Chemical Awareness and Safety

1
Chemical Awareness and Safety
2
Chemical Hygiene Plan

• Marshall University has one
• Available on Safety Health web site
• www.marshall.edu/safety/chemical
• Each lab should have a lab-specific one
• Referencing University CHP
• Include lab-specific procedures and hazards
• Chemical spill information and small spill
  cleanup procedures, reporting information

3
Training

• Does your lab have a custom Chemical Hygiene Plan
  with lab-specific hazards addressed?
• staff and students must be trained on this
  information upon hire and annually thereafter
• Do you know the location of the nearest
• fire alarm pull stations
• fire extinguisher
• eyewash and emergency shower
• route of emergency exit from lab AND office
• MSDS book and internet resources
• chemical spill cleanup equipment

4
Chemical Spills

• Can you answer YES to all of these questions?
• If so, it may be safe to clean up the
  spill
• Do you know what chemical was spilled?
• Do you know hazards of spilled chemical?
• Do you have a chemical spill kit?
• Can you protect yourself from the hazards?

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Chemical Spill Response

• In the event of any hazardous chemical spill, or
  a non-hazardous spill in excess of 1 liter
• Remain Calm
• Avoid breathing vapors or fumes
• Activate fire alarm to evacuate building if
  chemical is a respiratory hazard
• Notify MUPD at 6-4357 then Safety at 6-3461
• Provide chemical name and quantity if possible
• Secure the spill location to prevent others from
  entering until MUPD or Safety arrive

6
Chemical Spill Response

• If spill is flammable, turn off ignition and heat
  sources
• Try to contain the spill if possible
• Do not risk injury to do these tasks
• If personnel were exposed, move to safe location
  and flush with copious amounts of water (at least
  15 minutes)
• If spill on clothing, remove all clothing in
  emergency showerthis is no time for modesty

7
Small Chemical Spill

• A small spill
• less that 1 liter of a non-hazardous chemical
• NO hazardous chemicals
• can be cleaned up by lab personnel
• contact Safety Health for assistance if
  necessary
• Steps for Clean Up
• use personal protective equipment
• stop source of leak
• neutralize acids/bases
• contain spill with paper towel, kitty litter,
  etc.
• contact Safety Health to report incident and
  for waste disposal

8
Fire Safety

• Fire Extinguishers
• Always activate building alarm first!
• Most common type on campus is red class ABC
• Some labs equipped with CO2
• Library and dorms have water in silver class A
• Only attempt to extinguish small fires that you
  feel comfortable fighting
• Keep an exit at your back and fire in front
• Use appropriate extinguisher for the type of fire
• Label indicates approved uses

9
Fire Safety

• Remember the word PASS
• Pull the pin
• Aim the extinguisher nozzle at the base of the
  fire
• Squeeze the handle
• Sweep the nozzle from side to side
• Only have media enough for about 10 seconds of
  operation
• Should be 8-10 feet from fire, moving closer as
  flames go out or away if not

10
After an Emergency

• Must submit a report after any significant event,
  even if no injury occurs, so that we can track
  close calls and minor problems
• Employee Incident, Injury, Illness Report Form
• Student and Visitor Incident, Injury, Illness
  Report Form
• Biohazard Spill Occurrence Form
• Fill out as much information as possible
• Before an incident, you can report a safety
  concern on the Safety Health web site

11
Who is Responsible for Chemicals?

• Before purchasing decisions are made
• Are there less hazardous alternatives?
• When hazardous materials must be used, proper
  management is critical
• Starts with chemical procurement
• Proceeds to safe work procedures
• Storage and handling
• Ultimately, waste disposal

12
Ordering Chemicals

• Prepare orders early and thoughtfully.
• Only order the amount of product that you can use
  in a reasonable time.
• Bigger is NOT cheaper in the long run!
• Check to see if recycled solvents are available.
• Review hazards of chemical(s)
• Is special PPE required, and available?
• Is special storage required?
• Is space available?
• Is it a time-sensitive chemical that must be
  disposed after a particular time frame?

