plants due to the fact that some dusts are hydrophobic and that the wet residue cannot be easily reused in SAF production. b) Bag filter (see characteristics in Table 14) Principle: Solid particles are trapped by a woven fabric while gas can flow through it. Advantages: - High collection efficiency for both coarse and small particles - Efficient with a large concentration range - Collected dust may be reused in the AF process Disadvantages: - Explosion risk c) Cyclofilter Principle: Coarse particles are captured by a cyclone. This technique is not commonly used in the AF sector. The technique may be only used in combination with bag filter. Advantages: - Efficient with a large concentration range - Collected dust may be reused in the process. Disadvantages:

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- Not efficient for small particles - High wear with abrasive dust - High electricity consumption d) Electrostatic filter Principle: Dust particles are electrically charged and captured in an electric field. Comment: This technique is not suited for organic particles due to high explosion risk. Table 14 Characteristics of bag filter for dust filtration Characteristics Value ranges Input gas flow (Nm3/h) 1,000 - 50,000Input dust concentration (mg/Nm3) 100 - 5,000Output dust concentration (mg/Nm3) < 10Risks explosionElectricity consumed (kWh/ton SAF) 2.5-3.5Investment cost (€/ton SAF/year) ≤ 4Operational costs (€/ton SAF/year) 0.15Maintenance cost (€/ton SAF/year) 0.1

7.2 Preventive measures and reduction techniques for VOC and smell Preventive measures are closed and under-pressurised room for VOC and smelling wastes (see chapter 7.1 on dust). Emission captures (grouped a-e) during: a) Sampling Packaged wastes must be sampled inside or in closed areas kept in under-pressure or inside dedicated chamber with extractor hood. b) Unloading operations • Liquid: Exhaust gas from vessels and tanks are collected • Solid and sludge: Depending on the potential of emissions of VOC of the wastes, unloading

should be done in a closed and under-pressurised building. c) Storage •Bulk materials: In closed tank or in dedicated area. Containers and drums must not cause VOC

emissions. • Liquid storage: Exhaust gas must be collected and properly treated. d) Processing: The process lines described in chapter 5 have to be kept in confined atmosphere with under-pressure. e) Loading: The loading station must be designed and operated in order to prevent emissions. VOC is collected in each above mentioned points, as near as possible to the emissions sources. The

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collected stream is oriented to the appropriate VOC treatment facilities taking into consideration that de-dusting is necessary in most cases. VOC emission treatments can be grouped a-d as below. A comparison overview is given in Table 15: a) Liquid nitrogen trap Principle: Condensation of VOC with liquid nitrogen. Used for relatively small volumes to be treated, when liquid nitrogen is available and concentration of VOC is high. Advantage: - The condensed VOC can be recovered. Disadvantages: - The presence of water vapour in the air can block the system by the condensation of ice. A de-

freezing period is then necessary. - This technology is suitable for stable volumes and compositions. b) Biological treatment Principle: VOC degradation by bacterial beds; biological treatment is used for VOC streams that have a consistent and biodegradable composition. Advantages: - Low cost - Low energy consumption Disadvantages: - Reliable only for some kind of emissions. - Sensitive to some components / chemicals that can be toxic for the micro-organisms. c) Activated carbon Principle: VOC adsorption through activated carbon filter. The use of activated carbon is efficient for the capture of VOC mainly in storage facilities. The absorption capacity of the activated carbon depends on the VOC nature but is limited to maximum 300 g of VOC / kg of activated carbon. Advantages: - Low operating cost for low concentrations of VOC - Usable for a wide range of components - Simple design - Stable over time - Accepts high spot concentrations - Used activated carbon can be recovered several times or included in the alternative fuel process. Disadvantages: - Cost of activated carbon renewal - In some concentrations with air, the adsorption is exothermic and has to be controlled in order to avoid fire / explosions. - Not suitable for high concentrations or small molecules or in presence of dust and not adapted for some molecules, such as acetone. d) Thermal treatment (sub-divided 1-3): 1) Combined combustion Principle:

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In some plants where combustion takes place, it is possible to inject polluted air collected in the workshop in the secondary air circuit of the burner of thermal equipment or the primary air of the burner. This may involve specific adaptation of the combustion process (modification of gas cleaning and stability of combustion). Advantages: - Synergy with existing combustion facilities. - Energy recovery of the VOC in the combustion Disadvantages: - Not available during maintenance of the burner - Need prior dilution with air when an explosive concentration can be reached - Specific instrumentation and valves must be installed to prevent “domino effect” between each

process. - Adaptation cost can be high - Fluctuations in quality or quantity of the VOC could cause some troubles in the combustion system. 2) Catalytic combustion Principle: The polluted air is burnt but the combustion temperature is reduced by the use of a catalyst. The catalyst helps to get the same destruction efficiency of the VOC as at a lower temperature. Advantages: - Low fuel consumption - Complete destruction of VOC Disadvantages: - The catalyst is sensitive to some compounds (metal, organic, etc.) and its efficiency can

progressively decrease. - Cost of investment is relatively high - Need of a gas treatment in some cases (EP or textile filters, gas scrubber) - Needs prior dilution with air when explosive concentrations are reached 3) Regenerative Thermal Oxidiser Principle: VOC are burnt in combustion chambers at a temperature ranging from 750-950°C. The energy produced by the combustion of the VOC is used to preheat the polluted air on the ceramic bed before the combustion. The combustion temperature can be adapted according to the VOC concentration. Advantages: - High VOC destruction rate (> 99%). - Accepts concentration fluctuations of VOC. - Reduced use of fossil fuel or waste fuel (high energy efficiency) - Auto-thermal temperature can be approached, so that the combustion of the VOC is almost

sufficient to maintain the temperature (in that case, the quantity of make-up fuel is minimal) - Low operation cost Disadvantages: - High investment cost - Needs prior dilution with air when an explosive concentration may be reached - Needs a de-dusting when dust concentration is higher than 20 mg/Nm3 - High energy consumption in case of low VOC concentration.

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7.3 Preventing pollution of surface and ground water Preventive actions to avoid surface and ground water pollution can be: - Site waterproof and storage retention. - Implement regulatory verification procedure for tanks and pits. - Separated water drainage according to pollution load (roof water, road water, process water). - Security collection basin - Piezometers network for ground water monitoring According to degree and nature of the pollution agents and to the output (surface water, on site water treatment, collective industrial or urban station, incineration), different techniques may be used to treat process water alone or combined: - Settling, hydrocarbons /oils/ sludge separators, - Activated carbon (should be sufficient for low contaminated water) - Physico-chemical treatment - Biological treatment - Thermal treatment (for highly polluted water) The by-products of these installations (used activated carbon, sludge, hydrocarbons, oils, etc.) can been reintroduced in the AF production process or directed to external treatment plants. Table 15 Comparison of VOC treatment processes Nitrogen

trap Biological treatment

Activated carbon

Combined combustion

Catalytic combustion

Regenerative Thermal ox.

Characteristics Input gas flow range (m3/h)

< 100 < 100,000 < 50,000 < 50,000 20,000 - 50,000

20,000 - 80,000

Input VOC concentration (mg/Nm3)

2,000 - 500,000

< 1,000 < 500 ≈3,000< explosion

limit

1,000 - 3,000

2,000 - 4,000 with peak until

10,000 Output VOC concentration (mg/Nm3)

- - 40 - 110 10 - 50 10 - 50 15 - 50

Efficiency (%) > 95% < 90% - - - > 99%Preliminary de-dusting

No No Yes No Yes Yes

Risks - Destruction of micro-

organisms

Quick saturation

- Catalyst poisoning

-

Residues No Yes No No No NoConsumption (per ton AF produced) Electricity (kWh)

25 15 25 - 75 a 25 - 75 10 - 50

Fuel/gas (kWh) - - - a 70 - 140 50-200b

AF or biogas - - - - - YesReactant Nitrogen Barks 0.1 - 0.5 kg

active C/kg VOC - Catalyst -Costs Investment (€/ton capacity)

20 - 60 10 - 20 10 - 30 a 20 - 30 10 - 25

Operational (€/ton AF) Electricity Fuel/gas Others Total

2 - 6 < 1

1 - 30

1.65b

a

1 - 3 1 - 2 1 - 3

2 - 6

Maintenance - - - a < 1 < 1aDepends on each case. bAccording to VOC concentration

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7.4 By-product recovery and waste treatment Treatment of by-products coming from packaging of delivered wastes can be grouped into a-d: a) Consigned IBC, containers or drums can either be sent back directly to the producer or, after being emptied, cleaned up with appropriate devices. b) Metallic containers and drums • Reuse • Drum recycling, after eventually cleaning. • Recovery after cleaning and shredding or crushing, in the process or separately. • Disposal by incineration with iron recovery c) Plastic containers and drums • Reuse • Drum recycling, after eventually cleaning. • Recovery after cleaning and shredding or crushing, in the process or separately. • Co-processing use as an alternative fuel • Disposal by incineration d) Palettes • Reuse if in a large majority of case (no damage) • Wood recycling, also as absorbents • Co-processing use as an alternative fuel • Disposal by incineration Treatment of by-products from production can be grouped a-c: a) Residues coming from the scrap extraction They are collected separately during the fabrication process. After an eventual cleaning step, they will be sent with the cleaned metallic containers and drums for recovery. b) Residues coming from rotating and vibrating sieve rejects They are eventually shredded and sent to the co-processing facilities. If there is no possibility to co-process them, they have to be brought to a hazardous waste incinerator. c) Effluent treatment residues Activated carbon from waste water and air effluent treatment are incorporated in co-process. Laboratory wastes that are mentioned in the permit of the pre-processing facility can be treated directly, and used in the production. Those which are banned in the permit have to be properly disposed off in external dedicated facilities.

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8 BEST AVAILABLE TECHNOLOGIES (BAT)

8.1 General BAT is enforcing multi step traceability (as described in chapter 4.2). BAT is enforcing at least the minimum control plan as described in Table 8.

8.2 Preventive measures for dust, VOC and smell emissions BAT is an appropriate combination of following recommendations: • Closing and establishing under-pressure in all process rooms • Handling pulverulent wastes in closed areas* • Before transport, loads of fresh sawdust, pulverulent wastes or SAF have to be covered.* Preventives measures marked with * in the list above could be applied on existing facilities without complete redesign of the facility. BAT for dust treatment is bag filters. Table 16 compares bag filter with wet scrubber. Table 16 Dust treatment BAT criteria. Legend: - means poor,

+ means acceptable and ++ means well adapted.

BAT criteria Bag filter Wet scrubberDust treatment performance + - Flexibility + + Consumption ++ - Costs ++ - Risks (fire, explosions, etc.) + ++ Cross media effects + -

8.3 VOC emission capture and treatment For VOC emission capture, BAT is an appropriate combination of following recommendations: • Sampling of packaged wastes has to be done, at minimum in a covered area and inside. • Unloading operations for solid wastes and sludges have to be done in a closed area and in

building with under-pressure if the potential of VOC emissions is high. • In unloading operations for liquid wastes, exhaust air from vessel and tank are collected. • Storage must be made in closed tanks or buildings for bulk materials. Containers and drums

must not cause emissions of VOC. • Exhaust gas must be collected and properly treated for liquid storage. • Process lines described in chapter 5 have to be kept in confined atmosphere with under-pressure. • Loading station must be designed and operated in order to prevent emissions. • VOC is collected in each point mentioned above, as near as possible to the emissions sources.

The collected stream is directed to the appropriate VOC treatment facilities taking into consideration that de-dusting is necessary in most cases.

For VOC emissions treatments BAT are;

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- Combined combustion, but only if combustion facilities are available nearby, or - Regenerative thermal oxidation, - Activated carbon for low concentration VOC flow (storage etc.). BAT criteria for VOC emission treatment are compared in Table 17. Other comments to treatments in Table 17 are for:

• Nitrogen trap: Non-appropriate due to low flow range, high operating cost and sensitivity to water presence.

• Biological treatment: Appropriate for big volume with low and stable concentration. Performance sensitive to composition (ammonia, etc.) and weather conditions.

• Activated carbon: Appropriate for low concentration flows (e.g. storage). In this case, low cost. Performance may be limited because of incomplete capture of some organic molecules. May also present fire and explosion risks.

Table 17 BAT criteria for VOC emission treatment. Legend: - means poor,

+ means acceptable and ++ means well adapted. BAT criteria N2

trap Biological treatment

Active carbon

Combined combustion

Catalytic combustion

Regenerative thermal oxidizer

VOC performance

++ - -/+ + + ++

Consumption - ++ ++/- ++ + + Cost + ++ ++ ++ - + Flexibility - - + + - ++ Risks + + - + + + Cross media effects

- - - + + +

8.4 Water emission prevention and treatment BAT is an appropriate combination of the following recommendations: • Preventive actions such as - Waterproof site and storage retention. - Regulatory verification procedure has to be done when tank and pits are underground. - Separated water drainage according to pollution load (roof water, road water, process water). - Security collection basin • Water treatment systems - Activated carbon treatment should be sufficient for low contaminated water - Thermal treatment should be used for highly polluted water

8.5 Used packaging BAT is an appropriate combination of the following recommendations: • Favouring use whenever possible of consigned packaging (drum, container, IBC, palettes, etc.) • Recycling of drums should be the following option before recovery as fuel or raw material in co-processing. Disposal by incineration and/or land filling should be avoided whenever possible.

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9 HEALTH AND INDUSTRIAL HYGIENE

9.1 General The objective of chapter 9 is to raise awareness of health and safety issues in the cement industry, but it will also partly apply for pre-processing plants of alternative fuel and raw materials (AFR). The chapter also explains some relevant terminology in health and industrial hygiene. Major parts of the text are collected from Kirk (2004c).

9.2 Industrial hygiene (IH) Industrial hygiene (IH), also known as occupational hygiene, is the science of anticipating, recognizing, evaluating and controlling workplace environmental factors and stressors that can lead to illness or impaired health of workers or those in the surrounding community (American Industrial Hygiene Association, 1995). Industrial hygiene practice requires detailed knowledge of a broad array of physical and life sciences, and an organized and analytical approach to problem solving.

9.2.1 Terminology In industrial hygiene terminology, toxicity refers to the ability of a substance to injure a bodily organ or system, interrupt a biochemical process or affect an enzyme system. Hazard refers to the injurious properties of a substance and the probability of injury. Risk refers to the degree of hazard and exposure factors such as route of entry into the body, how much of a substance is released and how easily it is absorbed into the body, length of exposure and effectiveness of control methods.

