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CHEMICAL HYGIENE MANUAL

September 2011

Version 2.2

Oklahoma State UniversityCenter for Health SciencesCHEMICAL HYGIENE MANUAL

TABLE OF CONTENTS________________________________________________________________________Section Page

1.0 Introduction...................................................................................................... 3

2.0 Applicability..................................................................................................... 3

3.0 Abbreviations.................................................................................................... 3

4.0 Definitions........................................................................................................ 4

5.0 Responsibilities................................................................................................. 5

6.0 Hazard Control Guidelines............................................................................... 7

6.1 Procurement............................................................................................. 7

6.2 Handling and Storage.............................................................................. 7

6.2.1 Inventory Control......................................................................... 10

6.2.2 Exposure Monitoring................................................................... 11

6.2.3 Personal Protection...................................................................... 12

6.3 Waste Disposal and Effluent Control...................................................... 13

6.4 Activity Closeout..................................................................................... 14

6.5 Chemical Hazard Information and References........................................ 15

6.6 Training.................................................................................................... 15

7.0 Medical Surveillance........................................................................................ 16

8.0 Employee Rights and Responsibilities.............................................................. 17

9.0 Emergency Procedures...................................................................................... 18

Appendix A - Eye and Face Protection Selection Chart............................................... 21

Appendix B – Safety and Emergency Equipment for the Laboratory……………….. 24

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Appendix C – Safe Storage & Use of Peroxide-Forming Chemicals………………... 25Appendix D – Laboratory Incident Evaluation Form………………………………... 30Appendix E – Voluntary Respirator Use ……………………………………............. 31

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1.0 INTRODUCTION

The Oklahoma State University Center for Health Sciences (OSU-CHS) is committed to managing chemicals used by employees/students in a responsible, safe, and environmentally sound manner. This manual has been written to define the program adhered to for the management of chemicals in laboratory activities. It contains requirements specified by the Occupational Safety and Health Administration (OSHA) standard codified in the Code of Federal Regulations (CFR), Title 29, 1910.1450, "Occupational Exposure to Hazardous Chemicals in Laboratories" as agreed to and enforced by Oklahoma Department of Labor in Title 380, Chapter 40. The standard may be requested from the principal investigator (PI)/supervisor or the research office, Laboratory Safety Coordinator (LSC). The standard can also be found on the internet at 29 CFR 1910.1450. A hard copy of the Chemical Hygiene Manual shall be made available in each laboratory by the PI. The Chemical Hygiene Manual will be reviewed annually by the LSC and updated as necessary.

2.0 APPLICABILITY

The Chemical Hygiene Manual shall be implemented by all employees/students who work with hazardous chemicals in laboratories. The procedures herein are mandatory. Laboratory use of hazardous chemicals means handling or use of such chemicals in which all of the following conditions are met:

(i) Chemical manipulations are carried out on a "laboratory scale," handling of substances are designed to be easily and safety manipulated by one person;

(ii) Multiple chemical procedures or chemicals are used;

(iii) The procedures involved are not part of a production process, nor in any way simulate a production process; and

(iv) "Protective laboratory practices and equipment" are available and in common use to minimize the potential for employee exposure to hazardous chemicals.

All other chemical activities not included by this definition shall follow the requirements of the OSHA regulations found in 29 CFR 1910.1200 “Hazardous Communications.”

Although OSHA regulations are written for employees, the safety precautions contained within this manual are also to be applied to students who are present in laboratories but are not employed by OSU-CHS.

3.0 ABBREVIATIONS

CAS Chemical Abstract ServiceCFR Code of Federal RegulationsCIL Chemical Inventory List

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LSC Laboratory Safety CoordinatorMSDS material safety data sheetOSHA Occupational Safety and Health AdministrationOSU-CHS Oklahoma State University Center for Health SciencesPEL permissible exposure limitPI Principal InvestigatorPPE personal protective equipmentSOP Safe Operating Procedure

4.0 DEFINITIONS

Chemical Abstracts Services Registry number (CAS#): a numeric designation assigned by the American Chemical Society's Chemical Abstracts Service that uniquely identifies a specific chemical compound. This number allows one to conclusively identify a material regardless of the name or naming system used.

Employee: all full-time and part-time faculty, administrative/professional, and hourly staff-may include students; all those who are on the OSU-CHS payroll.

Hazardous chemical: any chemical that is a physical hazard or a health hazard. Physical hazard means a chemical that is a combustible liquid, compressed gas, explosive, flammable liquid or solid, organic peroxide, oxidizer, pyrophoric, unstable (reactive), or water-reactive. Health hazard means a chemical for which acute (sudden) or chronic (long-term) health effects may occur in exposed employees/students. The term "health hazard" includes chemicals that are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, hepatotoxins, nephrotoxins, neurotoxins, agents that act on the hematopoietic system and agents that damage the lungs, skin, eyes, or mucous membranes.

Hazard evaluation: looking at basic job steps; the hazards associated with each step; and the recommended equipment, safe job procedures and/or personal protective equipment (PPE) used to eliminate and/or minimize each identified hazard.

Material safety data sheet (MSDS): written information about the hazards of products and materials and the correct safety measures to be followed when using them.

Permissible exposure limit (PEL): the regulatory exposure limit adopted by OSHA in 29 CFR 1910.1000, a concentration usually expressed as a time-weighted average in units of mg/m3 or parts per million based on an 8-hour day, 40-hour week during which nearly all workers may be repeatedly exposed without adverse effects. PEL's can be found in the MSDS or other reference materials such as 29 CFR 1910.1000 Tables Z1-3 and should not be exceeded.

PI/Supervisor: those faculty/employees of OSU-CHS who have responsibility to direct the work of others in a particular laboratory. The department chair is generally listed as the first person in the department phone lists in the CHS Directory located on the OSU-CHS website. The responsibilities outlined in this program for the "PI/supervisor" are

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directed toward the department chair or PI; but may be delegated to others in the department or groups who have been assigned supervisory roles by the department chair or PI.

5.0 RESPONSIBILITIES

President:

- Support OSU-CHS efforts to provide a safe and healthy work environment for all employees/students, in compliance with OSHA standards

- Plan budgeting resources to provide equipment and safety supplies intended to protect employees/students from hazards of chemicals in the workplace

Laboratory Safety Coordinator

- Act as OSU-CHS Chemical Hygiene Officer- Develop, coordinate implementation, and review the OSU-CHS Chemical Hygiene

Manual- Assess implementation during routine inspections- Maintain an OSU-CHS centralized file (CHS-A211) of MSDSs received from

chemical manufacturers and other reference materials on chemical hazards- Receive Chemical Inventory Lists (CILs) from PIs and consolidate into an OSU-

CHS composite CIL- Provide materials for Laboratory Safety training, including videos, to be accessed

online (see section 6.6) and maintain training documentation database- Respond to or assist PI/supervisor in responding to employee/student concerns

regarding chemical hazards or potential chemical exposures. Employees must have a written reply within 15 days

- Stop work where imminent hazards to the health and safety of employees/students exist until the hazards are eliminated that may require documented assurance of mitigation such as hazard assessments, monitoring, and or training

- Arrange for hazardous waste disposal

PI/Supervisor:

The PI/supervisor has accountability for the inclusion of environmental protection, safety and health practices in the lab; in addition to training and performance of employees/students under their supervision. The PI/supervisor is accountable for the safe operational use of space with authority for start-up and shut-down of activities performed in the work area. The PI/supervisor shall be familiar with laboratory equipment, ongoing processes, and utilities available in the laboratory. Also the PI/supervisor shall:

- Post this manual in laboratory and explain to all lab personnel that procedures herein are mandatory

