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Hazardous Waste Training
Dawn Lee, Chemical Hygiene Coordinator for the Sciences
x 5873
[email protected]
www.brockport.edu/chemsafe
Who Needs Training?
Any Faculty, Staff, Student or Volunteer who
is responsible for
 generating waste
 determining what is or is not haz waste (& how to
dispose)
 transporting haz waste (SAACAA)
 inspecting haz waste storage areas
 responding to spills involving haz waste
Extent of training depends on responsibilities
Governing Agencies
Federal - US EPA (Title 40 CFR)
www.gpoaccess.gov/ecfr (Title 40, Parts 260-265)
State - NYS DEC (6 NYCRR)
http://www.dec.ny.gov/regs/2491.html (370 series)
Local - Monroe County Water Authority
http://www.monroecounty.gov/p/pw-RulesAndRegulations.pdf
http://www.monroecounty.gov/p/pw-SewerUseLaw.pdf
Solid Waste
1. Discarded or Abandoned material that may be:
 Solid, Semisolid, Liquid or Gas
“Discarded” or “Abandoned”
 “Thrown away” due to being spent, contaminated, or
unwanted
 Burned or incinerated
 Accumulated, stored or treated in lieu of disposal/burning
or before recycling
2. Recycled
 Reclaimed – recovery of usable product; regeneration
 Reused – used as ingredient in secondary process
 Exemptions:
 Direct use/reuse – used as an ingredient without
first being reclaimed
 Product substitution – the material acts as a viable
product without first being reclaimed
 Return to production process – reintroduction at
any point of the production process without first
being reclaimed
2. Recycled cont’d
Direct placement on
land (unless that is its
intended purpose)
Burn directly or use to produce
fuel (unless the chemical is
intended to be a fuel)
Make usable again
Use Constituting
Disposal
(1)
Energy
Recovery/ Fuel
(2)
•No viable market
•Can’t recycle 75% in
a calendar year
Reclamation
(3)
Speculative
Accumulation
(4)
Spent materials
(*)
(*)
(*)
(*)
Sludges listed in 371.4(b) and (c)
(*)
(*)
(*)
(*)
Sludges exhibiting a characteristic of
hazardous waste
(*)
(*)
--
(*)
By-products listed in 371.4(b) and (c)
(*)
(*)
(*)
(*)
By-products exhibiting a characteristic
of hazardous waste
(*)
(*)
--
(*)
Commercial chemical products listed
in 371.4(d)
(*)
(*)
--
--
Scrap Metal other than excluded
scrap metal (see 371.1(a)(9)
(*)
(*)
(*)
(*)
Solid Waste cont’d
3. Inherently Waste-Like
 Industry specific and dioxins
 Halogen acid furnaces
4. Military Munitions
Solid Waste Exclusions




Domestic sewage
Scrap metal
The rest is fairly industry specific
If you plan to use an exclusion or an exemption to
recycle, you must notify the NYSDEC
Hazardous Waste
 A solid waste that can pose a substantial or potential hazard
to human health or the environment when improperly
managed
 Determined at Point of Generation to have at least one
of four characteristics
 Ignitability (D001)
 Corrosivity (D002)
 Reactivity (D003)
 Toxicity (D004-D043)
and/or appear on special EPA lists (F, K P, U)
Haz Waste: Ignitability
A liquid with a Flash Point < 140º F (60°C)
Flash Point - lowest temperature at which a liquid has a vapor
pressure that forms an ignitable mixture with air near the surface of
the liquid
• Lower Flash Point  Greater Hazard
Exception: Aqueous alcohol < 24%
Non-liquid capable of causing fire thru friction,
absorption of moisture, or spontaneous chemical
change and when ignited, burns vigorously
Ignitable compressed gases
Certain strong oxidizers – able to donate or
promote oxygen
(chromates, nitrates, permanganates, perchlorates, peroxides, etc.)
Haz Waste: Ignitability
Examples
Many organic solvents (acetone, toluene, ether,
xylenes, methanol, ethanol, etc.)
