Safety Science 88 (2016) 1–15
Contents lists available at ScienceDirect
Safety Science
journal homepage: www.elsevier.com/locate/ssci
Using very toxic or especially hazardous chemical substances
in a research and teaching institution
Sebastian Brückner a, Jean-Luc Marendaz a, Thierry Meyer a,b,⇑
a
b
Occupational Safety and Health, School of Basic Sciences, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland
Group of Chemical and Physical Safety, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland
a r t i c l e
i n f o
Article history:
Received 27 November 2015
Received in revised form 24 March 2016
Accepted 20 April 2016
Keywords:
Authorization
Chemicals
Safety
Handling
Storage
Disposal
a b s t r a c t
Wrong manipulation, storage or disposal of chemicals can cause great damage whether it occurs on
industrial plants, in academia or at home. Amongst the numerous reasons, lack of knowledge and haste
are the most common ones. Except for a few substances subject to international agreements, the
academic world benefits from a great latitude in the use of chemicals. To make colleagues aware of
the hazards and risks associated to chemicals, and protect them accordingly, the Occupational Safety
and Health service of the School of Basic Sciences (SB-SST) has decided to submit to authorization the
purchase and manipulation of very hazardous chemicals. The process starts by a thoughtful discussion
with the requester about the substance and whether a less hazardous alternative could be used instead.
If the request is validated, the work procedure is analyzed and the protective measures for safe
manipulation of the chemical checked. Consequently the SB-SST authorizes or not the personnel to order
the compound. This innovative participative risk-management concept is illustrated herein with osmium
tetroxide, as an example of a lethal compound used in chemistry, biology and electronic microscopy. The data
resulting from the authorization process is recorded in a database and the need to review the associated procedure and/or the authorization itself is performed twice a year during safety audits of the workplaces.
Ó 2016 Elsevier Ltd. All rights reserved.
1. Introduction
Chemicals are wonderful tools which can improve people’s life
by, for example, generating better tyres, more efficient dyesensitised solar cells and healing people. However chemicals are
often considered as been too risky because they are believed to
be reactive, very reactive. Actually this is true if they are not used
in a controlled manner; intrinsically chemicals can be hazardous
per se and, to lower the risk, operating conditions must be set up
accordingly. Thus, because of some mistrust, fear, lack of
knowledge, people might feel uncomfortable when confronted to
a chemical. On the other hand, chemicals might be used unconsciously to impress pupils. Some might also believe adding several
chemicals will benefit from a sort of add-on effect and get rid of
some resistant dirt and/or disinfect more efficiently. Thus it is
crucial that people required to use chemicals are informed
thoroughly about the hazards and the way the substances must
be used to keep the risk as low as possible.
⇑ Corresponding author at: Occupational Safety and Health, School of Basic
Sciences, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
E-mail address: [email protected] (T. Meyer).
http://dx.doi.org/10.1016/j.ssci.2016.04.019
0925-7535/Ó 2016 Elsevier Ltd. All rights reserved.
Thanks to Sax (Lewis, 2012) and Bretherick’s (Urben and
Bretherick, 2006) investigations, compilations of precious information about how hazardous substances should be handled exist
since the 1950s. Many other sources provide additional advises
(Picot and Grenouillet, 1994; Lunn and Sansone, 2012). All of them
constitute essential readings in this manner. Whatever the level of
education and the work environment, safety should be taught and
reconsidered on a continuous basis as it evolves, but also because
crucial behaviors to adopt in case of emergency might have been
forgotten.
To make people aware of hazards and risks associated to chemicals an approach has been set up by the Dangerous Substances
Directive (EC, 1967), one of the main European Union laws concerning chemical safety. It regulates the classification and labelling
of chemicals in Europe. However as a compound may have been
classified differently from one country to another, this directive
had to be reinforced. This is the purpose of the implementation
of the Globally Harmonized System of classification and labelling
of chemicals (GHS, 2003). With the GHS, all countries worldwide
have to classify their chemical substances according to the same
regulation. This homogeneous classification will also facilitate
international import and export of chemicals. With the GHS, new
thresholds for classifying and labelling chemicals have been set.
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S. Brückner et al. / Safety Science 88 (2016) 1–15
As a result more pictograms, signal words and fully written hazard
and precautionary statements can be read on the label. Moreover
the European Community Regulation on chemicals and their safe
use (REACH, 2006) established complementary obligations. For
example, it specifies the availability and set-up of the Safety Data
Sheet (SDS). Thus these regulations classify chemicals according
to their hazards, define their labelling, packaging and the safety
information made available to the customer via the SDS. Reading
the latter document is essential as it contains precious information
about how the substance shall be handled from its storage, to its
use and disposal. Precious intervention measures for first aid, firefighting and accidental release are also listed in chapters 4, 5 and 6,
respectively.
This available information, as well as corrective actions following accidents or near misses, helps developing preventive and protective technologies to avoid chemical exposure risk. After
analyzing injuries occurring in the industry over a 15-year period
(1992–2006), Mannan et al. (2009) report injuries due to chemicals
are decreasing more rapidly than injuries in general. However the
number of illnesses and casualties related to chemical exposure is
still too high. For example, Leigh et al. (1997) estimate that workplace related exposures lead to several thousand of cases annually
in the United States of America alone. Mannan et al. (2009) worked
out 94% of injuries due to chemicals are from single exposure.
Whether the workplace related injuries/illnesses due to exposure
to chemicals are the result of ignorance, carelessness of the
employee or employer is subject to debate. This is even more difficult, there is a trend to underreport workplace injuries/illnesses
(Miller, 2008). Long term (chronic) diseases may also come from
lifestyle-related factors and environmental agents (Irigaray et al.,
2007). Foreseeing this type of toxicities will always remain the
ultimate challenge because the technology might not be that accurate yet. As a result, it might cause difficulties when trying to rank
molecules of high concern and, without clear criteria, lead to serious implications for the regulations (Santillo and Johnston, 2006).
