www.jst.umn.edu
Safety Moment Collection
of the Joint Safety Team at the University of Minnesota,
Department of Chemistry and Department of Chemical
Engineering and Material Science.
www.jst.umn.edu
Use these safety
moments as you see fit.
Feel free to adapt a safety moment to meet the specific
needs and time constraints of an audience or occasion;
this may mean using only a portion of the prepared
slides for a topic or including additional
resources for an in-depth discussion.
www.jst.umn.edu
Have a safety moment?
Contribute it to this collection.
Send safety moments to jst@umn.edu
with Safety Moment <topic> in the subject line.
Please put content in the provided template
and cite reliable, credited sources.
Thank you!
Chemicals
and their Hazards
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Liquid Nitrogen
Liquid Nitrogen
Bp: -320 ˚F (-196 ˚C, 77 K)
Expansion ratio: 1 : 694
Burns – similar to frostbite or thermal buns
Explosions (Texas A&M, 2006; $~500,000)
•
Relief valve was sealed shut
Asphyxiation( 8 deaths/yr in US)
•
Oxygen deficiency from not being able to breathe
normally
Liquid N2 ingestion (18th birthday celebration,
England, 2012)
• Emergency surgery to remove stomach after drinking
a cocktail containing liquid N2
www.jst.umn.edu
Liquid Nitrogen
Liquid N2 in the lab
Can solidify with a vacuum pump (mp 60 K)
Can condense oxygen (bp 90 K)
• Liquid O2 can cause explosions
• Don’t leave liquid nitrogen traps open to atmosphere!
• If liquid O2 formation is suspected, alert other sto the danger
and evacuate the area.
• Allow the vented system to warm to room temperature
Can condense argon
• Use nitrogen gas instead
www.jst.umn.edu
Liquid oxygen
is pale blue
Controls
• Always wear appropriate PPE (cryo gloves, lab coat, and goggles)
and never allow any unprotected part of the body to come into
contact with LN2 or any uninsulated vessels or pipes.
• Do not overfill vacuum flasks and never store LN2 in a sealed
container at a temperature above the BP of LN2.
• Always inspect and maintain vacuum flasks. If they are cracked,
they may fail explosively.
• Eliminate sources of ignition around the LN2. The risk of O2
condensation is also reduced when working with smaller quantities
of LN2.
• If pale blue liquid O2 is seen, remove LN2 traps (if any), flammables,
and any ignition sources and let O2 boil off slowly.
www.jst.umn.edu
References
• Material Safety Data Sheet: Nitrogen, Refrigerated
liquid.
<http://www.liquidnitrogenservices.com.au/safety/
ln2_msds_e1.pdf>
• Asphyxiation with liquid nitrogen – hazard alert,
Monash University.
<http://www.monash.edu.au/ohs/topics/hazardalerts/liquid-nitrogen-asphyxiation.html>
• Standard operating procedure (SOP) for handling
cryogenic (liquid nitrogen).
<https://eee.uci.edu/programs/chemstockroom/SO
P/Liquid%20Nitrogen%20SOP.pdf>
www.jst.umn.edu
www.jst.umn.edu
Liquid Nitrogen Transport
10
Liquid Nitrogen Presents
Major Safety Concerns
• Extreme temperature (-196°C)
• Rapid evaporation and suffocation (1 L liquid  25 cubic ft)
www.jst.umn.edu
Ted Pella Inc. “Safe Handling of Liquid Nitrogen.” 2013
http://www.tedpella.com/cryo-supplies_html/HandlingLiquidNitrogen.htm
Transport – Plan for the Worst
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Transporting Chemicals
for Outreach
Transporting Chemicals for Outreach
• Using chemicals for outreach activities carries
the additional hazard of chemical transport in
civilian vehicles
• Potential dangers:
– Asphyxiation from gases
– Chemical spills
– Chemical reactions
www.jst.umn.edu
“Transporting chemicals for lecture demonstrations & similar purposes.”
Royal Society of Chemistry. 2008
Simple Rules
When possible, avoid transport
Transport small amounts
Maintain inventory of transported chemicals
Ensure adequate labeling, including hazard
information
• Avoid spills
•
•
•
•
– Tight packing with soft material (cloth, bubble wrap, etc.)
– Closed containers
– Secondary containment (boxes, buckets)
• Avoid reactions
– Store incompatible chemicals in separate containers
www.jst.umn.edu
“Transporting chemicals for lecture demonstrations & similar purposes.”
