Hazardous Waste and Chemical Management

Glenn Magley

MKC Enterprises, Inc.

glenn@mkcenterprises.com1

Hazardous Waste Management Learning Objectives

The generator of hazardous waste will be able to:

1. Identify hazardous waste

2. Ensure it is properly managed

1.2.

3.4.

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Hazardous Waste Module

State and federal regulations require that employees who produce (generate) hazardous waste must be trained.

This module has been developed to meet this expectation.

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By Katheleen Conti, Boston Globe Staff  |  April 10, 2005

Chemistry lesson one: Accidents happen, like the recent spill at Exeter High School in New Hampshire, when fumes in a lab class sent three students to the hospital and shut down the school for the day.

Chemistry lesson two: Adding unknowns to the mix -- like improper storage and handling of toxic substances -- can be a formula for disaster.

In January, firefighters responding to an alarm triggered by a chemistry experiment at Pope John XXIII High School in Everett found a jar containing a potentially volatile material that is used to produce rocket fuel. Deemed unstable, the chemical -- 2, 4-dinitrophenol -- was detonated by the State Police Bomb Squad.

Hidden HazardsDangerous chemicals in school labs an explosive situation

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By Tarron Lively, THE WASHINGTON TIMES, Published March 25, 2005

D.C. Public Schools Superintendent Clifford B. Janey issued a protocol yesterday for removing potentially dangerous chemicals from schools, after a series of mercury contaminations and the revelation that a previous removal effort was incomplete.     The nine-page protocol lists more than 200 chemicals including mercury, chlorine, chloroform, ether, hexyl alcohol and nicotine. The protocol was issued to the principals of each of the city's roughly 150 public schools. The school system's Hazmat Removal Team, D.C. Fire and Emergency Medical Services and the American Association for the Advancement of Science helped create the protocol and will handle the removal and disposal of the materials.       School administrators ordered all potentially hazardous materials removed after an October 2003 mercury spill at Ballou High School in Southeast. The incident closed the building for more than a month, and cleanup cost at least $1 million. A student who was charged in the case had taken the mercury from a science lab.     However, investigations into the recent mercury incidents at Cardozo High School and Hardy Middle School revealed that potentially hazardous materials were still inside schools.

Chemicals Ordered Removed

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          99% had inherited their inventories          98% had incompatible storage          94% had shock sensitive compounds          85% had inadequate chemical hygiene plans          65% had inadequate functioning fume hoods          30% had explosive chemicals          15% had radioactive materials

They Reported:

Recently In Colorado, 300 schools were inspected.

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The EPA “Reaches Out”

In February 2007, EPA Region 4 launched the Colleges and Universities Compliance Incentive Initiative, encouraging. Region 4 mailed letters to public and private colleges in the southeastern United States to “highlight the opportunity to take advantage of voluntary environmental self-audits” .This provides incentives for schools to voluntarily discover, disclose, and correct non-compliance.Disclosures may receive a partial or complete reduction in financial penalties.

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Summary of Incentives under

EPA’s Audit Policy

Penalty mitigation

No recommendation for criminal prosecution.

No routine requests for audit reports.

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Contact: Sheryl Rosner, EPA Office of Public Affairs, (617) 918-1865

For Immediate Release March 3, 2005; Press Release #sr050301

The U.S. Environmental Protection Agency announced today that it has proposed a $171,050 penalty against Plymouth State University, in Plymouth, NH for violations of hazardous waste laws. ….

Specifically, EPA claims that the University failed to:• make hazardous waste determinations; • properly store hazardous waste; • maintain spill and fire control equipment; • post “no smoking” signs; • post emergency telephone numbers;• keep hazardous waste containers closed; • mark hazardous waste containers with accumulation dates;• conduct inspections of hazardous waste storage areas.

EPA seeks $171,050 from Plymouth State University, Plymouth, NH for Hazardous Waste Violations

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The U.S. Environmental Protection Agency (EPA) has cited the University of Puerto Rico (UPR) in Mayagüez for violating EPA Regulations… and proposed that the university pay nearly $1 million in penalties for these violations. …….

UPR submitted self-disclosures under EPA's Audit Policy … Normally, EPA would grant relief from financial penalties for self- disclosed violations, but it was determined that UPR was not eligible for full relief because UPR was not correcting all its violations. As a result, EPA conducted its own comprehensive inspection .. and found numerous violations.

EPA and the Commonwealth found that UPR failed to operate its facility in a manner that would minimize the risk of releasing hazardous wastes … The containers held wastes ranging from used oil, various acids and spent solvents to formaldehyde. UPR was also storing hundreds of containers of old and expired chemicals, such as picric acid, in an unsafe manner.

EPA Cites Puerto Rico University at Mayaguez for Multiple Violations of Environmental Safety RulesWednesday, October 5, 2005

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What is a Waste?

