CHEMICALS MANAGEMENT

Use of chemicals is one of the critical issues for most of industrial companies. Chemicals are used different processes, e.g. surface treatment, painting, lacquering, printing process, gluing, cleaning machinery, and these chemicals can be hazardous.  Workers can get contact with chemicals in working places and consumers can directly be exposed by contact with products.  The objective of chemicals risk management is to avoid or to limit exposure of man and environment to dangerous chemicals. Frequent exposure problems occur e.g. in the following areas:

• Workers are exposed to dangerous chemical agents at workplaces
• Environmental exposure
• Wastewater may contain persistent, toxic and bioaccumulating substances
• Volatile organic substances evaporate to the air from products and processes
• Hazardous waste is disposed off in an insufficient way that environmental exposure occurs
• Substances may cause, enhance or promote accidents due to their physico-chemical properties
• Consumers are exposed to chemical substances contained in manufactured products, intended or unintended.

Chapter covers information on chemicals related legislation, chemicals hazard and risk information and describes different management instruments like chemicals inventory, obtaining risk information (labels, Safety Data Sheets). Chapter do not include the information about chemicals-related risk assessments to environment and working places, the risk assessment regard consumer is described in product safety chapter.

Communication in supply chain is very important factor in chemicals management and relevant for industrial company. Hazard information should accompany the chemical along the supply chain. If it is not ensured then producing company can have problems complying with legislation. If company do not receive all relevant information for used chemicals and therefore cannot guarantee the safety of products or may discharge unintended emissions, it can be punished because in supply chain exists so-called ‘shared responsibility' requirement.

Knowing one's own role in the chemicals supply chain is essential for determining which legislation applies to oneself and for understanding which responsibilities and requirements result from it.

• What are risks related to chemicals?
• Which chemical substances and preparations are used for which purposes (inventory)?
• How to get chemicals related information (obtaining hazard information)?
• How to check label correctness (information in chemicals label)?
• How to know if information in Safety Data Sheet is correct (checklist for the control of SDS information)?
• Procedure for hazardous materials substitution

Furniture company

• Train the workers regularly (at least twice a year) on chemicals hazards and safe handling.
• Storage and handling of organic solvents and materials containing organic solvents:
• use of enclosed mixing and storage vessels;
• collect and store wood coatings and thinners in closed containers;
• keep lids on containers closed during working operations;
• label containers and each small pot of chemicals used at working places.
• Make visual information of chemicals hazards and hang on the working rooms walls.
• Make your chemicals register electronically.
• Evaluate the information given in Safety Data Sheet before purchasing chemical; assess environmental, health and technical aspects of chemical.
• Substitute chemicals to prevent and minimize emissions:
• water borne coatings (low organic solvent content);
• low-VOC coating;
• powder coatings;
• organic solvent free liquid coatings;
• vegetable oil based coatings.

Printing company

• Operational procedures:
  • Clean presses immediately to minimize cleaner consumption and prevent build-up of ink.
  • Evaluate the information given in Safety Data Sheet before purchasing chemical; assess environmental, health and technical aspects of chemical.
• Inventory:
  • Purchase materials on an as-needed basis, it will further help prevent spoilage or obsolescence.
  • Make your chemicals register electronically.
• Training:
  • Train the workers regularly (at least twice a year) on chemicals hazards and safe handling. Train employees to use the least amount of cleaner possible.
  • Require SDS for all used chemicals and train employees to read them.
  • Keep SDSs in an area where employees have access to and may examine them.
• Storage and handling of organic solvents and hazardous chemicals:
  • Use of enclosed mixing and storage vessels;
  • Keep lids on containers closed during working operations;
  • Label containers and each small pot of chemicals used at working places.
• Make visual information of chemicals hazards and hang on the working rooms walls.
• Minimise the use of isopropyl alcohol:
  • Use alcohol substitutes, low- or non-alcohol solutions.
  • Use a recirculating chiller unit that keeps fountain solution clean and reduces evaporation.
  • Check pH for consistency in each fountain solution batch (some printers find that a pH of 4-5 is effective for maintaining quality).
• Substitute inks and/or manage inks effectively to reduce emissions:
  • heat-reactive inks
  • UV-cured ink systems
  • electron-beam-dried ink systems
  • soy- and water-based inks (for non-lithographic printers)
  • inks which do not contain metals
  • keep ink containers sealed and contents leveled

