Chemical Safety

Missouri S&T Laboratory Chemical Hygiene Plan

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Table of Contents

Section 1-Chemical Hygiene Plan

Introduction

Chemical Hygiene Responsibilities

Definitions

Training and Information

Chemical Exposure Assessment

Chemical Hood Evaluation

Respiratory Protection Program

Section 2- Standard Operating Procedures for Working with Chemicals

Good Work Practices/Procedures for Handling Laboratory Chemicals

When Not To Proceed Without Reviewing Safety Procedures

Protective Clothing & Safety Equipment

Chemical Procurement, Distribution & Storage

Chemical Spills & Accidents

Personal Contamination & Injury

Fire and Fire Related Emergencies

Chemical Waste Disposal Program

Section 3- Information for Work with Chemicals of Specific Hazard Class

Flammable Liquids

Highly Reactive Chemicals & Energy Oxidizers

Compressed Gases

Corrosive Chemicals

Chemicals of Acute and High Toxicity

Protocols for Dealing with Carcinogens, Mutagens and Teratogens

Section 4- Chemical Toxicology

Chemical Toxicology Overview

Some Target Organ Effects

Occupational Health Standards

Section 5- Glossary of Terms

Glossary of Terms

Appendices

Appendix A - Select Carcinogens List

Appendix B - Peroxide Test Protocol

Appendix C - Department Standard Operating Procedures

Appendix D - OSHA Laboratory Standard

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Section 1- Chemical Hygiene Plan 

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Introduction

The Missouri University of Science and Technology (Missouri S&T) is committed to providing a safe learning and working environment for our students and employees. As part of this commitment, this chemical hygiene plan has been developed to establish a standard format for chemical safety in the laboratories of the university following the guidance of the Occupational Safety & Health Administration (OSHA) Laboratory Safety Standard (29 Code of Federal Regulations (CFR) 1910.1450). The standard was developed to ensure that laboratory employees are informed about the hazards associated with the chemicals used in their work area and that appropriate work practices and procedures are in place to use these chemicals in a safe and informed manner based on the known hazards for the chemicals. This plan will ensure personnel will be trained and learn to recognize and comply with workplace safety requirements.

The standard operating procedures (lab practices and engineering controls) recommended by this plan identify safeguards that should be taken when working with hazardous materials. These safeguards will protect workers in a majority of situations. In some instances the physical or chemical properties, the proposed use, the quantity of material used or the toxicity will require more controls than this plan provides. Professional judgment is an essential requirement for interpretation of these operating procedures and individual laboratories will need to modify these procedures to meet the requirements of their specific research and operational needs.

The implementation of this plan and development of lab specific procedures should result in a safer work and learning environment for employees and students.

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Chemical Hygiene Responsibilities

Responsibility for chemical health and safety rests at all levels at the university. A detailed listing of management responsibilities is found in the overall lab safety program manual and applies to this chemical hygiene plan as well. The responsibilities of supervisors, lab employees and the department of Environmental Health and Safety under this plan are as follows:

Department Chairs

Designate a Chemical Hygiene Officer for department, communicate with faculty, staff, students, and visitors to ensure responsibilities are carried out, monitor implementation of the program, provide resources to support safety program.

Chemical Hygiene Officer

• Develop, implement and revise this chemical hygiene plan, policies and practices. Maintain an awareness of current requirements concerning regulated substances. Responsible for program oversight.

•  Monitor purchasing, use, and disposal of chemicals and biological materials used in these laboratories.

• Assure appropriate records are maintained (training, audit reports, injury reports etc.).

• Ensure that faculty, staff and students know and follow the chemical hygiene rules.

• Provide regular formal laboratory hygiene and housekeeping inspections including routine inspections of any emergency equipment required by this plan for this laboratory.

• Assist the PI in determining the required or appropriate levels of protective apparel and equipment.

Principal Investigator

• Maintain an awareness of current requirements concerning regulated substances. Responsible for daily operations.

• Monitor purchasing, use, and disposal of chemicals and biological materials used in these laboratories.

• Assure appropriate records are maintained for the individual lab if required (e.g. training, audit reports, injury reports etc.).

• Ensure that individuals working in this laboratory know and follow the chemical hygiene rules.

• Provide informal daily laboratory and housekeeping inspections including any emergency equipment as required.

• Develop laboratory specific operating procedures based on chemical and physical hazards associated with lab operations.

• Determine the required or appropriate levels of personal protective equipment (PPE). Make sure this equipment is in good working order and make sure it is used properly and that all personnel receive the necessary training needed to properly use equipment.

• Ensure that facilities and training for use of any new materials being ordered are adequate for the material.
• Seek ways to improve the hygiene plan.

 Laboratory Staff

• Planning and conducting each experiment in accordance with the laboratory chemical hygiene plan and procedures.

• Determine any additional safety considerations needed, carefully consider each aspect of the experiment, even if it is a protocol you do repeatedly and are very familiar with all areas of the protocol.

• Develop and practice good personal chemical hygiene habits.

• Attend all required training.