9.2.2 Recognizing factors and stressors Due to the nature of the cement manufacturing process, the industry has its own set of unique IH hazards that should be recognized and controlled before they become harmful. These hazards can be divided into four main categories: 1) chemical hazards that can be irritating or toxic to the body’s organs or systems, 2) physical hazards, such as noise, vibration, radiation, and thermal or pressure extremes, 3) ergonomic stresses resulting from an improper interface of workers and workplace machines, tools and procedures that repetitively stress vulnerable areas of the body, and 4) biological hazards from living organisms that can adversely affect bodily functions. This is further outlined in Table 18. Table 18 Summary of industrial hygiene hazards Chemical Physical Ergonomic Biological Air contaminants Solvents Irritants Corrosives Oxidizers Carcinogens Organ/System toxins

Noise Vibration Heat Cold Ionizing radiation Non-ionizing radiationPressure extremes

Lifting Posture Static work Repetitive motion Contact with surfacesVibration Cold

Blood borne pathogensViruses Bacteria Fungi Animals Insects

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9.2.3 Evaluations Decisions about the risks industrial hygiene hazards pose to workers must be based on careful evaluation. Information needed includes: 1) the type and magnitude of each hazard, 2) whether they are acute (injurious in the short term) or chronic (injurious after long term exposure, usually many years), 3) degree of worker exposure, and 4) the adequacy of current control measures. Hazard exposure can be determined qualitatively by examining the work area, its processes and materials, and quantitatively by measuring worker exposures using area surveys and personal sampling techniques. Samples should be analyzed at accredited laboratories and results studied and compared to recommended or permissible exposure levels. Industrial hygiene standards often require special interpretation and may require the assistance of someone with specialized training.

9.2.4 Control measures There are three basic types of control measures, listed in order of preference of application: 1) engineering controls, which remove or reduce the hazard by improving, adding or replacing equipment that cleans, isolates, encloses or ventilates an area or process, 2) administrative measures, which include reducing worker exposure time, and training to improve hazard recognition and exposure avoidance procedures, and 3) personal protective equipment, which workers wear to limit exposure to the various environmental factors and stressors they encounter in the workplace.

9.3 Chemical hazards and controls

9.3.1 General Chemical hazards occur in the cement industry when certain chemicals, compounds and substances are not properly used or controlled, and when there are excessive concentrations of air contaminants in the workplace. Toxic effects occur only when a chemical substance reaches a target receptor in a high enough concentration and for a sufficient time (Doull and others, 1980).

9.3.2 Chemicals and compounds

9.3.2.1 General Chemical substances may enter the body and possibly affect its systems through inhalation, ingestion or absorption through the skin. Corrosives, irritants and solvents are examples of chemical hazards. Certain other substances are considered carcinogens or may affect specific organs or systems. All chemical substances should be used according to the manufacturers’ instructions, and all recommended precautionary exposure measures should be followed. Some types of hazardous chemical compound classes are given in alphabetic order in the following sub-chapters.

9.3.2.2 Carcinogens Carcinogens are substances that can cause tumours to form or tissues to grow abnormally. There are few substances employed in the cement manufacturing process that are carcinogenic in nature. However, certain products used in maintenance operations may contain compounds that are listed as carcinogens or suspected carcinogens by the International Agency for Research on Cancer

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(IARC), the National Toxicology Program (NTP) or other agencies. Facilities should identify which carcinogenic substances or compounds may be present in the work environment, advise employees and minimize or prevent exposure. Substitution with alternate substances, application of engineering or administrative controls and use of personal protective equipment are techniques that can be employed to reduce risk. Some cement plants use alternative energy sources (AFR) such as hazardous waste-derived fuels. These fuels are often blends of many different solvents and may contain varying concentrations of chemicals or metals known to be carcinogens. Personnel handling such fuels and their by-products should be made aware of the potential hazards and appropriate controls should be employed. For instance is hexachloro hexane, 1-3 % present in earth to be co-processed by Beijing cement, listed as carcinogenic (see its material data safety sheet in Appendix 2).

9.3.2.3 Corrosives Corrosive substances are strongly acidic or alkaline, and have pH ranges of 0-2 or 12-14, respectively. Although they are usually found in laboratories, corrosives also include battery acid, rust removers and drain cleaners. They can cause severe blistering of the skin or burns of up to the third degree. Corrosives are an eye hazard and may produce irritating or toxic gas if burned or heated. Tissue damage may be permanent. Corrosives may ignite combustibles such as wood or paper, and can produce flammable gas on contact with metal. Best practices for handling corrosives includes use of: 1) rubber gloves, 2) an apron, 3) eye and face protection, such as indirectly vented splash goggles and a face shield, and 4) a fume hood or respirator if vapours or mists are present. Personnel should not: 1) smell or inhale vapours, 2) siphon with one’s mouth, or 3) store or transport corrosives near flammable solids, oxidizers, ammunition, explosives or reactive chemicals. Corrosives containers should be labelled clearly. Acids and alkalis (sometimes called bases) should not be stored together. Spill cleaning and disposal is best accomplished by neutralizing, not by rinsing down drains. Diluting strong acids and alkalis can reduce: 1) their hazard when handling, and 2) their potentially harmful effects should a spill or splash occur. Eye washes and deluge showers should be provided near work and storage areas in case corrosives contact the eyes or skin.

9.3.2.4 Haematopoietic toxins Haematopoietic toxins can damage the blood or the body’s ability to form blood. Route of entry into the body is usually by inhalation. Examples of haematopoietic toxins include carbon monoxide (automated detector shown in Fig. 4), benzene and epoxies that contain xylol, which in sufficient doses, can affect the blood’s ability to transport oxygen. Epoxies should only be used where good ventilation exists.

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Fig. 4. Continuously monitoring instruments can alarm if chemical hazards in the workplace

reach action levels. The example is for the haematopoietic carbon monoxide (CO).

9.3.2.5 Hepatoxins Hepatoxins are substances that can cause liver damage. Route of entry into the body is usually by inhalation. Examples of hepatoxins include propylene glycol, which e.g. is found in some epoxies. As with other toxic substances, provision of good ventilation is always the first priority when handling hepatoxins.

9.3.2.6 Irritants Irritants are substances that can cause an inflammatory response or reaction of the eye, skin or respiratory system, if it contacts the tissue in sufficient dose. Many substances are considered irritants, including numerous solids, liquids and gases. Good ventilation, safe handling and storage practices and use of personal protective equipment are measures that will prevent tissue irritation. Irritation is usually completely reversible; when the irritant is removed, the inflammation subsides. Clinker, cement and cement kiln dust (CKD) are alkaline materials that are also considered irritants. Mildly acidic neutralizing solutions and barrier creams are marketed to spread on the skin prior to exposure, but using gloves, disposable protective clothing and practicing good personal hygiene are the best means to achieve injury prevention.

9.3.2.7 Mercury and mercury spill control Mercury may be used in certain plants for instrumentation and laboratory purposes. It is a heavy liquid that will vaporize, especially when it contacts hot surfaces. Inhalation of mercury vapours or contact with the liquid itself can cause eye or skin irritation, weakness, fatigue, chest pain, coughing, tremors, glandular disorders and more.

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Best practice is to store mercury in a closed, high-density polyethylene container. Glass is a second choice, but it is breakable. Mercury spill kits containing gloves, respirator, mercury sponges, suction tubes, absorbent powder and detailed use instructions should be placed in key areas, and employees should be trained to use it properly. Mercury spills should be cleaned up immediately and spill areas should be ventilated thoroughly. If mercury recycling is not possible, a reputable firm should be contracted to dispose of the collected waste mercury and used sponges (National Institute for Occupational Safety and Health, 1997).

9.3.2.8 Mutagens Mutagens are substances that alter a cell’s genetic information and may lead to undesirable inherited conditions. The presence of mutagenic substances in cement plants would be considered unusual, but it may be present in waste to be processed for AFR or hazardous waste to be destroyed in cement kilns. For instance is hexachloro hexane, 1-3 % present in earth to be co-processed by Beijing cement, found to be mutagenic in animals (see Appendix 2 for the complete materials data safety sheet).

9.3.2.9 Nephrotoxins Nephrotoxins are substances that can cause kidney damage. Lead, such as found in some older paint products, xylol and propylene glycol, such as used in some epoxies, are examples of nephrotoxins. Inhalation is the principal route of entry into the body, but ingestion is also possible.

9.3.2.10 Neurotoxins Neurotoxins are substances that can affect the brain, central nervous system or nerve cells. They usually enter the body through inhalation, and may produce emotional or behaviour abnormalities, or interfere with the body’s ability to control certain functions. Examples of neurotoxins include lead in paint products, or alcohols, petroleum naphtha and ethylene glycols, such as found in some paint thinners. Substitution with less hazardous alternative substances should be explored. Good ventilation and the use of protective respiratory equipment are considered to be best practices.

9.3.2.11 Reproductive toxins Reproductive toxins are substances that affect both male or female reproductive systems and which may impair one’s ability to have children. The presence of reproductive toxins in cement plants would be considered unusual, but it may be present in waste to be processed for AFR or hazardous waste to be destroyed in cement kilns.

9.3.2.12 Sensitizers Sensitizers are substances, which on first exposure causes little or no reaction, but which on subsequent or repeated exposure may cause a marked response, not necessarily limited to the contact point. Sensitizers most commonly affect the skin, but can also affect the respiratory system. Sensitivity to a substance is usually dependent upon personal characteristics; what may sensitize one person will not necessarily affect another.

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9.3.2.13 Solvents Solvents are substances that will dissolve another material, such as acetone, metal cleaners, and paint thinners, even water. Although they are often thought to be hazardous, the degree of hazard varies from none to high. Solvents may be flammable or toxic through contact or inhalation of vapours. Substitution of potent products with less hazardous solvents is always a best practice. Other best practices include: 1) using gloves when handling solvents, 2) storing solvents in clearly labelled containers that are closed or covered when not in use, 3) providing good ventilation in work areas, 4) removing and washing clothing that comes in contact with solvents, and 5) removing solvent-exposed persons to fresh air if overexposure symptoms occur.

9.3.2.14 Systemic poisons Systemic poisons are substances that spread throughout the body, damaging all organs and bodily systems. Systemic poisons are rarely found in a cement plant, although certain herbicides or animal poisons, if used or stored irresponsibly, could possibly cause systemic damage. Substances that are potentially systemic poisons should be used only when necessary, and then only in accordance with the manufacturer’s instructions. Systemic poisons may be candidates for destruction in cement kilns. All recommended precautionary control measures should be followed. For instance is DDT present in the contaminated soil to be co-processed by Beijing cement listed as a systemic poison (see Appendix 3 for the complete materials safety data sheet).

9.3.2.15 Teratogens Teratogens are substances that can cause birth defects in the fetus of a pregnant female. The presence of teratogens in cement plants would be considered unusual, but it may be present in waste to be processed for AFR or hazardous waste to be destroyed in cement kilns.

9.3.3 Air contaminants

9.3.3.1 General Air contaminants include dusts, fibers, fumes, gases, mists and vapours. If inhaled in sufficient doses, they could be hazardous to workers’ health. Facilities should identify which air contaminants are present in the workplace and survey employees’ potential and actual exposure by performing bulk, area and personal sampling. When engineering and administrative controls are not feasible, or while they are being installed, exposure should be controlled with personal protective equipment. (See also sub-chapter 9.3.6 Respiratory Protection).

9.3.3.2 Dust Dusts are solid particles suspended in air. Limestone and Portland cement dust are classified as “nuisance particulates.” When inhaled or swallowed in small doses, they dissolve, pass through the kidneys and out of the body without adverse health effects (Holt, 1987). It should be noted, however, that some scientists believe no dust is completely inert and precautions should be taken to prevent overexposures even to dusts given the “nuisance” designation. Calcined limestone and cement kiln dust (CKD), because of their percentage of calcium oxide (CaO), are considered chemical substances and have permissible respirable dust exposures that are fractions of those for nuisance particulates. Consult current regulations for exposure limits.

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Dusts that include a certain fraction of respirable crystalline silica (SiO2) also have reduced permissible exposure limits. Silica accumulation in the lungs can cause silicosis, and crystalline silica has been classified as a known human carcinogen (Group I) by the International Agency for Research on Cancer (IARC). Permissible dust exposure limits vary according to the jurisdiction of regulatory agencies and authorities, and the current regulations should be consulted for each operation. Some agencies incorporate the percentage of crystalline silica into an exposure limit for respirable dust, while others express the exposure limit in terms of the actual concentration of silica present. Dust control best practices include source enclosure, spill and leak prevention, use of air pollution control devices, moisture addition and vacuuming instead of dry sweeping. Respirator selection and use should be based on contaminant type and concentration, and on respirator rated protection factors.

9.3.3.3 Fibres Fibers are particulates that have an aspect ratio (such as length to width ratio) equal to or greater than three to one (3:1). Fibers most likely found in cement facilities are naturally occurring mineral fibers, such as asbestos, or synthetic vitreous fibers (SVF), also known as man-made vitreous fibers (MMVF) or man-made mineral fibers (MMMF). Asbestos formerly enjoyed widespread use for insulation purposes, but serious illnesses associated with inhaling or ingesting friable asbestos have curtailed or ended its use in many portions of the world. In many locations, regulations do not permit the use or storage of asbestos, and many facilities have removed asbestos from the workplace. Asbestos is listed by IARC as a Class 1 carcinogen. Those facilities where asbestos is still in use should conduct a plant wide survey to determine the type, location and quantity of asbestos, and its condition. Surveys can aid in prioritizing abatement efforts, and in budgeting for systematic removal or encapsulation. Plants should ensure that friable asbestos does not become airborne, and train employees on asbestos hazards. The use of certified asbestos inspectors and abatement companies is recommended because strict environmental and engineering controls are required, including ventilation and use of high-efficiency particulate air (HEPA) filters and respirators. Synthetic Vitreous Fibers (SVF) products are insulating materials that include 1) fibre glass, 2) mineral wools, 3) refractory ceramic fibers (also known as RCF or vitreous alumino-silicate fibers), and 4) amorphous calcium-magnesium-silicate fibers. Fibre glass and mineral wools have been classified by IARC as 2B carcinogens (possibly causing cancer in humans). Refractory ceramic fibers have also been classified by IARC as 2B carcinogens (possibly causing cancer in humans). As manufactured, calcium-magnesium-silicate fibers and RCF do not contain respirable crystalline silica, but when they are exposed to sustained, high temperature (>980°C) use, portions of the material may de-vitrify into crystalline silica, such as Cristobalite or Quartz, Group 1 carcinogens (Unifrax Corporation, 1998, 1999). If used in certain high-temperature cement applications, they could present a greater lung disease hazard when removed after use. There are major differences between SVF products and asbestos: 1) SVF does not split longitudinally as do asbestos fibers, and 2) they are much more quickly dissolved by body fluids and therefore less durable as a source of acute or chronic irritation (Rauscher, 1990). Durability is measured by the in-vitro dissolution rate of a fibre in simulated lung fluid, (kdis, laboratory testing), or in-vivo bio-persistence factor (fibre half-life, T1/2, animal testing.) See Table 19, for a summary of the results from several studies.

