Hazardous Waste Training

Dawn Lee, Chemical Hygiene Coordinator for the Sciencesx 5873

dlee@brockport.eduwww.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 (SAACAA) 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 Authorityhttp://www.monroecounty.gov/p/pw-RulesAndRegulations.pdf

http://www.monroecounty.gov/p/pw-SewerUseLaw.pdf

Solid Waste1. 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

Use Constituting Disposal

(1)

Energy Recovery/ Fuel

(2)

Reclama-tion (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)

(*) (*) (*) (*)

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

•No viable market•Can’t recycle 75% in a calendar year

Solid Waste cont’d3. 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: IgnitabilityA 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 vigorouslyIgnitable compressed gasesCertain strong oxidizers – able to donate or promote oxygen (chromates, nitrates, permanganates, perchlorates, peroxides, etc.)

Haz Waste: Ignitability

ExamplesMany 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.)

Must be liquid and have pH 2 or 12.5

Sewer ordinance pH 5.5 or 10

“Elemental Neutralization” - change pH for disposal is allowedPart of the experiment/lab procedure/SOPBulk 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

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 heatGenerates toxic gases when reacted with waterCN-1 or S –2 which liberate toxic gas in acidic or

basic conditionsMay 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 FuranAlkenes Isopropanol THFGeneral 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

Golden Rules – segregate incompatibles!• oxidizers from everything! (inc. HOAc & HNO3)

• acids and bases

• acids and metals

• corrosives and organics

• flammables and reactives

Mixing Wastes: Reactive Issue Prevention

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 levelHeavy 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 WastesP08 155–63–0 Nitroglycerine (R)

U002 67–64–1 Acetone (I)

U006 75–36–5 Acetyl chloride (C,R,T)

F001 The following spent halogenated solvents used in degreasing: Tetrachloroethylene, trichloroethylene, methylene chloride, 1,1,1-trichloroethane, 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 hazardousSpill materialsFilter 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-hazardousLimitations without permittingCertain recycling processesElemental Neutralization

Other InformationAbsolutely 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 WasteContainers 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 WasteAll 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 TagsHAZARDOUS WASTE Bottle Code___________Print Building &Your Name:_______________________ Room No.________ Phone:_________

Total Amount in Container:__________ Container Size:_________Dept:________________

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 WasteOrganic Liquid

Flammable

General Contents:

For EXACT composition, refer to log sheet _______

Room: Satellite Accumulation Start Date:

Mixed Haz Waste Manifest (pg. 1)

Date Generated Chemical Composition Volume Signature

       

       

       

       

Organic Liquid Hazardous Waste OnlySUNY College at Brockport

 

Room ________ Name of Person Responsible______________ Bottle Code_____

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 Hazardous characteristic(s)*

Room Collected: __________ Name of Person Responsible______________________ Date Bottle Filled:____________ 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 generatedMay 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 conditionClosed containersCompatibilityIf 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 RequirementsMust determine hazardous waste Never store more than 1000 kg total or 1 kg

acute – no time limitsMay treat or dispose on site or regulated off-

site facilityMonroe County Department of Environmental

Services will work with CESQG

SQG RequirementsMust 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 compatibilityPreparedness & Prevention PlanLess stringent “Contingency Plan”Manifest

LQG RequirementsMust have EPA ID# & determine waste90 day storageProper container & tank maintenance,

including labeling and compatibilityTRAINING and documentation yearly as

appropriate to job functionA variety of plans and manifests needed for

complianceWeekly 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 inventoryDon’t buy what you already haveDon’t buy more than you need

Sharing within a business, but not outside

MicroscaleLegal treatment options

Penalties

Penalties for non-compliance:Warning – no fineCivil Penalties ($32,500 per violation/day)

Company Individual

Criminal Penalties (malicious intent - $50k) IndividualCompany

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