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Safety, Health & Environment Section

FM SHE 041

Procedural Guidance for the Safe

Storage of Hazardous Substances

August 2014
Version 2.0

Document review due: August 2016

Please Note :This is a controlled document, please ensure you are using the most recent
version available at [SHE Website]

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Section Contents Page

1.0 Introduction 3

2.0 Scope 3

3.0 Definition of Hazardous Substance 3

4.0 Hazards 3

5.0 Control Measures 6

5.1 Safe System of Work 6

5.2 Risk Assessment 7

5.3 Management Control 7

5.4 Information and training 7

5.5 Maintenance and modification 7

5.6 Labelling 8

5.7 Storage and segregation policy 8

5.7.1 Corrosive substances 9

5.7.2 Flammable substances 9

5.7.3 Very Toxic substances 9

5.7.4 Product degradation 9

Appendix 1 10

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1.0 Introduction

The storage of hazardous substances may create serious risk, not only to University staff and
students, but also to emergency services, the general public and the environment. The aim of this
procedure is to reduce the risk of damage to people and property from the hazards associated with the
storage of these substances.

2.0 Scope

This document provides guidance on the control measures to adopt for the safe storage of hazardous
substances and applies to all locations on University premises where hazardous substances are
stored.

3.0 Definition of Hazardous Substance

Any substance classified as hazardous by the following regulations:

 The Carriage of Dangerous Goods and Use of Transportable Pressure Equipment Regulations
2009
 Chemicals (Hazard Information for Packaging and Supply) Regulations 2002
 Dangerous Substances and Explosive Atmosphere Regulations 2002

Hazard classifications include:

 Flammable gas;
 Compressed gas;
 Toxic gas;
 Flammable liquid;
 Flammable solid;
 Spontaneously combustible;
 Dangerous when wet;
 Oxidising agent;
 Organic peroxide;
 Toxic, Harmful;
 Corrosive, Irritant;
 Dangerous for the environment.

4.0 Hazards

The types of incidents that present the highest risk are those involving fires. Such fires expose
employees, members of the emergency services and the general public to the threat of radiated heat,
missiles, harmful smoke and fumes. In addition, significant incidents may cause widespread
distribution of substances harmful to the environment, either in plumes or water used to fight fires.
Other types of incident include loss of containment and accidental combination of incompatible
substances which may result in violent chemical reactions. The following table details some of the
common hazards:

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Classification Hazard

Minor leaks from cylinders of compressed gases may

disperse more readily if the cylinders are stored in the
open air. Cylinders of liquefied gases should be stored in
Compressed gas an upright position so that any leaks from valves etc will be
of vapour or gas rather than liquid.
Most types of cylinder will explode if exposed to intense
heat, causing a risk of impact to people in the vicinity even
if the cylinder contents are non-hazardous. Acetylene
cylinders in particular are liable to explode without warning,
during or for some time after exposure to heat, because of
Toxic gas the self-decomposition of the product.
Where flammable or toxic gas cylinders are stored in
buildings, good ventilation is needed to ensure that minor
leaks will disperse safely. When considering storage
locations and determining ventilation design criteria, your
assessment will need to consider the densities of the
Flammable gas gases involved. For example whether they are heavier or
lighter than air.

Flammable liquid fires can grow rapidly once the integrity

of the container is breached, the fire spreading quickly as
the escaping liquid flows from the stored material. If the fire
Flammable liquid comes into contact with other flammable or oxidising
materials, it will increase significantly in size, and there will
be more difficulty bringing it under control. Sealed
containers may explode if exposed to intense heat.
Depending on ground conditions at the time, liquids may
travel some distance while a leak remains undetected.
Precautions to be taken include storing flammable liquids
in a cool dry place, away from sources of ignition and heat,
and in securely closed containers specifically designed for
the purpose.

These are readily combustible solids that can be ignited by

brief contact with a source of ignition or be sensitive to
friction, and will continue to burn after removal of the
Flammable solid source of ignition. Examples are matches, fire lighters,
nitrocellulose and sulphur. Self-reactive substances are
included in this division. These may decompose with the
evolution of heat and fumes at moderate temperatures.
Examples include various azo compounds. Also included
in this division are desensitised explosives. These contain
sufficient water, solvent or plasticiser to suppress their
explosive properties. You need to take care that the water
or solvent-wetted explosives are not able to dry out.
Examples include picric acid and urea nitrate.

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Classification Hazard

Pyrophoric (spontaneously combustible) substances have

packaging which is designed to exclude air. If air enters a
damaged package the substances may start to burn at
Spontaneously room temperature or when gently heated. Examples
combustible include yellow phosphorus and some metal alkyls.
Oxidative self-heating substances may react with the air,
and so raise the temperature to the point at which
spontaneous combustion takes place. This is normally a
slow process which can be controlled by restricting the
pack size, limiting storage duration, monitoring
temperatures or excluding air. Examples include some
types of carbon dust and oily natural products.

