Chemical Hygiene Plan

UCSF

Chemical Hygiene Plan

Last Updated

August 1, 2016

 

Date

Version

Description

Page #

08/01/2016

1.6

Standard Operating procedure

23

07/21/2016

1.5

Medical consultation section

28

07/08/2016

1.4

Chemical Spill section

30

07/08/2016

1.4

Update links to: peroxide forming chemicals, and safe use of pyrophoric organolithium reagents

20, 22

06/29/2016

1.3

Add a laboratory and chemical security section

24

04/08/2016

1.2

Revised the following sections: Special PPE for handling pyrophorics, storage of flammable chemicals and proper waste storage

14, 27

01/06/2016

1.0

Complete revision of all sections

 
Revision History

The Revision History pertains only to changes in the content of the document or any updates made after distribution. It does not apply to the formatting of the template.

 

Table of Contents

Revision History. 2

Introduction. 5

Responsibilities. 5

Hazard Communication. 6

Signs, Labels and Postings. 8

Safety Data Sheets. 11

General Safety Requirements. 11

Safe Use and Storage of Chemicals. 12

Flammable and Combustible Liquids. 12

Corrosive Chemicals. 14

Oxidizers. 15

Acutely Toxic Chemicals. 17

Carcinogens. 17

Pyrophoric Materials. 18

Explosive Chemicals. 19

Peroxide Forming Chemicals. 21

Compressed Gasses. 21

Cryogens. 21

Standard Operating Procedure (SOP). 22

Laboratory and Chemical Security. 23

Maintaining a Chemical Inventory. 24

Control Measures to Reduce Exposures. 24

Administrative Controls. 24

Engineering controls. 25

Fume Hoods. 25

Personal Protective Equipment (PPE). 25

Glove Selection. 26

Special PPE for Handling Pyrophorics. 26

Respiratory Protection. 26

Medical Consultation and Treatment. 27

Purchasing Restrictions. 28

Occupational Monitoring. 28

Chemical Spills. 29

Disposal of Hazardous Chemicals. 31

Regulations. 33


Introduction

UCSF is required by Title 8, Section 5191 of the California Code of Regulations to maintain a written Chemical Hygiene Plan with provisions capable of protecting employees from health hazards associated with hazardous chemicals in laboratories. All campus and medical center employees working in laboratories are required to follow the procedures and policies outlined in this plan.

Responsibilities

Chancellor

The Chancellor is responsible for the establishment and implementation of environmental health and safety policies at all facilities under campus control. Appropriate vice chancellors, deans, chairs, laboratory directors, department managers, principal investigators, supervisors, and EH&S personnel are jointly and cooperatively responsible for the implementation, monitoring, and enforcement of these policies.

Chemical and Environmental Safety Committee

The Chemical and Environmental Safety Committee (CESC) consists of UCSF faculty and provides expert advice on Chemical Safety to the chancellor. The committee reviews technical, environmental and safety-related aspects of laboratory research and the use of hazardous and toxic substances, and recommends procedures and practices for the safe use of hazardous chemicals at UCSF. The committee also arbitrates campus disagreements regarding laboratory practices and has the authority to limit or revoke, as authorized by the chancellor an investigator’s authority to use hazardous or toxic materials at UCSF.

Office of Environment Health and Safety

The Office of Environmental Health and Safety (EH&S) is responsible for implementation and oversight of the Laboratory Safety Program. It provides technical guidance to personnel at all levels of responsibility on matters pertaining to laboratory use of hazardous chemicals and substances. Department Safety Advisors within EH&S are responsible for conducting quarterly inspections of laboratories to ensure safe practices. EH&S is also responsible in maintaining communications with regulatory agencies that includes preparation of reports, correspondence, maintaining records, and obtaining permits. The EH&S Executive Director acts for the Chancellor in this role.

Chemical Hygiene Officer

The Chemical Hygiene Officer within EH&S is responsible for maintaining the Chemical Hygiene Plan which must be updated at least annually. The chemical hygiene officer serves as an expert on chemical safety and in conjunction with the CESC recommends safe practices for the safe use of chemicals and creates and implements policies on hazardous chemical use at UCSF.

Deans and Department Chairpersons

Deans and department chairpersons are responsible for ensuring Principal Investigators within their departments are providing a safe work place for their students and employees, and following UCSF policies as well as all local, state, and federal regulations relating to chemical safety.

Principal Investigators and Laboratory Managers

Principal investigators have a responsibility to provide a safe work place to all employees, students and visitors working in their laboratory. Principal Investigators must ensure all laboratory personnel receive adequate training, follow standard operating procedures for the safe use of hazardous chemicals in the laboratory including the proper use of personal protective equipment and the use of engineering controls where required. Principal investigators must take appropriate action to correct unsafe conditions and practices relating to the use of hazardous chemicals. Principal Investigators can delegate responsibilities to laboratory managers but are ultimately responsible for ensuring safe work practices are followed in their laboratories.

Employees and Students

All employees and students are required to follow standard operating procedures for the safe use of chemicals in the laboratory and are required to use adequate PPE when working with hazardous chemicals.

Hazard Communication

Definition of a Hazardous Chemical

A hazardous chemical is any chemical which can cause a physical or a health hazard. The term "health hazard" includes chemicals which are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, pyrophorics, cryogenics, hepatotoxins, nephrotoxins, neurotoxins, agents which act on the hematopoietic systems and agents which damage the lungs, skin, eyes, or mucous membranes.

Training

All UCSF employees and students are required to be trained before using hazardous chemicals in the laboratory. At UCSF training is provided through a combination of general online safety training provided by EH&S and lab specific training provided by the Principal Investigator or laboratory supervisor. To help ensure compliance with training requirements, PI’s are required to complete a Laboratory Safety Orientation Checklist for all new employees.

Online Training

Table 1 summarizes all online trainings required for the use of hazardous chemicals in laboratories. These trainings must be completed before employees begin work.

