September 1994

The New Chemical Store:  Chemicals in 
One Gallon or Less

The chemical stores on campus will sell chemicals in quantities of one gallon
or less only.  This should promote both safe laboratory storage and waste
minimization practices.

There cannot be more than three gallons of any one hazardous chemical
liquid on storage shelves at any one time.  Any hazardous liquid in quantities
more than three gallons must be stored in specifically designed flammable
storage cabinets.   By selling one-gallon containers, we hope to encourage safer
storage practices by not exceeding a safe amount.

In addition, the smaller units of sale will promote waste minimization on
campus-buying less means there will be less left over.   While it may seem
economical at the time to buy a chemical in bulk, thinking the extra can be
used later, the chemical often gets forgotten beyond its original intent and
goes to waste.  Disposal down the road costs appreciably more than new
"extra" chemical amounts cost.

However, a five-gallon container of a hazardous liquid can be ordered with
approval from DOES.  Approval will partly depend on the availability of a
flammable storage cabinet in which to store the excess chemical.  Any
questions call DOES at x2907.


Spontaneous Eruption:  Explosion in the BRB

The BRB got an unexpected shock this July when  a bottle of chemical waste
being stored in one of the labs exploded without warning, causing the
evacuation of the entire floor of the BRB.  Fortunately, no one was seriously
injured, though hospital attention was necessary for one of the lab workers.

There are two possible explanations for the explosion.  Trace amounts of lead
and zinc were found in the residual waste.  Possibly a lead or zinc picrate
formed over time while the waste was sitting in the bottle.  These picrates are
extremely shock-sensitive and the contents of the waste container could have
been set off by the water bath/shaker that was operating beside it.

The other possibility is that amounts of 4-nitrophenol, which were found in a
scan of the residual waste, decomposed over time and the by-products created
by the decomposition-various oxides of nitrogen-could have created enough
internal pressure to cause the bottle to explode.

In either case, the explosion could have been avoided through timely waste 
disposal.   In both scenarios, the explosion was caused by long-standing waste,
enclosed long enough and under enough pressure to create hazards that were
not originally there.  We encourage all researchers to dispose of waste as
quickly as possible. (Call x2580 between 8:30-4:00).

Also, researchers are required to record on an accompanying Hazardous
Waste disposal sheets the chemical waste disposed, all chemical constituents,
and the date. This way incompatible waste will not be stored together and
cause some sort of reaction over time.

Please call Safety Services (x2907) if you have any questions about waste
disposal or storage.  To avoid accidents like this, knowing what gets thrown
away is as important as what remains on the shelves.



The MSDS:  a chemical user's safety resource

As required by the OSHA Lab Standard, the Material Safety Data Sheet, or
MSDS, for each chemical used in a laboratory must be accessible to every
employee of that lab.  

A chemical's MSDS is a printed sheet that gives users information on a
particular chemical.   The information on the MSDS is provided by the
manufacturer or distributor of that chemical and tells users how to protect
themselves from exposure and what to do in cases of emergency.

The MSDS for any chemical you use is readily available at any time on
computer or hard copy.   All labs are required by OSHA to have MSDSs
available.  If you cannot find one in your lab, follow one of the procedures
listed below.

Availability on Campus

DURING WORKING HOURS (8:30am-4:30pm)

The Department of Occupational and Environmental Safety (DOES) has
about 40,000 hard copies of MSDSs in an extensive library and has computer
access to the Occupational Health Services (OHS) MSDS database. We can
provide you with copies of MSDSs in one of two ways:  we can send you one
or two previously requested MSDSs via campus mail, or  in an emergency or
if you need the MSDS  right away, we can fax you a copy.

If you would like DOES to copy a large amount of MSDSs to make your
laboratory's collection complete, send us a list of needed MSDSs along with
IBM-compatible disks (one disk can hold approximately 40 MSDSs).  Both 3
1/2" and 5-1/2" disks will work.  We will copy these into an ASCII file which
can be read with any IBM word processing program.  Each lab may then either
keep the MSDSs on disk or print out hard copies. Either version is acceptable
as long as everyone knows how to access them.

The Sigma-Aldrich Company has released a complete set of their MSDSs
on CD-ROM, available through CWRUnet.  The system is accessible using an
MS-DOS computer hooked up to the network.  NOTE:  not all areas can access
this information.


DURING NONWORKING HOURS (4:30pm-8:30am)

Security (x3333) can access the Sigma-Aldrich Network during
nonworking hours.  Call them in an emergency.


Always read the MSDS before using a chemical.  Even if you have used the
chemical before, the manufacturer may have changed its formula which may
change the steps you should take to protect yourself.   Your safety depends on
it.


New Hazardous Waste Tag

The Department of Occupational and Environmental Safety has created a new
Hazardous Waste Tag to make it easier for researchers to clearly list
constituents of waste in a container.

The new tag, to be hung from every bottle of hazardous waste, will replace the
Hazardous Waste sticker previously used.  Most of the information asked for
on the new tag is taken directly from the Hazardous Waste Pick-up Form:  the
PI, the location, the contact, bottle number, account number and phone
number.  The section beneath "Office Use Only" (the sequence number and
the P/U date) on the new tag should be left blank.