- Perform a hazard evaluation to identify all work activities where there is exposure or potential for exposure to carcinogens, highly toxic chemicals, and reproductive toxins and develop control measures to eliminate or reduce hazards; prohibit project

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start where hazards cannot be reduced to an acceptable risk level- Where hazards cannot be eliminated; provide engineering controls, administrative

controls and personal protective equipment (PPE), in that order, where necessary to prevent adverse physical and health effects

- Develop Safe Operating Procedures (SOPs) for all hazards, including equipment operations, that are not addressed by this manual; appendix B “Safety and Emergency Equipment for the Laboratory” may be used to assist in determining appropriate lab PPE and emergency equipment necessary

- Assess work activities, including equipment operation, and provide hazard information and on-the-job training to employees/students (see Section 6.6 Training); send a copy of attendance sheet to the LSC

- Ensure spill clean up material and eye and body wash facilities, appropriate to chemicals used or stored in area, are present and maintained

- Respond promptly to employee/student concerns regarding chemical hazards or potential chemical exposures. Employees must have a written reply within 15 days (see Section 6.2.2, 7.0, and Appendix D form for exposures)

- Maintain inventory data of all chemicals used or stored on the Chemical Inventory List (CIL) form, keep updated (within 30 days) and send current copy to the LSC (see Section 6.2.1) annually, at a minimum

- Ensure that all stock chemical containers are labeled, at a minimum, with the chemical name, manufacturer name and phone number and hazards; and that transfer containers and laboratory prepared solutions are labeled with chemical name, date of transfer or preparation and initials of person who prepared the solution. Hazards should be added where possible

- Maintain a MSDS in the work area for each chemical used or stored that is immediately accessible to employees/students during all working hours

- Periodically audit for compliance with chemical safety policies including:a. Safe work practicesb. Engineering controlsc. PPERetrain where inconsistencies are found

- Ensure proper working condition and maintenance (documentation that came with equipment purchase should be immediately available) of hazard control equipment such as centrifuge, fume hood, biosafety cabinet, autoclave – post sign where not working properly. Provide training to operate equipment

- Stop work where imminent hazards to the health and safety of employees/students exist until the hazards are eliminated

All PIs/Staff/Students:

- Follow all procedures within this manual- Obtain hazard information; at a minimum, review MSDS on all chemicals prior to

use- Wear protective equipment identified by PI/supervisor and follow OSU-CHS

Chemical Hygiene Manual policies and instructions provided during training and in reviewing this manual

- Keep chemical container labels readable and label all transfer and laboratory prepared solution containers as above

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- Report noncompliance with these policies, any unsafe work practices or procedures observed, potential chemical exposure incidents, and other concerns promptly to PI/supervisor or the LSC

- Know the location and proper use of emergency equipment, such as showers and eye flushing equipment. Flush eyewash assembly for 3 minutes every week

6.0 HAZARD CONTROL GUIDELINES

The purpose of hazard control guidelines in the OSU-CHS Chemical Hygiene Manual is to evaluate and monitor chemical hazards and where possible, design and implement control measures to reduce hazard exposure; and provide training and information to employees regarding the hazardous chemicals they may work with. The following subsections 6.1 - 6.6 contain procedures and instructions that shall be observed in purchasing, handling, storage, or disposal of hazardous chemicals.

6.1 Procurement

Before purchasing new chemicals all efforts shall be made to use chemicals already on site by requesting them from others who may have an excess. You may contact the LSC to find out if the chemical is present on campus and to act as a liaison with the chemical’s contact person. Each PI/supervisor responsible, or designee, who will be ordering chemicals shall:

a. Ensure that a MSDS is available in the work area(s) where the chemical will be used, obtain by 1) checking current files, 2) requesting when ordering from the chemical manufacturer, 3) printing from online search; and,

b. The PI/supervisor responsible shall ensure that all employees/students who will be working with the new material are aware of the hazards associated with the material prior to use and know where to locate the MSDS.

6.2 Handling and Storage

Each employee/student should use caution in handling and storage of hazardous chemicals to ensure the least exposure and physical hazards possible. The PI/supervisor shall perform a documented hazard evaluation for each activity under their authority where carcinogens, chemicals with a high degree of acute toxicity, reproductive toxins, and chemicals with extreme physical hazards are used, to determine potential hazards of use and storage. Where hazards cannot be eliminated, the PI/supervisor shall provide information, SOPs, applicable engineering and administrative controls, and protective clothing and equipment to reduce hazards as low as reasonably possible for all chemical activities following directives contained in this manual and other hazard resources. Attach written safe operating procedure or hazard evaluation addendums to the copy of this manual located in applicable laboratory for specific procedures/processes that require hazard controls beyond those that are addressed in this manual. Contact LSC for templates and examples.

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Employees/students should avoid working alone during off-hours (before 7:00 am and after 5:00 pm) in activities involving the use of hazardous materials that have the potential for causing personal injury requiring an emergency response. When working alone is necessary, the PI/supervisor shall establish a written surveillance procedure, such as a check in with the working employee/student at predetermined times.

Original chemical container labels shall not be defaced. If a label is becoming unreadable a new label should be added with a minimum of the name of the chemical, the manufacturers name and phone number and the associated hazards. In addition to chemical name, prepared solutions shall be labeled with the preparer's initials and date of preparation, (include hazards where possible) and samples shall be labeled with a contact person's name and some type of identifier of contents.

Use and storage conditions are intended to reduce exposure and physical hazards from chemicals to as low as reasonably achievable. The information provided in the applicable MSDSs or other chemical hazard resource should be used as a reference source. Generally chemical container storage in alphabetical order is not appropriate unless chemicals are compatible. Some guidelines that shall be followed for specific types of chemicals are indicated below. Definitions of most of the health hazards discussed below and many others can be found at 1910 CFR 1200, Appendix A.

a. Carcinogens, highly toxic chemicals, and reproductive toxins shall be used in an area designated and posted for their use; and within ventilated equipment, within an enclosed system such as a glove box, hood, or in such a manner that will ensure a comparable degree of safety and is approved by the LSC. The chemicals shall be maintained when not in use in a storage cabinet or a room that has adequate ventilation for the chemical being stored and is locked when not supervised or in use. Storage areas shall be accessible to authorized persons only. Storage areas shall be posted "Carcinogen Storage", "Highly Toxic Chemical Storage", and/or "Reproductive Toxin Storage" if applicable.

Examples of strong carcinogens, in addition to those OSHA has designated on page 10: benzo[a]pyrene (CAS 50-32-8), 3-methylcholanthrene (CAS 56-49-5), 7,12-dimethylbenz[a]anthracene (CAS 57-97-6), dimethylcarbamoyl chloride (CAS 79-44-7), hexamethylphosphoramide (CAS 680-31-9), 2-nitronaphthalene (CAS 581-89-5), propane sultone (CAS 1120-71-4), many N-nitrosamines, many N-nitrosamides; bis(chloromethyl)ether (CAS 542-88-1), aflatoxin B1 (CAS 1162-65-8), 2-acetylaminofluorene (CAS 53-96-3).

b. Flammable and combustible liquids shall be used in a work area with no ignition sources, unless procedures have been written by the PI and approved by the LSC that describe how the fire danger has been mitigated. The liquids shall be stored in approved and labeled flammable liquids storage cabinets or containers. The current days working supply may be maintained outside approved storage containers if directly supervised by a technically qualified PI/staff/student or the amount left out on benches, etc. is less than 5 gallons. Ventilation shall be required where potential to exceed 10% of the lower explosive limit exists. Use conditions other than outlined above shall be

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approved by the LSC.

c. Toxic and highly toxic gases shall be used only under ventilated conditions.