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Table 19 Comparison of in-vivo bio-persistence, in-vitro dissolution and chronic lung

disease (fibrosis/tumour) studies in animals. Fibre material Bio-persistence; t1/2 (days) in-vitro; kdis Chronic lung

fibrosis / tumours Asbestos, crocidolite1 817 < 1 +/ +Asbestos, amosite1 418 < 1 + / +RCF - a2 90 8 + / +RCF - b1 55 3 + / +Rock wool - a1 79 17 + / -Fibre glass wool - a1 49 12 + / -Fibre glass wool - b2 11 95 - / -Slag wool1 9 400 - / -Ca, Mg - silicate2 6 150 Not yet reviewed or rated1 Johns Manville: “Health & Safety Aspects of Fibre Glass,” 1999. 2Zoitos (1999). For the purpose of comparing the relative hazard of certain fibers, several Year 2000 Permissible Exposure Levels (PELs) and Recommended Exposure Guidelines (REGs) are listed. Because these PELs and REGs may not be applicable in all jurisdictions, or because they may change over time, current regulations should be consulted for each operation. The United States Occupational Health and Safety Administration’s PEL for asbestos is 0.1 fibers/cubic centimetre (f/cc or f/cm3), and 1.0 f/cc for fibre glass and mineral wools. The REG for refractory ceramic fibers set by the Refractory Ceramic Fibre Coalition is 0.5 f/cc. The European Union has established another set of guidelines to classify SVF products as to their hazard potential. These guidelines consider fibre respirability, chemistry, and bio-persistence in animal testing. The Year 2000 regulatory criteria are: if 50% of fibers greater than 20μm long are cleared from the lungs in less than 10 days (the fibre half-life, T1/2), that fibre is not classified as a potential carcinogen (Zoitos, 1999). In recent years, several SVF products have seen the European carcinogenic labelling requirement lifted. In addition, vitreous fibre manufacturers have developed new products that have low bio-persistence (T1/2) ratings. SVF manufacturers recommend the following best practices when handling their products: 1) wearing loose clothing, 2) wearing safety glasses or goggles, 3) preventing dust production, 4) providing good ventilation, 5) using respiratory protection when fibre concentration exceeds the PEL value, 6) keeping work and home clothing separate, and 7) rinsing the washing machine after washing work clothes (Johns Manville, 1999).

9.3.3.4 Fumes Fumes are airborne solid particles of metal that condense from heated vapours in the air. Examples of welding fumes are oxides of iron, lead, nickel, chromium, manganese, etc. Fumes, if inhaled in sufficient quantity, can cause nausea, dizziness, headache, metal fume fever, damaged body organs or reduce the efficiency of bodily systems. Material safety data sheets (MSDSs) should be reviewed to determine hazards to which persons are exposed, and exposure limits. Local exhaust ventilation is a good engineering control because it draws fumes out of workers’ breathing zones. Filtering respirators offer secondary protection.

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9.3.3.5 Gases Gases are formless fluids that take the shape and size of their container. Their chemistry may pose health hazards, or they may serve as asphyxiates if they collect and displace oxygen in work areas. There are many gases to which cement plant employees could be exposed, including numerous products of the fuel burning process. Preventing and minimizing the release of gas into the air, ventilation and dilution are preferred control measures. Fixed and portable atmospheric monitoring equipment are available to detect gases and measure their concentrations. Respirators should be worn if concentrations exceed permissible limits and cannot be controlled through engineering controls. Carbon dioxide (CO2) is odourless, colourless and slightly heavier than air. It is an asphyxiant (suffocating compound) and a cerebral vasodilator (i.e. agent expanding blood vessels). If inhaled in large concentrations it can cause CO2 narcosis, a condition marked by rapid circulatory insufficiency, advanced lung failure, hypoventilation, coma and death. Inhalation in low concentrations may cause acute increased respiration and headache, but chronic harmful effects are not known. CO2 is often used as a fire control chemical and may accumulate as a hazard in process vessels or outside near ground level if it leaks from storage tanks or is discharged from fire control apparatus. If one must enter such an environment, supplied-air respirators are required; filtering respirators offer no protection. Carbon monoxide (CO) is another product of the combustion process. CO is odourless and colourless, and levels are generally far below conditions immediately dangerous to life and health (IDLH). Exposure to low concentrations of vented kiln gases or vehicle emissions above safe levels can interfere with oxygen exchange in the lungs and produce severe headaches. Exhausts from pyro-processing and vehicles or tools powered by internal combustion engines should be vented safely out of enclosed work areas. Facility personnel should be aware that entry into confined spaces requires measuring CO levels, and that filtering respirators offer no protection to CO. Air should be supplied when concentrations exceed safe levels. Flammable gases such as acetylene, LPG-MAPP®, natural gas and propane have numerous applications in the cement industry and are considered serious fire and explosion hazards. In addition to these physical hazards, flammable gases are simple asphyxiants that, if leaked into the air, could exclude an adequate supply of oxygen to the lungs. Depending on the concentration and length of exposure, they could cause symptoms ranging from rapid breathing, fatigue or nausea to loss of consciousness, coma or death. Filtering respirators do not afford any protection. Use of monitors that measure flammable and oxygen deficient atmospheres is recommended before entering an area where leaked gas is suspected. Hydrogen sulphide (H2S) is generated when organic matter decomposes in anaerobic conditions. Although it is sometimes called sewer gas, it has been found in wash pits for mobile equipment. Leaves, dirt and other organic material washed off vehicles and rotting below the water level can produce H2S. If a thin oil film covers the wash water, H2S can be trapped below the surface, and then released when the surface is disturbed, such as when solid materials are cleaned from the pit bottom. H2S gas accumulation can be prevented if the water’s surface is roiled, such as when air is bubbled through it. Nitrogen may be found in plant laboratories or used in the headspaces of fuel tanks as inert gas. Although it makes up roughly 80% of the air we breathe, it is a simple asphyxiant if leaked in sufficient quantities into the work environment. It could displace oxygen and cause serious injury or death.

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Oxides of nitrogen (such as nitrogen dioxide, NO2) are found in kiln vent gases and diesel exhaust. Concentrations in process gases are generally dilute, but poorly maintained diesel engines or exhaust systems, or operation in enclosed or underground areas could overexpose operators and persons working nearby. Symptoms of overexposure include eye or respiratory tract irritation, coughing, chest pain, difficulty breathing or drowsiness. Filtering respirators do not offer protection from oxides of nitrogen; rather, supplied air respirators are required. Oxides of sulphur (such as sulphur dioxide, SO2) are acidic gases produced when certain fuels are burned, particularly coal. Kiln exhaust gases are usually safely vented out of the kiln and diluted in the atmosphere. However, workers may be exposed if unusual meteorological conditions force exhaust gases down to lower levels, or if leaks develop in process ductwork or air pollution control devices. If workers are exposed, irritation of the respiratory system can occur. In that case, injury potential depends on dose. One cannot rely on the sense of smell to measure SO2 concentration, as its odour threshold is only about one-tenth the threshold limit value (TLV). Monitoring instruments are needed to measure concentrations, and should be deployed with automatic alarms at key locations if surveys or exposure experience indicates stack height or location is a problem. Ozone (O3) is a powerful oxidizer and irritant to the eyes and mucous membranes of the respiratory tract. It is generated by corona discharges in electrostatic precipitators and can be recognized by its bleach- or electrical burn-like odour. If kiln precipitators are energized and not positively vented, ozone can back-draft into the kiln or leak out of open equipment doors. Ozone causes headache, sore throat, coughing, chest tightness, burning eyes, profuse perspiration, nausea and fatigue. Best practices to control ozone exposure include hazard training employees, ensuring precipitators are de-energized, locked out and positively ventilated, and using an ozone monitor before and during kiln system entries (Sanderson and others, 1999).

9.3.3.6 Mists Mists are liquid droplets suspended in air. Mixing, stirring, splashing, foaming or spraying liquids, such as paints or oils, may generate mists. The skin, lungs and eyes are potentially susceptible to injury if exposed, so mist production should be contained and controlled (National Mine Health and Safety Academy, 1999). Protective clothing and filtering respirators should be supplied when required.

9.3.3.7 Vapours Vapours are the gaseous form of substances that are liquids or solids at room temperature. Depending upon substance characteristics and physical conditions, they will evolve out of the substance if containers are not closed. Vapours posing potential human health hazards include gasoline and other fuels, oils, paints and solvents. Vapours can cause adverse local effects to the skin, throat or lungs, produce narcotic effects in the central nervous system or cause toxic effects in the blood or other organs (National Mine Health and Safety Academy, 1999). Preventing and minimizing vapour release into the air is best accomplished by safe storage and handling, in particular keeping containers closed. Ventilation or dilution should be considered a secondary measure, and evaluated for effectiveness. Liquid fuel and additive storage tank vents should be equipped with chemical cartridges to control “tank breathing” vapour release during filling and withdrawal processes, or their headspaces provided with a blanket of nitrogen. Safe fuel and additive delivery and unloading procedures should be developed. Spilled liquids present the possibility that large quantities of vapours can be released in a relatively small area, therefore

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personal protective equipment should be provided and safe work procedures developed in the event of a spill. Facilities should consider when substitution of any chemical with a less hazardous substance is appropriate to reduce employee exposure. If engineering and administrative controls do not maintain vapour concentrations below safe levels, properly fitted respirators with appropriate chemical filters should be provided.

9.3.4 Chemical hygiene plan Facilities should adopt a chemical hygiene plan to address and reduce exposure to hazardous chemicals. Written operating procedures must be formulated to address relevant safety and health issues. Procedures should specify criteria to be used

1. To determine chemical exposures 2. To determine exposure control methods 3. For use of fume hoods and personal protective equipment 4. In all laboratory operations or activities needing special approvals 5. In provisions for medical consultation and testing 6. For additional protective measures to be used when working with highly hazardous

chemicals 7. In decontamination procedures to be used in the event of a spill

Laboratory employees should be trained about permissible exposure limits, physical and health hazards, symptoms of overexposure, safe chemical use procedures and use of written reference materials such as MSDSs. Personal exposure monitoring and medical examinations are required at certain times.

9.3.5 Hazard communication Facilities use numerous chemicals and substances that pose potential chemical and physical hazards to employees using or exposed to them. Compressed gases, explosive and reactive chemicals, flammable and combustible liquids, solvents, corrosives, irritants, oxidizers, and substances with adverse toxicological properties are examples of such chemicals. Facilities should adopt a plan to ensure all hazardous materials are identified, employees informed of potential hazards to which they may be exposed and trained on safe handling procedures. Hazard Communication (HazCom) or Workplace Hazardous Materials Information Systems (WHMIS) should include a written program and provision of hazard reference materials (MSDSs). Labelling of containers and use of personal protective equipment and procedures should be proscribed and followed. Note that MSDSs and labelled chemicals often contain numbered risk- and safety-phrases. These are listed for the user’s convenience in Appendices 4 and 5, respectively.

9.3.6 Respiratory protection

9.3.6.1 General Best practice for respiratory protection involves identifying air contaminants and controlling them through engineering and administrative controls. When engineering and administrative controls are not feasible or completely effective, while they are being installed or during emergencies, respirators may be used to protect workers.

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9.3.6.2 Respiratory protection program When respiratory protection is needed, a respiratory control program should be implemented. Key elements include: 1) exposure assessment through sampling and analysis, 2) central program control of assessments and respirator selection, record maintenance and program effectiveness evaluation, 3) adoption of written standard operating procedures regarding respirator issuance and use policies, 4) medical evaluations of respirator users to assure wearers do not have medical conditions that would put them at further risk, 5) selection of respirators commensurate with hazards and exposure, 6) training on respiratory hazards (respirator function, capabilities and limitations, how to properly fit, wear, and care for a respirator), 7) fit testing to assure a respirator is correctly sized and properly adjusted to one’s face, and 8) respirator maintenance, including inspection, cleaning and storage.

9.3.6.3 Respirators Respirators may be classified as: 1) air purifying, 2) atmosphere-supplying, or 3) combination of air purifying/atmosphere-supplying. Air purifying respirators remove contaminants from the air by filtering out dusts, mists and fumes, or by chemically adsorbing gases and vapours. These include disposable respirators, half mask or full face-piece cartridge or canister models, and battery powered air-purifying respirators (PAPR). Air-supplying respirators include demand, pressure demand and continuous flow airline models, and self-contained breathing apparatus (SCBA). Combination air purifying/atmosphere-supplying respirator provide protection if the air supply is lost. Combination-type units are restricted to atmospheres that are not IDLH. Respirator selection should be based upon the type of contaminant; its concentration, work activity, ambient conditions and respirator wear time. Respirators have been rated according to the level of protection they afford, such as specifying up to what multiple of permissible exposure particular respirators are effective. This is commonly referred to as the respirator protection factor. Respirators are increasingly protective in this order: half mask disposable, half mask air purifying, half mask air supplying, full face-piece air purifying, full face-piece atmosphere-supplying. Table 20 lists approximate relative protection factors for various respirators. Table 20 Typical respirator protection factors (PF) Respirator type PF1

Half mask: disposable or air purifying 10Half mask: PAPR; atmosphere-supplying air line (pressure demand / continuous flow) 50Full face-piece: atmosphere-supplying, SCBA or air line (demand) 100Full face-piece: air purifying, or powered air purifying with dust filter 100Full face-piece: powered air purifying with cartridge or canister 1000Full face-piece: atmosphere-supplying air line (pressure demand or continuous flow) 10001Protection factors shown are approximate and are presented for comparison purposes only. Actual protection factors may vary. Consult the manufacturer’s literature and use instructions for the rated protection factor of a specific respirator. New disposable respirator rating systems evaluate the effectiveness of particulate-filtering respirators according to their filtering efficiency, and whether or not they should be used in the presence of oil mists. This system uses the numbers 95, 99 or 100 to designate filtering efficiency (95%, 99% or 99.97%, respectively), and the letters “N,” “R,” and “P” to designate selection criteria in the presence or absence of oil particles. Oil mists can break down the filtering effectiveness of respirators, so proper respirator selection is important. “N” stands for “Not Resistant to Oil,” “R” stands for “Oil Resistant” and “P” stands for “Oil Proof.” The minimal

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rating for a cement plant disposable respirator should be N95. If oil mists are present, “R” or “P” series respirators should be used. When “N” series respirators are used in dirty environments, they should be used for one work shift only, and then discarded. When “R” series respirators are used in oily environments, they should be used for one work shift only. Any respirator should be changed when it becomes clogged, damaged or breathing becomes difficult.

9.4 Physical hazards and controls

9.4.1 General Physical hazards include noise, pressure extremes, radiation and thermal hazards.

9.4.2 Noise and hearing conservation

9.4.2.1 General Cement manufacturing processes generate noise from crushers, screens, mills, blowers, fans, vibrators, power transmission devices, mobile equipment, tools, laboratory and office equipment (Kirk, 1998). If persons are exposed to excessive noise, particularly if they are not protected, they may suffer hearing loss. Best practices include establishing a hearing conservation program, identifying occupational noise sources and controlling employees’ exposure through engineering and administrative controls. When such controls are not feasible or completely effective, while they are being installed or during emergencies, personal protective equipment, also called Hearing Protection Devices (HPDs), may be used to protect workers.

