Hazardous substances

PGS 15 shows guidelines for the storage of packaged dangerous substances in the field of fire safety, occupational and environmental safety. The directive is used by the authorities in the provision of the Environmental Management Act permit

The PGS-15 is based on the transport legislation (European ADR).
The PGS-15 is particularly drawn for industrial warehouses and storage facilities. The packages here are the packages (and labels) used in the transport of dangerous substances.

The different classes in the PGS 15 are:

Through the presence of hazardous substances at the UT, risks may exist or arise. Hazardous substances are present at different places. Work stocks at or near the workplace, remnants or waste chemicals and storage of larger work stocks and products in warehouses

If the storage of hazardous substances does not comply with the rules, a chain of events can sometimes arise, due to one leaky packaging. This can lead to an emergency. Consider, for example, a corrosive substance, the packaging of which leaks and which seals the packaging of another substance. If that is a volatile and flammable liquid, there is a risk of fire and explosion. There may also be reactions between the two substances, which may lead to additional danger. For this reason, all sorts of requirements have been imposed on the storage of hazardous substances, for example the use of drip trays.

Laboratories at the UT are characterized by the presence of many different types of substances, often in limited volumes. The packaging size is up to 2.5 liters for liquid bottles to 20 liters for barrels. The packaging label according GHS is used. Many bottles are for direct use in the laboratory. There are also containers for solid and liquid hazardous waste.

The storage of hazardous substances must be in accordance with the UT’s environmental permit (in accordance with PGS 15 guidelines or equivalent). General starting points for storage of hazardous substances are:

• Toxic substances to be placed in a lockable (chemicals) cupboard;
• Irritating substances in (aired) safety cupboards;
• Acids and bases – separated – to be stored in drip-trays in aired cupboards;

- Flammable substances to be placed in aired fire-resistant cupboards (compliant with NEN-EN-14470-1). Flammable substances in the refrigerator only if it is explosion-proof and it concerns small quantities (< 100 ml) that have been properly closed off. It needs to be properly indicated on the refrigerator whether it has been made explosion-proof. If the refrigerator has not been made explosion-proof, it needs to be clearly stated on the refrigerator that it is unsuitable for storing combustible substances. See for more information: 

Further information on (aired) fire-resistance refrigerators can be obtained from the VGM-er.

• Oxidising substances only in small quantities to be placed with other substances (e.g. concentrated acids) or in separate cupboards;

Reacting substances that can release hazardous gases or vapors or create dangerous situations such as explosions or heat generation must be stored compartmentalised. Consult the chemical card book or safety data sheet of each substance regarding possible hazardous combinations of chemicals.

Joint storage in one compartment is prohibited for, among other things, the following combinations:

• Acids and alkalis;
• Acids and chlorite and hypochlorite solutions;
• Nitric acid in formic acid, acetic acid or formaldehyde solutions;
• Acids and cyanides;
• Acids and sulphides

These substances must be stored separately in drip trays in a designated container storage facility. When storing in a safety cupboard, a separation of materials from incompatible combinations must be ensured. This can be done by placing the different categories of substances in separate drip trays. A drip tray must be present for each category to be compartmentalised.
The table below indicates which classes must be stored together or separately. The table can be deviated from in a motivated way on the basis of e.g. safety data sheets or if substances can react but are present in such a limited concentration that no reactions are to be expected with special risks. 

Explanation
V: Storage of substances to be separated in separate compartments. If no separate compartments can be realized, storage must take place in a separate fire compartment, in other words a separate storage facility.

B: Separate storage unless it has been assessed that the substances do not react with each other or both substances are classified as solid. The assessment (B) is in principle based on
the information as stated in the Safety Data Sheets (MSDS), of for generic products the information as stated in the Chemistry Card Book.

- Separate storage not necessary.

* Substances with acute toxicity or CMR substances must be distinguished in a separate fire compartment, or the compartment where these substances are stored, in such a way that the employees become more aware of the dangers.
For the other toxic substances, it is desirable to use a separate compartment with substances of class 3

A comprehensive overview of dangerous reactions for combinations of different substances is included in appendix 2 of the regulation hazardous waste UT.

