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Creating markets for recycled resources

The PAN Colour Indicator Technique to Detect Copper Contamination in Wood Waste for Recycling A Guide for Use

Project code: WOO0034

Date of commencement of research: 18th October 2004 Finish date: 17th March 2005

Written by: Mr. Gervais Sawyer and Dr. Mark Irle

Forest Products Research Centre

Buckinghamshire Chilterns University College, High Wycombe, Buckinghamshire,

HP11 2JZ

Published by: The Waste & Resources Action Programme The Old Academy, 21 Horse Fair, Banbury, Oxon OX16 0AH Tel: 01295 819900 Fax: 01295 819911 www.wrap.org.uk

WRAP Business Helpline: Freephone: 0808 100 2040

Date (published)

20th June, 2005

http://www.wrap.org.uk/

Table of Contents 1. DEFINITIONS .......................................................................................1

1. INTRODUCTION ...................................................................................2

2. HEALTH AND SAFETY ISSUES...............................................................3

2.1. MATERIAL SAFETY DATA INFORMATION ..........................................................................3

3. INDICATOR PREPARATION ..................................................................4

4. INDICATOR USE ...................................................................................5

4.1. APPLICATION .................................................................................................................5

4.2. COLOUR ASSESSMENT ....................................................................................................6 4.2.1. False Positives...........................................................................................................8

APPENDICES................................................................................................9

i

1. Definitions

Abbreviation Definition

CCA Copper-chrome-arsenate (a wood preservative now restricted to industrial use)

Cr chromium

PAN 1-(2-pyridylazo)-2-naphthol (a colour indicator of copper)

Cu copper

TBTO tributyltin oxide ( a previously used wood preservative)

XRF X-ray fluorescence

IMPRET project: Dissemination Document 1

The PAN Colour Indicator Technique to Detect Copper Contamination in Wood Waste for Recycling 1. Introduction

This manual describes how to make, store and use a colour indicator, based on PAN (1-(2-pyridylazo)-2-naphthol), for the detection of copper-based preservatives in wood waste streams for recycling. Examples of wood preservatives that contain copper include:

• CCA, copper-chrome-arsenate, which is the most commonly found wood preservative that contains copper, especially in waste wood streams. A wide range of formulations have been used in the past. CCA is now limited to a few industrial uses.

• CCB, copper-chrome-boron. An alternative to arsenic formulations.

• CCP, copper-chrome-phosphate. An alternative to arsenic formulations.

• Copper organics, these could contain the fungicides propiconazole and or tebuconazole or quaternary ammonium compounds. Other azoles are in development. These types of wood preservatives are becoming increasingly popular after the restrictions on the use of CCA were published.


2. Health and Safety Issues

2.1. Material Safety Data Information Health and safety information on the individual components of the indicator described in this document have been obtained via Material Safety Data (MSD) sheets offered by suppliers of the components. At least two MSD sheets have been found from different sources and they have not been found to differ. An example of an MSD for each component is presented in Appendix 1.

The advice on the actual indicator chemical, PAN, is limited. In a sense, this is evidence that it is not considered dangerous. More concrete evidence comes from the MSD sheets:

MSD sheets from Fisher state: “No information found” for Chronic health effects; nor is PAN listed for carcinogenicity; and it is not listed as hazardous.

In order to facilitate photocopying, an MSD for the PAN indicator described here is presented as a separate page in Appendix 2.

Note that this indicator formulation contains organic solvents and, consequently, may have to be stored in fire resistant cupboards according to type and size of container.


3. Indicator Preparation

The optimised PAN indicator contains:

Component Quantity

PAN 0.1 g

methanol 40.0 ml

n-propanol 40.0 ml

mono-ethylene glycol 10.0 ml

distilled or deionised water 10.0 ml

To make the indicator:

1. It is strongly recommended that preparation of the indicator is carried out in a fume cupboard.

2. Place the methanol in a suitable container, add the PAN and stir.

3. Dissolution of the PAN can take some time. Dissolution can be accelerated by warming gently. Avoid excessive heat because the flash point of methanol is only 11 °C. Ensure that there are no ignition sources when warming or preparing solutions.

4. When fully dissolved, allow to cool.

5. Then add the n-propanol, mono-ethylene glycol and water. Mix thoroughly by stirring.

6. Store in tightly closed container.

Note: that this indicator formulation contains organic solvents and, consequently, may have to be stored in fire resistant cupboards

according to type and size of container.

The shelf life of the indicator is anticipated to be at least one year if it is stored correctly. Since only small quantities are required for assessments, it is recommended that no more than 200 ml of indicator is made at any one time.


4. Indicator Use

4.1. Application The indicator can be applied by various methods including: brushing, sponge and spraying.

The preferred method is spraying with a hand operated sprayer like that shown opposite. If used correctly, sprayers offer very little risk of operator contamination through drips, drift, leakage, etc., and the spray pattern gives good wetting of horizontal and inclined surfaces with one quick shot. Ideally, the spray should provide good coverage in that the individual droplets coalesce on the surface. It is inefficient to apply so much indicator that it runs off the surface; as long as the surface is coated then there is enough indicator to give a colour change if copper is present. Consequently, the proximity of the nozzle to the surface is dependent on the characteristics of the atomised cone of indicator.