Scientific studies should be encouraged in order to assess these
possible undesirable health impairments, find alternatives and
help authorities to continue on legislating further restrictions
(Christensen et al., 2011; Hass, 2006). In this way the Organisation
for Economic Co-operation and Development (OECD) has approved
experimental studies proving neurotoxicity of some chemicals and,
thereof, has published a guideline for the testing of chemicals
(OECD, 2007). The European trade unions have also analyzed the
benefits of REACH for workers’ health (Pickvance et al., 2005).
The study shows that the regulation could save Europe 50,000
cases of work-related respiratory diseases and 40,000 cases of
work-related skin diseases each year. In other words, reforming
policies has health and economic benefits. Finally, to improve
and promote worldwide chemical exposure-risk assessments, the
World Health Organization has recently launched a new chemical
risk assessment network (WHO, 2014). Amongst others, it aims
at developing scientific and technical exchange, and assist in the
identification of emerging risks to human health from chemicals.
At the School of Basic Sciences (FSB), over 2000 researchers
from over 100 different nationalities are working in more than
850 laboratories. Chemicals, for example, are used all over the
campus as starting material to synthesise molecules, as tools to
analyze, transform other chemicals, materials and objects. Hence
they can be used in different activities, by persons having different
qualifications, often without education in chemistry, and on various scales. Moreover, constantly new procedures, processes and
techniques are created, implemented, tested and eventually developed. Projects evolve quickly and the turnover of staff is also very
important (3 years on average). Together with tight deadlines,
unawareness of regulations, occupational exposure limits and
other constraints, these factors could contribute to underestimate
hazards and risks associated to the tools (chemicals, lasers, electromagnetic fields, etc.) used in these laboratories. Consequently it is
very likely that no risk assessment to identify appropriate measures will, or could, be done.
The mission of the FSB’s Occupational Safety and Health service
(SB-SST) is to implement rational solutions to preserve human’s
integrity by preventing health impairments. With this in mind,
the SB-SST has set up required activities and organized them as a
(MICE) program. The latter is composed of the following four
categories: Management, Information, Control and Emergency
(Marendaz et al., 2011; Meyer, 2012; SB-SST website).
To avoid learning safety by accident, an important effort is put
on making collaborators aware of safety policies as soon as possible. When an employee starts in our institution she/he has to
attend a mandatory introductory course on occupational safety
and health instructions. If the employee will be involved in
laboratory-based-activities, a complementary basic laboratory
safety course is also organized (SB-SST website). At this point,
the importance of risk management when handling chemicals is
taught to the employee, regardless of the person’s background.
Taking into consideration the fast evolution of projects and the
necessity to intervene correctly in case of an event, it is crucial
people understand why and how to react. As previously reported
by Carney (2003), ‘‘Training differs from education in that it seeks
to impart a set of established facts and skills and to obtain a uniform predictable behavior from the trainees without the necessity
of their understanding why they should act in the prescribed
manner.” This is why participative trainings and accompanying
support, rather than just telling what has to be done courses, are
organized by the SB-SST. Thus Meyer (2012) encourages every
employee to follow additional courses to broaden their knowledge
in chemistry, physics, biology and risk management in these fields.
The purpose is making users responsible, in order to protect
themselves and their colleagues whilst they manipulate chemical
substances, for example. Moreover to actively help the students
and the research groups to carry out their activities safely, our
institution has decided to go a step further by developing a tool
restricting the use of especially hazardous compounds. More than
just a list of substances with very high concern, this authorization
concept is intended making sure a detailed risk assessment will be
performed. Indeed, because of the above mentioned stress factors,
the work force needs to be informed and trained accordingly. This
is done best by involving and accompanying them straight from
the beginning. To our knowledge, this approach is innovative in
terms of collaborative support and risk assessment it offers to a
campus comprising teaching and research activities. The strength
of this concept is also the consideration of the entire lifecycle of
the substance and that the authorizations are challenged again
once in use.
To sustain this management, achieve adequate training and
control, it is important to implement a simple and practical system.
Therefore the following quality system has been set up to keep a
good track-record of chemicals at the FSB. As shown in Fig. 1, the
management of chemicals at the FSB considers the chemical’s
whole lifetime cycle (zones A to C) and proceeds as follows:
The procedure steps shown in Fig. 1 are:
– chemical’s evaluation (zone A):
(1) Account of the chemical substance’s nature ①. To make sure
that colleagues are aware of the risks associated to the
chemical and will follow the recommendations, especially
hazardous substances cannot be ordered without an authorization ②. The interested person needs to obtain it from the
SB-SST. This has been also established to encourage users to
find less hazardous tools for their needs whenever possible.
The same task can be often achieved using a less hazardous
S. Brückner et al. / Safety Science 88 (2016) 1–15
3
Fig. 1. Management of chemicals at the FSB.
chemical and might even be less expensive. For example,
reading the health and precautionary statements in the
SDS may help in this reconsideration. Very intuitive and
exhaustive databases, like ReaxysÓ (http://www.reaxys.
com) and SciFinderÓ (http://www.scifinder.org) may be
consulted to check if a less hazardous chemical can be used
instead.
(2) If an authorization is needed, an evaluation process will
consider different safety parameters: from the chemical’s
hazards to the way it is going to be used, up to the produced
waste as explained in the following chapters. When the
evaluation of the requested chemical does not allow establishing a safe work procedure, the authorization is refused
③. Thus the colleague will not be able to use the chemical
and has to find an alternative ④.
(3) If the request is accepted, the authorization is completed
with the work procedure and guidelines according to the
existing laws/rules and directives. Consequently, the ordering
process ⑤ will be unlocked.
– chemical’s use and inventory (zone B):
(4) Ordering ⑤ proceeds via the chemical stores on site and a
common database registering the order. The chemical
substance arrives at the store’s reception ⑥.
