COMPLIANCE IS MANDATORY

Ames Health and Safety Procedural Requirements

Chapter 13 - Chemical Hygiene Program

13.1 Background

13.1.1. This chapter of APR 8715.1 establishes minimum requirements to protect laboratory workers from chemical hazards through hazard assessment, hazard communication, training, safe work practices, and special controls for some specific hazardous chemicals.

13.1.2 This chapter of APR 8715.1 together with laboratory safety plans specific to each laboratory together comprise the Center’s written Chemical Hygiene Plan required by 29 CFR 1910.1450, Occupational Exposure to Hazardous Chemicals in Laboratories.

13.1.3 Laboratory Safety Plans:

1. Contain site-specific information, work practices, and control measures expressly tailored to the individual laboratory workplace.
2. Evaluate hazards associated with the handling and use of chemicals in the laboratory
3. Inform laboratory workers of those hazards and the techniques, procedures, and equipment necessary for their protection.

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13.2 Responsibilities

13.2.1 The Center Director shall designate in writing an employee who is qualified by training or experience to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan as the installation Chemical Hygiene Officer.

13.2.2 Safety, Health and Medical Services Division shall:

1. Review and evaluate Laboratory Safety Plans and associated documentation and approve Laboratory Safety Plans that conform to the requirements of this chapter.
2. Perform medical certification examinations for laboratory workers as specified in applicable NASA directives.
3. Perform medical consultations and provide written medical opinions as specified in 29 CFR 1910.1450, or other OSHA/NASA regulations, as appropriate.

13.2.3 Ames Chemical Hygiene Officer shall:

1. Oversee development and implementation of the Ames Chemical Hygiene Plan and applicable procedures.
2. Provide advice, oversight, and consultation to directorate/branch chemical hygiene officers and laboratory supervisors to ensure compliance with the Ames Chemical Hygiene Plan.
3. Provide direction and oversight of exposure assessment and chemical monitoring programs.
4. Ensure that chemical exposure assessments are conducted for proposed laboratory use of carcinogens, genotoxins, reproductive toxins, and compounds with a high degree of acute toxicity.
5. Ensure that technical advice is available on exposure assessments, chemical hazards, less hazardous substitutes, containment, decontamination, neutralization, personal protective equipment, engineering controls and emergency procedures.
6. Ensure that exposure-monitoring records are maintained and employees are notified of the results.
7. Provide for annual review of this Chemical Hygiene Plan, update as needed.

13.2.4 Supervisors (all levels) shall:

1. Maintain a safe work environment as prescribed in APR 8715.1 Chapter 2, and as modified or augmented in this section.
2. Assign a Principal Investigator or Laboratory Chemical Hygiene Officer qualified to meet the responsibilities listed in 13.2.5.
3. Approve Laboratory Safety Plans when the submitted plan addresses the planned laboratory operations and risks associated with those operations.
4. Require review and update of Laboratory Safety Plans for new or significantly modified operations.
5. Ensure that sufficient coordination is employed so that regulatory requirements relating to procurement, storage, use, collection, transportation, and disposal of chemicals used in laboratories are followed.

13.2.5 Principal Investigators/Laboratory Chemical Hygiene Officers shall:

1. Serve as or designate the Chemical Hygiene Officer for the laboratory.
2. Acquire and maintain the knowledge and information needed to control chemical hazards in the laboratory including knowing the current legal requirements.
3. Ensure that an accurate inventory is maintained for all hazardous substances used in the laboratory. Update the inventory whenever hazardous substances are added or removed.
4. Prepare the Laboratory Safety Plan and review it annually. Update it whenever procedures change.
5. Identify and assess the hazards present in the laboratory (see Appendix C).
6. Request, when needed, technical advice on exposure assessments, chemical hazards, less hazardous substitutes, containment, decontamination, neutralization, personal protective equipment, engineering controls, emergency procedures, and special precautions for carcinogens, reproductive toxins or highly toxic substances.
7. Ensure (in coordination with the Ames Chemical Hygiene Officer) that hazard/exposure assessments are conducted for all operations where hazardous chemicals are handled, and that exposure monitoring is conducted if there is reason to believe (based upon the exposure assessment) that exposure levels of a chemical substance could routinely exceed the action level (or PEL/TLV in the absence of an action level).
8. Develop written handling procedures for carcinogens, reproductive toxins or highly toxic substances that restrict use to authorized individuals and limit activities to designated and appropriately restricted work areas (see Appendix E for requirements and Appendix F for a sample procedure).
9. Identify required control measures for each hazardous laboratory operation.
10. Maintain copies of exposure monitoring records.
11. Ensure that medical attention is provided to any employee whenever signs and symptoms develop that may be associated with exposure to a hazardous chemical or whenever monitoring reveals exposure levels in excess of the action level. Provide relevant information (identity of the materials and amounts, if known, and circumstances of the exposure, employee symptoms) to the attending medical professional.
12. Ensure that the composition of laboratory-generated mixtures is described in the Laboratory Safety Plan.
13. Provide information and training about potential health hazards, safe handling procedures, chemical storage, physical safety hazards, the Laboratory Safety Plan, task-specific hazard control methods, and emergency response.
14. Ensure the toxicity/hazard information is available for all laboratory chemicals used. List the location of this information in the Laboratory Safety Plan. Material Safety Data Sheets (MSDS) are a primary source of this information. Any MSDSs received from the chemical supplier shall be readily available to employees.
15. Provide employees access to the Chemical Hygiene Plan, the Laboratory Safety Plan, and other appropriate documents and references applicable to health and safety programs.
16. Ensure that labels on incoming containers are not removed or defaced.
17. Define (in the Laboratory Safety Plan) the labeling system used in the laboratory for secondary containers of hazardous chemicals.
18. Ensure that each laboratory is posted with a list of responsible persons (emergency contacts) and their Ames phone numbers and National Fire Protection Association (NFPA) codes for chemical hazards within the laboratory. Standard labels are available for this purpose.
19. Prepare a PPE assessment for laboratory operations. Include it in the Laboratory Safety Plan.
20. Ensure that facilities, storage areas, and equipment are adequate for laboratory procedures being conducted.
21. Ensure (in coordination with the Safety Division) that monitoring is conducted to evaluate the proper functioning of fume hoods and other engineering controls, and that fume hoods that do not meet performance standards are not used until repaired.
22. Comply with all applicable Federal, State, and local regulations, and facility procedures for chemical disposal.
23. Maintain records required by this chapter, other applicable Ames Health and Safety Manual chapters and the Ames Environmental Procedural Requirements APR 8500.1.

13.2.6. Laboratory Employees shall:

1. Be responsible for personal safety as prescribed in APR 8715.1 Chapter 2, and as modified or augmented in this section.
2. Follow safe, established work practices found in the Chemical Hygiene Program and laboratory safety plans.
3. Review the MSDSs and/or other available literature for information on the chemicals being used, including: hazards, exposure limits, symptoms of exposure, PPE, and engineering controls.
4. Treat a chemical of unknown composition as a hazardous substance.
5. Keep the quantity of chemicals stored in a laboratory to the minimum needed.
6. Develop good personal chemical hygiene habits.
7. Implement appropriate protective measures prior to undertaking any hazardous operation.

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13.3 Laboratory Safety Plan

13.3.1 Each laboratory must maintain a Laboratory Safety Plan as a site-specific supplement to this Chemical Hygiene Plan.