In a laboratory, the work stock must be as small as possible, but it may preferably be not more than 1 kg or liter per m2 or equal to the stock required for the consumption of one day or one batch ". The calculation of 1 kg or liter per m2 is in line with the safety standards for fire safety. The working stock in a laboratory is the amount of hazardous substances that is strictly necessary for carrying out the analyzes and experiments, such as the reagents in the analyzers and the reagent bottles for determinations. The quantity must also be kept as low as possible from the working conditions legislation and measures must be taken to prevent exposure to undesirable events. Therefore, place the working stock of (flammable) liquids on the laboratory table as much as possible in a drip tray. Store the barrels and bottles at the end of the day in the appropriate safety cupboard. Work stocks are often too large and remain too long. Fume cupboards may not be used as storage space for work stocks. Waste kegs that are used for the collection of hazardous waste are not covered by a working stock: they are mainly aqueous solutions. Full waste drums should be disposed of as quickly as possible, if this is not possible, storage will take place in a safety cabinet. When hazardous waste is transported through the corridors and in the elevators, this must be transported on a cart in a drip tray.

Definition and requirements for a drip tray according to PGS 15

A drip tray is a liquid-tight facility with limited collection capacity, of which the soil protection effect is ensured by targeted supervision and efficient emptying. The drip tray must be designed in such a way that it can withstand the effects of liquids stored above it. Requirements are set for e.g. the collection capacity and the resistance to the stored substances. A drip tray must have a collection capacity of at least 110% of the contents of the largest packaging unit, or if this is greater, 10% of the contents of all stored substances. This collection capacity can not prevent calamities, but the risks are considered acceptable. Any liquids leaked must be removed from the drip tray.

Calculation example drip tray

The following packages are available: 10 barrels with 5 liters, 10 bottles of 2.5 liters and 25 bottles of 1 liter, in total a storage of 100 liters.
110% of the contents of the largest packaging unit = 110% of 5 liters = 5.5 liters.
10% of the content of all stored substances = 10% of 100 liters = 10 liters. The collection capacity of the drip tray should therefore be at least 10 liters.

The drip tray must be able to withstand the effects of liquids that are stored. There are e.g. plastic and steel drip trays.

In the use and storage of hazardous substances in a laboratory the GHS classification is used and not the ADR classification..

The table below is for the different hazard classes, based on the hazardous label of a substance and the hazard statements, the method of storage in a laboratory displayed.

Substances which can cause or promote cancer in humans are considered to be carcinogenic. This can take place by means of exposure to a single (carcinogenic) agent or a (carcinogenic) mixture. Mutagenic agent scan alter a cell’s genetic material (mutate).

Certain substances do not threaten the health of the employees themselves, but the possibility to produce offspring or the health of this offspring. These substances are referred to as reprotoxic and often classified as follows:

• Effects on the reproductive organs (for example damage to the hormonal regulation);
• Effects on reproductive cells (sperm and/or egg-cells) by mutations in the DNA or damage to the chromosomes;
• Effects on the unborn baby in the womb. These agents are also referred to as feto-toxic;
• Effects on the baby through breast milk.

Carcinogenic, mutagenic and reprotoxic agents are recognisable by the danger symbol and the hazard statements:

• H340: May cause genetic defects;
• H350: May cause cancer;
• H360: May damage fertility or the unborn child.

In addition, there are agents which are suspect. These agents are recognisable by the same danger symbol but other hazard statements:

• H341: Suspected of causing genetic defects;
• H351: Suspected of causing cancer;
• H361: Suspected of damaging fertility or the unborn child.

If it is certain or likely that an employee will perform activities involving carcinogens or reprotoxic agents, the guidelines – as described in this document – have to be followed. The influence of any work-related damaging factors on the fertility and genetic material of both men and women is relevant before any pregnancy. The regulation on reprotoxic agents therefore applies not only during the pregnancy or the period of breast-feeding, but also in particular in the preceding period for persons (male/female) with a desire to have children.

Activities involving carcinogenic or reprotoxic agents may only be carried out under certain preconditions. These conditions are laid down in both the environmental and working conditions legislation.