9.4.2.2 Physics of sound and noise Sound is any pressure variation that can be detected by the human ear, whereas noise is sound that is unwanted by the listener. Sound is transmitted by waves, and is measured by amplitude (intensity), frequency in cycles per second (Hertz or Hz) and duration (time). Other parameters are sound power and sound pressure. Since these values cover a wide range, it is convenient to express intensity, power, and pressure in terms of their respective levels, or decibels (dB). As the value of these properties increases, the potential damaging effect on human auditory system increases. Decibels are logarithmic values and cannot be added algebraically. As a rule of thumb, the additive effect of noise sources can be estimated as shown in Table 21. Noise exchange rate is an important term. This means: A reduction of 3 dB in sound intensity level requires a 50% reduction in sound intensity. When calculating permissible noise exposure, some regulatory agencies apply a 5 dB exchange rate instead of using the true value of 3 dB. That is, by regulation, a worker’s noise exposure can be increased by 5 decibels if exposure time is halved, or, exposure time can be doubled if noise exposure is reduced by 5 decibels. For industrial hearing protection programs, application of the 5 dB exchange rate is much less stringent than where the true 3 dB exchange rate used.

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Table 21 Approximate additive effect of sound pressure levels Numerical sound difference between two sound pressure levels to be added (dB)

Amount to be added to the larger sound pressure level to obtain the sum (dB)

0 - 1 3 2 - 4 2 5 - 9 1 ≥ 10 0

9.4.2.3 Effects of noise exposure One type of hearing loss is sensorineural, i.e. noise induced hearing loss (NIHL), caused by damage to the hearing cells in the inner ear. This condition is always irreversible. Besides excessive exposure to noise over a period of time, usually over many months or years, hearing loss can also be due to aging (presbycusis), or to conductive hearing loss. The latter may be caused by obstructions in the ear, such as wax build-up, or by certain illnesses or other medical conditions. Non-auditory effects of excessive noise exposure can include nausea, headache, vasoconstriction, high blood pressure, equilibrium and visual disturbances. Loss of hearing acuity can make it difficult for one to understand, often because it becomes hard to distinguish between consonants. The power of speech is generally contained in the vowel sounds, but intelligibility comes primarily from the consonants. Occupational hearing loss in the important human speech frequencies of 2000-4000 Hz may be considered a disability and compensable under workers’ compensation laws.

9.4.2.4 Instrumentation for noise evaluation Sound level meters (SLMs) measure sound pressure levels in decibels (dBs). Three weighting networks, A, B, & C, are common to sound level meters and cause meter sensitivity to vary with frequency. The A scale most closely approximates the range of the human ear and is most commonly used. Whenever expressing sound levels, the scale must be identified, such as “dBA.” Octave band analyzers determine sound pressure levels at frequencies ranging from 31.5 Hz to 16,000 Hz. They are usually used in conjunction with SLMs and are necessary when designing engineering solutions for noise control. Sound level meters with octave band analyzers enable facility engineering and safety personnel to identify high noise level equipment and select appropriate materials or equipment to reduce workplace noise levels. Noise dosimeters worn by workers continuously measure personal exposure to changing sound levels over the course of a workday. They integrate and record the total sound energy to which workers are exposed, calculate the daily dose in dBA or percent allowable, and record peak levels. Sampling individual workers using sound dosimeters can indicate workplace sound exposure for various tasks and help identify hearing loss risk.

9.4.2.5 Hearing conservation programs Facilities with high noise levels should implement a comprehensive hearing conservation program. Program components should include: 1) monitoring to determine task-specific noise exposure levels, 2) performing area surveys to identify loud equipment, 3) posting workplace noise levels, 4) using engineering controls and administrative procedures to reduce exposure, 5) training on the effects of noise exposure, including the benefit and use of HPDs, 6) audiometric

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testing of employees’ baseline hearing acuity, 7) audiometric monitoring over the course of employment, 8) keeping records, and 9) notifying employees of changes in hearing ability.

9.4.2.6 Control methods Regular maintenance and proper lubrication will solve many noise level problems. When they do not, engineering controls may be installed. These controls include fan and blower silencers, acoustical linings, curtains, doors and enclosures to block and absorb sound, substituting loud equipment like power transmission devices and vibrators with quieter models, relocating or enclosing loud equipment, and providing mobile equipment cabs and operators’ stations. Whenever feasible, engineering controls should be specified, purchased and installed with new equipment during the design and construction process. Replacing or retrofitting existing equipment is possible, but may be more costly and less effective. Facility operations and maintenance personnel should be aware that engineering controls must be properly installed and maintained in order to achieve maximum and continued benefit. Administrative controls include limiting work times in loud areas, and requiring certain safe work practices, such as keeping windows closed in air-conditioned mobile equipment cabins. Personal protective equipment (specifically, HPDs) includes several styles of earplugs and earmuffs. In order to provide hearing protection, earplugs must be installed properly in the ear canal, and earmuffs must have a good seal around the ear. Plugs and muffs vary in their effectiveness according to their design and the materials used in their construction. Noise Reduction Rating (NRR) measures HPD effectiveness, with higher NRR-rated HPDs affording more protection. Advertised NRRs reflect protection under optimum conditions. Actual worker protection is, however, much lower than rated, sometimes only half the NRR or less. Wearing time is very important; when HPDs are removed, even for a short time, the risk of hearing loss increases dramatically. Exposure to noise totalling just 15 percent of the time is equivalent to using little or no protection at all. Table 22 illustrates this point and makes a strong case for wearing hearing protection all the time, not just when it is convenient (Sterret, 2002). Table 22 Maximum protection provided by non-continuous use of hearing protection.1

Percentage time used

Maximum protection

50 % 3 dB 60 % 4 dB 70 % 5 dB 80 % 7 dB 90 % 10 dB 95 % 13 dB 99 % 20 dB

99.9 % 30 dB 1 Canadian Centre for Occupational Health and Safety, Hamilton, Ontario, 1997-2002.

At high sound pressure levels, sound can by-pass the ear canal and be conducted through the skull. This is referred to as “bone conduction” and can also damage a person’s hearing. Ear muff-type HPDs can lessen this effect. Therefore, for sound levels of 105 dBA or more, dual hearing protection, such as use of both earplugs and ear muffs, is recommended. Exposure to sound levels

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above 115 dBA, as measured by a slow response dosimeter or sound level meter, should not be allowed, although much higher instantaneous peak levels may be experienced.

9.4.3 Pressure extremes

9.4.3.1 General Extremes of pressure are found in spray cans, compressed gases and hydraulic fluid systems. Pressures of 700 kPa (100 psi) can be found in plant compressed air systems, while pressures in compressed gas cylinders can reach 15,000 kPa (2,200 psi), or more. Hydraulic system pressures can equal or exceed these figures. Uncontrolled or rapid release of pressure poses an injury hazard to personnel.

9.4.3.2 Aerosol spray cans Spray cans have been known to explode when stored in hot areas, even on the dashboards of vehicles parked in direct sunlight. They should be stored in cool locations. If flammable propellants are present, spray cans should be stored in flammable storage lockers or caged bins when not in use. These objects pose a fire hazard, and have been known to spread fire rapidly throughout a building when heat from an incipient fire causes them to explode and fly to various locations, simultaneously igniting more fuel.

9.4.3.3 Compressed gas cylinders Compressed gas cylinder valves should be protected with the screw-on cap whenever they are stored or transported. A broken valve will allow the pressurized gas inside to escape and cause the cylinder to fly like a rocket, posing personal injury or property damage risk to anyone or anything nearby. Cylinders should be stored in clean, dry, well-ventilated areas, with full cylinders separated from empties. They should be secured in the upright position to prevent them from falling over and damaging the valve. Compressed gas cylinders should never be stored near high heat sources, to avoid pressure build-up and possible explosion. Damaged, corroded, or leaking cylinders should be removed from service, tagged, moved to a secure location and the supplier notified. Pressure regulators should be employed and maintained in good condition to control the use of compressed gases according to manufacturers’ instructions. Flammable gas cylinders warrant special handling.

9.4.3.4 Plant compressed air systems Compressed air directed at a person can force foreign objects through the skin, create embolisms in blood vessels, rupture the bowels or remove an eye from its socket. Compressed air should never be directed at a person.

9.4.4 Radiation and control

9.4.4.1 Ionizing radiation Ionizing radiation sources in cement plants include laboratory X-ray machines, storage tank level indicators and mass flow measurement devices. These devices produce gamma and X-rays that can penetrate the body and damage internal organs. To protect employees against injury or illness resulting from overexposure to ionizing radiation, facilities should adopt a written radiation control plan.

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Best practices include: 1) licensing, if required, 2) appointing a qualified Radiation Control Officer, 3) securing radiation sources to prevent unauthorized removal, 4) shielding sources to prevent radiation from entering non-safe areas, 5) labelling areas where radiation equipment is used or stored with the standard magenta warning symbol (see Fig. 5), 6) locking source shutters closed before working on or entering equipment or structures that are radiation equipped, 7) surveying posted areas with radiation detection equipment, 8) training personnel on radiation hazards, safe work practices and emergency procedures, 9) monitoring exposure of personnel likely to receive in excess of 25% of the maximum permissible dose in any calendar quarter, or who enter high radiation areas, and 10) keeping records of radiation surveys, training, monitoring and personnel exposures. Notification of any spills, injuries, fires or other incidents involving radioactive materials should be made to the appropriate authorities.

Fig. 5 Example of instruments using radioactive materials being properly shielded and labelled.

9.4.4.2 Non-ionizing radiation Non-ionizing radiation sources include lasers, infrared sensors, hot objects and ultraviolet light sources such as generated by pyro-processing and welding. Because these energies do not penetrate beyond the body’s surface, overexposure poses burn hazards mainly to the skin or eye. Injury prevention is accomplished by: 1) reducing energy levels, 2) erecting barriers, 3) reflecting radiation (such as heat), 4) increasing distance between workers and radiation sources, 5) limiting time of exposure, and 6) using personal protective equipment.

9.4.5 Thermal hazards

9.4.5.1 General The human body functions best within a narrow temperature range of 36°C to 38°C (97°F to 100°F), and it regulates itself by generating or losing heat as needed. Factors that influence body temperature include: 1) air temperature and air movement (convection), 2) contact with heated and cold surfaces (conduction), 3) transfer of heat through air (radiation), 4) humidity and perspiration (evaporation), and 5) body heat production (metabolism).

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9.4.5.2 Heated materials and equipment Because cement manufacturing requires extremes of heat throughout the process, heated materials are of particular concern, as they may range in temperature from ambient to super-heated. Raw meal, kiln and preheated feed, clinker and clinker dust, kiln burning zone coating, cement kiln dust, and refractoriness may look cool, but they can be extremely hot. Hot material or dust accumulations, piles, spills and coating build-ups may be found in process vessels, dust collectors, conveyors, elevators, etc., or they may be expelled into the atmosphere, spilled or emptied onto floors or walkways. Because these materials, especially piles or accumulations, are often self-insulating or are contained in heated or refractory-lined vessels, they may be cool on the surface, but very hot inside or at their base. They may remain very hot for many hours or days. To avoid serious burns, no one should ever pick up, handle or hold materials of unknown temperature. Hot material piles should be barricaded and/or signed and no one should ever walk on, reach into or step into any pile or accumulation of material. The unseen burn hazards of heated materials should be included in task and site-specific hazard training. Heated equipment includes raw and finish mills, pyro-processing apparatus such as preheated cyclones, calciners, kilns, burners, furnaces, and hot gas generators, conveyors, electrostatic precipitators and other dust collectors, engines, motors and equipment that has been welded or cut with an oxy-fuel torch. Even handrails in certain sections of a plant may be a hot surface hazard. Hot surfaces should be signed where feasible and no one should ever handle or touch any potentially hot surface without properly selected personal protective equipment.

9.4.5.3 Heat stress Heat stress occurs when the total heat load on one’s body from internal and external sources exceeds the body’s ability to cool itself. High temperatures and radiant heat sources identified with pyro-processing and grinding processes combine with metabolic heat produced by exercise to drive the body temperature up. If high humidity limits the body’s ability to evaporate perspiration and cool itself, heat overload is possible. Although evaporation is usually aided by increased air velocity, if the surrounding air temperature is greater than the body temperature, more heat will be transferred to the body than can be removed by evaporation. If the heat rise is too great, or is sustained for too long, injury can occur. Symptoms range from fatigue to fainting, and from cramps to exhaustion. In extreme cases, severe symptoms can occur. If failure of the central nervous system’s sweat regulating centre causes perspiration to cease, the body’s temperature can rise rapidly and convulsions or coma may result. Heat stress hazard assessment can be accomplished by measuring the Wet Bulb Globe Temperature (WBGT). WBGT factors air temperature, radiant heat, humidity and air movement into one thermal index that can be used to guide work time and exertion. Heat stress prevention methods include: 1) training, 2) drinking plenty of water, 3) taking rest breaks, 4) wearing loose fitting clothes, 5) using protective clothing or cooling vests, 6) ventilating work areas, 7) spot cooling with mists, and 8) installing heat shields (Workers Compensation Board of British Columbia, 2000). Caffeine, which is a diuretic, alcohol, and metabolism-affecting drugs, such as diet pills, can inhibit the body’s ability to regulate itself, and should be avoided. Acclimatization is the body’s process to adjust body functions to be more efficient in hot circumstances. Over a two-week period of exposure to moderate heat, one’s sweat rate increases and sweat salt content drops. Oxygen consumption and heart rate decrease, resulting in a lower body temperature given the same environmental and work exertion conditions.

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9.4.5.4 Hypothermia Hypothermia can occur when core body temperature drops due to lengthy exposure to cold and/or wet conditions. Progressive symptoms are: 1) shivering and weakness, 2) disorientation and slurred speech, 3) heart and breathing rate reduction, 4) drowsiness, 5) unconsciousness and collapse, and 6) possible death. Prevention methods include: 1) avoiding cold, wet exposure, 2) insulating against heat loss by dressing in layers, especially using woollen blends, and 3) depending on co-workers to help recognize danger signs, escape the cold and get the body re-warmed before it is too late.

9.4.5.5 Frost bites Frostbite occurs when liquids in the body’s extremities freeze. Relatively large, sharp crystals can damage flesh, or lack of blood flow through constricted blood vessels can cause tissues to die. Prevention is best accomplished by limiting exposure to cold conditions, especially when they are accompanied by wind. The hands, toes, ears and nose are most at-risk and should be protected when cold weather work is required.