13.3.2 The Laboratory Safety Plan shall contain laboratory-specific information that will be used to protect employees from health hazards.

13.3.3 It shall include standard operating procedures relevant to health and safety, criteria for determining control measures to reduce employee exposure to hazardous chemicals, instructions for use of personal protective equipment and hygiene practices, measures to ensure proper functioning of fume hoods and other protective equipment, provisions for employee training, designation of circumstances that require prior approval, provisions for medical consultation and medical examinations, and designation of personnel responsible for implementation of the Laboratory safety Plan.

13.3.4. Particular attention shall be given to control measures for operations that involve the use of carcinogens, reproductive hazards, or acutely toxic chemicals.

13.3.5 Laboratory plans shall be reviewed/updated annually, or whenever a new hazard is introduced into the workplace.

13.3.6 Related environmental records, including spill logs and hazardous waste accumulation area inspection logs, are discussed in the Ames Environmental Procedural Requirements APR 8500.1.

13.3.7 Detailed information on the preparation of Laboratory Safety Plans including a suggested outline is provided in Appendix G.

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13.4 Hazard Control Measures

13.4.1 Criteria for Selection of Hazard Control Measures

13.4.2 Administrative Controls and Prior Approval

13.4.3 General Laboratory Safety Rules

13.4.4 Special Hazard Controls

The OSHA Laboratory Standard requires special care for work with known human carcinogens and other substances that are defined as particularly hazardous substances (see Appendix E for additional information).

13.4.5 Chemical Fume Hood Inspection and Maintenance

13.4.6 Personal Protective Equipment

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13.5 Exposure Assessment and Monitoring

13.5.1 Requirements for Chemical Exposure Assessment

13.5.1.1 Exposure assessment to determine priority for monitoring shall occur when carcinogens, genotoxins, reproductive toxins, and compounds with a high degree of acute toxicity are used regularly (3 or more separate handling sessions per week), used for an extended period of time (greater than 2 to 4 hours at a time), or used in especially large quantities.

13.5.1.2 The exposures of laboratory employees who suspect and report that they have been over-exposed to a toxic chemical in the laboratory, or are displaying symptoms of overexposure to toxic chemicals, will be assessed.

13.5.1.3 The assessment shall initially be qualitative and, based upon the professional judgment of the Ames Chemical Hygiene Officer, may be followed up by specific quantitative monitoring.

13.5.1.4 A memorandum, or report, documenting the assessment shall be sent to the employees involved and their supervisors within fifteen days of receipt of the results.

13.5.1.5 Individual concerns about excessive exposures occurring in the laboratory shall be brought to the attention of the employee’s supervisor or the Laboratory Chemical Hygiene Officer immediately.

13.5.2 Requirements for Exposure Monitoring

13.5.3 Occupational Exposure Limits (OEL)

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13.6 Spills and Accidents

13.6.1 Each person who handles hazardous materials in the laboratory shall receive task-specific training on spill and accident response.

13.6.2 Spill control and reporting policies, procedures, and requirements are specified in the Ames Environmental Procedural Requirements, APR 8500.1, EWi-5.1 Hazardous Materials Management.

13.6.3 Any employee who may have experienced a hazardous exposure due to a spill, accident, or any other circumstance shall report to the Ames Health Unit for medical consultation.

13.6.4 Information concerning the nature, amount, and circumstances of the exposure shall be provided to the medical professional along with a copy of the MSDS.

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13.7 Medical Consultation and Examination

13.7.1 The Ames Health Unit provides medical consultation and examination to Government employees with concern about health effects from occupational exposure to chemicals.

13.7.2 A physical examination and/or medical monitoring is provided when physician opinion, employee concerns, regulatory requirements, industrial hygiene survey, or exposure monitoring indicate a need for medical monitoring.

13.7.3 Each employee may review his or her personal medical records upon request.

13.7.4 In an emergency or for the initial evaluation of job-related chemical exposures or accidents, contractors may report to the Ames Health Unit. For routine medical treatment, contractors must report to their own medical clinic.

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13.8 Employee Notification and Training

Training shall be provided:

1. To all new employees
2. To all employees given new job assignments for which training has not previously been received
3. To supervisors (of employees handling hazardous materials)

13.8.1 At the time of initial assignment to a work area where hazardous chemical are present, each employee shall be provided the following information:

1. A copy of the applicable laboratory safety plan
2. A means to read this Chemical Hygiene Plan by website access or hard copy document
3. A means to read the OSHA Chemical Hygiene Standard (available on the OSHA website)

13.8.2 Before using hazardous materials, full time laboratory employees shall have completed the following training classes:

1. Hazard Communication for Chemical Workers
2. Chemical Hygiene for Laboratories
3. Hazardous Waste/Environmental Essentials
4. Additional classes specified by the laboratory supervisor

13.8.3 Before using hazardous materials, visiting scientists, student interns, and part-time employees shall have completed the following training classes:

1. Laboratory safety bootcamp for Interns
2. Building Emergency Evacuation Plan
3. Additional classes specified by the laboratory supervisor

13.8.4 Principal Investigator/Laboratory Chemical Hygiene Officers shall provide on-the-job training to employees on:

1. All hazards to which they may be exposed in the operations that they may perform, both routine and emergency situation;
2. Details of the Laboratory Safety Plan including applicable prudent practices;
3. The signs and symptoms associated with exposures to the hazardous chemicals that they are handling;
4. The methods and observations that may be used to detect the presence or release of a hazardous chemical (i.e. visual appearance or odor);
5. Physical hazards of hazardous chemicals in the laboratory;
6. The location and availability of reference material on hazards; (note: this can include, but is not limited to, MSDSs);
7. Specific laboratory provisions for storage and handling of materials and disposal of hazardous waste chemicals;
8. Standard Operating Procedures for any specialized laboratory operations;
9. Safe work practices and techniques;
10. The selection and use of designated PPE;
11. Manufacturer's instructions for tools and equipment;
12. Foreseeable emergencies;
13. The procedures to use with picric acid and peroxide forming chemicals;
14. Decontamination procedures; and
15. Inspection requirements.

13.8.5 Supervisors shall verify that laboratory workers have sufficient training to work safely before allowing them to work in a laboratory.

13.8.6 Additional safety and environmental compliance classes related to specific hazards in their work area, such as blood borne pathogens, cryogens, compressed gases, lasers, or radioisotopes are required prior to working with those hazards.

13.8.7 Initial and follow-up training for laboratory workers shall be documented on training records maintained with the Laboratory Safety Plan.

13.8.8 Contractors shall provide/arrange for equivalent training for their employees; they may attend Ames Safety Training classes on a space available basis.

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13.9 Chemical Procurement, Distribution, Storage, and Waste Disposal

13.9.1 The acquisition of chemicals shall follow the policies and procedures described in the Chemical Hazard Communication Plan, Ames Health and Safety Manual, APR 1700.1, Chapter 24).

13.9.2 Chemical Storage in Laboratories

13.9.3 Picric Acid and Peroxide-forming Chemicals

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13.10 Reports of Unsafe or Unhealthy Working Conditions

13.10.1 Any condition that appears to be an immediate health risk shall be reported to the supervisor, the Safety Division, and 911 immediately.