13
Time-Sensitive Chemicals
A Lifecycle Issue Chemicals that are stored
beyond their safe shelf-life present a hazard to
faculty, staff, and studentsbut thats not
all. Disposal is expensive because of the threat
of explosion, and the added precautions that must
be taken.
Here Calcium carbide reacted with copper in the
metal lid forming acetylene gas (note the bulging
lid), a potentially explosive situation!
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Chemical Management

• Infrastructural
• Storage cabinets
• Corrosives
• Flammables
• Chemical fume hoods
• Report hoods that arent working
• Institutional
• Purchasing practices
• Buy least amount necessary, not bulk
• Storage handling practices
• Annual inventory
• Date time-sensitive chemicals on receipt
• Secondary containment for all liquids
• Transport in chemical carrier or on cart
• Process
• Chemical use
• Less hazardous whenever possible
• Waste disposal
• Contact Safety Health

15
Storage cupboards and safety cabinets are
excellent, but there are too many chemicals
stored on counters here. Must eliminate cluttered
work spaces.
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Hazard Identification

• What do I Need to Know about a chemical?
• What kind of hazard(s) does it present
• What is the route of exposure
• Does the dose represent an acute or chronic
  exposure
• how much am I working with
• and for how long?

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Hazard Identification

• Where Do I Get the Information?
• Container label
• target organs, hazards, warnings
• Material Safety Data Sheets (MSDS)
• Internet search resources at http//www.marshall.e
  du/safety/chemical/msds.asp
• Manufacturer or Distributor
• Lab TA or Supervisor
• Safety Health (6-3461)
• COS Chemistry Stockroom and/or Lab Manager

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Material Safety Data Sheets (MSDS)

• Each University department is responsible for
  maintaining an available record of hazardous
  chemicals
• Useful sections
• 3. Hazards identification
• 4. First-aid measures
• 6. Accidental release measures
• 7. Handling and Storage
• 8. Exposure controls/personal protection
• 10. Stability and reactivity
• 11. Toxicological information
• Must be kept for 30 years after use discontinued

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Labeling

• Must give full chemical name in English
• ALL containers must be labeled with their
  contents and hazards
• Only secondary containers used the same day are
  permitted to not be labeled
• Mixtures include percent by component
• Date time-sensitive chemicals upon arrival
• Peroxide-forming chemicals labeled and dated
  according to guide
• Management of Peroxide-Forming Chemicals

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HMIS vs. NFPA Label
1

4 3 2
3
0
OX W
A-K

• For Employee Safety
• Generally more protective (higher numbers)

• For First Responder Safety
• Every lab entry door should be labeled

• Hazard ratings info can be obtained from the MSDS
• On a scale of 0 to 4

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Chemical Storage

• Store chemicals according to hazard class
• acids must be stored away from bases and
  flammables
• Review storage guidance documents on Safety and
  Health web site
• Hazardous Chemicals of Concern List and Storage
  Guide
• Quick Guide to Chemical Compatibility
• Flammable gases must be 20 ft from oxidizers
• Place spark or flame generating
• equipment away from flammables
• Fluids stored in secondary
• containment trays

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Chemical Storage

• Some manufacturers/suppliers (Fisher,
  Cole-Parmer, Davis) provide their own hazard
  coding storage system - ChemAlert
• RED (R) Flammable. Store in area segregated for
  flammable reagents.
• BLUE (B) Health hazard. Toxic if inhaled,
  ingested or absorbed through skin. Store in
  secure area.
• YELLOW (Y) Reactive and oxidizing reagents. May
  react violently with air, water, or other
  substances. Store away from flammable and
  combustible materials.
• WHITE (W) Corrosive. May harm skin, eyes, mucous
  membranes. Store away from red-, yellow- and
  blue-coded reagents.
• GRAY (G) Presents no more than moderate hazard
  in any of the other categories. For general
  chemical storage.
• Reagents in same color bar not compatible,
  store separately.

STOP
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Storage Segregate Incompatibles
Mix these and flaming acid will result.
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Chemical Compatibility
--- Corrosives ---
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Hazard Labeling
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US DOT Hazmat Placards
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Chemicals that Pose Exposure Hazards

• Health Hazard (benzene, chloroform)
• Carcinogens cause cancer in humans or animals
• Includes mutagens, teratogens, target organ
  toxicity
• Acute Toxics (ethidium bromide, mercury)
• Severe - causes death or disease at these
  concentrations
• Corrosives (sulfuric acid, sodium hydroxide)
• a substance that causes visible destruction or
  irreversible alteration of living tissue or
  metals
• DOT - pH lt2 or gt12.5
• In lab can use pH lt4 or gt9 for added safety

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Acids

• Always pour acid into water, not the reverse.
• Strong acids require rubber aprons.
• Store on lower shelves, preferably in a corrosive
  cabinet.
• Spills from poor transfer and housekeeping will
  corrode metal surfaces and equipment, and can
  lead to chemical burns.

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Bases

• Skin contact is potentially more dangerous than
  acids.
• Bases do not coagulate protein like acids
  (impeding penetration), resulting in deeper
  tissue penetration before it is apparent and
  causing severe, slow-healing burns.
• Inhalation of high concentrations can cause
  delayed, severe pulmonary edema.
• Appropriate gloves and chemical splash goggles
  should be worn when pouring bases.