Table 1: Required Online Training

Training

Required For

Frequency

Laboratory Safety for Researchers (Topics includes: Managing Hazardous Chemicals, Fume hoods, Cryogens, Hazardous Waste Management)

All Laboratory Workers

Initial training before starting assignment

Every 3 years

Carcinogen Training

All carcinogen users

Initial training before starting assignment

Annually

Formaldehyde Training

All formaldehyde users

Initial training before starting assignment

Annually

Laboratory Specific Training

Principal Investigators must ensure their employees receive training specific to the procedures and hazardous chemicals used in their laboratory. The training must address the hazards of the chemicals being used and precautionary measures that must be followed to safely use the chemicals. At minimum this training must include the following:

1.Training on Standard Operating Procedures (SOP’s) for the use of hazardous chemicals.

2.Where to find Safety Data Sheets (SDS) for hazardous chemicals.

3.Selection and use of PPE that adequately protects against the hazards.

4.Proper use of engineering controls such as fume hoods to control exposures.

5.What to do in case of an emergency such as an exposure or chemical spill.

6.Location and proper use of emergency equipment including deluge showers, emergency showers, and fire extinguishers.

7.How to report unsafe work conditions and get them fixed.

Signs, Labels and Postings

Hazard ID sign

All main entrances to laboratories at UCSF must be posted with a Hazard Identification Sign that identifies the principal investigator of the laboratory and laboratory contacts. The sign identifies what types of hazardous materials are stored and used in the laboratory and describes what type of PPE is required for safely working in the laboratory.

Carcinogen Postings

Designated areas where known or suspected carcinogens are used must be posted with an appropriate sign. Additional information about the proper signage is available on the Carcinogen Program webpage.

Do Not Enter Postings

Entry into some areas at UCSF is restricted to personnel trained for entry due to specific radiation, biological or chemical hazards. This communicates to custodians and facility management personnel not to enter the room before contacting the laboratory or EH&S. More information is available in the Custodial Staff Entering Restricted Areas Safety Update.

Chemical Storage Area labeling

Where flammable and corrosive chemicals are stored in cabinets or in refrigerators approved for their storage, the storage location must be labeled with the chemical hazard.

Labeling of Chemical Containers

Chemical containers from manufacturers are required to be labeled with pictograms, a signal word, hazard and precautionary statements, the product identifier, and supplier identification. A sample revised label, identifying the required label elements, is shown below:

The pictograms used on manufacturer’s labels and their meanings are shown below:

At UCSF whenever a hazardous chemical is transferred to another container, the container must be labeled with the contents and hazards. See the Proper Labeling of Chemical Containers safety update for more information on labeling of chemical containers.

To assist with labeling of chemicals, a label template is available for download on the EHS website

Safety Data Sheets

Safety Data Sheets (formerly called Material Safety Data Sheets) are a detailed informational document prepared by the manufacturer of a hazardous chemical. They describe the physical and chemical properties including information on the hazards, engineering controls, personal protective equipment, storage and handling information, reactivities, and procedures for spills and first aid. Safety Data Sheets are available on the internet: https://ehs.ucop.edu/sds/#/

Other Sources for Chemical Safety:

Cameo Chemicals is a database of hazardous chemicals which provides safety related information on thousands of chemicals, and contains a reactivity prediction tool which can be used to predict potential reactive hazards between chemicals.

International Chemical Safety Card Database is a searchable database that contains safety related information for specific chemicals.

General Safety Requirements

Work Areas

  • Actively working alone with hazardous chemicals in the laboratory is prohibited.
  • Always wear PPE upon entering the laboratory.
  • Maintain a clear lab bench by returning containers and supplies to their storage location when not in use.
  • Keep aisles and corridors clear of clutter and obstructions.
  • Maintain an 18-inch clearance under the fire sprinklers across the room.
  • Never leave ongoing chemical reactions, exposed sharps, or energized electrical, mechanical, or heating equipment unattended.

Personal Hygiene

  • Food and drink are prohibited in the laboratory.
  • Never handle chemical containers or laboratory equipment without gloves.
  • Never reuse disposable gloves.
  • Wash your hands after removing your gloves and before leaving the laboratory.
  • Keep loose hair tied back.
Safe Use and Storage of Chemicals

Chemicals must always be stored according to compatibility. A chemical storage segregation chart is available on the EH&S webpage to assist with this process. Incompatible chemicals must be stored in different locations or segregated from other chemicals using secondary containment.

Flammable and Combustible Liquids

Flammable solvents are defined as having a flash point of less than 100°F. Flashpoint is the minimum temperature at which a liquid forms a vapor above its surface in sufficient concentration that it can be ignited. Liquids with lower flashpoints ignite easier. Combustible liquids have a flashpoint at or above 100°F.

The National Fire Protection Association (NFPA) hazard classifications for flammable and combustible liquids are listed in Table 2:

Table 2: Hazard classification for flammable liquids

Class

Flash point

Boiling point

Examples

I-A

below 73°F (23°C)

below 100°F (38°C)

Acetaldehyde, Ethylamine, Chloroethane Ethyl Ether, Ethyl Mercaptan, Isopropylamine, 2-Methylbutane, Propylene Oxide, Tetramethylsilane Trichlorosilane

I-B

below 73°F (23°C)

at or above 100°F (38°C)

Acetone, Acetyl Chloride, Acetonitrile Benzene, Cyclohexane, 1, 2- Dichloroethane,

Diethylamine, Ethyl Acetate, >50% Ethyl Alcohol, Gasoline, Hexane, Isopropyl Alcohol, Methanol, Methyl Ethyl Ketone

Petroleum Ether, Pyridine, Tetrahydrofuran Toluene, Vinyl Acetate, Triethylamine

I-C

73-100°F (24-38°C)

----

Amyl Acetate, Azidotrimethylsilane, 1-Butanol, Chlorobenzene, Dicyclopentadiene, Ethylenediamine, Hydrazine, Methyl Isobutyl Ketone,

Morpholine, Nitromethane, 2,4-Pentanedione, 1-Pentanol, Propyl Alcohol Styrene, Trichloroethylene

Hazard classification for combustible liquids

II

101-140°F (39-60°C)

----

> 80% Acetic Acid, Acetic Anhydride, Boron Trifluoride, N,N-Dimethyl Formamide, Formaldehyde, Formic Acid, Kerosene 2-Methoxyethanol, 3-Methyl-1-Butanol Propionic Acid, Thiophenol, WD-40® Lubricant

III-A

141-199°F (61-93°C)

----

Acetophenone, Aniline, Benzaldehyde Benzoyl Chloride, Benzyl Bromide, Benzylamine, Butyric Acid, Diethyl-Pyrocarbonate, Dimethyl Sulfate, N,N-Dimethylacetamide,