• Be aware of the hazards of the materials worked with and handle those materials in a safe manner. Wear all required PPE.

• Report unsafe conditions to supervisor, or the department chemical hygiene officer.

 Students

• Attend all training sessions and follow all standard operating procedures for working in a laboratory.

• Wear personal protective equipment as directed by principal investigator.

• At a minimum, wear safety glasses at all times when in the laboratory.

• Report to the teaching assistant, faculty member, or department chemical hygiene officer/laboratory supervisor any accidents that result in the exposure to toxic chemicals, and any action or condition that may exist that could result in an accident.

 Environmental Health and Safety

• Evaluate and implement safety policies and review new and existing equipment and operating practices to minimize hazards from fire, electricity, hazardous materials, explosion, pressure, and machinery.

• Conduct accident investigations and suggest remedial measures and procedures.

• Hazardous waste disposal services for chemical, biological, and radioactive materials.

• Training and assistance are available as required.

• Oversight and control of physical hazards in the workplace, including general and laboratory safety.

 *All members of the University should feel free to consult with the Department of Environmental Health and Safety (EHS) at anytime regarding potential toxic chemical, microbiological or radiation exposure. EHS services are available in both emergency and advisory capacities to answer questions from anyone at the University. However, procedures for the safe use and disposal of chemicals or radioactive substances start in the laboratory with students and staff. They must be informed about their responsibilities and the procedures to be followed by the Principal Investigator.

In the event of an emergency, please call the University Police at x4300.

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Definitions

Laboratory

A laboratory is defined as a facility in which hazardous chemicals are handled or manipulated in reactions, transfers, etc. in small quantities on a non-production basis. Typically multiple chemical procedures are used.

Hazardous Chemicals

Any element, chemical compound, or mixture of elements and/or compounds which is a physical hazard or health hazard regardless of quantity.

A chemical is a physical hazard if there is scientific, valid evidence that it is a combustible liquid, a compressed gas, an explosive, an organic peroxide, an oxidizer or pyrophoric, flammable, or reactive.

A chemical is a health hazard if there is statistically significant evidence, based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees.

 Classes of health hazards include:

The chemical container label will indicate if the chemical is hazardous. Look for key words like caution, hazardous, toxic, dangerous, corrosive, irritant, carcinogen, etc. Chemicals manufactured or acquired prior to 1985 may not contain appropriate warnings. Always consult theMaterial Safety Data Sheet(MSDS) prior to using a chemical to identify the hazards associated with the material.

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Training and Information

Chemical Safety Training

All employees potentially exposed or exposed to hazardous chemicals while performing their laboratory duties should receive annual training on the chemical hygiene plan and laboratory safety. All new graduate students should attend training provided by EHS at the beginning of each fall semester and should have additional training or guidance from their supervisor prior to beginning lab work.

The training program shall include information on:

• Physical and health hazards of various classes of laboratory chemicals handled;

• Methods/procedures for safely handling and detecting the release of hazardous chemicals present in the laboratory;

• Appropriate spill response;

• Chemical safety policies;

• Applicable details of the Chemical Hygiene Plan (e.g. Standard Operating Procedures (SOPs), etc.)

When a non-routine task is to be performed by an employee for which they have not received training, the employee's supervisor is responsible for informing the employee about the hazards of the task and any special measures (e.g. personal protective equipment (PPE) or engineering controls that may be required to protect the employee.

Every lab worker should know the location and proper use of available PPE and emergency equipment and procedures. Information on protective clothing and equipment is contained in Section 2.3 of this manual.

Students, visitors, and other authorized personnel must receive appropriate training prior to working in any laboratory where hazardous chemicals are stored or used.

Safety Information

There are many sources of safety information available. Health and Safety references are available in the EHS office and the labels on the containers of chemicals offer a great deal of information. The best source for chemical specific data is the MSDS for the chemical that will be used in the lab. MSDS are available on the web and can be accessed from the EHS website: ehs.mst.edu, however, it is strongly suggested that hard copies of the MSDS's for the material with greatest hazards be readily available in the lab in a clearly labeled notebook. Otherwise, a computer must be available to all lab workers in order to access the information. Laboratory signage is also a good source of information about the hazards present in the laboratory.

If you find a container with no label, report it to your supervisor. Also report labels that are torn or illegible so the label can be replaced immediately. Never remove the manufacturer label from a container unless the container is completely empty, rinsed, and being used for another purpose. Always read the label and MSDS on newly purchased material and become familiar with its hazards.

Material Safety Data Sheets

A material safety data sheet, MSDS, contains detailed information prepared by the manufacturer or importer of a hazardous chemical describing the physical and chemical properties of the material. This information can help in the selection of safe products, and help employees understand potential health and physical hazards of a chemical and how to respond effectively to exposure situations.

The format of MSDS's is not uniform and can vary. However, there is specific information that must be included. All of the following information should be found on any MSDS:

Section I: Identifies the manufacturer, address, phone number, number to call in case of emergency, chemical name and symbol, trade name and synonyms, the chemical abstract service number (CAS#).