Metal company

• Train the workers regularly (at least twice a year) on chemicals hazards and safe handling.
• Make visual information of chemicals hazards and hang on the working rooms walls.
• Make your chemicals register electronically.
• Evaluate the information given in Safety Data Sheet before purchasing chemical; assess environmental, health and technical aspects of chemical.
• Storage and handling of organic solvents and materials containing organic solvents:
  • Use of enclosed mixing and storage vessels;
  • Collect and store wood coatings and thinners in closed containers;
  • Keep lids on containers closed during working operations;
  • Label containers and each small pot of chemicals used at working places.
• Choice and maintenance of cooling lubricants
  • Reduce the number of different types of cooling lubricants (1 or 2 water-miscible cooling lubricants and 1 or 2 non-water-miscible cooling lubricants will meet the processing needs of most manufacturing areas) that you use will simplify your material management and allow a central cooling lubricants supply (with reduced checking and maintenance costs, particularly for water-miscible cooling lubricants).
  • Avoid of cooling lubricants containing certain materials: cooling lubricants containing chlorine should be avoided. If you currently use them they can be replaced.
  • Use of biogen cooling lubricants and ester-based cooling lubricants: these types of cooling lubricants tend to have fewer adverse affects on skin than mineral oil-based cooling lubricants. They are however more sensitive to the affects of micro-organisms so particularly careful maintenance is necessary.
  • Check cooling lubricants baths regularly, to provide early warning of the need for adjustments and maintenance. This may include the addition of water, de-mineralised water or calcium salts, to alter the hardness of the water, depending of the foaming behaviour of the cooling lubricants. Other maintenance activities include the addition of concentrate and the removal of impurities.
  • Optimise the cooling lubricants consumption: to ensure the quality of results you must monitor and adjust parameters such as cooling lubricants flow (dm3 / h) as necessary.
• Avoid certain materials in galvanising process:
  • Cyanides: for galvanising acid and cyanide-free alkaline baths are alternatives to cyanide, but they cannot be used for all applications.
  • Chrome (VI): for decorative chrome plating Chrome (III) can be an alternative although wastewater treatment is complicated. However, its range of possible applications and cost effects has not been estimated with any certainty at the moment. Alternatives for hard chrome are, currently, other metals such as electroless nickel or other coating procedures. Chrome (III) is used increasingly for passivating.

Chemicals legislation sets direct obligations to producers and importers of chemicals. However companies handling chemicals must know these obligations as well in order to ensure compliance with legislation relevant for them: comply with work safety requirements, know their rights and responsibilities. Responsibility to have and provide correct information lays also on companies using chemicals (under enforcement legislation).

• Databases on substance properties
• EINECS – European Inventory of Existing Commercial Substances. Information on 100196 substances included in the EINECS (inventory of “existing” substances). CAS number, EINECS number, substance name and chemical formula can be looked up
  http://ecb.jrc.it/existing-chemicals/
• ECB Classlab database . Harmonised classification and labelling for substances or groups of substances included in Annex I of Directive 67/548/EEC. Search is possible using EC, CAS number or substance name.
  http://ecb.jrc.it/classification-labelling/
• N-CLASS Database on Environmental Hazard Classification . Contains the classification and additional information on approximately 7400 dangerous substances.
  http://apps.kemi.se/nclass/default.asp
• TOXNET – Toxicology Data Network. The Toxnet is an integrated system of toxicology and environmental health databases that are available free of charge on the web.
  http://toxnet.nlm.nih.gov/
• Some databases, which are available for searching via:
• HSDB (Hazardous Substances Data Bank) ? extensive information on toxicity, environmental fate, human exposure, chemical safety, waste disposal, emergency handling
• IRIS (Integrated Risk Information System) ? carcinogenic and non-carcinogenic health risk assessment
• Haz-Map to health effects of exposure to chemicals at work, jobs and hazardous tasks with occupational diseases and their symptoms
• CCRIS (Chemical Carcinogenesis Research Information System) is a factual data bank , which contains evaluated data and information on over 8,000 chemicals (carcinogens, mutagens, tumor promoters, cocarcinogens, metabolites and inhibitors of carcinogens).
• ECOTOX Database. Provides toxicity information for aquatic and terrestrial life. It is useful for examining impacts of chemicals on the environment.
  http://www.epa.gov/ecotox/
• RISKLINE Database. Contains information on both environment and health related substance properties. Search is possible with CAS No., substance name or key word.
  http://apps.kemi.se/riskline/index.htm