9.5 Ergonomic hazards and control

9.5.1 General Ergonomics refers to efforts to adapt the workplace to the individuals working in it, and to eliminate or minimize job task risk factors that can cause physical disorders. Disorders develop over time due to continued exposure to certain environmental factors or physical stresses. Heavy weights, excessive force requirements, repetitive motions, contact stresses, adverse postural stresses, vibration, cold temperatures, and the use of heavy work gloves can lead to ergonomic problems. At-risk tasks often involve manual material handling. Lifting heavy or bulky objects from the floor, above shoulder height, while seated or while twisting may place employees at-risk. Exertion with the joints flexed, extended or rotated, pinch grips, pushing and pulling loads, poor posture or bending, especially under load, are also influencing factors. Any of these, especially when multiple factors are involved, or when coupled with work tasks of long duration or short recovery periods, play a role in determining whether or not an employee will develop disorders.

9.5.2 Body systems at risk

9.5.2.1 General Body systems subjected to ergonomic disorders are the muscular-skeletal system, the nervous system and the cardiovascular system.

9.5.2.2 Muscular-skeletal system Muscular-skeletal system disorders include: 1) joint sprains, caused by twisting or hyper-extending, 2) muscle strains caused by over-exertion or over-stretching, 3) tendon inflammation (tendonitis) caused by repetitive motions or excessive force, 4) arthritic conditions of the joints, perhaps caused by awkward positioning under load, 5) repetitive shock to the spine, such as from long operation of a haulage truck, and 6) degeneration of spinal discs, often caused by repetitive lifting with poor posture. These disorders develop over a period of time, ranging from a few hours to many years.

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9.5.2.3 Nervous system Nervous system conditions include: 1) compression of the median nerve in the wrist (carpal tunnel syndrome) due to repetitive motions, 2) compression of the ulnar nerve in the arm (cubital tunnel syndrome), from resting the elbows on hard surfaces, and 3) compression of the nerves at the shoulder (thoracic outlet syndrome) from working with one’s arms above the head.

9.5.2.4 Cardiovascular system Cardiovascular system disorders include: 1) obstruction of blood flow to body tissue (compression ischemia) due to resting one’s limbs on hard or sharp objects, or 2) reduction of blood flow to the hands or fingers (segmental vibration, white finger) resulting from vibration while using hand held power tools.

9.5.3 Evaluation Operations should analyze the work environment for indicators of ergonomic stressors, assess work tasks for the listed risk factors, review records to determine trends or history of cumulative trauma or repetitive stress disorders, interview workers and look for adaptations made to workstations or tools. Videos, slides and photographs are good tools to use when analyzing job situations.

9.5.4 Controls To reduce the risk of ergonomic problems, facilities should make efforts to neutralize as many risk factors as possible. Adaptations of tools, equipment or workstations to avoid reaching, twisting, pinching or excessive force are often all that are required to improve a condition. New equipment may be helpful, but is not always indicated, nor is it always ergonomically friendly to workers unless ergonomic considerations are made in the design phase. Tools are available to reduce the effort or change the posture required to perform jobs. Consideration should be made as to whether power tools or manual tools with a different sized or shaped handle are in order. Likewise, decisions should be made whether lifting problems can be solved with power-assisted vacuum lifters, power operated tables to lift or position loads, loads with reduced weights or smaller dimensions, or teaching employees simple techniques like the one-hand assisted lift method.

9.5.5 Training It is important to train workers so they know how to care for their bodies and prevent ergonomic disorders from occurring. Training should include physical limitations, how repetitive stress injuries develop, how to avoid injury by stretching prior to performing certain tasks, and the hazards associated with certain postural positions.

9.6 Biological hazards and controls

9.6.1 General Biological hazards include bio-aerosols, blood-borne pathogens and zoonotic diseases.

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9.6.2 Bio-aerosols

9.6.2.1 General Bio-aerosols are airborne liquid or solid particulates released from a living organism, small enough to remain dispersed in air for a prolonged period of time. Bacteria and fungi are the most commonplace bio-aerosols. Most environments contain a wide variety of bacteria and fungi; their types and concentrations are dictated by the prevailing conditions. Individual aerosolized particulates range in size from less than 0.1 μm to greater than 100 μm as reported in the American Conference of Governmental Industrial Hygienists’ guidelines (ACGIH, 1989). Typical bio-aerosols encountered in the indoor cement environment are bacteria and fungi, and may be further actualized when pre-processing municipal waste for AFR.

9.6.2.2 Bacteria Bacteria are microscopic organisms with single-celled or non-cellular bodies that collect in colonies in soil, water, organic matter, or in the bodies of plants and animals. Bacteria have pathogenic potential, and can cause adverse chemical effects, especially in food.

9.6.2.3 Fungi Fungi are microscopic plants that include molds, mildew, mushrooms and yeast, and live or feed on dead or decaying organic matter. For the average person, exposure to small and moderate amounts of molds is a fact of daily life, and those with normally functioning immune systems do not get ill. However, if workers are exposed to high concentrations of molds, especially if over a long period of time, or if they have existing lung disease or weak or challenged immune systems, the risk is higher. Potential health effects from toxigenic fungi like Stachybotrys and Aspergillus range from no effect to mild cold or flu symptoms, diarrhoea, fatigue, allergic reactions or serious respiratory illnesses like bronchopulmonary aspergillosis.

9.6.2.4 Controls Fungal molds and bacteria have been found when the right combination of moisture, temperature and food supply come together, such as in laboratory constant temperature and humidity rooms. Best practices to prevent fungal or bacterial growth and potential human illness include: 1) eliminating the fungi’s food supply by constructing the room of non-cellulose-based products (i.e. not using wood or paper), 2) decreasing the room’s humidity level by installing moisture cabinets of stainless steel construction, and 3) inspecting exposed surfaces, wall interiors, ceiling spaces or other hidden areas for evidence of fungal growth. Should minor cleaning be necessary, an application of 10% household bleach solution (one part household bleach to nine parts water) will control the hazard, but even the “dead” remains of fungi and their mycotoxins can be toxigenic and should be removed. Should major fungal colonies be discovered, remediation efforts should include: 1) removing cellulose-based wall and ceiling materials, 2) using removal, disposal and worker protection practices similar to those employed in asbestos abatement, and 3) cleaning and disinfecting all surfaces with a 10% or greater household bleach solution (Rice, 2000). (See also other fungal hazards discussed in 9.5.4 Zoonotic Diseases.)

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9.6.3 Blood borne pathogens (BBP) Of the large number of types of micro-organisms that inhabit the planet, only a small proportion is harmful to man (Heinsohn, 1995). Exposure to those biological agents can result in acute and chronic disease. Blood borne pathogens may pose risk to facility personnel, particularly first responders, if they are exposed to blood and other body fluids. Such pathogens include viruses, chlamydiae, rickettsiae, and mycoplasmas. Viruses are sub-microscopic, sub-cellular agents that range in size from 0.02 to 0.30 μm. There is some question as to whether viruses are actually living organisms. Chlamydiae are obligate parasites that are similar to bacteria but are much smaller in size. They have complex developmental cycles and preferentially infect mucous membrane tissue. Similar to chlamydiae, rickettsiae are obligate parasites that are similar to bacteria and can survive only within living cells. These agents are transmitted to man by arthropods, such as ticks, fleas, and lice. Mycoplasmas are the smallest cells that may exist independently and some are smaller than large viruses. Viruses such as those that cause hepatitis B (HBV) and human immunodeficiency (HIV) are the blood borne pathogens most likely to be passed from one person to another. Although workplace exposure of BBP is rare (unless hospital waste is to be handled for destruction in the cement kiln), facilities should adopt an exposure control plan that includes: 1) provision of BBP kits containing personal protection equipment and decontamination solutions, 2) training on kit use, 3) adopting universal precautions, i.e. considering all blood to be infected and treating it as if it were, to minimize the possibility of exposure, 4) reporting and recording blood and bodily fluid exposures, 5) offering exposed persons and all first aid providers the hepatitis B vaccination, 6) promptly decontaminating all surfaces, clothing and tools, and 7) properly disposing of waste.

9.6.4 Zoonotic diseases

9.6.4.1 General Zoonoses are diseases that can be transmitted to humans by animals through contact with bacteria, rickettsiae, viruses, fungi or parasites. Diseases or illnesses that cement plant workers could contract include histoplasmosis, tetanus, Lyme disease, Rocky Mountain spotted fever, rabies and certain dermatoses. The risk is usually small and in many cases largely dependent upon geographical location and task assignments. Facilities should assess the likelihood of contracting such diseases and implement preventive measures commensurate with risk, such as controlling or eliminating populations of small animals and insects such as raccoons, skunks, cats and mosquitoes, and providing insect repellent and prompt, competent treatment of infections, wounds or bites.

9.6.4.2 Histoplasmosis Histoplasmosis is an avian borne fungal illness that can possibly be contracted by cement workers. The fungus Histoplasma capsulatum is found worldwide, but is particularly endemic in the eastern half of North America. Fungal spores grow in manure-nourished moist soil and can be spread by pigeons, blackbirds, chickens and bats. When spores are disturbed, become airborne and are inhaled, infection of the respiratory system is possible. Although the disease can be life threatening, most infections are quite mild, no worse than the flu. Testing of human blood or bird manure samples to determine infection or the presence of spores is expensive, inconclusive and not recommended.

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Best practice is to assume the fungus is present in endemic areas and focus on preventing human infection by: 1) excluding birds from roosting areas by screening eaves, netting rooftop ventilators, installing doors and hanging vinyl strips at passageways and around materials transport systems, 2) minimizing the chance of spores forming and becoming airborne by regularly removing and disposing of bird droppings using wet clean-up procedures, protective clothing and respirators, and 3) treating accumulations of manure and contaminated surfaces with a quaternary ammonium chloride blend that functions as a combination wetting agent, disinfectant, fungicide and deodorizer (Rhodes et al., 2000).

9.6.4.3 Lyme disease and Rocky Mountain spotted fever Lyme disease and Rocky Mountain spotted fever are examples of tick-spread diseases that are potentially harmful to man. Cement plant exposure to ticks depends upon the plant’s geographical location and an individual’s work assignment. Persons whose job requires them to venture into grass and woods are much more likely to be exposed to ticks than those working in the mill. Those who may be at-risk should be trained to: 1) wear light coloured clothing, with pants legs tucked into boots, 2) check frequently and remove ticks that may attach themselves to clothing or one’s person, 3) know the symptoms of each disease and seek medical attention if they suspect they have been bitten by an infected tick. Vaccinations are available for Lyme disease, but should be administered only if medical personnel consider the risk of contracting the disease to warrant such intervention.

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10 AFR FEED POINTS IN CEMENT KILNS A short description of adequate feed points of AFR in a cement kiln may be in place at the end although it is not the main focus of this report. The most common feed points are (see also Fig. 6):

1. via the main burner at the rotary kiln outlet end 2. via a feed chute at the transition chamber at the rotary kiln inlet end (for lump fuel) 3. via secondary burners to the riser duct 4. via precalciner burners to the precalciner 5. via a feed chute to the precalciner (for lump fuel) 6. via a mid kiln valve in the case of long wet and dry kilns (for lump fuel)

Alternative raw materials (ARs) are typically fed to the kiln system in the same way as traditional raw materials, e.g. via the normal raw meal supply. Alternative raw materials containing components that can be volatilized at low temperatures (for example, hydrocarbons) have to be fed into the high temperature zones of the kiln system. Co-processing has the following characteristics during the production process:

• The alkaline conditions and the intensive mixing favour the absorption of volatile components from the gas phase. This internal gas cleaning results in low emissions of components such as SO2, HCl, and, with the exception of mercury and thallium, this is also true for most of the heavy metals.

• The clinker reactions at 1,450°C allow incorporation of ashes and in particular the chemical binding of metals to the clinker.

• The direct substitution of primary fuel by high calorific waste material causes a higher efficiency on energy recovery in comparison to other “waste to energy” technologies

Adequate feed points will be selected according to the physical, chemical, and (if relevant) toxicological characteristics of the AFR used, as well as the type of kiln (see Fig. 7).

Fig. 6 Clinker process and special characteristics in a pre-calciner kiln

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Alternative fuels (AFs) are always fed into the high-temperature combustion zones of the kiln system. The physical and chemical natures of the fuel determine the exact feed point, i.e. either the main burner, the precalciner burner, the secondary firing at the preheater, or the mid-kiln (for long dry and wet kilns). Alternative fuels containing stable toxic components should be fed to the main burner to ensure complete combustion due to the high temperature and the long retention time. Feeding of alternative raw materials containing volatile (organic and inorganic) components to the kiln via the normal raw meal supply is forbidden unless it has been demonstrated by controlled test runs in the kiln or by adequate laboratory tests that undesired stack emissions can be avoided.

Fig. 7 Possible feed points for AFR depending on kiln type

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11 CONCLUSIONS A review has been made of the following;

1. Waste materials recommended for co-processing in cement kilns, and of those who are not deemed suitable.

2. Recommended guidelines and operational aspects of pre-processing waste to alternative

fuel and raw materials (AFRs) for co-processing in cement kilns.

3. Feed point for AFRs into cement kilns Occupational health and safety (OH&S) for pre-processing waste to AFR in particular, but also generally for industry like cement plants.

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12 REFERENCES ACGIH, Guidelines for the Assessment of Bio-aerosols in the Indoor Environment, American Conference of Governmental Industrial Hygienists, Cincinnati, 1989. American Industrial Hygiene Association, 1994 – 1995 Membership Directory, Fairfax, Virginia, 1995. Canadian Centre for Occupational Health and Safety (CCOHS), 250 Main Street East, Hamilton, Ontario, L8N 1H6; Tel: (905) 572-4400; (800) 263-8466; Fax (905) 572-4500; E-mail: inquiries@CCOHS.ca. Doull, J., Klassen, C. D. and Amdur, M. O. (editors), Casarett and Doull’s Toxicology: The Basic Science of Poisons, Second Edition, Macmillan Publishing Co., Inc., New York, 1980. GTZ - Holcim “Guidelines on co-processing waste materials in cement production”, The GTZ-Holcim Public Private Partnership, 2006, www.coprocem.com Heinsohn, P.A., Jacobs, R.R., and Concoby, B.A. (Editors), Biosafety Reference Manual, Second Edition, American Industrial Hygiene Association, Fairfax, Virginia, 1995. Holt, P. F., Inhaled Dust and Disease, John Wiley & Sons Ltd., Chichester, England, 1987. Johns Manville, Health, Safety and Environment Department Bulletin HSE-64C, Health and Safety Aspects of Fibre Glass, Littleton, Colorado, 1999. Justnes, H. and Engelsen, C.J.: Environmentally Sound Management of Hazardous and Industrial Wastes in Cement Kilns - Waste as Alternative Raw Materials, SINTEF Report SBF IN A07322, December 2007, 121 pp. Karstensen, K.H. and Justnes, H.: Environmentally sound management of hazardous and industrial wastes in cement kilns in China Proceedings of the International Symposium on Sustainability in the Cement and Concrete Industry, Edited by S. Jacobsen, P. Jahren and K.O. Kjellsen, Lillehammer, Norway, 16-19 September, 2007, pp. 334 - 342. Kirk, L. H. III, “Engineering Controls for Noise Attenuation in the Cement Industry,” 40th Cement Industry Technical Conference Record, Institute of Electrical and Electronics Engineers, Inc., Piscataway, New Jersey; and Portland Cement Association, Skokie, Illinois, May 1998. Kirk, L.H. III: “Safety Management and Organization”, Chapter 7.1 in “Innovations in Portland Cement Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland Cement Association (PCA), Illinois, USA, 2004a, ISBN: 0-89312-234-3. Kirk, L.H. III: “Effective Safety Practices”, Chapter 7.2 in “Innovations in Portland Cement Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland Cement Association (PCA), Illinois, USA, 2004b, ISBN: 0-89312-234-3. Kirk, L.H. III: “Health and Industrial Hygiene”, Chapter 7.3 in “Innovations in Portland Cement Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland Cement Association (PCA), Illinois, USA, 2004c, ISBN: 0-89312-234-3.