Royal Society of Chemistry. 2008
Special Cases
• Liquid Nitrogen
– Only use approved, vented dewars
– Store in separate space from
driver/passengers (i.e. car trunk) to
avoid asphyxiation hazards
– Pack dewar such that it cannot fall
over or spill
• Gas Cylinders
– When possible, use small and nonrefillable containers
www.jst.umn.edu
“Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008
http://www.phy.cam.ac.uk/hands/hazards/gases.php
www.jst.umn.edu
How to Handle “The Heat”
Fire hazards and
autoignition temperatures
Temperatures
• Furnaces, ovens, hot plate, oil baths
550-1000 oC, 100-200 oC, up to 100 oC
• Saturated steam (1 bar): 100 oC
• Minnesota summer:
23 oC, 73 oF (Jul. avg in TC)
• Ice/water: 0 oC
www.jst.umn.edu
Wikipedia: Climate of Minnesota
18
Flames (adiabatic flame T, const p)
Acetylene (C2H2)
in oxygen
3480 oC
Hydrogen (H2)
in oxygen
3200 oC
Propane (C3H8)
in air
2392 oC
Hydrogen (H2)
in air
2210 oC
Bituminous Coal
in air
2172 oC
Light fuel oil
in air
2104 oC
Wood
in air
1980 oC
Butane (C4H10)
in air
1970 oC
Natural gas
in air
1960 oC
Candle (outer zone)
in air
1400 oC
www.jst.umn.edu
Wikipedia: Adiabatic flame temperature
Physics Stack Exchange
19
Autoignition temperatures
•
•
•
•
•
•
Diethyl ether (160 oC)
Diesel (210 oC)
Paper (218-246 oC; 451 oF)
Gasoline (246-280 oC)
Ethanol (363 oC)
Butane (405 oC)
All similar to heating eq. in the lab,
lower than flames.
www.jst.umn.edu
Wikipedia: Autoignition temperature
20
Hazards
• Fire
flammables in contact with hot objects
• Thermal burns
skin in contact with hot objects
www.jst.umn.edu
21
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Open reactive volatiles
in the hood
Example from a
Learning Experience Report (LER)
Reactive Volatiles
During working hours, bottle of acetaldehyde
was opened outside of the fume hood. A plume
of vapor was released into the lab and the lab
was evacuated.
No injury resulted.
The participate knew what do in the incident (8/10), but did not
have much prior experience with the activity/technique (2/ 5).
To prevent incident:
1. Open the bottle inside of a fume hood.
www.jst.umn.edu
23
Acetaldehyde - SDS
Flammable
Health Hazard
Acute toxicity,
Inhalation
Boiling point =
21°C
www.jst.umn.edu
Acetaldehyde. MSDS. Sigma-Aldrich. http://www.sigmaaldrich.com
24
www.jst.umn.edu
Peroxide Forming Chemicals
Diethyl ether
Isopropyl alcohol
THF
Ether Safety
overview
• Ether can form peroxides when exposed to air
• Peroxides are shock-sensitive explosion hazards
To minimize risks:
• Purchase what will be used within the month
• Purchase Ethyl Ether that contains peroxide inhibitors such as BHT or ethanol
• Store away from heat and light
• Test for peroxide formation monthly after expiration
Less than 80 ppm peroxides
80 ppm to 400 ppm
Greater than 400 ppm
Solution is okay to use
Call the Chemical Waste Program for
packaging and removal
Call the Chemical Waste Program, who will
contact the Bomb Squad
26
Peroxide Forming Chemicals
• Many solvents can form
shock-sensitive peroxides over
time
Explosion was partially contained in
water bath, residue visible on rotovap
glassware
– Diethyl ether
– Isopropyl alcohol
– THF
• Friction, shock, or
concentration can cause an
explosion
– Graduate student at UC-Irvine
sustained cuts from exploding
glassware while concentrating
diethyl ether
“Lesson Learned” from University of California Irvine 2006
<http://www.ehs.uci.edu/salerts/Lesson%20Learned_Peroxide.pdf>
27
Peroxide Forming Chemicals
Ordering and Storage
• Only order the amount needed
for one month
• Label when first received and
when first opened
• Store away from light, ignition
sources, and oxidizers
• Test for peroxides every month
after listed expiration date has
passed
Department of Environmental Health and Safety Hazardous Chemical Waste Management
Guidebook, Section 5 “Waste Requiring Special Processing”
<http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec5.htm#pfc>
28
Peroxide Forming Chemicals
Testing for Peroxides
• Call DEHS if
– Crystals are present in or around
the container
– Container has a metal screw cap
– Container has been stored for more
than two years
• If the above are not present,
test with peroxide test strips
– Less than 80 ppm is okay
– Greater than 80 ppm, call DEHS for
disposal
http://www.conncoll.edu/offices/ehs/peroxide-forming-chemicals.htm
http://www.rhr-inc.com/bigcrys.htm
29
www.jst.umn.edu
Base Bath
Causes Chemical Burns
Example from a
Learning Experience Report (LER)
Base Bath
During working hours, a researcher removed glassware
from the base bath wearing wrist length nitrile gloves. The
basic solution went over the gloves and was trapped against
the skin causing severe chemical burns on the wrist.
The participate knew what do in the incident (10/10), and had
prior experience with the activity/technique (5/ 5).
To prevent incident:
1. Wear gloves that extend up past the wrist.
2. Use gloves made of a compatible material (like neoprene).
www.jst.umn.edu
31
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Aqua Regia
Aqua Regia
Materials and Methods: Aqua Regia is a mixture of concentrated nitric acid and
hydrochloric acid used clean glassware of trace contaminants.
If a milder reagent can accomplish the same task,
aqua regia is not recommended.
Prepare only the smallest amount needed.
Mix 1 part HNO3 with 3 parts HCl.