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Chemicals that Pose Exposure Hazards

• Irritant (ammonia, sodium hydroxide)
• a substance that causes reversible inflammatory
  effect on living tissue
• Sensitizer (latex, formaldehyde)
• a substance that causes an allergic reaction on
  the skin or respiratory system
• usually happens after repeated exposures

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Chemicals that Pose Physical Hazards

• Flammable Liquid (acetaldehyde, ethanol)
• presents exposure hazard also because of
  volatility
• flash point below 100 oF
• Must be stored in Flammable Materials Cabinet
• Flammable Solid (magnesium, sulfur)
• a solid that can ignite through friction,
  absorption of moisture, or when ignited burns so
  vigorously it creates a serious hazard
• require chemical-specific fire extinguisher
  Class D
• Combustible (acetic acid, phenol)
• flash point above 100 oF and below 200 oF

34
Chemicals that Pose Physical Hazards

• Water Reactive (sodium, potassium)
• a chemical that reacts with water to release a
  gas that is either flammable or presents a health
  hazard
• Oxidizer (nitric acid, permanganate)
• a chemical that promotes the combustion of other
  materials by releasing oxygen when heated
• Explosive (known TNT, potential picric acid)
• a chemical that causes sudden release of
  pressure, gas, and heat when subjected to sudden
  shock, pressure, or high temperature

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Routes of Exposure

• Inhalation
• Work in fume hoods,
• especially with volatile chemicals
• Absorption
• Employer responsible to provide and ensure use
• Make sure PPE is appropriate for hazard
• Injection
• Ingestion
• No eating, drinking, applying makeup in labs

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Acute vs. Chronic Hazards

• Acute (ammonia, sulfuric acid)
• High dose, short duration
• Usually temporary effects that reverse after
  removal from exposure
• Chronic (asbestos, silica dust)
• Low dose, long duration
• Usually long-term illness, i.e. cancer

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Toxicology

• The right dose differentiates a
• poison and a remedy. - Paracelsus
• LD50 (Watch for lt 50 mg/kg)
• Factor for Absorption and Ingestion
• LC50 (Watch for lt 200 ppm)
• Factor for Inhalation, used for gases, fumes,
  etc.
• OSHA Permissible Exposure Level (PEL)
• Time Weighted Average (TWA)
• Short Term Exposure Level (STEL)

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Methods for Protecting Yourself

• Engineering controls
• Barriers
• Flammable storage cabinets
• Ventilation
• Chemical fume hoods, snorkel exhaust ducts
• Administrative controls
• Marshall University Chemical Hygiene Plan
• Lab-specific CHP and safety guidelines
• Signage on doors and equipment
• Personal protective equipment

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Personal Protective Equipment

• Eye and face protection
• safety glasses, vented goggles, chemical splash
  goggles, face shield
• Hand protection
• gloves
• Body protection
• lab coats
• Dress appropriately for lab work. No shorts, No
  sandals or open-toed shoes!

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Lab Safety Guidelines

• No eating, drinking, applying cosmetics in labs
• Wear appropriate personal protective equipment
• Always wash hands after working with chemicals,
  after removing gloves, and before leaving the lab
• Remove gloves before handling items such as
  telephones, door knobs, computers, etc
• Leave personal protective equipment in work area
  when leaving remove gloves

41
Lab Safety Guidelines

• Housekeeping - keep benches organized and free of
  clutter
• Proper labeling for ever container
• Chemical segregation by compatibility
• Dont store chemicals on the floor
• Never pipette by mouth
• Proper waste disposal
• Students should not work alone
• Move chemicals on carts with a
• spill tray or in a rubber bucket

42
High Risk Materials

• 4 Types of Time-Sensitive Chemicals
• Peroxide Formers
• Dioxane, Ether, Isopropyl Ether, Potassium,
  Tetrahydrofuran
• Peroxide Formers that Undergo Hazardous
  Polymerization
• Acrylic acid, Ethylene oxide, Vinyl acetate
• Shock or Friction Sensitive upon Evaporation of
  Stabilizer
• Salts (metal picrate, calcium salts) form around
  caps
• Multi-nitro aromatics such as Picric acid and
  Trinitrobenzene
• Significant Additional Hazards after Slow
  Chemical Reaction
• Alkali metals, Anhydrous hydrogen fluoride and
  hydrogen bromide, Chloroform, Formic acid, Heavy
  metal acetylides (Calcium carbide), Liquid
  hydrogen cyanide

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Perchloric Acid

• Never heat in an ordinary fume hood, must be used
  in a specially designed perchloric acid hood with
  a wash-down system
• Explosive perchloric acid salts build up in
  ordinary hood exhaust systems (w/o wash-down)
• Strong oxidizer! Do not allow contact with
  flammables, organic materials (wood), metal
  surfaces or floors. Remove these materials from
  hood when working with perchloric acid
• Do not allow to dry, forms explosive perchlorates
• Neutralize spills, flood area with water. Clean
  up area and place cleanup materials in plastic
  bag(s), seal shut.