13.10.2 Hazards shall be reported by any of the methods described in APR 8715.1 Chapter 4.

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13.11 Recordkeeping

13.11.1 The Laboratory Safety Plan and its attachments shall be available in each laboratory.

13.11.2 The Ames Health Unit maintains personal medical records, including medical monitoring.

13.11.3 Reports documenting exposure monitoring results shall be provided to involved personnel, the Safety Division and the Ames Health Unit.

13.11.4 The Safety Division maintains exposure-monitoring records and records that document reports of unsafe or unhealthy working conditions.

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13.12 Related Programs at ARC

Operations in chemical laboratories are subject to the procedures and policies listed below when the hazards they address are present in the laboratory:

1. Radioactive materials, see APR 8715.1, Chapter 7 Radiation Safety Guide
2. Lasers, see APR 1700.1, Chapter 8, Non-ionizing Radiation Safety Guide
3. Equipment operating above atmospheric pressure, see APR 1700.1, Chapter 10, Pressure Systems
4. Electrically powered equipment built or modified in the laboratory, see APR 1700.1, Electrical Safety
5. Cryogens, see APR 1700.1 Chapter 15, Cryogenic Safety
6. Controlled Substances, see APR 1700.1 Chapter 23, Control of Narcotics and other Controlled Drugs including Alcohol
7. Pathogenic organisms, cell cultures, human blood products, see APR 8715.1 Bloodborne Pathogens Protection Plan
8. Ethylene oxide, formaldehyde, methylene chloride, hexavalent chromium, cadmium, see APR 1700.1, Chapter 38, OSHA Regulated Carcinogen Control Program
9. Compressed gases, see APR 1700.1 Chapter 44, Compressed Gas Cylinder Safety
10. Carbon based nanomaterials, see APR 1700.1 Chapter 50, Nanomaterials Safety and Health Guideline for Carbon Based Nanomaterials

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13.13 Review and Update

13.13.1 This Chemical Hygiene Program Plan shall be reviewed annually by the Safety Division.

13.13.2 This document shall be updated by attachments issued as Interim Policy Statements.

13.13.2 Revisions shall incorporate new regulatory requirements and substantially modified procedures initiated since the previous update.

13.13.3 The checklist in Appendix L shall be used to assess implementation of this program.

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Appendix A: Definitions

Action level--an exposure level, calculated as an eight-hour time-weighted average, which initiates certain required activities, such as exposure monitoring, medical surveillance, training and record keeping.

Carcinogen-- A substance that is strongly implicated as a potential cause of cancer in humans and identified by one of the following authorities:

• OSHA regulates it as a carcinogen.
• It is listed as "known to be a carcinogen" in the latest Annual Report on Carcinogens issued by the National Toxicology Program (NTP)
• It is listed under Group 1 ("carcinogenic to humans") by the International Agency for Research on Cancer (IARC).
• It is listed under IARC Group 2A ("probably carcinogenic to humans") or 2B (possibly carcinogenic to humans) or under the category "reasonably anticipated to be a carcinogen" by the NTP, and causes statistically significant tumor incidence in experimental animals in accordance with published criteria.

Chemical Hygiene Officer (CHO)--An employee designated to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan(s). Qualifications include training in industrial hygiene, chemistry, or other pertinent related fields.

Chemical Hygiene Plan (CHP)--A written plan that sets forth procedures, laboratory and control equipment, personal protective gear, and work practices that are capable of protecting employees from the hazards presented by hazardous chemicals used in a particular laboratory workplace.

Chemical Inventory--a written or electronic record of chemicals used in a laboratory, by container, which includes the chemical name of all ingredients, CAS number(s), manufacturer, size of container, owner, and location.

Corrosive Material--Any solid, liquid, or gaseous substance that attacks building materials and metals, and burns, irritates, or destructively attacks organic tissues (mostly notably the skin, lungs, or stomach when taken internally).

Cryogenic Fluids (cryogens)--Elements and compounds that vaporize at temperatures well below room temperature. Most common cryogens have a normal boiling point below approximately 120K. Helium (4.2K), hydrogen (20K), nitrogen (77K), oxygen (90K), and methane (112K) [normal boiling point temperatures in parentheses] are examples of cryogens. Note that the cold vapor of solid carbon dioxide (sublimation temperature of 195 K at one atmosphere) can be considered a cryogenic fluid.

Designated Area--A laboratory, laboratory area, or device such as a fume hood where carcinogens, known human reproductive toxins, or substances with a high degree of acute or chronic toxicity are used. A designated area may be the entire laboratory, an area within the laboratory, or a device such as a laboratory-type hood.

Genotoxin--a toxin that can interact with and alter genetic material. Hazardous Chemical--Any material that, because of its quantity, concentration, or physical or chemical characteristics, poses a significant present or potential hazard to human health and safety or environment if released into the workplace or the environment. If hazardous chemical comprises 1% (0.1% for carcinogens) or greater of a compound or mixture, the compound or mixture must be treated as a hazardous chemical.

Health Hazard--A chemical for which 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. Categories of health hazards include:

• Carcinogens
• Toxic or highly toxic agents
• Reproductive toxins
• Chemical asphyxiant
• Irritants
• Corrosives
• Sensitizers
• Chemicals that cause effects in organs (e.g. liver, lungs, kidney, central nervous systems, blood, eyes, skin or mucous membranes)

Laboratory--A facility in which research or analytical chemical procedures are performed, where hazardous materials are stored and used in quantities that may easily be handled by one person (container sizes do not exceed five gallons); a workplace where relatively small quantities of hazardous chemicals are used on a non-production basis.

Laboratory use--means chemical manipulations are carried out on a laboratory scale (containers for reactions, transfers, and other handling can be easily and safely manipulated by one person); multiple chemical procedures or chemicals are used; and procedures involved are not part of a production process, nor do they in any way simulate a production process.

Laboratory Safety Plan (LSP)--contains information about each laboratory operation, including the hazards present, hazards/exposure assessment, hazard control measures, PPE required, identification of carcinogens, genotoxins, reproductive toxins, and compounds with a high degree of acute toxicity used and the location of the designated area for their use, operation-specific training, and employee responsibilities.

Material Safety Data Sheet (MSDS)--Written, printed or electronically transmitted information on the hazards and properties of a particular material, including instructions for its safe use.

Organic Peroxides and Peroxide Formers--Organic peroxides are a special class of compounds with unusual stability problems (stability can be significantly affected by age and contamination). They may be (or become) sensitive to shock, heat, sparks, or other forms of accidental ignition. Some compounds such as ethers auto-oxidize in the presence of oxygen and light to form peroxides.

Permissible Exposure Limit (PEL)--Limit established by OSHA usually expressed as an 8-hour Time Weighted Average (TWA), meaning an airborne contaminant concentration that shall not be exceeded for an 8-hour work shift of a 40 hour work-week. Exposure limits for many hazardous materials are listed in 29 CFR 1910.1000.

Personal Protective Equipment (PPE)--Includes chemical and thermal resistant gloves, safety glasses, goggles and face shields, aprons, respirators, earplugs and muffs, etc.

Physical Hazard--the following categories are included:

• Combustible liquid
• Compressed gas
• Cryogen
• Explosive material
• Flammable material
• Oxidizer
• Organic peroxide
• Pyrophoric material
• Asphyxiant
• Unstable or reactive material
• Water-reactive material

Prudent Practices--Recommended guidelines for storage and use of hazardous materials, cited in 29 CFR 1910.1450, based on the National Research Council text Prudent Practices for Handling Hazardous Chemicals in Laboratories, 1981, and the updated text, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals, 1995, National Academy Press, Washington, D.C.

