Training in Handling Hazardous Materials SDSU Microfabrication Facility

Chemical Inventory Each Laboratory must maintain a complete, accurate and up to date chemical inventory. The inventory should include: All Chemicals Hazardous Non-hazardous Compressed Gasses

Chemical Inventory When you are doing the inventory, it is a good time to discard any chemicals that are: Expired No longer being used Container has been compromised, i.e. Cracked lid Label is illegible Submit your updated inventory to EH&S on the yearly basis.

Material Safety Data Sheets - MSDS A Material Safety Data Sheet or MSDS is information provided by the manufacturer and maintain by the employer to inform employees of the possible hazards associated with chemicals being used in their work area. It is part of a hazard communication program.

Material Safety Data Sheets - MSDS As stated in 29 CFR 1910.1200(g)(8), “the employer (Lab) shall maintain in the workplace copies of the required MSDS…and shall ensure that they are readily accessible during each work shift to employees when they are in their work area.” This can be done by: Shared database in which all laboratory workers have access. Stored hardcopies that are sent from the manufacturer.

Material Safety Data Sheets - MSDS Each Laboratory must maintain a current MSDS for each chemical or compound being stored or used in the laboratory. MSDS location must be clearly marked. Each laboratory worker need know how to use and understand MSDS’s.

MSDS Content Chemical Id Hazardous Ingredients Physical Data Synonyms Hazardous Ingredients PEL, TLV Physical Data Appearance and odor Fire & Explosion Data Flash-point Health Hazards Toxic, Carcinogen, etc. Physical Hazards Corrosive, Oxidizer, etc. Reactivity data Incompatibles Spill Procedures Follow MSDS directions. Special Protection Wear appropriate PPE Signs and Symptoms of Exposure Headache, Nausea, etc. The structure of a MSDS’s differs between manufacturers. GENERALLY 1) Product Identification, chemical manufacturers address, emergency tel #. 2) Whats in the chemical that can harm you. They mention the PEL’s (permissible Exposure levels established by OSHA in PPM. Over the PELS may constitute a toxic environment 3) appearance, odor, volatility 4) temperature chem ignites (100degrees F), extinguishing media 5) symptoms, First Aid _____ 6) chemical react with materials or conditions 7) Primary duty is notification-Coworkers, what use to clean-up 8) Personal Protective Equipment 9) other info

MSDS Emergency In an emergency and you cannot retrieve an MSDS, one can be obtained by calling the 3E Company’s 24 Hour phone #: 800-451-8346 Or 760-602-8703

Chemical Storage Separate incompatible chemicals. Separate organics from inorganic Separate oxidizers from organics Separate flammable liquids, acids and bases Provide earthquake restraints for all shelving when storing chemicals or glassware.

Chemical Storage Storage container MUST be compatible with material. Example: Metal containers cannot be used for acids and bases. Food containers MUST NEVER BE USED!

Flammable Liquids Storage If a lab has quantities greater than 10 gallons, they must be stored in an approved flammable liquids storage cabinet. Containers that can be shattered or punctured easily must be in secondary containment. Do not store with acids or bases.

Acids Store in secondary containment Cannot be stored at or above eye level. Label cabinets “Acid” with 3” letters Store by acid class in separate secondary containment Organic Inorganic Oxidizing

Common Organic Acids Glacial Acetic Acid Trichloroacetic Trifluoroacetic Acid Formic Acid Citric Acid Benzoic Acid Butyric Acid Propionic Acid

Common Inorganic Acids Hydrochloric Acid Hydrofluoric Acid Hydrobromic Acid Phosphoric Acid Chromic Acid

Common Oxidizing Acids Nitric Acid Perchloric Acid Sulfuric Acid

Bases Store in secondary containment Store away from acids and solvents Cannot be stored at or above eye level. Label cabinets “Base” with 3” letters Examples: Hydroxides Amines Ammonia Bleach

Compressed Gasses Must be upright and restrained At least two chains Separate incompatible gasses Flammable & Oxidizing by 20 feet Keep caps on unless in use

Chemical Labeling All containers in the laboratory must be properly labeled with the name of the material being stored in the container. This includes non-hazardous materials such as: Full name with “no” abbreviations. Water Weak buffers Methanol

Chemical Labeling Containers of hazardous materials must not only include the name of the material but also the physical and health hazards associated with the use of the material.