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National Institute for Occupational Safety and Health, Pocket Guide to Chemical Hazards, U.S, Department for Health and Human Services, Public Health Service, Centres for Disease Control, U.S. Government Printing Office, Washington, DC, June, 1997. National Mine Health and Safety Academy, Industrial Hygiene: Sampling for Silica and Noise, U.S. Department of Labour, Mine Safety and Health Administration, 1999. Rauscher, F. J. Jr. “Asbestos Substitutes are Safe, Effective,” Asbestos Issues, May 1990. Rhodes, S. W., Kirk, L. H., and Murray, C., Histoplasmosis, etc. – Teaming Up to Protect Respiratory Health, American Society of Safety Engineers, Cumberland Valley Section, Chesapeake Chapter, February 2000. Rice, M., Anticipation, Evaluation and Remediation of a Fungal Amplification Problem (Biocontamination by Molds), Edmonton, Alberta, Canada, March 2000. Sanderson, W., Kirk, L. H., and Almaguer D., “Ozone-induced respiratory illness during the repair of a portland cement kiln,” Scandinavian Journal of Work, Environment and Health, Vol. 25, No. 3, July 1999. Sterret, M. L., “Keeping an Ear to the Ground: Tech Solutions to Hearing Protection Compliance,” Professional Safety magazine, American Society of Safety Engineers, Des Plaines, Illinois, August 2002. Unifrax Corporation, MSDS Number M0251, Fiberfrax® Ceramic Fibre Products, Niagara Falls, New York, 1998. Unifrax Corporation, MSDS Number M4115, Insulfrax™ Thermal Insulation Products, Niagara Falls, New York, 1999.

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ABBREVIATIONS ADR = Agreement on Dangerous goods by Road AF = Alternative Fuel AFR = Alternative Fuel and Raw materials AR = Alternative Raw materials BAFU = Bundesamt für Umwelt (Federal office for the environment), www.bafu.admin.ch BAT = Best Available Technology BOD = Biochemical Oxygen Demand BUWAL = Bundesamt für Umwelt, Wald und Landschaft (Swiss Agency for the

Environment, Forest and Landscapes), www.umwelt-schweitz.ch CKD = Cement Kiln Dust COD = Chemical Oxygen Demand CSI = Cement Sustainability Initiative H&S = Health and Safety HazCom = Hazard Communication HCB = hexachlorobenzene HEPA = High-Efficiency Particulate Air (prefix to filter) HPD = Hearing Protection Device IARC = International Agency for Research on Cancer IBC = International Bulk Container IDLH = Immediate Danger to Life and Health IH = Industrial Hygiene LAF = Liquid Alternative Fuel LCV = Low Calorific Value MAC = Maximal Acceptable Concentration MMMF = Man-Made Mineral Fibres MMVF = Man-Made Vitreous Fibres MSDS = Material Safety Data Sheet NA = Not Applicable NIHL = Noise Induced Hearing Loss NRR = Noise Reduction Rating NTP = National Toxicology Program OH&S = Occupational Health and Safety PAPR = Powered Air-Purifying Respirator PCBs = Polychlorinated biphenyls PCDDs = Polychlorinated dibenzodioxins PCDFs = Polychlorinated dibenzofurans PEL = Permissible Exposure Limit POPs = Persistent Organic Pollutants PF = Protection Factor RCF = Refractory Ceramic Fibers RDF = Refuse Derived Fuels REG = Recommended Exposure Guidelines SAF = Solid Alternative Fuel SCBA = Self-Contained Breathing Apparatus SLM = Sound Level Meter Sv = Sievert (SI unit of equivalent radiation dose) SVF = Synthetic Vitreous Fibers TLV = Threshold Limit Value

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TOC = Total Organic Carbon TSS = Total Suspended Solids VOC = Volatile Organic Carbon WBCSD = World Business Council for Sustainable Development WBGT = Wet Bulb Globe Temperature WHMIS = Workplace Hazardous Materials Information System WMC = Waste Management Company

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APPENDIX 1: LIST OF WASTE MATERIALS SUITABLE FOR AFR This list is derived from the European Waste Catalogue but is not an exclusive and compulsory document. Complete catalogue: http://www.vrom.nl/get.asp?file=/docs/milieu/eural_engelse_versie.pdf This list gives a general overview of possible wastes to be used as AFR in cement kilns. A. Industrial Wastes 1. 0 Organic Chemical Wastes 1.1 Mineral oils, synthetic oils and fats 05 01 00 oil sludges and solid wastes 05 01 01 sludges from on-site effluent treatment 05 01 03 tank bottom sludges 12 01 00 wastes from shaping (including forging, welding, pressing, drawing, turning, cutting and filing) 12 01 06 waste machining oils containing halogens (not emulsioned) 12 01 07 waste machining oils free of halogens (not emulsioned) 12 01 08 waste machining emulsions containing halogens 12 01 09 waste machining emulsions free of halogens 12 01 10 synthetic machining oils 13 01 00 waste hydraulic oils and brake fluids 13 01 01 hydraulic oils, containing PCBs or PCTs 13 01 02 other chlorinated hydraulic oils (not emulsions) 13 01 03 non-chlorinated hydraulic oils (not emulsions) 13 01 04 chlorinated emulsions 13 01 05 non-chlorinated emulsions 13 01 06 hydraulic oils containing only mineral oil 13 01 07 other hydraulic oils 13 02 00 waste engine, gear and lubricating oils 13 02 01 chlorinated engine, gear and lubricating oils 13 02 02 non-chlorinated engine, gear and lubricating oils 13 02 03 other engine, gear and lubricating oils 13 03 00 waste insulating and heat transmission oils and other liquids 13 03 01 insulating or heat transmission oils and other liquids containing PCBs (chlorinated waste

and PCB are subject to legal limitations, maximum concentration in input and maximum T/year allowed)

13 03 02 other chlorinated insulating and heat transmission oils and other liquids 13 03 03 non-chlorinated insulating and heat transmission oils and other liquids 13 03 04 synthetic insulating and heat transmission oils and other liquids 13 03 05 mineral insulating and heat transmission oils and other liquids 13 04 00 bilge oils 13 04 01 bilge oils from inland navigation 13 04 02 bilge oils from jetty sewers 13 04 03 bilge oils from other navigation

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APPENDIX 1: List of waste materials suitable for AFR - Page 2 of 7 13 05 00 oil/water separator contents 13 05 02 oil/water separator sludges 13 05 03 interceptor sludges 13 05 04 desalter sludges or emulsions 13 05 05 other emulsions 13 06 00 oil waste not otherwise specified 13 06 01 oil waste not otherwise specified 1.2. Petrochemical wastes 05 01 00 oil sludges and solid wastes 05 01 01 sludges from on-site effluent treatment 05 01 02 desalter sludges 05 01 03 tank bottom sludges 05 01 04 acid alkyl sludges 05 01 05 oil spills 05 01 06 sludges from plant, equipment and maintenance operations 05 01 99 wastes not otherwise specified 05 05 00 oil desulphurisation waste 05 05 01 waste containing sulphur 05 06 00 waste from the pyrolytic treatment of coal 05 06 01 acid tars 05 06 03 other tars 05 06 04 waste from cooling columns 1.3 Solvents, paints, varnishes, glues (adhesive, sealants), organic rubbers 07 03 00 waste for the MFSU of organic dyes and pigments (excluding 06 11 00) 07 03 01 aqueous washing liquids and mother liquors 07 03 02 sludges from on-site effluent treatment 07 03 03 organic halogenated solvents, washing liquids and mother liquors 07 03 04 other organic solvents, washing liquids and mother liquors 07 03 07 halogenated still bottoms and reaction residues 07 03 09 halogenated filter cakes, spent absorbents 08 01 00 wastes from the MFSU of paint and varnish 08 01 01 waste paints and varnish containing halogenated solvents 08 01 02 waste paints and varnish free of halogenated solvents 08 01 03 waste from water-based paints and varnishes 08 01 06 sludges from paint and varnish removal containing halogenated solvents 08 01 07 sludges from paint and varnish removal free of halogenated solvents 08 01 08 aqueous sludges containing paint or varnish 08 01 09 wastes from paint or varnish (except 08 01 05 and 08 01 06) 08 01 99 wastes not otherwise specified

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APPENDIX 1: List waste materials suitable for AFR - Page 3 of 7 08 03 00 wastes from the MFSU of printing inks 08 03 01 waste ink containing halogenated solvents 08 03 02 waste ink free of halogenated solvents 08 04 00 wastes from the MFSU of adhesives and sealants (Including waterproofing products) 08 04 01 waste adhesive and sealants containing halogenated solvents 08 04 02 waste adhesive and sealants free of halogenated solvents 08 04 03 waste from water-based adhesive and sealants 08 04 05 adhesive and sealants sludges containing halogenated solvents 08 04 06 adhesive and sealants sludges free of halogenated solvents 08 04 07 aqueous sludges containing adhesive and sealants 08 04 08 aqueous liquid waste containing adhesive and sealants 14 05 00 wastes from solvent and coolant recovery (still bottoms) 14 05 01 chlorofluorocarbons 14 05 02 other halogenated solvents and solvent mixes 14 05 03 other solvents and solvent mixes 14 05 04 sludges containing halogenated solvents 14 05 05 sludges containing other solvents 1.4 Wastes from synthetic materials and rubbers 07 02 00 waste for the MFSU of plastics, synthetic rubber and man-made fibres 07 02 01 aqueous washing liquids and mother liquors 07 02 02 sludges from on-site effluent treatment 07 02 03 organic halogenated solvents, washing liquids and mother liquors 07 02 04 other organic solvents, washing liquids and mother liquors 07 02 07 halogenated still bottoms and reaction residues 07 02 08 other still bottoms and reaction residues 2. 0 Other Chemical Wastes 03 02 00 wood preservation waste 03 02 01 non-halogenated organic wood preservatives 03 02 02 organochlorinated wood preservatives 03 03 00 wastes from pulp, paper and cardboard production and processing 03 03 05 de-inking sludges from paper recycling 03 03 06 fibre and paper sludge 04 01 00 wastes from the leather industry 04 01 03 degreasing wastes containing solvents without a liquor phase 04 02 00 wastes from textile industry 04 02 11 halogenated waste from dressing and finishing 04 02 13 dye stuffs and pigments

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APPENDIX 1: List of waste materials suitable for AFR - Page 4 of 7 07 01 00 waste from the manufacture, formulation, supply and use (MFSU) of basic organic chemicals 07 01 01 aqueous washing liquids and mother liquors 07 01 02 sludges from on-site effluent treatment 07 01 03 organic halogenated solvents, washing liquids and mother liquors 07 01 04 other organic solvents, washing liquids and mother liquors 07 01 07 halogenated still bottoms and reaction residues 07 01 08 other still bottoms and reaction residues 07 04 00 waste for the MFSU of organic pesticides 07 04 01 aqueous washing liquids and mother liquors 07 04 02 sludges from on-site effluent treatment 07 04 03 organic halogenated solvents, washing liquids and mother liquors 07 04 04 other organic solvents, washing liquids and mother liquors 07 04 07 halogenated still bottoms and reaction residues 07 04 08 other still bottoms and reaction residues 07 05 00 waste for the MFSU of pharmaceuticals 07 05 01 aqueous washing liquids and mother liquors 07 05 02 sludges from on-site effluent treatment 07 05 03 organic halogenated solvents, washing liquids and mother liquors 07 05 04 other organic solvents, washing liquids and mother liquors 07 05 07 halogenated still bottoms and reaction residues 07 05 08 other still bottoms and reaction residues 07 06 00 waste for the MFSU of fats, grease, soaps, detergents, disinfectants and cosmetics 07 06 01 aqueous washing liquids and mother liquors 07 06 02 sludges from on-site effluent treatment 07 06 03 organic halogenated solvents, washing liquids and mother liquors 07 06 04 other organic solvents, washing liquids and mother liquors 07 06 07 halogenated still bottoms and reaction residues 07 06 08 other still bottoms and reaction residues 07 07 00 waste for the MFSU of fine chemical products not otherwise specified 07 07 01 aqueous washing liquids and mother liquors 07 07 02 sludges from on-site effluent treatment 07 07 03 organic halogenated solvents, washing liquids and mother liquors 07 07 04 other organic solvents, washing liquids and mother liquors 07 07 07 halogenated still bottoms and reaction residues 07 07 08 other still bottoms and reaction residues 08 03 00 wastes from the MFSU of printing inks 08 03 03 waste from water-based inks 08 03 05 ink sludges containing halogenated solvents 08 03 06 ink sludges free of halogenated solvents 08 03 07 aqueous sludges containing ink 08 03 08 aqueous liquid waste containing ink 08 03 99 wastes not otherwise specified

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APPENDIX 1: List of waste materials suitable for AFR - Page 5 of 7 09 01 00 wastes from the photographic industries 09 01 01 water based developer and activator solutions 09 01 02 water based offset plate developer solutions 09 01 03 solvent based developer solutions 09 01 04 fixer solution 09 01 05 bleach solutions and bleach fixer solutions 10 03 00 wastes from aluminium thermal metallurgy 10 03 01 tars and other carbon-containing wastes from anode manufacture 14 01 00 waste from metal degreasing and machinery maintenance 14 01 01 chlorofluorocarbons 14 01 02 other halogenated solvents and solvent mixes 14 01 03 other solvents and solvent mixes 14 01 04 aqueous solvent mixes containing halogens 14 01 05 aqueous solvent mixes free of halogens 14 01 06 sludges and solid wastes containing halogenated solvents 14 01 07 sludges and solid wastes free of halogenated solvents 14 02 00 wastes from textile cleaning and degreasing of natural products 14 02 01 halogenated solvents and solvent mixes 14 02 02 solvent mixes or organic liquids free of halogenated solvents 14 02 03 sludges and solid wastes containing halogenated solvents 14 02 04 sludges and solid wastes containing other solvents 14 03 00 wastes from the electronic industry 14 03 01 chlorofluorocarbons 14 03 02 other halogenated solvents and solvent mixes 14 03 03 other solvents and solvent mixes 14 03 04 sludges and solid wastes containing halogenated solvents 14 03 05 sludges and solid wastes containing other solvents 14 04 00 wastes from coolants, foam/aerosols propellants 14 04 01 chlorofluorocarbons 14 04 02 other halogenated solvents and solvent mixes 14 04 03 other solvents and solvent mixes 14 04 04 sludges and solid wastes containing halogenated solvents 14 04 05 sludges and solid wastes containing other solvents 16 03 00 off-specification batches 16 03 02 organic off-specification batches 16 05 00 chemicals and gases in containers 16 05 03 other wastes containing organic chemicals, e.g. lab chemicals not otherwise specified 17 03 00 asphalt, tar and tarred products 17 03 03 tar and tar products