Pyrophoric--A substance that is so rapidly oxidized by oxygen or the moisture in air that it ignites (spontaneous combustion).

Reproductive toxin (known human)--substances that are known to cause adverse effects on the reproductive system, have lethal effects on the fertilized egg developing embryo or fetus, or to cause malformation in the fetus (teratogenesis).

Safety Hazard--Any condition, action, or situation that may result in bodily injury.

Secondary Container--Any chemical container other than an original container that will be used by more than one person or will be used beyond a single workday. This definition should not be confused with secondary containment for chemical release prevention or control.

Short-term exposure limit--a limit usually defined as a 15-minute time-weighted average.

Threshold Limit Value (TLV-TWA)--the exposure limit (established by American Conference of Government Industrial Hygienists), expressed as a time-weighted average airborne "concentration for a normal 8-hour workday and a 40hr work week, to which nearly all workers may be repeatedly exposed, day after day, without adverse effect."

Toxic--Able to injure biological tissue.

Toxicity--The adverse effects resulting from a dose of, or exposure to, a material.

Training--A documented, organized presentation of information fulfilling educational objectives and regulatory requirements.

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Appendix B: Acronyms

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Appendix C: Hazard Screening Tool for Laboratory Operations (Not Mandatory)

Directions: This screening tool can be used to document the hazard identification process. The questions are intended to help identify the hazards present or absent in the laboratory. The Laboratory Safety Plan must describe the hazards present and the means of controlling those hazards.

Ionizing and Non-Ionizing Radiation

Chemicals

***If the answer is NO to the above question, then the workplace falls under the hazard communication standard.

Please check the Material Safety Data Sheet or other reference for information on each specific chemical and fill-out the next table.

Biological

Physical

Environmental

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Appendix D:General Procedures for Working with Hazardous Chemicals

Reprinted with permission from PRUDENT PRACTICES IN THE LABORATORY. Copyright 1995 by the National Academy of Sciences. Courtesy of the National Academy Press, Washington D.C. Qualifying notes for Ames Research Center are printed in italics.

Personal Behavior

Professional standards of personal behavior are required in any laboratory:

• Avoid distracting or startling other workers.
• Do not allow practical jokes and horseplay at any time.
• Use laboratory equipment only for its designated purpose.
• Do not allow visitors, including children and pets, in laboratories where hazardous substances are stored or are in use or hazardous activities are in progress.
• If children are permitted in laboratories, for example, as part of an educational or classroom activity, ensure that they are under the direct supervision of qualified adults.
• Make sure that teaching materials and publicity photographs show people wearing appropriate safety gear, in particular, eye protection.

Minimizing Exposure to Chemicals

Precautions should be taken to avoid exposure by the principal routes, that is, contact with skin and eyes, inhalation, and ingestion.

1. Avoiding Eye Injury

• Eye protection should be required for all personnel and visitors in all locations where chemicals are stored or used. Eye protection is required whether or not one is actually performing a chemical operation. Visitor safety glasses should be made available at the entrances to all laboratories.
• Researchers should assess the risks associated with an experiment and use the appropriate level of eye protection.
• Safety glasses with side shields provide the minimum protection acceptable for regular use. Safety glasses must meet the American National Standards Institute (ANSI) standard Z87.1-1989, Standard for Occupational and Educational Eye and Face Protection, which specifies a minimum lens thickness, certain impact resistance requirements, and so on.
• Safety splash goggles or face shields should be worn when carrying out operations in which there is any danger from splashing chemicals or flying particles. These thin shields do not provide protection from projectiles, however, goggles are preferred over regular safety glasses to protect against hazards such as projectiles, as well as when working with glassware under reduced or elevated pressures (e.g., sealed tube reactions), when handling potentially explosive compounds (particularly during distillations), and when employing glassware in high-temperature operations.
• Because goggles offer little protection to the face and neck, full-face shields should be worn when conducting particularly hazardous laboratory operations. In addition, glassblowing and the use of laser or ultraviolet light sources require special glasses or goggles.

Ordinary prescription glasses do not provide adequate protection against injury. Prescription safety glasses and goggles can be obtained.

Contact lenses offer no protection against eye injury and cannot be substituted for safety glasses and goggles. It is best not to wear contact lenses when carrying out operations where chemical vapors are present or a chemical splash to the eyes or chemical dust is possible because contact lenses can increase the degree of harm and can interfere with first aid and eye-flushing procedures. If an individual must wear contact lenses for medical reasons, then safety glasses with side shields or tight-fitting safety goggles must be worn over the contact lenses. Employees are advised to inform the supervisor when contact lenses will be worn for operations with hazardous chemicals.

2. Avoiding Ingestion of Hazardous Chemicals

Eating, drinking, smoking, gum chewing, applying cosmetics, and taking medicine in laboratories where hazardous chemicals are used should be strictly prohibited. Food, beverages, cups, and other drinking and eating utensils should not be stored in areas where hazardous chemicals are handled or stored. Glassware used for laboratory operations should never be used to prepare or consume food or beverages. Laboratory refrigerators, ice chests, cold rooms, ovens, and so forth should not be used for food storage or preparation. Laboratory water sources and de-ionized laboratory water should not be used for drinking water.

Laboratory chemicals should never be tasted. A pipette bulb or aspirator should be used to pipette chemicals or to start a siphon; pipetting should never be done by mouth. Hands should be washed with soap and water immediately after working with any laboratory chemicals, even if gloves have been worn.

3. Avoiding Inhalation of Hazardous Chemicals

Toxic chemicals or compounds of unknown toxicity should never be smelled. Procedures involving volatile toxic substances and operations involving solid or liquid toxic substances that may result in the generation of aerosols should be conducted in a laboratory hood. Dusts should be recognized as potentially contaminated and hazardous. Hoods should not be used for disposal of hazardous volatile materials by evaporation. Such materials should be treated as chemical waste and disposed of in appropriate containers in accord with institutional procedures.

The following general rules should be followed when using laboratory hoods:

Note: For more information, see OSHA Personal Protective Equipment Standard (29 CFR 1910.132-138) for hand protection.

6. Clothing and Protective Apparel

Long hair and loose clothing or jewelry must be confined when working in the laboratory. Unrestrained long hair, loose or torn clothing, and jewelry can dip into chemicals or become ensnared in equipment and moving machinery. Clothing and hair can catch fire. Sandals and open-toed shoes should never be worn in a laboratory in which hazardous chemicals are in use.

It is advisable to wear a laboratory coat when working with hazardous chemicals. This is particularly important if personal clothing leaves skin exposed. Apparel giving additional protection (e.g., non-permeable laboratory aprons) is required for work with certain hazardous substances. Because many synthetic fabrics are flammable and can adhere to the skin, they can increase the severity of a burn. Therefore, cotton is the preferred fabric.