Physical Hazards Explosive Flammable Compressed gas Carcinogen Toxic Oxidizer Corrosive Reactive

Health Hazards Corrosive Carcinogen Sensitizer Hepatotoxin Irritant Neurotoxin Nephrotoxin Reproductive toxin Corrosive Sensitizer Irritant Highly Toxic Toxic Chemical exposures routes of entry -Inhalation: breathing and taking up material into the lungs -Ingestion: poor hygiene or eating, -Absorption :skin -Injection: sharp instruments Labs are instructed to properly segregate chemicals by hazard class. Unfortunately due to space constraints. Some hazard classes that should physically be separated are not.

“Hazardous Materials Identification System” HMIS “Hazardous Materials Identification System” The HMIS rating is a color-coded, alphanumeric system which gives information about the health, flammability and reactivity of the chemical in question. The system rates a material from a minimal hazard through a serious hazard. It also recommends the appropriate personal protective equipment to be worn when handling the particular chemical.

Example of HMIS

HM Labeling System - Sample 3 San Diego State University 5500 Campanile Drive San Diego, CA 92182 1 Ethanol x -Available through EH while supplies last -Can be photocopied, reduced, cut up to only show those that apply. The contact name doesn’t apply. -All hazardous materials should have a label that states the name, the physical and health hazards as well as the target organ. -Difficult cause we do microchemistry here and this is a big label for little bottle. Labs may use the NFPA or HMIS system. Example fill out x x x x

HMIS Health 0 - Minimal Hazard Not significant risk to health. 1 - Slight Hazard Irritation or minor reversible injury possible. 2 - Moderate Hazard Temporary or minor injury may occur.  3 - Serious Hazard Major injury likely unless prompt action is taken and medical treatment is given. 4 - Severe Hazard Life-threatening, major or permanent damage may result from single or repeated over exposures.

HMIS Flammability 0 - Minimal Hazard Materials that will not burn. Usually includes any material that will not burn in air when exposed to a temperature of 1500°F. for a period of 5 minutes 1 - Slight Hazard Materials that must be preheated before ignition can occur. 2 - Moderate Hazard Materials that must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur.  3 - Serious Hazard Materials capable of ignition under almost all ambient temperature conditions. 4 - Severe Hazard Materials that will rapidly or completely vaporize at atmospheric pressure and normal ambient temperatures with a flashpoint below 73°F. Materials may ignite spontaneously with air.

HMIS Reactivity 0 - Minimal Hazard Materials that are normally stable even under fire conditions. 1 - Slight Hazard Materials that are normally stable but that can become unstable at elevated temperatures and pressures. 2 - Moderate Hazard Materials that readily undergo violent chemical change at elevated temperatures and pressures. These materials may also react violently with water. 3 - Serious Hazard Materials that are capable of detonation or explosive decomposition but require a strong initiating source or materials the react explosively with water. 4 - Severe Hazard Materials that are readily capable of detonation or explosive decomposition or explosive reaction at normal temperatures and pressures.

HMIS Protective Equipment

This labeling is not acceptable

Exposure Routes of Exposure Inhalation Absorption Ingestion Injection

Exposure Control Prevent exposures to hazardous materials. Inhalation – Keep containers closed, use the fume hood, reduce volumes Absorption – Wear gloves, lab coat, safety glasses, clean up spills promptly. Ingestion – Don’t eat, drink, smoke of apply cosmetics in the laboratory. Don’t store hazardous material in food containers. Injection – Use care when handling sharps. Properly dispose of sharps.

Exposure Control Engineering controls: - hoods, cabinets, safety cans, trays Work practices: - operating procedures Personal protective equipment: - safety glasses, lab coats, gloves, no open-toed shoes

Types of Emergencies Medical emergency Fire Chemical spill Biohazardous material spill Bomb threat Earthquake Power outage

Emergency Response If an emergency occurs, notify: Notify your safety officer or EH&S (X46778) and the supervisor of the area. If after business hours, notify Public Safety (X41991).

Fire Happens!