The Working Conditions Decree states in articles 4.2 and 4.13 that within the context of the risk identification and assessment at each workplace the possible exposure to carcinogenic and reprotoxic substances is to assessed and, if necessary, measured in order to determine where and to what extent staff members may be exposed to hazardous substances.

In addition to the general obligation to register hazardous substances there is an additional obligation to register carcinogenic and reprotoxic substances (see under Performing a risk identification and assessment).

A large organisation that employs a lot of women will always have a number of pregnant and breastfeeding women among them. Employers are to have a policy in place on pregnancy. An employer should organise the work performed by a pregnant or breastfeeding women in such a way that it does not pose any danger to her own safety and that of the (unborn) child. See for this the UT-scheme Working during pregnancy and breastfeeding.

Within the UT most of the carcinogenic and reprotoxic substances are found at the technical faculties. These substances are used for research or – to a limited extent – educational purposes. Since knowledge and expertise relating to these substances is concentrated with the staff members involved in this research, the responsibility to observe the rules and regulations lies in particular with the supervisors and users of these substances.

Performing a risk identification and assessment

A risk identification should be aimed at the nature, extent and length of the staff member’s exposure to (suspect) carcinogenic/reprotoxic substances. The following is to be taken into account:

1. The identity of the substance or mixture

• Carcinogenic/reprotoxic substance 
  record the chemical name and the Einecs-number (possibly CAS-number) and any limiting values of the substance (MAC) and information on the existence of a ‘safe value' .
• Carcinogenic/reprotoxic mixture or preparation
  record the trade name(s), the chemical name of these carcinogenic component(s) and the weight percentages of these carcinogenic component(s).

2.  The nature and dangers of the substance(s) the substances used are in solid, liquid or gaseous state

• regarding solid substances: possible quick diffusion of powders or crystals;
• regarding liquids: if there is a risk of splashing, a vapour may quickly form;
• regarding gases: weight of the gas (in relation to air), possible formation of haze.

3.  Motivation for the required use of the substance or process,

as well as an explanation why replacement of the substance(s) is not possible. It is important that reasons are stated as to why replacing the carcinogenic/reprotoxic substance is not possible (no alternative available).

4. The department where the substances are found or the process takes place

(name, number of the space(s) where the substance(s) is (are) used and stored).

5. The amount of the substance available each year for use by staff members and the frequency of application of the process.

6. The nature of the activities performed

• is the substance handled manually, mechanically or in an automated way?
• is there an open or closed system?

7. The way in which the exposure may take place.

This concerns exposure that would exist if no precautionary measures were taken (so-called potential exposure).

• examine whether exposure may take place as a result of inhalation of vapour (aerosol) or via the skin or mouth;
• take into account any reinforcing effects that may arise when exposed to several substances (for example in combination with a solvent, easy penetration via skin);
• identify the calamities that may occur at the various steps during the process.

8. On the basis of the risk identification of the above point (groups of) staff members may be identified who may come into contact with the substances.

For example: scientific staff, students and technicians. The names of these staff members should be recorded.

9. Plan of action

Indicate what measures are taken to prevent exposure.

• As control at the source is reasonably unfeasible: ventilation, separation of person and source or in extreme cases, using personal protective gear to protect against residual risks.
• What needs to be done to prevent calamities (identified in step 7).

Using a separate space

Activities involving carcinogenic and reprotoxic substances should take place in a separate work space or in a separate workplace that is separate from the work space and workplaces where it is not permitted to work with carcinogenic or reprotoxic substances. This separate space should be clearly marked by warning signs (for example: “prohibited space for unauthorised persons”). Persons not working in these spaces should be barred from these spaces as much as possible. Eating and drinking in these spaces is of course not permitted.

Labelling, storage and transport

Packaging containing carcinogenic or reprotoxic substances should always be recognisable as such. The label on the packaging must provide the following information:

• Chemical name of the hazardous substances;
• Danger symbols (see chapter 1);
• H-sentences and P-sentences.