Fuels such as gasoline and kerosene
Oil-based paints
Acetylene gas
Pyrophoric chemicals (some fine metal
powders, phosphorus, some organometallics,
metal & non-metal hydrides, etc.)
Haz Waste: Corrosivity
Must be liquid and have pH  2 or 12.5
Sewer ordinance pH  5.5 or  10
“Elemental Neutralization” - change pH for
disposal is allowed
Part of the experiment/lab procedure/SOP
Bulk neutralization (initially stored)
6NYCRR 373-1.1(d)(1)(xii) – elemental neut.
6NYCRR 373-1.1(d)(1)(ix) – treatment in
containers
Haz Waste: Corrosivity
Examples:








Any high or low pH-cleaning products
Sulfuric acid (Battery acid)
Hydrochloric acid (Muriatic acid)
Acetic acid (Vinegar)
Nitric acid
Chromic acid **
Sodium hydroxide
Ammonia solutions (Ammonium hydroxide)
Haz Waste: Reactivity
 Normally unstable or explodes with or without
detonation
 Reacts violently with water, air, or heat
 Generates toxic gases when reacted with water
 CN-1 or S –2 which liberate toxic gas in acidic or
basic conditions
 May not be labeled as reactive when new
(become reactive with time)
Reactivity
Water Reactive – reaction with water releases toxic gases, heat, O2 or H2
(CN-1 and S-2 salts, IA & IIA metals (Li, Na, K, Ca), organometallics, adding
acids/bases, etc.)
Pyrophore - ignites with air contact (finely powdered Zn, Mg, P, C, some
organometallics, etc.)
Unstable liquid - polymerize, decompose, or become self-reactive under
conditions of shock, pressure, or temperature
(styrene, vinyl chloride, etc.)
Explosive – goes boom
(C=C, C-N, nitro groups, azides, metal-N bonds, epoxides, etc.)
– Dryness sensitivity (dry picric acid, NI3, organic peroxides)
– Auto-oxidizers (peroxide formers)
Auto-oxidation – Formation of
Explosive Peroxides
• Most common:
Diethyl ether
MIBK
Furan
Alkenes
Isopropanol THF
General Info on Peroxide formation
http://www.ilpi.com/msds/ref/peroxide.html
• Stabilizers/inhibitors often added (free radical scavengers)
• Date upon receipt and when opened
• Test for peroxide formation every 3-6 months – test strips
available.
• Adhere to Expiration Dates
• Concentrating procedures such as evaporation or distillation.
• Sources of Friction…unscrewing a lid, popping out a glass
stopper, grinding solids with glass rods or spatulas
Mixing Wastes: Reactive Issue
Prevention
Golden Rules – segregate incompatibles!
•
•
•
•
•
oxidizers from everything! (inc. HOAc & HNO3)
acids and bases
acids and metals
corrosives and organics
flammables and reactives
Toxicity
Fails the TCLP (lab test) : when the waste
contains specified contaminants  the table
values (they will leach at a landfill)
D-listed waste with a ppm/ppb level
Heavy metals
Organic chemicals
B list = only in NY, PCBs
 50 ppm is hazardous waste
Listed Wastes
• F list – waste from non-specific sources
(F001-F005 spent solvents)
– 10% or more of any one or combo of the 31
solvents listed before use
– Used for solvent properties
• K list – waste from specific sources (industry)
• P & U lists – unused chemicals that are
deemed toxic or acutely toxic
(pure or in mixture)
Listed Wastes
In addition to F, K, P, U codes, you may find:
(I) - ignitable
(C) – corrosive
(R) – reactive
(E) – toxicity characteristic (D-list)
(T) – toxic (U-listed and appendix VIII)
(H) – acutely toxic (P listed)
Listed Wastes
P08
155–63–0
Nitroglycerine (R)
U002
U006
67–64–1
75–36–5
Acetone (I)
Acetyl chloride
(C,R,T)
F001
The following spent halogenated solvents used in degreasing:
Tetrachloroethylene, trichloroethylene, methylene chloride, 1,1,1trichloroethane, carbon tetrachloride, and chlorinated fluorocarbons; all
spent solvent mixtures/blends used in degreasing containing, before use, a
total of ten percent or more (by volume) of one or more of the above
halogenated solvents or those solvents listed in F002, F004, and F005; and
still bottoms from the recovery of these spent solvents and spent solvent
mixtures (T)
Is it Hazardous Waste?