Some cheap sprayers as shown are top-heavy and may drip chemical onto the operator’s hands as the pump mechanism becomes worn. These should NOT be used.

Brush or sponge application is also possible, but, the risk of operator contamination is thought to be greater. With care, however, there is no reason why a brush or sponge cannot be used.

The indicator is intended for use outside because of the fumes from the organic solvent component. If it is used inside, then it should be applied to the test pieces in a fume cupboard.

Note: the indicator solution contains flammable solvents. Do NOT smoke during application or expose the indicator to naked flames


4.2. Colour Assessment The indicator has a yellow orange colour when applied to clean wood and a distinct pink/red when applied to wood that has been previously treated with copper containing preservatives, e.g. CCA. The colour change should occur within 10 seconds. The photographs below show the colour changes to expect when the indicator is applied to untreated and treated wood.

Spruce Pine


The photograph opposite shows the results of PAN indicator sprayed on to coarsely shredded recycled wood. The yellow orange colour indicates that the wood is copper free, whereas the pink-magenta colour indicates the presence of copper.

The dull surface of waste wood often makes it difficult to see the colour change. In such situations it is best to cut the surface prior to applying the indicator. The easiest way is to cut a corner off a piece of wood, like that shown in the centre of the picture opposite, using an adze, which is an axe that cuts at right-angles to the shaft in stead of parallel to it. Any other cutting tool would suffice, however. The result is positive, indicating presence of copper, but in this case the piece of wood is clearly a piece of joinery and so this indicates that the reaction has been caused by TBTO, another wood preservative.


4.2.1. False Positives

Laboratory trials have shown that false positive results can occur as shown in Table 1. Field trials, on the other hand, have not realised any false positive results.

Table 1. The colour changes caused by substances that are not wood preservatives.

Colour Change ObservedFalse positive substances Potential Source Spruce Pine

Iron hydroxide rust stain corrosion products (rust)

none

none

Zinc chloride corrosion products

magenta

magenta

Cobalt chloride unlikely to be found

magenta

dark magenta

Tin chloride unlikely to be found

light tan

light tan

Nickel sulphate unlikely to be found

light mauve

light mauve

Tributyltin oxide (TBTO) wood preservative

pink

very pale pink

Sodium chloride road salt

pale orange

tan/orange


Appendix 1

Material Safety Data Sheets of Indicator Components



Fisher Scientific UK Web Catalogue **** MATERIAL SAFETY DATA SHEET **** 1-(2-Pyridylazo)-2-Naphthol, 98%, Indicator Grade) 01901 **** SECTION 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION **** MSDS Name: 1-(2-Pyridylazo)-2-Naphthol, 98%, Indicator Grade) Catalog Numbers: AC146310000, AC146310010, AC146310050, AC146310100 Synonyms: PAN. Company Identification: Fisher Scientific UK Bishop Meadow Road, Loughborough Leics. LE11 5RG For information, call: (01509) 231166 For emergencies, call: 01509 231166 **** SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS **** +----------------+--------------------------------------+----------+-----------+ | CAS# | Chemical Name | % | EINECS# | |----------------|--------------------------------------|----------|-----------| | 85-85-8 |1-(2-Pyridylazo)-2-Naphthol | ca. 98% | 201-637-9 | +----------------+--------------------------------------+----------+-----------+ Hazard Symbols: None Listed. Risk Phrases: None Listed. **** SECTION 3 - HAZARDS IDENTIFICATION **** EMERGENCY OVERVIEW Not available. Potential Health Effects Eye: May cause eye irritation. Skin: May cause skin irritation. Ingestion: May cause gastrointestinal irritation with nausea, vomiting and diarrhea. Low hazard for usual industrial handling. Inhalation: May cause respiratory tract irritation. Low hazard for usual industrial handling. Chronic: No information found. **** SECTION 4 - FIRST AID MEASURES **** Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. If irritation develops, get medical aid. Skin: Get medical aid if irritation develops or persists. Flush skin with plenty of soap and water. Ingestion: If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid. Inhalation:


Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Notes to Physician: **** 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. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Runoff from fire control or dilution water may cause pollution. Extinguishing Media: Use alcohol foam, carbon dioxide, or water spray when fighting fires involving this material. In case of fire, use water, dry chemical, chemical foam, or alcohol-resistant foam. **** 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. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions. Provide ventilation. **** SECTION 7 - HANDLING and STORAGE **** Handling: Wash thoroughly after handling. Wash hands before eating. 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 containers tightly closed. **** 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 CAS# 85-85-8: 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: Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Always use a NIOSH or European Standard EN 149 approved respirator when necessary. **** SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES **** Physical State: Solid Color: red to brown Odor: Not available. pH: Not available. Vapor Pressure: Negligible. Viscosity: Not available. Boiling Point: @ 760.00mm Hg Freezing/Melting Point: 138.00 - 141.00 deg C Autoignition Temperature: Not applicable. Flash Point: Not applicable. Explosion Limits, lower: Not available. Explosion Limits, upper: Not available. Decomposition Temperature: Solubility in water: Specific Gravity/Density: Molecular Formula: C15H11N3O Molecular Weight: 249.27 **** SECTION 10 - STABILITY AND REACTIVITY **** Chemical Stability: Stable under normal temperatures and pressures. Conditions to Avoid: Incompatible materials, dust generation, excess heat, strong oxidants. Incompatibilities with Other Materials: Strong bases, strong oxidizing agents. Hazardous Decomposition Products: Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, nitrogen oxides (NOx) and ammonia (NH3). Hazardous Polymerization: Will not occur. **** SECTION 11 - TOXICOLOGICAL INFORMATION **** RTECS#: CAS# 85-85-8 unlisted. LD50/LC50: Not available. Carcinogenicity: 1-(2-Pyridylazo)-2-Naphthol - Not listed by ACGIH, IARC, or NTP. **** SECTION 12 - ECOLOGICAL INFORMATION **** **** SECTION 13 - DISPOSAL CONSIDERATIONS **** Dispose of in a manner consistent with federal, state, and local regulations. **** SECTION 14 - TRANSPORT INFORMATION ****


IATA Not regulated as a hazardous material. IMO Not regulated as a hazardous material. RID/ADR Not regulated as a hazardous material. **** SECTION 15 - REGULATORY INFORMATION **** European/International Regulations European Labeling in Accordance with EC Directives Hazard Symbols: Not available. Risk Phrases: Safety Phrases: S 24/25 Avoid contact with skin and eyes. WGK (Water Danger/Protection) CAS# 85-85-8: No information available. Canada CAS# 85-85-8 is listed on Canada's DSL List. CAS# 85-85-8 is not listed on Canada's Ingredient Disclosure List. US FEDERAL TSCA CAS# 85-85-8 is listed on the TSCA inventory. **** SECTION 16 - ADDITIONAL INFORMATION **** MSDS Creation Date: 9/02/1997 Revision #5 Date: 3/18/2003 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages. -------------------------------------------------------------------------------- --------------------------------------------------------------------------------


Fisher Scientific UK Web Catalogue **** MATERIAL SAFETY DATA SHEET **** Methyl alcohol, 99.9%, spectrophotometric grade 95284 **** SECTION 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION **** MSDS Name: Methyl alcohol, 99.9%, spectrophotometric grade Catalog Numbers: AC167830000, AC167830025, AC167835000 Synonyms: Carbinol; Methyl alcohol; Methyl hydroxide; Monohydroxymethane; Wood alcohol; Wood naptha; Wood spirits; Columbian spirits; Methanol. Company Identification: Fisher Scientific UK Bishop Meadow Road, Loughborough Leics. LE11 5RG For information, call: (01509) 231166 For emergencies, call: 01509 231166 **** SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS **** +----------------+--------------------------------------+----------+-----------+ | CAS# | Chemical Name | % | EINECS# | |----------------|--------------------------------------|----------|-----------| | 67-56-1 |Methyl alcohol | 99.9 | 200-659-6 | +----------------+--------------------------------------+----------+-----------+ Hazard Symbols: T F Risk Phrases: 11 23/24/25 39/23/24/25 **** SECTION 3 - HAZARDS IDENTIFICATION **** EMERGENCY OVERVIEW Highly flammable. Toxic by inhalation, in contact with skin and if swallowed. Toxic : danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. Potential Health Effects Eye: Methanol is a mild to moderate eye irritant. Inhalation, ingestion or skin absorption of methanol can cause significant disturbances in vision, including blindness. Skin: Causes moderate skin irritation. Harmful if absorbed through the skin. Prolonged and/or repeated contact may cause defatting of the skin and dermatitis. Methanol can be absorbed through the skin, producing systemic effects that include visual disturbances. Ingestion: Harmful if swallowed. May be fatal or cause blindness if swallowed. Aspiration hazard. May cause systemic toxicity with acidosis. May cause central nervous system depression, characterized by excitement, followed by headache, dizziness, drowsiness, and nausea. Advanced stages may cause collapse, unconsciousness, coma and possible death due to respiratory failure. Inhalation: Methanol is toxic and can very readily form extremely high vapor concentrations at room temperature. Inhalation is the most common route of occupational exposure. At first, methanol causes CNS depression with nausea, headache, vomiting, dizziness and incoordination. A time period with no obvious symptoms follows (typically 8-24 hrs). This latent period is followed by metabolic acidosis and severe visual effects which may include reduced