• Databases on Material Safety Data Sheets (MSDS)

Almost all MSDS databases are run in the United States, thus containing American SDSs which do not comply with the EU standards. European producers and suppliers often have SDSs only on their own homepages. If you search an SDS for a specific product it is best to go to the producer's homepage and search there. If you look for information on a substance or comparable products the US-databases might still be a good information source.

• ChemExpert . MSDS database in Belgium (some European producers with European standard SDSs can be found). Search by product name, CAS no. A list of suppliers with links to their homepages is given.
  http://www.chemexper.com/
• Information for MSDS. Chemicals are sorted alphabetically or may be searched by name or synonym (approximately 16,271 entries and synonyms). Full MSDS are not available.
  http://physchem.ox.ac.uk/MSDS/
• Managing chemicals risks in enterprises – a handbook for professional users of chemicals. Provides information on how to improve chemicals risk management, describing many specific management instruments and practical guidance. Ask from Baltic Environmental Forum office.
  
• New European Chemicals policy – REACH. The website contains documents on the strategy for a new EU Chemicals Policy
  http://ec.europa.eu/enterprise/reach/index_en.htm
  
• COSHH-Essentials (Control Of Substances Hazardous to Health Regulations) Guidance for minimizing health risks from the use of hazardous substances at work. Seven basic steps to assess risks implement control measures and establish good working practices.
• 'Electronic COSHH Essentials' – a free internet tool to where you can insert information on your workplaces and get advice on what needs to be done to control chemicals.
  http://www.coshh-essentials.org.uk/
  

The hazard of a chemical is the inherent potential to cause harm. In accordance with chemicals legislation three types of properties are distinguished. They are determined by testing.

Physical-chemical properties determine how a substance “behaves” when handled in production and as component in products. More information about these properties you can find in SDS under headlines 9 - physical and chemical properties and 10 - stability and reactivity.

Explosive: solid, liquid, pasty or gelatinous chemicals which may also react exothermically without atmospheric oxygen, thereby quickly evolving gases, and which, under defined test conditions, detonate, quickly deflagrate or upon heating explode when partially confined.	Explosive		R2 Risk of explosion by shock, friction, fire or other sources of ignition R3 Extreme risk of explosion by shock, friction, fire or other source of ignition
Oxidizing: chemicals which give rise to highly exothermic reaction when in contact with other substances, particularly flammable substances.	Oxidising		R7 May cause fire R8 Contact with combustible material may cause fire R9 Explosive when mixed with combustible material
Extremely flammable: liquid and gaseous substances and preparation, which are flammable in contact with air at ambient temperature and pressure Flash point lower than 0 degrees of C and boiling point lower than or equal to 35 degrees of C	Extremely flammable		R12 Extremely flammable
Highly flammable: Chemicals which may become hot and finally catch fire in contact with air at ambient temperature without any application of energy, or Solid chemicals which may readily catch fire after brief contact with a source of ignition and which continue to burn or to be consumed after removal of the source of ignition, or Liquid chemicals having a very low flash point (Below 21 degrees of C ), or Chemicals which, in contact with water or damp air, evolve highly flammable gases in dangerous quantities	Highly flammable		R11 Highly flammable R15 Contact with water liberates extremely flammable gases R17 Spontaneously flammable in air
Flammable: liquid chemicals having a low flash point (Equal to or greater than 21 degrees of C and less than or equal to 55 degrees of C )	Flammable		R10 Flammable
Additional phrases (if classified as above):	R1 Explosive when dry R4 Forms very sensitive explosive metallic compounds R5 Heating may cause an explosion R6 Explosive with or without contact with air R7 May cause fire R14 Reacts violently with water R16 Explosive when mixed with oxidising substances R18 In use, may form flammable/explosive vapour-air mixture R19 May form explosive peroxides R30 Can become highly flammable in use R44 Risk of explosion if heated under confinement