Housekeeping

There is a definite correlation between orderliness and level of safety in the laboratory. In addition, a disorderly laboratory can hinder or endanger emergency response personnel. The following housekeeping rules should be adhered to:

• Never obstruct access to exits and emergency equipment such as fire extinguishers and safety showers.
• Clean work areas (including floors) regularly. Properly label . . . and store . . . all chemicals. Accumulated dust, chromatography adsorbents, and other chemicals pose respiratory hazards.
• Secure all compressed gas cylinders to walls or benches.
• Do not store chemical containers on the floor.
• Do not use floors, stairways, and hallways as storage areas.

Transport of Chemicals

Chemicals being transported outside the laboratory or between stockrooms and laboratories should be in break-resistant secondary containers. Secondary containers commercially available are made of rubber, metal, or plastic, with carrying handle(s), and are large enough to hold the contents of the chemical containers in the event of breakage. When transporting cylinders of compressed gases, the cylinder should always be strapped in a cylinder cart and the valve protected with a cover cap. When cylinders must be transported between floors, passengers should not be in the elevator.

Storage of Chemicals

The accumulation of excess chemicals can be avoided by purchasing the minimum quantities necessary for a research project. All containers of chemicals should be labeled properly. Any special hazards should be indicated on the label. For certain classes of compounds (e.g., ethers and other as peroxide formers), the date the container was opened should be written on the label. Peroxide formers should have the test history and date of discard written on the label as well. Only small quantities (less than 1 liter (L)) of flammable liquids should be kept at workbenches. Larger quantities should be stored in approved storage cabinets. Quantities greater than 1 L should be stored in metal or break-resistant containers. Large containers (more than 1 L) should be stored below eye level on low shelves. Hazardous chemicals and waste should not be stored on the floor.

Refrigerators used for storage of flammable chemicals must be explosion-proof, laboratory-safe units. Materials placed in refrigerators should be clearly labeled with water-resistant labels. Storage trays or secondary containers should be used to minimize the distribution of material in the event a container should leak or break. It is good practice to retain the shipping can for such secondary containers.

All chemicals should be stored with attention to incompatibilities so that if containers break in an accident, reactive materials do not mix and react violently.

Disposal of Chemicals

Note: This section contains practical guidelines for waste accumulation. For ARC policies and procedures, refer to Ames Environmental Procedural Requirement, APR 8500.1, EWi -5.2 Hazardous Waste Management.

Virtually every laboratory experiment generates some waste, which may include such items as used disposable lab-ware, filter media and similar materials, aqueous solutions, and hazardous chemicals. The overriding principle governing the handling of waste in prudent laboratory practice is that no activity should begin unless a plan for the disposal of nonhazardous and hazardous waste has been formulated. Application of this simple rule will ensure that the considerable regulatory requirements for waste handling are met and that unexpected difficulties, such as the generation of a form of waste (e.g., chemical-radioactive-biological) that the institution is not prepared to deal with, are avoided.

Each category of waste has certain appropriate disposal methods. In choosing among these methods, several general principles apply, but local considerations can strongly influence the application of these rules:

• Hazardous or flammable waste solvents should be collected in an appropriate container pending pickup by the ARC contractor for hazardous waste for transfer to the institution's central facility or satellite site for chemical waste handling or pickup by an outside disposal agency.
• Waste solvents can usually be mixed for disposal, with due regard for the compatibility of the components. Sometimes halogenated and non-halogenated wastes must be segregated for separate handling.

Note: The Safety Office will provide consultation and guidance on request.

• The container used for the collection of liquid waste must be appropriate for its use. Glass bottles are impervious to most chemicals but present a breakage hazard, and narrow necks can cause difficulty in emptying the bottles. The use of plastic (e.g., polyethylene jerrycans) or metal (galvanized or stainless steel) safety containers for the collection of liquid waste is strongly encouraged and, indeed, required for flammable liquids.<

Note: Approved containers are provided on request by the Ames contractor for hazardous waste.

• Galvanized steel safety cans should not be used for halogenated waste solvents because they tend to corrode and leak. Flame arresters in safety cans can easily become plugged if there is sediment and may need to be cleaned occasionally.
• Waste containers should be clearly and securely labeled as to their contents and securely capped when not in immediate use.
• Aqueous waste should be collected separately from organic solvent waste. Some laboratories may be served by a wastewater treatment facility that allows the disposal of aqueous waste to the sanitary sewer if it falls within a narrow range of acceptable waste types. Thus, solutions of nonhazardous salts or water-miscible organic materials may be acceptable in some localities. Note: Ames is served by both Sunnyvale and Palo Alto water treatment facilities. The Safety Office provides consultation and guidance regarding requirements that apply to each building at Ames. Solutions containing flammable or hazardous waste, even if water-miscible, are almost never allowed and water-immersible substances must never be put down the drain. Aqueous waste for non-sewer disposal should be collected in a container selected for resistance to corrosion. Glass should not be used for aqueous waste if there is danger of freezing. Depending on the requirements of the disposal facility, adjustment of the pH of aqueous waste may be required. Such adjustment requires consideration of the possible consequences of the neutralization reaction that might take place: gas evolution, heat generation, or precipitation.
• Solid chemical waste, such as reaction by-products, or contaminated filter or chromatography media, should be placed in an appropriately labeled container to await disposal or pickup. Unwanted reagents should be segregated for disposal in their original containers, if possible. If original containers are used, labels should be intact and fully legible. Every effort should be made to use, share, or recycle unwanted reagents rather than commit them to disposal.

Note: The Ames Chemical Exchange (ACE) program for sharing excess chemicals is described in the Ames Environmental Procedural Requirements.

• Nonhazardous solid waste can be disposed of in laboratory trash or segregated for recycling. Institutional policy should be consulted for these classifications (See Chapter 7 for further information regarding disposal, and check the appropriate LCSS to determine toxicity.)

Note: Ames policy is described in the Ames Procedural Requirement, APR 8500.1, EWi -5.2 Hazardous Waste Management.

Use and Maintenance of Equipment and Glassware

Good equipment maintenance is essential for safe and efficient operations. Laboratory equipment should be inspected and maintained regularly and serviced on schedules that are based on both the likelihood of and the hazards from failure. Maintenance plans should ensure that any lockout procedures cannot be violated.

Careful handling and storage procedures should be used to avoid damaging glassware. Chipped or cracked items should be discarded or repaired. Vacuum-jacketed glassware should be handled with extreme care to prevent implosions. Evacuated equipment such as Dewar flasks or vacuum desiccators should be taped or shielded. Only glassware designed for vacuum work should be used for that purpose.

Hand protection should be used when picking up broken glass. Small pieces should be swept up with a brush into a dustpan. Glassblowing operations should not be attempted unless proper annealing facilities are available. Adequate hand protection should be used when inserting glass tubing into rubber stoppers or corks or when placing rubber tubing on glass hose connections. Cuts from forcing glass tubing into stoppers or plastic tubing are the most common kind of laboratory accident and are often serious. Tubing should be fire polished or rounded and lubricated, and hands should be protected with toweling and held close together to limit movement of glass should it fracture. The use of plastic or metal connectors should be considered.

Handling Flammable Substances

Flammable substances present one of the most widespread hazards encountered in the laboratory. Because flammable materials are employed in so many common laboratory operations, basic prudent laboratory practice should always assume the presence of fire hazard unless a review of the materials and operations in the laboratory verifies the absence of significant hazard. For example, simple operations with aqueous solutions in a laboratory where no flammable organic liquids are present involve no appreciable fire hazard. In all other circumstances, the risk of fire should be recognized and kept to a minimum.