(5) The chemical’s characteristics and future location are
registered into the local database and the compound gets
a barcode. According to the internal rules, the chemical is
then used, possibly recycled and stored in the proper storage
location. To keep the inventory ⑦ of our institution’s
chemicals up to date, the research groups are asked to
register all their chemicals once every semester. To help in
this matter a user-friendly system with barcode scanner is
available (Fig. 2).
– chemical waste (zone C):
(6) Management of the waste, its disposal and removal. Since
waste has to be handled with as much caution as for new
chemicals, this process is also documented. Our institution’s
facilities allow safe handling, conditioning and storage of
the corresponding waste’s containers. This process also
enables their safe transportation when waste is removed
from our institution ⑧.
Fig. 2. Barcode scanner for buying chemicals, registering their localisation and their
content.
2. Selection of compounds under authorization
When it comes to implement measures to solve hazard problems and reduce risk exposure, a risk management system has to
be systematic with decision making steps. Great importance has
to be applied when it comes to sharing the information. Providing
an effective measure for reducing chemical exposure can be seen
as a challenge as more and more documentation is available and
the resultant decision has to be applied thoroughly. Thus a good
communication is crucial for identifying, communicating and
implementing the appropriate risk-management measure. Indeed,
the message has to be simple and practical by addressing the real
source of exposure. If the message is too technical it will not promote understanding nor induce the required change (Ferguson
et al., 2003). Numerous surveys continue to show that accidents
can be avoided. As an example, the Occupational Safety and Health
Administration (OSHA) has announced the preliminary top 10
most frequently cited workplace safety violations for fiscal year
2014 (OSHA, 2015). Ranked at the second place, is hazard communication including failure to have a written program, inadequate
employee education and training, improper or no labels on
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S. Brückner et al. / Safety Science 88 (2016) 1–15
containers, and no safety information sheet or lack of access to
them. Overall, this shows how crucial it is implementing appropriate safety measures and to teach workers thoroughly how to use
them. Moreover, the workers have to understand their purpose,
respect and use them accordingly. Thus the operator must be
trained to use the chemical properly as it will preserve his safety
and health and that of his colleagues. Indeed, laboratories are often
shared with several colleagues, since working alone is frequently
not recommended. As chemicals can be volatile, it is also essential
to have well established storage and waste disposal procedures. In
our school, once waste containers are full, they are brought to the
chemical stores at the FSB where they will be registered. They are
assembled and put onto pallets according the European Agreement
concerning the International Carriage of Dangerous Goods by Road
(ADR, 2015). Then transporters are involved in collecting and
bringing them to the company taking care of this special waste.
Generally, the internal policy of an organization gives the guidelines to work safely whilst respecting the colleagues’ safety and
health. Thus to be effective, an authorization process has to manage chemicals from their arrival throughout their elimination from
the institution.
For the selection of the compounds subject to authorization, the
FSB has decided that it affects substances with category 1 type
acute toxicity, 1A chronic toxicity, type 1 specific target organ
toxicity according to the European version of the GHS, the Classification, Labelling and Packaging legislation (CLP, 2008). Potentially
highly reactive compounds, like methyl isocyanate and picric acid,
requiring careful treatment, are also included in this selection
since, if not properly handled they can induce intoxication and
explosions (Broughton, 2005 and Cameron, 2002).
As shown in Table 1, chemicals classified as having category 1
(cat. 1 or T1) type acute toxicity according to GHS regulation are
compounds with very low lethal doses.
Table 2 reports long term (chronic) toxicities. 1A chronic toxicity is attributed to compounds which have been proven to cause or
increase Cancer, germ cell Mutagenicity and/or Reproductive
toxicity (CMR) in humans. Specific Target Organ Toxicity (STOT)
category is defined as non-lethal target organ toxicity. The effects
are significant, specific and occur after only one (single) or several
Table 1
Cat. 1 acute toxicity values.
GHS labelling
GHS classification
Lethal toxicity values
Cat. 1 (T1)
Oral (mg/kg)
Dermal (mg/kg)
Gases (ppm)
Vapors (mg/l)
Dust & mists (mg/l)
65
650
6100
60.5
60.05
(repeated) exposures. Type 1 STOTs have produced significant toxicity in humans.
To reinforce our selection it was also necessary to consider data
published by recognised occupational safety and health institutes.
Chronic toxicities have been assessed by the Swiss National
Accident Insurance Fund, an organization under public law and
considered as a national reference in Occupational Safety and
Health. On this topic, it publishes yearly the Swiss occupational
exposure limits directive (SUVA, 2015). The INRS, a French Institute
competent in protecting workers’ health and safety, and preventing occupational accidents or diseases is another recognised source
of reliable information. This institute has published a very complete regulatory classification of chemical substances with chronic
toxicity (INRS, 2012). In order to avoid missing out further long
term toxic substances, data from the National Institute for Occupational Safety and Health (NIOSH, 2014) and from the International
Agency for Research on Cancer (IARC, 2014) were also considered.
Both institutes have analyzed substances’ potential to cause
adverse effect to humans. Their collaborative work contributed to
classify industrial agents and to re-evaluate compounds based on
medical survey of workers (IARC’s monographs, 2014; Straif
et al., 2009). These data are an essential complement as their
results are based on different levels of scientific evidence of
carcinogenicity to humans. Indeed, these institutes have analyzed
exposure circumstances which is a crucial tool for occupational
risk assessments. Compounds with severe acute toxicity and/or
being explosive were identified thanks to their SDS set-up in accordance with the CLP (CLP, 2008) and REACH regulations (REACH,
2006). These documents are available from the suppliers as well
as consultable on the GESTIS-Substance Database (GESTIS, 2014).
Data established by the above mentioned organizations have
been compiled. If substances considered especially hazardous for
human safety and health were identified, they were reported in a
table with the complementary information, if relevant. The examples below (Tables 3–5) show how important it is to look at a broad
range of information to protect as much as possible a person’s
safety and health.