Section II: Describes the hazardous ingredients, the percentages, and exposure limits when applicable.

Section III: Describes the physical properties of the material (e.g. boiling point, vapor pressure, specific gravity, solubility in water)

Section IV:  Describes the fire and explosion hazard data for the material. Based on flash point and other fire data, the appropriate extinguishing agent will also be listed.

Section V: Describes the known health hazards associated with the material, applicable exposure limits and symptoms/health effects from overexposure.

Section VI:  Describes reactivity data.

Section VII:  Provides instructions for the steps to be taken in case of accidental release or spill.

Section VIII:  Details the protective equipment for the individual who might have to work with the substance. The section usually has worst-case conditions, so the extent of personal protective equipment required is task dependent. Contact your supervisor for specific instructions.

Section IX:  Describes handling and storage procedures for the material.

Section X:  Describes any special precautions or miscellaneous information regarding the material.

Manufacturers may withhold certain information as proprietary on the MSDS if the information is considered a trade secret, however the chemical hygiene officer has a legal right to obtain this information to evaluate potential health risks if potential overexposure or adverse health effects are suspected.

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Chemical Exposure Assessment

As chemicals are used for relatively short periods of time and in small quantities, regular environmental or employee exposure monitoring of airborne concentrations is not practical. However, sampling is appropriate when a highly toxic substance is used regularly (3 or more separate handling times per week) or if the material is used for an extended period of time (more that 3-4 hours at a time). An assessment should also be conducted if a highly toxic material is used in large quantities. (29 CFR 1910.1450 (d))

EHS will also assess exposures to employees who suspect and report that they have been overexposed to a toxic chemical or are displaying symptoms of over exposure to toxic chemicals. The assessment will initially be qualitative and, based on the professional judgment of safety personnel, may be followed with specific quantitative monitoring. A report documenting this assessment will be issued to the employee, along with any results of monitoring that was conducted. Individual concerns about excessive exposures occurring in laboratories should be brought to the attention of your supervisor or EHS immediately.

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Chemical Hood Evaluation

All laboratory ventilation hoods used for control of air contaminants will be tested annually to assure adequate airflow is being maintained to provide necessary protection against employee over-exposure. Hood airflow will be considered adequate when the average face velocity equals a minimum of a 100 linear feet/minute with the hood sash at a working height (14-20 inches). Results of laboratory ventilation tests shall be recorded and maintained by EHS.

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Respiratory Protection Program

Missouri S&T works to minimize employee respiratory exposure to potentially hazardous chemical substances through engineering or administrative controls. However, for certain situations or operations, use of these controls may not be practical and respiratory protective equipment may be necessary. Emergency situations may necessitate the use of a respirator and a sound and effective program is essential to assure personnel using such equipment are adequately protected.

EHS personnel provide fit testing for any employee wishing to use a respirator and will provide recommendations for situations that require respiratory protection and the type of respirator needed in accordance with the university written Respiratory Protection Program. Please contact EHS with any requests for respiratory protection or questions concerning situations that might require protection. Be aware a physical is required prior to the fit testing and wearing of a respirator to insure the employee can safely work in a respirator.

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Section 2- Standard Operating Procedures for Working with Chemicals

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Good Work Practices /Procedures for Handling Laboratory Chemicals

General Guidelines

Carefully read the label before using any chemical. Also read the manufacturers or supplier's MSDS for any special handling instructions and hazards associated with the material. Be aware of potential hazards present in the lab and the appropriate safety precautions. This may include what other lab workers and students are working with, so pay attention to others working in the lab. Know the location and proper use of emergency equipment, the appropriate procedures for responding to emergencies, and the proper methods for storage and disposal of chemicals within the laboratory.

DO NOT WORK ALONE IN THE LABORATORY WITH HAZARDOUS MATERIAL OR PROTOCOLS. If you must work alone or in the evening, work only with non-hazardous materials and obtain permission from your principal investigator and let someone know you will be in the lab so they may check on you periodically.

Label all secondary containers with appropriate identification and hazard information. Use only those chemicals for which you have the appropriate exposure controls (hoods) and administrative programs/procedures (training, restrictive access, etc.). Always use adequate ventilation. Operations using large quantities (500 mls) of volatile substances with exposure limits at or below 50 ppm should be performed in a chemical hood.

Use hazardous chemicals and all laboratory equipment only as directed and for their intended purposes. Do not mute hood alarms or circumvent any other safety devices provided on laboratory equipment. Inspect all equipment or apparatus for damage before use or addition of hazardous chemicals. Do not use damaged equipment.

Inspect personal protective equipment for integrity or proper functioning prior to each use. Malfunctioning laboratory equipment should be labeled or tagged "out of service" so others will not use prior to repairs being made.

Handle and store laboratory glassware with care. Do not use damaged glassware. Use extra care with Dewar flasks and other evacuated glass apparatus; shield or wrap them to contain chemicals or fragments should implosion occur.

Do not dispense more of a hazardous chemical than is needed for immediate use.