This means that also bottles, erlenmeyer flasks and suchlike are to be provided with such labels if the content after production or pouring over is stored (for longer than one day). For one-day work solutions it will suffice to state the chemical name of the hazardous components.

The storage of these substances has to be in accordance with the UT’s environmental permit (in accordance with PGS 15 guidelines or equivalent). See for this the UT guideline Storage of hazardous substances on top of this page.

At the UT we have detailed rules relating to the collection of waste and the removal of hazardous substances, see: Waste management regulation University of Twente.

In-house emergency service

With the assistance of the in-house emergency service it should be examined whether a special calamities procedure is to be put in place. If so, this is to be included in the information to the relevant staff and in-house emergency service staff.

Ago (medical examination)

If exposure to carcinogenic substances is possible and this can also result in (discernable) health risks, it is necessary to have the staff member undergo an occupational health examination (AGO). The examination should at any rate take place the first time that the activities with the carcinogenic substances are performed. Staff members working with carcinogenic substances can state at any time that they wish to undergo a follow-up examination.

Precisely how the examination is conducted depends entirely on the substance used. This is to be consulted with the working conditions service (where the examination is to be conducted). For example, measuring the substance in the blood or urine or exhalation air. Points of attention for carrying out the AGO are:

• The working conditions service should be aware of the conditions and circumstances of the exposure;
• A medical file is to be drawn up in which also the occupational history of the relevant staff member is to be recorded;
• The working conditions service should have a personal interview with the staff member;
• If considered necessary (useful), measurements of blood, urine and exhalation air can be carried out.

Information

Staff members are to be informed of the risks they run by working with hazardous substances. The following should be made clear to the staff member:

• the possible health hazards as a result of exposure to the substances and vapours which the staff member handles;
• special attention is required for women and men in the reproductive age when they start working with substances that are hazardous to reproduction; if the substances present are hazardous to the unborn child women in the reproductive age should be informed of this immediately;
• the existing rules, the content and the significance of a medical (health) examination to be repeated periodically;
• the rules and regulations regarding the carcinogenic/reprotoxic substances;
• the safety and precautionary measures and the reasons why these have been taken;
• the protective gear made available and the way in which these are to be used and maintainedt.

Personal protective gear

When working with hazardous substances it is obligatory to wear safety goggles and a laboratory coat. Depending on the nature of the activities (see under Performing a risk identification and assessment) other protective gear is to be worn as well. For this see also the personnal protective-equipment (guideline working with personal protective gear).

1. Arbo-informatieblad, number 6: kankerverwekkende stoffen en processen(carcinogenic substances and processes) (publishers SDU)
2. Arbo-informatieblad, number 12: arbeid en zwangerschap (work and pregnancy) (publishers SDU)
3. Arbobesluit (Working conditions decree), Chapter 4
4. Arbo-themacahier, number 5: risicogroepen op de werkplek (risk groups at the workplace) (publishers SDU)

Under the Working Conditions Act an employer is obliged to have a policy in place that limits the risks for safety and health for the staff members as much as possible. This also applies to the situation in which hazardous substances are used.

Hazardous (or toxic) substances are understood to be:

• Single chemical compounds and elements (e.g. toluene, lead, hydrochloric acid);
• Mixtures of varied composition (e.g. petrol, paint);
• Mixture released as contamination, the composition of which is not always known (e.g. welding smoke, reaction mixtures, exhaust fumes).

LEGISLATION

The Working Conditions Decree contains a number of obligations in the area of the registration, packaging, designation and safe storage of hazardous substances. Also other legislation is relevant in this context, such as the Environmental Management Act (WM), the Pollution of Surface Waters Act (WVO), the Pesticides Act.

The legislation relating to carcinogenic and reprotoxic substances is described in the UT guideline “working with carcinogenic and reprotoxic substances”.

RISK IDENTIFICATION AND ASSESSMENT (RI&E) RELATING TO EXPOSURE

Statutory provisions are in place for hazardous substances in the workplace. Most of these can be found in chapter 4 of the Working Conditions Decree. An important article is article 2 of this chapter. Briefly, this article boils down to the following:

• If staff run a risk of exposure to substances that may be disadvantageous to their safety and health, the employer is to identify the risks, taking into account the nature, extent and duration of the exposure;
• This identification of risks is to include at any rate the substances involved, the situations which may involve exposure, and how this can take place.