Table 3 lists metals requiring an authorization due to their
related toxicities. Unless specified, the table does not include the
relative metallic salts or oxides which might exist. NIOSH/IARC
data as well as the SDS of cadmium highlight its toxicity toward
humans whereas SUVA and INRS don’t. The known reproductive
toxicity (R1A) of lead is pointed out in all consulted media.
Osmium tetroxide’s acute toxicity is stressed in Table 5.
As reported in the upper part of Table 4, the following
non-metallic substances are toxic because they coordinate and/or
intercalate nucleic acids, like the DNA (double stranded deoxyribonucleic acid). Benzo[a]pyrene shows the importance of having
also considered data from IARC’s monographs (2014). Indeed the
SDS of this polycyclic hydrocarbon reports that it is carcinogenic,
mutagenic and reprotoxic to animals (C1B, M1B and R1B). IARC
evaluates wide range of human exposures when classifying
substances and has ranked this chemical into its 1st category,
Table 2
Chronic toxicity types for humans.
GHS labelling
GHS classification
Toxicity
Carcinogenic
C1A
Significant in humans
Mutagenic
M1A
Reprotoxic
R1A
Specific target organ toxicity
Single exposure
Repeated exposure
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S. Brückner et al. / Safety Science 88 (2016) 1–15
Table 3
Highly toxic metallic substances.
Metallic substances
Main toxicity due to
SUVA directive 1903
Arsenic
Beryllium
Cadmium
Chromium (VI)
Nickel
Lead
Accumulation in the soft living tissues
C1A
M1A
INRS ed. 967
R1A
C1A
U
U
U
U
U
U
U
U
U
M1A
NIOSH/IARC
SDS
U
U
U
U
U
U
STOT1
STOT1
STOT1
STOT1
R1A
R1A
U
U
Table 4
Highly toxic organic substances.
Organic substances
Main toxicity due to
SUVA directive
1903
1,3-Butadiene
2-Naphtylamine
Benzene
Benzo[a]pyrene
Acrylamide
Vinyl chloride
4-Chloro-o-toluidine
Phosgene
Coordination/intercalation of biologically
important molecules
C1A
M1A
INRS ed. 967
R1A
U
Alkylation
NIOSH/IARC
SDS
U
U
U
U
U
U
U
U
U
U
U
U
U
C1A
M1A
R1A
of biologically important molecules
U
U
Arylation
Acylation
STOT1
STOT1
Aspiration hazard 1 up to STOT1
Table 5
Highly hazardous substances.
Divers substances
Hazards
SUVA directive 1903
C1A
Cyanides (salts of)
Hydrofluoric acid
Osmium tetroxide
Carbon tetrachloride
Picric acid
M1A
INRS ed. 967
R1A
Divers
meaning that there is sufficient evidence of carcinogenicity in humans.
As the aim of occupational safety and health teams is to preserve
employees’ health, IARC’s category 1 shall be considered prior to
GHS’ category 1B. For acrylamide (second half of Table 4), the STOT1
has been considered as more important to point out than the
probable carcinogenicity reported by IARC. Phosgene’s severe
toxicity is highlighted in its SDS and depends on its concentration:
Table 5 reports the high toxicities (T1) associated to cyanides,
the STOT1 of carbon tetrachloride and the high reactivity of picric
acid. These toxicities are only indicated in the respective SDS.
Taking this cross-linked survey into consideration, if a compound represents an important hazard, the SDS will report it. This
is especially true for acute toxicities and for physical hazards. However, with the new regulation (REACH, 2006), it is the supplier’s
responsibility to set-up the SDS. As SDS with exposure scenarios
are only required if the annual production exceeds 10 tons
(REACH, 2006 and REACH factsheet, 2011), some relevant information might not be reported. Thus it remains crucial to keep on paying attention to incompatibilities either reported in chapter 10 of
the SDS or in other publications.
2.1. List of compounds requiring an authorization
The above mentioned highly hazardous chemicals were
compiled into a list depicted in Tables 6a–6c and available on
C1A
NIOSH/IARC
M1A
SDS
R1A
T1
T1
T1
STOT1
Flammable
our institution’s occupational safety and health website (SB-STT
website).
Colleagues interested in using these compounds may ask for
advice in order to find less hazardous alternatives. This is also beneficial in terms of time saving and accuracy gaining. Miscellaneous
safety data are easily accessible on the internet, for example, and
users looking for them might quickly find overwhelming information. Too much or vague information can be confusing and worse,
lead to wrong initiatives. Before using a chemical it is important to
read the corresponding SDS, as it contains essential information
and measures for safely manipulating it. Amongst the sixteen
chapters of the SDS, some of them are crucial as they are dedicated
to the hazard and risk descriptions, how the chemical should be
stored, handled and disposed of, the first aid measures, etc. However, as this control guidance document could be considered too
long and written in an inaccessible language, the risk is that the
user might not read it. To avoid that the precious SDS is not read
at all because its content might be considered useless by the user,
the SB-SST also proposes oriented reading through the most relevant topics (protective measures, storage, use, elimination, etc.)
of the SDS.
Thus if colleagues need to use one of these substances, they
have to ask for an authorization. Only when the process is agreed
and the authorization delivered, the requester is allowed to order
and use the chemical. In order to ensure that all the personnel
involved gets the appropriate information and adapted measures,
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Table 6a
Organic substances subject to authorization.