• In fume hood, add the HNO3 to a glass container. Then add HCl. Gently
swirl to mix. Pour acids from smaller containers, not from stock bottles.
Aqua regia should NEVER be taken out of the hood.
Slowly pour or pipet the aqua regia solution into the glassware to be cleaned.
Gently swirl or rinse with a flow from a pipet. Allow glassware to soak for
several minutes if solids do not readily dissolve.
www.jst.umn.edu
Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization
Aqua Regia
Waste Disposal Methods
Dilution and Neutralization:
1. Use secondary containment for Aqua Regia waste container that is free from
all organic chemicals/solvents.
2. Dilute used Aqua Regia with water by a factor of 7.5. In a beaker, SLOWLY
add the Aqua Regia to the full volume of water. Avoid overheating, and stir
solution on a stir-plate.
3. SLOWLY neutralize by adding sodium bicarbonate solution dropwise.
Periodically check the pH with pH paper (aiming for pH 6-9).
4. Allow solution to cool to room temperature before moving to the waste
container, capping the container, or transferring the solution.
Disposal: After the solution has cooled to room temperature, all liquid may be
added to the waste container labeled “Neutralized Aqua Regia Waste.”
www.jst.umn.edu
Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization
Aqua Regia
Required PPE: Goggles, lab coat, chemical-resistant gloves (18 mm neoprene,
Silver Shield, or any other glove rated to protect against hydrochloric AND
nitric acid). Face shield and acid-resistant apron are recommended if
working with a larger volume (>200ml).
Hazards:
• Strong oxidant – Keep away from organics
• Corrosive – Wear goggles, thick gloves, lab coat
• Acidic – Strong reaction with bases
• Off-gassing of toxic fumes
– Keep in the hood at all times and never stopper or store.
Hazard Response:
• Spill of <200 mL spent solution in hood: soak up with HazMat pads
• Spill outside hood or > 200 mL : evacuate and call DEHS
www.jst.umn.edu
Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization
www.jst.umn.edu
Acid Piranha
Acid Piranha Solution
Traditionally a 3:1 solution of sulfuric acid to 30% hydrogen peroxide (v:v)
•
•
•
•
•
Highly exothermic
Acid piranha will melt plastics,
and the oxidative reaction is
accelerated by water, acid, and
base
Do not generate excess piranha
or cap your solutions!
Only use in a well ventilated
hood
Slowly add peroxide to acid
directly in the glassware to
avoid uncontrolled reactions
Glassware must be
cleaned and dried prior
to use!
www.jst.umn.edu
http://blink.ucsd.edu/safety/research-lab/chemical/specific/piranha.html
http://www.cmu.edu/ehs/fact-sheets/piranha-solution-handling.pdf
Piranha MUST be neutralized
or manifested separately due to
reactivity with organic molecules.
www.jst.umn.edu
Don’t mix
bleach and ammonia
38
Hazards of Mixing Bleach and Ammonia
When ammonia and bleach are mixed, this chemical reaction occurs:
NaOCl (bleach) + NH3  NaOH + NH2Cl
• NH2Cl (chloramine fumes) are hazardous when
concentrated
• Intermediate products include HCl and chlorine gas
• Biggest hazard is inhalation
• If mixed, leave the area and ensure good
ventilation before returning
Helmenstine, A.M. “Mixing Bleach and Ammonia: Chemical Reactions from Mixing Bleach and
Ammonia” About.com Chemistry.
<http://chemistry.about.com/od/toxicchemicals/a/Mixing-Bleach-And-Ammonia.htm>
39
www.jst.umn.edu
Palladium on Carbon
is a flammable solid
Example from a
Learning Experience Report (LER)
Pd/C
During working hours, method vapor was ignited in the presence
of a Pd/C catalyst used during a hydrogenation.
No injury resulted.
The participate knew what do in the incident (10/10), and had
prior experience with the activity/technique (5/ 5).
To prevent incident: See Pd/C Safety moment for more detail
1. Add catalyst to reaction vessel under an inert atmosphere.
2. Then add solvent slowly under inert gas.
3. Dispose of Pd/C in special waste bottle with water present.
www.jst.umn.edu
41
Pd/C Explosion
At another university,
a fire was started by a
bottle of Pd/C
disposed of in a plastic
waste container in the
lab.
Luckily, the fire did
not spread beyond the
trash receptacle and it
resulted in no injuries.
www.jst.umn.edu
Improper handling of waste lead to disaster. April 2012 Newsletter, U
W-Madison, Office of Chemical Safety.
Http://www.ehs.wisc.edu/chem-issue1Volume2-improperhandlingchems.htm
42
www.jst.umn.edu
Pd/C and Hydrogenation
Pd/ C Hydrogenations
• Danger comes from the active catalysts
–
–
–
–
Absorb hydrogen gas
Can spark spontaneously and may ignite on exposure to air
Readily causes ignition of flammable solvents in the presence of air.
Use in presence of H2 gas, sometimes at high pressure and temp.