Building quantity limits of toxic and highly toxic gases are limited to the following conditions:

Condition Exempt amounts(cubic feet at normal

temperature and pressure)Highly toxic Toxic

Inside storage (locked when room is not occupied) Unprotected by sprinklers, gas cabinets,

exhausted enclosures or separate gas storage rooms_______________________________________ 0 810

Within gas cabinets or exhausted enclosures in an unsprinklered structure or separate gas storage rooms_______________________________________20 1620

In sprinklered structures, not in gas cabinets, exhausted enclosures or separate gas storage rooms_________20 1620

In sprinklered structures, within gas cabinets, exhausted enclosures or separate gas storage rooms_________40 3240

Outside storage (locked)_______________________________20 1620

Quantities exceeding the amounts listed above per building shall be stored in internally sprinklered gas cabinets or exhausted enclosures. Treatment systems shall be provided to process any accidental release of gas. Gas monitoring, detection, and alarm system shall be installed.

d. Peroxide-Formers (see appendix C) use shall be evaluated carefully and controls implemented to reduce hazard potential, due to decomposition into potentially explosive compounds. They shall not be stored in clear glass bottles or in daylight conditions. They shall be labeled with date purchased, date opened and date they are tested for peroxides as described in Appendix C. They shall be scheduled for disposal one year after receipt or three to 12 months after opening, unless testing indicates a peroxide concentration less than 80 ppm. The responsible PI/supervisor shall track testing or disposal dates.

e. Corrosives are chemicals that destroy or damage living tissue irreversibly by chemical action. Corrosives are generally found in the form of strong acids or strong caustics (bases). They are dangerous to the human body because they tend to dissolve body tissue. When in contact with the skin, they produce chemical burns. Some corrosives form mists when they are exposed to air and when they are inhaled, they can damage the respiratory system. Appropriate PPE; such as goggles, apron and elbow length impervious gloves are required for manipulating of one gallon containers or larger. If not using a small, diluted amount; corrosives should be used within a chemical fume hood.

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Corrosives should be stored in such a manner that if there is a spill, acids will not mix with bases or leak to a drain. Use of an approved caustic storage cabinet that has impervious shelves with raised edges is a preferred method of storage.

f. Reproductive and Developmental Toxins are substances that have adverse effects on various aspects of reproduction, including fertility, gestation, lactation, and general reproductive performance (e.g. formamide, organomercurials, and lead compounds). Developmental toxins are substances that act during pregnancy to cause adverse effects on the embryo or fetus. These effects can include lethality (death of the fertilized egg, the embryo, or the fetus), malformations (this class of substances is also called teratogens), retarded growth, and postnatal functional deficiencies. When a pregnant woman is exposed to a chemical, generally the fetus is exposed as well because the placenta is an extremely poor barrier to chemicals. Reproductive toxins can affect both men and women. Male reproductive toxins can in some cases lead to sterility. Two well-known male reproductive toxins are ethylene dibromide and dibromochloropropane.

g. Other chemicals with extreme physical hazards such as explosives shall not be used without approval of the Chemical Hygiene and Radioisotope Use Committee and the research office.

6.2.1 Inventory Control

The responsible PI/supervisor or delegate shall maintain a Chemical Inventory Listing (CIL) of chemicals/products under their jurisdiction. The CIL blank form can be found on Centernet or may be requested from the LSC. It is in an excel format and is required to be completed and saved in the excel format and a copy returned to the LSC electronically as it is updated or at a minimum, annually. A copy should be maintained and posted by the laboratory completing the form and updated as containers are emptied and disposed and also as new items are purchased. A CIL of the OSU-CHS shall be maintained at the LSC office by consolidating the excel CIL forms from all laboratories.

All original chemical containers or transfer containers shall be labeled, at a minimum, with the chemical name, manufacturer name and phone number and hazards. All labels that are becoming unreadable shall be replaced with above information. All laboratory prepared solutions shall be labeled with chemical name, date of preparation, hazards (where feasible) and initials of person who prepared the solution.

If the city Fire Department requests, all quantities of chemicals in each building must be maintained below the limits specified for various chemical categories by the city Fire Department, unless a permit has been approved to exceed those limits. Contact the LSC for specific limit information.

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6.2.2 Exposure Monitoring

a. OSHA has written specific procedures for exposure monitoring (and use) when using any of the following substances above the "action level" (usually 50% of the PEL.) Further information on the OSHA requirements can be found at 29 CFR 1910.1001-1052 Subpart Z, Toxic and Hazardous Substances:

Asbestos (CAS # various)4-Nitrobiphenyl (CAS # 92933)alpha-Naphthylamine (CAS # 134327)Methyl chloromethyl ether (CAS # 107302)3,3'-Dichlorobenzidine (and its salts) (CAS # 91941)bis-Chloromethyl ether (CAS # 542881)beta-Naphthylamine (CAS # 91598)Benzidine (CAS # 92875)4-Aminodiphenyl (CAS # 92671)Ethyleneimine (CAS # 151564)beta-Propiolactone (CAS # 57578)2-Acetylaminofluorene (CAS # 53963)4-Dimethylaminoazobenzene (CAS # 60117)N-Nitrosodimethylamine (CAS # 62759)Vinyl Chloride (CAS # 75014)Arsenic (CAS # 7440382) and inorganic compounds except arsineLead compounds (CAS # various)Chromium (VI) (CAS # 18540299) in all its forms and compoundsCadmium (CAS # 7440439) and its compoundsBenzene (CAS # 71432)Coke oven emissionsCotton dust1,2-Dibromo-3-chloropropane (DBCP) (CAS # 96128)Acrylonitrile (CAS # 107131)Ethylene Oxide (CAS # 75218)Formaldehyde (CAS # 50000)4,4’-Methylenedianiline (CAS # 101779)1,3-Butadiene (CAS # 106990)Methylene Chloride (CAS # 75092)

All work with the above listed materials, that exceed the action level, must be coordinated through the LSC. Some of the specific requirements in addition to exposure monitoring may include medical examinations, working within a closed system only, and posting requirements.

When using formaldehyde the standard applies to work in histology, pathology, or anatomy laboratories.

b. If there is reason to believe that the action level; or in absence of an action level, the PEL established by OSHA (these can be found in the

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MSDS), is or will be exceeded during work activities for any chemical for which an action level or PEL has been established, initial exposure monitoring shall be conducted. This includes the PELs listed for chemicals as air contaminants at 29 CFR 1910.1000 and Tables 1-3, Subpart Z, Toxic and Hazardous Substances.

c. The PI/supervisor may choose to perform any required exposure monitoring or request assistance from the LSC. In requesting assistance, PI/supervisor must provide the chemical name, concentration in use, use conditions, and possibly invoice instructions.

d. The results of all monitoring must be communicated to affected employees by the PI/supervisor responsible within 15 days of receipt either by providing each employee an individual copy or posting a copy accessible to employees. A copy must be sent to the LSC to be placed in the employees file.

e. If initial exposure monitoring indicates exposure levels above the action level or PEL, the PI/supervisor shall provide controls to lower the exposure to an acceptable level if at all possible. Where this is not possible, respiratory protection appropriate to use conditions shall be provided and used. The LSC shall be contacted and the OSHA requirements in the Respiratory Protection standard, 29 CFR 1910.134 shall be followed. In addition, periodic monitoring shall continue to be conducted as determined by the LSC and possible medical surveillance as described in section 7.0 until results indicate levels are in the acceptable range.