Name
CAS No
1,3-Butadiene
106-99-0
2-Napthylamine
91-59-8
4-Aminobiphenyle
92-67-1
4,40 -Diaminobiphenyl, benzidine and its salts
92-87-5
4-Chloro-2-methylaniline
95-69-2
Picric acid, 2,4,6-trinitrophenol
88-89-1
Acrylamide
79-06-1
Methyl isocyanate
624-83-9
Benz[a]anthracene
56-55-3
Benzo[b]fluoranthene
205-99-2
Benzo[a]pyrene
50-32-8
Formula
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S. Brückner et al. / Safety Science 88 (2016) 1–15
Table 6a (continued)
Name
CAS No
Ethidium bromide
1239-45-8
Dimethylcarbamoyl chloride
79-44-7
Vinyl chloride
75-01-4
Vinyl fluoride
75-02-5
Chloromethyl methyl ether
107-30-2
Phosgene
75-44-5
Bis(chloromethyl) ether
542-88-1
Bis(2-chloroethyl) sulfide (mustard gas)
505-60-2
Dimethyl sulfate
77-78-1
Diethyl sulfate
64-67-5
a-Chlorotoluene: benzyl chloride
100-44-7
a,a-Dichlorotoluene: (dichloromethyl)benzene
98-87-3
a,a,a-Trichlorotoluene: (trichloromethyl)benzene
98-07-7
especially hazardous compounds are also blocked in our institution’s chemical database. Therefore, the colleague will be informed
that he needs an authorization either because he consulted the list
of compounds subject to authorization or by a pop-up message
from the institution’s database.
Formula
COCl2
3. Authorization request process
In order to enable an effective coaching about substances under
authorization as well as an effective implementation of possible
measures, a systematic process has been set up in our institution.
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S. Brückner et al. / Safety Science 88 (2016) 1–15
3.1. Authorization request form
Table 6b
Inorganic substances subject to authorization.
Name
Cyanides (salts of)
Hydrofluoric acid
Arsenic and its derivatives
Beryllium and its derivatives
Chromium(VI) oxide
Chromate salts
Dichromate salts
Lead and its derivatives
Mercury and its derivatives
Nickel and its derivatives
Osmium tetroxide
Tin and its derivatives
CAS No
Formula
7664-39-3
HF
1333-82-0
CrO3
(CrO4)2(Cr2O7)2-
20816-12-0
OsO4
Table 6c
Solvents subject to authorization.
Name
CAS No
Formula
Benzene
Deuterated benzene
Chloroform
Carbon tetrachloride
Trichlorethylene
71-43-2
1076-43-3
67-66-3
56-23-5
79-01-6
C6H6
C6D6
CHCl3
CCl4
ClCH@CCl2
It complies with the SUVA’s Substitution, Technical, Organisational
and Personal protective measures principle (Koller et al., 2013) and
aims at protecting the user from any exposure to the hazardous
substance. This is achieved by considering step-wise whether it
is possible to implement Substitution, Technical, Organisational
and/or Personal protective measures along the work procedure
involving the requested substance. The more the protective measure is close to and affects the source (i.e. the hazardous substance)
the greater the impact will be on the target (i.e. the user). Indeed,
the more confined the hazard is, the safer the user is. For a greater
efficiency, the authorization process reported herein analyses
sequentially whether the protective measures may be applied at
the source, between the source and the user (i.e. at the interface),
and on the target as shown in Fig. 3.
Every colleague who needs an authorization has to fill in the
request form available on the occupational safety and health website (SB-SST website), shown in Fig. 4.
In the upper identification part of the form, the requester has to
indicate which substance is needed, the unit he is working in, his
name, education and telephone number.
In the identification part just below, the requester has to precise
the formula of the chemical substance, the quantity to be stored
and how much is going to be used in the experiment.
The description part, just underneath, describes the substance
use and how it will be manipulated. The information reported
herein will be developed with the help of the SB-SST team in an
additional procedure sheet. The latter details the different steps
and compounds which might be used in the experiment. It also
includes any particular downstream process (purification, polishing, etc.) which might release some of the compound under authorization. When applicable, any maintenance or special emergency
procedure shall be reported in the procedure. In the justification
part, the requester can report a published paper or any other documents supporting the use of that substance.
Then a crucial question to answer is whether the hazard could
be eradicated by considering an alternative substance. This is
aimed at raising the colleagues’ awareness and reminding them
that non- or less hazardous chemicals might exist and, if possible,
should be used instead.
Providing all this information starts a good record tracking of
the chemical’s whole lifetime cycle. At the end of this step, the
unit’s director has to sign the form and the requesting colleague
sends it to the responsible person in the SB-SST team. Once the
request has been received, the occupational safety and health team
will add the date the form has been received and a request number.
The following discussion and analysis with the requester will
evaluate the suitability of the use of the requested compound as
well as the workplace and the entire work procedure. It is only
once the different steps of this risk management process have been
defined, checked and set-up accordingly that the boxes workplace
checked and checked by a hygienist will be completed.
Fig. 3. STOP principle.
S. Brückner et al. / Safety Science 88 (2016) 1–15
9
Fig. 4. Authorization request form.
3.2. Evaluation of the request
The evaluation of the requested compound is aimed at making sure
no safer alternatives exist and that safe work conditions will be implemented. This discussion also includes the evaluation of the amount of
substance to be used. If it is the first time the compound will be tested
for the application, it would be better to have as less as possible
remaining, possibly unusable, chemical left over in case the experiment should not work. Within the procedure, the used amount or
the concentration of the dissolved compound is also analyzed. Finally,
the way the compound is meant to be used is also checked. Consequently, this evaluation step can lead to three possible outcomes:
(1) The requester has to find a less hazardous alternative. This
can happen because:
a. the substance and/or procedure is too hazardous,
b. a better alternative exists or
c. the reorganization of the work place is too
demanding.
(2) The request is refused. This can happen because:
a. no safe work can be ensured,
b. no alternative is possible or
c. no sustainable protective measures can be implemented.
(3) Safe work conditions can be implemented and the process
proceeds further to chapter 3.3.
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S. Brückner et al. / Safety Science 88 (2016) 1–15
If the request is accepted, the analysis continues with the following assessments:
– the place where the chemical will be stored: it must be suitable,
compatible, ventilated and lockable.