Permissible Exposure Limits (PEL): OSHA has provided a list of permissible exposure limits (PELs) for a number of chemicals. The Missouri University of Science and Technology Chemical Hygiene Plan includes a Hazardous Chemical and Select Carcinogen List. These list all chemicals for which OSHA has prescribed a PEL. Carcinogens are listed separately because special handling is required for these chemicals.

 Personal Hygiene

• Remove contaminated clothing and gloves before leaving the laboratory.

• Avoid direct contact with any chemical and underestimation of risk. Minimize all chemical exposures. Exposures should be minimized even for substances with no known significant hazard. Never smell, inhale or taste a hazardous chemical. Wash thoroughly with soap and water after handling any chemical.
• Smoking, drinking, eating, storing food, and the application of cosmetics is forbidden in laboratories where hazardous chemicals are used. Do not store food or drink in laboratory refrigerators or freezers.

• Never pipet by mouth. Use a pipet bulb or other mechanical pipet filling device.

• Confine long hair and loose clothing. Wear shoes at all times in the laboratory but do not wear clogs, sandals, perforated, or cloth shoes.

 Housekeeping

• Keep floors clean and dry. Keep all aisles, hallways, and stairs clear of all chemicals. Stairways and hallways should not be used as storage areas.

• Keep all work areas, especially work benches, clear of clutter and obstructions. All work surfaces should be cleaned regularly.

• Access to emergency equipment, utility controls, showers, eyewashes, fire extinguishers and exits should never be blocked.

• All wastes should be properly containerized and labeled according to Missouri S&T chemical waste manual requirements and EMS requirements.

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When Not to Proceed Without Reviewing Safety Procedures

Certain indicators, such as procedural changes, should cause an employee to stop and review safety procedures for the new procedure or change to existing procedure. Even if the task seems familiar, hazards may exist that are not fully recognized and should be evaluated. These indicators may include:

• A new procedure, process or test, even if very similar to older practices.
• A change or substitution of any chemical ingredients in the procedure.
• A substantial change in the amount of chemicals used; review if increase is more than 200%.
• A failure of any equipment used in the procedure, especially safety equipment such as chemical hoods.
• Unexpected experimental results (pressure increase, increased reaction rates) or when the experimental result is different from the predicted. Review to determine if   changes in safety practices should be made.
• Chemical odors, illness in lab staff that may be related to chemical exposure or other indicators of failed engineering safeguards.

Occurrence of any of these conditions should initiate a re-evaluation of safety precautions and impacts on safety equipment or safety procedures. Changes should be made if necessary and the procedure may continue with caution.

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Protective Clothing & Safety Equipment

General PPE

Engineering and administrative controls should always be considered first when reducing or eliminating exposures to hazardous chemicals. These controls would include:

• Substitution of a less hazardous material
• Reduce the size of the experiment and quantity of hazardous chemicals
• Use less hazardous equipment or process (safety cans instead of glass)
• Isolation of operator or process
• Use chemical hoods or other type of local ventilation

The MSDS's will list PPE recommended for the material, but this will be a worst case, so all listed equipment may not be required for use with the chemical. Your supervisor and other sections of this manual will help with the choice of correct PPE for specific tasks and type of hazard.

Body / Skin Protection

In order to protect the entire body, protective clothing will be required that covers all parts of the body. PPE should be selected on a task basis and checked prior to each use to ensure it is in good condition prior to use. Do not wear shorts or skirts in the laboratory. A lab coat should be worn over street clothes and regularly laundered. Closed toed shoes should be worn in the lab, no sandals, open toed, or perforated shoes are allowed in the lab. Long hair and loose clothing should be confined.

Protective Clothing

Some types of procedures or chemical use will require additional protective clothing. This clothing may include impermeable aprons and gloves or plastic coated coveralls, shoe covers, and arm sleeves. Always consider arm sleeves when using aprons. Never wear protective clothing outside the lab. Choice of protection depends on degree of protection required and which areas of the body may become contaminated. Rubberized aprons, plastic coated coveralls, shoe covers, and arm sleeves offer greater resistance to chemical permeation that lab coats and give more time to react (remove) if contaminated. Consider head covering as well if contamination is possible to protect scalp.

Chemical resistant gloves should be worn when the potential for contact with corrosive or toxic material and substances of unknown toxicity exists. Gloves are selected based on the material being handled, the hazard present with that material, and the suitability for operation being conducted. Check gloves for integrity before each use (even disposable). If using non-disposable gloves should be washed prior to removal to prevent skin contamination and these gloves must be replaced periodically, depending on frequency of use and resistance to chemicals handled.

Protective garments are not all equally effective for every hazardous chemical. Always check the MSDS for recommendations for glove selections, but some general criteria is found in the following table: 

 Glove Type Selection Guide

S=Superior, E=Excellent, G=Good, F=Fair, NR=Not Recommended

Source: Northeastern University's Chemical Hygiene Plan

Eye Protection

Eye protection should be provided for all personnel and any visitors in all areas where chemicals are handled and a chemical splash hazard exists. Safety glasses, goggles, and goggles plus face shield should be worn in the laboratory based on physical state, operation, or level of toxicity of chemicals used. When used properly, safety glasses protect against solid materials (dusts and flying objects) but are less effective protecting against chemical splash to the face.