Dimethylsulfoxide, Ethanolamine, Hexyl Alcohol, 2-Mercaptoethanol, 1-Methyl-2-pyrrolidinone, Nitrobenzene, 1-Octanol,

Phenol

III-B

200°F (93°C) or above

----

p-Anisaldehyde, Benzyl Alcohol, 2-Bromoethanol, Diethanolamine, Ethylene Glycol, Formamide, Glycerol, Hexadecane, Hydraulic Oil, Methyl Salicylate, Mineral Oil, Oxalyl Chloride, Polyethylene Glycol, Triethanolamine, Triton X®, Tween 20®, Hexanoic Acid

         

General Storage and Handling Precautions

  • Keep flammables away from all ignition sources including sparks, open flames, hot surfaces, and direct sunlight.
  • Store flammables separate from other hazard classes, especially oxidizers and corrosives. Use secondary containment if incompatibles must be stored in the same location.
  • Separate flammable gases from oxidizing gases with an approved non-combustible partition or by a distance of 20 feet.
  • Store flammable liquids in approved safety containers or cabinets.
  • In instances where static electricity may accumulate and ignite flammable vapors, ground and bond flammable liquid containers.
  • Keep flammable liquids that require cold storage in laboratory safe and explosion proof refrigerators and freezers to avoid ignition of the materials by sparks or static electricity. Never store flammables in a refrigerator not designed and approved for flammable storage.

Container Size Limits:

  • Individual glass containers of Class I-A liquids must not exceed 1 pint (500 mL) capacity. Individual glass containers Class 1-B liquids must not exceed 1 quart (1 liter) capacity. Exception: Class I-A and I-B liquids may be stored in factory-shipped glass containers up to 1-gallon or 4-liter capacity if the required liquid purity would be affected by storage in metal containers or if the liquid would cause excessive corrosion of a metal container.
  • Class I-A liquids can be stored in metal containers not larger than 1 gallon (4 liters) capacity, or U.L. listed safety cans not larger than 2 gallons (8 liters) capacity. A safety can is a listed container, having a spring-closing lid, spout cover and a flame arrester and so designed that it will safely relieve internal pressure when subjected to fire exposure.
  • For liquids other than Class I-A liquids, the capacity of metal containers and safety cans must not exceed five gallons each.

Flammable Storage Limits Outside of a Cabinet

  • Limit quantities of flammable liquids stored outside of safety cans and flammable storage cabinets.
  • Laboratories are allowed to store no more than 10 gallons of flammable liquids outside of a flammable cabinet.
  • Laboratories are allowed a maximum of 20 gallons of flammable liquids stored in safety cans outside of a flammable cabinet.

Flammable Storage Limits Inside of a Cabinet

The maximum quantity of Class 1A flammable liquids allowed to be stored in a flammable cabinet is 60 gallons. The maximum quantity allowed for all classes of flammable liquids is 120 gallons per cabinet.

Corrosive Chemicals

Corrosive chemicals include strong acids and bases which can destroy human tissue and corrode metals. Acids and bases are incompatible with one another and may react with many other hazard classes. Table 3 outlines the different types of corrosives.

Table 3: Types of Corrosives

Corrosive

Examples

Inorganic Acids (non-oxidizing)

Hydrochloric Acid, Phosphoric Acid

Inorganic Acids (oxidizing)

Nitric Acid, Perchloric Acid, Chromic Acid, Sulfuric Acid

Organic Acids

Acetic Acid, Formic Acid, Trichloroacetic Acid, Trifluoroacetic Acid

Bases

Ammonium Hydroxide, Calcium Hydroxide, Potassium Hydroxide, Sodium Hydroxide

General Storage and Safety Precautions

  • Segregate acids from bases. Segregate inorganic oxidizing acids (e.g., nitric acid) from organic acids (e.g., acetic acid), flammables, and combustibles.
  • Segregate acids from chemicals that could generate toxic gases upon contact (e.g., sodium cyanide and iron sulfide).
  • Segregate acids from water reactive metals such as sodium, potassium, and magnesium.
  • Always handle concentrated corrosives in a fume hood with the sash properly aligned to provide splash protection.
  • Store corrosives on lower shelves, at least below eye level and in compatible secondary containers.
  • Concentrated solutions must always be handled in a fume hood.
  • A laboratory coat, splash goggles, and chemically resistant gloves are required when handling corrosives.
  • When diluting concentrated acids and bases, always add the concentrated solution to water slowly.
  • All laboratories that use Hydrofluoric acid (HF) are required to have calcium gluconate on hand in case of an exposure. Users of HF must be trained on using the gluconate.
  • Chemicals must always be stored according to compatibility. Incompatible chemicals must be stored in different locations or segregated from other chemicals using secondary containment.

Additional Safety Information:

Hydrofluoric Acid Safety Update

Oxidizers

An oxidizer is any material that readily yields oxygen or other oxidizing gas, or that readily reacts to promote or initiate combustion of combustible materials, and under some circumstances, can undergo a vigorous self-sustained decomposition due to contamination or heat exposure.

The hazards associated with chemical oxidizers include the potential to:

  1. Increase the burning rate of flammable and combustible materials.
  2. Cause spontaneous ignition of flammable and combustible materials.
  3. Decompose rapidly.
  4. Evolve or emit hazardous gases.
  5. Undergo self-sustained decomposition, which can result in an explosion.
  6. React explosively if mixed with incompatible materials or if involved in a fire.

