Chemical Risks

Dr. Bruno Papaleo

Bruno Papaleo

Risk assessment: steps

1.
2.

3.
4.

Identification of Chemical risks.

Optimization of procedures and organization of
work, reducing at lowest as possible substances
handle (number, quantity and volume), persons
exposed and time of exposure.
quantification of residual chemical risks.
identification of preventive and protective
measures for:
A) handling
B) Storage and transport
C) elimination as waste

Bruno Papaleo

LAW ON THE PROTECTION OF THE HEALTH AND

SAFETY OF WORKERS FROM THE RISKS RELATED
TO CHEMICAL AGENTS AT WORK TALKS ABOUT:
Minimum requirements for the protection of workers
from risks to their safety and health arising, or likely to
arise, from the effects of chemical agents that are
present at the workplace or as a result of any work
activity involving chemical agents.

Bruno Papaleo

Definition of Chemical Agent

'Chemical agent` means any chemical
element or compound, on its own or
admixed, as it occurs in the natural
state

or

as

produced,

used

or

released, including release as waste,

by any work activity, whether or not
produced intentionally and whether or
not placed on the market.
Bruno Papaleo

Hazardous chemical agent means:

1.

Any chemical agent which meets the criteria for classification as a

dangerous substance according to the criteria in Annex VI to Directive
67/548/EEC

2.

Any chemical agent which meets the criteria for classification as a

dangerous preparation within the meaning of Directive 88/379/EEC

3.

Any chemical agent which, whilst not definible dangerous in accordance

with (1) and (2), may, because of its physico-chemical, chemical or
toxicological properties and the way it is used or is present in the
workplace, present a risk to the safety and health of workers,
including any chemical agent assigned an occupational exposure limit
Bruno Papaleo

DEFINITIONS
Danger: Intrinsic property of a chemical agent that can cause a
harm, depends on its toxicity
Risk: The probability that a real damage is caused in the
condition of use by a chemical agent, depends on its phisical
state and concentration.
Exposure: The amount of substance that passes from the
environment to the biological system of the worker during the
work time: the dose
Bruno Papaleo

IDENTIFICATION OF DANGERS
The employer lists ALL the substances that can be present
in the work environment considering the following
information:
1. The dangerous properties of the chemical agents from
the Risk phrases. Factors to be considered are: physical
state
(pressure
and
temperature
dependent),
interactions with other chemicals, instability, dose
response curve.
2. Information provided in the safety data sheet of the
products by the supplier
Bruno Papaleo

Classification on the basis of intrinsic danger

properties from standard risk phrases and
standard danger symbols

E - explosive

F highly flammable

F+ - Extremely
flammable
O - oxidising
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T+ - Very toxic
T - Toxic
T and R45 or R49 - Carcinogenic
cat. 1 and 2
T and R46 - Mutagenic cat 1
and 2
T and R60 or R61 Reproductive toxin cat 1 and 2
Bruno Papaleo

European Classification of Cancinogenic substances

Group 1

known human carcinogenic

Group 2

Possible human carcinogenic

Group 3

Not classificable as human carcinogenic

European Classification of Mutagenic substances

Group 1

known human mutagenic

Group 2

Possible human mutagenic

Group 3

Not classificable as human mutagenic

European Classification of reproductive toxin

Category 1

observed effects in man

Category 2

observed effects in animals

Category 3

observed effects in animals but less quality of data

Bruno Papaleo

 Classification is presently generally built

on observed effects in man (Cat1) or
animals (Cat2/3) and secondly upon the
quality of data (Cat2 versus Cat3). Thus,
Cat1 and Cat2 classifications are built
upon a sufficient database.

Bruno Papaleo

Xn - Harmful
Xi - Irritant
Xn and R40 - Carcinogenic Cat 3
Xn and R68 - Mutagenic cat 3
Xn and R62 or R63 - Reproductive
toxin cat 3
C - Corrosive
N - Dangerous for the
environment
Bruno Papaleo

Risk phrases
All packagings must be labelled with:
the name of the substance
the origin of the substance
the danger symbol and indication of danger
involved in the use of the substance
a reference to the special risks arising from
such dangers (risk phrases= R n)

Bruno Papaleo

Regulation (CE) n. 1272/2008 on

classification, packaging and labeling (CPL) of
substances and mixtures
entered into force on 20th January 2009
Transitional provisions are set out in CPL, defining
essentially two target dates that affect the classification,
hazard communication and packaging of hazardous
substances and mixtures namely:
1st December 2010 for substances
1st June 2015 for mixtures
Bruno Papaleo