Goggles should be worn when bulk quantities of chemicals are used or when splashes to the face are possible. When highly reactive substances or large quantities of hazardous chemicals, corrosives, poisons, or hot chemicals are used a face shield with goggles should be used.

It is not necessary to require removal of contact lenses prior to entering eye hazardous environments. It is required that proper personal eye protection is to be worn by all persons including contact lens wearers in eye protection working areas.

Respiratory Protection

Inhalation hazards are controlled through the use of respirators or ventilation systems. Check the MSDS for inhalation hazards and ventilation requirements. Control of inhalation hazards is best accomplished with engineering methods (hoods, ventilation). Respirator efficiency depends on employee work practices and training. All employees should receive a physical and be fit tested and trained prior to respirator use to ensure proper fit and selection of the respirator for the material in use.

Laboratory Safety Equipment

Chemical Hoods

The chemical hood is the primary means of controlling inhalation exposures. Hoods are designed to protect the operator by retaining vapors and gases released within them. This protection is accomplished by having a curtain of air (100 linear feet per minute approximately) move constantly through the face (open sash) of the hood. Hoods can also be used to isolate apparatus for chemicals that may present physical hazards to employees. The closed sash serves as an effective barrier to fire, flying objects, chemical splashes or spattering, and small implosions and explosions. Small spills can also be effectively contained in a hood while chemicals are being dispensed, especially if trays are placed in the bottom of the hoods.

 When using a chemical hood keep the following principles of safe operation in mind:

• Keep all chemicals and apparatus at least six inches inside the hood behind the sash.
• Hoods are not intended for storage and material in them should be kept to a minimum. Chemicals should not block vents or alter air flow patterns.
• Keep the sash at a minimum height (4 to 6 inches) when not manipulating chemicals or adjusting apparatus within the hood, but preferably closed completely.
• Make sure the sash opening is appropriate when working in a hood, typically 14-20 inches. Each hood is tested annually by EHS and is marked at the appropriate level. This opening will ensure an adequate air velocity through the face of the hood.
• Do not allow objects such as paper to enter the exhaust ducts. This can clog ducts and adversely affect the proper operation.

The chemical manufacturer or supplier provides instructions for controlling inhalation exposures on the MSDS or label of the hazardous material. If specific guidance is not available or inappropriate for the lab environment, contact your chemical hygiene officer or EHS.

Eyewashes and Safety Showers

If there is a possibility that chemicals may cause damage to the skin or eyes, an emergency supply of water must be available. Any laboratories using bulk quantities of hazardous chemicals should have access to eyewash stations and safety showers. This safety equipment is only useful if it is accessible, therefore:

• Keep all passageways to the eyewash and shower clear of any obstacle (even a temporary one such as a chemical cart.)
• Eyewashes should be checked routinely to be certain that water flows through it.
• Showers should be checked routinely to assure that access is not restricted and the start chain is within reach.
•  Eyewashes and showers should be inspected annually. Lab personnel are encouraged to check eyewashes monthly or at least quarterly.

Fire Safety Equipment

A fire extinguisher must be available within 50 feet of each laboratory and easily accessible to personnel. Other equipment may include fire blankets or automatic extinguishing systems.

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Chemical Procurement, Distribution & Storage

Procurement

Information on the proper handling, storage and disposal of a new substance should be known to those who will handle the material. It is the responsibility of the supervisor to ensure that the laboratory facility is adequate for the material and that those who will handle the material have received proper training. Only the quantity that can be immediately used should be ordered. Large amounts of material should not be stored in the laboratories.

Material Receipt

All chemicals ordered for use on the Missouri S&T campus must be received by an authorized materials receiver (AMR) and bar-coded prior to delivery to researcher. Chemical information is entered into the CHEMTRACK system to inventory the material and each chemical receives a unique barcode number. No material should be received or stored without being bar-coded and entered into CHEMTRACK.

Chemical Storage in the Laboratory

Carefully read the label before storing a hazardous chemical. The MSDS will provide any special storage information as well as information on incompatibilities. Do not store unsegregated chemicals in alphabetical order. Do not store incompatible chemicals in close proximity to each other.

Chemicals should be segregated into the following hazard classes for safe storage:

• Flammables
• Oxidizers
• Corrosives-acids, bases
• Highly Reactive
• Extreme Toxic/Regulated Material
• Low Hazard

One problem with this type of storage plan is the actual identification of the hazards themselves. First determine the priorities then choose a storage location. Look at flammability first and how corrosive the item is next. There will always be some material that does not fit neatly into one category or another, but after carefully considering the hazards associated with the material, most situations can be resolved and appropriate storage determined.

Use approved storage containers and safety cans for flammable liquids. It is preferred and advised to store flammable chemicals in a National Fire Protection Association (NFPA) approved flammable liquid storage cabinet. Flammable chemicals requiring refrigeration must be stored only in refrigerators and freezers designed for flammable storage.