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EPA describes several ways something becomes a waste:•Discarded•Inherently waste-like (dioxins)•Use constituting disposal•Speculative accumulation•40 CFR Part 261 (www.access.gpo.gov)

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Speculativeaccumulation:pack rats

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Compliance Tips

Helpful Tip #1: How do you tell whether it’s waste?

• Is it in good condition and labeled?• Is it currently legal for use in the

U.S.?• Has anyone used it in the last year

or two? Be honest.• Will anyone use it in the next year

or two? Be brutally honest.

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Compliance Tips

Helpful Tip #2: How old is that bottle?

• Plastic Screw Caps: 1912• Fisher Scientific incorporated: 1926 • ZIP codes: 1963• CAS numbers: 1966

You DO date your bottles, don’t you?

Is it a Hazardous Waste?

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Hazardous Waste Classification

Can be a:SolidLiquidGasSludge

Hazardous waste is a material that no longer has an intended value

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Hazardous Waste Definition

The following categories are not considered hazardous waste:

1. Sewage

2. Regular trash

3. Radioactive waste

4. Biohazard waste

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Determination of Waste Status

The burden of proof to determine if a waste material is defined as “hazardous” is on the generator

May need to analyze the waste to determine its status

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Waste is Hazardous for:

Characteristics:

• Ignitability: Flash Point <140°F (60C): diethyl ether, acetone, magnesium, perchlorates

• Corrosivity: pH <2 or >12.5, 10% solution

• Reactivity: water-reactive, pyrophoric, generates sulfides or cyanides, shock-sensitive: picric acid, white phosphorus, sodium, NaCN, NaS

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Arsenic

Barium

Cadmium

Chromium

Lead

Mercury

Selenium

Silver

Benzene

Carbon tetrachloride

Chloroform

Methyl ethyl ketone

Pyridine

Tetrachloroethylene

Trichloroethylene

Vinyl chloride

Plus……

Toxicity:Waste is Hazardous for:

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Beryllium powder Carbon disulfideDieldrin

Vanadium pentoxide

Acetaldehyde

Acrylamide

Creosote

Diethylstilbesterol Formaldehyde

Maleic anhydride

Phenol

Plus…..

Listed wastes:

Waste is Hazardous for:

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Some

hazardous

wastes are

obvious

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Some are not

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How do you tell it’s hazardous?

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Hazardous Waste 101

How do you tell?• Ask the vendor• Use the MSDS Book• Use the MSDS

Online

Hazardous Waste

Examples of hazardous waste:Mercury from a broken thermometerAcetonitrile from HPLC Ethidium bromide Flammable Paints and SolventsWaste isopropyl alcoholAerosolsElectronic circuit boards (lead solder)

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Hazardous Waste Locations

Laboratories and Classrooms

Maintenance Facilities (paint, pesticides, maintenance fluids)

Light Bulbs

Nursing Schools / Health Services

Buildings repurposed from science curriculum

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What do I do once I found it?

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Improper Waste Management

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Separate incompatible material

Label Each Waste Container

Seal each waste container

Keep track of constituents (rough quantities)

Store waste in appropriate locations (cabinets, not in active hoods)

Management of Chemical Waste

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Proper LabelingAll waste containers must be properly labeled.Hazardous Materials Must have the words “Hazardous Waste”“Used Oil”“Universal Waste -- Lamp(s),” or “Waste Lamp(s),” or “Used Lamp(s)", Must include all hazardous components

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Improper Labeling

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Improper Methods of Disposal for Hazardous Waste

Hazardous waste should not be:Placed In regular trashMixed with biohazard waste (red bag or

sharps)Flushed down the drainAllowed to reach surface water (rivers,

lakes) via storm sewer systemAllowed to evaporate (note - open

containers imply evaporation)

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Where did the waste go?

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Satellite Accumulate Area

Satellite accumulate area – is defined as the area (typically a room) where the hazardous waste is generated. Must be designated with signsContainers must remain closed except when adding material.Containers must be marked with the words “Hazardous Waste”.

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Satellite Accumulation Area

Can accumulate up to 55 gallons of hazardous waste or a maximum of one quart of acutely hazardous waste

May need to segregate chemicals and provide secondary containment

Do not date hazardous waste label until the container is moved out of lab

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Reduction of Chemical Waste

Replace reagents with less toxic alternatives (green chemistry)Work in smaller scalesCentralize purchasingBuy only what you need for 1 yearSupervise what is coming into stock

Neutralize acids and bases (not chromic or fuming acid)

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Containers

Contents must be compatible with container material

Problems: Certain solvents

placed in plastic containers

Hydrofluoric acid in glass containers

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Containers

Do not mix incompatibles that will produce: Heat Violent reactions Fire/Explosion Flammable or toxic

gases

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Empty Containers

Empty containers that once held a hazardous material may be placed in the regular trash.