6.2.3 Personal Protection

The PI/supervisor shall assess the workplace to determine if hazards are present, or are likely to be present, that necessitate the use of PPE. This assessment must be documented. If such hazards are present, or likely to be present, the PI/supervisor responsible shall select, and have each affected employee/student use the types of PPE that will protect the affected employees/students from the hazards identified in the hazard assessment; communicate selection decisions to each affected employee/student; and, select PPE that properly fits each affected employee/student. The PI/supervisor shall ensure that each employee/student is trained on the proper use, maintenance and disposal of selected PPE. The PI shall provide employees with PPE. Departmental policy shall determine if students (who are not employees) are to purchase their own PPE or it will be purchased by the department/laboratory funds.

All employees/students working with hazardous chemicals shall wear, at a minimum, gloves or other hand protection appropriate for the chemical being used (see safety product catalog’s glove compatibility charts) and safety glasses or splash goggles (if there is a possibility of a splash of liquids

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hazardous to the eyes); and if possible a chemical resistant lab coat (preferably with snap fasteners) when hazardous chemicals are being used in the lab. The eye and face protection selection chart located in Appendix A, provides guidelines for determining appropriate protection levels. Appendix B, “Recommended Safety and Emergency Equipment for the Laboratory” may be used in choosing appropriate PPE and emergency equipment. All PPE shall be inspected prior to use and stored in a manner that will prevent damage.

Where respirators are required to be used in the work area the OSHA standard 29 CFR 1910.134, “Respiratory Protection” shall be followed. The requirements include medical evaluation, fit testing, and training. If planning to use respiratory equipment, contact the LSC. If using a filtering facepiece (dust mask) voluntarily without there being a medical requirement to do so, complete the form in Appendix E and return a copy to the LSC.

No cosmetics will be applied or food/drink shall be allowed in the laboratory. Wearing of contact lenses will be avoided. Hands and forearms will be washed prior to leaving the work area. Further protection guidelines to be implemented, where applicable, can be found in the MSDS and other reference materials. A useful book that is referenced by the OSHA Lab Standard and other chemical organizations is Prudent Practices in the Laboratory: Handling and Disposal of Chemicals (2011).

6.3 Waste Disposal and Effluent Control

A release (e.g. down a sink drain, to the trash, exhausted through a ventilation system) of a regulated hazardous material or waste shall be prohibited, unless an exception has been approved by the LSC. All hazardous material, including waste, having the potential for release to a drain must be double contained. Unless chemicals are double contained in ventilation hoods, hood drains shall contain standpipes, be completely sealed or the drains sealed by a temporary cover.

PIs/staff/students shall use pollution prevention and waste minimization strategies to reduce the quantity and toxicity of waste generated, where possible. Guidelines may be found in the Environmental Management Guide for Small Laboratories, United States Environmental Protection Agency, EPA 233-B-00-001. Initially a determination shall be made by PI/supervisor/staff as to whether waste generated is hazardous or not. If this is not readily known, LSC shall be consulted to assist in making the determination.

All regulated hazardous waste shall be:

a. collected in nonreactive containers in good condition;

b. closed following each addition or removal (evaporation of volatile hazardous waste is prohibited);

c. labeled with contents, hazards, and the legend "Hazardous Waste"; oil waste shall be labeled with the exact words: “Used Oil”; and,

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d. collected and stored safely (e.g. flammable liquid waste shall be stored in approved flammable liquid storage containers or cabinet, incompatible wastes separated).

PI/supervisor/staff in charge of the process that generates waste or their designee is responsible for proper disposal of regulated hazardous waste coordinated through the office of the LSC. The waste shall be disposed through a certified waste disposal company, predetermined for OSU-CHS by the LSC. The following information shall be provided to the LSC when a waste pickup has been scheduled:

- contents, including percentages of each component if a mixture- amount of waste- size and type of container- hazards- contact name and phone number- department name and PI

OSU-CHS research office may not accept listings of unidentified substance(s) for disposal. However, the research office has made arrangements with our current waste contractor to conduct a hazard characterization for chemicals of unknown composition. The generating department shall make every effort to identify unknown chemicals prior to the characterization. In instances where unknown chemicals have been generated, the generating department shall provide a separate storage area to hold these materials until characterization can be conducted. In addition, the generating department may be required to provide lab space and a fume hood for the characterization procedure.

6.4 Activity Closeout

The nature of activities at OSU-CHS requires set guidelines to be implemented to safely close out activities and ensure that materials are managed in an environmentally sound manner. This will prevent chemicals and solutions from becoming "orphaned", exceeding their shelf life, or being discovered at a later date with no labeling or historical information. Some projects are short term or have a turnover of persons who were immediately responsible for the project and they were the only persons knowledgeable about the chemicals being left behind.

On program closeout, the chair of the department will be ultimately responsible for ensuring, through set departmental procedures, that all project associated materials such as chemicals, prepared reagents, samples, and waste will be disposed of using the previously described waste disposal guidelines or assigned to another project and custodian. All efforts shall be made to transfer or recycle material that is still usable.

The work area will be decontaminated using methods that will not generate hazardous aerosols or dust. All waste generated during cleanup will be disposed of according to waste disposal guidelines. Detection methods will be used where possible or required to ensure that all hazardous materials have been removed.

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6.5 Chemical Hazard Information and References

MSDSs provide information on the hazards of the chemical, PELs, and PPE to use when handling the chemical. The PI/supervisor is responsible for ensuring that each employee/student reads and understands the MSDS for each chemical they may be exposed to in their work activities; and that the MSDS is available in the work area at all times an employee/student is working, either in hard copy form or through immediate electronic access. Copies of MSDSs may be obtained by contacting the chemical manufacturer directly. A centralized file of many of OSU-CHS’s MSDSs is located in room A211 in the Barson wing of the Center for Health Sciences. Those MSDSs on file may be copied.

Each PI/supervisor that uses chemicals shall maintain a copy of this Chemical Hygiene Manual and make it available to all employees and students before use of chemicals to study and to reference. In addition, online documents and resources and other hard copy documents should be used to obtain chemical hazard information such as:

OSU’s “Online Safety Resource Library.” Environmental Management Guide for Small Laboratories; United States Environmental Protection Agency; EPA 233-B-00-001Prudent Practices in the Laboratory: Handling and Disposal of Chemicals (2011); Committee on Prudent Practices for Handling, Storage, and Disposal of Chemicals in Laboratories, National Research CouncilSchool Chemistry Laboratory Safety Guide (2006); Department of Health and Human Services Centers for Disease Control and Prevention, National Institute for Occupational Safety and HealthBiosafety in Microbiological and Biomedical Laboratories   (BMBL) 5th Edition; Center for Disease Control and PreventionChemical Safety (NIOSH databases)The Laboratory Safety Institute’s Web Links Resources

6.6 Laboratory Safety Training

The PI/supervisor shall determine the method in which training will be provided and ensure that the training occurs, for themselves and each employee/student under their supervision at the time of their initial assignment, every 3 years thereafter, and whenever a new chemical hazard is introduced into their work area. Training will consist of, at a minimum, the following three components, study of MSDSs and other hazard information related to the chemicals they will use; comprehensive online or classroom training; and on-the-job training. Supplemental videos/DVDs can be obtained from the LSC; however, they are included in the online training. Training completion shall be documented and included in the OSU-CHS research-training database. The submitted quiz from the online training will be considered as documentation of training attendance.