After filling in the top information, begin listing the chemical constituents
and the estimated quantity of each waste being put into the bottle.  Then mark
the date that the waste was put into the bottle.  This hopefully will prevent
waste from being collected over too long a period.  Note that on the back of
the tag are more blanks if necessary.

Safety technicians will bring the new tags to researchers when they do waste
pick-ups.  If you have questions, please ask the technician  or call our office
(x2907).


Safety With Perchlorates

As a group, perchlorates are unstable chemicals which are highly irritating to
the skin and mucous membranes.  All inorganic oxidizing agents containing
the perchlorate ion(CIO4-),  such as potassium perchlorate and magnesium
perchlorate, are examples of the group.  Perchlorates and perchloric acid are
potentially explosive when heated or mixed with organic compounds, so
safety precautions when using them are necessary. 

Storage and Use

Shelves on which perchloric acid is stored should be of steel, tile, or epoxy 
composite construction.  Wood will absorb spilled perchlorates which, when
dry, are friction-sensitive and reactive.   An organic chemical spilled on an
absorbent wooden benchtop or shelf where perchloric acid has been spilled,
even if it is years later, can cause a fire or explosion to occur immediately.

In no case should perchlorates be stored adjacent to any organic materials or
flammables.  Perchloric acid should be stored apart from all other chemicals,
especially from any metals (with which it forms explosive compounds), in a
low-traffic area of the lab.

In Experiments

Heating

Direct flame heating or oil bath (because of its incompatibility) methods
should not be used for perchlorates.  Electrically or steam heated devices
should be used instead.

Glassware

Make certain that all glassware used for perchloric acid experimentation or
waste is free of contaminants and metals and is well-supported.  Secondary
containment should be used due to the hazards that may ensue if an
apparatus cracks or breaks due to thermal or mechanical shock.

Miscellaneous

Use alternatives to perchloric acid whenever possible-trichloroacetic (TCA)
may work in some cases.

Rubber stoppers and tubes or stop-cocks requiring organic-based lubricants
should not be used in perchloric acid assemblies.  Use teflon sleeves instead.

In Fume Hoods

Using perchlorates in a fume hood also demands special safety measures.

Lower the sash of the hood whenever possible during work with perchlorates
as an explosion barrier; if this is not feasible, use a portable barricade in front
of your perchloric equipment.  

One of the greatest dangers of using perchloric acid in a fume hood,
however,is the potential for spontaneous combustion or explosion caused by
perchlorate residues in fume hood casing and ductwork.  To prevent mixing
of perchloric fumes with any others, all perchlorate usage should be done in
one hood only, designed for and dedicated to that purpose.  Label the
designated fume hood clearly.   

Unfortunately and despite safeguards, most accidents involving perchloric
acid are severe.  Take every possible precaution in working with and storing
perchlorates-never store them adjacent to organic materials or flammables,
and keep them in a low-traffic section of the lab.


Following the Rules:  Why the "Regs" Don't Always
Make Sense

Many researchers hesitate when asked to comply with a certain regulation
especially when that regulation seems to go against common sense.  But there
is more involved in compliance with the law than what may appear to make
sense on the surface.

CWRU must follow the standards of various federal and state agencies and
Congressional acts-the Nuclear Regulatory Commission (NRC), the
Occupational Safety and Health Act (OSHA), the Resource Conservation and
Recovery Act (RCRA).  Tracing the origin of these acts will help explain why
various regulations exist.

For example, regulations under OSHA are created with occupational exposure
in mind.  OSHA standards are designed to protect the employee who may be
exposed to small amounts of exposure every day for twenty years.  Standards
are set stringently in order to give workers long-term protection.  Keeping
this in mind, OSHA's list of regulated materials and the exposure  limits for
use of those materials usually make sense in a lab situation.

RCRA hazardous waste regulations, on the other hand, often do not make
sense to researchers in the lab.  RCRA was enacted in 1976 to prevent fraud in
the disposal of bulk industrial waste.  Often companies would dilute a hazardous substance-say potassium cyanide-and reduce its strength below the 
set concentration limit, thereby trying to avoid disposal costs.  What they
were doing, of course, was simply spreading the poison over a larger area and
creating a more hazardous situation in the long run.  

RCRA regulations, though designed for industry, apply to all generators of
hazardous waste-including universities.  RCRA requires the university to
classify hazardous wastes according to certain properties-ignitable/flammable,
toxic, corrosive, or reactive-in addition to creating a regulated materials list.  

All generators of hazardous substances must meet  a certain standard under
RCRA regulations, and the university is held to a different performance
standard than the home or an industrial site.  Take ethyl alcohol-classifying
and disposing of ethyl alcohol as a regulated hazardous substance in the lab is
one of those rules that does not seem logical or necessary.  In your home, you
could dump a solution of ethyl alcohol down the drain, on the ground-you
could drink it if you wanted. However, in the university setting, any solution
with an ethyl alcohol concentration of 24% or greater must be disposed of as a
hazardous waste because it is flammable, and flammable materials are
regulated under RCRA.

Keep in mind too that RCRA was developed to protect the environment, not
individuals, like OSHA was (although it assumes that what protects the one
will help protect the other).  A rule might not make sense to you or seem to
apply to your situation, but it is essential in RCRA's structuring, and the
university is held accountable for a vast number of these health and safety
regulatory controls.  

If you have questions concerning a particular hazardous material regulation,
call DOES (x2907).


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