For a fire to start, an ignition source, fuel, and oxidizer must be present. Prudent laboratory practice in avoiding fire is based on avoiding the presence of one of these components. The flammability and explosive characteristics of the materials being used should be known. Solvent labels, LCSSs, or other sources of information can be consulted to learn the flash point, vapor pressure and explosive limit in air of each chemical handled. While all flammable substances should be handled prudently, the extreme flammability of some materials requires additional precautions.

To ensure that laboratory workers respond appropriately, they should be briefed on the necessary steps to take in case of a fire. The laboratory should be set up in such a way that the locations of fire alarms, pull stations, fire extinguishers, safety showers, and other emergency equipment are marked and all laboratory personnel alerted to them. Exit routes in case of fire should be reviewed. Fire extinguishers in the immediate vicinity of an experiment should be appropriate to the particular fire hazards. Proper extinguishers must be used because fires can be exacerbated by use of an inappropriate extinguisher. Telephone numbers to call in case of an accident should be readily available.

Responsibility for Unattended Experiments and Working Alone

Generally, it is prudent to avoid working alone at the bench in a laboratory building. Individuals working in separate laboratories outside of working hours should make arrangements to check on each other periodically, or ask security guards to check on them. Experiments known to be hazardous should not be undertaken by a worker who is alone in a laboratory. Under unusually hazardous conditions, special rules may be necessary.

Laboratory operations involving hazardous substances are sometimes carried out continuously or overnight with no one present. It is the responsibility of the worker to design these experiments so as to prevent the release of hazardous substances in the event of interruptions in utility services such as electricity, cooling water, and inert gas. Laboratory lights should be left on, and signs should be posted identifying the nature of the experiment and the hazardous substances in use. If appropriate, arrangements should be made for other workers to periodically inspect the operation. Information should be posted indicating how to contact the responsible individual in the event of an emergency.

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Appendix E: Special Rules for Working with Carcinogens, Genotoxins, Reproductive Toxins, And Compounds with a High Degree of Acute Toxicity

PRUDENT PRACTICES IN THE LABORATORY. Copyright 1995 by the National Academy of Sciences. Chapter 5D

Note: Guidelines have been adapted for Ames Research Center policies and procedures.

Approvals

Prepare a Standard Operating Procedure for use of these materials and obtain the approval of the laboratory supervisor. Attach the SOP to the Laboratory Safety Plan. See suggested format (Appendix G).

Access

Conduct all transfers and work with these substances in a "designated area;" (hood, glove box, or portion of a lab). Document the location and that all people with access are aware of the substances being used and necessary precautions in the SOP.

Fume Hoods

Always use a hood (previously evaluated to confirm adequate performance with an average face velocity of 100+ 20 linear feet per minute (ARC standard) or other containment device for procedures that may result in the generation of aerosols or vapors containing the substance.

Glove Boxes

Contact the Safety Division for assistance.

Decontamination

Document decontamination procedures in the SOP. Decontamination vacuum pumps or other contaminated equipment, including glassware, in the hood before removing them from the designated area. Decontaminate the designated controlled area before normal work is resumed there.

Exiting

On leaving a controlled area, remove any protective apparel (placing it in an appropriate, labeled container) and thoroughly wash hands, forearms, face, and neck.

Medical surveillance

If using toxicologically significant quantities of such a substance on a regular basis (e.g., 3 times per week), consult with the Ames Chemical Hygiene Officer concerning desirability of regular medical surveillance. Include this information in the SOP.

Records

Keep accurate records of the amounts of Particularly Hazardous Chemicals stored and used, the dates of use, and names of users.

Signs and labels

Assure that the designated area is conspicuously marked with warning and restricted access signs.

Assure that all storage cabinets and containers of these substances are appropriately labeled with identity and warning labels.

Storage

Store containers of Particularly Hazardous Chemicals only in a ventilated, limited access area in appropriately labeled, unbreakable, chemically resistant containers.

Spills

Assure that contingency plans, equipment, and materials to minimize exposures of people and property in case of accident are available. (See Ames Environmental Procedural Requirements, APR 8500.1, EWi 5.1 Hazardous Materials Management;) for spill reporting requirements)

Waste

Ensure that containers of contaminated waste (including washings from contaminated flasks) are transferred from the designated area in a secondary container under the supervision of authorized personnel.

Bag, label, and dispose as hazardous waste any contaminated clothing or shoes.

Store contaminated waste in closed, suitably labeled, impervious containers.

See also: APR 8500.1, EWi 5.2, Hazardous Waste Management

Appendix F: Example of a Standard Operating Procedure for Carcinogens, Genotoxins, Reproductive Toxins, and Compounds with a High Degree of Acute Toxicity

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Appendix G: Suggested Format and Content for a Laboratory Safety Plan

The Laboratory Safety Plan must contain laboratory-specific information that will be used to protect employees from health hazards. It must include standard operating procedures relevant to health and safety, criteria for determining control measures to reduce employee exposure to hazardous chemicals, instructions for use of personal protective equipment and hygiene practices, measures to ensure proper functioning of fume hoods and other protective equipment, provisions for employee training, designation of circumstances that require prior approval, provisions for medical consultation and medical examinations, and designation of personnel responsible for implementation of the Laboratory safety Plan.

The Laboratory Safety Plan may also include information about the facility and evaluation of potentially hazardous operations (The Laboratory Safety Plan can be used to document both the supervisor’s hazard assessment and the PPE assessment required by OSHA). Standard Operating Procedures that contain safety instructions and precautions for hazardous operation may be included in the laboratory safety plan or their location referenced.

The Ames Chemical Hygiene Officer can assist researchers in developing safety procedures for specific hazards. Laboratory plans are reviewed/updated annually, or whenever a new hazard is introduced into the workplace. Related environmental records, including spill logs and hazardous waste accumulation area inspection logs, are discussed in the Ames Environmental Procedural Requirements APR 8500.1.

Suggested Outline

• Name of Facility/Operation
• Location (building/room)
• Definition of Work: Explain your project clearly and concisely, include a description of operation and processes.
• Identify the principal hazards/exposures: See Appendix C for an optional screening tool. It can be used to document the presence/absence of hazardous operations. Contact the Ames Chemical Hygiene Officer for assistance in evaluating/monitoring chemical exposures.

Evaluate the risk to the employee from the hazards present and describe the control measures. See Appendix H: Laboratory Risk Assessment, for additional information.

Example:

— Laboratory-specific rules, procedures, and controls (See Appendix C).

These are based upon the hazards/exposures identified.

Examples:

• Materials that require special fire-fighting procedures (e.g. reactive metals)
• Location of hazardous chemical and flammable storage cabinets
• Labeling requirements for secondary containers and for laboratory-generated chemicals
• Laboratory-specific training
• Location of electrical panels serving the laboratory
• Location of health and safety references
• Location of equipment operating manuals and other documents
• Description of engineering control equipment (i.e. chemical fume hoods, Biosafety cabinets, etc.) and approved activities for the equipment
• Where personal protective equipment is kept and when it is used
• Location of spill kit
• Location of emergency equipment (i.e. eyewash, shower, oxygen deficiency alarm, toxic gas alarm, etc.) and emergency procedures
• Discussion of satellite waste storage areas

— Standard Operating Procedures for work with "Particularly Hazardous Substances" or other high hazard operations (see Appendices E and F for additional information):

• Special maintenance and repair issues,
• Special training requirements and restrictions,
• Personnel access (e.g. designated areas for use of carcinogens, genotoxins, reproductive toxins, or compounds with a high degree of acute toxicity),
• Special emergency procedures (shut down, etc.)
• Responsible Individuals (name, organization, ARC extension)
• Inspection Schedule
• Waste accumulation and disposal procedures
• Attachments (add as applicable):
Chemical Inventory
Training Records
Inspection Records
Composition of Laboratory-Generated Chemical Mixtures
Project permits (radioisotope, laser, controlled drug, confined space, etc.)