1. Is it solid waste (by RCRA definition)?
2. Is it on one or more of the RCRA/DEC lists?
3. Does it exhibit one or more of the characteristics of
ignitability, corrosivity, reactivity, or toxicity?
4. What if it does not fall on a list or in any of the
characteristic waste definitions? How to dispose?
• ethidium bromide
• solid sodium hydroxide
• known or suspected carcinogens or reproductive
toxins
Mixture & Derived-from Rules for
Listed Wastes
 Mixture rule - if you mix a listed hazardous waste
with non-hazardous waste, it’s ALL hazardous
 Spill materials
 Filter aids
 Derived-from rule – if a listed hazardous waste is
treated or changed in some way, the new waste is
considered hazardous
 Once listed, always listed!
Mixture & Derived-from Rules for
Characteristic Wastes
 Mixture rule – only hazardous if it still exhibits
the hazardous characteristic
 Derived-from rule – product is only deemed
hazardous if it exhibits a hazardous characteristic
 This includes “listed” materials that are listed
strictly due to characteristic
 Treatment can be done to render non-hazardous
 Limitations without permitting
 Certain recycling processes
 Elemental Neutralization
Other Information
Absolutely NO disposal of hazardous
materials in trash, down the drain, or by
evaporation
Waste oil w/ no solvent can be tested &
recycled
Samples for testing are exempt while
collecting and shipping
RCRA Empty
For Non-Acutely Hazardous Materials, A
container is RCRA empty when:
All wastes removed (poured, pumped or
aspirated)
and no more than 1” of non-removable material
remains on the container bottom
or no more than 3% by weight of the total
capacity of the container remains
(containers smaller than 119 gallons)
RCRA Empty
Acutely Hazardous Materials:
 Triple-rinse with appropriate solvent (treating all
rinses as haz waste)
Compressed gas cylinders:
 Are “empty” when internal pressure approaches 1 atm
 Labware considered “empty” is NOT haz waste
Packaging Hazardous Waste
Containers MUST be
• In good condition (no leaks, bulges, rust, etc.)
• Compatible with the waste being stored in them, as well
as holding only compatible waste streams
• KEPT CLOSED except when adding or removing
waste.
• Labeled appropriately – “Hazardous Waste”
• Free of residual around caps and outside of bottles
• Handled & stored in a manner that prevents potential
exposure to the environment (2º containment)
• Compliant with air emission standards
Packaging Hazardous Waste
Containers SHOULD be
• large enough to hold the waste being generated, yet small
enough so the container can be filled quickly & removed
• filled only to a level that allows for some head space for
vapor expansion
Labeling Hazardous Waste
All hazardous waste containers MUST be labeled with:
 The words “Hazardous Waste”
 The contents of the container
 Chemical names - not symbols, acronyms, or structures
(unless a key is readily available)
 Mixtures need to have a list of approximate
quantity/concentration of each component
 The hazards associated with contents (toxic, flammable,
etc.)
 Date that accumulation started (in central storage- not in
SAA)
 Contact info for responsible party (PI, Lab Manager, etc.)
Hazardous Waste Tags
HAZARDOUS WASTE
Print
Your Name:_______________________
Bottle Code___________
Building &
Room No.________
Total Amount in Container:__________
Container Size:_________Dept:________________
Phone:_________
COMPLETE CHEMICAL COMPOSITION: (List approximate % of each constituent
including water/solvent)
1. ____________________________%
6. ___________________________%
2. ____________________________%
7. ___________________________%
3. ____________________________%
8. ___________________________%
4. ____________________________%
9. ___________________________%
5. ____________________________%
10.___________________________%.