– In the event of fire, contain it with water
• Types of Catalysts
– Degussa – safest
– Wet – safer. Higher % of water
– Dry
www.jst.umn.edu
Perry, David. Hazards in Hydrogenation.
http://chemicalspace.wordpress.com/2010/07/27/hazards-in-hydrogenation/
Do not
operate near
flammable
materials
Pd/ C Hydrogenations
• Correctly done, these reactions can be routinely run safely
– Weigh and add catalyst first
– Flush vessel with nitrogen. Handle Pd/C under inert atmosphere.
– Add solvent. (Degas solvent with large scale > 100 mL)
Use ethanol, not methanol (very flammable, invisible flame)
– Flush reaction vessel with N2 , run reaction, repeat flush with N2
– Remove Pd/C through filtration (celite on glass frit), and cover with wet sand.
Filter cake should never be allowed to dry, and the moist material should be added to a
large quantity of water and disposed of properly.
– Dispose of waste in dedicated container that contains water.
• Know how to use the equipment
– Don’t over-pressurize
– Don’t use damaged equipment or glassware.
www.jst.umn.edu
Prudent Practices in the Laboratory: Handling and Disposal of Chemicals
Laboratory Chemical Safety Summary: Palladium on Carbon
Pd/C
According to Prudent Practices in the Laboratory,
palladium on carbon catalysts
containing adsorbed hydrogen are pyrophoric,
particularly when dry
and may ignite on exposure to air
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46
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Mercury Spill
From a broken thermometer
Broken Mercury Thermometer
A.
If Hg droplets or pools are observed:
1.
2.
3.
4.
B.
Isolate spill area and do not walk through the area
Call DEHS: 612-626-6002/ 9-1-1 after hours
Leave any shoes or clothing contaminated with Hg droplets aside for cleaning
A specialized staff will come to monitor, decontaminate and cleanup
If Hg spills on a heated surface (hot plates, ovens)
1.
2.
C.
Turn off equipment and evacuate the lab.
Call DEHS: 612-626-6002/ 9-1-1 after hours
If a Hg thermometer bulb is cracked:
1.
2.
Seal in plastic bag and dab immediate area with a wet towel and add to plastic bag.
Manifest as Hg-containing waste
D. Accidental releases (drain, soil, trash)
1.
Report to DEHS
www.jst.umn.edu
http://www.dehs.umn.edu/hazwaste_mercthemom.htm
Broken Mercury Thermometer
Prevention:
Use the free Hg thermometer exchange program through DEHS:
http://www.dehs.umn.edu/hazwaste_mercthemom.htm
• One to one exchange of Hg thermometers for non-mercury
thermometers
• Non-mercurcy thermometers are suitable for temperatures up to
260°C
• If Hg thermometer is absolutely necessary, use a teflon coated
Hg thermometer
www.jst.umn.edu
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Chromium Reagents
H2CrO4, CrO3, PCC, PDC, CrO2Cl2
Finding alternatives is highly encouraged!
Hazards of Cr Reagents
• Inhalation => breathing difficulties,
gastrointestinal and neurological effects.
• Dermal exposure => skin burns.
• Cr(VI) is more toxic than Cr(III).
• Cr(VI) is carcinogenic => lung cancer upon
inhalation
• 3 – 4 mg could be fatal!!!
www.jst.umn.edu
Clinical Toxicology Jan 1999, Vol. 37, No. 2: 173–194
Read More: http://informahealthcare.com/toc/ctx/37/2
51
Handling Cr compounds
• Use Cr compounds only after proper training
and approval by your PI.
• Use only in fume hood.
• Use cotton lab coat, gloves, face mask and
goggles.
• Work with low hood sash.
• Store separately from oxidizers, strong acids or
bases.
www.jst.umn.edu
52
Spills, Waste & Clean-up
• Have a separate, designated Cr waste bottle(s).
– Dispose contaminated gloves/clothing/paper towels in
appropriate Cr waste.
• Contain spills inside hood with
sand/vermiculite.
• Wipe up and dispose in designated waste bottle.
• For large spills outside hood, vacate lab and
contact DEHS.
• Make sure to remove Cr residues from glassware
before cleaning them.
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53
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Working with H2S
Hydrogen Sulfide Safety
• What is H2S?
– Colorless (transparent) gas
– Heavier than air and tends to accumulate in low-lying areas
– POISONOUS = PARALYZE THE BREATHING SYSTEM/CAN
KILL IN MINUTES!!!!!!!!
– Highly toxic and Very corrosive
– Rotten Egg – smell
www.jst.umn.edu
55
Hydrogen Sulfide Safety
P.E.L. = Permissible Exposure Limit
Defined as the maximum concentration you can be exposed to in an 8hour period, 40 hours per week, without respirator problems.
P.E.L. FOR H2S: 10ppm
S.T.E.L. = Short-Term Exposure Limit
Based on a 15-minute time period
S.T.E.L. FOR H2S: 15ppm
I.D.L.H. = Immediately Dangerous to Life and
Health
I.D.L.H. = 100ppm and above
www.jst.umn.edu
Hydrogen Sulfide Safety
• Effects of H2S
– Target Organs
• Olfactory nerves, lungs, eyes, brain, respiratory control
– Entry into the body
• Ingestion, injection, skin absorption, inhalation
– Symptoms
•
•
•
•
Respiratory irritation, coughing
Headache, dizziness, fatigue
Burning eyes, sore throat
Loss of sense of smell
www.jst.umn.edu
57
Hydrogen Sulfide Safety
• Monitoring in
Amundson 381
Personal
monitor
Wall-mount
monitor
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Hydrogen Sulfide Safety
• H2S Adsorption setup
www.jst.umn.edu
www.jst.umn.edu
HF
HF Safety
•
HYDROFLUORIC ACID IS one of the
MOST ACUTELY TOXIC CHEMICALS
•
There is no concentration of HF which
can be relied upon as safe!