reactivity and/or increased sensitivity to light, blurred, double and/or snowy vision, and blindness. Depending on the severity of exposure and the promptness of treatment, survivors may recover completely or may have permanent blindness, vision disturbances and/or nervous system effects. Chronic: Prolonged or repeated skin contact may cause dermatitis. Chronic exposure may cause effects similar to those of acute exposure. Methanol is only very slowly eliminated from the body. Because of this slow elimination, methanol should be regarded as a cumulative poison. Though a single exposure may cause no effect, daily exposures may result in the accumulation of a harmful amount. Methanol has produced fetotoxicity in rats and teratogenicity in mice exposed by inhalation to high concentrations that did not produce significant maternal toxicity. **** SECTION 4 - FIRST AID MEASURES **** Eyes: In case of contact, immediately flush eyes with plenty of water for at least 15 minutes. Get medical aid. Skin: In case of contact, immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid immediately. Wash clothing before reuse. Ingestion: Potential for aspiration if swallowed. Get medical aid immediately. Do not induce vomiting unless directed to do so by medical personnel. Never give anything by mouth to an unconscious person. Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Notes to Physician: Effects may be delayed. Antidote: Ethanol may inhibit methanol metabolism. **** SECTION 5 - FIRE FIGHTING MEASURES **** General Information: Containers can build up pressure if exposed to heat and/or fire. As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. 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. Water may be ineffective. Material is lighter than water and a fire may be spread by the use of water. Flammable liquid and vapor. Vapors are heavier than air and may travel to a source of ignition and flash back. Vapors can spread along the ground and collect in low or confined areas. Extinguishing Media: For small fires, use dry chemical, carbon dioxide, water spray or alcohol-resistant foam. Water may be ineffective. For large fires, use water spray, fog or alcohol-resistant foam. Do NOT use straight streams of water. **** SECTION 6 - ACCIDENTAL RELEASE MEASURES **** General Information: Use proper personal protective equipment as indicated in Section 8. Spills/Leaks:


Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Use water spray to disperse the gas/vapor. Remove all sources of ignition. Provide ventilation. A vapor suppressing foam may be used to reduce vapors. Water spray may reduce vapor but may not prevent ignition in closed spaces. **** SECTION 7 - HANDLING and STORAGE **** Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Ground and bond containers when transferring material. Avoid contact with eyes, skin, and clothing. Empty containers retain product residue, (liquid and/or vapor), and can be dangerous. Keep container tightly closed. Do not ingest or inhale. Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Use only with adequate ventilation. Keep away from heat, sparks and flame. Avoid use in confined spaces. Avoid breathing vapor or mist. Storage: Keep away from heat, sparks, and flame. Keep away from sources of ignition. Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area. Keep containers tightly closed. **** SECTION 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION **** Engineering Controls: Use explosion-proof ventilation equipment. Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits. Personal Protective Equipment Eyes: Wear chemical goggles. 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 a respirator's use. **** SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES **** Physical State: Liquid Color: clear, colorless Odor: alcohol-like - weak odor pH: Not available. Vapor Pressure: 127 mm Hg @ 25 deg C Viscosity: 0.55 cP 20 deg C Boiling Point: 64.7 deg C @ 760 mm Hg Freezing/Melting Point: -98 deg C Autoignition Temperature: 464 deg C ( 867.20 deg F) Flash Point: 11 deg C ( 51.80 deg F) Explosion Limits, lower: 6.0 vol % Explosion Limits, upper: 36.00 vol %


Decomposition Temperature: Not available. Solubility in water: miscible Specific Gravity/Density: .7910 g/cm3 @ 20�C Molecular Formula: CH4O Molecular Weight: 32.04 **** SECTION 10 - STABILITY AND REACTIVITY **** Chemical Stability: Stable under normal temperatures and pressures. Conditions to Avoid: High temperatures, ignition sources, confined spaces. Incompatibilities with Other Materials: Strong oxidizing agents, strong acids, powdered aluminum, powdered magnesium. Hazardous Decomposition Products: Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide, formaldehyde. Hazardous Polymerization: Will not occur. **** SECTION 11 - TOXICOLOGICAL INFORMATION **** RTECS#: CAS# 67-56-1: PC1400000 LD50/LC50: CAS# 67-56-1: Draize test, rabbit, eye: 40 mg Moderate; Draize test, rabbit, eye: 100 mg/24H Moderate; Draize test, rabbit, skin: 20 mg/24H Moderate; Inhalation, rabbit: LC50 = 81000 mg/m3/14H; Inhalation, rat: LC50 = 64000 ppm/4H; Oral, mouse: LD50 = 7300 mg/kg; Oral, rabbit: LD50 = 14200 mg/kg; Oral, rat: LD50 = 5600 mg/kg; Skin, rabbit: LD50 = 15800 mg/kg. Human LDLo Oral: 143 mg/kg. Inhalation; 300 ppm caused visual field changes & headache. LDLo Skin: 393 mg/kg. experimental animals than humans, because most animal species metabolize methanol differently. Non-primate species do not ordinarily show symptoms of metabolic acidosis or the visual effects which have been observed in primates and humans. Carcinogenicity: Methyl alcohol - Not listed by ACGIH, IARC, or NTP. Other: See actual entry in RTECS for complete information. **** SECTION 12 - ECOLOGICAL INFORMATION **** Ecotoxicity: Fish: Fathead Minnow: 29.4 g/L; 96 Hr; LC50 (unspecified)Fish: Goldfish: 250 ppm; 11 Hr; resulted in deathFish: Rainbow trout: 8000 mg/L; 48 Hr; LC50 (unspecified)Fish: Rainbow trout: LC50 = 13-68 mg/L; 96 Hr.; 12 degrees CFish: Fathead Minnow: LC50 = 29400 mg/L; 96 Hr.; 25 degrees C, pH 7.63Fish: Rainbow trout: LC50 = 8000 mg/L; 48 Hr.; UnspecifiedBacteria: Phytobacterium phosphoreum: EC50 = 51,000-320,000 mg/L; 30 minutes; Microtox test **** SECTION 13 - DISPOSAL CONSIDERATIONS **** Dispose of in a manner consistent with federal, state, and local regulations. **** SECTION 14 - TRANSPORT INFORMATION **** IATA