New GHS Labelling Symbols

Globally Harmonised System of Classification and Labelling of
Chemicals.
The GHS symbols will replace the traditional orange symbols
With GHS the first-ever uniform system for the classification
and labelling of chemicals was established.
Bruno Papaleo

DANGER- WARNING= Flammables, self

reactives, pyrophorics, self-heating, emits
flammable gas, organic peroxides

DANGER- WARNING = oxidizers

DANGER = Explosives, selfreactives, organic peroxides

ABSENT
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WARNING = gasses under pressure

WARNING= Irritant, Dermal

sensitizer, Acute toxicity (harmful),
Narcotic effects, Respiratory tract
irritations

DANGER- WARNING = corrosive

WARNING = Environmental Toxicity

Bruno Papaleo

DANGER = Acute Toxicity (Severe)

DANGER- WARNING=
Carcinogen, respiratory sentitizer,
reproductive toxicity, target organ
toxicity, mutagenicity, aspiration
toxicity

Risk phrases = R n

Hazard Statement = H n

Safety Phrase = S n

Precautionary Statement = P n

Bruno Papaleo

The employer is expected to request the safety data sheet to the

producers or to the suppliers, that shall contain the following
obligatory headings:

SAFETY DATA SHEETS

1. identification of the
substance/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;
Bruno Papaleo

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.

The employer shall ensure that the risk is reduced to a

minimum by means of:
design of appropriate work processes and engineering controls and
use of adequate equipment and materials, so as to avoid or minimize
the release of hazardous chemicals
application of collective protection measures at the source of the
risk, such as adequate ventilation and organization
where exposure cannot be prevented by other means, application of
individual protection measures including personal protective
equipment (clothes, gloves, masks etc.)

Bruno Papaleo

 Appropriate technical and/or organizational

measures to the nature of the operation,
including storage, handling and segregation of
incompatible chemical agents,
Arrangements to deal with accidents, incidents
and emergencies
Medical surveillance performed by an
Occupational Health Care Professional
Bruno Papaleo

Preliminary Exposure Assessment

to Chemical Agents
The nature, level and duration of the exposure
have firstly to be assessed by means of :
Measures or assessment previously performed
Measures or assessment performed ad hoc
Preliminary Qualitative evaluation (checklists)

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Preliminary risk assessment

SLIGHT

the nature and extent of the

risks related to chemical
agents make a further
detailed risk assessment
unnecessary.

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NOT SLIGHT

Detailed risk
assessment including
environmental and
biological monitoring

Prevention and protection measure to be

applied in all cases
design and organization of systems of work at the workplace
provision of suitable equipment and maintenance procedures
which ensure the health and safety of workers
reducing to a minimum the number of workers exposed or likely
to be exposed
reducing to a minimum the duration and intensity of exposure,
appropriate hygiene measures
reducing the quantity of chemical agents to the minimum
suitable working procedures including arrangements for the safe
handling, storage and transport within the workplace of
hazardous chemical agents and waste containing such chemical
agents.
Bruno Papaleo

Specific protection and prevention measures

to be applied in case of
not slight RISK
The employer shall avoid the use of a
hazardous chemical agent by replacing it
with a chemical agent or process which,
under its condition of use, is not hazardous
or less hazardous to workers' safety and
health (if possible).
Bruno Papaleo

WHEN TO MEASURE CHEMICAL AGENTS?

Any

time conditions are modified so that can modify

the exposure:
quality, quantity, mode of use of
chemicals, modifications to the plant or to the process

Periodically
workers

in order to asses real exposure of the

Mesures must be representative of the possible

exposure in terms of space and time. Sampling must be
done during the whole work shift and all the phases of
the process, and also all the in different places involved

Bruno Papaleo

Measurement of
chemicals
WORKING ENVIRONMENT
in air or surfaces (if
necessary)
EXTERNAL DOSE

WORKER
In biological fluids
INTERNAL DOSE

measurements should be correlated with appropriate benchmarks

Bruno Papaleo

Occupational exposure
limits
Exposure levels considered ACCEPTABLE or
PERMISSIVE, ie those levels based on the most
recent data available that are considered do not
cause deterioration of health status of workers
exposed

Bruno Papaleo

 OEL (Occupational Exposure Limits), the limit concentration timeweighted average of a chemical agent in the air within the breathing
zone of a worker in relation to the specified reference period (8h or
short time) [Europe]
TLV-TWA (Threshold Limit Value-Time Weight Avarage), limit
concentration for a conventional 8-hour workday and a 40-hour
workweek, to which it is believed nearly all workers may be
repeatedly exposed, day after day, without adverse effect. [ACGIH]
(Threshold
Limit
Value-Short
Term
Exposure
TLV-STEL
Limit),concentration to which it is believed that workers can be
exposed continuously for a short period of time without suffering
from irritation, chronic or irreversible tissue damage, or narcosis of
sufficient degree to increase the likelihood of accidental injury,
impair self rescue or materially reduce work efficiency, and provided
that the daily TLV-TWA is not exceeded [ACGIH]
Bruno Papaleo

