Hazardous materials

Hazardous Materials & Waste Overview
Agenda
 Purchasing
 Storage
 Use
 Disposal
5/9/2016 Saurabh Tiwari 2

Hazardous Materials

Purchasing
Approvals/Permits
Biohazards (Brenda Wong)
Animals(vertebrates, arthropods, arachnids…)
Plants (exotics, invasive, genetically modified org.)
Radioisotopes & Radiation
Producing Machines (Craig Maxwell)
Chemicals (select agents, controlled substances, listed &
precursor chemicals, explosives, etc.)

Biohazards
Viruses
 Bacteria
 Prions
Select Agents
 7 CFR Part 331, 9 CFR Part 121, and 42 CFR Part 73

Select Agent Examples
Ebola Virus
bacillus anthracis spores
Lawmakers,
Officials Press for
More Biosecurity
Controls on Labs

Purchase/Use Approval Biohazards
 Institutional Biosafety Committee (IBC)
National Institute of Health Guidelines
 rDNA committee (GMO)
Faculty Committee with Community Members
 Biological Use Authorizations (BUA)
Protocols submitted & reviewed
Establish requirements in accord with BMBL
 BioSafety Levels 1, 2, 3, 4
IBC requirements enforced by BSO

TheWholeofLife(onEarth)
http://tolweb.org/tree/phylogeny.html

Purchase/Use Approval
Vertebrate Animals
 Institutional Animal Care and Use Committee
(IACUC)
Federal Laws
 Animal Welfare Act Regulations (7 U.S.C. 2131 et. seq.)
 USDA 1995 (9 C.F.R., Chapter 1, Subchapter A)
 Health Research Extension Act of 1985
 Public Law 99-158 (NIST)
 Animal Use Authorizations
IACUC enforced by Campus Vet

Insects & Plants
 Animal & Plant Health Inspection Service
Import/Export permits & controls
Intrastate movement of plants and animals
 California Department of Food & Agriculture
CCR Title 3 et al. www.cdfa.ca.gov/Regulations.html

Plant Protection & Quarantine
 Harmful nonnative species cost billions of dollars in
control or loss of marketable goods & affect
agriculture, forestry, human health, and tourism
economically or
environmentally harmful
nonnative species in US

Radioactive Materials & Equipment
 Radiation Safety Committee (RSC)
Radiologic Health Branch
 Radiation Control Law
 Health & Safety Code Sec. 114960 et seq.
 Radiologic Technology Act
 Health & Safety Code Sec. 27(f)
 Nuclear Medicine Technology Certification
 Health & Safety Code Secs. 107150 through 107175
 Title 17, California Code of Regulations, Division 1,
Chapter 5, Subchapters 4.0, 4.5, & 4.6.

Non-ionizing Radiation
 Lasers (Light Amplification by the
Stimulated Emission of Radiation)
 Class 1, 2, 3R, 3B, 4

Laser Classes
 CLASS 1
 Safe under all conditions of normal use
 Class 1M -Safe for all conditions except when passed
through magnifying optics
 Class 2
 Safe because the blink reflex will limit the exposure to
no more than 0.25 seconds
 Class 2M- safe because of the blink reflex if not
viewed through optical instruments
 Class 3R
 Safe if handled carefully with restricted beam viewing

Laser Classes (continued)
 Class 3B
 Hazardous if the eye is exposed directly, but diffuse
reflections are not harmful
 Protective eyewear is required where direct viewing of
a class 3B laser beam may occur
 Must be equipped with a key switch and a safety
interlock
LASER RADIATION
AVOID EXPOSURE TO THE BEAM
CLASS 3B LASER PRODUCT

Laser Classes
(con’t)
 Class 4
 All lasers with beam power greater than class 3B
 Can burn the skin and permanently damage eyes as a
result of direct or diffuse beam viewing
 These lasers may ignite combustible materials, and thus
may represent a fire risk
 Must be equipped with a key switch and a safety interlock
LASER RADIATION
AVOID EYE OR SKIN EXPOSURE TO
DIRECT OR SCATTERED RADIATION
CLASS 4 LASER PRODUCT

Plants
 Exotic & non-native species
 Genetically modified organisms
 Soils and more…
 ePermits www.aphis.usda.gov/permits
U.S. Department of Agriculture (USDA), Animal
and Plant Health Inspection Service (APHIS),
Veterinary Services (VS), National Center for
Import and Export (NCIE)