Identifying oxidizers by Chemical Name and Formula

Oxidizers have excess oxygen and can sometimes be identified by prefixes and suffixes in the chemical name. Many oxidizers contain the prefix “per” and suffix “ate”. Table 4 lists some common oxidizer functional groups:

Table 4: Common Oxidizing Groups

Chemical Group

Chemical Formula

Peroxides

O2-2

Nitrates

NO3-

Nitrites

NO2-

Perchlorates

ClO4-

Chlorates

ClO3-

Chlorites

ClO2-

Hypochlorites

ClO-

Dichromates

Cr2O7-2

Permanganates

MnO4-

Persulfates

S2O8-2

 

Common Examples of Oxidizers

Liquids

  • Benzoyl Peroxide
  • Bleach (sodium hypochlorite)
  • Bromine
  • Chromic Acid
  • Nitric Acid
  • Perchloric Acid
  • Piranha Solution (sulfuric acid and hydrogen peroxide)

Solids

  • Ammonium Nitrate
  • Potassium Nitrate
  • Potassium Chlorate
  • Sodium Nitrate

Gases

  • Chlorine
  • Oxygen
  • Nitric Oxide

Safe Handling and Storage of Oxidizers

  • Segregate oxidizers from flammables and combustibles.
  • Segregate oxidizers from reducing agents (zinc, alkaline metals, formic acid).
  • Segregate organic oxidizers such as benzoyl peroxide from all other oxidizers.
  • Special consideration must always be given when choosing containers for storage of oxidizers for both use and waste collection. A container formerly containing a combustible or flammable material should never be used to store an oxidizer and vice versa. Doing so may result in a delayed or spontaneous explosion .
  • Special pressure vented caps are available from EH&S for containers that may evolve gas such as Piranha Solution. These caps can also be used for waste containers used to store other oxidizers and may help prevent an explosion due to accidental contamination of a waste container containing an oxidizer.

Acutely Toxic Chemicals

Overexposure to toxic chemicals can cause injury or death. LD50 is the most common way to express relative toxicity of a chemical. LD50 is the amount of a chemical that is sufficient to kill 50 percent of a population of test animals usually within a certain time. It is expressed in mg/kg, or milligrams of substance per kilogram of body weight. Generally, chemicals with an oral LD50 between 50-500 mg/kg are considered toxic, and chemicals with an LD50 of less than 50 mg/kg are considered highly toxic.

General Safety Precautions for Toxics and Highly Toxics

  • Toxic chemicals that produce fumes or dust should always be handled within a chemical fume hood.
  • Maintain the lowest possible quantities of toxics in your laboratory.
  • Keep containers tightly sealed to minimize exposure to personnel and contamination of other chemicals.

Carcinogens

A carcinogen (defined as “select carcinogen” by Cal/OSHA) is a substance or agent that meets one of the following criteria:

  1. It is regulated by Cal/OSHA as a carcinogen.
  2. It is listed under the category, “known to be carcinogens” in the Annual Report on Carcinogens published by the National Toxicology Program (NTP) (latest edition); or
  3. It is listed under Group 1 (“carcinogenic to humans”) by the International Agency for Research on Cancer (IARC)
  4. It is listed in either Group 2A or 2B by IARC or under the category, “reasonably anticipated to be carcinogens” by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria:
    1. After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m3.
    2. After repeated skin application of less than 300 mg/kg of body weight per week; or
    3. After oral dosages of less than 50 mg/kg of body weight per day.

General Safety Guidelines

Carcinogens are considered Particularly Hazardous Chemicals (PHC’s) at UCSF. Principal Investigators with carcinogens in their inventories are required to create SOP addressing the safe use of the carcinogen they are using. The following guidelines are generally applicable for experiments involving carcinogens:

  • Use the smallest amount of chemical that is consistent with the requirements of the work to be performed.
  • Use containment devices such as laboratory fume hoods or glove boxes when volatilizing these substances, manipulating substances that may generate aerosols, and performing laboratory procedures that may result in uncontrolled release of the substance.
  • Use high efficiency particulate air (HEPA) filters, carbon filters, or scrubber systems with containment devices to protect effluent and vacuum lines, pumps, and the environment whenever feasible.
  • Use ventilated containment to weigh out solid chemicals. Alternatively, the tare method can be used to prevent inhalation of the chemical. While working in a laboratory hood, the chemical is added to a pre-weighed container. The container is then sealed and can be re-weighed outside of the hood. If chemical needs to be added or removed, this manipulation is carried out in the hood. In this manner, all open chemical handling is conducted in the laboratory hood.
  • Use a properly functioning lab fume hood when handling carcinogens.
  • If the process does not permit the handing of such materials in a fume hood, contact your DSA for reviewing the adequacy of ventilation measures.
  • In addition to proper street clothing (long pants or equivalent) that covers legs and ankles, and close-toed non-perforated shoes that completely cover the feet, wear a lab coat, appropriate eye protection and chemically resistant gloves.

More Information about Carcinogen Use at UCSF:

Quick Guide for Principal Investigators and Lab Supervisors Carcinogen Safety Program

Formaldehyde Use Guidelines

Pyrophoric Materials

Pyrophoric materials are chemicals that spontaneously ignite in the presence of air, some are reactive with water vapor, and most are reactive with oxygen. Because pyrophoric substances can spontaneously ignite on contact with air and/or water, they must be handled under an inert atmosphere and in such a way that rigorously excludes air and moisture. Some pyrophoric materials are also toxic and many are dissolved or immersed in a flammable solvent.

Two common examples are organolithium reagents and white phosphorus.

General Storage Requirements for Pyrophoric Materials

  • Only minimal amounts of pyrophoric chemicals should be used in experiments or stored in the laboratory.
  • These chemicals must be stored as recommended by the Manufacturer’s SDS. Suitable storage locations may include inert gas-filled desiccators or glove boxes; however, some pyrophoric materials must be stored in a flammable substance approved freezer.
  • If pyrophoric or water reactive reagents are received in a specially designed shipping, storage or dispensing container (such as the Aldrich Sure/Seal packaging system), ensure that the integrity of that container is maintained.
  • Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the container while pyrophoric materials are stored.