These substances react with water and evolve flammable

gases. Fire involving, or in the vicinity of, such materials
should obviously not be tackled with water. Examples
Dangerous when include calcium carbide, metal hydrides, powders of
wet reactive metals such as magnesium or aluminium, and the
alkali metals such as sodium.

These are substances which, although not generally in

themselves combustible, can assist other materials to burn
rapidly even if air is excluded. When heated in a fire, many
Oxidising agent of these substances decompose and give off oxygen which
can cause an increase in the rate of burning with possible
catastrophic consequences. Most oxidising substances are
extremely reactive. They may be solids or liquids. They
need to be stored away from flammable materials, so
preventing any contamination or any possibility of them
becoming involved in a fire. They may be stored with other
similar strong oxidising agents provided they are
compatible.

Organic peroxides are a particularly reactive type of

oxidising substance. They may be solids, liquids or pastes,
and have one or more of the following properties:
Organic peroxide (a) be liable to explosive decomposition;
(b) burn rapidly;
(c) be sensitive to impact or friction;
(d) react dangerously with other substances;
(e) decompose at comparatively low temperatures.
Some organic peroxides may need to be marked with a
subsidiary explosion risk label. Organic peroxides need to
be stored separately from flammable, corrosive and toxic
materials. Advice on the storage and handling of organic
peroxides is given in the HSE guidance note CS21.
Specific advice and information on particular organic
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Classification Hazard
peroxides can be obtained from the material safety data
sheets (MSDS) or the supplier.

The main risk from toxic substances during storage is

failure of containment. Appropriate pre-planning can
minimise the consequences of isolated punctured drums or
Toxic burst packages. However in the event of fire, such
protection is likely to be compromised by the failure of
many containers due to the effects of flame and heat. As
well as posing an immediate threat to anybody in the
vicinity, for example fire fighters, the toxic substance can
also be spread large distances in the plume of smoke, or
they may be washed into water courses by a fire fighting
operation. The precautions necessary to minimise these
risks depend on the quantities of toxic substances
involved, their degree of toxicity, and their persistence in
the environment. Toxic substances vary widely in the
hazard they create. During storage, the acute hazards
arising from short-term exposure, due to for example
breakage of a bottle, are more likely to arise than the
chronic effects from low-level long-term exposure. In
particular, any labelling under the Carriage of Dangerous
Substances (Classification, Packaging and Labelling) and
Use of Transportable Pressure Receptacles Regulations
2004 will give basic advice on the primary hazards and
precautions, but material safety data sheets (MSDS) will
need to be consulted for comprehensive information.

Hazardous substances may be classified as corrosive

because they burn the skin or otherwise harm anyone
coming into contact with them. Many corrosive substances
Corrosive will also react with incompatible unsuitable packaging or
metals, for example shelving. Leaking corrosive
substances may damage the packaging of other
dangerous substances, creating further leaks.

5.0 Control measures

5.1 Safe system of work

Adopt a safe system of work when dealing with spillages. Procedures for dealing with spillages are
contained within the University Emergency Management Plan and local emergency plans. Staff
dealing with spillages should have appropriate training and equipment to deal with spillages within
their own areas. COSHH Assessments and Material Safety Data Sheets (MSDS) will detail any
specific action to be taken for dealing with spillages. These documents must be readily available for all
the substances stored or used on site.

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5.2 Risk assessment:

A risk assessment must be carried out for all hazardous substance storage locations. (Note: This risk
assessment in some instances may be incorporated into the building Fire Risk Assessment).

Deans of Schools and Directors of Services are responsible for ensuring that risk assessments are
undertaken, significant findings documented and any necessary controls to minimise risk are
implemented. They must ensure that risk assessments are adopted within their areas of responsibility
and nominate sufficient staff to help them undertake this. They must ensure that these staff are
competent and afforded sufficient time to undertake the risk assessment process. For the majority of
areas storing hazardous substances there are four main events which individually or jointly have the
potential to cause significant harm or damage:

(a) fire;
(b) explosion;
(c) release of a toxic substance;
(d) release of a corrosive substance.

These events should be considered during the risk assessment process.

5.3 Management Control

Where hazardous substances are to be stored, local managers need to consider the risks created and
the means adopted to control such risks. The storage of multi-hazard goods together is a high-risk
activity demanding high-level management considerations and a senior member of staff should be
directly responsible for safe storage operations. Safety management needs to be a key responsibility
of the position and it is important that this person is responsible for the identification, assessment,
handling and storage of all the dangerous goods held within their area of responsibility. Clearly this
person (or people) needs to be competent to do the job and should be adequately trained and have
sufficient knowledge.