Plant Import & Export Info
 Plant Protection and Quarantine (PPQ)
 www.aphis.usda.gov/import_export/plants/manuals/online_manuals.shtml
 Domestic Programs
Detection, eradication, containment, or suppression of
pests or endangered plants protection
 Port Programs
exclude pests or to protect endangered plants
 Emergency Programs
immediate actions to eradicate a pest

Plant Permits Required
 To import or transport designated
plants, plant products and soil
into or through the U.S.
 To import plant pests and biological control
organisms into the U.S.
 To move plant pests and biological control
organisms between States.
 www.aphis.usda.gov/plant_health/permits/index.shtml

Chemicals
Controlled Substances
Chemical Precursors
Chemical Warfare Agents
Select Agents

Controlled Substances
 Five Schedules:
Schedule II through V are prescribed
Not Schedule I
 substance has a high potential for abuse
 no currently accepted medical use in treatment in
the United States
 lack of accepted safety for use
under medical supervision

Prescribed Drugs
Schedule II
 High abuse potential
 May lead to severe
psychological or physical
dependence
Schedule III
 Lower abuse potential
 May lead to moderate
dependence
Schedule IV
 Low abuse potential
 Lower likelihood to
lead to dependence
Schedule V
 Low abuse potential
 Limited dependence
likelihood

Chemical Warfare Agents
 Chemical Weapons Convention of 1993
 Organisation for the Prohibition of Chemical Weapons www.opcw.org
Schedule 1
 few, if any, legitimate uses; examples nerve agents, ricin,
lewisite and mustard gas
 Any production > 100 g notify OPCW
Schedule 2
 no large-scale industrial uses; examples dimethyl
methylphosphonate, a precursor to sarin and thiodiglycol
 Schedule 3
 legitimate large-scale industrial uses; examples phosgene
and chloropicrin

Select Agents
HHS AND USDA Select Agents AND TOXINS 7 CFR
Part 331, 9 CFR Part 121, and 42 CFR Part 73
 Abrin
 Botulinum neurotoxins
 Botulinum neurotoxin
producing species of
Clostridium
 Clostridium perfringens
epsilon toxin
 Conotoxins
 Diacetoxyscirpenol
 Ricin
 Saxitoxin
 Shiga-like ribosome
inactivating proteins
 Shigatoxin
 Staphylococcal enterotoxins
 T-2 toxin
 Tetrodotoxin
 Bovine spongiform
encephalopathy agent

Hazardous Materials

Main Issues
 Access (Security)
 Drugs, select agents,
terrorism potential
 Adequate warning
 Signs
 Labels
 Abbreviation lists
 Incompatible chemicals
mixing
 Earthquakes
 Exceeding storage limits
 Time
○ Safety
○ Efficacy
 Quantity
○ Fire Code
 Building limits
○ Homeland Security
 Address limits
○ Building Design Limits
 Green Buildings

Chemical Hazard Classes
 Corrosives
 Flammables
 Oxidizers
 Toxins
 Reactive Chemicals

Corrosives
 Acids
 Strong acids give up protons (accepts electron pairs)
 Bases (Alkalis, Caustics)
 Strong bases accept protons (donate an electron pair)
 Storage Segregation

Acid Type Examples
 Inorganic:
 hydrochloric acid
 nitric acid
 phosphoric acid
 sulfuric acid
 boric acid
 hydrofluoric acid
 hydrobromic acid
 Organic:
 lactic acid
 acetic acid
 formic acid
 citric acid
 oxalic acid
 Oxidizing:
 nitric acid
 perchloric acid
 chromic acid

Flammables
 NFPA Class IA, IB, IC

Oxidize
4Fe + 3O2  2[Fe2O3]
Fe0  Fe+3 (O0  O-2)
1. combine with oxygen
2. dehydrogenate esp by action of oxygen
3. change (an element or ion) from a lower
to a higher positive valence : remove one
or more electrons
4. coat with oxide; make into an oxide

Oxidizing Polyatomic Ions
Chemical Group Chemical Formula
peroxides O2
-2
nitrates NO3
-
nitrites NO2
-
perchlorates ClO4
-
chlorates ClO3
-
chlorites ClO2
-
Hypochlorites ClO-
dichromates Cr2O7
-2
permanganates MnO4
-
persulfates S2O8
-2

Oxidizers (Class 1, 2, 3, 4)
Class 4
 An oxidizing material that can undergo an explosive reaction
when catalyzed or exposed to heat, shock or friction
Class 3
 An oxidizing material that will cause a severe increase in the
burning rate of combustible material which it contacts or will
undergo vigorous self-sustained decomposition when catalyzed or
heat
Class 2
 An oxidizing material that will moderately increase the burning
rate or which may cause spontaneous ignition of combustible
material which it contacts
Class 1
 An oxidizing material whose primary hazard is that it may
increase the burning rate of combustible material with which it
comes in contact
LeastMostReactive