– the produced waste: an established and documented work-up
of the substance leading to a stable waste media must exist. If
the waste is unstable, a procedure to neutralise it has to be
implemented. This will trigger further protective measures covering all involved additional risks. Even at this latter stage the
authorization request can be refused.
3.3. Compound’s hazards and how it should be used
Ideally, the first steps any user of a chemical should do are looking for and considering hazards associated to the chemical even
before ordering the chemical. Given the importance of the SDS,
the SB-SST has decided to sum it up in a shorter and easily understandable document, which will be added to the initial request
form. Obviously this information is already communicated to the
requester during the initial meeting. This second information sheet
summarizes the main hazards related to the substance, as well as
any relevant values, like lethal dose 50 (LD50) and permissible
exposure limit values (TLV: threshold limit value and BEI: biological exposure index). These references are important as they stress
the hazard and show it can be monitored. Furthermore, they indicate that the substance is known which might have a reassuring
effect on users. To illustrate the concept explained so far, a request
to use osmium tetroxide, a lethal chemical compound, will be considered. Osmium tetroxide can be used as oxidizing reagent in
organic chemistry or as staining agent in biology. Using an
‘‘osmium sputter coater” machine also allows making inert
samples conductive and detectable by electronic microscopy. The
hazard information form for osmium tetroxide is shown in Fig. 5.
The information form also reminds the Chemical Abstract
Service number (CAS) of the chemical; this number is essential to
find the correct SDS which will be discussed with the requester.
Legend:
T:
S:
The main SDS chapters to be read are also listed and a reminder
about the chemical’s toxicology is added as well. The way the
chemical substance will be used within the FSB is discussed in detail
with the requester and the outcome reported on this same sheet.
3.4. Discussion, establishment and implementation of the technical,
organisational and personal protective measures
This section illustrates the importance of the discussion with
the requester to cover the whole lifetime cycle of the requested
substance.
3.4.1. Manipulation
A risk management analysis of a chemical compound will deliver adapted and efficient measures only if it is conducted with the
person who will use the compound in the laboratory where the he
will use it. Taking into account the laboratory’s installation and
equipment, the question about an alternative chemical might be
asked again. The analysis of the suitability of the chemical, of the
work procedure and the protective measures which have to be
put in place at the source, the interface and/or the target are realised in compliance with the SDS, the SB-SST’s expertise and the
STOP principle (Koller et al., 2013). All these steps are necessary
in order to ensure that the laboratory is, or will be, organized
and equipped accordingly; thus enabling the worker to work
safely. The exposure assessment, including exposure scenarios
and estimation of exposure is made by an expert; i.e. an occupational safety and health officer and/or a hygienist. Alertness will
also be raised regarding the possible by-products, which might
not have hazard nor precautionary statements (H- and Pstatements replacing the R- and S-phrases according to the GHS).
Even though more data on multiple chemical exposure-risk scenarios is becoming available, this operation will be done on the basis
of a systematic exposure-risk analysis to the requested compound
and, if appropriated, to its potential by-products. There will be a
strong remark about possible incompatibilities with other chemicals but the analysis will not consider the synergic toxicological
Toxicity, classes 1 to 5 (1: most toxic; 5: less toxic)
Irritates skin, eye and respiratory track
C:
Carcinogenic: 1A (for humans), 1B (for animals, potentially for humans)
and 2 (suspected)
M:
R:
STOT:
Mutagenic: classes 1A, 1B and 2
Reprotoxic (alteration of fertility and/ or of the fœtus' development): classes 1A, 1B and 2
Specific Target Organ Toxicity
LD50:
Lethal dose 50: the point where 50% of test subjects exposed (either by inhalation or
injection) would died
TLV:
BEI:
i:
CLP:
SUVA:
Recommended airborne exposure limit for 8h work/ day (SUVA)
Biological limit value (SUVA)
Airborne dust concentration = breathable dust
Regulation on Classification, Labelling and Packaging of substances and mixtures
Swiss National Accident Insurance Fund
Essential information in the Safety Data Sheet of the product (CAS number: 20816-12-0):
read chapters 2 (hazards), 4, 5, 6 (first aid and intervention measures), 7 (handling & storage), 8 (PPE)
and 10 (reactivity & stability).
Physico-chemical & toxicological considerations:
Osmium tetroxide’s toxicity is due to its high volatility andreactivity. Its toxicity is comparable to poison
gas used during the war.
Osmium tetroxide is a lethal solid which sublimes at 39°C.
Fig. 5. Hazard information form.
S. Brückner et al. / Safety Science 88 (2016) 1–15
11
Fig. 6. Air supply system.
interactions (SUVA, 2015; Teuschler and Hertzberg, 1995) the
chemical under authorization and/or the by-products might have
with other chemicals.
In the lethal toxic osmium tetroxide (OsO4) example, it has
been agreed that the work will only be carried out by an authorized person in a confined fume hood located in a laboratory
with positive pressure differential designed to prevent migration
of contaminants. Only one person equipped with a lone-workersafety-device is allowed to work in there. To further reduce the
risk of uncontrolled chemical contaminants leaving the working
space, the laboratory has been subdivided. This was achieved
by putting a special mobile room divider that creates a barrier
between the working area and a small space before the exit
door. In this way, the authorized person working in the laboratory benefits from a clean area within the laboratory itself before
entering the working area. This is also beneficial in the case the
operator has to leave the room for emergency reasons as the
hazard left behind the barrier will be separated from the
entrance.