5.4 Information and training

Adequate training and knowledge of the properties of hazardous substances are essential for their
safe storage. All relevant staff need to be informed of the risks of storing hazardous substances and
the precautions necessary to safely store substances which have different hazards. Specific training in
emergency procedures and periodic retraining may also be required. The training should include the
following aspects:

(a) The types of hazardous substances stored, their properties, incompatibilities and hazards,
including hazard label recognition and understanding of the contents of MSDSs;
(b) General procedures for safe handling;
(c) Use of protective clothing and procedures for dealing with leaks and spillages;
(d) Housekeeping and record keeping;
(e) Reporting of faults and incidents, including minor leaks and spills;
(f) Emergency procedures, including raising the alarm and the use of appropriate fire-fighting
equipment.

5.5 Maintenance and modifications

Some incidents involving spillages and fires may occur during, or as a result of, maintenance and
repairs. The likelihood is increased if the work is done by staff or external contractors who have little
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knowledge of the hazards associated with the substances stored. It must be ensured that any
contractors who work on site are competent to carry out the work required.
It is essential that no maintenance work is done until:

(a) The potential hazards of the work have been clearly identified and assessed;
(b) The precautions needed have been specified in detail;
(c) The necessary safety equipment has been provided; and
(d) Adequate and clear instruction has been given to all those concerned.

In most cases, a permit-to-work (PTW) system will be required to control those maintenance
operations which create a source of ignition, or could cause damage to the packages. PTWs are
formal management documents and should only be issued by those with clearly assigned authority to
do so. The requirements stated in them must be complied with before the permit is issued and before
the work covered by it is undertaken. Individual PTWs should relate to clearly defined individual pieces
of work.

Hot work:- There are some simple controls that must be adopted to reduce the risks of fire or
explosion during ‘hot’ maintenance work. Materials which can burn or be affected by fire must
be removed from the storage/work area. If it is not reasonably practicable to remove such
materials, then suitable screens or partitions should be positioned to protect the hazardous
inventory. Once the work has finished, the area should be thoroughly inspected for about an
hour to ensure that there is no smouldering material present.

5.6 Labelling

All suppliers, manufacturers and importers of hazardous substances must comply with the Chemicals
(Hazard Information and Packaging for Supply) Regulations (CHIP). This requirement ensures that:

(a) The hazard of the substance has been classified;

(b) The substance is suitably labelled with specific risk and safety phrases, and packaged accordingly;
and
(c) Information, in the form of a material safety data sheet, is available.

Those responsible for the storage of hazardous substances must ensure that all containers are clearly
labelled at all times. It is especially important to label containers that material has been decanted into.

5.7 Storage and segregation policy

All substances must be stored in securely closed containers specifically designed for the purpose and
clearly labelled in order to determine the hazards of the material and how it should be stored.

The table in Appendix 1 gives recommendations for the segregation of hazardous substances
according to their hazard classification. The table excludes Class 1 (explosives), Class 6.2 (infectious
substances) and Class 7 (radioactive substances). The SHE Section should be contacted to obtain
guidance for the storage of these classes of hazardous substances.

Following the guidance in Appendix 1 will not achieve safe storage conditions in all situations. Material
safety data sheets (MSDS) need to be consulted for reactivity data to determine whether substances
are incompatible.

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5.7.1 Corrosive substances:

Many corrosive substances are incompatible. These may react with other substances to
produce heat or toxic gases. Examples are:
 Acids/hypochlorites - generate chlorine gas;
 Acids/cyanides - generate hydrogen cyanide gas;
 Acids/alkalis - generate heat;
 Acids/sulphides - generate hydrogen sulphide.

All of the above mentioned incompatible substances must be stored in separate steel cabinets.
Shelving should offer a level of containment (e.g. tray shaped) and be of a resistant material.
Generally, the segregation of acids from other substances will go some way to ensuring
incompatible substances are not stored together. The extent of such incompatibility problems
may be reduced if damage to two packages must occur before any reaction can take place.
Additionally, mixing and reaction is likely to be slow if both incompatible components are
solids.

5.7.2 Flammable substances

 The maximum inventory for a workshop or a laboratory must not exceed 50 litres (including
waste solvents).
 All flammable substances, including waste solvents, must be stored in:

o Securely closed containers specifically designed for the purpose and clearly labelled;
o A fire resistant cabinet reserved specifically for the purpose and appropriately labelled.

In relation to fire risk, it may not be a hazardous substance which is the first material ignited. It
may be possible that other combustible materials act as the initial source. Typical cases can
involve plastic packaging, pallets, rubbish ignited by an electrical fault or a spark from
inappropriately controlled hot work. The intensity of a fire, or its rate of growth, may be
increased if incompatible materials are stored together. For example, oxidising agents will
greatly increase the severity of a flammable liquid fire. In addition, a fire may grow and involve
dangerous substances which in themselves are not combustible. In this way, toxic materials
can be widely dispersed in the smoke plume or carried in the fire-fighting water, leading to
potential consequences off-site to people or the environment.