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The basic training subjects shall include:

- methods and observations that may be used to detect the presence or release of a hazardous chemical

- physical and health hazards of chemicals in the work area- measures employees/students can take to protect themselves from these

hazards, such as appropriate work practices, emergency procedures (including spill response), and PPE to be used

- details and location of the OSU-CHS Chemical Hygiene Manual - study all MSDSs for chemicals being used in work area, including permissible

or recommended exposure limits- signs and symptoms associated with exposures to hazardous chemicals used in

the laboratory- study of SOPs associated with work activities

On-the-job training is specific to the actual work situation and activities of employees/students. On-the-job training shall include such subjects as:

- details of specific procedures where handling of hazardous substances occurs - dealing with laboratory spills - glass breakage - disposal of hazardous substances - location of safety equipment/MSDSs - lab emergency procedures- how to operate and maintain equipment

Because of the specificity of the training, it is not practical to develop a generic classroom-training course to comply with the job specific needs. The PI/supervisor is responsible for defining this aspect of training and for determining how the requisite training will be provided and documented.

7.0 MEDICAL SURVEILLANCE

OSU-CHS shall make available, at no cost and at a reasonable time and place, medical consultation, applicable medical examinations, and necessary follow-up examinations performed by or under the direct supervision of a licensed physician to faculty/employees/graduate students under the following conditions:

a. Whenever faculty/employee/graduate student develop signs or symptoms associated with a hazardous chemical to which the faculty/employee may have been exposed during work activities;

b. Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the PEL) for an OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements (see section 6.2.2 "Exposure Monitoring");

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c. Whenever an event takes place in the work area such as a spill, leak, explosion or other occurrence resulting in the likelihood of a hazardous exposure; and,

d. For all physical injuries to the body.

Obtain medical care immediately, if the condition appears serious, when a possible exposure situation should occur as described. The PI/supervisor shall contact the Manager of Safety and HIPPA Compliance at (918) 561-8391 or if they cannot be reached, contact human resources at (918) 594-8221, as soon as possible, to report the incident and obtain further instructions, as necessary. The incident shall be reported to the LSC, research office at (918) 561-1403. See section 9.0 “Emergency Procedures” for more information.

The faculty/employee/graduate student shall file a research office record, “Laboratory Incident Evaluation” form found on Centernet or in Appendix D of this manual; and the human resources form “Employee Injury Report” immediately following a potential exposure situation or when conditions permit. Once completed by a medical professional, a copy of the human resources form should be sent to the Manager of Safety and HIPPA Compliance or human resources and the research office form should be sent to the LSC.

An injured faculty/employee/graduate student should go to the OSU Health Care Clinic and provide the information that the visit will potentially be a worker’s compensation claim. If there is an exposure on a weekend or after 5:00 p.m. to 8:00 a.m. or whenever the exposure may have serious consequences, the employee may go to OSU Medical Center emergency room, St. John emergency room, Hillcrest emergency room or other emergency room of their choice. The cost of medical assistance for a work related injury will be incurred first by personal insurance and the remainder by OSU.

For other student exposures or injuries, see phone numbers and addresses of medical facilities in Section 9.0 “Emergency Procedures; Injuries.” The cost of medical assistance for a work related injury for students who are not employed by OSU-CHS will be incurred by personal insurance.

8.0 EMPLOYEE RIGHTS AND RESPONSIBILITIES

Each staff/student has the right to request from supervisory staff (PI) access to the MSDS for any chemical being used in the work area and have them provided as soon as possible in a reasonable time, place, and manner, but in no event later than one working day after the request for access is made. If a request for a copy of the MSDS is made by the staff/student, those copies will be provided by the person’s supervisor (PI) within fifteen days of the request. If any staff/student has requested the above information, and has not received the information; within the specified time period, the staff/student may then refuse to work with the substances or at the location for which the request was made. An employer may not discharge or initiate any adverse personnel action against any staff/student because the staff/student has exercised their right under this provision.

Faculty/staff/students working in areas where exposures to hazardous substances exist shall be required to perform their jobs in accordance with precautions communicated to them during training and education programs, including MSDSs, this manual, safety meetings and on the job training. Employers may take appropriate

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disciplinary action, through reporting to human resources and determining a plan of action, when faculty/staff/students do not comply with OSU-CHS's policies and procedures that have been communicated to them.

Staff/students working for the university with toxic chemicals, carcinogens, reproductive toxins, or biological infectious materials must be at least 18 years old and have received the training specified in section 6.6 of this manual. Students younger than 18 years must have the approval of the lab PI and the Compliance Manager.

In addition, faculty/staff/students should use good judgment in maintaining a high level of safety and reducing potential risk factors. The faculty/staff/student working with hazardous materials or operations is the person who is ultimately responsible for following safe work practices for which they have been trained. Faculty/staff/students are required to stop work if any unsafe condition exists and report the unsafe condition to faculty/PI, or any level of authority necessary to elicit prompt response.

9.0 EMERGENCY PROCEDURES

FIRE OR EXPLOSION:

- If clothing catches fire STOP, DROP, and ROLL to smother the flames- Pull fire alarm or provide verbal warning to leave the building- Leave the building by nearest safe exit, go to area upwind of the fire. Secure critical

research operations, close ventilation hoods, shut down equipment, turn off ignition sources, and close doors and windows, if time permits

- If there is smoke or heat in area while leaving the building, keep low, crawling if necessary

- Contact Fire Department by dialing 9-911, ensure that address of location is provided- Contact the main Campus Security at (918) 625-8592 (cell)- Contact LSC at (918) 561-1403/(918) 241-3656 or research office at (918) 561-1400- If the fire is extensive or causes injury follow instructions under the “Injuries”

heading- After warning other occupants to leave the building, an employee may choose to fight

the fire, if the fire is small and can be extinguished using an available fire extinguisher, where there is no danger to the employee

- Occupants may go back into building only when someone in authority, such as the Fire Marshall, says it is safe to do so

HAZARDOUS SPILL OR CONTAMINANT RELEASE:

- If time permits and safety is ensured, contain the spill or release and turn off ignition sources

- For emergency spills or releases; such as a high concentration of toxic substances, situation that is life or injury threatening, condition that poses a fire or explosion hazard, a situation that poses a safety or health hazard to employees cleaning the release up or has the potential for uncontrolled environmental contamination:

Pull fire alarm, emergency alarm or provide verbal warning to leave the building

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Leave the facility by nearest exit, secure critical research operations if time permits, go to area at least 100 feet upwind from the facility out of the way of responding entities

Contact Campus Security at (918) 625-8592 (cell) Contact LSC at (918) 561-1403/(918) 241-3656 or research office at (918) 561-

1400; the LSC will make any required local, state or federal reports Contact the CHS hazardous waste removal contractor, Envirosolve call Center at

(918) 587-9664 or 877-927-8311 (24 hr), who are trained in cleaning up hazardous spills; or contact city Fire Department Hazardous Response Team by dialing 9-911

If spill or release has caused injury follow instructions under heading “Injuries”

If a hazardous response team has been called they will respond to remediate the spill or provide instructions for remediation by OSU-CHS; the LSC or other person trained in First Response will coordinate the OSU-CHS response, as necessary

Information as to the nature of the spill or release will be provided by the LSC, building contact, or other persons who have direct knowledge of the incident or activities involved, to the responding entities

The LSC will work with appropriate officials in determining possible hazards to health or the environment and necessity for any further area evacuation

The building may be reentered once the Response Team, LSC or other OSU-CHS authority has indicated it is safe to do so

If the spill is outside, evacuate to a safe distance out of the way of responding entities

- For small, incidental (confined to immediate work/activity area, not threatening to safety or health of building occupants or the public) spills or releases, including unknown odors:

Isolate the area from unauthorized entry, if necessary Contact immediate supervisor, department chair, or LSC; as necessary Respond as appropriate, e.g. ventilate area; using appropriate spill cleanup

materials, clean up spill, if trained; repair any leaks; use respirators as necessary (only properly certified personnel may use respirators)