Check if applicable: __ Flammable __ Corrosive (pH ___) __ Oxidizer
__ Highly Toxic
___ Stench
__ Reactive (__ Water___Shock ___Other ______________)
To the best of my knowledge, I certify the information provided is accurate and the hazardous
waste generated has been minimized. Sign & date when moved to Central Storage.
Sign Name:___________________________________ Date:_____________
Mixed Haz Waste Manifest (pg. 1)
Hazardous Waste
Organic Liquid
Flammable
General Contents:
For EXACT composition, refer to log sheet _______
Room:
Satellite Accumulation Start Date:
Mixed Haz Waste Manifest (pg. 1)
Organic Liquid Hazardous Waste Only
SUNY College at Brockport
Room ________
Date Generated
Name of Person Responsible______________ Bottle Code_____
Chemical Composition
Volume
Signature
Date Bottle Filled:______________________Total Volume:_________________
Date Bottle Removed to Central Storage:_________________
Mixed Haz Waste Manifest (pg. 2)
Please attach this sheet to the hazardous waste bottle upon removal to Central storage.
The detailed profile should be retained by the faculty member/department.
Summary of Hazardous Waste Profile:
*Hazardous characteristic categorized as ignitable, corrosive, reactive, toxic, acute
hazard or other special traits such as oxidizer or poison
Total Volume
Chemical
Room Collected: __________
Name of Person Responsible______________________
Date Bottle Filled:____________
Hazardous characteristic(s)*
Total Volume:_________________
Date Bottle Removed to Central Storage:__________
Satellite Accumulation
Storage Requirements
Place where wastes are generated and stored
prior to moving to central accumulation
area:
Must be stored in the same room it is generated
May accumulate up to 55 gal of haz waste (all
types collectively) or up to 1 qt. of acutely
hazardous waste
Must be under the control of the person that
created it
There are no time limits on accumulation times
SAA
Follow all appropriate container management
regulations:
Labeling (“Hazardous Waste”)
Good condition
Closed containers
Compatibility
If 55 gallons or 1 quart P-listed container is full,
must date and remove to Central Accumulation Area
(CAA) within 3 days
Categories of Generators
Conditionally exempt small quantity (CESQG)
 Less than 100 kg/month or 1 kg acute
Small Quantity Generator (SQG)
 Between 100 kg and 1,000 kg /month
Large Quantity Generator (LQG)
 More than 1,000 kg/month or 1 kg acute
Count all generated except: exemptions, immediate elementary neutralization,
immediate recycling, oil, lead-acid batteries and Universal Waste
CESQG Requirements
Must determine hazardous waste
Never store more than 1000 kg total or 1 kg
acute – no time limits
May treat or dispose on site or regulated offsite facility
Monroe County Department of Environmental
Services will work with CESQG
SQG Requirements
Must have EPA ID#
Must determine hazardous waste
Up to 6000 kg for 180 day storage
(270 days if TSDF is 200 miles away)
 Proper container & tank maintenance, including
labeling and compatibility
 Preparedness & Prevention Plan
 Less stringent “Contingency Plan”
 Manifest
LQG Requirements
Must have EPA ID# & determine waste
90 day storage
Proper container & tank maintenance,
including labeling and compatibility
TRAINING and documentation yearly as
appropriate to job function
A variety of plans and manifests needed for
compliance
Weekly inspections of CAA
Storage Security
•
•
•
•
Practical & legal issues
Lock doors when no one is in the area
Limit key distribution
Particularly hazardous chemicals – 2° security
Ways to minimize hazardous waste
Updated inventory
Don’t buy what you already have
Don’t buy more than you need
Sharing within a business, but not
outside
Microscale
Legal treatment options
Penalties
Penalties for non-compliance:
 Warning – no fine
 Civil Penalties ($32,500 per violation/day)
 Company
 Individual
 Criminal Penalties (malicious intent - $50k)
 Individual
 Company
Websites
• EPA Training Modules
http://www.epa.gov/osw/inforesources/pubs/hotline/rmods.htm
• EPA RCRA User-Friendly Reference Guide
http://www.epa.gov/osw/hazard/downloads/tool.pdf