Additional Safety Resources:

Safe Use of Pyrophoric Organolithium Reagents

Explosive Chemicals

Explosive chemicals can rapidly release tremendous amounts of destructive energy and cause death, serious injury, or severe property damage. Heat, shock, friction, or even static electricity can initiate explosions of these chemicals. Explosive chemicals include the following classes of chemicals:

Nitrogen Oxides (e.g., Nitrates, Nitro)

  • ethylidene dinitrate
  • picric acid (dry)
  • thallium aci-phenylnitromethanide
  • trinitrotoluene (TNT)
  • hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)
  • octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)

Oxides, Peroxides, and Related Chemicals

  • benzoyl peroxide (97%) (dry)
  • bis (1-chloroethylthallium chloride) oxide

Nitrogen-Rich Chemicals (e.g., Azo-, Diazo, Triazo, Tetrazole)

 

  • aluminum azide
  • 5-aminotetrazole
  • 1-bromoaziridine
  • chromyl azide chloride
  • diethyl diazomalonate
  • hydrogen azide (>17%)
  • lead azide
  • mercury (I&II) azide
  • molybdenum diazide tetrachloride
  • sodium diazomethanide
  • tetrazole
  • 1,2,3-triazole

 

Perchlorate Chemicals

  • ammonium perchlorate
  • ethyl perchlorate (the most explosive chemical known)
  • hexyl perchlorate

Acetylenic Chemicals

  • n-chloro-3-aminopropyne
  • propiolic acid
  • 3-propynethiol
  • 4-sodium hexakis(propynyl)ferrate

Potentially Explosive Chemicals

In addition to explosive chemicals, which constitute a known high hazard, there are chemicals that may become explosive, depending on how they are handled. This category is commonly referred to as potentially explosive chemicals and includes:

  • Organic chemicals, such as ethers, that form peroxides through exposure to air or light
  • Hydrated chemicals such as picric acid and 2,4-Dinitrophenlyhydrazine that can become shock sensitive when dry.
  • Sodium amide that reacts with air or moisture.
  • Certain alkyl nitrates (e.g., butyl nitrate or propyl nitrate) that become contaminated with nitrogen oxides.
  • Certain normally stable perchlorates (e.g., pyridinium perchlorate or tetraethylammonium perchlorate) that becomes unstable at elevated temperatures.

Precautions for Explosive and Potentially Explosive Chemicals

  • Identify all explosive and potentially explosive chemicals in your inventory.
  • Always follow the safe storage guidelines outlined in the manufacturer’s SDS.
  • For chemicals that may degrade to become potentially explosive, record the opening date and discard date directly onto the container.
  • Keep explosive chemicals away from all ignition sources including open flames, hot surfaces, direct sunlight, and spark sources.

Peroxide Forming Chemicals

Overtime these chemicals can react with air to form peroxides that may explode with shock, heat, or friction. Some chemicals may also form peroxides when concentrated by evaporation or distillation. More information on the safe storage, handling and disposal of peroxide forming chemicals is available in the Managing Peroxide Forming Compounds Safety Update on the EH&S website.

General Precautions for Peroxide Forming Chemicals

  • Where possible always purchase peroxide formers with an inhibitor.
  • All peroxide formers must be dated with date received and the date opened.
  • Peroxide formers must be tested for peroxides periodically and before distillation to ensure dangerous peroxide formation has not occurred.
  • Uninhibited peroxide formers such as Tetrahydrofuran should be stored under an inert gas to prevent peroxide formation.

Compressed Gasses

Gas cylinders containing compressed gases contain a lot of stored energy that can cause serious injury and property damage if the cylinder is damaged or knocked over. Additional hazards can arise from the toxicity, flammability, corrosively, or reactivity of the gas in the cylinder.

Storage Precautions for Compressed Gases

  • Segregate incompatible gases as you would other incompatible chemicals.
  • Limit the quantity of compressed gas cylinders on site to what will be used within a reasonable period of time.
  • Store cylinders upright.
  • Two chains or straps must be used to secure cylinders - one across the lower third and one across the upper third of the cylinder.
  • Keep cylinders away from heat and open flames.
  • Leave the valve protection cap on the cylinder unless it is in use.

More requirements and guidelines for the safe use of gas cylinders is available in the Compressed Gas Cylinder and Cryogenic Liquid Safety Update

Cryogens

These materials are extremely cold (-100°C to -270°C). Upon contact with cryogenic materials, living tissue can freeze and become brittle enough to shatter. Additional hazards include rapid pressure buildup, oxygen enrichment, and asphyxiation. Rapid pressure buildup could lead to an explosion if a cryogen is improperly contained. Cryogenic liquids and gases have many properties and hazardous characteristics in common with compressed gases.

General Precautions for Using Cryogens

  • Store and handle in a well-ventilated area. When liquid cryogens are converted to the gaseous phase, they may create an oxygen deficiency. Do not use cryogens in small enclosed areas.
  • Use only approved storage vessels (i.e., thermos-like evacuated, double-walled containers) with pressure relief mechanisms. Non-approved vessels may explode.
  • Secure containers so they will not tip over or obstruct an aisle, hallway, or corridor during an earthquake.
  • Liquid nitrogen and liquid helium are capable of liquefying oxygen from air. This form of oxygen enrichment can become a strong fire or explosion hazard.
  • Use appropriate protective equipment for handling cryogens: insulated holders for carrying vessels; eye protection, goggles, or face shields, and cryogenic gloves.

More requirements and guidelines for the safe use of cryogens available on the Compressed Gas Cylinder and Cryogenic Liquid Safety Update

Standard Operating Procedure (SOP)

Requirements

The Laboratory Standard, under the provisions of the Chemical Hygiene Plan, requires standard operating procedures (SOPs) be established for work with hazardous chemicals: "Standard operating procedures relevant to safety and health considerations must be followed when laboratory work involves the use of hazardous chemicals.” All lab personnel, who perform hazardous operations, need to document that they have read and understand all SOPs relevant to their research. New students/employees shall be given hands-on training by their supervisor for hazardous operations which should include all relevant SOPs.

Standard Operating Procedure

  • UCSF requires investigators who work with hazardous chemicals to log in to RIO to upload SOP.
  • SOPs are written instructions that detail the requirements for working with hazardous chemicals and/or processes.
  • All SOP templates used is approved by the USCF Chemical Environmental Safety Committee (CESC) for work with hazardous chemicals.

At UCSF, a standard operating procedure can be found within the EHS webpage. SOPs must be developed, reviewed, approved, and confirmed before using chemicals.

Particularly hazardous substances

Particularly hazardous substances include (but is not limited to) select carcinogens, reproductive toxins, and substances which have a high degree of acute toxicity. Provisions for additional employee protection are required for work with particularly hazardous substances.

Important – For all work with particularly hazardous substances, the PI / lab supervisor must complete an appropriate Standard Operating Procedure, including:

  • Carcinogens
  • Reproductive hazards
  • Acutely toxic materials

Provisions for additional employee protection for work with particularly hazardous substances. These include "select carcinogens," reproductive toxins and substances which have a high degree of acute toxicity. Specific consideration shall be given to the following provisions which shall be included where appropriate;

  • Establishment of a designated area;
  • Use of containment devices such as fume hoods or glove boxes;
  • Procedures for safe removal of contaminated waste; and
  • Decontamination procedures.