Even if strategic protective measures, like changing to a safer
protocol or by automating a hazardous process, can be implemented to minimize the exposure risk, the user will have to wear
the correct type of equipment to protect his entire body efficiently
from the substance and/or the energies (laser, UV, heat, pressurised
gases, etc.) required during the process. Bearing in mind that this
authorization procedure also aims at educating people, the colleagues’ knowledge about Personal Protective Equipment (PPE)
and how to wear them properly will be checked at this point. As
no universal PPE exists, a research might have to be carried out
to find the required and adapted PPEs for each case. The SB-SST
responsible person decides on the appropriate protective measures
to be implemented in agreement with the user. Given the risk that
OsO4 might sublimate accidentally outside the confined ventilated
areas due to a possible leak or a fall and break of the ampoule outside the fume hood, it has been decided that the user must wear a
respiratory air supply system with full facial protection, as shown
in Fig. 6:
Only when fully equipped the user can take out, from a locked
cabinet inside the fume hood, an ampoule containing OsO4. The
latter is then broken with a special apparatus and the chemical
used in the next step of the established procedure.
The required respiratory protective measure is reported in a
third information sheet (Fig. 7) together with all other required
PPEs:
This third information form will also show information on how
the chemical should be stored and how to dispose of any related
waste. For example, the substance might need to be stored in a
fire-proof cabinet or in an ATEX (ATEX, 2014) approved refrigerator
and/or specifically treated according to its nature before being
thrown into a compatible waste container.
3.4.2. Storage
To ensure a safe storage, the rules about substances’ incompatibilities, the storage place as well as appropriate labelling to inform
about the presence of the hazardous chemical are discussed.
Then, according to the laboratory’s set-up, the right equipment is
being installed. Legally, all toxic compounds have to be stored in
a ventilated and lockable cabinet to restrict access only to trained
and authorized persons (Swiss ordinances OChim, 2015 and
ORRChim, 2014).
If an expiry date for the chemical is reported or a specific storing
procedure must be followed, as for example always keep an unstable chemical in a neutral media, the protocol and periodicity are
agreed with the requester. The necessary information is reported
in the document, as shown in Fig. 8:
3.4.3. Waste disposal
Finally the waste disposal is discussed. Very often waste is treated with less care than the initial chemical or the obtained product.
This is understandable as its value is not comparable with either
one of the latter. However, waste should be treated very carefully,
even more than any other chemical as undesirable reactions may
occur in the container possibly harming the person who produced
it, the colleagues sharing the laboratory or the staff taking care of
it. If the wrong destruction-procedure (temperature, filters, etc.)
is applied, the released fumes will also harm the environment. Furthermore, if the material of the waste container is not compatible
with the waste it could lead to damage and spill. People receiving
the waste to be packed, transported or destroyed need to know
what the waste is in order to wear the corresponding PPE and
avoid incompatibilities. This is also true for material (glove, tissue,
syringes, etc.) contaminated with the substance subject to authorization. Thus it is mandatory to use the right container and label
it with the description of waste (SB-STT website, Swiss ordinances
DETEC, 2010 and OMoD, 2014).
Given the fact waste resulting from the use of osmium tetroxide
is also hazardous, it is required to deactivate it in the laboratory
before bringing it to the stores for disposal, as indicated in Section 3
of the PPE and management form shown in Fig. 9. In this case,
sodium sulfite (aq. saturated solution) is added to the waste and
the mixture stirred for an hour at room temperature in a fume
hood. A dark turbidity will indicate the reduction of the tetroxide
to the less hazardous dioxide from.
12
S. Brückner et al. / Safety Science 88 (2016) 1–15
Wearing goggles, gloves, a lab coat and working in a fume hood is mandatory
1. Protection of the worker
Special personal protection:
Respiratory protection
Skin/ hands
Detection
Biological monitoring
Yes
Yes
Yes
Yes
see 1.1
see 1.2
see 1.3
see 1.4
1.1 Respiratory protection
Particulate mask
Full face mask
Work in a glove box
Respirator with supplied air system
Yes
Yes
Yes
Yes
No
No
No
No
1.2 Skin protection (hands, body)
Disposable gloves (thin gloves):
Latex
Vinyl
Nitrile
Yes
Yes
Yes
No
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Type:
Type:
Type:
Type:
Type:
Yes
No
Type:
Yes
Yes
No
No
Yes
Yes
No
No
Remarks:
High protection gloves:
Viton
Neoprene
Sol-Vex
Butyl
PVC(vinyl)
Coverall:
1.3 Detection
Detection type
1.4 Biological monitoring
Monitoring type
Contact person
2.
Storage
Ventilated cupboard/ cabinet
Locked cupboard/ cabinet
Remarks:
3.
Waste destruction and recycling
In-house neutralization/ destruction
Separate recycling
Remarks:
Fig. 7. PPE and management form.
Storage
Ventilated cupboard/ cabinet
Locked cupboard/ cabinet
Remarks:
X
X
Yes
Yes
No
No
Store away from any source of heat and warm items.
Fig. 8. Storage requirements (part 2 of the PPE and management form).
Furthermore, the colleague will also be asked how to behave in
case of an accident, where to find first aid equipment and the
emergency items (eye-washer, extinguisher, spill kit).
Finally the authorization’s validity period is determined. It is
fixed according to the substance’s type and the duration of the project. To avoid unnecessary storage and accumulation of chemicals,
the authorizations for liquids or solids are valid for a maximum of
up to three years. Authorization for gases must be renewed every
year. If a project changes or if unsafe management has been
noticed, the authorization can be cancelled and the chemical
removed from our institution at any time.
3.4.4. Unique document authorizing the use of an especially hazardous
chemical substance
Thanks to these global discussions, considerations and implementations, the colleague is informed and trained regarding the
13
S. Brückner et al. / Safety Science 88 (2016) 1–15
Fig. 9. Waste management (part 3 of the PPE and management form).
Received on:
17.07.2013
Workplace checked:
Checked by a hygienist:
Authorization:
Authorization n°:
Request number:
X
Yes
Yes
X Accepted
Os4-0713
X
No
No
Rejected
Valid until:
2013-016
Date:
Date:
17.07.2013
August 2018
Fig. 10. Approval (lower part of the authorization request form).
Table 7
Database of the delivered authorizations (snapshot).