Toxic properties determine which effects a substance would have on human health when exposure exceeded a certain dosage. Substance may enter the human body via ingestion, inhalation and direct contact with skin or eyes. In principle two types of toxicity are distinguished:

• Acute toxicity --> indicator for the risk of effects after single exposure within a short time.
• Chronic toxicity --> indicator for the risk of effects after repeated or prolonged exposure to sub-acute doses.

More information about these properties you can find in SDS under headline 11 - toxicological information

Very toxic: chemicals which in very low quantities cause death or acute or chronic damage to health, if they are inhaled or ingested or if they are absorbed via the skin. ( Lethal doses for rat: < 25 mg/kg body weight by ingestion, < 50 mg/kg via skin or < 0.5 mg/kg by inhalation)	Very toxic		R26 Very toxic by inhalation R27 Very toxic in contact with skin R28 Very toxic if swallowed R39 Danger of very serious irreversible effects
Toxic: chemicals which in low quantities cause death or acute or chronic damage to health, if they are inhaled or ingested or if they are absorbed via the skin.	Toxic		R23 Toxic by inhalation R24 Toxic in contact with skin R25 Toxic if swallowed R39 Danger of very serious irreversible effects R48 Danger of serious damage to health by prolonged exposure
Harmful: chemicals which may cause death or acute or chronic damage to health, if they are inhaled or ingested or if they are absorbed via the skin (Lethal doses for rat: < 2000 mg/kg body weight by ingestion, < 2000 mg/kg via skin, < 20 mg/kg by inhalation )	Harmful		R20 Harmful by inhalation R21 Harmful in contact with skin R22 Harmful if swallowed R48 Danger of serious damage to health by prolonged exposure R65 Harmful: may cause lung damage if swallowed R68 Possible risk of irreversible effects
Carcinogenic: chemicals which, if they are inhaled or ingested or if they penetrate the skin, may induce cancer in man or increase its incidence. Depending on evidence level, three categories are distinguished: Cat I - known carcinogens to humans. Cat II – should be treated as if they were carcinogenic, evidence exists from long-term animal studies or other information. Cat III – there is concern but not yet enough evidence for placing it into category II.	Carcinogenic Categories 1 and 2		R45 May cause cancer R49 May cause cancer by inhalation
	Carcinogenic Category 3		R40 Limited evidence of a carcinogenic effect
Mutagenic: chemicals which, if they are inhaled or ingested or if they penetrate the skin, may induce heritable genetic defects or increase their incidence. The three categories of certainty are defined analogous to those of carcinogenic substances	Mutagenic Categories 1 and 2		R46 May cause heritable genetic damage
	Mutagenic Category 3		R68 Possible risk of irreversible effects
Toxic for reproduction: chemicals which, if they are inhaled or ingested or if they penetrate the skin, may produce, or increase the incidence of, non-heritable adverse effects in the progeny (harm to unborn child) and/or impairment of male or female reproductive functions or capacity. The three categories of certainty are defined analogous to those of carcinogenic substances	Toxic to reproduction Categories 1 and 2		R60 May impair fertility R61 May cause harm to the unborn child
	Toxic to reproduction Category 3		R62 Possible risk of impaired fertility R63 Possible risk of harm to the unborn child.
Corrosive: chemicals which may, on contact with living tissues, destroy them. E.g. cause severe burns to skin.	Corrosive		R34 Causes burns R35 Causes severe burns
Irritant: non-corrosive chemicals which, through immediate, prolonged or repeated contact with the skin or mucous membrane, can cause inflammation. of the skin, ocular lesions, serious damage to the eyes or irritations of the respiratory system	Irritant		R36 Irritating to eyes R37 Irritating to respiratory system R38 Irritating to skin R41 Risk of serious damage to eyes
Sensitising: substances and preparations which, if they are inhaled or if they penetrate the skin, are capable of eliciting a reaction of hyper-sensitisation such that on further exposure to the substance or preparation, characteristic adverse effects are produced e.g. respiratory hypersensitivity (asthma) or sensitisation of the skin (e.g. contact dermatitis).	Harmful		R42 May cause sensitisation by inhalation
	Irritant		R43 May cause sensitisation by skin contact
Additional risk phrases ( if classified as above):	Mutagenic substances		R29 Contact with water liberates toxic gas R31 Contact with acids liberates toxic gas R32 Contact with acids liberates very toxic gas R33 Danger of cumulative effects R64 May cause harm to breastfed babies R66 Repeated exposure may cause skin dryness or cracking R67 Vapours may cause drowsiness and dizziness