Purchasing Chemicals, Security and Maintaining Chemical Inventories

The decision to procure a specific quantity of a specific chemical is a commitment to handle it responsibly from receipt to disposal. Laboratories should make a conscious effort to only order the quantity needed for their laboratory procedures which can be safely stored in their laboratory. Whenever there is a significant change in chemical amounts, chemical functionality, the introduction of new equipment, new chemicals, a new procedure, or a new work space, PI approval must be given prior to ordering the chemical to ensure that conditions exist to protect the worker.

Laboratory and Chemical Security

All laboratory personnel have a responsibility to protect university property from misuse and theft of hazardous materials, particularly those that could threaten human health. To minimize the theft and improper use of hazardous chemicals including toxic and corrosive substances the following actions should be employed in all campus laboratories:

  • Inventories must be maintained for all hazardous chemicals. Hazardous chemicals include chemicals for which there is statistically significant evidence of health effects following exposure as well as flammable and explosive substances.
  • Access to all hazardous chemicals, including toxic and corrosive substances, must be restricted. Specifically, these materials should be stored in laboratories or storerooms that are kept locked when laboratory personnel are not present.
  • In the case of unusually toxic or hazardous materials, additional precautions are required, such as keeping the materials in locked storage cabinets or storerooms.
  • All chemicals listed as chemicals of interest by Department of Homeland Security must be kept locked, with one designated lab personnel keeping a log of usage.
  • Unusually toxic or hazardous materials include substances with a high degree of acute and/or chronic toxicity and also may include explosives, certain highly reactive and/or corrosive substances. Unusually toxic chemicals are those that meet the OSHA definition of high acute toxicity (oral LD50 <50mg/kg, skin contact LD50 < 200 mg/kg, or inhalation LC50 <200 ppm in air).
  • Areas where biological agents and radioactive material are stored must be kept secure when not in use.
  • Restrict access to the laboratory to authorized personnel only and become familiar with these people.
  • The laboratory door should remain locked when not occupied.
  • Always feel free to question anyone that enters the lab that you do not know and ask to see identification if necessary.
  • If you see anything suspicious or someone displays suspicious behavior, immediately report it to the UCSF Police Department by dialing 9-911 (emergency) or (415) 476-1414 (non-emergency).

Maintaining a Chemical Inventory

Principal Investigators are responsible for maintaining an accurate chemical inventory of their laboratory. At UCSF inventories must be updated annually through RIO.

More information about how to submit a chemical inventory for your laboratory can be found in the Online Chemical Inventory FAQ.

Control Measures to Reduce Exposures

Limiting exposure to chemicals can be achieved through administrative controls, engineering controls and personal protective equipment.

Administrative Controls

Administrative controls are changes in work practices to reduce the duration, frequency and severity of exposure. Examples of administrative controls include

  • Substituting a less hazardous chemical for a more hazardous one.
  • Modifying a procedure to make it less hazardous
  • Develop and follow standard operating procedures that are designed to reduce the chances of exposure.

Engineering controls

All laboratories at UCSF are designed to have a minimum of 6 air changes per hour. This airflow reduces employee exposure to airborne contaminants and removes excess heat. Because airflow is greater in laboratory areas compared to non-laboratory areas, airflow is negative with respect to the hallway, keeping odors and hazardous gases, dusts, and vapors out of the hallway and other public areas.

Fume Hoods

Fume hoods are ventilated enclosures designed to trap airborne contaminants and chemical vapors and exhaust them outside the building away from the user and the laboratory environment. At UCSF, EH&S tests and certifies all fume hoods annually. When used properly they can be an effective tool to protect laboratory workers from chemical hazards. When using a fume hood always follow these safe practices:

  • Ensure the fume hood has been certified within the last year by checking the calibration sticker on the front of the hood.
  • Close the sash to the 18-inch mark indicated on the front of the hood to ensure adequate face velocity and to protect against splashes, fire, and explosions.
  • Always work as far back as possible within the hood or at least 6 inches from the face of the hood.
  • Do not use the hood for storage of chemicals.
  • Cap all containers when not in use.
  • Avoid storing bulky items or equipment in the hood when possible as this can restrict airflow in the hood. When equipment is required to be placed in a hood, it should be elevated at least 2-3 inches by placing securely on blocks to assist with airflow.
  • Always verify proper function of the hood before use by checking the fume hood monitor or alarm before beginning work.
  • If you notice a fume hood is not functioning properly stop using the hood, close all the containers, close the sash, post a do not use sign on the fume hood, and submit a work order to Facilities Management for repair.

Personal Protective Equipment (PPE)

All campus research laboratories are required to complete the Laboratory Hazard Assessment Tool (LHAT) and update it at least annually. LHAT facilitates identification of hazards and identifies the Personal Protective Equipment (PPE) to be used during the specified work activities. All laboratory personnel are required to wear PPE when working with chemicals. At a minimum this includes pants and closed toe shoes, chemically resistant gloves, a laboratory coat, and eye protection.

Glove Selection

When working with hazardous chemicals, select gloves that provide adequate protection to the chemical hazards. Disposable nitrile gloves provide short term protection against a broad range of chemicals but do not protect against all chemicals. Glove manufacturer’s websites can be consulted to determine the best glove for protecting against a chemical. Glove selection resources are available on the UCSF webpage here: http://www.ehs.ucsf.edu/glove-selection-guide

Special PPE for Handling Pyrophorics

When working with pyrophorics the following PPE must be worn from setup to quenching of the reaction.

  • Chemical Splash goggles or safety glasses that meet the ANSI Z.87.1 1989 standard.
  • A face shield worn over safe ty glasses, is required any time there is a risk of explosion, large splash hazard or a highly exothermic reaction.
  • Ansell Kevlar® Goldknit® Lightweight 70-200 reusable base gloves must be worn and covered with a disposable neoprene glove (equal or greater size to preserve dexterity). Neoprene/Nitrile gloves should be inspected prior to each use and changed at any contact and disposed of after each use. Note: The tags on the Kevlar glove must be removed before use, since the tags themselves are not flame resistant.
  • A Nomex® laboratory coat with cotton type clothing underneath. Lab coats need to be buttoned and fit properly to cover as much skin as possible.
  • Appropriate shoes that cover the entire foot (closed toe, closed heel, no holes in the top) and long pants must be worn.
  • Avoid clothing fabrics that are made of polyester or acrylic material.