As little as 7 ml of anhydrous HF in
contact with the skin untreated can bind
all the free calcium in an adult
•
•
With burns involving greater than 25
square inches significant and sometimes
fatal hypocalcaemia can occur
•
There is no material that is completely
resistant to HF degradation
www.jst.umn.edu
• Baird D. and Cooper C., “Hydrofluoric Acid
Safety”, Fermilab.
HF Safety
PROPERTIES
• Colorless liquid with strong irritating odor
• Very strong corrosive inorganic acid
• Nonflammable
How Is HF Different from other acids?
• HF is readily absorbed into skin binding to calcium and
magnesium in the body to form insoluble salts that interfere
with cellular metabolism causing cellular death and necrosis
– Immediate necrosis and pain at high concentrations
www.jst.umn.edu
Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
62
HF Safety
EXPOSURE
• Liquid exposure (splash)
• Gas exposure (lungs, skin & eyes)
–
–
–
–
–
Severe burns
Opacification of cornea
Blindness
Coughing/Choking
Cyanosis (blue lips)
Worker Airborne Exposure Regulations
• Irritation to nose and throat at 3 ppm
• Short-term exposure limit 15 min - 2 ppm
• 30 ppm is considered immediately dangerous to life and health
www.jst.umn.edu
Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
63
HF Safety
SAFE WORK PRACTICES
• Never use HF alone
• Training
• Always Wear Personal Protective Equipment
• Documentation & Signs
• Always use HF in the lab hood
www.jst.umn.edu
Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
64
HF Safety
PPE
•
•
•
•
Neoprene gloves (Resistant for more than 8 hours)
Saranex coated coveralls
Face shield
Foot protection
www.jst.umn.edu
Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
65
HF Safety
EMERGENCY PROCEDURE
• Do not panic! Think Think Think
• Assistant response
– Help individual to eyewash/safety shower flush the area with
large amounts of water for 5 minutes. Have the person remove all
contaminated clothing while under the shower.
• DO NOT CONTAMINATE YOURSELF
• HF first aid treatment is not limited to washing
off the skin (Calcium Gluconate Antidote).
www.jst.umn.edu
Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
66
www.jst.umn.edu
Radioactivity
An introduction for the non-user
Overview of Radioactive Decay
Nucleon emission
Alpha decay: 238U to 234Th
Beta decay
e- emission: 14C to 14N
Nuclear Transition
gamma ray: 125I* to 125I
www.jst.umn.edu
Common Radioactive Isotopes
Radioactive material are used for a variety of
applications in chemistry.
Most common radioisotopes used in chemical biology
3H:
Organic molecules
14C: Organic molecules
35S: Proteins
32P/33P: Nucleic acids
125I:
Protein modification
18F:
FDG
www.jst.umn.edu
Radioactive Materials and You
What you should do to minimize exposure
Understand universal signs for radioactivity
Radioactivity is detected using survey meters
or wipe testing/scintillation counting
Avoid direct contact with radioactive materials
If a spill occurs, alert DEHS
www.jst.umn.edu
www.jst.umn.edu
TLD Rings
Thermoluminiscent dosimeters
• A must for anybody working with radiation sources
• Rings contain a radiation sensitive lithium fluoride crystal
• Exposure to radiation energizes electrons and traps them
in an excited state
• Upon heating excited electrons fall back to the ground
state and release visible photons
• Luminiscence is used to determine radiation dose
TLD rings DO NOT protect you from radiation!!!
www.jst.umn.edu
http://web.princeton.edu/sites/ehs/dosimeter/dosimetryinfo.htm
72
Safe practices
• ALWAYS wear a TLD ring when working with xray equipment at the CharFac
• NEVER leave a TLD ring inside the safety
enclosure
• NEVER take a TLD ring outside the x-ray facility
• AVOID using multiple rings
www.jst.umn.edu
www.jst.umn.edu
Naphthalene
Safety Moment
Naphthalene
Flammable
solid
Flash Point
79 °C
(174.2 °F)
Acute oral
toxicity
Respiratory
hazard
Suspected of causing
cancer.
LD50 Oral
(rat)
490.0 mg/kg
LC50 Inhalation
(rat)
> 340 mg/L
1h
Aquatic toxicity
Very toxic to
aquatic life
LC50
(trout)
0.9 - 9.8 mg/L
96 h
Safety Moment
Naphthalene
Exposure Routes: inhalation, skin absorption,
ingestion, eye contact
Symptoms: irritation, headache, confusion, nausea,
vomiting, abdominal pain, irritated bladder…
Best practices:
 Ensure adequate ventilation and avoid breathing vapors
 Handle with gloves to prevent contact with skin.