Shipping Name: METHANOL Hazard Class: 3 UN Number: 1230 Packing Group: II IMO Shipping Name: METHANOL Hazard Class: 3.2 UN Number: 1230 Packing Group: II RID/ADR Shipping Name: METHANOL Hazard Class: 3 UN Number: 1230 Packing group: II USA RQ:CAS# 67-56-1: 5000 lb final RQ; 2270 kg final RQ **** SECTION 15 - REGULATORY INFORMATION **** European/International Regulations European Labeling in Accordance with EC Directives Hazard Symbols: T F Risk Phrases: R 11 Highly flammable. R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed. R 39/23/24/25 Toxic : danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. Safety Phrases: S 7 Keep container tightly closed. S 16 Keep away from sources of ignition - No smoking. S 36/37 Wear suitable protective clothing and gloves. S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). WGK (Water Danger/Protection) CAS# 67-56-1: 1 United Kingdom Occupational Exposure Limits CAS# 67-56-1: OES-United Kingdom, TWA 200 ppm TWA; 266 mg/m3 TWA CAS# 67-56-1: OES-United Kingdom, STEL 250 ppm STEL; 333 mg/m3 STEL United Kingdom Maximum Exposure Limits Canada CAS# 67-56-1 is listed on Canada's DSL List. CAS# 67-56-1 is listed on Canada's Ingredient Disclosure List. Exposure Limits CAS# 67-56-1: OEL-ARAB Republic of Egypt:TWA 200 ppm (260 mg/m3);Skin US FEDERAL TSCA CAS# 67-56-1 is listed on the TSCA inventory. **** SECTION 16 - ADDITIONAL INFORMATION **** MSDS Creation Date: 7/21/1999 Revision #6 Date: 10/22/2002 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the


information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages. -------------------------------------------------------------------------------- --------------------------------------------------------------------------------


Fisher Scientific UK Web Catalogue **** MATERIAL SAFETY DATA SHEET **** 1-Propanol, 99+% 96449 **** SECTION 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION **** MSDS Name: 1-Propanol, 99+% Catalog Numbers: AC149480000, AC149480010, AC149480025 Synonyms: Propyl Alcohol; n-Propyl Alcohol; n-Propanol; 1-Hydroxy Propane; Ethyl Carbinol. Company Identification: Fisher Scientific UK Bishop Meadow Road, Loughborough Leics. LE11 5RG For information, call: (01509) 231166 For emergencies, call: 01509 231166 **** SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS **** +----------------+--------------------------------------+----------+-----------+ | CAS# | Chemical Name | % | EINECS# | |----------------|--------------------------------------|----------|-----------| | 71-23-8 |n-Propyl alcohol | >99 | 200-746-9 | +----------------+--------------------------------------+----------+-----------+ Hazard Symbols: XI F Risk Phrases: 11 41 67 **** SECTION 3 - HAZARDS IDENTIFICATION **** EMERGENCY OVERVIEW Highly flammable. Risk of serious damage to eyes. Vapours may cause drowsiness and dizziness.Hygroscopic (absorbs moisture from the air). Potential Health Effects Eye: May cause moderate eye irritation. May result in corneal injury. Skin: May cause moderate skin irritation. Prolonged and/or repeated contact may cause defatting of the skin and dermatitis. Ingestion: May cause gastrointestinal irritation with nausea, vomiting and diarrhea. May cause central nervous system depression, characterized by excitement, followed by headache, dizziness, drowsiness, and nausea. Advanced stages may cause collapse, unconsciousness, coma and possible death due to respiratory failure. Inhalation: Inhalation of vapor may cause respiratory tract irritation. May cause effects similar to those described for ingestion. Chronic: Prolonged or repeated skin contact may cause defatting and dermatitis. Chronic exposure may cause liver damage. **** 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. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Ingestion: Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid. Inhalation: Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Notes to Physician: **** SECTION 5 - FIRE FIGHTING MEASURES **** General Information: Containers can build up pressure if exposed to heat and/or fire. As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. Combustion generates toxic fumes. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Flammable Liquid. Can release vapors that form explosive mixtures at temperatures above the flashpoint. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. Extinguishing Media: Use water spray to cool fire-exposed containers. Use dry chemical, carbon dioxide, or alcohol-resistant foam. Do NOT use straight streams of water. **** SECTION 6 - ACCIDENTAL RELEASE MEASURES **** General Information: Use proper personal protective equipment as indicated in Section 8. Spills/Leaks: Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Avoid runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately, observing precautions in the Protective Equipment section. Use water spray to disperse the gas/vapor. Remove all sources of ignition. Provide ventilation. **** SECTION 7 - HANDLING and STORAGE **** Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Use spark-proof tools and explosion proof equipment. Empty containers retain product residue, (liquid and/or vapor), and can be dangerous. Do not get on skin or in eyes. Do not ingest or inhale. Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Storage: Keep away from heat, sparks, and flame. Do not store near combustible materials. Store in a cool, dry place. Store in a tightly closed container. Keep from contact with oxidizing materials. Flammables-area. **** 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 general or