44
Sodium Azide

• Biostatic, common preservative of samples and
  stock solutions
• High acute toxicity, mutagenic - extremely toxic
  hydrazoic acid generated upon dissolving, must be
  prepared in a hood
• Explosive when heated near its decomposition
  temperature (300C) or reacted with metals
• Heating sodium azide should be avoided
• Metal shelves and metal items used to handle
  sodium azide can react to form explosive heavy
  metal azides
• Solid or concentrated solutions should never be
  flushed down the drain, can cause drain line
  explosions
• Solutions of sodium azide do not pose the danger
  of shock-sensitivity associated with the solid
  form
• If not dissolved, solid sodium azide should be
  stored in a secured cabinet because of the shock
  hazard

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Peroxide Formers

• Organic peroxides are one of the most hazardous
  substances used in the lab, large amount of
  substances are considered peroxide formers
• Low-power explosives sensitive to friction, heat,
  sparks or other accidental initiation
• Extremely flammable, many will autoxidize when
  exposed to the oxygen in air
• Ether is especially prone
• 4 classes of peroxide-forming chemicals
• Review Management of Peroxide-Forming Chemicals
  on Safety and Health web site

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Organic Peroxide Hazard

• Disposal of 1 liter of peroxided ether
• These cans of ether were expired 15 years ago.
• Ether has a shelf life of roughly 90 days when
  opened. Organic peroxides may then form after
  opening, thus creating a violent explosive
  hazard.
• Have you checked your expiration dates?

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Highly Explosive Peroxide Crystals
Crystals on acid bottle, not a problem.
Crystals on solvent lid or inside, assume
explosive!!! Also watch for discoloration and
layer stratification. Do not move or open,
call Safety and Health for disposal.
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Peroxide Formers

• 4 most common Isopropyl ether, Ethyl ether,
  Dioxane and Tetrahydrofuran
• Follow the manufacturers recommendations on the
  minimum safe temp for storage. Do not store
  below this temp (makes inhibitor less effective)!
  
• Do not store diethyl ether in a refrigerator or a
  freezer, precipitates could form.
• Store peroxide formers away from heat and light
  in closed vessels from the manufacturer.
• Limit the quantity kept in the lab to smallest
  amount necessary for immediate use.
• Dont return unused portions to the original
  container.
• Never use metal spatulas only plastic.

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Peroxide Formers

• Should not use glass containers with screw cap
  lids, never glass stoppers. Plastic bottles
  preferable.
• Label and Date all bottles as they arrive.
• True for all Time-Sensitive Chemicals
• Test for peroxides, record results on label
• 25 ppm is cut off, must be disposed at and above
• If a peroxide former is discolored, has formed
  crystals, or layers are stratified do not touch.
  
• Secure the area then call Safety Health to have
  it removed.

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Potassium

• Used to demonstrate comparative water reactivity
  in earth metals
• Supposed to be gray-silver
• Color changes as oxidized
• White to yellow
• (corrosive oxide dispose)
• Orange, red, purple
• (explosive super oxide)
• Very slow, expensive deactivation procedure

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Hydrofluoric Acid

• Anesthetic effect, doesnt burn immediately on
  contact
• Extremely corrosive to all tissues will cause
  deep burns and bone disintegration through
  decalcification
• Brief exposure (5 min) of 50 ppm can be fatal to
  humans. Spills of 70 on an area the size of your
  hand are fatal.

• Contact with solutions of 1-20 may not be felt
  for several hours and can still be fatal.

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Hydrofluoric Acid

• Extreme pain, can require fingernail removal or
  amputation, can cause gangrene
• HF vapor can cause permanent lung damage and
  blindness.
• HF reacts with glass ceramics and some metals
  forming H2 gas.
• It should be stored in secondary containers and
  only used by trained personnel.
• Calcium Gluconate gel must be on hand in all labs
  that use HF.