 Wash skin thoroughly after handling.
 Store away from heat/sparks in dry and well-ventilated place
 Avoid release to the environment
 Do not put down the drain
Naphthalene SDS, Sigma Aldrich.
http://www.sigmaaldrich.com/catalog/product/aldrich/185604?lang=en&region=US
Naphthalene, NIOSH Pocket Guide to Hazardous Chemicals, Center for Disease Control.
http://www.cdc.gov/niosh/npg/npgd0439.html
www.jst.umn.edu
Benzene
Benzene
Colorless liquid with sweet scent often produced from petroleum
Flammable (flashpoint below 37.8 °C)
Carcinogenic, reproductive toxin
Toxic, skin irritation and burns
Extremely toxic to aquatic life
www.jst.umn.edu
http://www1.uwindsor.ca/chemicalcontrol/system/files/safety_programs/chemical/
http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/benzene.html
Benzene
Incompatible with:
Decomposes to:
Halogens
Oxidizing agents
Flame/heat
Nitric acid
Aldehydes
Carbon
monoxide
Carbon
dioxide
Benzene may retain static charge, which could spark and ignite own vapors
Ground benzene containers and all equipment
Keep in fume hood, use PVA glove (Viton gloves with large amounts)
www.jst.umn.edu
http://www1.uwindsor.ca/chemicalcontrol/system/files/safety_programs/chemical/
http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/benzene.html
Hazardous Waste
www.jst.umn.edu
www.jst.umn.edu
Chemical Waste
An Introduction
Chemical Waste
You can be held criminally liable for
misrepresenting the contents of your waste
and improper disposal.
So, learn about the chemical.
• Online Chemical Waste Registry
– http://www.dehs.umn.edu/hazwaste_chemwastereg.htm
 DCC code
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
82
Chemical Waste
DCC (Drum Designator Code):
Hazard class code
•
•
2 numbers and 2 letters
##XX
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
Disposal type code
Chemical Waste
DCC (Drum Designator Code):
2 numbers and 2 letters
##NH
If disposal code is NH,
then the chemical can be disposed of as nonhazardous waste
(trash or sink).
Complete form (Permission to dispose by trash
or sewer) before disposing
http://www.dehs.umn.edu/PDFs/disposal.pdf
If a chemical does not have the "xxNH" nonhazardous designation, then
it is considered hazardous and must not be disposed of by evaporation,
sewer or trash.
•
•
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
Disposal type code
Chemical Waste
DCC (Drum Designator Code):
Hazard class code
For all hazardous chemicals (not ##NH)
- Segregate by hazard class code (##)
- Liquids (with secondary containment)
- Solid waste containers.
Keep ‘em separated:
-
•
•
Acids and bases
Flammable liquids, organic peroxides, and oxidizers.
Oxidizers (chlorates, permanganates, peroxides,
nitrates) separate from organic materials.
Water-reactive, not with water
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3
Chemical Waste
Properly label the bottles
1. Attach the label with start date to the bottle as
soon as the bottle is started. Add fill date when
bottle is full.
2. Keep track of what is added. All solvents,
including water in solutions and sludges, must
be recorded. The ledger must be kept next to the
container.
3. Bottles must be kept capped and stored in
secondary containment.
4. When submitting for disposal, the following
information must be recorded on both the label
and waste packing form: components and their
percentages, pH, presence of precipitate.
•
•
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3
x
Chemical Waste
What is wrong here?
No covers!
www.jst.umn.edu
Hazardous Waste Disposal
Hazardous Waste
- Unwanted chemical that exhibits ignitability, corrosivity, reactivity,
lethality, or toxicity
- UMN Chemical Waste Registry used to evaluate chemicals
- Find online
Common chemical
DDC
CAS Number
EPA Code
Acetone
08BS
67641A
U002,D001,F003
Water
NONE
7732185A
None
Diethyl ether
08PF
60297A
U117,D001,F003
Methanol
08BS
67561A
U154,D001,F003
Probucol
Phenytoin
05SO
05SO
23288495A
57410B
None
None
Contaminated glassware
05SO
UOFM147A
None
www.jst.umn.edu
University of Minnesota DEHS: Chemical Waste Registry Searchable Database.
<http://www.dehs.umn.edu/hazwaste_chemwastereg.htm> (accessed Jan 22, 2014)
89
Waste Destination
• Collected waste to University’s Thompson Center for
Environmental Management (TCEM) for recycling,
redistribution, storage, treatment, and disposal.
• TCEM processes approximately 600,000 lbs of hazardous
waste annually
• Research site for pollution prevention
• Located on the Twin Cities campus
www.jst.umn.edu
University of Minnesota: Chemical Waste Facility.
<http://www.dehs.umn.edu/hazwaste_thompsoncntr.htm> (accessed Jan. 22, 2014).
90
www.jst.umn.edu
Chemical Waste
How full is too full?
An explanation of the reason why…
Chemical Waste
How full is too full?
Too much!
Dump some out.
Just Right
Chemical Waste
How full is too full?
• The reason why: if liquid fills the bottle up to the
neck, there will be little room for expansion.
• If temperature increases, the liquid will expand.