Oxidizer examples (Classified by NFPA)
 Class 4
 ammonium perchlorate
 ammonium permanganate
 guanidine nitrate
 hydrogen peroxide (>91% conc.)
 perchloric acid (>72.5%)
 potassium superoxide
NH4
+
H2O2
KO2

Oxidizer Examples (continued)
 Class 3
 ammonium dichromate
 potassium chlorate
 hydrogen peroxide (52-91% conc.)
 potassium dichloroisocyanurate
 calcium hypochlorite (>50% wgt.)
 sodium chlorate
 perchloric acid (60-72.5% conc.)
 sodium chlorite (>40% wgt.)
 potassium bromate
 sodium dichloro-s-triazinetrione
H2O2
K+

Example
 Linseed oil (flax seed oil)
 Class 2 oxidizer  spontaneous ignition of
combustible material which it contacts

Toxins
 Acute & Chronic Poisons; Highly Toxic
 Carcinogens
 Select Carcinogens – Occupational (31 substances -
www.dir.ca.gov/Title8/sb7g16a110.html)
 Prop 65 (845 items - www.oehha.org/prop65/prop65_list/Newlist.html)
 National Toxicology Program, Report on Carcinogens (245 -
http://ntp.niehs.nih.gov/go/roc)
 International Agency for Research on Cancer
(http://monographs.iarc.fr/ENG/Classification/index.php)
○ Group 1: Carcinogenic to humans (108 agents)
○ Group 2A: Probably carcinogenic to humans (63 agents)
 Reproductive & Developmental Toxins
 www.cdc.gov/niosh/topics/repro
 Neurotoxins, organ specific toxins, Irritants

Reactive Chemicals
Purchase small amounts, use up rapidly
 Water Reactive
 Store in an isolated area within the lab, in a water-tight
cabinet or secondary container
 Pyrophoric
 Store in air-tight containers without oxygen or
moisture (sure seal bottles, glove boxes)
 Separate from flammables, but in flame resistant
container when practical
 Self Decomposing
 Check frequently

Water Reactive Substances
Dangerous When Wet
Reactions results
 flammable gas release
 strong oxidizing gas release
 toxic gas release
 metal oxide fume release
 corrosive acids formation
Reactions
 Alkali metals (Na, K, Li) +
water  detonation, heat,
formation of hydroxide,
hydrogen gas
 Alkaline earths (Mg, Be,
Ca, Ba) + water 
detonation, hydrogen gas

Dangerous When Wet Reactions
(continued)
 Hydrides (LiH, LiAlH4) +
water  hydrogen, caustic
solution
 Carbides of Al, Ca, Mg +
water  acetylene
liberated
 Phosphides + water 
phosphine gas
 Nitrides + water 
ammonia, caustic solution
 Metallic (inorganic, such
as potassium) peroxides +
water  oxygen gas and
heat
 Chlorides of group III
metals, transition metals,
non-metals (Al, Ti, S) +
water  hydrogen
chloride gas

Pyrophoric
 Can spontaneously ignite in air
 Derived from Greek for “fire-bearing”
 Includes organometallic reagents:
 Alkyllithiums
 Alkylzincs
 alkylmagnesiums (Grignards)
 and some finely divided metal powders
 Specific ex.
 Diborane
 Diethylzinc
 tert-butyllithium
 diphosphine

Decomposition by Fission & Fusion
NO2 + CO2 +H2O + …
+ O2

Hazardous Materials

Hazard Classification Category Example
Acute Toxicity
5/9/2016 44Saurabh Tiwari

Carcinogens

ReproductiveToxins

Safety Data Sheets
revision
§ 1910.1200—Safety Data Sheets, for the specific content of each
section of the safety data sheet.)
(i) Section 1, Identification;
(ii) Section 2, Hazard(s) identification;
(iii) Section 3, Composition/ information on ingredients;
(iv) Section 4, First-aid measures;
(v) Section 5, Fire-fighting measures;
(vi) Section 6, Accidental release measures;
(vii) Section 7, Handling and storage;
(viii) Section 8, Exposure controls/ personal protection;
(ix) Section 9, Physical and chemical properties;
(x) Section 10, Stability and reactivity;
(xi) Section 11, Toxicological information.