Ecotoxic properties determine a chemical's hazards to and fate in the environment. Environmental classification is currently mainly based on i) acute aquatic toxicity and the behaviour of substances in the aquatic ecosystem and ii) substance properties dangerous to the ozone layer iii) some properties dangerous to the terrestrial environment. The criateria for environmnetal hazards is still under development.

More information about these properties you can find in SDS under headline 12 - ecological information.

Substances and preparations which, were they to enter the environment, would present or may present an immediate or delayed danger for one or more compartments of the environment.

Dangerous for the environment

R50 Very toxic to aquatic organisms R51 Toxic to aquatic organisms R52 Harmful to aquatic organisms & R53 May cause long-term adverse effects in the aquatic environment R54 Toxic to flora R55 Toxic to fauna R56 Toxic to soil organisms R57 Toxic to bees R58 May cause long-term adverse effects in the environment R59 Dangerous for the ozone layer

The hazardousness to the aquatic environment is determined by a substance's aquatic toxicity, biodegradability and bioaccumulative potential. Harm for the environment depends largely on the combination of these properties:

• Acute aquatic toxicity --> indicator for effects occurring after single exposure of aquatic organisms in a short period of time.
• Biodegradability --> indicator for the persistence of a substance in the environment, the slower the degradation the longer the substance remains in the environment.
• Bioaccumulation --> indicator for the tendency to concentrate in organisms from surrounding media, the quicker a substance is taken up and the slower it is metabolised or excreted the higher is the bioaccumulation.

If the aquatic toxicity, bioaccumulation and persistence (e.g. extremely low biodegradations) reach certain treashold levels, we talk about P ersistent B ioaccumulative and T oxic substances (PBTs) which are of high concern for the environment. Environmental harm may result in the disturbance of structure and functioning of ecosystems. Besides acute toxic effects, it is difficult to observe environmental damage and link it to chemicals, as environmental concentrations are very low, substances are also found far from their emission sources (atmospheric transport) and effects may be delayed in time.

Criteria for identification of PBT/vPvB substances according European Commission's Technical Guidance Document for risk assessment of substances:

If you have no information on bioaccumulation potential, you can look in Water solubility and partitioning coefficient (log K ow ) --> indicator for behaviour in wastewater treatment plants and the environment. Substances with a low water solubility will adsorb to particles / sediments or can accumulate in the body fat of water organisms. Substances with a log K ow > 3 are regarded as liable to bioaccumulate as long as bio-concentration tests (fish test) do not indicate the opposite.

A chemicals inventory is a database for managing information on chemicals used in an enterprise. The type of stored data depends for what the information shall be used. Inventory can be used in assessing risks to consumers, workers etc, it makes easier to comply with different legislation (e.g. air, waste, water etc), it helps in reporting and permitting procedure.

Legislation requires basic database on used chemicals, in this chapter we recommend to expand this requirement.

The core data in a chemicals inventory should include the chemicals' identity, supplier and/or producer, its classification (danger symbols, R- and S-phrases), used amounts as well as the locations where the chemical is used in the company. Information on the technical function of the chemical in products/processes may be added.