• It has happened: one summer on a hot day the
air-conditioning went down and a waste bottle of
THF shattered when the liquid expanded.
www.jst.umn.edu
Chemical Waste
How full is too full?
So never fill
liquid above the
wide portion of
the bottle!
Chemical Waste
Common Chemical Collection and Packaging Problems
•
Chemicals not labeled
•
Incomplete information on labels and waste packing forms, e.g., contents descriptions,
percentages, pH, and amounts
•
Chemical names and descriptions on waste packing form do not match those on container
labels
•
Some containers are not listed on forms
•
Hazardous liquid containers packed on their side
•
Bottles not tightly capped
•
Incompatible chemicals packed together
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3
www.jst.umn.edu
Empty Chemical Containers
What should I do with it?
Is it empty?
Empty Chemical Bottles
• Cross out chemical name
• Write EMPTY on the bottle
Next, learn more about the chemical.
• Online Chemical Waste Registry
– http://www.dehs.umn.edu/hazwaste_chemwastereg.htm
 EPA number
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
97
Empty Containers
EPA (Environ. Protection Agency) Number
Primary hazard of a chemical
If Uxxx
or Pxxx, then:
- Submit the empty container
as hazardous waste.
- Preferred method
- OR triple rinse the container,
keep all rinses as hazardous
waste, and dispose of
container as non-hazardous.
- Not preferred
- Generates more waste
www.jst.umn.edu
Empty Containers
For all other chemicals:
- Allow liquids to fully evaporate in fume hood.
- Dispose of remaining solids
- (hazardous or non-hazardous waste,
depending on chemical)
- Dispose of container as non-hazardous waste
 Recycling or trash
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
99
Empty Containers
• Examples
Uxxx chemical,
container is
hazardous waste
c
c
•
•
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
Container is
non-hazardous
waste
Is it “Empty”?
• If a trace (< 3 % ) of the chemical remains, the
bottle is empty.
– Dispose of container as non-hazardous waste
 recycling or trash
– Remember that Uxxx and Pxxx chemical containers should be
submitted as hazardous waste.
www.jst.umn.edu
UofM, DESH
http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm
10
1
Where to put empty bottles?
Plastic containers
www.jst.umn.edu
Location of boxes for empty bottles: ___________
Glass containers
Good and Bad Examples
TPABr solid, D002
HF Acid,
U134, D002
×
Label as Empty
×
TPAOH, D002
×
Unknown
U-listed chemical
 submit bottle as
hazardous waste
www.jst.umn.edu
Biohazard Waste
Biohazard Waste
Place needles in the
sharps containers
Biological solutions should
be treated with 10% bleach
for 30 minutes
Solid waste should be
stored in autoclave bags
until autoclaving
www.jst.umn.edu
10
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www.jst.umn.edu
Pharmaceutical Waste
Evaluating Pharmaceutical Wastes
www.jst.umn.edu
Reference: Minnesota Pollution Control Agency, 2012.
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General Chemical Information
www.jst.umn.edu
www.jst.umn.edu
MSDS vs. SDS
What’s the difference?
Safety Data Sheets
“Hazard Communication Standard has been revised by OSHA to align
with the Globally Harmonized System of Classification and
Labelling of Chemicals (GHS)”
• There were many acceptable MSDS formats
• Now the GHS format has 16 sections in a
set order (very similar to the ANSI
Standard 16 section MSDS commonly
• used in the U.S.)
• Visit MSDSonline.come to see an
ordered list of sections
www.jst.umn.edu
http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/
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MSDS  SDS Transition
• Expect to get a mixture of MSDS and SDS
formats from manufacturer until transition
complete
– Dec. 1, 2013- employees trained to read SDS and GHS labels
– June 1, 2015- chemical manufacturers/distributors start
shipping with only GHS format
– Dec. 1, 2015- only GHS formats shipped
– June 1, 2016- Employees fully compliant with HazCom 2012
(Hazard Communication revised 2012, new OSHA standards)
www.jst.umn.edu
http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/
111
Recommendations
• Best practice for the transition:
1. Designate a group handler of GHS transition
2. All group members check for updated
SDS when shipments arrive
3. Establish system to compare SDS to MSDS
for new hazards
4. Train all group members to read SDS,
especially hazards in Section 2
5. Archive MSDS until all converted to SDS
• Digital MSDS system can make the transition easier
6. Make any safety changes to accommodate new hazards
www.jst.umn.edu
http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/
http://compliance.safetysmart.com/
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www.jst.umn.edu
Know your hazards
An overview of chemical hazards and
the associated pictograms
Physical Hazards
Flammable
liquid, gas
solid
Oxidizers
gases, solids, liquids
Also can denote:
Pyrophorics, Emits flammable gas, and Self reactive
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Physical Hazards
Explosives
Gases
under pressure
Also can denote:
Self reactives and organic peroxides
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Corrosives
Physical Hazards
Pyrophoric
Organic
Peroxides
(spontaneously
combustible)
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Reactive
with Water
(emit flammable
gases when wet)
Health Hazards
Acute Toxicity
Carcinogen
Irritant
(severe)
Respiratory Sensitizer
Dermal
Sensitizer
Reproductive Toxin
Narcotic Effects
Organ Toxicity
Mutagenicity
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Health Hazards
Acute Oral Toxicity Categories
The pictogram, signal words, and hazard statements on chemical
labels are defined by the median lethal dose (LD50) of the chemical.
