Produced by the Health and Safety Department, the University of Edinburgh

Safe Storage of Hazardous Substances

Introduction
Improper storage of hazardous substances may create serious risk, not only
to University staff and students, but also to emergency services personnel,
the general public and the environment. The aim of this guidance is to reduce
the risk to peoples health and to property from the hazards associated with
the storage of such substances.
This guidance uses transport classification and signage as an aid to explain
what hazards certain chemicals possess, their compatibility and storage
requirements. Transport signage consists of diamond shaped signs of
differing colours and differing pictograms dependant on the hazard presented
by the substance during storage and transport, they are to be found on the
external of materials packaged for transport and in some cases on the
external of vehicles carrying the substances.

They should not be confused with Hazardous warning pictograms applied to

packaging under the Classification, Labelling and Packaging Regulations
(CLP Regs) which are there to give users an indication of the hazards of the
container/package content. These have a white background with a red border
and black interior. This style of signage has replaced the old style which had
an orange background and contained black pictogram which were replaced in
June2015
(http://www.ed.ac.uk/schools-departments/health-safety/guidance/hazardoussubstances/ghs-clp for more information).
Examples of the old style and new style;

CHIP Hazard pictogram

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CLP Hazard pictogram

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Hazardous Substance
A hazardous substance can be defined as any substance classified as
hazardous by the following Regulations:

The Carriage of Dangerous Goods and Use of Transportable Pressure

Equipment Regulations 2004
Highly Flammable Liquids and Liquefied Petroleum Gases Regulations
1972
The Control of Substances Hazardous to Health Regulations 2005 (as
amended)
Dangerous Substances and Explosive Atmospheres 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 to the environment

Hazards
Loss of containment and accidental combination of incompatible substances
may result in extremely serious violent chemical reactions. The highest risk
incidents however are those involving fire where in addition to the actual fire
there is risk from radiated heat, missiles from explosions, harmful smoke and
chemical containing fume, significant incidents may also result in harm to the
environment through distribution of contaminated water that has been used to
fight the fire or by fallout from contaminated smoke and fume.

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Common hazards:
Transport Sign

Classification

Compressed
Gas

Toxic Gas

Flammable Gas

Flammable
liquid

Created on 10/12/2015

Hazard
Gas cylinders may explode if exposed to
intense heat, even if the cylinder contents
are non-hazardous, causing a risk of
impact to people and property in the
vicinity. Acetylene cylinders in particular are
liable to explode without warning, during or
for some time after exposure to heat, this
because of 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 gases
involved, for example whether they are
heavier or lighter than air.
In this University at all new builds or during
refurbishment of buildings provision must
be made for storage of compressed gases
outwith the building and the gases piped
into the building via a gas manifold. Minor
leaks from cylinders of compressed gases
will disperse more readily if the cylinders
are stored in the open air and in the event
of fire the cylinders are not involved in the
fire and gas supplies can be turned off from
the external of the building. Cylinders of
compressed gases must be stored in an
upright position.

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 comes into contact with
other flammable or oxidising materials, it
will increase significantly in size. Sealed
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containers may explode if exposed to

intense heat. Depending on ground
conditions liquids may travel some distance
while a leak remains undetected.
Precautions to be taken include storing
flammable liquids in a purpose built
flammable resistant cabinet, on drip trays.
Large quantities must be stored in a
purpose built flammables store with a bund
equal to, or more than, 110% of the largest
container. Quantities of flammable liquids
must not be left on the open bench
overnight.

Flammable
Solid

Spontaneously
Compustible

Created on 10/12/2015

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 source of ignition. Examples are
matches, fire lighters, nitrocellulose and
sulphur. Self-reactive substances are
included in this classification. These may
decompose with the evolution of heat and
fumes
at
moderate
temperatures.
Examples include various azo compounds.
Also included in this classification are
desensitised
explosives.
These
are
explosive substances which are wetted,
diluted, dissolved or suspended with a
phlegmatiser in order to suppress their
explosive properties care must be taken
that the phlegmatiser does not dry out
during long term storage. Examples include
picric
acid,
urea
nitrate
and
1Hydroxybenzotriazole (Hobt).
Spontaneously combustible (Pyrophoric)
substances have packaging which is
designed to exclude air. If air enters a
damaged package the substances may
start to burn at room temperature.
Examples 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
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natural products.

Dangerous
when wet

Oxidising Agent

These substances react with water and

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

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 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 liquid form. They need to
be stored separate from flammable
materials, so preventing any contamination
or the possibility of them becoming an
accelerant if 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

are
liable
to
explosive
decomposition;
burn rapidly;
are sensitive to impact or friction;
react
dangerously
with
other
substances;
decompose at comparatively low
temperatures.

Some organic peroxides may need to be

marked with a subsidiary explosion risk
label. Organic peroxides must be stored
separately from flammable, corrosive and
toxic materials. Specific advice and
information on particular organic peroxides
can be obtained from the Safety Data
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Sheets (SDS) or the supplier.

Toxic

Corrosive

Created on 10/12/2015

The main risk from toxic substances during

storage
is failure of
containment.
Appropriate pre-planning can minimise the
consequences of isolated punctured drums
or burst packages. However in the event of
fire, such protection is likely to be
compromised by the failure of containers
due to the effects of flame and/or heat. As
well as posing a threat to anybody in the
immediate vicinity e.g. fire fighters, the toxic
substance may also be spread over large
distances in the smoke plume, or they may
be washed into water courses by fire
fighting water operations. 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, e.g. from
spillage/breakage of a bottle/package, are
more likely to arise than the chronic effects
from
low-level
long-term
exposure.
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 Safety Data
Sheets (SDS) will need to be consulted for
comprehensive information.
Hazardous substances may be classified
as corrosive because they burn the skin on
contact, or burn the mucous membranes of
the respiratory tract by inhalation. Many
corrosive substances will also react with
incompatible unsuitable packaging or
metals, for example shelving. Leaking
corrosive substances may damage the
packaging of other dangerous substances,
thus creating further leaks.