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APPENDIX 1: List of waste materials suitable for AFR - Page 6 of 7 18 02 00 waste from research, diagnosis, prevention of diseases involving animals 18 02 04 discarded chemicals B. Wastes of Animal and Vegetal Origin (Except municipal, textile, agricultural and hospital wastes) 1.0 Fats and oils from animal and vegetal origin 02 01 00 primary production waste 02 01 01 sludges from washing and cleaning 02 01 06 animal faeces, urine and manure (including spoiled straw), effluent, collected separately and treated off-site 02 02 00 wastes from the preparation and processing of meat, fish and other foods of animal origin 02 02 01 sludges from washing and cleaning 02 02 03 materials unsuitable for consumption or processing 02 02 04 sludges from on-site effluent treatment 02 03 00 wastes from fruit, vegetables, cereals, edible oils, cocoa, coffee and tobacco preparation, processing; conserve production; tobacco processing 02 03 01 sludges from washing, cleaning, peeling, centrifuging and separation 02 03 02 wastes from preserving agents 02 03 03 wastes from solvent extraction 02 03 04 materials unsuitable for consumption or processing 02 03 05 sludges from on-site effluent treatment 02 04 00 wastes from sugar processing 02 04 03 sludges from on-site effluent treatment 02 05 00 wastes from dairy products industry 02 05 01 materials unsuitable for consumption or processing 02 05 02 sludges from on-site effluent treatment 02 06 00 wastes from backing and confectionery industry 02 06 02 wastes from preserving agents 02 06 03 sludges from on-site effluent treatment 02 07 00 wastes from the production of alcoholic and non-alcoholic beverages (Excluding coffee, tea and cocoa) 02 07 01 wastes from washing, cleaning and mechanical reduction of the raw material 02 07 02 wastes from spirits distillation 02 07 03 wastes from chemical treatment 02 07 04 materials unsuitable for consumption or processing 02 07 05 sludges from on-site effluent treatment

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APPENDIX 1: List of waste materials suitable for AFR - Page 7 of 7 C. Other Wastes 1.0 Disposed, sorted and/or stocked wastes from a waste treatment facility 05 08 00 waste from oil regeneration 05 08 02 acid tars 05 08 03 other tars 05 08 04 aqueous liquid waste from oil regeneration 14 05 00 wastes from solvent and coolant recovery (still bottoms) 14 05 01 chlorofluorocarbons 14 05 02 other halogenated solvents and solvent mixtures 14 05 03 other solvents and solvent mixtures 14 05 04 sludge containing halogenated solvents 14 05 05 sludge containing other solvents 16 07 00 waste from transport and storage tank cleaning (except 05 00 00 & 12 00 00) 16 07 01 wastes from marine transport tank cleaning, containing chemicals 16 07 02 wastes from marine transport tank cleaning, containing oil 16 07 02 wastes from marine transport tank cleaning, containing oil 16 07 03 wastes from railway and road transport tank cleaning, containing oil 16 07 04 wastes from railway and road transport tank cleaning, containing chemicals 16 07 05 wastes from storage tank cleaning, containing chemicals 16 07 06 wastes from storage tank cleaning, containing oil Wastes from drums and tanks treatment facility, contaminated by one or more Constituent enumerated in Annex II of Directive 91/689/CEE 19 01 00 wastes from incineration or pyrolysis of municipal and similar commercial, industrial and institutional waste 19 01 08 pyrolysis wastes 19 06 00 wastes from anaerobic treatment of wastes 19 06 01 anaerobic treatment sludges of municipal and similar wastes 19 06 02 anaerobic treatment sludges of animal and vegetable wastes 19 07 00 landfill leachate 19 07 01 landfill leachate 19 08 00 wastes from waste water treatment plants not otherwise specified 19 08 03 grease and oil mixture from oil/waste water separation 20 01 00 separately collected fractions 20 01 09 oil and fat 20 01 12 paint, inks, adhesive and resins 20 01 13 solvents 20 01 16 detergents 20 01 18 medicines 20 01 19 pesticides 20 03 00 other municipal waste

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APPENDIX 2: MATERIAL SAFETY DATA SHEET OF LINDANE The MSDS can also be found at https://fscimage.fishersci.com/msds/95168.htm Section 1 - Chemical Product and Company Identification MSDS Name: 1,2,3,4,5,6-Hexachlorocyclohexane, gamma-isomer Catalogue Numbers: AC411350000, AC411350030, AC411355000 Synonyms: Benzene hexachloride; gamma-Benzene hexachloride; Viton; Lindane; Hexachlorocyclohexane; BHC; gamma-BHC. Company Identification: Acros Organics N.V. One Reagent Lane Fair Lawn, NJ 07410 For information in North America, call: 800-ACROS-01 For emergencies in the US, call CHEMTREC: 800-424-9300 Section 2 - Composition, Information on Ingrédients CAS# Chemical Name Percent EINECS/ELINCS 58-89-9 Lindane 100 200-401-2 Section 3 - Hazards Identification EMERGENCY OVERVIEW Appearance: white crystalline powder crystalline powder. Danger! May be fatal if absorbed through the skin. Harmful if swallowed. Causes eye and skin irritation. May cause central nervous system effects. Potential cancer hazard. May cause cancer based on animal studies. May cause kidney damage. Dangerous for the environment. May cause reproductive and fatal effects. Target Organs: Blood, kidneys, central nervous system and liver. Potential Health Effects Eye: Causes eye irritation. May cause chemical conjonctivites. Skin: Causes skin irritation. May be fatal if absorbed through the skin. Ingestion: Harmful if swallowed. May cause gastrointestinal irritation with nausea, vomiting and diarrhoea. May cause liver and kidney damage. Human fatalities have been reported from acute poisoning. Large doses may cause convulsions. May cause central nervous system stimulation. Inhalation: Causes respiratory tract irritation. May cause liver and kidney damage. Exposure may result in irritation, excitement, and convulsions. Can produce delayed pulmonary oedema. May cause central, peripheral, and autonomic nervous system effects. Chronic: May cause liver and kidney damage. May cause cancer according to animal studies. May cause reproductive and fatal effects. Effects may be delayed. Section 4 - First Aid Measures Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid. Skin: Get medical aid immediately. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Ingestion: Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Inhalation: Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.

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Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 2 of 6 Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask. Notes to Physician: Treat symptomatically and supportively. Section 5 - Fire Fighting Measures General Information: As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. Water runoff can cause environmental damage. Dike and collect water used to fight fire. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to keep fire-exposed containers cool. Containers may explode when heated. Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Extinguishing Media: Do NOT get water inside containers. Do NOT use straight streams of water. For small fires, use dry chemical, carbon dioxide, or water spray. For large fires, use water spray, fog or regular foam. Cool containers with flooding quantities of water until well after fire is out. Flash Point: 150°C (302°F) Autoignition Temperature: Not applicable. Explosion Limits, Lower: Not available. Explosion limits, Upper: Not available. NFPA Rating: (estimated) Health: 2; Flammability: 1; Instability: 0 Section 6 - Accidental Release Measures General Information: Use proper personal protective equipment as indicated in Section 8. Spills/Leaks: Vacuum or sweep up material and place into a suitable disposal container. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions. Provide ventilation. Do not get water inside containers. Do not let this chemical enter the environment. Section 7 - Handling and Storage Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation. Storage: Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Keep away from metals. Poison room locked. Section 8 - Exposure Controls, Personal Protection Engineering Controls: Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low. Exposure Limits

OSHA Vacated PELs: Lindane: 0.5 mg/m3 TWA

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Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 3 of 6 Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166. Skin: Wear appropriate protective gloves to prevent skin exposure. Clothing: Wear appropriate protective clothing to prevent skin exposure. Respirators: A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use. Section 9 - Physical and Chemical Properties Physical State: Crystalline powder Appearance: white crystalline powder Odour: aromatic odour pH: Not available. Vapour Pressure: Negligible Vapour Density: Not available. Evaporation Rate: Not available. Viscosity: Not available. Boiling Point: 323°C Freezing/Melting Point: 111.5-114.5 °C Decomposition Temperature: Not available. Solubility: Slightly soluble in water. Specific Gravity/Density: 1.85 Molecular Formula: C6H6Cl6 Molecular Weight: 290.82 Section 10 - Stability and Reactivity Chemical Stability: Stable at room temperature in closed containers under normal storage and handling conditions. Conditions to Avoid: Incompatible materials, dust generation, excess heat, strong oxidants, powdered metals. Incompatibilities with Other Materials: Strong oxidizing agents. Hazardous Decomposition Products: Carbon monoxide, oxides of nitrogen, irritating and toxic fumes and gases, carbon dioxide. Hazardous Polymerization: Has not been reported Section 11 - Toxicological Information RTECS#: CAS# 58-89-9: GV4900000 LD50/LC50: CAS# 58-89-9: Oral, mouse: LD50 = 44 mg/kg; Oral, mouse: LD50 = 85.8 mg/kg; Oral, rabbit: LD50 = 60 mg/kg; Oral, rat: LD50 = 76 mg/kg; Skin, rabbit: LD50 = 50 mg/kg; Skin, rabbit: LD50 = 500 mg/kg; Skin, rat: LD50 = 414 mg/kg; .

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Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 4 of 6 Carcinogenicity: CAS# 58-89-9: ACGIH: A3 - Confirmed animal carcinogen with unknown relevance to humans California: carcinogen, initial date 10/1/89 NTP: Suspect carcinogen IARC: Group 2B carcinogen (listed as Hexachlorocyclohexane (mixed isomers)). Epidemiology: Experimental reproductive and teratogenic effects have been reported. Teratogenicity: No information available. Reproductive Effects: Adverse reproductive effects have occurred in humans. Adverse reproductive effects have occurred in experimental animals. Mutagenicity: Mutagenic effects have occurred in experimental animals. Neurotoxicity: No information available. Section 12 - Ecological Information Ecotoxicity: Fish: Fathead Minnow: 87µg/L; 96H; Fish: Brown trout: 1.7µg/L; 96H; No data available. Environmental: Expected to biodegrade and bio concentrate. Physical: No information available. Other: For more information, see "HANDBOOK OF ENVIRONMENTAL FATE AND EXPOSURE DATA." Biodegradable. Section 13 - Disposal Considerations Chemical waste generators must determine whether a discarded chemical is classified as a hazardous waste. US EPA guidelines for the classification determination are listed in 40 CFR Parts 261.3. Additionally, waste generators must consult state and local hazardous waste regulations to ensure complete and accurate classification. RCRA P-Series: None listed. RCRA U-Series: CAS# 58-89-9: waste number U129. Section 14 - Transport Information

Section 15 - Regulatory Information US FEDERAL TSCA CAS# 58-89-9 is listed on the TSCA inventory. Health & Safety Reporting List None of the chemicals are on the Health & Safety Reporting List. Chemical Test Rules None of the chemicals in this product are under a Chemical Test Rule. Section 12b None of the chemicals are listed under TSCA Section 12b. TSCA Significant New Use Rule None of the chemicals in this material have a SNUR under TSCA.

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Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 5 of 6 CERCLA Hazardous Substances and corresponding RQs CAS# 58-89-9: 1 lb final RQ; 0.454 kg final RQ SARA Section 302 Extremely Hazardous Substances CAS# 58-89-9: 1000 lb TPQ (lower threshold); 10000 lb TPQ (upper threshold) SARA Codes CAS # 58-89-9: immediate, delayed. Section 313 This material contains Lindane (CAS# 58-89-9, 100%), which is subject to the reporting requirements of Section 313 of SARA Title III and 40 CFR Part 373. Clean Air Act: CAS# 58-89-9 is listed as a hazardous air pollutant (HAP). This material does not contain any Class 1 Ozone depletors. This material does not contain any Class 2 Ozone depletors. Clean Water Act: CAS# 58-89-9 is listed as a Hazardous Substance under the CWA. CAS# 58-89-9 is listed as a Priority Pollutant under the Clean Water Act. CAS# 58-89-9 is listed as a Toxic Pollutant under the Clean Water Act. OSHA: None of the chemicals in this product are considered highly hazardous by OSHA. STATE CAS# 58-89-9 can be found on the following state right to know lists: California, New Jersey, Pennsylvania, Minnesota, and Massachusetts. California Prop 65 The following statement(s) is (are) made in order to comply with the California Safe Drinking Water Act: WARNING: This product contains Lindane, a chemical known to the state of California to cause cancer. California No Significant Risk Level: CAS# 58-89-9: 0.6 µg/day NSRL European/International Regulations European Labelling in Accordance with EC Directives Hazard Symbols: T N Risk Phrases (see also Appendix 4): R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed. R 36/38 Irritating to eyes and skin. R 50/53 Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. Safety Phrases (see also Appendix 5): S 13 Keep away from food, drink and animal feeding stuffs. S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). S 60 This material and its container must be disposed of as hazardous waste. S 61 Avoid release to the environment. Refer to special instructions/safety data sheets. WGK (Water Danger/Protection) CAS# 58-89-9: 3 Canada - DSL/NDSL CAS# 58-89-9 is listed on Canada's DSL List. Canada - WHMIS This product has a WHMIS classification of D1A, D1B, D2A, D2B.