 TLV-C
(Threshold
Limit
Value-Ceiling),
concentration of a potentially toxic substance that
should not be exceeded during any part of the
working exposure [ACGIH]
BEI (Biological Exposure Index), concentration of a
chemical, or its metabolites, that are most likely
to be observed in specimens collected from a
healthy worker who has been exposed to chemicals
to the same extent as a worker with inhalation
exposure to the TLV . [ACGIH]
Bruno Papaleo

Bruno Papaleo

The risk assessment shall be kept up-to-date, particularly if

there have been significant changes which could render it
out-of-date, or when the results of health surveillance show
it to be necessary.
Activities such as maintenance, shall be included in the risk
assessment.
In Activities involving exposure to several hazardous
chemical agents, the risk shall be assessed on the basis of
the risk presented by all such chemical agents in
combination.
Bruno Papaleo

Medical Surveillance
Above the threshold of slight risk for health, medical
surveillance is mandatory.
It is conducted in accordance every year or a schedule
otherwise determined by physician.
the medical examination is conducted
Before you assign an employee to the job specification
with a schedule established by the company doctor on
the basis of risk assessment and the characteristics of
individual workers
The physician establishes for each employee a medical
risk record, which will be kept in the company.
Bruno Papaleo

OBJECTIVES OF HEALTH SURVEILLANCE

Identify initial conditions

Identify susceptible subjects
Is an integral part of risk assessment
Help the accuracy of risk assessment
Verify the effectiveness of preventive
measures

Bruno Papaleo

Biological Monitoring and Health Surveillance

analysis of metabolites or
substances in biological
fluids of workers for
determining the internal
dose or effect

Is an important
instrument for
physician to evaluate
the real dose that a
worker has absorbed

Where a binding biological limit value has been

set Biological Monitoring shall be a compulsory
requirement of health surveillance for work
with the hazardous chemical agent
Bruno Papaleo

If the clinical findings point to an anomaly due to

exposure the physician shall inform the employer

The physician will inform the workers on the

outcome of health surveillance in relation to the
appropriateness to undergo further health
checks, even after retiremen

Bruno Papaleo

Choice and Use of

Personal Protective Equipments (PPEs)
Any equipment intended to be worn and kept by an employee
in order to protect him from one or more risks for his health
and/or safety at work.
They must be:
adequate to the risks, without be a risk their own.
adapted to conditions in the workplace
take into account the ergonomic needs and health
of the worker
Be compatible with each other in case of multiple
risks
Bruno Papaleo

Three categories
1. those of simple design that aim to protect from
risk of minor damage, such as waterproof
clothing for the protection of the rain or
cotton hospital gowns
2. all those who are not covered in the other two
3. those of complex design intended to protect
from risk of death or serious injury.
Bruno Papaleo

PPEs:Essential Requirements
marking CE

pictograms
Compliance with technical standards of reference
These are documents that define the characteristics (size,
performance, environmental, security and organization) of
the
individual
products,
processes
or
services
Bruno Papaleo

Example of informative note

Every PPEs must be accompanied by the note of the
manufacturer with all necessary information for the proper
use

Bruno Papaleo

Choice of PPEs: a working way

1.
2.
3.
4.

risk assessment and identification of job phases and

tasks that require PPEs.
Analysis of PPEs available on the market
Delivery of the PPEs to each worker, along with a
special report.
Training of workers:
1.
2.
3.
4.
5.

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Information on: CE and "information note"

Information provided on the PPEs (class of protection and
corresponding limits of use)
Instructions for storage, use, cleaning, disinfection and
maintenance where required.
Date and time of expiry of the PPEs and/or some of its
components.
Training for use

Gloves
Gloves must adhere closely to the wrist, may be chosen
from different materials that constitute a better
barrier against chemical agents. Technical standard EN
374.
The most common materials are
PVC
Nitrile
Vynil
Neoprene
latex
Bruno Papaleo

NITRILE

NEOPRENE

LATEX

PVC

Acetaldehyde
Acetone
Acetonitrile
Acetic acid
Hydrochloric acid
Phosphoric acid
Nitric acid
Sulfuric acid
hydrogen peroxide
Not use with this chemical
Use with this chemical but for few time and change it often.
Use for this chemical is ideal
Bruno Papaleo

VYNIL

PPEs for eyes

Models available on the
market are as different as
needed.
The technical standard of
reference is the EN 166
Then have a specific
marking

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position

meaning

type of filtered radiation and

gradation of protection

II

identification code of the

manufacturer

III

Optic class

IV

the level of mechanical strength

Type of protection

VI

If is present the letter "K" it

shows the possible protection
from dust with a diameter of
less than 5 Micron

VII

Expressed by the letter "N" the

possible anti-feature.