5.7.3 Very Toxic substances

Substances classified as ‘Very Toxic’ should be stored in a locked cabinet with only authorised
access by approved members of staff. An inventory of the cabinet contents should be
maintained and frequently checked by the person with management responsibility for the area.

5.7.4 Product degradation

In cases where substances are likely to degrade during storage, producers or suppliers need
to be consulted concerning the possible hazardous effects of such degradation. Ask
suppliers/producers to provide you with:

 The remedial actions to be taken;

 The recommended storage conditions (e.g. keep cold);
 Maximum storage times and inspection frequencies.
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Appendix 1 CLASS 2 3 4 5 6 8
The table shows general
recommendations for the

CLASS
separation or segregation of
different classes of dangerous
substances

COMPRESSED Segregate
GASSES KEEP from OR Segregate Segregate Segregate Segregate Segregate KEEP KEEP
ISOLATE
2.1 Flammable APART KEEP APART
from from from from from APART APART

2.2 Non- KEEP KEEP KEEP Separation Segregate Separation Separation Segregate Separation
flammable/non-toxic may not be from may not be may not be from may not be KEEP
APART APART APART
APART
2
necessary necessary necessary necessary

Segregate
Segregate Segregate Separation Segregate Separation
2.3 Toxic from OR KEEP KEEP KEEP KEEP
from from may not be from may not be
APART APART APART necessary necessary
APART
KEEP APART

FLAMMABLE
LIQUIDS Segregate KEEP Segregate KEEP Segregate Segregate Segregate KEEP KEEP
ISOLATE
3

from APART from APART from from from APART APART

FLAMMABLE
Separation Separation
SOLIDS Segregate KEEP KEEP KEEP Segregate Segregate Segregate KEEP
4.1 Readily may not be may not be
from
necessary
APART APART APART from from from APART necessary
combustible

4.2 Spontaneously
combustible Segregate Segregate Segregate Segregate KEEP KEEP Segregate KEEP KEEP
4

ISOLATE
from from from from APART APART from APART APART

4.3 Dangerous
Separation Segregate Separation Separation
when wet Segregate KEEP Segregate Segregate KEEP KEEP
may not be from may not be may not be
from
necessary
APART from from APART APART necessary necessary

OXIDISING
Separation Separation
SUBSTANCES Segregate Segregate Segregate Segregate KEEP Segregate KEEP KEEP
may not be may not be
5.1 Oxidising from
necessary necessary
from from from APART from APART APART
Substances
5

5.2 Organic Segregate Segregate Segregate Segregate KEEP KEEP

ISOLAT ISOLAT Segregate ISOLAT
peroxides from from
from
from from APART APART
E E E

TOXIC Separation Separation Separation Separation

KEEP KEEP KEEP KEEP KEEP KEEP
SUBSTANCES may not be may not be may not be may not be
6

APART necessary necessary

APART APART APART necessary
APART APART necessary

Separation Separation Separation

CORROSIVE KEEP KEEP KEEP KEEP KEEP KEEP KEEP
may not be may not be may not be
8

SUBSTANCES APART APART APART APART necessary

APART necessary
APART APART necessary

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Key to table in appendix 1

Separation may not be necessary, but suppliers should be consulted about requirements for
Separation
individual substances. In particular, it should be noted that some types of chemicals within the
may not be
necessary
same class, particularly Class 8 corrosives may react violently, generate a lot of heat if mixed or
evolve toxic fumes.
Separate packages by at least 3 metres or one gangway width, whichever is the greater distance,
in the storeroom or storage area outdoors. Materials in non-combustible packaging which are not
KEEP
dangerous substances and which present a low fire hazard may be stored in the separation area.
APART
This standard of separation should be regarded as a minimum between substances known to react
together readily, if that reaction would increase the danger of an escalating incident.
These combinations should not be kept in the same building compartment or outdoor storage
compound. Compartment walls should be imperforate, of at least 30 minutes fire resistance and
Segregate
from
sufficiently durable to withstand normal wear and tear. Brick or concrete construction is
recommended. An alternative is to provide separate outdoor storage compounds with an adequate
space between them.
This is used for organic peroxides, for which dedicated buildings are recommended. Alternatively,
some peroxides may be stored outside in fire resisting secure cabinets. In either case, adequate
ISOLATE
separation from other buildings and boundaries is required.

Segregate * The lower standard refers to the outside storage of gas cylinders. Where non-liquefied
from or flammable gases are concerned the 3 metres separation distance may be reduced to 1 metre.
KEEP APART

Where a particular material has the properties of more than one class, the classification giving the
more onerous segregation requirements should be used.

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