Respiratory Protection

Administrative and Engineering Controls should always be used first to help ensure exposures to dust and fumes are below the Permissible Exposure Limits (PEL’s). If this is not feasible, a respirator is required. Use of a respirator has several requirements which may include the following:

  • Annual medical evaluations and fit testing.
  • Education and training on the proper use, storage and cleaning procedures for respirators.
  • Training on how to adjust equipment and ensure proper fit to maximize protection from dusts and fumes.

If you think your laboratory procedures require the use of a respirator contact your Department Safety Advisor for assistance.

Medical Consultation and Treatment

All non-emergent work-related medical assessments will be performed under the direction of the UCSF Occupational Health Services (OHS) by licensed physicians or staff under the direct supervision of a licensed physician. Medical evaluations, examinations, clinical investigations and consultations will be provided without cost to the employee, without loss of pay, and at a reasonable time and place.

Sometimes access to medical care is required immediately, or emergently. Employees, student workers, and laboratory staff should seek immediate care as follows:

1. For immediate medical attention, always proceed to the nearest emergency room or call 9-911.

2. For immediate access to information about the health effects of a chemical, contact the Poison Control Hotline at 1-800-222-1222.

All employees, student workers, or laboratory personnel who work with hazardous chemicals shall have the opportunity to receive a medical assessment, including supplemental examinations which the evaluating physician determines necessary, under the following circumstances:

  1. Whenever an employee develops signs or symptoms associated with a hazardous chemical to which an employee may have been exposed to in a laboratory;
  1. Where personnel monitoring indicates exposure to a hazardous chemical is above a Cal/OSHA Action Level (AL) or Permissible Exposure Limit (PEL) or recommended exposure levels established by the National Institute for Occupational Safety & Health (NIOSH) or the American Conference of Government Industrial Hygienists (ACGIH) in the event Cal/OSHA has not established an AL or PEL for a particular hazardous chemical;
  1. Whenever an uncontrolled event takes place in the work area such as spill, leak, explosion, fire, etc., resulting in the likelihood of exposure to hazardous chemical; or
  1. Upon reasonable request of the employee to discuss medical issues and health concerns regarding work-related exposure to hazardous chemicals.

Employees, student workers, and laboratory personnel can access OHS following a significant work-related exposure to a hazardous chemical, or following a visit to the emergency department by telephoning 415-885-7580 to arrange an appointment.

In preparation for the medical assessment, please bring the following information to the appointment:

  1. Common and/or IUPAC name of the hazardous chemical(s) to which the individual may have been exposed;
  2. A description of the conditions under which the exposure occurred;
  3. Quantitative exposure data, if available;
  4. A description of the signs and symptoms experienced from the exposure, if any;
  5. A copy of the Safety Data Sheet (SDS) of the hazardous chemical(s) in question;
  6. History of exposure including previous employment and non-occupational (recreational) hobbies; and
  7. Any additional information helpful to OHS in assessing or treating an exposure or injury such as a biological component of exposure or existence of an antitoxin.

Medical Assessment Results

OHS will provide the results of any medical examination, clinical investigations and consultations to the employee. In addition, OHS will provide a written statement to the supervisor informing the supervisor that the employee has received the results of the medical assessment and has been advised of any medical conditions that may require further examination and treatment. The written opinion shall include any medical condition which may place the employee at increased risk from chemical exposures in the workplace and any work restrictions recommended by the physician.

Confidentially & Individual’s Access to Personal Medical Records

All patient medical information is protected by California and federal law and is considered strictly confidential. OHS is prohibited from disclosing any patient medical information that is not directly related to the work-related exposure under evaluation and should not reveal any diagnosis unrelated to exposure. Any patient information disclosed by OHS to the employee’s supervisor will be limited to information necessary in assessing an employee’s return to work, including recommended restrictions in work activities, if any. Any patient information disclosed by OHS to EH&S will be limited to information necessary to develop a course of exposure monitoring, or perform hazard assessments and incident investigations, if appropriate. OHS will otherwise disclose patient medical information only as required by California and Federal law, such as for Worker’s Compensation Insurance claims. Each employee has the right to access his/her own personal medical and exposure records. OHS will provide an employee with a copy of his/her medical records upon written request.

Purchasing Restrictions

Ordering regulated carcinogens listed under Title 8 of CCR, §5209. Carcinogens requires prior approval from EH&S. Whenever these chemicals are ordered, the order is flagged and sent to the Chemical Hygiene Officer (CHO) for approval prior to the order being completed. The carcinogens listed under this regulation have additional requirements that the CHO must verify are in place prior to authorizing a lab to use one of these chemicals.

Occupational Monitoring

Cal/OSHA Laboratory Standards require employers to monitor hazardous material levels in the work area if there is concern that the exposure levels may exceed permissible exposure levels. Evidence that may suggest overexposure includes symptoms of overexposure such as dizziness or headache, a hazardous materials accident, or monitoring that reveals routine levels exceeding permissible exposure levels. If such monitoring indicates that possible overexposure occurred, the employer must reduce those levels. The employer must re-monitor the hazardous levels after implementation of corrective action to make sure the problem has been abated. Occupational Exposure may include radiation, chemicals, biological, or be physical in nature. These include noise, chemical vapor, ergonomics, indoor air quality, electrical safety, radioactive waste, and others. EH&S can monitor for most air contaminants. Upon request, can provide air monitoring for labs using formaldehyde or other chemicals, and non-routine air monitoring.

Chemical Spills

Chemical spills can result in chemical exposures and contaminations. Whether a chemical spill can be safely cleaned up by laboratory staff depends on multiple factors including the hazards of the chemicals spilled, the size of the spill, the presence of incompatible materials, and whether you have adequate training and supplies to safely clean up the spill. DO NOT enter the area if you cannot assess the conditions of the environment well enough to be sure of your own safety.

Small chemical spills of low toxicity which do not present the potential for over exposure or a significant inhalation hazard by being volatile or a dust can generally be safe to clean up by laboratory personnel. Small spill is general a spill involving a chemical that is not highly toxic, does not present a significant fire or environmental hazard, and is not in a public area such as a common hallway. Large chemical spills include spills of any quantity of highly toxic chemicals or chemicals in public areas or adjacent to drains. Large spills require emergency response.