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Nitric Acid

• Highly corrosive
• Severe burns on contact
• Powerful oxidizer
• Eats plastic caps in 7 to 10 years

Red cap nitric acid. Yellow cap sulfuric acid.
Green cap ammonium hydroxide. Strong acids
bases are incompatible. White crystals are
ammonium nitrate formed by leaking vapors of
nitric acid ammonia.
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If chloroform is not preserved with alcohol and
is exposed to light, assume Phosgene gas is
present. Contact Safety Health for disposal.
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EPA Regulations

• Pollution Prevention and Waste Minimization
• Separate hazardous and non-hazardous wastes
• Substitute less-hazardous whenever possible
• Toluene For Benzene
• Non-Mercury Thermometers
• Teflon-coated mercury thermometers used only when
  absolutely necessary for precise, high
  temperature work (300 oC)
• Filtered vacuum systems, water aspirators
• Scale Reduction
• Dont Over Purchase
• Cost of Chemicals vs. Cost of Disposal

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Waste Management

• Heavy metal limits are very low for sewer
  discharges.
• The following are highly regulated and should
  not be drain disposed
• Arsenic, Cadmium, Chromium, Copper, Cyanide,
  Lead, Mercury, Nickel, Silver, Zinc

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Waste Management

• Evaporation of solvents, drain disposal, and
  disposal in trash containers is banned
• Keep vacuum pump oil uncontaminated
• Unwanted chemicals are not waste
• Collect in container compatible with chemistry of
  waste chemicals, with secondary containment trays
• Ex empty chemical bottles of same chemical
• Remove or mark out old label first

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Waste Management

• Collection containers must remain closed at all
  times, no funnels left in them when not in use
• Only add waste to a properly labeled container
• Label must have words waste and description of
  contents. Percentage of contents if mixture,
  approximation is ok
• Manage waste to prevent unknowns
• Label, always and accurately

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Hand-written word Nitro Tested was
nitroglycerine
We do not want to discover toxic 5 water
NOT GOOD!
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Waste Management

• Allow 10 of volume for head space , or 1
• Separate and store containers by compatibility
• Containers must not be leaking or bulging
• Submit pick-up request to Safety Health, form
  on web site
• www.marshall.edu/safety/chemical
• For both unwanted chemicals and chemical wastes

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Compliance / Inspections

• Safety Health conducts random compliance
  inspections and will generate a written report
  for each lab that addresses areas of concern
• Each lab should conduct self-audits
• form is available on the Safety Health web site
• perfect time is in conjunction with annual
  inventory, along with disposal of unwanted
  chemicals
• WV DEP US EPA have inspected our labs

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What happens when peroxidized ether is distilled
The End Questions?
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TEST

• ALL CONTAINERS SHOULD BE LABELED
• with full chemical names in English
• with all hazard warnings found on original label
• mixtures must list of each component
• WHAT CHEMICALS MAY BE POURED DOWN THE DRAIN
• no heavy metals
• only non-hazardous substances
• FOR A LARGE CHEMICAL SPILL...
• remain calm
• pull fire alarm if respiratory hazard
• call MUPD then Safety, report Chemical, Quantity
  Location
• contain spill if not hazardous
• if flammable turn off ignition sources and
  evacuate
• SAFETY HEALTH WILL REMOVE HAZARDOUS WASTE
• after generator submits a completed pick-up
  request

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TEST CONTINUED

• BASIC GROUPS OF INCOMPATIBLE CHEMICALS...
• Corrosives, Flammables, Oxidizers, Reactives, and
  Toxics
• CHEMICAL WASTE CONTAINERS MUST BE
• compatible with the chemical waste
• in secondary containment trays
• kept closed
• labeled with WASTE and contents
• have 10 of volume for head space
• not leaking or bulging
• pick-up request sent to Safety Health
• PEROXIDE-FORMING CHEMICALS MUST BE
• labeled and dated when received
• disposed according to timelines for their class
• tested and results recorded on label if retained
  longer than disposal timeline
• treated as hazardous waste if peroxides reach 25
  ppm

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TEST CONTINUED

• SPECIFIC CHEMICAL HAZARD INFORMATION SHOULD BE
  AVAILABLE...
• in your work area on hardcopy MSDS and/or
  internet MSDS sources
• on the container label
• from the manufacturer or distributor
• from Safety and Health and COS Chemistry
  Department lab manager
• ANNUAL HAZARDOUS WASTE TRAINING MUST BE
  COMPLETED
• by all laboratory faculty, staff, and students
  working in a lab
• MORE CHEMICAL SAFETY INFORMATION CAN BE FOUND
• on the Safety Health web site
• http//www.marshall.edu/safety

Thank You for your Time and Attention