New & Familiar Symbols

HazardSymbols&
Classes

Labeling Example
Acutely Toxic (Cat 4)

Acutely Toxic (Cat 3)

Acutely Toxic (Cat 2 &1)

Corrosive

Respiratory Sensitization

Unstable Explosive

Flammable Gas

Compressed Gas

Self-Reactive Substances

Oxidizing Liquid

Comparison of Data Sheets
MSDS (required now) SDS (Proposed)
1. Chemical Identity
2. Manufacturer's Name and
Contact Information
3. Hazardous Ingredients/Identity
Information
4. Physical/Chemical Characteristics
5. Fire and Explosion Hazard Data
6. Reactivity Data
7. Health Hazard Data
8. Precautions for Safe Handling
and Use
9. Control Measures
1. Identification
2. Hazard(s) identification
3. Composition/information on ingredients
4. First-aid measures
5. Fire-fighting measures
6. Accidental release measures
7. Handling and storage
8. Handling and storage
9. Physical and chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information (Non-mandatory)
13. Disposal considerations (Non-mandatory)
14. Transport information (Non-mandatory)
15. Regulatory information (Non-mandatory)
16. Other information, including date of
preparation or last revision

Hazardous Materials

Disposal Summary
www.ehs.ucr.edu/resourceswastedisposalrequirements.pdf

Waste Determination
What types of waste
are generated?
5/9/2016
Saurabh Tiwari
63

Radioactive Waste
Examples
 32P
 3H
 14C
 35S
 Scintillation vials
 Stock vials

Biohazardous Waste
 Laboratory or research waste, that is
potentially infectious to humans, plants
or animals, or would pose a potential
threat to the the environment

Biohazardous Waste includes
 Cell, bacteria and viral cultures
 Transgenic plants
 Tissue culture supplies
BIOHAZARD

Medical Waste
 Diagnosis, treatment or immunization of
humans/animals
 Research on diagnosis, treatment or
immunization of humans/animals
 Can be biohazardous or sharps
 Includes all hypodermic needles
BIOHAZARD

Medical Waste Examples
 Blood and blood products
 Lab wastes of significant virulence and
quantity
When in doubt give Biosafety a shout

Chemical Waste Identification
 Is it…?
 Universal waste or Special waste
 On a list of regulated wastes?
○ Acutely or extremely hazardous
 www.ehs.uci.edu/programs/enviro/ChemicalList.xls
 Hazardous due to a characteristic
 Inherently waste-like or Unknown
 Or is non-hazardous?

Universal Waste
 Batteries
 Lamps (fluorescent)
 Thermostats (with hg ampoules)
 Cathode ray tubes (PC monitors) &
other ‘e-waste’
 Anything with a circuit board

Special Waste
 Used oil
 Used oil filters
 Lead-acid batteries

Mixed Waste Examples
 Scintillation cocktail
 Tissue samples containing known or
suspect infectious substances labeled
with radioactive isotopes.

Chemical Hazardous Waste
Hazardous Waste as defined by the regulations
 On a list?
 Extremely or Acutely Hazardous
 Characteristic Waste
 Ignitable
 Corrosive
 Reactive
 Toxic

Extremely & Acutely
Hazardous Waste Examples
 Ammonia
 Benzyl chloride
 Chlordane
 Chloroform
 Formaldehyde
http://www.epa.gov/swercepp/ehs/ehsalpha.html
www.dir.ca.gov/title8/5189a.html
 Hydrogen fluoride
 Nitric acid
 Phenol
 Sodium azide
 Vinyl acetate monomer

Chemical Waste
 Ignitable
 Flash point less than 140F
○ Most organic solvents
 Acetone, methanol, toluene
 Corrosive
 pH less than 2, greater than 12.5
○ Strong acids, bases

Chemical Waste
 Reactive
 Reacts violently and spontaneously under STP
with water, air, light, friction
○ Examples of reactive chemicals
 Sodium metal
 Dry nitrocellulose
 Old organic peroxides
 Contaminated, crystallized picric acid

Chemical Waste
 Toxic
 LD50 (lethal dose at which 50% of the test
population dies) <5000 mg/kg
 May cause environmental harm
 Thousands of chemicals
 Difficult to determine at bench

Examples of “Inherently Waste-like”
 Original stock chemicals
 Conditions which cause EPA to consider them waste
 Retrograde containers
○ Bottles cracked
○ Caps corroded or cracked
○ Dirty
 Labels
○ Illegible
○ Falling off
 Expiration dates exceeded

Mixed Waste
(Avoid creating when possible – very expensive)
 Radioactive + chemically hazardous
 Radioactive + biohazardous
 Chemically hazardous + biohazardous