How to handle a small spill:

  • Evacuate all non-essential persons from the spill area.
  • If needed call for medical assistance by dialing 9-911 from campus phone or 415-476-6911 from an off-campus or cell phone.
  • Confine the spill small area. Do not let it spread.
  • Avoid breathing in vapors from the spill. If the spill is in a non-ventilated area, do not attempt to clean it up. Call for emergency personnel to respond and clean up the spill.
  • Don appropriate PPE including a laboratory coat, splash goggles, and appropriate chemically resistant gloves.
  • Work with another person to clean-up the spill. Do not clean-up a spill alone.
  • DO NOT ADD WATER TO THE SPILL.
  • Use appropriate kit to neutralize and absorb inorganic acids and bases. For other chemicals use the appropriate kit or absorb the spill with sorbent pads, vermiculite or dry sand.
  • Collect the residue and place it in a clear plastic bag. Double bag the waste and label the bag with the contents. Fill out a WASTe tag for pick-up.

Large chemical spills require emergency response. Call 9-911 from a campus phone or (415) 476-6911 on a cell phone or (415) 206-8522 for SFGH. If the spill presents situation that is immediately dangerous to life or health (IDLH) or present significant fire risk, activate a fire alarm, evacuate the area and wait for emergency response to arrive.

  • Remove the injured and/or contaminated person(s) and provide first aid
  • Call for emergency medical response
  • As you evacuate the laboratory, close the door behind you, and:
    • Post someone safely outside and away from the spill area to keep people from entering
    • Confine the spill if possible and safe to do so
    • Leave on or establish exhaust ventilation
    • If possible, turn off all sources of flames, electrical heaters, and other electrical equipment if the spill material is flammable
    • Avoid walking through contaminated areas or breathing vapors of the spilled material
  • Any employee with known contact with a particular hazardous chemical must shower, including washing of the hair as soon as possible unless contraindicated by physical injuries

Highly Toxic Chemical Spills

Do not try to clean up spills of any size. All spills require emergency response:

Aromatic amines Hydrazine

Bromines Nitriles

Carbon disulfide Nitro-compounds

Cyanides Organic halides

Ethers

Emergency showers and eyewashes

Before beginning work in the laboratory all employees must be familiar with the location of emergency showers and eyewashes and how to use them. The pathways to and around emergency equipment must be kept clear at all times to allow for unobstructed access.

Emergency Eyewashes

  • Immediately flush eyes for at least 15 minutes. Any delays can result in serious damage. Ask someone in the laboratory to assist you.
  • Use your hands to open your eyelids while rotating the eyeballs in all directions to remove contamination from around the eyes.
  • Seek medical attention after washing the affected area for 15 minutes by calling 9-911 or proceeding to the nearest emergency care facility.

Emergency Showers

  • Remove contaminated clothing, shoes, jewelry and your laboratory coat. Ask someone in the laboratory to assist you.
  • Immediately flush the area with copious amounts of water for at least 15 minutes. If your eyes do not require flushing attempt to protect the eyes from cross contamination.
  • Seek medical attention after washing the affected area for 15 minutes by calling 9-911 or proceeding to the nearest emergency care facility.

Disposal of Hazardous Chemicals

Waste Determination

A chemical waste is considered a hazardous waste if it is listed as a hazardous waste by state and federal regulations or exhibits certain characteristics of ignitability, corrosiveness, reactivity, and toxicity. Hazardous waste has important labeling, storage, and disposal requirements which must always be followed. EH&S lists chemicals which are Non-Hazardous Chemical Waste on the EH&S webpage. These chemicals are approved to be disposed down the drain. All other chemicals must be managed as a hazardous waste at UCSF.

Chemicals which are Considered Hazardous by Exhibiting a Characteristic

Ignitable: Ignitable wastes can create fires under certain conditions, undergo spontaneous combustion, or have a flash point less than 60°C (140°F). Primary alcohols in concentrations of 24% or less by volume are not considered ignitable.

Corrosive: Aqueous wastes with a pH less than or equal to 2.0 or greater than or equal to 12.5 are corrosive. A liquid waste may also be corrosive if it is able to corrode metal containers, such as storage tanks, drums, and barrels.

Reactive: Reactive wastes are unstable under normal conditions. They can cause explosions or release toxic fumes, gases, or vapors when heated, compressed, or mixed with water. Examples include lithium-sulfur batteries and unused explosives.

Toxic: A waste is considered toxic if it has an Oral LD50 less than 2,500mg/kg, Dermal LD50 less than 4,300 mg/kg, 96-hour Aquatic Bioassay less than 500 mg/kg, or contains 0.001% by weight of 16 different carcinogens.

Labeling of Waste

All hazardous waste containers must be labeled with a hazardous waste tag using WASTe as soon as the first drop of waste is added to the container.

Proper Storage

Hazardous waste should be stored in a designated location according to compatibility and storage recommendation for the chemical hazard. Incompatible waste should be stored in separate locations or segregated with secondary containment. Flammable waste should be stored in an approved flammable cabinet and corrosive waste should be stored in an approved corrosive cabinet. Special pressure vented caps are available from EH&S for waste containers that may evolve gas or for other oxidizers and may help prevent an explosion due to accidental contamination of a waste container containing an oxidizer.

Arranging for Disposal

WASTe automatically notifies EH&S to pick up waste containers once they reach the maximum accumulation time of 180 days storage in the laboratory. Arranging for disposal prior to 180 days can be done through WASTe

Questions about Hazardous Waste and Using WASTe

Most questions about using WASTe are addressed in the online FAQ and Tutorials. For additional questions about managing hazardous waste or to set up a WASTe account for your laboratory email: waste@ucsf.edu


Regulations

§5191. Occupational Exposure to Hazardous Chemicals in Laboratories.

§5194. Hazard Communication

§3203. Injury and Illness Prevention Program.

§3380. Personal Protective Devices.

Article 110. Regulated Carcinogens

§5209. Carcinogens.

§5533. Design, Construction, and Capacity of Storage Cabinets.

§5532. Design, Construction, and Capacity of Containers.

§5538. Office, Educational and Institutional Occupancies.