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Environmental Hazards
Environmental
toxicity
Marine
pollutant
www.jst.umn.edu
OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
http://www.osha.gov/dsg/hazcom/ghs.html#4.2
Ozone
depleting
Hazard Diamond
for labeling chemical containers
www.jst.umn.edu
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A quiz:
What does each symbol signify?
www.jst.umn.edu
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A quiz:
What does each symbol signify?
Toxic
Flammable
Irritant
Oxidizer
Carcinogen
Environmental
(and Respiratory
Sensitizer)
Hazard
Explosive
Corrosive
www.jst.umn.edu
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www.jst.umn.edu
“Chemicals of Interest”
Collaborating with DEHS for the proper acquisition,
use, and disposal of drugs of abuse, explosive
compounds, known chemical warfare agents, precursors
to these compounds, and various toxic gases
What are “Chemicals of Interest”?
• Drugs of abuse, explosive compounds, known chemical warfare
agents, precursors to these compounds, and various toxic gases
• DEHS has comprised a list of these compounds available as a pdf
document at: www.dehs.umn.edu/PDFs/chemical_poster.pdf
• These compounds MUST be purchased only through UStores and
CANNOT be purchased using a P-card
• DEHS MUST also be notified if you intend to purchase any of these
compounds
• Depending upon the quantity you wish to purchase various federal
agencies such as DHS or DEA must also be notified
www.jst.umn.edu
When do the federal agencies get notified?
• If you purchase a quantity that exceeds the Screening
Threshold Quantity(STQ) for the compound established
by the Dept. of Homeland Security (This will mainly
apply to chemical warfare agents and explosive
compounds)
• If you purchase a compound that requires a federal
license to possess(This will mainly apply to drugs of
abuse)
www.jst.umn.edu
Why do federal agencies get notified?
• Due to the nature of most of the compounds in the list,
federal agencies are required to verify that the purchaser
has a valid license to possess the compounds and proper
security to store the compounds(e.g. a safe bolted to the
floor)
• DEHS should be able to provide you with the compounds
and the quantities that require a license(STQ) and/or
notification to the federal agency
www.jst.umn.edu
Working with DEHS
• Notify DEHS of the compounds and quantities you wish
to purchase
• Review the MSDS for each compound to determine the
appropriate PPE and notify DEHS
• DEHS will provide you with any further requirements to
handle these compounds
www.jst.umn.edu
Take Home Message
• Keep DEHS Informed if you are planning to use any of
the “chemicals of interest”
• If these chemicals are available as reference standards,
purchase them instead of the undissolved compound
• Read the MSDS
www.jst.umn.edu
Important Points of contact
• Questions about “Chemicals of Interest”:
– Brian Brosnan bros0020@umn.edu
• DEHS CHEM/CEMS Dept. contact:
– Anna Englund
www.jst.umn.edu
engl0131@umn.edu
www.jst.umn.edu
SDS Required for Shipping
Synthesized Products
In the News
• Alfa Chemistry allegedly shipped pints of
acrolein without Safety Data Sheets
– Particular hazardous chemical is prohibited on planes and was
shipped via FedEx cargo flights
• Federal Aviation Administration (FAA) proposed
$325,000 fine
www.jst.umn.edu
Long Islang Newsday webpage. Accessed April 7, 2014 <http://www.newsday.com/business/faa-urgesfines-against-stony-brook-chemical-company-for-2-shipments-of-hazardous-material-1.7574578>
13
1
Shipping Requirements
OSHA shipping requirements:
1. Include SDS
- If material is novel or not fully characterized, include all know
information such as starting materials and predicted hazards
- Also include emergency handling and contact information
2. No amount is too small to be exempted from
requirements
3. SDS not required if materials are not being
publicly shipped
www.jst.umn.edu
OSHA webpage. Accessed April 7, 2014
<https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=INTERPRETATIONS&p_i
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d=24782>
2
Available Resources
www.jst.umn.edu
DEHS Contact
Anna Sitek (Englund)
E-mail: engl0131@umn.edu
Phone: (612) 625-8925
Office W-147 Boynton
Research Safety Specialist assigned to our department, and
newly-created DEHS safety contact for our entire college.
She will serve as a member of our department Safety
Committee and will work with the JST.
Feel free to contact her with any questions!
www.jst.umn.edu
www.jst.umn.edu
JST website
www.jst.umn.edu
Dow Safety Academy
http://safety.dow.com/
www.jst.umn.edu
www.jst.umn.edu
1
www.jst.umn.edu
Have a safety moment?
Contribute it to this collection.
Send safety moments to jst@umn.edu
with Safety Moment <topic> in the subject line.
Please put content in the provided template
and cite reliable, credited sources.
Thank you!
www.jst.umn.edu
www.jst.umn.edu
Templates
www.jst.umn.edu
www.jst.umn.edu
Safety Moment Title
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www.jst.umn.edu