In addition, the exposure level during the activities is also to be identified.

REGISTRATION

In order to assess the nature of the exposure, the employer is held to keep a register containing the hazardous substances present. Within the UT the GROS system is used for this purpose. Hazardous substances in this context are the substances which under the WMS are to be classified into one of the hazard categories of this Act (see for this the UT guideline Storage of hazardous substances. The obligation applies to the WMS hazardous substances ‘which with some regularity’ and ‘due to the nature of the activities’ are present within the organisation.

IMPLEMENTATION AT THE UT

At the UT the hazardous substances are in particular present in the buildings of the ‘technical’ faculties.

PERFORMING AN RI&E

An identification of risks is, according to the statutory standards, to focus on the nature, extent and duration of the exposure of the staff member(s) to the hazardous substances. For the UT this means that it is important in particular to identify ‘how’ and ‘with which substance(s)’ exposure can occur. The following is to be taken note of in this context:

I Identity of the substance or mixture worked with (in the early, intermediate and end phase)

• Identity of the substance
  Register the chemical name and CAS number and any limit values of the substance (MAC). If the CAS number of the substance is unknown, (e.g. in case of newly synthesised substances) the chemical name/structure formula will suffice
• Identity of the mixture
  Register per component the percentage and CAS number

II Data on the risks of the substance or mixture. Sources of information are:

• GROS system (System at the UT for the registration of hazardous substances);
• The supplier’s security information sheet. A supplier is obliged to provide a safety information sheet. This sheet is to be present at the workplace.
• Chemfix (ChemWatch, system with a lot of MSDS).
• Chemical cards book or other literature on chemicals;

(If no or little information is available on the substance, similar substances can be referred to, the details of which are known), or the AMC of the faculty can be consulted.

III The nature of the activities performed. The following possibilities can be applicable:

1. The process takes place in a closed system: Under normal circumstances, there will not be any exposure. Exceptions are calamities, build-up or break-down and maintenance of the system. The risk of exposure is normally low.
2. The process runs via a semi-closed system (e.g. a bath with lid, a fume cupboard) and substances are involved which do not evaporate, do not create dust particles and cannot be absorbed by undamaged skin: The risk of exposure is limited.
3. The process runs via a semi-closed system and substances are involved which evaporate at 20 °C, create dust particles or can be absorbed by undamaged skin: The risk of exposure is moderate.
4. The process runs via an open system and substances are involved which do not evaporate, do not create dust particles and cannot be absorbed via undamaged skin: The risk of exposure is low.
5. The process runs via an open system and substances are involved which evaporate at 20 °C, create dust particles or which can be absorbed by undamaged skin: The risk of exposure is high.

IV The way in which exposure can take place. This involves exposure which would occur if no protective measures are taken (so-called potential exposure).

• describing the nature of the substance(s) used and the related hazards in solid, liquid or gas condition:
  • as to solid substances: easy dissemination of powders or crystals;
  • as to liquids: if there is a risk of splashing, a vapour (aerosol) is easily formed;
  • as to gasses: weight of the gas (in relation to air), creating of mists.
• checking whether there will be exposure if aerosol or mist is breathed in via skin or mouth;
• taking into account any reinforcing effects that may occur during exposure to several substances (e.g. in combination with solvent, easy absorption via skin); taking into account any hazardous environmental factors in the research activities (working at high or low temperature, using high pressures and such).
• it is to be investigated which calamities may occur during the various steps of the process; taking into account the researcher’s own installation, any installations in the same compartment and other environmental factors.

V Information on the use of the substance or mixture (litres or microlitres), the storage location, knowledge of the staff involved.

VI Based on the identification of the above point, (groups of) staff can be designated who run a risk of being exposed (for example: scientific researchers, students and technicians). 

If the level of exposure is difficult to establish, but there is a risk of harmful concentrations of a substance, taking environmental measurements may be necessary. For this contact an expert of the Human Resources department (HR).

