Title: Hazardous Materials & Waste
1Hazardous Materials Waste
- BY
- Russell Vernon, Ph.D.
- Laboratory / Research Manager
2Hazardous Materials Waste Overview Agenda
- Purchasing
- Storage
- Use
- Disposal
3Purchase
4Purchasing
- 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.)
5Biohazards
- Viruses
- Bacteria
- Prions
- Select Agents
- www.selectagents.gov
- 7 CFR Part 331, 9 CFR Part 121, and 42 CFR Part 73
6Select Agent Examples
Lawmakers, Officials Press for More Biosecurity
Controls on Labs 9/22/2009
7Purchase/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
8The Whole of Life (on Earth)
- http//tolweb.org/tree/phylogeny.html
9Purchase/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)
- Faculty Committee with Community Members
- Animal Use Authorizations
- IACUC enforced by Campus Vet
10Purchase/Use Approval 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.htm
l
11Plant Protection Quarantine
- Harmful nonnative species cost billions of
dollars in control or loss of marketable goods
affect agriculture, forestry, human health, and
tourism
12Purchase/Use Approval Radioactive Materials
Equipment
- Radiation Safety Committee (RSC)
- Faculty Committee with Community Members
- 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.
13Purchase/Use ApprovalNon-ionizing Radiation
- Lasers (Light Amplification by the Stimulated
Emission of Radiation) - Class 1, 2, 3R, 3B, 4
14Laser 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
15Laser 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 RADIATIONAVOID EXPOSURE TO THE BEAMCLASS
3B LASER PRODUCT
16Laser Classes(cont)
LASER RADIATIONAVOID EYE OR SKIN EXPOSURE
TODIRECT OR SCATTERED RADIATIONCLASS 4 LASER
PRODUCT
- 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
17Plants
- 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)
18Plant Import Export Info
- Plant Protection and Quarantine (PPQ)
- www.aphis.usda.gov/import_export/plants/manuals/on
line_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
19Plant 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.shtm
l
20Chemicals
- Controlled Substances
- Chemical Precursors
- Chemical Warfare Agents
- Select Agents
21Controlled Substances
- Five SchedulesSchedule 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
22Prescribed 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
23DEA Listed Chemicalswww.deadiversion.usdoj.gov/ch
em_prog/34chems.htmregulated transactions
- anthranilic acid, benzyl cyanide ,
ephedrine , ergonovine , ergotamine ,
N-acetylanthranilic acid , norpseudoephedrine ,
phenylacetic acid , phenylpropanolamine ,
piperidine , pseudoephedrine ,
3,4-methylenedioxyphenyl-2-propanone ,
methylamine , ethylamine , propionic anhydride
, isosafrole , safrole , piperonal ,
N-methylephedrine , N-methylpseudoephedrine ,
hydriodic acid , benzaldehyde, nitroethane ,
gamma-butyrolactone, red phosphorus, white
phosphorus, hypophosphorous acid ,
N-phenethyl-4-piperidone, iodine
- acetic anhydride, acetone, benzyl chloride,
ethyl ether, potassium permanganate, 2-butanone,
toluene, hydrochloric acid, sulfuric acid,
methyl isobutyl ketone, sodium permanganate
24California Department of JusticePrecursor
Chemicals
- phenyl-2-propanone, methylamine, ethylamine,
D-lysergic acid, ergotamine tartrate, diethyl
malonate, malonic acid, ethyl malonate,
barbituric acid, piperidine, N-acetylanthranilic
acid, pyrrolidine, phenylacetic acid, anthranilic
acid, morpholine, ephedrine, pseudoephedrine,
norpseudoephedrine, phenylpropanolamine,
propionic anhydride, isosafrole, safrole,
piperonal, thionylchloride, benzyl cyanide,
ergonovine maleate, N-methylephedrine,
N-ethylephedrine, N-methylpseudoephedrine,
N-ethylpseudoephedrine, chloroephedrine,
chloropseudoephedrine, hydriodic acid,
gamma-butyrolactone, butyrolactone butyrolactone
gamma, 4-butyrolactone 2(3H)-furanone dihydro
dihydro-2 (3H)-furanone tetrahydro-2-furanone
1,2-butanolide 1,4-butanolide 4-butanolide
gamma-ydroxybutyric acid lactone
3-hydroxybutyric acid lactone and
4-hydroxybutanoic acid lactone, 1,4-butanediol,
butanediol butane-1,4-diol 1,4-butylene glycol
butylene glycol 1,4-dihydroxybutane
1,4-tetramethylene glycol tetramethylene glycol
tetramethylene 1,4-diol, red phosphorous, white
phosphorous, hypophosphorous acid
25Chemical 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 gt 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
26Select AgentsHHS 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
27Storage
28Main 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
29Chemical Hazard Classes
- Corrosives
- Flammables
- Oxidizers
- Toxins
- Reactive Chemicals
30Corrosives
- Acids
- Strong acids give up protons (accepts electron
pairs) - Bases (Alkalis, Caustics)
- Strong bases accept protons (donate an electron
pair) - Storage Segregation
31Acid 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
32Flammables
33Oxidize4Fe 3O2 ? 2Fe2O3Fe0 ? Fe3 (O0 ?