local exhaust ventilation to keep airborne concentrations below the permissible exposure limits. Exposure Limits CAS# 71-23-8: United Kingdom, OES - TWA: 200 ppm TWA; 500 mg/m3 TWA United Kingdom, OES - STEL: 250 ppm STEL; 625 mg/m3 STEL United States OSHA: 200 ppm TWA; 500 mg/m3 TWA Belgium - TWA: 200 ppm VLE; 499 mg/m3 VLE Belgium - STEL: 250 ppm VLE; 623 mg/m3 VLE France - VME: 200 ppm VME; 500 mg/m3 VME Malaysia: 200 ppm TWA; 492 mg/m3 TWA Russia: 10 mg/m3 TWA Spain: 200 ppm VLA-ED; 500 mg/m3 VLA-ED Spain: 250 ppm VLA-EC; 625 mg/m3 VLA-EC Personal Protective Equipment Eyes: Wear chemical splash goggles. Skin: Wear appropriate protective gloves to prevent skin exposure. Clothing: Wear appropriate protective clothing to minimize contact with skin. 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 a respirator's use. **** SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES **** Physical State: Liquid Color: clear, colorless Odor: alcohol-like pH: Not available. Vapor Pressure: 14.3 mm Hg @ 20 Viscosity: 2.2 mPas 20 deg C Boiling Point: 97 deg C @ 760mm Hg Freezing/Melting Point: -127 deg C Autoignition Temperature: 405 deg C ( 761.00 deg F) Flash Point: 15 deg C ( 59.00 deg F) Explosion Limits, lower: 2.2 vol % Explosion Limits, upper: 13.7 vol % Decomposition Temperature: Solubility in water: Miscible. Specific Gravity/Density: .8040g/cm3 Molecular Formula: C3H8O Molecular Weight: 60.10 **** SECTION 10 - STABILITY AND REACTIVITY **** Chemical Stability: Stable under normal temperatures and pressures. Conditions to Avoid: Incompatible materials, ignition sources. Incompatibilities with Other Materials: Acid chlorides, acid anhydrides, oxidizing agents, potassium tert-butoxide. Hazardous Decomposition Products: Carbon monoxide, carbon dioxide.


Hazardous Polymerization: Will not occur. **** SECTION 11 - TOXICOLOGICAL INFORMATION **** RTECS#: CAS# 71-23-8: UH8225000 LD50/LC50: CAS# 71-23-8: Draize test, rabbit, eye: 20 mg/24H Moderate; Inhalation, mouse: LC50 = 48 gm/m3; Inhalation, mouse: LC50 = 48000 mg/m3; Oral, mouse: LD50 = 6800 mg/kg; Oral, rabbit: LD50 = 2825 mg/kg; Oral, rat: LD50 = 1870 mg/kg; Oral, rat: LD50 = 2200 mg/kg; Skin, rabbit: LD50 = 5040 mg/kg. Carcinogenicity: n-Propyl alcohol - ACGIH: A3 - Confirmed animal carcinogen with unknown relevance to Other: See actual entry in RTECS for complete information. **** SECTION 12 - ECOLOGICAL INFORMATION **** Other No information available. **** SECTION 13 - DISPOSAL CONSIDERATIONS **** Dispose of in a manner consistent with federal, state, and local regulations. **** SECTION 14 - TRANSPORT INFORMATION **** IATA Shipping Name: n-PROPANOL Hazard Class: 3 UN Number: 1274 Packing Group: II IMO Shipping Name: normal-PROPANOL Hazard Class: 3.2 UN Number: 1274 Packing Group: II RID/ADR Shipping Name: n-PROPANOL Hazard Class: 3 UN Number: 1274 Packing group: II **** SECTION 15 - REGULATORY INFORMATION **** European/International Regulations European Labeling in Accordance with EC Directives Hazard Symbols: XI F Risk Phrases: R 11 Highly flammable. R 41 Risk of serious damage to eyes. R 67 Vapours may cause drowsiness and dizziness. Safety Phrases: S 7 Keep container tightly closed. S 16 Keep away from sources of ignition - No smoking. S 24 Avoid contact with skin. S 26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. S 39 Wear eye/face protection.