A good place to store hazardous chemicals is in a vented cabinet under the hood. Chemicals of different chemical classes can be segregated by placing them in trays. Do not store chemicals on bench tops or in hoods. Store liquids (especially corrosives or solvents) below eye level. Use secondary containers for especially hazardous chemicals.

Conduct periodic inventory checks of chemicals stored in the lab and dispose of old or unwanted chemicals promptly in accordance with the Chemical Waste program or the Chemical Redistribution program.

Chemical Storage-Chemical Stability

Stability refers to the susceptibility of a chemical to dangerous decomposition. The label and MSDS will give guidance on the chemical stability.

Peroxide Formers- Ethers, liquid paraffins, and olefins form peroxides on exposure to air and light. Certain peroxides are extremely sensitive to shock, sparks, or other forms of accidental ignition (even more sensitive than primary explosives such as TNT). If these chemicals are packaged in an air atmosphere, peroxides can form even though the containers have not been opened. Unless an inhibitor was added by the manufacturer, sealed containers of ethers should be discarded after one year and opened containers should also be discarded after one year. These types of materials should be dated when received and when opened. Tests to determine if peroxides have formed in materials are available commercially or a protocol is provided in Appendix B.

Chemical Storage-Incompatible Chemicals

A severe or toxic reaction can take place when certain hazardous chemicals are mixed or stored with other chemicals. The label and MSDS will contain information on incompatibilities.

The following table contains examples of incompatible chemicals:

(From Manufacturing Chemists' Association, Guide for Safety in the Chemical Laboratory, pp.215-217.)

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Chemical Spills and Accidents

Try to anticipate the types of spills that can occur in your laboratory and provide for the proper spill equipment to respond to a minor spill. The MSDS for the material will contain spill response information. Only attempt to respond to small spills that you can safely respond to and leave larger spills to knowledgeable and experienced personnel. Spill response procedures should be posted in the lab and are available in the EHS manual found online. (Link to Haz. Waste Mgt. Manual).

If a spill is too large for you to handle, call for assistance immediately: Campus Police at extension 4300.

Cleaning Up Chemical Spills

If you are cleaning up a small spill, make sure you are aware of the hazards associated with the materials spilled, have adequate ventilation (open window, chemical hood on) and proper PPE (minimum-gloves, goggles, and lab coat). Consider all residual chemical and cleanup materials as hazardous waste. Place these materials in a sealed container (plastic bags) and store in a chemical hood. Contact EHS for disposal instructions.

Minor Chemical Spill

• Alert people in immediate area of spill.
• Increase ventilation in area of spill (open window, turn on hood).
• Wear protective equipment, including safety goggles, gloves and long-sleeve lab coat.
• Avoid breathing vapors from spill.
• Use appropriate kit to neutralize and absorb inorganic acids and bases. Collect residue, place in a container, and dispose of container as hazardous waste.
• For other chemicals, use appropriate kit or absorb spill with vermiculite, dry sand, diatomaceous earth or paper towels. Collect residue, place in container, and dispose  of as chemical waste.
• Clean spill area.

Major Chemical Spill

• Attend to injured or contaminated persons and remove from exposure.
• Alert people in the lab to evacuate.
• If spilled material is flammable, turn off ignition and heat sources. Place other device (plastic bag) over spilled material to keep substance from volatilizing.
• Call Missouri S&T-PD at x4300.
• Close doors to affected area.
• Have a person with knowledge of the incident and laboratory available to answer questions from responding emergency personnel.

Mercury Spills

EHS has a mercury vacuum and should be called for all large mercury spills. Kits are available commercially for small spills that may occur in the lab. Small droplets in inaccessible areas may be covered with powdered zinc and place residue in a labeled container and dispose of as hazardous chemical waste.

Alkali Metal Spills

Smother with powdered graphite, sodium carbonate, calcium carbonate or "Met-L-X", call the Chemical Hygiene Officer for assistance.

White Phosphorus

Smother with wet sand or wet "noncombustible" absorbent, call the Chemical Hygiene Officer for assistance.

Hydrofluoric Acid

Neutralize with soda ash or lime (or absorb with special HF spill pillow). Absorb with an inert absorbent material.

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Personal Contamination and Injury

General Information

The following information is provided as a general guide for handling chemical exposure and is not intended to be comprehensive. Personnel working with hazardous materials should read the MSDS for that material and become familiar with the hazards and the treatments needed should an exposure occur.

• Know the location of the nearest safety shower and eye wash station.
• Report all incidents and injuries to your supervisor.
• If an individual is contaminated or exposed to a hazardous material in your laboratory, do what is necessary to protect their life and health as well as your own. Determine  what the individual was exposed to and consult the MSDS for first aid information.
• Do not move an injured person unless they are in further danger (inhalation or skin exposure).
• A blanket should be used immediately to protect the victim from shock and exposure.
• Get medical attention promptly by dialing University Police at x4300

Chemical Spills on the Body

• Quickly remove all contaminated clothing and footwear.
• Immediately flood the affected area in cold water for at least 15 minutes. Remove jewelry to facilitate removal of any residual material.
• Wash off chemical with water only. Do Not Use neutralizing chemicals, unguents, creams, lotions, or salves unless the spill involves Hydrofluoric Acid.
• Get medical attention promptly.