INJURIES (including hazardous chemical exposure)

- Where possible remove the hazard or the affected person from the hazard (e.g. remove person to fresh air for hazardous inhalation exposure, assist or remove person from fire danger, wash harmful chemicals from skin or eyes for a period of fifteen minutes), obtain medical assistance

- If ambulance transportation is needed dial 9-911; however, the injured person may reject service

- Use barriers such as gloves or other protective material to prevent contact with a victim's blood

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- If injury needs to be seen by a medical professional contact the Manager of Safety and HIPPA Compliance at (918) 561-8391 or if they cannot be reached, contact human resources at (918) 594-8221

- Contact LSC at (918) 561-1403/(918) 241-3656 or research office at (918) 561-1400- Employees: for life or limb threatening injuries or for after hours injuries (5 p.m. to 8

a.m. and weekends) and

Students: for all serious injuries,

the victim should be transported to the nearest available emergency room, such as:

OSU Medical Center, 744 W. 9th (918) 599-5100Hillcrest Medical Center, 1120 S. Utica (11th and Utica) (918) 579-6150St. John, 1923 S. Utica (21st and Utica) (918) 744-2191

For employees, the supervisor shall ensure that the resources form “Employee Injury Report” is completed the day of the incident, if time allows, or as soon as possible and forwarded to OSU-CHS's Manager of Safety and HIPPA Compliance (if that position is filled) or human resources. The human resources form can be found by clicking on the human resources site at http://centernet.okstate.edu/services.cfm. The research office form “Laboratory Incident Evaluation” must also be completed and a copy sent to the LSC.

- For injuries that are not life or limb threatening, employees should go to the OSU Health Care Center, between 8 a.m. to 5 p.m. weekdays for work related injuries, or their own personal physician. When the injured person goes to a medical facility, the facility personnel must be told that the injury is work related. The Manager of Safety and HIPPA Compliance (if that position is filled) or human resources should be contacted, (918) 594-8221, so that they might contact the medical facility of choice. Again, the supervisor shall ensure that the “Employee Injury Report” and the “Laboratory Incident Evaluation” form are completed to the extent possible and taken to the medical facility. Once the employee has been seen by a medical provider and the forms are completed they should be given to the persons indicated on the forms.

OSU Health Care Center, 2345 SW Boulevard (918) 582-1980

- Students may go to a medical professional of choice or the OSU Health Care Center, 2435 SW Blvd., for injuries that are not serious

September 2011

If there is one work related employee death or hospitalization of 3 or more employees relatedto one incident, human resources shall be contacted immediately, (918) 594-8222 or 8221, to make required OSHA notifications within 8 hours of incident.

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APPENDIX A

EYE AND FACE PROTECTION SELECTION CHART

Source Assessment of Hazard Protection_ (See note (5) IMPACT--Chipping, grinding machining, masonry work, woodworking, sawing, drilling, chiseling, powered fastening, riveting, and sanding.

HEAT--Furnace operations, pouring, casting, hot dipping, and welding

CHEMICALS--Acid and chemical handling, degreasing, plating.

DUST--Woodworking, buffing, general dusty conditions.

Flying fragments, objects, large chips, particles, sand, dirt, etc.

Hot sparks

Splash from molten metals

Splash

Irritating mists

Nuisance dusts

Spectacles with side protection, goggles, face shields. See notes (1), (3), (5), (6), (10). For severe exposure, use faceshield.

Faceshields, goggles, spectacles with side protection. For severe exposure use faceshield. See notes (1), (2), (3).

Faceshields worn over goggles. See notes (1), (2), (3).

Goggles, eyecup and cover types. For severe exposure, use face shield. See notes (3), (11).

Special purpose goggles

Goggles, eyecup and cover types. See note (8).

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Source Assessment of Hazard ________ Protection _____ (See note (5)

LIGHT and/or RADIATION--welding: Electric arc Optical radiation Welding helmets or welding shields.

Typical shades: 10 - 14. See notes (9), (12).

welding: Gas Optical radiation Welding goggles or welding face shield. Typical shades: gas welding 4 - 8, cutting 3 - 6, brazing 3 - 4. See note (9).

Cutting, Torch brazing, Torch soldering

Optical radiation Spectacles or welding face shield. Typical shades, 1.5 - 3. See notes (3), (9).

Glare

Laser: Class IIIA-IV

Poor vision

Optical radiation

Spectacles with shaded or special purpose lenses, as suitable. See notes (9), (10).

Spectacles with side shieldsTypical shades: 5 – 8. See notes (3), (9).

Notes to Eye and Face Protection Selection Chart:

(1) Care should be taken to recognize the possibility of multiple and simultaneous exposure to a variety of hazards. Adequate protection against the highest level of each of the hazards should be provided. Protective devices do not provide unlimited protection.(2) Operations involving heat may also involve light radiation. As required by the standard, protection from both hazards must be provided.(3) Faceshields should only be worn over primary eye protection (spectacles or goggles).(4) As required by the standard, filter lenses must meet the requirements for shade designations in 29 CFR 1910.133 (a) (5). Tinted and shaded lenses are not filter lenses unless they are marked or identified as such.(5) As required by the standard, persons whose vision requires the use of prescription (Rx) lenses must wear either protective devices fitted with prescription (Rx) lenses or protective devices designed to be worn over regular prescription (Rx) eyewear.(6) Wearers of contact lenses must also wear appropriate eye and face protection devices in a hazardous environment. It should be recognized that dusty and/or chemical environments may represent an additional hazard to contact lens wearers.(7) Caution should be exercised in the use of metal frame protective devices in electrical hazard areas.(8) Atmospheric conditions and the restricted ventilation of the protector can cause lenses to fog. Frequent cleansing may be necessary.(9) Welding helmets or faceshields, should be used only over primary eye protection (spectacles or goggles).(10) Non-sideshield spectacles are available for frontal protection only, but are not acceptable eye protection for hazards that may come from the side.(11) Ventilation should be adequate, but well protected from splash entry. Eye and face protection should be designed and used so that it provides both adequate ventilation and protects the wearer from splash entry.(12) Protection from light radiation is directly related to filter lens density. See note (4). Select the darkest shade that allows task performance

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Appendix B: Recommended Safety and Emergency Equipment for the LaboratoryThe following are checklists for determining safety and emergency equipment for the laboratory:

Personal Protective Equipment

Chemical splash goggles Safety glasses with side shields Face shields Lab coat Lab apron (acid resistant) Gloves (selected based on the material being handled and the particular hazard

involved) Shoe covers Hair covers Respirators, including filtering facepiece - also known as a “dust mask”

Safety and Emergency Equipment and Supplies

Hand-free eye-wash stations (not eye-wash bottles) that conform to ANSI Z358.1–2004

Deluge safety showers that conform to ANSI Z358.1–2004 Safety shields with heavy base Fire extinguishers (dry chemical and carbon dioxide extinguishers) Sand bucket Fire blankets Emergency lights Emergency and safety hazard labels, signs and placards Fire detection or alarm system First-aid kits Spill control kit (absorbent and neutralizing agents) specific to chemicals used Chemical storage cabinets (e.g. flammable, corrosive) Gallon-size carrier buckets for carrying chemical bottles Laboratory chemical hood (80–120 ft/minute capture velocity, vented outside) Ground-fault circuit interrupter electrical outlets Container for broken glass and a separate one for sharps Material Safety Data Sheets (MSDSs) Biosafety cabinet Safer sharps devices Automatic External Defibrillator Ergonomically designed equipment and furniture Bags colored and labeled for specific hazards Radiation monitoring equipment Disinfectant Flashlight