WGK (Water Danger/Protection) CAS# 71-23-8: 1 Canada CAS# 71-23-8 is listed on Canada's DSL List. CAS# 71-23-8 is listed on Canada's Ingredient Disclosure List. US FEDERAL TSCA CAS# 71-23-8 is listed on the TSCA inventory. **** SECTION 16 - ADDITIONAL INFORMATION **** MSDS Creation Date: 12/11/1997 Revision #6 Date: 3/18/2003 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages. -------------------------------------------------------------------------------- --------------------------------------------------------------------------------


Fisher Scientific UK Web Catalogue **** MATERIAL SAFETY DATA SHEET **** Ethylene glycol, 99+%, anhydrous 95628 **** SECTION 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION **** MSDS Name: Ethylene glycol, 99+%, anhydrous Catalog Numbers: AC146750000, AC146750010, AC146750025, AC146750250 Synonyms: 1,2-Dihydroxyethane; 1,2-Ethanediol; Ethylene alcohol; Ethylene dihydrate. Company Identification: Fisher Scientific UK Bishop Meadow Road Loughborough, Leicestershire LE11 5RG, UK For information, call: 01509 231166 For emergencies, call: 01509 231166 **** SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS **** +----------------+--------------------------------------+----------+-----------+ | CAS# | Chemical Name | % | EINECS# | |----------------|--------------------------------------|----------|-----------| | 107-21-1 |Ethylene glycol | 99.0+ | 203-473-3 +----------------+--------------------------------------+----------+-----------+ Hazard Symbols: XN Risk Phrases: 22 **** SECTION 3 - HAZARDS IDENTIFICATION **** EMERGENCY OVERVIEW Harmful if swallowed. Potential Health Effects Eye: Contact with liquid causes irritation. Skin: Contact with liquid causes irritation. Ingestion: May cause nausea and vomiting. Inhalation: Vapors are nonirritating to the respiratory tract. Chronic: May cause kidney injury. **** 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 immediately. Do NOT allow victim to rub or keep eyes closed. Skin: Flush skin with plenty of soap and water for at least 15 minutes while removing contaminated clothing and shoes. Get medical aid if irritation develops or persists. Wash clothing before reuse. Ingestion: If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid immediately.


Inhalation: Remove from exposure to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid if cough or other symptoms appear. Notes to Physician: Ethanol may inhibit methanol metabolism. **** 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. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Containers may explode when heated. Runoff from fire control or dilution water may cause pollution. Extinguishing Media: In case of fire, use water, dry chemical, chemical foam, or alcohol-resistant foam. Water or foam may cause frothing. Use agent most appropriate to extinguish fire. **** SECTION 6 - ACCIDENTAL RELEASE MEASURES **** General Information: Use proper personal protective equipment as indicated in Section 8. Spills/Leaks: Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Avoid runoff into storm sewers and ditches which lead to waterways. Remove all sources of ignition. Provide ventilation. **** SECTION 7 - HANDLING and STORAGE **** Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Ground and bond containers when transferring material. Avoid contact with eyes, skin, and clothing. Avoid ingestion and inhalation. Storage: Keep container closed when not in use. Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. **** 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 general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits. 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: Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Always use a NIOSH or European Standard EN 149 approved respirator when necessary. **** SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES **** Physical State: Liquid Color: clear, colorless Odor: odorless pH: Not available. Vapor Pressure: .05 mm Hg @ 20C Viscosity: mPas 20 deg C Boiling Point: 195 deg C @ 760.00mm Hg Freezing/Melting Point: -13 deg C Autoignition Temperature: 410 deg C ( 770.00 deg F) Flash Point: 111 deg C ( 231.80 deg F) Explosion Limits, lower: 3.20 vol % Explosion Limits, upper: 15.30 vol % Decomposition Temperature: Solubility in water: soluble in water Specific Gravity/Density: 1.1200g/cm3 Molecular Formula: C2H6O2 Molecular Weight: 62.06 **** 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, ignition sources, excess heat, strong oxidants. Incompatibilities with Other Materials: Chlorosulfonic acid, dimethyl terephthalate, oleum, phosphorus pentasulfide, silvered-copper wire, sodium hydroxide, sulfuric acid, titanium butoxide. Causes ignition at room temperature with chromium trioxide, potassium permanganate, and sodium peroxide. Causes ignition at 100C with ammonium dichromate, silver chlorate, sodium chloride, and uranyl nitrate. Hazardous Decomposition Products: Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide. Hazardous Polymerization: Has not been reported. **** SECTION 11 - TOXICOLOGICAL INFORMATION **** RTECS#: CAS# 107-21-1: KW2975000 LD50/LC50: CAS# 107-21-1: Draize test, rabbit, eye: 500 mg/24H Mild; Draize test, rabbit, eye: 100 mg/1H Mild; Draize test, rabbit, eye: 1440 mg/6H Moderate; Oral, mouse: LD50 = 5500 mg/kg; Oral, rat: LD50 = 4700 mg/kg; Skin, rabbit: LD50 = 9530 uL/kg. Carcinogenicity: Ethylene glycol - Not listed by ACGIH, IARC, NIOSH, NTP, or OSHA. Other: See actual entry in RTECS for complete information.