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Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 6 of 6 This product has been classified in accordance with the hazard criteria of the Controlled Products Regulations and the MSDS contains all of the information required by those regulations. Canadian Ingredient Disclosure List CAS# 58-89-9 is not listed on the Canadian Ingredient Disclosure List. Section 16 - Additional Information MSDS Creation Date: 7/08/1999 Revision #4 Date: 10/03/2005

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APPENDIX 3: MATERIAL SAFETY DATA SHEET (MSDS) OF DDT This MSDS can be found at http://www.pcl.ox.ac.uk/MSDS/DD/DDT.html General Synonyms: 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane, 4,4'-DDT, α,α-bis(p-chlorophenyl)-β,β,β-trichloroethane, dichlorodiphenyltrichloroethane, diphenyltrichloroethane, chlorophenothane, p,p'-dichlorodiphenyltrichloroethane, 4,4'-dichlorodiphenyltrichloroethane, 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane, numerous trade and other non-systematic names, including those given below (Note: The use of DDT has been largely discontinued, so most - perhaps all - of these trade names are no longer used.): anofex, p,p'-DDT, dicophane, didigam, didimac, ENT 1,506, estonate, genitox, gesafid, gesarol, gyron, ixodex, NCI-C00464, neocid, pentachlorin, santobane, trichlorobis(4-chlorophenyl)ethane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, zeidane, zerdane, agritan, arkotine, azotox, 1,1'-(2,2,2-trichloroethylidene)bis(4-chlorobenzene), bosan, supra, boviderm, chlorphenothan, chlorophenotoxum, citox, clofenotane, dedlo, deoval, detox, detoxan, dibovan, dodat, dykol, gesafid, gesapon, gesarex, guesapon, havero-extra, hildit, ivoran, kopsol, micro, DDT 75, mutoxin, NA 2761, OMS 16, parachlorocium, peb1, pentech, ppzeidan Use: insecticide, formerly one of the most widely used insecticides in the world; now used in only limited areas because of environmental concerns Molecular formula: C14H9Cl5 CAS No: 50-29-3 EINECS No: Physical data Appearance: colourless to white crystalline powder Melting point: 108-109°C Boiling point: 260°C Vapour density: Vapour pressure: Density: 1.56 g/cm3 Flash point: 165°C Explosion limits: Autoignition temperature: Water solubility: very slight Stability Stable. Combustible. Incompatible with strong oxidizing agents, iron and aluminium and their salts, alkalis. Toxicology Poison if swallowed. May be harmful if inhaled or absorbed through the skin. Absorption is considerably enhanced by the presence of oils. Possible human carcinogen. Human mutagenic effects. May cause reproductive damage. May act as a systemic poison. Unlikely to be fatal on its own, but the toxic effects of this chemical appear to be enhanced when exposure simultaneously includes other chemicals. DDT and its degradation products, particularly DDE, are stored in fat in the body, and this can lead to a total body load of chemical which is potentially much greater than the fatal dose. This stored material is removed only gradually from the body.

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Appendix 3: Material Safety Data Sheet (MSDS) of DDT - page 2 of 2 Toxicity data (The meaning of any toxicological abbreviations which appear in this section is given here: http://ptcl.chem.ox.ac.uk/MSDS/toxicity_abbreviations.html) ORL-RAT LD50 87 mg/kg SKN-RAT LD50 1931 mg/kg ORL-HMN LDLO 500 mg/kg (though far lower figures are also quoted) SCU-RAT LD50 1500 mg/kg ORL-MUS LD50 135 mg/kg ORL-RBT LD50 250 mg/kg Transport information UN No 2761. Hazard class 6.1. Packing group III. Environmental information A serious environmental hazard due to bioaccumulation and transport up the food chain. Concentrations in animals near the top of the food chain (such as predatory birds) may become high enough in areas in which DDT has been heavily used, to have devastating effects upon reproductive ability. Degrades extremely slowly in the environment and is removed very slowly from animal tissue. Personal protection Safety glasses, gloves, good ventilation. Treat as a possible carcinogen. Other information Note that use of DDT as an insecticide is banned in most countries. This information was last updated on March 29, 2005.

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APPENDIX 4: RISK PHRASES RISK PHRASES - R-phrases. (Reproduced from the Approved Supply List (6th edition, 2000) by HSC from Annex 1 of the Dangerous Substances Directive (67/548/EEC), effective in the European Union from October 2000.

R-phrase references 1: Explosive when dry 2: Risk of explosion by shock, friction, fire or other sources of ignition 3: Extreme risk of explosion by shock, friction, fire or other sources of ignition 4: Forms very sensitive explosive metallic compounds 5: Heating may cause an explosion 6: Explosive with or without contact with air 7: May cause fire 8: Contact with combustible material may cause fire 9: Explosive when mixed with combustible material 10: Flammable 11: Highly flammable 12: Extremely flammable 14: Reacts violently with water 15: Contact with water liberates extremely flammable gases 16: Explosive when mixed with oxidizing substances 17: Spontaneously flammable in air 18: In use may form flammable/explosive vapour-air mixture 19: May form explosive peroxides 20: Harmful by inhalation 21: Harmful in contact with skin 22: Harmful if swallowed 23: Toxic by inhalation 24: Toxic in contact with skin 25: Toxic if swallowed 26: Very toxic by inhalation 27: Very toxic in contact with skin 28: Very toxic if swallowed 29: Contact with water liberates toxic gas 30: Can become highly flammable in use 31: Contact with acids liberates toxic gas 32: Contact with acids liberates very toxic gas 33: Danger of cumulative effects 34: Causes burns 35: Causes severe burns 36: Irritating to the eyes 37: Irritating to the respiratory system 38: Irritating to the skin 39: Danger of very serious irreversible effects 40: Possible risk of irreversible effects 41: Risk of serious damage to eyes 42: May cause sensitisation by inhalation 43: May cause sensitisation by skin contact 44: Risk of explosion if heated under confinement

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Appendix 4: Risk phrases - page 2 of 4 45: May cause cancer 46: May cause heritable genetic damage 48: Danger of serious damage to health by prolonged exposure 49: May cause cancer by inhalation 50: Very toxic to aquatic organisms 51: Toxic to aquatic organisms 52: Harmful to aquatic organisms 53: May cause long-term adverse effects in the aquatic environment 54: Toxic to flora 55: Toxic to fauna 56: Toxic to soil organisms 57: Toxic to bees 58: May cause long-term adverse effects in the environment 59: Dangerous for the ozone layer 60: May impair fertility 61: May cause harm to the unborn child 62: Possible risk of impaired fertility 63: Possible risk of harm to the unborn child 64: May cause harm to breastfed babies 65: Harmful: may cause lung damage if swallowed 66: Repeated exposure may cause skin dryness or cracking 67: Vapours may cause drowsiness and dizziness Combination of particular risks 14/15: Reacts violently with water, liberating extremely flammable gases 15/29: Contact with water liberates toxic, extremely flammable gas 20/21: Harmful by inhalation and in contact with skin 20/21/22: Harmful by inhalation, in contact with skin and if swallowed 20/22: Harmful by inhalation and if swallowed 21/22: Harmful in contact with skin and if swallowed 23/24: Toxic by inhalation and in contact with skin 23/24/25: Toxic by inhalation, in contact with skin and if swallowed 23/25: Toxic by inhalation and if swallowed 24/25: Toxic in contact with skin and if swallowed 26/27: Very toxic by inhalation and in contact with skin 26/27/28: Very toxic by inhalation, in contact with skin and if swallowed 26/28: Very toxic by inhalation and if swallowed 27/28: Very toxic in contact with skin and if swallowed 36/37: Irritating to eyes and respiratory system 36/37/38: Irritating to eyes, respiratory system and skin 36/38: Irritating to eyes and skin 37/38: Irritating to respiratory system and skin 39/23: Toxic: danger of very serious irreversible effects through inhalation 39/23/24: Toxic: danger of very serious irreversible effects through inhalation and in

contact with skin 39/23/24/25: Toxic: danger of very serious irreversible effects through inhalation, in

contact with skin and if swallowed 39/23/25: Toxic: danger of very serious irreversible effects through inhalation and if

swallowed

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Appendix 4: Risk phrases - page 3 of 4 39/24: Toxic: danger of very serious irreversible effects in contact with skin 39/24/25: Toxic: danger of very serious irreversible effects in contact with skin and if

swallowed 39/25: Toxic: danger of very serious irreversible effects if swallowed 39/26: Very toxic: danger of very serious irreversible effects through inhalation 39/26/27: Very toxic: danger of very serious irreversible effects through inhalation and

in contact with skin 39/26/27/28: Very toxic: danger of very serious irreversible effects through inhalation,

in contact with skin and if swallowed 39/26/28: Very toxic: danger of very serious irreversible effects through inhalation and

if swallowed 39/27: Very toxic: danger of very serious irreversible effects in contact with skin 39/27/28: Very toxic: danger of very serious irreversible effects in contact with skin

and if swallowed 39/28: Very toxic: danger of very serious irreversible effects if swallowed 40/20: Harmful: possible risk of irreversible effects through inhalation 40/20/21: Harmful: possible risk of irreversible effects through inhalation and in

contact with skin 40/20/21/22: Harmful: possible risk of irreversible effects through inhalation, in

contact with skin and if swallowed 40/20/22: Harmful: possible risk of irreversible effects through inhalation and if

swallowed 40/22: Harmful: possible risk of irreversible effects if swallowed 40/21: Harmful: possible risk of irreversible effects in contact with skin 40/21/22: Harmful: possible risk of irreversible effects in contact with skin and if

swallowed 42/43: May cause sensitisation by inhalation and skin contact 48/20: Harmful: danger of serious damage to health by prolonged exposure through

inhalation 48/20/21: Harmful: danger of serious damage to health by prolonged exposure through

inhalation and in contact with skin 48/20/21/22: Harmful: danger of serious damage to health by prolonged exposure through

inhalation, in contact with skin and if swallowed 48/20/22: Harmful: danger of serious damage to health by prolonged exposure through

inhalation and if swallowed 48/21: Harmful: danger of serious damage to health by prolonged exposure in

contact with skin 48/21/22: Harmful: danger of serious damage to health by prolonged exposure in

contact with skin and if swallowed 48/22: Harmful: danger of serious damage to health by prolonged exposure if

swallowed 48/23: Toxic: danger of serious damage to health by prolonged exposure

through inhalation 48/23/24: Toxic: danger of serious damage to health by prolonged exposure

through inhalation and in contact with skin 48/23/24/25: Toxic: danger of serious damage to health by prolonged exposure

through inhalation, in contact with skin and if swallowed 48/23/25: Toxic: danger of serious damage to health by prolonged exposure

through inhalation and if swallowed

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Appendix 4: Risk phrases - page 4 of 4 48/24: Toxic: danger of serious damage to health by prolonged exposure in

contact with skin 48/24/25: Toxic: danger of serious damage to health by prolonged exposure in

contact with skin and if swallowed 48/25: Toxic: danger of serious damage to health by prolonged exposure if

swallowed 50/53: Very toxic to aquatic organisms, may cause long-term adverse effects in the

aquatic environment 51/53: Toxic to aquatic organisms. May cause long-term adverse effects in the

environment 52/53: Harmful to aquatic organism; may cause long-term aquatic

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APPENDIX 5: SAFETY PHRASES SAFETY PHRASES - S-phrases. (Reproduced from the Approved Supply List (6th edition 2000) by HSC from Annex 1 of the Dangerous Substances Directive (67/548/ EEC), effective in the European Union from October 2000, and from the Merck catalogue. S-phrase references 1: Keep locked up 2: Keep out of reach of children 3: Keep in a cool place 4: Keep away from living quarters 5: Keep contents under ... (appropriate liquid to be specified by the manufacturer) 6: Keep under.. . (inert gas to be specified by the manufacturer) 7: Keep container tightly closed 8: Keep container dry 9: Keep container in a well ventilated place 12: Do not keep the container sealed 13: Keep away from food, drink and animal feeding stuffs 14: Keep away from ... (incompatible materials to be indicated by the manufacturer) 15: Keep away from heat 16: Keep away from sources of ignition - No Smoking 17: Keep away from combustible material 18: Handle and open container with care 20: When using do not eat or drink 21: When using do not smoke 22: Do not breathe dust 23: Do not breathe gas/fumes/vapour/spray (appropriate wording to he specified by

manufacturer) 24: Avoid contact with skin 25: Avoid contact with eyes 26: In case of contact with eyes, rinse immediately with plenty of water and seek

medical advice 27: Take off immediately all contaminated clothing 28: After contact with skin, wash immediately with plenty of... (to be specified by the

manufacturer) 28.1: After contact with skin, wash immediately with plenty of water 28.3: After contact with skin, wash immediately with plenty of soap and water, if

possible also with polyethylene glycol 400 29: Do not empty into drains 30: Never add water to this product 33: Take precautionary measures against static discharges 35: This material and its container must be disposed of in a safe way 36: Wear suitable protective clothing 37: Wear suitable gloves 38: In case of insufficient ventilation, wear suitable respiratory equipment 39: Wear eye/face protection 40: To clean the floor and all objects contaminated by this material use... (to be

specified by the manufacturer) 41: In case of fire and/or explosion do not breathe fumes

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Appendix 5: Safety phrases - page 2 of 3 42: During fumigation/spraying wear suitable respiratory equipment (appropriate

wording to be specified) 43: In case of fire, use... (indicate in the space the precise type of fire-fighting

equipment. If water increases the risk, add ... Never use water) 43.1: In case of fire, use water 43.2: In case of fire, use water or powder extinguisher 43.3: In case of fire, use powder extinguisher - never use water 43.4: In case of fire, use CO2 - never use water 43.6: In case of fire, use sand - never use water 43.7: In case of fire, use metal fire powder - never use water 43.8: In case of fire, use sand, CO2 or powder extinguisher - never use water 45: In case of accident or if you feel unwell, seek medical advice immediately (show

the label where possible) 46: If swallowed seek medical advice immediately and show this container or label 47: Keep at temperature not exceeding . . . °C (to be specified by the manufacturer) 48: Keep wetted with ... (appropriate material to be specified by the manufacturer) 49: Keep only in the original container 50: Do not mix with ... (to be specified by the manufacturer) 50.1: Do not mix with acids 51: Use only in well ventilated areas 52: Not recommended for interior use on large surface areas 53: Avoid exposure - obtain special instruction before use 56: Dispose of this material and its container to hazardous or special waste collection

point 57: Use appropriate containment to avoid environmental contamination 59: Refer to manufacturer/supplier for information on recovery/recycling 60: This material and/or its container must be disposed of as hazardous waste 61: Avoid release to the environment. Refer to special instructions/safety data sheet 62: If swallowed, do not induce vomiting: seek medical advice immediately and show

this container or label 63: In case of accident by inhalation: remove casualty to fresh air and keep at rest 64: If swallowed, rinse mouth with water (only if the person is conscious) Combination of safety precautions 1/2: Keep locked up and out of reach of children 3/9/14: Keep in a cool, well-ventilated place away from ... (incompatible materials

to he indicated by the manufacturer) 3/9/14/49: Keep only in the original container in a cool, well-ventilated place away

from ... (incompatible materials to be indicated by the manufacturer) 3/9/49: Keep only in the original container in a cool, well-ventilated place 3/14: Keep in a cool place away from ... (incompatible materials to be indicated by

the manufacturer) 3/7: Keep container tightly closed in a cool place 7/8: Keep container tightly closed and dry 7/9: Keep container tightly closed and in a well-ventilated place 7/47: Keep container tightly closed and at a temperature not exceeding . . . °C (to

specified by manufacturer) 20/21: When using do not eat, drink or smoke 24/25: Avoid contact with skin and eyes

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Appendix 5: Safety phrases - page 3 of 3 29/56: Do not empty into drains; dispose of this material and its container to

hazardous or special waste collection point 36/37: Wear suitable protective clothing and gloves 36/37/39: Wear suitable protective clothing, gloves and eye/face protection 36/39: Wear suitable protective clothing and eye/face protection 37/39: Wear suitable gloves and eye/face protection 47/49: Keep only in the original container at temperature not exceeding. . . °C (to be

specified by the manufacturer).