It should be noted that some chemicals (phenol, aniline) are rapidly adsorbed through the skin. If a large enough area is contaminated, an adverse health effect may occur immediately to several hours after the initial exposure depending on the chemical. If more than 9 square inches of skin area has been exposed to a hazardous chemical, seek medical attention after washing the material off the skin. If the material involved is hydrofluoric acid (HF), seek immediate medical attention. Provide the chemical name to the physician.

Chemical Splash in the Eye

• Irrigate the eyeball and inner surface of the eyelid with plenty of cool water for at least 15 minutes. Use eyewash or other water source. Forcibly hold eyelids open to  ensure effective wash.
• Check for and remove contact lenses.
• Get medical attention promptly.

Ingestion of Hazardous Chemical

• Identify the chemical ingested.
• Call for an ambulance by dialing x4300.
• Cover the injured person to prevent shock.
• Provide the ambulance crew and physician with the chemical name and any other relevant information. If possible, send the container, MSDS or the label with the victim.

Inhalation of Smoke, Vapors and Fumes

• Anyone overcome with smoke or chemical vapors or fumes should be removed to uncontaminated air and treated for shock.
• Do not enter the area if you expect that a life threatening condition still exists-oxygen depletion, explosive vapors or highly toxic gases (cyanide gas, hydrogen sulfide,  nitrogen oxides, carbon monoxide).
• If CPR certified, follow standard CPR protocols.
• Get medical attention promptly.

Burning Chemicals on Clothing

• Extinguish burning clothing by using the drop-and-roll technique or by dousing with cold water, or use an emergency shower if it is immediately available.
• Remove contaminated clothing: however, avoid further damage to the burned area. If possible, send clothing with the victim.
• Remove heat with cool water or ice packs until tissue around burn feels normal to the touch.
• Cover injured person to prevent shock.
• Get medical attention promptly.

Actions to be Avoided During Emergencies

There are some actions which must not be taken when handling emergencies. These include:

• Do not force any liquids into the mouth of an unconscious person.
• Do not handle emergencies alone, especially without notifying someone that the accident has occurred.
• Do not linger at the accident scene if you are not one of the emergency responders or the point of contact for the area.

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Fire and Fire Related Emergencies

Personnel should plan ahead and know the locations of fire extinguishers, alarm pull stations and emergency exits. If you discover a fire or fire-related emergency, immediately follow these procedures:

• Notify the University Police x4300.
• Activate the building alarm (fire pull station). If not available or operational, verbally notify people in the building.
• Isolate the area by closing windows and doors and evacuate the building.
• Shut down equipment in the immediate area, if possible.

Use a portable fire extinguisher to:

• assist oneself to evacuate;
• assist another to evacuate; and
• control a small fire, if possible.
• Provide the fire/police teams with the details of the problem upon their arrival. Special hazard information you might know is essential for the safety of the emergency responders.

If the fire alarms are ringing in you building:

• Shut down equipment if possible and evacuate the building and stay out until notified to return.
• Move up wind from the building and stay clear of streets, driveways, sidewalks, and other access ways to the building.
• If you are a supervisor, try to account for your employees, keep them together and report any missing persons to the emergency personnel at the scene.

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Chemical Waste Disposal Program

Laboratory chemical waste must be disposed of in accordance with local, state, federal, and Missouri S&T requirements. These waste management practices are designed to ensure maintenance of a safe and healthful environment for laboratory employees and the surrounding community without adversely affecting the environment. This is accomplished through regular removal of chemical waste and disposal of these wastes in compliance with all regulations and policies. Specific guidance on how to identify, handle, and request disposal pickup can be found in the Chemical Waste section of the Waste Management Program available at the EHS website.

All waste must be tagged with chemical waste tags (available from EHS). These tags should be filled out and dated with the accumulation start date, the generators name, location of waste and contents of waste container. Missouri S&T policy limits the storage time for waste in laboratories and other areas to a maximum of 90 days. Waste containers must be closed unless waste is being added or removed and stored properly until pickup.

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Section 3- Information for Work with Chemicals of Specific Hazard Class

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Flammable Liquids

General Information

Flammable liquids are among the most common of the hazardous materials found in laboratories. They are usually highly volatile (have high vapor pressures at room temperature) and their vapors, mixed with air at the appropriate ratio, can ignite and burn. By definition, the lowest temperature at which they can form an ignitable vapor/air mixture (flash point) is less than 37.8ÃÆ'‚Ã-šÃ‚°C and for several common laboratory solvents (ether, acetone, toluene, acetaldehyde) the flash point is well below that. As with all solvents, their vapor pressure increases with temperature. Therefore, as temperatures increase the material becomes more hazardous.