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Risk Assessment
A risk assessment must be carried out for all hazardous substance storage
locations. If fire/explosion is the main hazard a risk assessment in compliance
with the Dangerous Substances and Explosive Atmospheres Regulations
2002 (DSEAR) must be undertaken, if the main hazard is release of a toxic,
harmful, irritant or corrosive substance then a risk assessment in compliance
with the Control of Substances Hazardous to Health 2005 (COSHH) must be
undertaken.
For the majority of areas storing hazardous substances the following events,
both individually or jointly, have the potential to cause significant harm or
damage and must be considered during the risk assessment process:

fire;
explosion;
release of a toxic substance;
release of a corrosive substance

Heads of School/ Support Units are responsible for ensuring that risk
assessments are undertaken, significant findings documented and any
necessary measures to minimise risk completed. Whilst they cannot transfer
responsibility, Heads of School may nominate/delegate sufficient staff to help
them undertake this. They must ensure that these staff are trained and
afforded sufficient time to undertake the risk assessment process.

Information and training

Adequate training and knowledge of the properties of hazardous substances
is essential for their safe storage. All relevant staff must be informed of the
risks allied to the storing of hazardous substances, and the precautions
necessary to safely store substances which have different hazards. Those
responsible for safe storage of hazardous substances need specific training in
emergency procedures. Periodic refresher training will normally be required.
The training should include the following topics:

The types of hazardous substances stored, their properties,

incompatibilities and hazards, including hazard label recognition and
understanding of the contents of Safety Data Sheets (SDSs);
General procedures for safe handling;
Use of protective clothing and respirators;
Local procedures for dealing with leaks and spillages;
Housekeeping and record keeping;
Reporting of faults and incidents, including minor leaks and spills;
Emergency procedures, including raising the alarm and the use of
appropriate fire-fighting equipment.

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Labelling of containers
Suppliers of hazardous substances must comply with the requirements of the
Classification, Labelling and Packaging of Substances and Mixtures (CLP
Regulation). Compliance ensures that:

The hazard of the substance has been classified;

The substance is suitably labelled with both hazard pictograms and
specific risk and safety phrases, packaged accordingly; and
Information, in the form of a Safety Data Sheet (SDS), is available.

If an SDS is not supplied with the first order of a hazardous substance this
should be sought from the supplier who is legally obliged to supply an SDS at
no cost. In the case of many reputable chemical suppliers (e.g. Fisher
Scientific, Sigma Aldrich) the SDS for chemicals that they supply is available
online.
Containers containing hazardous substances must be clearly labelled at all
times. It is especially important to label containers that hazardous substances
have been decanted into with at least the name of the chemical and the
white/red hazard warning pictogram. Hazard warning pictogram labels are
available in differing sizes, to suit container size, from your normal laboratory
suppliers.

Flammable substances (excerpt from University Code of Practice

P5CL2.12):

In order to minimise the risk of a serious laboratory fire, the maximum

amount of flammable reagents and solvents etc., stored in any one
laboratory must not exceed 50 litres.
Reasonable quantities of flammable reagents and solvents may be
kept in the open laboratory in suitable closed vessels of volume not
greater than 500ml; these small quantities are excluded from the 50
litre storage limit suggested for each room.
All chemicals, other than those small amounts in use, must be stored in
proper fire resistant chemical storage cupboards on drip trays and the
external of the cupboard appropriately signed with a hazard warning
sign(s) (black on yellow) relevant to the hazardous properties of the
stored chemicals. Storage cupboards or bins must be constructed of
materials that ensure that the sides, top, bottom, door(s) and lid are
capable of providing 30 minutes fire resistance. These storage
cupboards must not be sited adjacent to doors or other means of
escape from the laboratory.

Toxic substances (excerpt from University Code of Practice P5CL

2.12):

Regulations governing the storage and labelling of toxic and other

hazardous materials must always be observed. Schedule 1 Poisons
(e.g. arsenic compounds, mercury compounds, sodium and potassium

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cyanide) Highly or Very Toxic substances and Cytotoxic substances

must always be kept in secure storage, access to which is available
only to nominated key holders. Accurate records of chemicals issued
from a secure store must be kept by a nominated person. Lists of
chemical substances within the above categories is available via the
School of Chemistrys website at:
http://www.chem.ed.ac.uk/safety/notices/index.html

Corrosive substances
Many corrosive substances in Class 8 (see table 1) are incompatible. These
may react together 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 and on drip trays of resistant material. 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.

Storage and segregation

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.
Table 1 (below) 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). In the case of Class 6.2 substances the University Biological
Safety Adviser, and in the case of Class 7 substances, the University
Radiation Safety Adviser should be contacted to obtain guidance for the
storage of these classes of hazardous substances.
Following the guidance in Table 1 may not achieve safe storage conditions in
all situations. SDSs must be consulted for reactivity data to determine
whether substances are incompatible.
Table 1 available as a PDF version only http://www.docs.csg.ed.ac.uk/Safety/general/safe_storage_hazsubs_table.pdf

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