Managing Hazardous Chemical Waste

What is Hazardous Waste EPA Definition: A material is a hazardous waste if due to its quantity, concentration, physical, chemical or infectious characteristics it possesses a substantial present, or potential hazard to human health and the environment and has no known use.

What chemical waste must be managed? Wastes that meet any of the following characteristics. Ignitable – Flashpoint of ≤ 140°F Corrosive – pH ≤2 or ≥ 12.5 Toxic – LD-50 < 5000 mg/kg Reactive – Reacts with anything

Hazardous waste must not be disposed of on site. This includes Storm or Sewer Drains …The Trash Can

Hazardous waste must not be disposed of on site. Especially… Through Waste Treatment!!

Satellite Accumulation These are areas that generate small quantities of Hazardous Waste. This means laboratories. Definition: An Area that within 9 months accumulates- No more than 55 gallons of any hazardous waste stream. No more than 1 quart of any acutely or extremely hazardous waste stream.

Hazardous Waste Storage A funnel is not a cap This open waste containers needs a cap Poor waste labeling here as well Good Secondary Containment Waste containers must be kept closed/capped unless waste is being added or removed! Waste must

Hazardous Waste Storage Containers with closable/sealable lids or covers. Containers must be in good condition: no holes, creases, cracks, rust. They must be compatible to the waste stored in it. Container open with no label

Hazardous Waste Storage No Food or Beverage Containers.

Waste Labeling Label must have the words: “Hazardous Waste” The name and address of the generator (SDSU) The waste composition and physical state Percent volume Type of Hazard, ie. Flammable, Corrosive, Toxic The accumulation start date (Month, Day, Year) Incomplete waste label -Component label smeared -No percent volume -No hazards checked

In other words, fill out the entire hazardous waste label!! Waste Labeling In other words, fill out the entire hazardous waste label!!

“Empty” Containers > 5 gallons in size which previously held hazardous materials must be managed < 5 gallons don’t need to be managed Empty containers that previously held Highly toxic materials must be handled as hazardous waste, ie. “Sodium azide”.

“California Empty” Collect: Collect in a safe location Invert to dry: Invert bottle over paper towels and shake to dry. (Do not air dry in fume hoods or by leaving the lid off) Deface: Thoroughly deface the chemical label. Dispose: To dispose of the bottle call EH&S.

Waste Minimization Key methods for waste minimization Reduce Reuse Purchase only what you need Set up experiments so that less solvent or chemicals are needed Reuse Reuse empty containers to collect waste Reuse a solvents if purity is not an issue Recycle Some waste oils can be recycled Some metal cables and tubing can be recycled

Waste Container removal Call EH&S Department at x46778 or x46098. Never allow more than the maximum amounts to be accumulated. Satellite containers will be removed within seven working days.

Chemical Spills Have a Spill Kit Ready Set-up kit for your specific needs Take inventory of the kit frequently Quickly replace used of missing items

Spill Response For Small Spills: Spills one gallon or less, clean the spill using the material in your spill kit. Don your proper protective equipment (PPE). Place contaminated material into your spill bag, seal, and attach a hazardous waste label. Request a waste pick up of the material from EH&S. Rats

Spill Response For Larger Spills: Contain the spill if possible, notify others in the area, and evacuate the area. Notify your safety officer or EH&S and the supervisor of the area. If after business hours, notify Public Safety (X41991/911 for campus phones). Do not call Off-campus emergency services. This can lead to longer response time!!

Safety Precautions Keep all hazardous materials or other objects at least 3 feet from electrical panel Have eye wash station nearby for emergency use

Frequently Asked Questions Q: How do I know if my waste product is actually hazardous? A: Other than going though a long and costly waste determination process, give the material to EH&S and let them make that determination.

Frequently Asked Questions Q: How do I know if a chemical is acute hazardous waste? A: Acute hazardous waste is given what is called a P-code by the EPA and can be found at the following link: http://www.epa.gov/osw/hazwaste.htm and click on The P-list and the U-list. Or go to 40 CFR 261.33(e)

Frequently Asked Questions Q: Do I need the exact percentage on the hazardous waste label? A: No, they can be done in percent ranges like 10-30%. If there are too many components and there is not enough room to list them, then list the three major components or any acute hazardous waste, no matter the amount.

The End