For a fire to occur, three conditions must exist simultaneously:

1.  The concentration of the vapor must be between the upper and lower flammable limits of the substance (the right fuel / air mix);

2.  an oxidizing atmosphere, usually air, must be available; and

3.  a source of ignition must be present.

Removal of any of these three conditions will prevent the start of a fire. Flammable liquids may form flammable mixtures in either open or closed containers or spaces (such as refrigerators), when leaks or spills occur in the laboratory, and when heated.

Strategies for preventing ignition of flammable vapors include removing all sources of ignition or maintaining the concentration of flammable vapors below the lower flammability limit by using local exhaust ventilation such as a hood. Removing sources of ignition is more difficult because of the numerous sources available in laboratories such as open flames, hot surfaces, operation of electrical equipment, and static electricity.

The concentrated vapors of flammable liquids may be heavier than air and can travel away from a source for some distance (across lab, into hallways, down elevator shafts or stairways). If the vapors reach a source of ignition, a flame can result that may flash back to the source of the vapor.

The danger of fire and explosion presented by flammable liquids can usually be eliminated or minimized by strict observance of safe handling, dispensing, and storing procedures.

Special Handling Procedures

While working with flammable liquids you should wear gloves, protective glasses, and long sleeved lab coats. Wear goggles if dispensing solvents or performing an operation which could result in a splash to the face.

Large quantities of flammable liquids should be handled in a chemical hood or under some type of local exhaust ventilation. Five-gallon containers must be dispensed into smaller containers in a hood or under local exhaust ventilation. Dispense flammable substances into metal or plastic containers or safety cans, avoid glass containers.

Make sure that metal surfaces or containers through which flammable substances are flowing are properly grounded, discharging static electricity. Free flowing liquids generate static electricity, which can produce a spark and ignite the solvent. Large quantities of flammable liquids must be handled in areas free of ignition sources (including spark emitting motors and equipment) using non-sparking tools. Remember that vapors are heavier than air and can travel to a distant source of ignition.

Do not heat flammable substances by using an open flame. Use any of the following instead: steam baths, water baths, oil baths, heating mantles or hot air baths.

Store flammable substances away from ignition sources in NFPA approved flammable storage cabinets. If no flammable storage cabinet is available, store these substances in a cabinet under the hood or bench. Five-gallon containers should only be stored in a flammable storage cabinet or under a hood. Glass containers used for flammable liquids must not exceed 4 liters in capacity. Keep flammable liquids inside the hood for a short period of time and do not store long term. Chemical storage in hoods reduces hood performance by obstructing air flow.

Oxidizing and corrosive materials should not be stored in close proximity to flammable liquids. Do not store or chill flammable liquids in domestic refrigerators and freezers but in units specifically designed for this purpose. If flammable liquids are placed in ovens, make sure they are properly designed for flammable liquids with no internal ignition source and/or vented mechanically.

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Highly Reactive Chemicals & Energy Oxidizers

General Information

Highly reactive chemicals include those which are inherently unstable and susceptible to rapid decomposition as well as chemicals which, under specific conditions, can react alone or with other substances in a violent uncontrolled manner, liberating heat, toxic gases, or leading to an explosion. Reaction rates almost always increase dramatically with temperature increases. If the heat evolved from a reaction is not dissipated, the reaction can accelerate out of control and possibly result in injuries or costly accidents.

Air, light, heat, mechanical shock (when struck, vibrated or otherwise agitated), water, and certain catalysts can cause decomposition of some highly reactive chemicals, and initiate an explosive reaction. Hydrogen and chlorine react explosively in the presence of light. Alkali metals, such as sodium, potassium and lithium, react violently with water giving off hydrogen gas. Examples of shock sensitive materials include acetylides, azides, organic nitrates, nitro compounds, and many peroxides.

Organic peroxides are a special class of compounds that have unusual stability problems, making them among the most hazardous substances normally handled in the laboratories. As a class, organic peroxides are low powered explosives. Organic peroxides are extremely sensitive to light, heat, shock, sparks, and other forms of accidental ignition; as well as to strong oxidizing and reducing materials. All organic peroxides are highly flammable.

Peroxide formers can form peroxides during storage and especially after exposure to the air (once opened). Peroxide forming substances include: aldehydes, ethers (especially cyclic ether), compounds containing benzylic hydrogen atoms, compounds containing the allylic structure (including most alkenes), vinyl and vinylidine compounds.

Examples of shock sensitive chemicals, high-energy oxidizers and substances, which can form explosive peroxides, are listed at the end of this section. The Missouri S&T peroxide testing procedure/policy is found in Appendix B.

Special Handling Procedures

Before working with a highly reactive material or high-energy oxidizer, review available reference literature to obtain specific safety information. The proposed reactions should be discussed with your supervisor. Always minimize the amount of material involved in the experiment. Scale-ups should be handled with great care, giving consideration to the reaction, vessel size and cooling, heating, stirring, and equilibration rates.

Excessive amounts of highly reactive compounds should not be purchased, synthesized, o