Example for an inventory table

Each company must have information about chemicals to fulfil own obligations. Therefore each company should establish communication routines with chemicals suppliers to get up-to-date and good quality safety data sheets (SDS) and further chemical risk management information if necessary. The persons responsible for the communication need to know which information must be provided, which can be requested additionally and how to use and interpret it.

Before purchasing the chemical we recommend to evaluate the SDS and consider all environment, health and technical aspects.

For example when asking for safety data sheets, users frequently are responded that the chemical is not dangerous and does not require a safety data sheet. The following two “decision trees” show how this answer can be questioned.

Although a preparation may not be classified dangerous, it may contain dangerous components. If dangerous components are contained exceeding defined thresholds, a safety data sheet must be provided on request.

The checklist is a support tool for those who use chemical products in order to make sure that the safety data sheet contains all information they need, or see if there is a need to contact the supplier and ask for more information.

Note that the checklist is not a ‘list of musts’ (all information mentioned in list is not required by law), in many cases it might well be that the information is not relevant for the product, or is not given for any other easily understandable reason. A serious and responsible supplier should however always be able to justify why the information is not given in the SDS.

The checklist is made by Association of Swedish Chemical Industries and the Swedish Plastics and Chemicals Federation “The art of reading Safety Data Sheets – Check list”.

Contents of SDS

1. Identification of the substances/ preparation and of the company/ undertaking
2. Composition/ information on ingredients
3. Hazards identification
4. First aid measures
5. Fire-fighting measures
6. Accidental release measures
7. Handling and storage
8. Exposure controls/ personal protection
9. Physical and chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information
13. Disposal considerations
14. Transport information
15. Regulatory information
16. Other information

General information

1. Identification of the substance/preparation and company/undertaking

2. Composition/information on ingredients

3. Hazards identification

4. First-aid measures

5. Fire-fighting measures

6. Accidental release measures

7. Handling and storage

8. Exposure controls/Personal protection

9. Physical and chemical properties

10. Stability and reactivity

11. Toxicological information

12. Ecological information

13. Disposal considerations

14. Transport information

15. Regulatory information

16. Other information

Substitution of currently-used materials with less hazardous materials is one of the most effective ways of eliminating or reducing exposure to materials that are toxic or pose other hazards:

• Identify hazards and assess risks. This step involves deciding whether the current substance or process is a hazard. Is there a significant risk involved in storing, using or disposing of a substance?
• Identify alternatives. Investigate a wide range of options. Compare all of the hazard assessment information as previously mentioned in this document. Compare the different states of a chemical (e.g. will a granular form create less dust than a powder form?) Also consider whether the job is necessary or not (e.g. can the part be replaced rather than cleaned).
• Think about what could happen if you use the alternatives. It is important that you have gathered all available information before this step so that you can make a realistic comparison of both the good and bad points. Remember that you must also consider the way employees use it and how likely it is that they may be exposed. Choosing an alternative chemical may require changes in:
• the way the work is done,
• the kind of equipment or parts needed to be compatible with the substitute chemical,
• the ventilation system that may be required,
• the disposal methods, and
• regulatory requirements that may apply.
• Compare alternatives. In this step, compare the alternatives with each other, and with the substance or process currently being used. Think of the effects in simple terms such as "Is the substitute going to explode, or poison people? Will it only affect people who work with it, or could it affect other people in the area?" Remember to consider how and where the alternative will be used.
• Decide whether to substitute. This step is the most difficult. Remember that a change in one step of a process can affect many others. Consult with the workers who will be handling the material directly for their input. It may be a good idea to introduce the substitute on a trial or small quantity basis at first.
• Introduce the substitute. Plan the change in material or process carefully. Remember to train and educate the workers involved.
• Assess the change. Check to see if the substitution has produced the intended results. You may find monitoring the health of the workers, monitoring the level of contaminants in the air, or fulfilling legal requirements useful parameters to measure.

http://www.ccohs.ca/oshanswers/chemicals/substitution.html

For substitution and evaluation the substitute substance ‘Column Model' can be used.
http://www.hvbg.de/e/bia/pra/pdf_bild/spaltmod.pdf

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