O-2)
- combine with oxygen
- dehydrogenate esp by action of oxygen
- change (an element or ion) from a lower to a
higher positive valence remove one or more
electrons - coat with oxide make into an oxide
34Oxidizing Polyatomic Ions
35Oxidizers (Class 1, 2, 3, 4)
Least ? Most Reactive
- 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
36Oxidizer examples (Classified by NFPA)
- Class 4
- ammonium perchlorate
- ammonium permanganate
- guanidine nitrate
- hydrogen peroxide (gt91 conc.)
- perchloric acid (gt72.5)
- potassium superoxide
H2O2
37Oxidizer Examples (continued)
- Class 3
- ammonium dichromate
- potassium chlorate
- hydrogen peroxide (52-91 conc.)
- potassium dichloroisocyanurate
- calcium hypochlorite (gt50 wgt.)
- sodium chlorate
- perchloric acid (60-72.5 conc.)
- sodium chlorite (gt40 wgt.)
- potassium bromate
- sodium dichloro-s-triazinetrione
H2O2
38Example
- Linseed oil (flax seed oil)
- Class 2 oxidizer ? spontaneous ignition of
combustible material which it contacts
39Toxins
- 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/inde
x.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
40Reactive ChemicalsPurchase 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
41Water Reactive Substances Dangerous When Wet
- Reactions
- Alkali metals (Na, K, Li) water ? detonation,
heat, formation of hydroxide, hydrogen gas - Alkaline earths (Mg, Be, Ca, Ba) water ?
detonation, hydrogen gas
- Reactions results
- flammable gas release
- strong oxidizing gas release
- toxic gas release
- metal oxide fume release
- corrosive acids formation
42Dangerous 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
43Pyrophoric
- 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
44Decomposition by Fission Fusion
45Use
46Hazardous Communication
- Employer/Employee relationships
- Outside a Lab, HazCom Standard applies
- www.dir.ca.gov/Title8/5194.html
- Process Safety Management (140 substances)
- Acutely Hazardous Chemicals, Toxics and Reactives
- www.dir.ca.gov/Title8/5189.html
- In a Lab, the Lab Standard Applies
- www.dir.ca.gov/Title8/5191.html
- Students visitors tort law precedence
- 3rd party contract law
47Proposed changes to the OSHA Hazard Communication
Standard
- http//edocket.access.gpo.gov/2009/pdf/E9-22483.pd
f
48proposed modifications
- revised criteria for classification of chemical
hazards - revised labeling provisions that include
requirements for use of standardized signal
words, pictograms, hazard statements, and
precautionary statements - a specified format for safety data sheets and
- related revisions to definitions of terms used in
the standard, requirements for employee training
on labels and safety data sheets.
49Hazard Classification Category ExampleAcute
Toxicity
50Carcinogens
51Reproductive Toxins
52Safety Data Sheetsrevision
- 1910.1200Safety 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.