Containers that held acutely toxic materials (selected list from EPA) are considered hazardous waste and may not be placed in regular trash.

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Empty Container Definition

An empty container is defined as: All waste has been

emptied using common practice

Maximum of 1 inch of product remains in container

No more than 3% by weight of the container remains (tanks <110 gallons)

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Examples of Violations

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Summary of Most Common Violations

Waste containers were not marked “Hazardous Waste”

Waste Containers without dates of accumulation

Waste Containers are not closed

Universal waste light bulbs were not being managed properly

Training of employees who handle hazardous waste is not documented

Inspections were not recorded on a weekly basis

Onsite Treatment of wastes is occurring.

Waste material has not been determined as being hazardous

Not all MSDS’s47

Violations

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Violations (cont.)

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Liabilities

Injury to Students / Personnel

Violations can be up to $5,000 each Willful Neglect Repeat Offenses

Violations with Immediate Threat to Human Health or Environment - $25,000 Unreported spills, Dumping, Misrepresentation

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Chemical Management and Handling

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Be certain to label all containers including date of receipt or formulation. Ink should be waterproof and fade resistant.

Must have accurate chemical inventory and MSDS’s accessible throughout school.

Labeling

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Placement of the items on a stockroom shelf should be based upon compatibility--not alphabetical succession.

• Ammonium nitrate + acetic acidmixture will ignite especially if acid is concentrated

• Cupric sulfide + cadmium chlorateexplode on contact

• Sodium + sulfurreaction proceeds with explosive violence

• Sodium cyanide + sulfuric acidrelease of HCN gas, death vigorous reaction, highly exothermic

The Flinn Scientific Catalog has an excellent system to store chemicals based upon their compatibility.

Arrangement

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Improper Arrangement

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Shallow trays (e.g. Rubbermaid) will provide spill protection.

Shelving needs to be secured to a wall or floor.

Shelves with raised lips help to prevent bottles being pushed onto the floor.

Shelving

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Improper Shelving Usage

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Large containers should be avoided by ordering chemicals in the smallest practical size. (The initial cost savings are not worth the disposal costs and liability.)

They should be placed on lower shelves.

Large Containers

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Flammable liquids should be stored in safety cabinets.

Appropriate cabinets for Organic Acids, Inorganic Acids (at least separate trays in cabinet), and Nitric Acid should be used if volumes appropriate.

Bases need to be stored separately.

www.lab-safety.com

Flammables / Acids / Bases Storage

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Acid Cabinet Too Full

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Compressed gas cylinders should be avoided.

If cylinders are in a stockroom they should be secured to a fixed object (e.g. a wall).

Compressed Gasses

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Unsecured Cylinder

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Health and Safety Equipment

Safety showers and Eye Washes (accessible and inspected)Laboratory Fume Hoods (inspected and clear)Personal Protective Equipment (PPE) (used and required in lab, posted)

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Chemicals to Remove

Anything not used last year this year or next year.Reactive ChemicalsHygroscopic (Wet) ChemicalsLow molecular weight organicsStrong OxidizersOlder than 10 yearsPoor packaging (repackage?)Unlabeled / Unknowns

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Should occur often and be recorded.

Looking for material that may be leaking, not properly closed, or out of place.

Annually the shelves should be examined and any chemicals disposed of that will not be used in the next year.

Inspections

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Unacceptable Storage Found in Inspection

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Spilled / Leaking Chemical

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LABORATORY SAFETY INSPECTION CHECKLIST Page 1

This form shall be used as a guideline for performing a laboratory inspection; it is not intended to bring a lab into full compliance. The design of the form is to identify areas that need improvement with respect to regulatory compliance. “Y” answers indicate a satisfactory situation, while “N” indicates an area that needs improvement. These areas can then be prioritized in order of severity. “N/A” indicates a not applicable situation. Building #:________

Room #:______ Date:____________ Time:_______

Principal Investigator:___________________________

Department:__________________________

Survey Conducted By:______________________________________________________________ Y - Satisfactory N - Needs Improvement N/A - Not Applicable

Y N N/A HAZARDOUS MATERIALS

1. DOCUMENT AVAILABILITY

a. Chemical inventory is complete, current and readily accessible to employees at a central location. Location: ______________________________________

b. MSDSs are on file in department and readily accessible to employees. Location:_______________________________________

Laboratory Inspection Sheet

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Helpful ReferencesMIT Environmental Virtual Campus www.c2e2.org/evc/home.html

USEPA Website for Reference http://www.epa.gov/epa

Chemical Safety Information http://wiser.nlm.nih.gov/

www.mkcenterprises.com

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www.mkcenterprises.com

Thank You

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