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Appendix C

SOP for the Safe Storage &Use of Peroxide-Forming Chemicals

A wide variety of organic compounds spontaneously form peroxides by a free radical reaction of the hydrocarbon with molecular oxygen. Under normal storage conditions, formed peroxides can accumulate in the chemical container and may explode when subjected to heat, friction or mechanical shock. For this reason, it is imperative that all researchers learn to recognize and safely handle peroxide-forming compounds. Recommended storage limits and specific guidance for common chemicals that can form peroxides are listed in Table 1. The chemicals listed in List A as “peroxide hazard on storage – without concentration” in the table can form peroxides that are difficult to detect and eliminate. These peroxides can come out of solution and form crystals or a gel in the bottom of the container. They are extremely unstable and can violently decompose with the smallest disturbance, sometimes even spontaneously. They can be hazardous even if not opened. Do not store these chemicals more than 12 months unless tests show that they contain less than 80 ppm of peroxides. The chemicals listed in List B as “hazard due to peroxide concentration” can undergo explosive polymerization initiated by dissolved oxygen. This class of peroxide-forming chemicals has a propensity for exploding when used experimentally in operations such as distillations. Do not store these chemicals more than 12 months unless tests show that they contain less than 80 ppm of peroxides. The chemicals listed in List C as “autopolymerize as a result of peroxide accumulation” may explode when relatively small quantities of peroxides are formed. It is common to distill these peroxide-forming solvents before use and this concentrates the dissolved peroxides and subjects them to heat and mechanical shock. The chemicals listed in Table 2 represent other peroxide-forming chemicals that cannot be placed into the other categories but nevertheless require handling with precautions.

 Practices for Control of Peroxide-forming Organic Materials

 

Inhibitors Many methods can be used to stabilize or inhibit the peroxidation of susceptible chemicals. If it does not interfere with the use of the chemical and if available, peroxide scavengers (inhibitors) shall be added in small quantities, and peroxide-forming chemicals shall be ordered with inhibitor added.

 

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Purchase Ideally, purchases of peroxide-forming chemicals should be restricted to ensure that these chemicals are used up completely before they can become peroxidized. This requires careful experiment planning. Researchers should purchase no more material than is needed to complete an experiment within the chemical’s safe shelf life. 

Storage Peroxide-forming chemicals shall be stored in sealed, air-impermeable, light-resistant containers and should be kept away from light (light can initiate peroxide formation). Peroxide-forming chemicals should be stored in their original manufacturer’s container whenever possible. This is very important in the case of diethyl ether because the iron in the steel containers that the material is shipped in acts as a peroxide inhibitor. 

Labeling and Shelf-Life Limitation Peroxides tend to form in materials as a function of age. Therefore, it is imperative that researchers are keenly aware of the age of their peroxide-forming chemicals. Researchers must date each container upon arrival in the laboratory. Containers must be dated again when opened for the first time. An appropriate expiration date based on the information found in Table 1 should also be on the label.  Testing and Deperoxidation When the date on the container expires, the peroxide-forming chemical shall either be 1) tested for peroxide content or 2) assumed to contain excessive peroxides and disposed of as hazardous waste. The maximum allowable concentration of peroxide in chemicals is 80 ppm. If a value over 80 ppm is detected, the owner shall deperoxidize the chemical or dispose of it as hazardous waste. Materials that are older than the suggested shelf life but have been tested and have no detectable peroxides or peroxide concentrations less than 80 ppm may be retained but should be tested at least quarterly. All chemicals to be distilled must be tested prior to distillation regardless of age. Researchers should never test containers of unknown age or origin. Older containers are far more likely to have concentrated peroxides or peroxide crystallization in the cap threads and therefore can present a serious hazard when opened for testing. The easiest method to test for peroxides is the use of peroxide test strips. These strips are simple to use and can be obtained from a variety of suppliers including Lab Safety and Fisher. For volatile organic chemicals, the test strip is immersed in the chemical for 1 second, then the tester breathes slowly on the strip for 15-30 seconds or until the color stabilizes. The color is then compared with a colormetric scale provided on the bottle. Test strips must be kept refrigerated and must have an expiration date on the bottle. 

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Management and disposal of old containers Older containers of peroxide-forming chemicals, or containers of unknown age or history, must be handled very carefully and should never be opened by researchers. Any peroxide-forming chemical with visible discoloration, crystallization or liquid stratification should be treated as potentially explosive. Older steel containers that have visible rust may also be extremely dangerous. If any of these conditions are observed on a peroxide-forming chemical container or if the origin and age are unknown, do not attempt to move or open the container. Contact LSC to have the container inspected and if necessary disposed of properly. Safe Distillation 

Eliminate the peroxides with a chemical reducing agent or pass the solvent through activated alumina.

Add mineral oil to the distillation pot. This has the combined effect of “cushioning” any bumping, maintaining dilution and serving as a viscous reaction moderator in case the peroxides begin to decompose.

 Carefully monitor the distillation process to ensure that it does not dry out completely, and then overheat. Distillation can concentrate peroxides, especially if taken to a dry state. Peroxides will be present mainly in the still bottoms. Reducing Peroxides during Distillation Small pieces of sodium metal can be added to the distillation vessel to reduce peroxides. Use benzophenone as an indicator for the presence of sodium metal (benzophenone in the presence of sodium metal forms a radical with a deep-blue color). When the blue color disappears, add more sodium metal. 

Safe Storage Periods for Peroxide Formers

Unopened chemicals from manufacturer: 18 months Opened containers: Chemicals in Table A. 3 months Chemicals in Tables B. and D. 12 months Uninhibited chemicals in Table C. 24 hours Inhibited chemicals in Table C.

(Do not store under an inert atmosphere) 12 months

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Table 1. Common chemicals that form explosive levels of peroxides and their storage limits

  

List AForm potentially explosiveperoxides withoutconcentrationa . Dispose ortest 3 months after opening.

List BForm potentially explosiveperoxides on concentrationb

Dispose or test 12 monthsafter opening.

List CAutopolymerize as a resultof peroxide accumulation.Dispose or test inhibitedmaterials after 12 months.

Butadienec

Chloroprened

Divinyl acetyleneChloropreneTetrafluoroethylenec

Vinylidene chlorideMethacrylateTetrafluoroethylene 

AcetalAcetaldehydeBenzyl alcoholIsopropyl etherCyclohexanol2-cyclohexen-1-olCumeneDecahydronaphthaleneDiacetyleneDicyclopentadiene Diethyl ether Diethylene glycolDimethyl etherDioxanesEthylene glycol dimethyl ether4-heptanolMethyl acetyleneMethyl isobutyl ketone3-methyl-1 butanolMethyl cyclopentane2-pentanol4-penten-1-ol1-phenylethanol2-phenylethanol2-propanol (isopropanol, “IPA”)TetrahydrofuranTetrahydronaphthaleneVinyl ethersOther secondary alcohols

Acrylic acidAcrylonitrileButadienee

2-butanolChlorotrifluoroethyleneMethyl methacrylateStryeneVinyl acetateVinyl acetyleneVinyl chlorideVinyl pyridine

aStore under nitrogen, if practical. bWARNING! May become unstable if concentrated intentionally or accidentally by user. cWhen stored as an inhibited liquid monomer. dWhen stored as a liquid monomer. 

eWhen stored as a gas. 

R.J. Kelly, “Review of Safety Guidelines for peroxide-forming Organic Chemicals”, Chemical Health & Safety, September/October 1996, pp 28-36.   