Building
Floor
Lab
Unit
Authorization
Chemical
Stock
Use/exp
Form
MX
BCH
BCH
BCH
CH
BCH
CH
BCH
BCH
BCH
BCH
BCH
BCH
BCH
BCH
BCH
INM
PH
BCH
BCH
BCH
BCH
1
5
5
4
1
2
1
5
5
4
4
3
4
4
3
4
0
0
2
3
5
2
117
5432
5230
4409
502
2212
502
5409
5409
4407
4407
3207
4407
4221
3403; 3413
4432
11
491
2438
3430
5422
2409
CIME
LSPN
LCBIM
LCSO
LPI
GE
LPI
LSPN
LSPN
LCSO
LCSO
LSCI
LCSO
LIP
LCS
LCSA
LMT
LPMC
LCOM
LCS
LSPN
LCOM
TE5-0613
Os4-0713
CN13-0713
Bz16-1013
Pb9-1013
Bz17-1113
Pb10-1113
CN14-1113
CN15-1113
DMC3-1213
CF26-1213
Ni23-0214
CN17-0214
BV1-0314
TC16-0314
Ni24-0514
Pb13-0614
As7-0614
BV2-0614
Sn1-0614
Pb14-0614
Ni25-0614
Trichloroethylene
Osmium tetroxide
Cyanogen bromide
Benzene-d6
Lead(II) thiocyanate
Benzene
Lead(II) chloride
Potassium cyanide
Copper(I) cyanide
Dimethylcarbamoyl chloride
Chloroform
Bis(1,5-cyclo-octadiene) nickel(0)
Cyanogen bromide
Vinyl bromide
Carbon tetrachloride
Bis(1,5-cyclo-octadiene) nickel(0)
Lead(II) iodide
Arsenic
Vinyl bromide
Bis(tributyltin)
Lead tetraacetate
Nickel(II) sulfate hexahydrate
1l
2 ml
25 g
25 ml
30 g
5g
50 g
100 g
100 g
5g
2l
2g
5g
100 ml
250 ml
2g
50 g
40 g
100 g
10 g
5g
250 g
150 ml
8 ml
2 mg
0.65 ml
100 mg
0.5 g
10 g
100 g
100 g
5g
0.65 ml
0.1 g
100 mg
6.7 mL
50 mL
3 mg
100 mg
0.4 g
20 g
1.7 g
100 mg
15 g
Liquid
Solid
Solid
Liquid
Solid
Liquid
Solid
Solid
Solid
Liquid
Liquid
Solid
Solid
Liquid
Liquid
Solid
Solid
Solid
Gas
Liquid
Solid
Solid
protective and preventive measures to be considered for the storage, handling and disposal of the requested hazardous substance.
In this way the entire lifetime cycle of the molecule has been considered and the safety criteria assessed. At this stage the lower part
of the request form can be filled out, as shown in Fig. 10.
At this point, all four information and procedure forms, composing the final and unique authorization document, are handed over
to the requester and the colleague is authorized to order and use
the substance in the laboratory according to the defined protocol
for a limited period of time.
Producing a unique document provides a standardized identifier for effective management of especially hazardous and/or toxic
chemical substances. Thus accurate up-dating, reporting, analyzing
and reviewing following possible issues may be done easily and
corrected more quickly. This also reduces possible errors enabling
occupational safety and health professionals to consider more
rapidly and precisely characteristics of authorizations related to
analogous compounds and procedures.
Moreover, the document also allows to readily register the
corresponding data and files into a database. As an example,
the snapshot presented in Table 7 shows how the location, the
authorization reference number, the chemical’s description and
its relative quantities are registered:
With this quality system, the SB-SST team keeps a good tracking, knows where especially hazardous chemicals are being used
and when the authorizations expire.
Altogether, this has led to the development of a management
system that is recognized all around our institution. The implemented system may also contribute to set standards for complementary occupational safety and health actions in other research
and teaching institutions or any entities working with chemicals.
4. Conclusion
In the interest of protecting the personnel straight from their
start in our institution, new collaborators have to follow a participative training and, according to the group they will work for,
receive dedicated occupational safety and health instructions. In
order to ensure that collaborators will take enough time considering the safety rules and work accordingly, the SB-SST team has put
in place a clear and straightforward authorization concept for
chemicals with very high concern. The established procedure
14
S. Brückner et al. / Safety Science 88 (2016) 1–15
requires that an authorization has to be obtained from the SB-SST
prior to ordering and manipulating chemicals which are either very
toxic and/or physically very reactive. The person is made aware
about the hazards and risks associated to the chemical and asked
to check whether a less hazardous chemical might be used. If
not, a discussion takes place to find solutions that eradicate or minimize exposure risks considering the chemical’s entire lifetime
cycle: from the ordering throughout the disposal process. All along
this systematic quality system, the requesting person, with the
help of the responsible occupational safety and health person, is
encouraged to find the appropriate measures to ensure that the
chemical is stored in the right place, handled in the right manner
by a trained person protected appropriately.
This innovative collaborative risk-management process makes
people more sensitive toward the handling, storage and disposal
of highly hazardous chemical substances and allows interesting
discussions in order to come promptly to adapted solutions by
improving the laboratory’s equipment, facilities and giving the
right PPEs. Positive feedbacks are also obtained since the process
is organized considering the collaborator’s schedule. Thus it also
encourages colleagues to ask for advises and possible safety measures in the case of compounds not subject to authorization.
This global approach generated an inventory of more than 300
substances which evolves when data about compounds’ toxicities,
occupational exposures are released. For a continuing effectiveness
of the authorizations and their implications, these unique documents are discussed again and/or re-evaluated whenever necessary. The re-evaluation of the authorizations also occurs during
the biannual safety audits of the School of Basic Sciences’ laboratories. Interestingly, since the implementation of the authorization
procedure in our institution no accident related to the manipulation of especially hazardous compounds has been reported.
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