**** SECTION 12 - ECOLOGICAL INFORMATION **** Ecotoxicity: Fish: Rainbow trout: LC50 = 41000 mg/L; 96 Hr.; UnspecifiedFish: Bluegill/Sunfish: LC50 = 27500-41000 mg/L; 96 Hr.; UnspecifiedFish: Goldfish: LC50 = 27500-41000 mg/L; 96 Hr.; UnspecifiedWater flea LC50 = 46300 mg/L; 48 Hr.; UnspecifiedBacteria: Phytobacterium phosphoreum: EC50 =620 mg/L; 30 minutes; Microtox testGoldfish LD50= >5000mg/L/24Hr Guppies LC50= 493,000ppm/7D Shrimp (salt water) LC50= >100ppm/48Hr **** SECTION 13 - DISPOSAL CONSIDERATIONS **** Dispose of in a manner consistent with federal, state, and local regulations. **** SECTION 14 - TRANSPORT INFORMATION **** IATA Not regulated as a hazardous material. IMO Not regulated as a hazardous material. RID/ADR Shipping Name: Not regulated. Hazard Class: UN Number: Packing group: **** SECTION 15 - REGULATORY INFORMATION **** European/International Regulations European Labeling in Accordance with EC Directives Hazard Symbols: XN Risk Phrases: R 22 Harmful if swallowed. Safety Phrases: S 2 Keep out of reach of children. S 15 Keep away from heat. S 17 Keep away from combustible material. S 24/25 Avoid contact with skin and eyes. WGK (Water Danger/Protection) CAS# 107-21-1: 0 United Kingdom Occupational Exposure Limits United Kingdom Maximum Exposure Limits Canada None of the chemicals in this product are listed on the DSL/NDSL list. CAS# 107-21-1 is not listed on Canada's Ingredient Disclosure List. Exposure Limits CAS# 107-21-1: OEL-AUSTRALIA:TWA 60 mg/m3;STEL 120 mg/m3 OEL-BELGIUM:STEL 50 ppm (127 mg/m3) OEL-DENMARK:STEL 50 ppm (130 mg/m3) OEL-DENMARK:TWA 10 mg/m3 OEL-FINLAND:TWA 10 mg/m3;STEL 20 mg/m3 OEL-FINLAND:TWA 50 ppm (125 mg/m3);STEL 75 ppm (190 mg/m3) OEL-FRANCE:STEL 50 ppm (125 mg/m3) OEL-HUNGARY:STEL 50 mg/m3;Skin OEL-THE NETHERLANDS:TWA 10 mg/m3 OEL-THE NETHERLANDS:TWA 50 ppm (125 mg/m3) OEL-RUSSIA:STEL 5 mg/m3 OEL-SWEDEN:TWA 50 ppm (130 mg/m3);STEL 75 ppm (19 mg/m3) OEL-SWITZERLAND:TWA 1 mg/m3


OEL-SWITZERLAND:TWA 50 ppm (125 mg/m3) OEL-UNITED KINGDOM:TWA 10 mg/m3 OEL-UNITED KINGDOM:TWA 60 mg/m3;STEL 125 mg/m3 OEL IN BULGARIA, COLOMBIA, JORDAN, KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check ACGI TLV US FEDERAL TSCA CAS# 107-21-1 is not listed on the TSCA inventory. It is for research and development use only. **** SECTION 16 - ADDITIONAL INFORMATION **** MSDS Creation Date: 5/12/1999 Revision #5 Date: 1/21/2003 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages. -------------------------------------------------------------------------------- --------------------------------------------------------------------------------


Appendix 2

Material Safety Data Sheet for PAN Indicator


MATERIAL SAFETY DATA SHEET PAN Indicator Solution PURPOSE. For the rapid identification of copper containing preservatives in wood.

APPLICATION. Apply to a cut surface by special applicator, brush or low atomisation spray. A magenta colour within a few seconds. Intended for use outdoors, or indoors with fume extraction.

If used as directed, there is a low risk of exposure. Stable at room temperatures.

Components

Chemical components: CAS Number

1-(2-pyridylazo)-2-naphthol (PAN) 85-85-8

Methanol 67-56-1

Monoethylene glycol 107-21-1

Propan-1-ol 71-23-8

General hazard data Flammable. Do not expose to naked flames. May cause skin, eye and respiratory irritation. Harmful if swallowed. In the event of fire, use water, powder or foam extinguisher.

Risk management Avoid skin contact by using appropriate applicator or by wearing protective gloves. Do not use in confined areas. Store in a cool place. In the event of spillage, use spill absorbent material and package for proper disposal. Product will evaporate moderately quickly.

First Aid Measures Eyes. Flush with plenty of water for 15 minutes. Seek medical attention.

Skin. Flush with water. Remove affected clothing.

Ingestion. Seek medical attention. Call poisons control centre. If victim is conscious, give 2-4 cupfuls of milk or water.

Inhalation. Remove victim to fresh air. Give oxygen if necessary.

Advice on constituent chemicals PAN. Not listed as a hazard, but may cause skin and eye and respiratory irritation.

Methanol. Causes moderate irritation to eyes and skin. Can also cause drowsiness and nausea. Can cause chronic effects.

Monethylene glycol. May cause moderate eye and skin irritation. Ingestion may cause nausea and vomiting. Can cause respiratory irritation, headache and irregular eye movement. May cause chronic kidney injury.

Propan-1-ol. Causes moderate irritation to eyes and skin. Can also cause drowsiness and nausea. Can cause chronic effects.

Disposal Incineration in a high temperature incinerator is the recommended method of disposal of unused indicator.

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