53New Familiar Symbols
54Hazard Symbols Classes
55Labeling ExampleAcutely Toxic (Cat 4)
56Acutely Toxic (Cat 3)
57Acutely Toxic (Cat 2 1)
58Corrosive
59Respiratory Sensitization
60Unstable Explosive
61Flammable Gas
62Compressed Gas
63Self-Reactive Substances
64Oxidizing Liquid
65Comparison of Data Sheets
- Identification
- Hazard(s) identification
- Composition/information on ingredients
- First-aid measures
- Fire-fighting measures
- Accidental release measures
- Handling and storage
- Handling and storage
- Physical and chemical properties
- Stability and reactivity
- Toxicological information
- Ecological information (Non-mandatory)
- Disposal considerations (Non-mandatory)
- Transport information (Non-mandatory)
- Regulatory information (Non-mandatory)
- Other information, including date of preparation
or last revision
- Chemical Identity
- Manufacturer's Name and Contact Information
- Hazardous Ingredients/Identity Information
- Physical/Chemical Characteristics
- Fire and Explosion Hazard Data
- Reactivity Data
- Health Hazard Data
- Precautions for Safe Handling and Use
- Control Measures
66Disposal
67Disposal Summarywww.ehs.ucr.edu/resourceswastedis
posalrequirements.pdf
68Waste Determination
- What types of waste are generated?
69Radioactive Waste Examples
- 32P
- 3H
- 14C
- 35S
- Scintillation vials
- Stock vials
70Biohazardous Waste
- Laboratory or research waste, that is potentially
infectious to humans, plants or animals, or would
pose a potential threat to the the environment
71Biohazardous Waste includes
- Cell, bacteria and viral cultures
- Transgenic plants
- Tissue culture supplies
72Medical 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
73Medical Waste Examples
- Blood and blood products
- Lab wastes of significant virulence and quantity
- When in doubt give Biosafety a shout
74Chemical 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?
75Universal Waste
- Batteries
- Lamps (fluorescent)
- Thermostats (with hg ampoules)
- Cathode ray tubes (PC monitors) other e-waste
- Anything with a circuit board
76Special Waste
- Used oil
- Used oil filters
- Lead-acid batteries
77Mixed Waste Examples
- Scintillation cocktail
- Tissue samples containing known or suspect
infectious substances labeled with radioactive
isotopes.
78Chemical Hazardous Waste
- Hazardous Waste as defined by the regulations
- On a list?
- Extremely or Acutely Hazardous
- Characteristic Waste
- Ignitable
- Corrosive
- Reactive
- Toxic
79Extremely AcutelyHazardous 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
80Chemical 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
81Chemical 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
82Chemical Waste
- Toxic
- LD50 (lethal dose at which 50 of the test
population dies) lt5000 mg/kg - May cause environmental harm
- Thousands of chemicals
- Difficult to determine at bench
83Examples 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
84Mixed Waste(Avoid creating when possible very
expensive)
- Radioactive chemically hazardous
- Radioactive biohazardous
- Chemically hazardous biohazardous
85Physically Hazardous Waste
- Sharp and Piercing objects
- Razor blades
- Broken glass
- Pipette tips
86College University Fines
87Cradle 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
88Minimize 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
89Minimize 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
90Illegal 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
91Store 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
92Satellite 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
93Extremely Hazardous Waste
- Triple rinse containers
- Collect rinseate as waste
- Deface the label
94Pesticide Waste
- Regulated
- Triple rinse containers
- Make containers unusable
- Use rinseate to dilute next batch when possible
95Preparing 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 lt 9 months
- Contain to prevent damage or leakage
96Preparing 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
97Preparing 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
98Segregating 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
99Waste 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
100Secondary Containment
- Waste container must be placed in secondary
containment - Holds 110 of the volume of the largest container
101Waste Disposal When?
- Container should be 80 full
- Reduces the number of containers shipped
- Reduces amount of time on pickups
- Minimizes costs to the university
102Accidents 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 wont get worse, do you have necessary
materials and proper training to clean it up?
103Accidental 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.
104Self-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
105Hazardous 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?
106Waste Labels
107Incineration (pictured is at Kimball,NB)
108For more information
- ehs.ucr.edu
- 951 827 5119
- russell.vernon_at_ucr.edu