PPEs for airways

Insulanting respiratory

NOT draw air from the environment. Should be used:

if the O2 is <19.5%
if the contamination is significant with a
concentration> limitations imposed by the filter.
If the olfactory threshold of the gas or vapor is
above the LEP

Filter respiratory

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Draw air from the environment. Are divided into:

Respiratory antigas (for gases and vapors)
Breathing dust (for dust, fibers, fumes and mists)
Combined respiratory

Filter respiratory
Typically there is an activated carbon filter treated
It performs the function of absorbing substrate for many
chemical

The filter should be replaced as soon as the odor of the

contaminant is perceptible.
It means that this type of respirator must be used ONLY in
the presence of substances whose olfactory threshold is
lower than the TLV.
Bruno Papaleo

Gas filters

technical standard

EN 141

three classes related to the concentration limit where the filter can be exposed

Class 1: filters with low filter capacity. Lim. Conc. 1000ppm

Class 2:filters with middle filter capacity. Conc. Lim 5000ppm
Class 3:filters with high filter capacity . Conc. Lim 10000ppm
A

Gas and organic vapors that boil at T >65C

i.e. toluene

Gas and inorganic vapors

i.e. H2S

Acid gas

i.e. HCl

Ammonia and derivatives

i.e. NH4

Bruno Papaleo

Dust filters

Technical standard

EN 143

P Dust filters for rubber masks

Class P1: filters with low separation against solid particles
Class P2: filters with mean separation against solid particles (P2S) or
liquid particles(P2L)

Class P3: filters with high separation against solid and liquid particles

Bruno Papaleo

Filtering facepieces

Technical standard

EN 149

Are identified with the marking FFP without any color.

Class FFP1:

filtering facepieces with low against solid particles

Class FFP2:Filtering facepieces with mean separation against solid

particles (FFP2S) or liquid particles (FFP2L)

Class FFP3:

Bruno Papaleo

Filtering facepieces with high separation against solid

particles and liquid (Absolute Filter)

Proper storage of chemicals

Proper chemical storage controls health or physical hazards
posed by chemical compounds during storage. It is designed to
1)protect flammables from ignition;
2)minimize the potential of exposure to poisons;
3)segregate incompatible compounds to prevent their
accidental mixing (via spills, residues, earthquakes, fires or
human error).

General Principles of Safe Chemical Storage

A designated storage place for each group of compounds with similar risks
must be identified
Each stock container of a chemical compound should be returned to that
location after each use. Storage locations can be marked on containers.
Bruno Papaleo

General Principles of Safe Chemical Storage

Do not store stock supplies of chemicals on benchtops where they
are unprotected from ignition sources and more easily knocked
over. Only chemicals in use should be benchtops.
Do not keep stock supplies of chemicals in fumehoods they may,
interfere with air flow in the hood, may provide fuel if there is a
fire.
Storage areas should not be exposed to extremes of heat or
sunlight.
Do not store any chemicals except bleach and compatible cleaning
agents under the sink.
All containers within the working area must be labeled. Suspect
and known carcinogens must be labeled as such and segregated
within trays to contain leaks and spills.
Storage of liquid chemicals is more hazardous than storage of
solids and is subject to numerous and varied storage requirements.
Bruno Papaleo

Flammable liquids
All containers of flammable liquids (flashpoint <140F) should be returned to
the flammable cabinet or explosion-safe/proof refrigerator/freezer
immediately after use.
Do not store flammable in cold rooms which are neither vented nor explosion
proof.
Peroxide formers must be stored in the flammable cabinets and must be regularly
inventoried to track their age.
Poisons
Store volatile poisons (evaporation rate above 1.0- ether=1.0) in a flammable
cabinet.
Store non-volatile liquid poisons in a refrigerator or cabinet. Amounts less than
1 liter may be stored in a cabinet above bench level if the cabinet has sliding
doors not swinging.
Acids and bases
Acids and bases should be physically separated.
All acids should be stored in a corrosive cabinet. Oxidizing acids (nitric,
sulfuric, phosphoric, perchloric) should have secondary containment and, as a
group, stored separately from other acids (organic and mineral).
Bruno Papaleo