Physically Hazardous Waste
Sharp and Piercing objects
 Razor blades
 Broken glass
 Pipette tips

College & University Fines

Cradle to Grave Management
 Managing waste is a highly regulated function;
Failure to adhere to requirements may result in
high fines and individual prosecution
UCR
Pesticide
Pits Project

Minimize Waste Generated
 When practical, reduce hazard
characteristics of by-products before they
become waste
 Reduce the potential for exposure
 “Green Chemistry”
www.epa.gov/greenchemistry

Minimize Waste Generated
 Neutralize
 If pH is the only hazard, and the pH of the waste is between
2 and 12.5, then
 The waste can be neutralized in batches of 5 gallons or less
to a pH of 5 to 9 and may be able to drain dispose
 Documentation & training is required
 Substitute non-hazardous chemicals
 Includes buffer solutions
 Work on a small scale whenever possible
 Use less reagents & create less waste

Illegal Actions
 Evaporate waste (atmospheric disposal)
 Drain disposal of untreated chemically
hazardous waste
 Strictly regulated, generally prohibited
 No ‘treatment’ in the pipes
 Only untreated chemicals allowed
○ Bleach (store grade)
○ Non-hazardous salt solutions

Store in Appropriate Area
(Large Quantity Generator)
 Satellite accumulation areas
 An area in the lab designated for the proper storage of
chemical hazardous waste
 Store only small quantities
 1 quart max of acutely hazardous waste
 Picked-up at 80 % full or after 6 months

Satellite Accumulation Areas
 Under the control of the operator of the
process generating the waste
 Inspected weekly by the lab
 Waste prepared appropriately and
incompatible materials segregated

Extremely Hazardous Waste
 Triple rinse containers
 Collect rinseate as waste
 Deface the label

Pesticide Waste
 Regulated
 Triple rinse containers
 Make containers unusable
 Use rinseate to dilute next batch when
possible

Preparing & Labeling
Universal Waste
 Label as “universal waste” or “used batteries”, or
“used lamps” etc.
 Not “dead batteries”
 Mark with the date that accumulation began
 Request pickup < 9 months
 Contain to prevent damage or leakage

Preparing Unknown Waste
 Avoid creating them in the first place!
 Provide as much information as you can
 Process that generated the waste
 Best guess on identification
 HAZCAT analysis

Preparing Biohazard/Medical Waste
 Storage requirements for red* bagged waste
and filled sharps containers
 Over zero C - not more than 7 days
 Under zero C – not more than 90 days
 If autoclaving medical waste must use
registered autoclaves
 Bag must be weighted and recorded
 Use autoclave indicator tape
 Contact Biosafety with questions
* Use Red Bags ONLY for biohazard waste, not as general trash bags

Segregating Waste
 Physical states
 Incompatible hazards
 Oxidizers from organics
 Acids from bases
○ See poster for complete list
 Minimize mixtures
 A solution that contains more than one hazard class
DOES NOT need to be separated
 Components of the mixture need to be tracked

Waste Preparation: Containers
 Container must be compatible with contents
 No food containers!
 Containers closed when not in use
 when not actively being filled
 Free from external contamination
 In good condition
 No evidence of cracks, dents, corrosion
 Labeled with Hazardous Waste Label

Secondary Containment
 Waste container must be placed in secondary
containment
 Holds 110% of the volume of the largest container

Waste Disposal: When?
 Container should be ~80% full
 Reduces the number of containers shipped
 Reduces amount of time on pickups
 Minimizes costs to the university

Accidents and Spills
Ask your self…
 If I do nothing, will it get worse or cause a
release to the environment?
 If it will get worse, call for help (9-1-1)
 If it won’t get worse, do you have necessary
materials and proper training to clean it up?

Accidental Releases to the Environment
 Stop
 Action causing the release
 Recover
 As much released material as you safely can
 Report
 The incident as soon as possible!
○ Local CUPA/PA
○ CA Office of Emergency Services 800-852-7550
○ National Response Center 800-424-8802.

Self-Audits
 Check conditions for hazardous waste
 Is everything properly labeled?
 Are all containers in good condition?
 Appropriate use of secondary containment?
 Is everything properly stored?
 Is waste properly segregated?
 Provide suggestions to improve service

Hazardous Chemical Storage
 Aged/unwanted inventory
 Donate to the Chemical Reuse Program
○ Prepare unneeded materials for disposal
 General Housekeeping
 Are the areas organized and labeled well?

Waste Labels
UC OTP System Prior version

Hazardous materials

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