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 Table 2

List D--Chemicals that may form peroxides but cannot be clearly placed in Lists A-C

Acrolein tert-Butyl methyl ether Di(1-propynl) ether n-MethylphenetoleAllyl ether n-Butyl phenyl ether Di(2-propynl) ether 2-MethyltetrahydrofuranAllyl ethyl ether n-Butyl vinyl ether Di-n-propoxymethane 3-Methoxy-1-butyl acetateAllyl phenyl ether Chloroacetaldehyde diethylacetal 1,2-Epoxy-3-

isopropoxypropane2-Methoxyethanol

p-(n-Amyloxy)benzoyl chloride 2-Chlorobutadiene 1,2-Epoxy-3-phenoxypropane 3-Methoxyethyl acetaten-Amyl ether 1-(2-Chloroethoxy)-2-

phenoxyethanep-Ethoxyacetophenone 2-Methoxyethyl vinyl ether

Benzyl n-butyl ether Chloroethylene 1-(2-Ethoxyethoxy)ethyl acetate

Methoxy-1,3,5,7-cyclooctatetraene

Benzyl ether Chloromethyl methyl ether 2-Ethoxyethyl acetate b-MethoxypropionitrileBenzyl ethyl ether b-Chlorophenetole (2-Ethoxyethyl)-a-benzoyl

benzoatem-Nitrophenetole

Benzyl methyl ether o-Chorophenetole 1-Ethoxynaphthalene 1-OcteneBenzyl-1-napthyl ether p-Chlorophenetole o,p-Ethoxyphenyl isocyanate Oxybis(2-ethyl acetate)1,2-Bis(2-chloroethoxyl)ethane Cyclooctene 1-Ethoxy-2-propyne Oxybis(2-ethyl benzoate)Bis(2-ethoxyethyl)ether Cyclopropyl methyl ether 3-Ethoxypropionitrile b,b-OxydipropionitrileBis(2-(methoxyethoxy)ethyl) ether

Diallyl ether 2-Ethylacrylaldehyde oxime 1-Pentene

Bis(2-chloroethyl) ether p-Di-n-butoxybenzene 2-Ethylbutanol Phenoxyacetyl chlorideBis(2-ethoxyethyl) adipate 1,2-Dibenzyloxyethane Ethyl-b-ethoxypropionate a-Phenoxypropionyl chlorideBis(2-methoxyethyl) carbonate p-Dibenzyloxybenzene 2-Ethylhexanal Phenyl-o-propyl etherBis(2-methoxyethyl) ether 1,2-Dichloroethyl ethyl ether Ethyl vinyl ether p-PhenylphenetoneBis(2-methoxyethyl) phthalate 2,4-Dichlorophenetole Furan n-Propyl etherBis(2-methoxymethyl) adipate Diethoxymethane 2,5-Hexadiyn-1-ol n-Propyl isopropyl etherBis(2-n-butoxyethyl) phthalate 2,2-Diethoxypropane 4,5-Hexadien-2-yn-1-ol Sodium 8-11-14-eicosatetraenoateBis(2-phenoxyethyl) ether Diethyl ethoxymethylenemalonate n-Hexyl ether Sodium ethoxyacetylideBis(4-chlorobutyl) ether Diethyl fumarate o.p-Iodophenetole TetrahydropyranBis(chloromethyl) ether Diethyl acetal Isoamyl benzyl ether Triethylene glycol diacetate2-Bromomethyl ethyl ether Diethylketene Isoamyl ether Triethylene glycol dipropionatebeta-Bromophenetole m,o,p-Diethoxybenzene Isobutyl vinyl ether 1,3,3-Trimethoxypropeneo-Bromophenetole 1,2-Diethoxyethane Isophorone 1,1,2,3-Tetrachloro-1,3-butadienep-Bromophenetole Dimethoxymethane b-Isopropoxypropionitrile 4-Vinyl cyclohexene

3-Bromopropyl phenyl ether 1,1-DimethoxyethaneIsopropyl-2,4,5-trichlorophenoxy acetate Vinylene carbonate

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Appendix D

OKLAHOMA STATE UNIVERSITY CENTER FOR HEALTH SCIENCESLABORATORY INCIDENT EVALUATION

The filing of this report and all information therein are to be held in strictest confidence.

The Oklahoma State University Center for Health Sciences employees or graduate students who work with hazardous chemicals have the opportunity to receive medical attention, including any follow-up examinations that the examining physician determines to be necessary, if signs and symptom associated with a hazardous chemical(s) used in the workplace should develop, potential exposure associated with accidental spills or releases occurs, or where exposure monitoring indicates an exposure level routinely above the action level for OSHA regulated chemicals.---------------------------------------------------------------------------------------------------------------------------------Employee/Graduate Student SectionI have been given the opportunity to receive medical attention for a potential hazardous chemical exposure and at this time I do do not wish to receive medical attention.

Signature Date ___________ ---------------------------------------------------------------------------------------------------------------------------------PI/Supervisor Section (attach applicable material safety data sheet(s)) Identify hazardous chemical(s) to which the employee may have been exposed:

Describe conditions under which the exposure occurred including quantitative exposure data, if available:

Describe signs and symptoms of exposure that the employee is experiencing, if any:

Signature Date ___________ ---------------------------------------------------------------------------------------------------------------------------------Physician's Written Opinion-OSHA 29 CFR 1910.1450(g)(4)(i)-(ii) (specific findings or diagnoses unrelated to occupational exposure shall not be revealed in this report)-only related to exposure:Recommendation for further medical follow-up:

Results of the medical examination and any associated tests (may be attached):

Medical condition that may place the employee at increased risk as a result of exposure to a hazardous chemical found in the workplace:

The results of the consultation or medical examination and any medical condition that may require further examination or treatment have been discussed with the employee.

Physician signature Date ___________ ---------------------------------------------------------------------------------------------------------------------------------

Copies: 1) Employee (you should preserve this report for future reference); 2) responsible PI/Supervisor; 3) Lab Safety Coordinator (employee exposure file)

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Appendix E-Voluntary Respiratory Use

Oklahoma State University Center for Health Sciences

Respiratory Protection Standard, OSHA 29 CFR 1910.134

(Mandatory) Information for Worker Using Respirators Voluntarily When Not Required Under the Standard

Respirators are an effective method of protection against designated hazards when properly selected and worn. Respirator use is encouraged, even when exposures are below the exposure limit, to provide an additional level of comfort and protection for workers. However, if a respirator is used improperly or not kept clean, the respirator itself can become a hazard to the worker. Sometimes, workers may wear respirators to avoid exposures to hazards, even if the amount of hazardous substance does not exceed the limits set by OSHA standards. If your employer provides respirators for your voluntary use, or if you provide your own respirator, you need to take certain precautions to be sure that the respirator itself does not present a hazard.

You should do the following:

1. Read and heed all instructions provided by the manufacturer on use, maintenance, cleaning and care, and warnings regarding the respirators limitations.

2. Choose respirators certified for use to protect against the contaminant of concern. NIOSH, the National Institute for Occupational Safety and Health of the U.S. Department of Health and Human Services, certifies respirators. A label or statement of certification should appear on the respirator or respirator packaging. It will tell you what the respirator is designed for and how much it will protect you.

3. Do not wear your respirator into atmospheres containing contaminants for which your respirator is not designed to protect against. For example, a respirator designed to filter dust particles will not protect you against gases, vapors, or very small solid particles of fumes or smoke.

4. Keep track of your respirator so that you do not mistakenly use someone else's respirator.

Signature below indicates the above information has been read and understood.

Worker_____________________________________________ Date ____________

Copies: 1) Worker, 2) Principal Investigator/Supervisor, 3) Laboratory Safety Coordinator

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