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Appendix H: Laboratory Risk Assessment

Laboratories deal with substances known to be hazardous, with substances with unknown hazard potential, and with unique/innovative experiments. Laboratory workers usually handle only small amounts of materials, laboratory exposures are typically brief and infrequent, and the need to use particular substances is often difficult to predict in advance. This appendix provides guidance for assessing the hazards in the laboratory.

For each chemical consider the toxicity, frequency and duration of use, the quantity of material handled, and the inhalation and skin exposure potential. Reference: PRUDENT PRACTICES IN THE LABORATORY. Copyright 1995 by the National Academy of Sciences. Courtesy of the National Academy Press, Washington, D.C. Quick Guide to Risk Assessment for Hazardous Chemicals

The major items:

• Identify chemicals to be used and circumstances of use.
• Consult sources of information.
• Evaluate type of toxicity.
• Consider possible routes of exposure.
• Evaluate quantitative information on toxicity.
• Select appropriate procedures to minimize exposure.
• Prepare for contingencies.

Note the signs and symptoms of exposure to the chemicals to be used in the proposed experiment. Note appropriate measures to be taken in the event of exposure or accidental release of any of the chemicals.

Toxicity:

Review the Material Safety Data Sheets and other available reference for toxicology and health hazard information. The table below can be used to assist the rating of acutely toxic chemicals.

Low: transitory, mild health effects

Moderate: effects from which the person would recover; would not produce chronic effects that would negatively impact on the quality of life.

High: all compounds which meet the "Particularly Hazardous Chemical" definition and any compound which has no available toxicity information.

Reprinted with permission from PRUDENT PRACTICES IN THE LABORATORY. Copyright 1995 by the National Academy of Sciences. Courtesy of the National Academy Press, Washington, D. C. Table 3.1.

Routes of Exposure:

Inhalation and skin exposure are the most probable types of exposure for laboratory workers. Accidental injection can also occur if needles or other sharp implements are used in any procedures. The actual potential for an exposure to occur can be reduced by the use of hazard/exposure control measures.

Examples:

Inhalation Exposure Potential:

• Low: Use is always in vented hoods or glove boxes with appropriate protection (i.e., gloves, lab coat); or in closed containers outside of fume hood; or, substance/material is a non-volatile solid or a dilute solution (e.g. < 0.1%) used in a manner which will not create significant airborne exposures.
• Moderate: Substance/material is volatile or a finely divided particulate and is used outside ventilated enclosure for a period of < 1/2 hr/mo.
• High: Open containers used outside of vented enclosures where substance/material is volatile or a finely divided particulate and/or the material is used > 1/2 hr/mo.

Skin Exposure Potential: Evaluate this exposure route independently of the inhalation route. Consider (1) the potential for contact with unprotected skin and the potential for surface contamination (e.g. dusts); (2) frequency of use; and, (3) the chemical's ability to be absorbed through the skin.

If the risk/exposure potential is high or moderate, the experimental protocol should be adjusted, whenever possible, to reduce the level. The correct use of engineering controls and personal protection equipment lowers the exposure potential. If the assessment is still high, contact the Ames Chemical Hygiene Officer for further evaluation.

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Appendix I: Chemical Compatibility/Incompatibility

Reprinted (adapted) with permission from Prudent Practices in the Laboratory. Copyright 1995 by the National Academy of Sciences. Courtesy of the National Academy Press, Washington, D.C.

Chemicals in the two columns should be kept separate. Consult the MSDS for substance-specific information.

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Appendix J: Picric Acid (2, 3, 6 - Trinitrophenol), and other Multi-Nitro Aromatic Compounds

Picric Acid and other multi-nitro aromatic compounds form shock-sensitive explosive crystals when dry. The Department of Transportation (DOT) classifies Picric Acid as a Class 1.1D Explosive if it contains less than 30% water by mass. If the material contains greater than 30% moisture, DOT classifies it as a Class 4.1 Flammable Solid. It is even more dangerous when stored in a container with a metal cap, as it can then form metal picrate salts, which are extremely shock-sensitive.

Guidelines for Storage of Picric Acid and other Multi-Nitro Aromatic Compounds: Principal Investigators/Chemical Hygiene Officers are responsible for identifying picric acid and other hazardous multi-nitro aromatics used in the work area. These PI's/Chemical Hygiene Officers are also responsible for ensuring that the following occur:

1. Place label on material with date of receipt and expiration date
2. Enter material into 4D System enter fields of date of receipt and expiration date
3. Make sure material is kept wet! Check hydration levels and re-date the material at least every 6 months, adding distilled water when necessary (maintain at least 30% hydration)
4. Clean the bottleneck, cap and threads with damp cloth before resealing cap
5. Dispose of all old bottles with metal caps
6. Do not store large amounts.
7. Dispose of containers on or before two years of date of receipt

If relocating from the lab, take material with you or ensure that next occupant is aware of presence of and dangers of the material, its date of purchase, its hydration status. Coordinate transfers and relocations with Code JQ

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Appendix K: Peroxide-Forming Chemicals

Many oxygenated organic compounds can spontaneously form explosive peroxides with age, via a free-radical auto-oxidation reaction. Although exposure to light and air enhances the formation of peroxides, there are examples of peroxides forming in unopened, shielded containers.

Unfortunately, though there are various tests for detecting peroxide-forming chemicals, there are no definitive data available regarding the specific conditions under which these peroxides will reach explosive levels. Several common test methods, such as using dip test strips, may detect some but not all types of unstable peroxides (e.g. some polyperoxides are not detected), and deperoxidation procedures might not mitigate all the hazards present.

In addition to the problems with testing for peroxides, with deperoxidation, and with defining the conditions that make peroxide-forming chemicals hazardous, there are no specific federal or Cal/OSHA regulations that address the subject matter. Despite this uncertainty, NASA-ARC has developed the following guidelines for employees to follow in handling peroxide forming chemicals. Guidelines for Storage/Testing/Disposal of Peroxide Forming Chemicals: Principal Investigators/Chemical Hygiene Officers are responsible for identifying peroxide forming chemicals used in the work area. They are also responsible for ensuring that the following occur:

1. Attempt to purchase peroxide-forming chemicals on an as-needed basis, and maintain the minimum practical inventory of these chemicals.
2. Store peroxide forming chemicals in sealed containers, protected from heat, light, and activities involving grinding, sparks, or friction.
3. Store diethyl ether in steel containers because iron tends to neutralize peroxides in this chemical.
4. Other peroxide forming chemicals should be stored in amber bottles or opaque containers (without glass stoppers) and under a blanket of nitrogen or another inert gas. Air should be flushed out of the free head space with an inert glass before re-sealing (except for List C chemicals with inhibitors, see below). ,
5. Containers should be marked with the date they arrive and the date of required disposal (expiration date). Please see label below. Enter this information into the 4D database.
6. Chemicals shall be disposed of according to the schedule outlined in Table 1 and accompanying Lists A, B, and C below.
7. Observe containers for visible evidence of peroxide formation (see below)
8. Never open containers of unknown origin or age, or those that have visible evidence of peroxide formation (i.e., clear liquid with suspended wisp-like structures; precipitated crystal formation; the appearance of ice-like structures, solid masses, or chips; discoloration; cloudiness; liquid stratification). Call Ames' Hazardous Waste Staff immediately (x4-5360)
9. If relocating from the lab, take material with you or ensure that next occupant is aware of presence of and dangers of the material, its date of purchase, its due date for disposal. Coordinate transfers and relocations with Code JQ.
10. Peroxides are less volatile than the parent compound; they thus become concentrated upon evaporation of the parent solvent (4). Always test prior to distillation/evaporation/concentration, using:

All the above test strips are the gentlest, fastest, easiest, and the most accurate of all testing methods (5,7). However, although these strips can detect hydroperoxides and most higher peroxides, some polyperoxides are not detected . Therefore, it is recommended that no distillation shall occur if the levels of peroxides detected are above 25 ppm (9).

Label for Peroxide Forming Chemicals:

Warning: May form Explosive Peroxides

Store, handle, and dispose of as per Ames' Peroxide Forming Chemical Policy, as outlined in Chemical Hygiene Program (Chapter 13 of Ames Health and Safety Manual. Keep in tightly closed, original container. Avoid exposure to light, air, and heat.

If crystals, discoloration, or layering are visible, do not open! Contact EH&S Hazardous Waste immediately for guidance 4-5360. Check for peroxides before distilling. Do not distill if peroxide concentration is > 25 ppm. If concentration is > 100 ppm, do not touch material! Call Hazardous Waste at x4-5360 immediately for disposal.

This chemical has a limited shelf life. Dispose of prior to expiration date:

Date Received:_________ Expiration (Disposal) Date*:________
*(as per "Disposal Guidelines for Peroxidizable Chemicals, Table 1, Appendix I, "Peroxide Forming Chemicals," Chapter 13, Ames Health and Safety Procedural Requirements, APR 8715.1)

Training:

Employees who either handle or who may be exposed to hazardous materials, including peroxide-forming chemicals, must complete the course, "Chemical Hygiene for Laboratories," Course No. A136. All employees in the work area require on-the-job training on the specific hazards and controls of the materials being handled. Area specific training is a line management responsibility.

Engineering Controls:

1. Use a fume hood when handling all peroxide-forming chemicals during transfer operations, preparation of mixtures, blending, sonification, spraying, heating, evaporation and distilling.
2. Place safety shields in front of reaction vessels, distillation columns, and other apparatuses when detonation may occur
3. Use explosion proof refrigerators when cold storage is needed. However, do not store them below the min recommended temperatures. The peroxides might precipitate from solution if the solvent is cooled to the near freezing point
4. these peroxides then become extremely shock and heat sensitive (please refer to MSDS). There is little or no evidence that refrigeration slows oxidation of ethyl ether (4)

1. Wear safety glasses with side shields, chemical protective gloves, lab coats, closed toe shoes at all times when working with these chemicals.

*Modified, from: National Research Council, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals; National Academy Press; Washington, D.C., 1999, and Kelly, Richard, "Review of Safety Guidelines for Peroxidizable Organic Chemicals," Chemical Health And Safety, American Chemical Society, Sept/Oct 1996, pp. 28-36

The following lists of chemicals are not exhaustive. Principal Investigators must consult the MSDSs and other information sources for the chemicals used in their work areas to determine the potential for peroxide-formation.

Notes: ** Please note that secondary alcohols can be peroxide-forming chemical hazards. However, this is true only for the anhydrous form of the alcohols, and it is also only true if they are used in chemical processes (e.g., heating, distilling, performing chemical reactions, performing bulk evaporations). If these chemicals are used only for wipe cleaning or solvent extractions, there is no evidence that these secondary alcohols are dangerous.

1. When stored as a liquid monomer.
2. Although these form peroxides, no explosions involving these monomers have been reported.
3. When stored as a gas in gas cylinders.
4. Kelly, R.J., Review of Safety Guidelines for Peroxidizable Organic Chemicals, Chemical Health and Safety, September/October, 1996
5. National Research Council, Prudent Practices in the Laboratory, Handling and Disposal of Chemicals; National Academy Press; Washington, D.C., 1999

Source: Kelly, R.J., Review of Safety Guidelines for Peroxidizable Organic Chemicals, Chemical Health and Safety, September/October, 1996.

• Cameron, Mark, "Picric Acid Hazards."
• Bailey, J., Blair, D., "Management of Time Sensitive Chemicals (I): Misconceptions Leading to Incidents."
• http://www.eh.doe.gov/chem_safety/Self_Assess/manuscript1.pdf
• Patai, Saul, "The Chemistry of the Ether Linkage," Interscience Publisher, Inc., 1967.
• Clark, Donald, Ph.D., FAIC, BSP, Texas A&M University, "Peroxides and Peroxide Forming Compounds," Chemical Health and Safety, American Chemical Society, Sept/Oct 2001
• UC Berkeley, Office of Environmental Health and Safety, "Guidelines for Explosive and Potentially Explosive Chemicals Safer Storage and Handling," http://www.ehs.berkeley.edu/pubs/guidelines/pecguidelines.html
• Cornell University, "Peroxide Forming Chemicals," http://www.ehs.cornell.edu.lrs.chp/12.peroxides.htm
• Kelly, Richard, Review of Safety Guidelines for Peroxidizable Organic Chemicals," Chemical Health And Safety, American Chemical Society, Sept/Oct 1996, pp. 28-36
• Kelly, Richard, Miler, Gordon, "Standard For Storing and Using Peroxidizable Organic Chemicals," (UCRL-AR-133218), Lawrence Livermore National Laboratory, March 1999"Control Procedures for Peroxide Forming Chemicals," Ernest Orlando Lawrence Berkeley National Laboratory, Chemical Hygiene Safety Plan, http://www.lbl.gov/ehs/chsp/indes/shtml

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Appendix L: Chemical Hygiene Program Self Assessment Guide

Principle Investigator:________________

Location: __________________________

Date: ______________________________

Example questions which laboratory personnel should be able to answer:

1. Where is the Chemical Hygiene Plan?
2. Who is the Chemical Hygiene Officer for the laboratory?
3. Where are the laboratory's safety rules located?
4. What carcinogens, genotoxins, reproductive toxins, and compounds with a high degree of acute toxicity do you work with?
5. Where are the written SOPs for handling them?
6. Where is the designated area for handling them?
7. What are the signs and symptoms of over-exposure to ________ (select a substance used by the employee)?
8. Where would you find information about the hazard of this compound?
9. What PPE should you wear when working with this compound?
10. Where is the chemical inventory? Is this substance listed correctly?
11. What would you do, if you spilled this chemical?
12. How do you know that your laboratory hood is functioning properly?
13. What are proper procedures for acquisition, labeling, implementing, storage time limits for peroxide forming chemicals?
14. What are proper procedures for acquisition, labeling, implementing, storage time limits and maintaining hydration of Picric acid?

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