VII Plan of action

State the measures to be taken to avoid exposure.

• If source control is not reasonably feasible: ventilation, separation of humans and source or in extreme cases using personal protection gear for protection against rest risks. Indicate which organisational or technical measures need to be taken.
• What needs to be done to avoid calamities (acknowledged in step IV).

LABELLING, STORAGE AND REMOVAL

Packaging containing hazardous substances is to be recognisable as such. The label on the packaging is to contain the following information:

• Chemical name of the hazardous substances;
• Any hazard symbols and designations;
• H/P sentences.

This means that also bottles, erlenmeyer flasks and such are to be provided with such labels if the contents after production or dousing is kept (for longer than one day). For solutions used during one day only, the chemical name of the hazardous elements suffices.

The storage of these substances is to be in accordance with the UT’s environmental permit (in accordance with PGS 15 guidelines or equivalent). See UT guideline Storage of hazardous substances at the top of this page.

Spilled (waste) substances are to be cleared immediately. Any spilled remnants of either organic solvents, acids or bases can be absorbed by a universal absorption agent (e.g. Chemizorb). All laboratories are to store an absorption agent.

Within the UT detailed rules are in place relating to waste collection and the removal of hazardous substances (see Waste management regulation University of Twente). Compliance with these rules is compulsory.

IN-HOUSE EMERGENCY AND FIRST-AID SERVICE

In consultation with the building’s in-house emergency and first-aid service, it is to be examined whether a special calamities procedure is to be put in place. If so, this is to be included in the information provided to staff and in-house emergency and first-aid service workers involved. In several laboratories substances are worked with which in the event of unintended exposure or unintended reactions, may lead to acute poisoning symptoms. These symptoms may, if not responded to adequately and quickly, result in death. Examples of these substances are among other things cyanide compounds and hydrogen fluoride. The UT has a first-aid protocol in place for such substances.

AGO (MEDICAL EXAMINATION)

The use of a PAGO ‘hazardous substances’ for laboratory staff is controversial. If exposure to hazardous substances may be involved and this also leads to observable health risks, it is obligatory to have the staff member involved undergo a medical examination (AGO). Precisely how the examination is to take place, depends entirely on the substance(s) used during work. There should be consultation with the working conditions service (where the actual examination is also to be performed). In practice, it turns out that it is often difficult for employees working in a laboratory to perform a specific AGO, because staff members are exposed to different substances. Besides, there are not many substances for which validated examination methods exist. If an examination is useful, the level of the substance in the blood, urine or breath may be examined. Points of attention for performing a AGO are:

• The working conditions service is to be aware of the conditions and circumstances of the exposure;
• A medical file is to be prepared in which the staff member involved’s occupational history is also to be included;
• The working conditions service is to have a personal talk with the staff member.

PROVIDING INFORMATION

Staff members, students and third parties are to be informed of the risks they run by working with certain substances. In this context the following is to be pointed out to the staff member:

• The possible dangers to health as a result of exposure to the substances and vapours used for the activities;
• The safety and preventive measures taken and the reasons for doing so;
• The means of protection made available and the way in which these are to be used and maintained;
• If applicable: the existing rules, content and purpose of a periodically to be repeated medical examination.

PERSONAL MEANS OF PROTECTION

When working with hazardous substances wearing safety goggles and a laboratory coat is compulsory. Depending on the nature of the activities (see under Performing an RI&E) in addition to these also other personal protection gear is to be worn. For this also refer to the guideline of working with personal protection gear.

1. Working conditions information sheet number 18: Laboratories (publisher SDU)
2. Working Conditions Decree, Chapter 4
3. CPR-15-1, Storage of hazardous substances in packaging; storage of liquid and solid substances (1 to 10 tons). Committee for the Prevention of Disasters.
4. Environmental permit University of Twente

ANNEX 1 STORAGE OF CHEMICALS

The table below shows combinations of groups which:

• May not be stored collectively ( - )
• May possibly be stored in the same compartment ( +)

Whereby A = oxidising substances

B = flammable liquids

C = flammable solids

D = (very) toxic substances

E = corrosive/caustic substances